BQYTE

HOA PHAN TicH

T~PI

.
PHAN TicH HOA HOC
SACH BAo TAO DUQC ~iBAI HQC
Mil so: D.20.Y.14
Chu bien: PGS.TS. TRAN T(1 AN

, A' ?
NHA XUAT BAN Y HQC
HA NQI- 2007
 • A

CHI £)~o BIEN SO~N

V~ Khoa hoc va Dao tao, BQ Y te'

CHI) BIEN

PGS.TS. Tran Tll An .

. NHONG NGUOI BIEN SO~N

PGS.TS. Tran Tll An - eN. T~n Tfch

THAM GIA T6 CH(1C BAN THAo

TS. Nguyen Manh Pha

.
ThS. Phi Van Tharn

© Ban quyen thuoc BQ Y te' (V~ khoa hoc va Dao 'tao)

_
..
 Thuc hien mQt s6 dieu cua Luat Giao due, BQ Giao due & Dao tao va BQ
Y te'da ban hanh chuong trinh khung dao tao DUQcsi dai hoc, BQY te' W chuc
.bien soan tai lieu day- hoc cac mon co sd, chuyen mon va co ban chuyen
nganh theo chuong trinh tren nham tung budc xay dung bQ sach chuan trong
cong tac dao tao nhan luc y te'.
Sach Hoa pluin. tich. T4p 1 dUQcbien soan dua tren chuong trinh giao due
cua Trudng Dai hoc DUQcHa NQi tren co sd chuong trinh khung da duoc phe
duyet, Sach dUQccac nha giao giau kinh nghiem va tam huye't vdi cong tac dao
tao bien soan theo phuong cham: Kie'n thuc co ban, h~ th6ng; nQi dung chinh
xac, khoa hQc; c~p nh~t cac tie'n bQ khoa hQc, ky thu~t hi~n d~i va thl,tc ti~n
Vi~t Nam. .
Sach Hoa phan tich T4p 1 da dUQCHQi d6ng chuyen mon tham dinh sach
va tai li~u d~y - hQc chuyen nganh DUQccua BQ Y te'tham dinh vao nam
2006. BQ Y te' ban hanh lam tai li~u d~y - hQCchinh thuc cua nganh y te'.
Trong thdi gian tu 3 de'n 5 nam, sach ph8.i dUQCchinh ly, b5 sung va c~p nh~t.
BQY te' xin chan thanh cam on PGS.'I.'S. Trfin Ti1 An va eN. Trfin Tich, BQ
mon Hoa phan tich Trudng D~i hQc DUQc~a NQi da danh nhieu cong suc hoan
thanh cu6n sach nay, cam dn GS.TS. Til VQng Nghi va PGS. Ph~m Gia Hu~ da
dqc, phan bi~n d~ cu6n sach dUQCl10an chinh kip thdi ph\lc ~ cho cong tac dao
tlilOnhan Il,tcy te'.
Lfin dAu xuflt ban, chUng toi mong nh~n dUQcy kie'n dong gop cua d6ng
nghi~p, cac b~ sinh vien va cac dQcgia d~ Ifin xuflt ban sau cu6n sach dUQChoan
thi~n hdn.

V,=,KHOA HQC vA aAo T~O

BQYTE

3
 Lal NOI aAU

Theo chuong trmh dao tao DUQcsi dai hoc dB.duoc BQY t€ phe duyet,
mon H6a h9Cphan. tich duoc giang day d nam thu hai (hoc ky 3 va 4) vdi muc
tieu giup sinh vien nam vimg nguyen tllc va tmg dung cac phuong phap phan
tich thuong' dung trong nganh DUQc.
• D~ thuan ti~n cho viec giang day va hoc t~p, sach H6a phan tich dUQc
chia lam hai hoc phan:
- H6a phan tfch T~p 1, dUQCgiang day d hoc ky 3,
- H6a phan tich T~p 2, dUQCgiang d hoc ky 4.
Day la cu6n Hoa phan tich T~p 1vdi hai muc tieu hoc t~p cu th~:
1. Trinh bay duoc nguyen t!c cua cac phuong phap phan tich hoa hoc: .
acid - base, tao phuc chat, oxyhoa khu, k€t tua va phudng phap kh6i
lUQng.
2. Tht;lchi~n dung cac thao tac dinh lUQng:do th~ tich, do kh6i lUQng,xi!
ly dUQcs61i~u tht;lcnghi~m.va trinh bay k€t qua phan tich.
D~ giup sinh vien hQct~p d~t hai m\lc tieu tren, nQi dung cua Hoa phan
tich t~p 1nay dU<;1ctrinh bay nhu sau:
* Phdn 1: Cd sa lj thuyet cua H6a phtin,tich: Trinh bay cac van de lien quan
trt;lcti€p d€n cac phudng phap phan ~ichhoa hQcva phan tich d\lllg C\lnhu:
- Cac cach bi~u thi n6ng dQdung dich,.
- B6n lo~i can b~ng hoa·hQc,
- Xli ly th6ng ke du li~u va trinh bay k€t qua.
Ph~n 1 co 5 chudng til chudng 1 den chudng 5.
* Phdn 2: Phan tich h6a h9C a?nh lztf/ng: Ph~n nay thao lu~n 5 phudng
phap chinh: 4 phudng phap chuftn dQ(acid-base, t~o phuc, oxy h6a khli va ket
tua) va phan tich kh6i lu<;1ng.Ph~n 2 bao g6m 6 chudng: til chudng 6 den
chudng 11.
Sach H6a phan tich T~p 1 nay khac voi tai li~u hQct~p H6a phan tich I
do BQmon Phan tich bien so~n nam 1998 va Trudng D~i hQcDU<;1c Ha NQiin
(luu hanh nQibQ) d mQtso'di~m:
- Sach nay chia ra hai ph~n rieng bi~t: ph~n Cd sd ly thuyet va ph~n Ph an
tich h6a hQcdinh lU<;1ng.
- D~ tranh trung ll).pvoi cac mon hQckhac, nen mQtso'khai ni~m cd ban ve
hoa hQcnhu: acid - base, phan lo~i danh phap phuc chat, chat oxy hoa
khii ... ho~c phan b6 chuAn eua toan th6ng ke khong dtt<;1c
nhllc l~i rna di
sau vao can b~ng ph\lc V\lcho nghien cuu phudng phap dinh h1<;1ng.

5
 -~-- ----.-.

- Khao sat cac can bang theo mQt phuong phap thong nhat.
- :85 sung them mdt so nQi dung dam bao cap nhat kien thuc.
Cuoi m6i chuong co ph An bai t~p. PhAn IOn bai t~p d rmrc trung binh d~
giup sinh vien lam sang to ly thuyet, t\i lu.qng gia kie'n thtrctiep thu ducc. -
Trong chuong trinh dao tao Dl1Qcsi. dai hoc, Hoa phan tich la mon hoc co
sd. No cung cap cho sinh vien nhfing kien thue cAn thie't d~ hoc cac mon khac
nhu: Hoa duoc, Dl1Qclieu, Bao che, Hoa sinh, DQc chat. M~t khac, co th~ coi •
Hoa phan tich rat gAn vdi cac mon hoc nghiep V1,1 vi no trang bi cho sinh vien
cac phuong phap phan tich (hoa hoc, dung C1,1) phuc V1,1 true tiep cho nghien
ctru, .danh gia chat 111Qng(v~ hoa hoc va sinh hQc) cua nguyen li~u va che'
ph~m thuoc.
Trong qua trinh bien so~n cae tac gia da co nhi~u co gAng, tuy v~y cling
kho tranh khoi nhung thie'u sot ho~c chua phil hQp. Chung toi rat vui mung
nh~n duQc nhung chi d~n, dong gop cua dang nghi~p va b~n dQc d~ cuon sach
ngay cang co chat lUQngcao hdn.

Hd N9i, thang 8 nam 2006

Chu bien
PGS. TS. Tr6n Tii An

6
 . LUC
MUC .
UJi gidi thieu. 3
UIi noi ct&u 5
• 15
Cac chu vie't tiit
Ph'n 1. CO Sa LY THUY~T CliA HOA PHAN T[CH 17

Chirong 1. D4I CU'dNG vE HOA PHAN TicH 17

PGS. TS. Trtin. Tii An
1. D6i ttt<;lngcua hoa phan tfch 17
2. Tinh ph6 bien cua hoa Phan Tich 18
3. Ph an loai cac phuong phap phan tfch 19
3.1. Dua vao ban ehB:t cua phuong phap 19
3.2. Dua vao luong mftu phan tich 21
3.3. Dua vao viec su dung chat chuan 21
3.4. M9t s6thu?t ngil khac 22
4. Cac budc chu ye'u cua m9t qui trinh ph an tich 22
4.1. Buoc 1- Xac dinh muc tieu va n9i dung phan tich 22
4.2. Buoc 2 - Chon phuong phap phan tfch 23
4.3. Budc 3 - LB:ymjiu va bao quan mftu 24
4.4. Budc 4 - Xuly mjiu 24
4.5. Budc 5 - Thuc hien cac phep do 25
4.6. Buoc 6 - Xuly so lieu va trinh bay ke't qua ph an tich 25
Cau hoi va hai t~p 25
Chlidng 2. NONG DQ DUNG DICH 27

PGS. TS. Tr&n Tii An

1. B6n cach bi~u thi n6ng dQ dung dich 27
1.1. N6ng dQ ph~n tram 27
1.2. N6ng dQ gam 28
1.3. N6ng dQ mol 28
1.4. N6ng dQ dttdng Itt<;lng 29

7
 1.5. MQt s6 each bi~u thi n6ng dQkhac 30
2.'Tinh toan v~ nong dQ dung dich 30
2.1. Bai to-an v~ pha dung dich . 31
2.2. B~i toan v~ chuydn d5i n6ng dQ 31
.cau hoi va hili t~p 32
,Cbu:~g 3; xtr LY DU tItu THVC NGHItM TRONG HOA pHAN TiCH 35

PGS. TS. Trtin. Tit An

1. DQdung va dQchinh xac cua du Ii~u 35
1.1. DQchinh xac 35
1.2: DQdung 37
2,. Oac loai sai s6 (cua du li~u thuc nghiem ) 38
2.1. Sai s6 h~ th6ng 39
2.2. Sai s6 ngiu nhien 40
3. Xi':i If th6ng ke cac du li~u thuc nghiem 40
3.1. Loai bi) du lieu ngoai Iai 41
3.2. Xac dinh khoang tin c~y 43
3.3. So sanh dQchinh xac cua hai hay nhi~u ke't qua thuc nghiem 43
3.4. So sanh hai hay nhi~u gia tri trung binh 46
3.5~ Xet sai s6h~ th6ng cua phuong phap 49
4. Caeh trinh bay cac du Ii~u phan tich 50
4.1. Cach lam tron s6 50
4.2. Chu s6 co nghia 50
Cau hoi va hili t~p 52

Chlidng 4. cAN BANG HOA HQC TRONG DUNG DICH 54

PGS. TS.· Tr&n Tit An
1. Can bAng hoa hQc . ho~t dQ 54
1.1. Ho~t dQ 54
1.2. S~ phan ly trong dung dich - lien h<,1pion 57
1.3. Phan lo~i can bAng hoa hQc 58
2. Can bAng acid· base 60
2.1. MQt s6khai ni~m 60
2.2. Tinh [H30+]va pH cua dung dich nudc 63
, 8
 2.3. Gian d6 phan b6 76

2.4. Can bAng acid - base trong dung moi khan 77

3. Can bAng tao phuc ch~t 79

3.1. HAng so' can bang tao phuc 79

3.2. HAng so' can bang' bi~u ki6n 83

•
3.3. Phuc cua kim loai vdi EDTA 86
92
4. Can bAng OXY hoa khi't
92
4.1. Dinh nghia
94
4.2. The oxy hoa khi't
99
4.3. Cac y6u to' anh ht1dng - Th6 bi~u kien
104
4.4. HAng so' can bAng cua ph an tmg' oxy hoa khi't
106
4.5. D~c di~m cua phan ung oxy h6a khi't
106
Cau hoi vil hili t~p
. ,.. ~... ,,~'9

Chirong 5. CAN BANG HOA TAN KET TUA 112·

PGS. TS. Trdn Tii An

1. D~i cuong 112

2. DQ tan cua chat khi 113

3. DQ tan d dang phan ti't 114

4. DQ tan ciia mu6i di~n li it tan 116

4.1. Anh hudng cua luc ion 117

4.2. Anh hUdng cua ion cling ten 117

4.3. Anh huong cua pH dung dich 117

119
4.4. Anh hudng' cua sl;t tao phuc
4.5. Anh hudng cua ph an ung oxy hoa khi't 122

5. Su hinh thanh k6t tua 122

5.1. Qua trinh k6t tua 122

5.2. Hai Io~i k6t tua 123

5.3. Keo va pepti hoa 124

5.4. Sl;t nhi~m bAn cua k6t tua 125

Cau hoi vil hili t~p 127

9
 Phan ,2. PHAN rtcu HOA HQC V!NHLl/QNG 130
Chtidng 6. PHA:N TICR K.HOJ LI1'QNG 130
en. Tr&n Tich
1. NQidung va ph~n Ioai 130
1.1.Phudng phap ke'ttua 130
1.2. Phuong phap bay hoi 131
2. Cach ttnh ke't qua 132
2.1. Trong phuong phap bay hoi 132
2.2. Trong :plntd:ngphap ke't tua 132
3. Cac dQng.tae eo ban cua phuong phap ke't tua 133
3.1. hoa tan ma.u phan tich 133
3.2.Ke't tiia 133
3.3. LQctiia 135
3.4. Rita tua 135
3.5.S(y va nung tua 136
3.6.Can 136
4. Cac thu6c thi'1ke't tiia 136
4.1. Thu6c thi'1ke't tua v6 co 136
4.2.Thu6'c thi'1.ke'ttua huu co 137
5. Danh gia phuong phap phan tfch kh6'i IUQng 139
5.1. Phan tich khoi IUQngIa mgt phuong phap phan tich true tie'p 139
DQnhay ciia phuong phap
5,·2. 139
5.3. Tinh d~c hi~u 139
5.4. DQdung 139
6. MQt s6 (tng d\mg ciia phan tich.khdi IUQng 140
6.1. Xac dinh mtdc ke't tinh va m,tdchut Am 140 \.

6.2.Dinh lUQngacid sulfuric va sulfat hoa tan 140

6.3.Dinh hiQng dun~ dich NaCI 141
6.4. Dinh hlQngthu6'c tiem vitamin B} 143
Ciu hoi va bili t~p 143

10

-~'----'- ._-------
 ,," "".,,,
_'
145
. CU'dNG VE PHU'dNG PHAP CHUAN DO.
Chuong 7. DAI
PGS. TS. Trdn. Tit An
1. Nguyen t~e ella phuong phap chuan dQ 145
1.1. Nguyen t~e 145
1.2. Yeu du ella phan ung hoa hoc dung trong chuan dQ 146
2. Cac phuong phap xac dinh di~m tuong duong 146
2.1. Di~m tuong duong 146
2.2. Di~m ke't thuc 146
2.3. Cac phuong phap xac dinh di~m tuong dirong 146
3. Phan loai cac phuong phap ehuAn dQ 147
4. Cac ky thuat chuan dQ 148
4.1. ChuAn dQtrue tie'p 148
4.2. Chuan dQngu<;le(chuan dQthua trir) 148
4.3. ChuAn dQthay the' 148
5. Cach pha che dung dich chuan 149
5.1. Ch~t g6c 149
5.2. Pha che dung dich g6c 149
5.3. Dung dich chuan 149
6. Cach tinh ke't qua trong phuong phap chuan dQ 150
6.1. Quy t~c chung 150
6.2. Tinh ke't qua theo n6ng d~ duong luong thu6c thi1 150
6.3. Tinh ke't qua theo dQ chuan cua thu6c thi1 151
6.4. H~ s6hi~u chinh 152
6.5. MQt so' di~m d.n luu y khi lam vi~e voi cae dung dich ehuftn 153
6.6. MQt so'vi dl}. 153
Cau hoi vil bili t~p 155

Chlidng 8. CHUAN DQ ACID.BASE 157

eN. Tr&n Tich
1. Nguyen t~c 157
2. Ch~t chi thi trong chuftn dQ acid-base 157

2.1. Khai ni~m 157

2.2. Khoang pH d6i mau eua ch~t chi thi acid - base 158

11
"··'1'·""" ,_,,_.•
'I 'iE' t;"., ~..
-.~"""-
..,- ", .

2.3. Yeu ca.u chung doi vdi cha:-tchi thi acid - base 159
3. Khao sat cac dUdng bi~u di{;n dinh luong 161
3.1. Kh8.osat dU<1ngbi~u di{;n dinh luc)ng In9t acid rnarrh bang' base manh 161
3.2. Khao sat d.udng bi~u di{;n dinh hrong' mQt sO acid ye'u bang mQt 164
base manh
3.3. Dinh. b.tQngrnQtbase ye'u bAng ID'Qt acid manh 166
3.4. Dinh IU<;Irig
ml}t acid trung binh b~ng rnQt base yeu 167
3.5. Dinh IUQngmet acid ye'u bAng mQt base ye'u hay ngt.R)c lai 169
3.6. Di~u kien dinh luQng rieng bi~t lnQt acid· (hay base) trong han hop 169
hai acid (hay base)
3.7. Dinh IUQngmQt da acid 170
3.8. Djnh hrong mQt da base 172
4. Tinh sai so chi thj 174
4.1. Cac loai sai so chi thi 174
4.2. Cach tinh cac loai sai so 174
4.3. Ap d\mg cac cong thtrc tren 'd~ chon chi thi 176
5. ChuAn dQacid-base kong moi trudng khan (hay dung moi khong' nude) .177
5.1. Dinh h~Qngcac base ye'u 177
5.2. Dinh lUQngcac acid ye'u 178
5.3. Binh lUQngcac hful hQp acid hay base 178
6. M(>t so Uilg dt,mg dinh lUQng bang phudng phap acid-base 178
6.1. Pha che' cac dung dich goc v~ dung dtch chuAn 178
6.2.'MQt so·ap dl,lng dinh lU<;Ingtrong thllc te' . 181
Ciiu hoi va hili t~p 183

Chudng 9. CHUAN'DQ T~O PHUC 185

eN. Trd.n Tich _ PGS. TS. Trd.n Tzi An
1. Nguyen tac 185
2. ChuAn dQ t~o phuc bAng thu6c thlt va cd 185
2.1. Phl1l1ngphap b~c 185
2.2. Phuong phap thuy ngan (II) 188
3. Phuong phap chuAn dQbang complelCon 189
3.1. DUdng eong chu.An dQcomplexon 190

12

-. --_._-------------------- ._-------- ---

 3.2. Chi thi kim loai 195

3.3. Cac ky thuat chuan dQeomplexon 200

201
3.4. (rng dung cua chuan dQcomplexon -
Cau hoi va bai t~p 202
",," ,.. A'" .,
203
• Chirong 10. CHUAN DQ KET TUA
CN. Trtin. Tich
1. Nguyen t~e 203

2. KhllOsat duong eong chuan dQdo bac 203

2.1. Khao sat sl;i bien d6i eua n6ng dQ Ag+ va Cl trong qua trinh dinh 203
luong
2.2. Duong bi~u di~n dinh luong 204

2.3. Nhan xet 205

3. Chi thi h6a hoc eho chuan dQdo bac 206

3.1. Phuong phap Mohr 206

3.2. Phuong phap Volhard 207

3.3. Phuong phap Fajans 209

210
3.4. Ung dung cua chuan dQdo bac
4. Phuong phap do thuy ngan (I) 211

4.1. Phuong phap dinh luong' dua VaG dung dich chuan cia mual Hgl+ 211

4.2. Chi thi thuong dung 211

5. MQt s6 (lng dung thuc te' 211

5.1. Cac dung dich chuan 211

5.2. Dinh luong NaCl thea phucng phap Mohr 212

5.3. Dinh luong KCNS 212

5.4. Dinh luong Br, 1" bAng phuong phap Volhard 212

5.5. Dinh ltiQng Cl' bAng phtidng phap Volhard 213

5.6. Dinh ltiQng Br', I' bAng phtidng phap Fajans 213

5.7. Dinh lliQng Cl' bAng phtidng phap Fajans 213

Cau hoi va bai t~p 214

,,",.. '" ., 216
Chudng 11. CHUAN DQ OXY HOA KHU
CN. Tr6n Tich
1. Nguyen t~e 216

13

----------------- -
 ---------~.-----~--- ---

--2.DUdng cong chuan dQ OXY hoa khii 217

2.1. Khao sats~ billl thien cua the' oxy hoa kll:ii trong qua trinh chuAn dQ 217
2.2. DUdng bi~u di~n 220
2.3. Nhan xet 2:20
3. Chi thi trong phuong phap oxy hoa khil: 221
4. Phan loai cac phuong phap oxy hoa khti 224
4.1. Phuong phap permanganat 224
.4.2. Phuong phap bAng iod 224
4.3. Phuong pliap bromat 226
4.4. Phuong phapbrom 226
4.5. Phuong phap nitrit 227
4.6. Phuong phap dieromat 227
4.7. Phuong phap Ceri 228
4.8. Phuong phap do d6ng 229
5. MQt s6 ling dung dinh hrong 231
5.1. Phuong phap permanganat 231
6.2. Phuong phap iod 232
5.3. Phuong phap nitrit dinh luong' sulfathiazol 235
Oau hoi va bAi t~p 235
DAp sO BAr T~·P 238

cAc PHV LVC 245

TAr Lrtu TH~ KIJAO 245

14
 CAC·CHO' VIET TAT

C Nang dQ
dd Dung dich
Phan s6 mol cua ea'u tit i
Hoa phan tich
Nang dQcan b~ng cua ion H'trong dung dich
Luc ion cua dung dich
Hang' s6 di~n ly ciia acid HA
Hang s6 cQng proton cua acid HA
Hang s6b~n timg na'c cua phuc
DQchuan cua dd (g/ml)
Tieh s6 tan cua cha't A
Ham tao phuc phu cua A vdi H
f3i Hang s6 b~n to an ph An cua phuc
8,0 Hang' s6 b~n cua ph an tmg' tao phuc phu
H~ng s6 di~n moi cua dung moi

15
 ---- - -----
---------~---------

PHAN 1

co sir Lt THUYET CUA HOA PHAN TlcH

Chirong' 1

.
£>AICllONG VE HOA PHAN TICH

1. DOl TI1QNG CUA HOA PIIAN rtcn

Phan tich mot chat vg mat hoa hoc Ia.xac dinh trong chat do co bao nhieu
thanh phan (dinh tinh) , ham luong cua m6i thanh phan (dinh luong) va cau
true hoa hoc cua no. Do chinh la nQi dung cua phan tich hoa hoc (chemical
analysis). Mon hoc nghien cuu xay dung, phat tri~n va ung dung cac phuong
phap cho phan tich hoa hoc duoc goi la Hoa h9C phan tich (analytical
chemistry). Trong tai lieu nay vie't t~t la HPT. Ph an tfch hoa hoc hie ban dftu
chu ye'u dua vao cac phuong phap hoa h9C. Nhu v~y Hoa phan tich thuc chat
la D;lQtmon hoc chuyen nganh cua hoa hoc (chemical sciences).
Tuy nhien do doi hoi cua s1;iphat tri~n kinh te' xa hQi, s1;igiao luu thudng
m:;ti toan cftu, cac phudng phap hoa hQc dung trong phan tich da khong dap
ung dUQcsuc ep ngay mQt tang len la cftn co mQt ke't qua ph an tich tin c~y. Vi
v~y ben c:;tnh cac phtidng phap hoa h9C ngudi lam phan tich con sit dv.ng cac
phudng phap v~t ly, sinh hQc va ca toan hQc. Ten mon h9C la Hoa ph an tich da
khong phan anh he't nQi dung khoa h9C cua no. Vi v~y mQt s5 tac gia da dg
nghi d5i ten mon hQc Hoa ph an tich thanh Phan tich hQc (analytical sciences).
Hi~n d Nh~t Ban da xuat ban T:;tp chi Ph an tich hQc (Journal of analytical
sciences). <) nuoc ta g~n day da ra ddi "T:;tp_chi Phan tich Ly Hoa Sinh". Tuy
nhien cho de'n nay, nglidi ta vAn dung ph5 bie'n ten gQi HPT v8i nQi dung dUQc
hi~u mQt cach rQng hdn.

17
 , Hien nay Hoa phan tich duoc cau thanh bdi 3 nQi dung chinh la: co sd ly
thuyet, dung cu do luong va ung dung.
- Co sd ly thuyet (Fundamentals) cua HP'F la v~t ly, hoa h9C va sinh hoc.
C~n khai quat hoa cac khai niem phuc vucho phat tri~n vaung dungoua
HPT. MQt s6tac gia con xep vao day cac -phuong phap toan h9C.trong do
co toan th6ng ke dung cho HPT voi muc tieu la xay dung ke' hoach thuc
nghiem nham t6i uu hoa thuc hanh va xi'i ly s61i~u.
- Dung cu do lUdng (Instrumentation): c~n phat tri8n dung cu do Iuong
(appareils, captors, detectors), phuong phap do luong. NQi dung hay dUQC
coi la trung tam cua HPT vi no tang cuong ky nang cua mon hoc, ky nang
ciia nguoi.Iam phan tfch.
- Ung d\lng (application): day la nQi dung C\l th~ cua HPT 'nhAm dap ung
nhu c~u ngay mQt tang cua nen kinh te va cUQCs6ng xa hQi.
D~ phat tri~n HPT mQt cacn ben vung c~n giU can bAng ca ba nQi dung:
ly thuyet, d\lng el,ldo IUdng va ung dl,lng khong chI d muc yI rno ma ca d trong
m8i phong thi nghi~m.
# ""," ,,' ? ", " '"
2. TINH PHO BIEN CUA HOA PHAN TICH
Ph~n quan trQng trong th\lC hanh ph an tich mAu la th\lc hi~n phep do
trong hoa h9C. Vi v~y co th~ noi HPT la cQt trv cua do IUdng hoa h9C (chemical
metrology). No co m~t d kh~p noi thuQc nhieu linh v\lc khoa hQc, kinh te ciing
nhu sinh ho~t va ddi s6ng xa hQi.
• Khoa hQc ung d\lng: nhieu lInh V\lc nghien cuu, san xua't thli nghi~m c~n
dung de'n phan tieh, vi d\l:
- Trong t5ng hQp huu cd c~n xac djnh cong thuc tho, cong thuc phan ti'i,
thanh ph~n djnh tinh va djnh IUQngeua san phAm.
- Trong nghien cuu sinh hQc c~n X8:Cdjnh thanh ph~n ca'u t~o cua te bao,
mo; thanh ph~n va cd ehe ho~t dQng cua enzym; chat h1Qngsim phAm cua
eong ngh~ sinh h9c.
• Kinh te: danh gia cha't hiQng san phAm eua cac nganh cong nghi~p, ki~m
tra ban thanh phAm trong day chuyen san xua't, xae dinh mue dQ an toan
cua nong thuy san xua't nh~p khAu (du IUQngkhang sinh trong thuy san; du •
IUQngthu6c thu y trong thjt gia suc, gia c~m....)
• Y dUQch9C
- Nghien cuu t~o nguyen li~u lam thu6c
- Bao che cae d~ng thu6c moi (bao g6m ca van. de tieu chuAn hoa, dQ 5n
djnh eua no).
- Ki~m nghi~m cha't IUQng trong qua trinh san xua't, phan ph6i va bao
quan si'i d\lng thu6e.

18
 - Nghien cuu duoc dQng hoc, kha dung sinh hoc va tuong duong sinh hoc
phuc vu nang cao chAt luong thuec.
- Y hoc d\l phong: chAtluong nuoc, tbuc pham, ki~m tra v~ sinh moi truong.
- Phuc vu cho dieu tri: xet nghiem hoa sinh, ca th~ hoa dieu tr] .
• Sinh hoat va ddi s6ng xa hQi.
- Danh gia tinh xac thuc cua cac chung cu trong tranh chap dan s\l hoac
xet xu tQipham hinh s\l truce co quan phap luat.
- Xac dinh tinh trang nghien rna tuy, ngQ dQcthuc phAm... trong ddi s6ng
sinh hoat cua cQngdang.
Co th~ k~ ra nhieu ung dung cua HPT trong khoa hoc, san xuat va ddi
s6ng xa hQi, chimg minh tinh ph6 bien, th~ hien vai tro cua no d nhieu linh
vl;tckhac nhau. d day ngudi ta su d\lng so'li~u phan tich nhu la mQtsan phAm.
Da 1a san ph Am thi yeu c~u cao nhat la thoa man nhu c~u clla ngudi tieu .
dung. Vi v~y xa hQi doi hoi s61i~u phan tich nhu la mQt san phAm hang hoa
phai dam bao tin c~y. Day la van de hi~n dang d~t ra cho HPT. Chat lUQngso'
li~u phan tich lien quan ch~t che den nguyen ly do ludng, ngay cang t~o ra s\l
quan tam khong chi clla cac phong thi nghi~m, rna ca clla ngudi xu d\lng ke't
qua phan tich. D~ cai thi~n chat lUQngs61i~u phan tich, khoang mudi nam trd
l~i day ngudi ta noi de'n s\l c~n thie't phai xay d\lng h~ thong do lliCmghaa h9C.
H~ th6ng nay ra ddi la cd sd d~:
- Danh gia dQtin c~y clla ke't qua phan tich.
- Co th~ so sanh dUQcke't qua theo thdi gian va khong gian (giua cac phong
thi nghi~m voi nhau).
- Giai quye't d~ dang nhung tranh chap lien quan de'n chat lUQngsO'li~u
phan tich.

3. PH.ANLO~ cAc PHUONG PHAp PH.ANTicH

Trong th\lc te, c6 th~ d\ia vao nhieu tieu chi d~ phan lo~i cac phudng
phap phan tich. 6 day chi gioi thi~u 3 cach phan lo~i dUQccho Hi c§.nthie't.

3.1.DVa vao ban chat ella phudng philp

C6 th~ chia cac phudng phap thanh 2 nhom IOn:
,
3.1.1. Cac phuong phap h6a h(}c
Day la cac phudng phap phan tich d\la vao m6i quan h~ giua tinh chat
h6a hQcva thanh ph~n hoa hQcclla mftu thu. Co th~ phan thanh 2 nhom:
a. Phan tich haa h9C dtnh lliCjng:
ThuQcve nh6m nay la cac phudng phap sau:

19
 ~~-~~-~----~-- ----
.-.---.-.~-~.--.--~---

- Phan tich kh6i Iuong (gravimetry): dua vao kh6i hrong cpflt ket tua tao
thanh hoac kh6i luong chflt khi du<_jc
giai phong hoac hap ehu d~dinh luong.
- Phan tich th~ tich (volumetry) bao g6m:
+ Phuong phap ehuan dQ(titrimetry): phan tich dua vao th~,tfch ffiQtdd
thu6c thi't co n6ng dQda biet goi Ia dung dicli chu6n d9. Thuoc nhom
nay la 5 loai chuan dQ duoc phan loai thea phan (tng h6a hoc: acid-
base, oxyhoa khi't,.40ophuc, tao c~p ion va tao ket tua.
+ Phuong phap th~·tich khi: dua vao viec do th~ tich khi tao thanh tii
m~u thi't hoac giam th~ tich cua han hop khi do mQtphan da bi hap th\l.
b. Phtin tich h6a h9Cdinh tinh
D~ xac dinh thanh phAn dinh tinh cua mQtm~u thi't, ngudi ta thudng dl;ia
vao phan (tng cua thu6c thi't vai cac chat co m~t trong m~u. Dl;tavao nhung
dflu hi~u d~c trung cua phan (tng nhu: d:;tngtinh th~ xuat hi~n, sl;tt:;tomau,
d6i mau, phat quang .... d~ xac dinh. NgUdita da xay d\tng du<_jc mQts6dztdng
LO'iphtin tich h~ th{{ng d~ tach va xac dinh cac cation va anion, chu yeu la vo
co. d day thudng dung thuGe thit nh6m d~ tach rieng tung nh6m, tung phan
nhom va tung ion. .
Cac phudng phap hoa h9Cdung cho dinh tinh thudng dOngian khong cAn
den thiet bi do ludng phuc t:;tp dAt ti~n nen d~ tri~n khai th\tc hi~n. Nhu<_jc
di~m cua chung la phiii tach chiet mflt nhi€u thi gid, dQ tin c~y va giill h~n
phat hi~n khong cao. Vi v~y hi~n nay ngudi ta thudng dung cac phudng phap
ph6 d~ dinh tinh m~u.thi't (quang ph6 UV-VIS, IR, NMR va MS).

3.1.2. Caephu(Jng phap v~t lj va hoa lj

Day la cac phuong phap phan tich d\ta vao m6i quan h~ giua thanh phAn
hoa h9Cva cac tinh chflt v~t ly ho~c h6a ly cua cac chflt. Ngtldi ta thUdhg chia
cac phuong phap nay thanh 3 nhom:
a. Cac phztdng phap Quang h9C:
Day la cac phuong phap dl;tavao tinh chat v~t ly nhu dQkhuc X:;t,nang
suflt quay c\tc, s\t hap th\l, buc x:;tho~c phat x:;tcua nguyen ti't, phan ti't ...
b. Cac phudng phap tach phan tich:
Bao g6m cac phuong phap sAc ky (sAc ky khi, sAc ky lOng, sAc ky lop
mong), cac phudng phap di~n di, th~m tich.
f
c. Cac phztdng phap di~n h6a: (c\tc ph6, do the ...).
Nhin chung cac phudng phap v~t ly va h{)aly co dQtin c~y va gioi h:;tn
phat hi~n cao, thdi gian phan tich nhanh; nhi€u phuong phap 'duqc dung cho
ca phan tich dinh tinh va dinh luqng. M~t khac, hi~n nay cac phuong phap
nay thudng dung cac thiet bi cong ngh~ cao, ket hqp cong ngh~ di~n ti't vai tin
h9c, toan h9c d~ do ludng va xi't ly s61i~u cho ket qua nhanh, tin c~y. Cho nen

20
ngay cang 4uQc dung ph5 bien trong san xuat va nghien ctru khoa hoc, Nhom
nay con co ten khac la cac phuang phap dung cl;t(instrumental methods).

3.2. Dua vito hi«1ngm§:u phan tich

Tuy theo luong mau thi'i d.n thie't d~ thuc hien phan tfch theo mQt qui
trinh nao do, ngU'dita phan biet:
- Phan tich tho (macro): luong m~u thi'i O,lg trd len
- Phan tich han vi (semimicro): luong m~u thi'i 10.2 de'n 10.1 g
- Phan tich vi luong (micro): hrong m~u thi'i 10.3 de'n 10.2 g
- Phan tfch dudi vi luong (submicro): luong m~u thi'i 10.4 de'n 10.3 g
- Phan tieh sieu vi luong (ultramicro) luong m~u thi'i dudi 0,1 mg
Trong mQt m~u thir, ne'u 1thanh ph fin co ham luong:
1% trd len duoc goi la thanh ph fin chinh,
0,01 - 1% la thanh phan thu ye'u,
< 0,01% la thanh phan vet
Do su phat tri~n cua cac thiet hi cong ngh~ cao, gioi h:il.ndinh lU'c;1ng
co
thap hdn nhigu 0,01%. Phan tich d muc ppm (Cdf.1g= 10·6g) la
th~ df;ltdU'c;1C
phan tich vet (trace analysis); d muc pph (Cd ng = 10·9g)1a phan tich sieu vet
(ultratrace analysis).

3.3. Dl!a vito vi~c sit d1;lng cha-t chudn

Dlja vaGvi~c si'i d\mg chat chuftn dB.dung trong phan tich ngU'dita co th~
phan ra 2 nhom IOn: .

3.3.1. Ccie phuong phcip tuy~t do'i (absolute methods)

Day 1a cac phU'dngphap phan tich cho ket qua thong qua tinh toan dlja
vaG cac qui lu~t chi ph6'i cac thong s6 v~t ly va hoa h9C trong h~ cling nhU' s6
li~u dAuVaGva dAu ra cua qua trinh phan tich nhU':
- Kh6i lU'c;1ng
m~u thi'i dB.dung, kh6i h.iqng cua tua,
- Th~ tieh dung dich chuftn,
- Di~n lU'qngdB.dung cho qua trinh di~n phan.

Cae phU'dng phap nay khong cAn dung den chat chuftn cua chat ph an
tich. Phan tich kh6i h.tqng, chuftn dQ th~ tich, phU'dng phap do di~n h.tqng
thuQc nhom nay. D~ tinh toan ngU'dita efin dung cae hang s6 nhU':kh6i lU'qng
nguyen ti'i, s6 Avogadro, s6 Faraday ... Vi v~y trong mQt s6 tai 1i~u con dung
thu~t ngu Phlidng phap tinh toan d~ chi nhom phU'dngphap nay hoac Phztdng
phap hfJp thuc (stoichiometric methods) d~ chi cac phU'dngphap chu~n dQ.

21
.,.~';>;";'~-"""'"~'''-'''-'~ -_.. _"..... _ ----_.---------.--~--.

3.3.2. Cae phuong ph6p tuang d{j'i (relative methods)

Day la cac phuong phap khong cAn de'n cac hang s6 d~ tinh toan nhu d
nhom 1.3.3.1 rna chi cAn so sanh tin hieu de luong ella m!u phan tich va cua
day dd chat chudn co nang dq da bie't. Tho~g qua ham dap ling (response
function) thuong la tuyen tinh d~ nQi BUY ke't qua. Cac phudng phap eua nhom
nay cAn dung chat chudn (standard) ella chat phan tieh. Cac phueng phap
dung C\1(trtr phep do di~n hrong) la phuong phap tuong d6i.

3.4. MQt so thu~t ngu khac

Ngoai each phan loai tren, trong thuc hanh phan tieh con dung mQt s6
thuat ngfi khac:

3.4.1.Phuong phap ddi chieu-phuang phap trong tdi (reference methods)

Day la phuong phap phan tich do cac t5 chuc quoc gia hoac q.u6cte' xay
dung nham m\1cdich thAm dinh nang ll;ie ella phong thi nghi~m thong qua ke't
qlla phan tich m!u chuAn (standard samples).

3.4.2. Phuong phap chinh thuc (official methods)

Day 1a cac phudng phap dUQcqui dinh bdi mQt cd quan ehlic nang co tinh
phap ly thong qua mQtlu~t, mQtphap l~nh hay qui che nao do. Vi d\l:
- Ki~m nghi~m che'phAmthu6e theo phudng phap CllaDUQcdi~n Vi~t Nam.
- Danh gia eha't luQng m10eu6ng theo tieu ehuAn ella BQY teo

3.4.3. Phuong phap thuiJng qui (routine methods)

Day la eac phudng phap duQCsi1 d\1llghang ngay trong cae phong thi nghi~m.

4. cAc BlJOC CHU YEU CUA MQT QUI TRiNH PHAN TicH
Ve nguyen tAc, xay dl;ing qui trinh phan tieh mQt m!u thi1 thudrtg thong
qua 6 buoc sau:

4.1. Bdoc 1. Xac djnh m\lc tieu va nQi dung phan tich:
a. Ml:lctieu phan tich
Dung ket qua phan tiehph\1c V\1eho eong vi~e gi? yeu cAu ella ngddi giti .
mAu thi1 ve phudng phap phan tieh, mue dQtin e~y ho~e tinh chat phap ly ella
keA't qua ... ?

b; N{)i dung
Tren cd sd m\1ctieu va yeu cAu cua ngddi giti mAu xac dinh nQi dung C\1
th~ ella ph an tieh: . .
- Xac dinh mQthay mQts6 chat trong mAu.

22

... ---~-----------
 - D~e di~m Iy hoa ella cac eh~t cAn ph an tich.
- Yeu eAu v~ thoi gian tra k~t qua.
- Xac dinh kinh phi thuc hien ph an tieh.
N{li dung ph an tieh, trach nhiem ella mai ben cAn dUQe qui dinh cu th~,
trong hop d6ng gifia hai ben: ben giii m§.u va ben phan tieh m~u.

4.2. Btioc 2. Chon phmmg phap phfin tich:

Chon phuong phap phan tieh la m{lt nhiem vu khong don gian, doi hoi
kinh nghiem ella nglidi phan tieh. Cac y~u· to' sau quy~t dinh vi~e lua chon
phuong phap:
a. Yeu cdu cua ben giii mdu:
. Neu ben' giii m~u da chi dinh phuong phap, vi du phuong phap cua DUQc
di~n Vi~t Nam III, thi nhiem vu trd nen don gian, Neu chi co yeu cAu ve d{l .
dung, d{lchinh xac cua k~t qua thi cAn 1t;tachQn phudng phap phu hQp. N~u
yeu eAucang cao thi cang cAn nhieu thdi gian va chi phi. Vi v~y vi~c 1t;tachQn
cAnlam sao thoa man yeu cAuclla ben giii m~u ca ve ky thu~t va chi phi.
b. FJiJ,edie"m eua phlidng phap phan tich:
Cae phudng phap phan tich thudng co tinh ch(;m1Qcva gioi h~n dinh
IUQngkhac nhau. Vung n6ng d{lthudng dung cho m{lt sO'phudng phap ph an
tich d\lng Cl,l:
- Quang ph6 hffp thl,l UV-VIS : ;?: 0,5 Ilg1 mL

- Huynh quang phan tii, sAcky lOng:5 + 1000 ng/ml

- siic ky khi: 0,1+ 100ng/ml.
- Phong x~ ;?: 0,05 ng/mL

Tuy n6ng dQch~t phan tich d~ chQnphudng phap thich hQp.

c. DiJ,ediem cua mdu thit:
Tuy thanh phAn m~u thi':id~ co cach xi':iIy thich h<;jp.M~u thi':ithudng rfft
phong phu va da d:;tng,co th~ Ia:
- Nguyen li~u, hQp chfft la thanh phAn chinh.
- D~ng bao che, ben c~nh ho:;ttchfft con co c8. ta dUQc,ch~tbao quan.
- Dieh sinh hQc:ch~t phan tich cAn dUQctach chi~t khoi m~u thi':i.
_ Cac m~u moi trudng phuc t~p: nhu cae m~u nuoc (nuoc ngAm, nuCIc
thai ...), d~t, bun ho~c tht;tc phAm.
d. DiJ,cdiem cua chat phan tich:
Nhilng tinh chfft hoa Iy cua no nhu: dQchay, nang su~t quay ct;tc,hap thl,l
buc x~ UV-VIS, IR, tinh ch~t hoa tan, tinh acid-base .... giup nglidi phan tieh
It;tachQnky thu~t tach chi~t va dinh 1UQngthich hQp.

23
 MQtvan de quan trong la nang h;1C ciia phong thf nghiem (bao gam trinh
dQngudi phan tich va trang thiet bi ky thuat) la mQtyeu to khong th~ khong
de cap tdi khi quyet dinh co hay khong nhan thuc hien phan tich mAu.

4.3. Btioe 3. L~y miiu va bao quan miiu:

Lay mAu la mQt giro doan chinh cua phan tich thudng bi coi nhe. No dl1Qc
COlfa khau gay sai so nhieu nhat, anh hl1dngIan nhat den dQtin c~y cua ket qua.
a. Khi xay dung chuang trinh lay mdu edn luu y:
- Muc tieu cua phan tich mAu,
- Tinh chat cua qudn th~ mAu: trang thai v~t ly (long, riln, khi) d dang
d6ng th~ hay di th~,
- So mAu cAnlay va tdn suat lay m~u.
b. Mt:lc tieu eua phan tich. xae djnh each lfiy mdu.
C6 th~ phan thanh 4 cach lay mAu chinh:
.. , ....
1. MAu d~i di~n: day la cach lay mAu d~i di~n cho qudn"th~.
2. MAu chQn IQC:lay mAu cho mQt m\lc tieu xac dinh, vi d\llay mAu d 10
nghi ngd khong d~t chat 1l1Qng,
3. M~u ngAu nhien: lay ngAu nhien d~ danh gia thong ke so li~u. Co th~
lay ngAu nhien ddn, ngAu nhien nhieu tAng, ngAu nhien h~ thong.
4. MAu t6 hQp: mAu bao g6m nhieu phdn lay d cung mQt thdi di~m tit
qudn th~ sao cho d~i di~n dl1Qctinh chat cua quAn th~ do.
Theo d~c di~m thong ke c6 th~ phan thanh 2 nh6m:
1. Nh6m lay mAukhong xac suat (nonprobability sampling),
2. Nh6m lay mAuxac suat (probabil~ sampling).
c. Bao quan mdu:

MAu phan tich sau khi lay cdn dl1Qcbao quan trong dieu ki~n thich hQp
(bao bi, nhi~t dQ,dQAm....) nh~m m\lc tieu bao dam dQ6n dinh cua no.

4.4. Btioe 4. Xii ly mdu

Trl10c khi phan tich, mAu cdn dl1Qcxu ly b~ng cac qua trinh v~t ly, hoa
hQcthich hQpnhl1:
- Say kho, nghien nho, nung chay ho~c hoa tan trong dung moi thich hQp
(dung djch acid, base, dung moi huu Cd).
- Lo~i t~p chat trd ng~i, tach lay chat cdn ph an tich thong qua thAm tich,
chiet b~ng dung moi huu cd, chiet pha rAn,...

24
 _ Lam phan ung h6a hoc d~ bien ch~t phan tich thanh dftn eh~t c6 th~ phat
hien duoc, do IUdng "duQC.

4.5. Buoc 5. Thtlc hi~n C{lC phep do:

- Chon dung C1). do, digu kien thuc nghiem,
- Hieu chuan thie't bi theo chu~n d6i chieu (reference standard),
- Do dac s6li~u vdi chuan va mftu thir,
Cong viec phan tich c6 th~ lam l~p nhieu l~n d~ e6 du thong tin dam bao
dQtin cay cua ke't qua.

4.6. Budc 6. xe ly so li~u va trinh bay ke't qua phan tich:

a. Vi~c xzlly het qua bao g6m 3 buac:
1. Xem xet dft lieu thuc nghiem, loai bOnhfmg s6li~u nghi ngd c6 sai so tho.
2. Thuc hien tinh toan ke't qua theo cac bi~u tlnrc da xac dinh (d6i vdi cac
phuong phap tfnh tom) hoac nQisuy ke't qua dua vao dUdngchu~n.
3. Xii ly thong ke so li~u: xac dinh dQ dung, dQchinh xac, tri sO'trung
binh, phudng sai va khoang tin c~y eua ke't qua.
b. Trinh bay het qua phan tich dum nhi€u dt;mg:
- MQtcon s6voi mQtso chft so c6 nghia xac djnh.
- MQtbang so li~u.
- MQtd5 thi, mQtbi~u d6.
c. Bcinh gici het qua va het lu(in
Tren day la nguyen t:'ic d~ xay d\lng qui trinh phan tich. Trong th\lc te'
khi tien hanh tren mQt m~u C\lth~ c6 th~ bo qua mQthay mQtso buoc lam sao
d~ qui trinh d6 phu hQpvoi d~c di~m cua m~u e~n phan tich.

cAu HOI
1.1. Hay trinh bay s~ khac nhau gifta cae khai ni~m: H6a hqc phan tich,
phan tich h6a hqc va phan tich hqc.
1.2. Giai thich 3 nQidung chinh cua h6a phan tich.
1.3. Hay cho 3 vi d\l minh hqa ung d\lng cua phan tich h6a hqe trong
cong tac dUQe.
1.4. Chung minh tinh phd bien cua phan tich h6a hqc trong cac Hnh v\lc
khac nhau cua khoa hqc ky thu~t.

25

._-----------------_._-----_.
 ---- -----_._
........

1.5. Dua tren co sd nao d~ ph an loai cac phuong phap phan tich thanh 2
nhom: phuong phap tuyet do'i va phuong phap tuong do'i. Y nghia
eua phan Ioai hay.
1.6. Cho vi du minh hoa s\i khac nhau giua 2 phuong phap truyet do'i va
.phuong' phap tuong do'i.
1.7. Phan bi~t phuong' phap do'i chieu va phuong phap chinh thuc trong
H6a phan tich. .
1.B. C~n xem xet nhfing ye'u to' nao khi chon phuong phap ph an tich mQt
mAu thi'i.
1.9. Giai thfch.sau budc chii ye'u trong qui trinh ph an tich mQt mAu thli.

26

- ..
 Chtidng2

NONG eo. DUNG DieM

.

Trong HPT nglidi ta thucng' xuyen sit dung cac dung dich thu6c thit co
nang dQ khac nhau phuc vu cho ph an tfch dinh tfnh va dinh luong. Trong
nganh Duoc, nguci Dude 81 cAn co hi~u bie't vfmg chA.cv~ each pha che' thu6c,
ki~m tra chfft luong ban thanh pham va thanh phdm ciing nhu ki~m nghiem
che' phdm thu6c trong qua trinh sit dung phan ph6i va bao quan.
A', ,," ,," "
1. BON CACH BIEU THI NONG DQ DUNG DICH
Trong HPT co 4 each chfnh bi~u thi nang dQ dung dich: do la luong chat
hoa tan trong mQt lucng dung dich hay dung moi.

1.1. N6ng dQph'n tram

Phan biet ra 3 loai:
1. C% (kl/kl): nang dQ% kh6i Ittc;lng/kh6i luong, do la sO' gam chat tan co
trong lOOgdung dich:
m m (2.1)
C%(kll kl) = -xIOO =-xIOO
m) Vd
Trong do: m la sO' gam chat tan co trong m, gam dung dich hoac V ml dd
C% co kh6i lucng rieng d.
Vi du: dd acid hydrocloric 37% co 37 g HCI trong 100 g dd.
2. C% (kl/tt): nang dQ % kh6i Ittc;lng/th~ tfch, do la sO' gam chat tan co .
trong 100 ml dd.
m
C%(kl Itt) = -x 100 (2.2)
V

27
 Trang do: m Ia 56 gam ohfit tan co trong V ml dd C%.
Vi du: dd tiemNaCl 0,9% co 0,9 g NaCl trong 100 ml dd.
3. C% (tt/tt): n~ng dQ % th~ tichlth~ tfch cho bie't 56 nil chfit tan co trong
100mI dd.
Vi du: Theo Duoc di~n Vi~t Nam c6n 95" 1ft dd 95% theo th~ tich (tt/tt), co
nghia 1ft trong 100ml C6h 95,°co 95 ml ethanol.
1.2. Nang di} gam
Thudng bi~u th] bang 2 each:
1: Nang d() gil: n~ng dQ gam/lit do la B6gam cha:t tan co trong 1 lit dd
.' m'
C(g /I) = V x lOOQ (2.3)

'llrong do: m III s6 gam chfit hoa tan c6 trong V ml dd dB.cho.

2. DQ chuan T .(titre): eho bie't 56 gam cha:t hoa tan co trong 1 ml dd
m
T(g/ml)=- (2.4)
V
Trong do: m gam chfit tan co trong V ml dd.
Trang thirc te' 5\1 dung thu6c th\:i nglidi ta con dung dQ chu~n tfnh thea
chat c~n dinh lUQng. Do la khdi lUQng cha:t c~n dinh luong' (ion, phan tit,
nguyen 11l1)ph an ung dung vdi 1 ml dd chuan va dUQcky hi~u 1ft T RIX trong do
RIa thuoc thi't va X la chfit c~n dinh luong. Cach bi~u thj nay rfit thuan ti~n
cho viec tfnh to an ke't qua, nha:t la khi ph§.n tich hang lo~t m~u trong san xuat
vft nghien cuu.
Yi dl:l: Ph an ung cua KMn04 voi :Fe2+ trong moi trudng acid .
Mn{)4' + 5Fe2+ + 8H+ ~ Mn2+ + 5Fe3+ + 4H20
Theo phttdng trinh tren 1 mol KMn04 phan itng voi 5 mol Fe2+. Ne'u dd
. KMn04 0,02M thi trong 1 ml dd nay chua 0,02/1000 =2.10.5 mol KMn04.
LU(jng nay phan Ung he't voi: 5. 2. 10.5 = 10.4mol Fe2+ ho~c 0,0056 g Fe.
V~y: TKMnO• O,02M I Fe = 0,0056 g Fe / ml

1.3. Nbng dQ mol

N6ng dQmol cua mQt chat cho ta bie't 56 mol cua cha:t d6 hoa tan trong 1
ky hi~u bAng chu M d~t sau chu s6 chi n6ng dQ.
lit dung djch. N6 thuoI;tg dUQ<!
m
CM = xlDOO (2.5)
MxV
Tr6ng do: m la s6 gam cha:t tan trong V ml dd, M la kh6i lUQng mol cua
chat tan.

28

...... ,-_._------_---
 Vi du: Tinh s6 gam acid oxalic (H2C204.2H20; M = 126) cAn d~ pha·2 lit
dd co n6ng dQO,lM.

Tit (2.5) ta co: 0,1 = m 1000 ~ m = 25,2 g

. 126x 2000

1.4. N6ng de)dtidng ltigng

Ndng dQduong hrong cua mQt chat cho ta bie't s6 duong luong cua chat do
hoa tan trong 1 lit dd hoac s6 mili duong hrong cua chat do trong 1ml dd. No
thuong duoc ky hieu bAng chtr N d~t sau chfi s6 chi n6ng dQ.
m
eN =_. -xIOOO (2.6)
ExV
Trong do: m la s6 g chat tan trong V ml dung dich, E la khdi luong duong
luong,
Kh6i luong duong Iuong' E cua mQt chat la s6 gam chat do thay the' hay
phan trng vita du vdi mQt mol H+ hoac OH· hoac 1/2 mol oxy. 'I'r] s6 E cua mQt
chat kh6ng phai la mQt hang s6 nhu kh6i luong mol rna thay d6i tuy theo phan
tmg rna n6 tham gia.
Nguoi ta thuong dung c6ng thuc tinh gia tri E:
M (2.7)
E=-
n
,Trong do: M la kh6i luong mol, n la s6 proton (H+) ma mQt phan tit acid
cho hay base nh?n trong phan (lng trung hoa,· s6 di~n tit cho nh?n trong phan
(lng oxy h6a khit ho~c s6 h6a trj cua phan tit tham gia phan (lng trao d6i.
Vi d¥:
- Ph an (lng trung hoa:
M
E H2S04 =-2

- Phan (lng oxy h6a khit:

Chi cAnvie't nita phan (lug tham gia vao qua trinh oxy h6a khit cua chat do:
282032- - 2e ~ 84062- E =M
AS033- + H20 - 2e ~ AS043- + 2H+ E=M/2
Mn04- + 4H+ + 3e ~ Mn02 + 2H20 E=M/3

29
 - Phan ung trao d6i:

M
EFe, (SO.), =-6

M
K2Cr207 T 2 BaC12 + H20 = 2BaCr04..J, + 2KCl+ 2HCI EKpP, =4
2KCN + AgNOa = K{Ag(CN)2J + KNOa EKCN = 2M (vi AgNOa = IE)

Hien nay each bi~u th] n6ng dq.dudag hiQng dUQcdung ngay mqt it dan.
Trong m9t so
sach giao khoa ve phah tich thudng khong de cap de'n hoac gidi
thieu trong phan phu luc.

1.5~M9t s6 cach bi~u th] nang d9 khae

Ngoai 4 each ph6 bi:e'nbi~uthi n~ng-dq d tren, trong HPT con dung mqt
s5 each khac:
1. Voi cac dung dich co n~ng dq chat-tan nho, thudng dung:
- N~ng dQphan tri~u (ppm):
Khoi luang chat tan (g) 6
C = . x 10
ppm Kh61 luang dung dich
- Nang dq phan ty (ppb): 1 ppb = 10. ppm
3

- N~ng dq phan nghin ty (pp'I'): 1 pp'I' = 10.3 ppb = 10-6ppm

2. Voi dd c6 n~ng dq ion nho, thudng dung ham p: .
. pX = -lgX
D6la logarit co so 10 cua n6ng dq mol ion X. Vi du:
(H+] = 10- M 4 pH::'!
[Ag+] = 10- M 6 pAg=6
3. Doi khi trong tai li~u con g~p:
- N8ng dq molan: cho bie't so mol eh~t tan trong 1000 g dung moi
- Phan so mol: la so mol ch~t tan trong t6ng so mol eua dd.
". ". ,,' ~ "
2. TINH TOAN VE NONG DQ DUNG DJCH
Trang th\le hanh tinh toan, chuy~n d6i n~ng dq dd, chi' cAn nho djnh
nghla, khong elin phai hQcthu9c cong thuc. Bdi vi tit dinh nghla d~ dang vie't
ra dUQccong thuc.

30
----------- -- ----

2.1. Bai toan v~ pha dung djch

• Vi du 1: Tinh s6 ml dd amoniac d~c 27,33%; d = 0,9000 cAn thiet d~ pha 2
lit dd amoniac 2N.
- D~ pha 2 lit dung dich 2N cAn 2 x 2N = 4N, cAn 4 x17g = 68 g NH3
- Dd d~c 27,33% nen kh6i hrong m chua 68 g NH31a:
m =68 100
27,33

A ch.?
Vay uyen sang th.?t'
e lCh can
~ lA'
ay l'a: V = -m = 68xl00 = 277, mI
. d 27,33x0,900
• Vi du. 2: Tinh 86 ml dd acid hydrocloric d~c 37,23%; d = 1,19 cAn d~ pha 500
ml dd acid 10%.

- TY l~ % la s6 g chat do trong 100g dd, tuc la C%= lOOxm

dxV

Ta biet C% = 10; V = 500 ml.

Tra bang tuong' quan giua d va C% cua cac dd HCl ta co dd 10%thi d = 1,047
- Kh6i luong m cua HCl se la:

m=10x1,047x500 =5235 g
100 '
- V~y 86 ml dd HCl d~c cAn lflY la:
V = m 100 = 52,35xl00 =118,2 ml
d x C% 37,23x 1,19

2.2. Bai toan v~ chuyen d5i nang de?

• Vi du. 3: Cho dd H2S04 14,35% co d = 1,10. Hay bi~u thi nong' dQ cua dd nay
theo T, C% (kl/tt), CN va CM
- Tit dinh nghta C% (kllkl) ta co th~ viet:
C%xdxV
C%(kl / kl) = .si: 100 ~m=----
dxV 100
- Vi T 13.n6ng dQ g/ml nen lay V = 1ml thi:

m = 14,35x 1,10x1 = 0 1579

100 ' g

m
T =-= 0,1579 g/ml
V

31
 C%(klltt) = Tx100 = 15,79

C = 0,1579 1000 =.3 22

N 49,0 x 1 '

C = ~,15791000 = i.sr
M 98xl '

cAu HOI vA BAI T~P

2.1. Hay dinh nghfa cac loai n6ng d9 sau:
a. Ba loai n6ng.d9 %: kllkl , k1Jtt va tt/tt
h. OM va ON
c. ppm va pph
2.2. Tinh n6ng d9 mol cua cac del sau day:
a. 0,694 mol hoa tan thanh 3,,55 L dd.
h. 2,19 mol NaOI hoa tan thanh 700,0 ml dd.
c. 0,3882 g KCI hoa tan thanh ,500,0 ml dd.
d. 1,003 g CuS04.5H20 hoa tan thanh 250,0 ml dd.
e. 30,00 ml dd NaOH 6,OM pha loang thanh 100,0 ml dd.
f. 0,100 L dd HOI 12,OMpha loang thanh 500,0 ml dd.
2.3. Tinh n6ng d9 duong IUQng(ON) cua cac dd sau:
a. 0,238 duong Iuong' m9t acid hoa tan thanh 1,500 L dd.
h. 1,29 mol acid sulfuric hoa tan thanh 500,00 ml dd dung cho ph an
ung sau: H2S04 + 2NaOH ~ Na2S04 + H20
c. 0,904 mol HaP04 hoa tan thanh 250,0 ml dd dung cho phan itng sau:
H3P04 + 3KOH ~ KSP04 + 3H20
d. 0,827 mol M(OH)3 hoa tan thanh 250,0 ml dd dUngoho phan itng sau:
Al(OH)3 + 3HOI ~ AIOl3 + 3H20
e. Hoa tan 1,38 g KOH thanh 500,0 ml dd dung cho phan ung d di~m c.
. f. 2,18 gNaH2P04 hoa tan thanh 1,500 L dd dung eho phan ung sau:
NaH2P04 + Al(OH)s ~ Al(NaHP04)4 + H20
g. Hoa tan 0,728 g KH2P04 thanh-250,0 ml dd -clUng cho phan itng sau:
KH2P04 + Ba(OH)2 ~ KBaP04 + 2H20

32
 -------- -------------- ----

2.4. Trinh bay each pha cac dd sau:

a. Tit chat rAn KOH tinh khie't pha 500,0 ml dd 0,10N
b. Tit NaCl tinh khiet pha 250,0 ml dd 0,15M
c. Tit glucose tinh khiet (C6H1z06) pha 100,0 ml dd 2,OM
d. Tit dd acid hydrocloric dac 12,OMpha 500,0 ml dd O,lM
e. Tit dd NaOH 2,OM pha 100,0 ml dd NaOH 0,25M
f. Tit H2S04 d~c 18,OMpha 2,0 lft dd 0,50M
2.5. Trinh bay each pha cac dd sau:
a. 500;0 ml dd KHzP04 0,20N dung cho phan tmg sau:
KHzP04 + 2NaOH ~ KNa2P04 + 2H20
b. 500,0 mldd H2S04 0,UN tit H2SO 4 d~c 18,OMdung cho phan irng sau:
H2S04 + Ca(OH)2 ~ CaS04 + 2 HzO
c. 750,0 ml dd Ba(OH)2 O,llN tit hoa chat Ba(OH}z tinh khiet dung
cho phan tmg sau: Ba(OH)2 + 2Na2HP04 ~ Ba(Na2P04)2 + 2H20
d. 200,0 ml dd base 0,15N dung trong phan img' sau:
2HBr + Na2COg ~ 2 NaBr + H20 + CO2
e. 700,0 ml dd acid 0,25N dung cho ph an ung sau:
2NaHCOg + Mg(OH)2 ~ Mg(NaCOg)2 + 2 H20
f. 300,0 ml dd HgP04 0,15N tit dd HgP04 d~c 15M dung cho phan img sau:
HgP04 + Al(OH)g ~ AlP04 + 3H20
2.6. C~n pha che' mQt dd trong do n6ng dQ acid acetic 0,17M va natri
acetat 0,29M. Trinh bay each pha 500 ml dd nay tit natri acetat tinh
khiet hoa hQCva acid acetic d~c 17M.
2.7. Can lay bao nhieu ml dd NaH2PO 4 da dUQCdieu che' bang each hoa
tan 0,384 g thanh 500;0 ml dd, d~ pha thanh 1000 ml dd 0,0200N
dung cho phan ling sau:
NaH2P04 + Ca(OH}z ~ NaCaP04 + 2H20
2.8. Tinh n6ng dQ mol cua glucose trong mau trudc va sau bfia an bie't
n6ng dQtinh theo mg/ml tuong ung la 80 va 120.
2.9. Cho 1 lit dd H2S04 98% (kllkl) co n6ng dQ 18,OM
a. C~n bao nhieu ml dd nay d~ pha duoc 1 lit dd H2S04 2,ON.
b. Tinh ty trong d cua dd H2S04 98% da eho.
2.10. Tinh so gam c~n d~ pha 1 lit dd co dQchuan T = 5,00 mg Fe20glml,
bie't d.ng Fe20g duoc kh1t thanh Fez+ truoc khi dinh lUQng b&ng
K2Cr207' Cho bie't K2Cr207 = 294,19 va Fe20g = 159,69.

33
 Chtidng8
? , _

xu LY co LIEU
. THLIC
. NGHIEM
1ft,. A.

. TRONG
HoA PHAN TICH

Trong thuc hanh phan tich miu, vi~c danh gia ke't qua la mQt trong
nhting budc quan trong, khong th~ thieu, No giiip ta danh gia ke't qua thu
duoc dung va chinh xac toi muc dQnao. NQidung cua chuong nay la xem xet
cac loai sai s6 g~p phai trong phan tich d~ uC1C luong dQdung va dQchinh xac
cua ke't qua.

..
1. DO DUNG vA DO CHiNH xAc CUA nu LIEU
.
Khi phan tich mQt miu theo qui trinh ky thuat da xac dinh nguoi ta
thuong lam 2 de'n 5 l~n. Trong truong hop tang quat neu lam n phep tha song
song nhu the'se thu dUQccac gia tri Xi (vdi i = 1, 2,.... N), nguoi ta thuong tfnh
x
gia tr] trung binh s6 hoc d~ bi~u thi ke't qua
N
LX;
-
x=--
;=] (3.1)
N
Gia tri trung binh x dUQcdanh gia theo hai d~i luQng th6ng ke la dQ
chinh xac va dQdung.

1.1. DQchinh X8C (precision)

DQchinh xac thudng dUQcbi~u thi bflng dQl~p l~i (repeatability), -dQtai
hi~n (reproducibility).

35
 DC)li}.p lai dude xac dinh dua tren cac du li~u (con goi la s6Ii~u) cua N
phep thi't song song tren cung mC)t mAu tai mC)t phong thf nghiem trong cung
dieu ki~n (do mC)t nguoi thuc hien-trong khoang thoi gian ngan).
DC)tai hien d1.iQeKaC dinh dua tren cac du li~u thu. ducc trong cac <lieu
kien khong hoan toan giong nhau (nhu ngudi khac, phong thi nghiern khac,
lam trongthoi gian khac, keo dai....)
DC)chinh xac danh gia muc dc1>
dao dC)ng cua cac phep thi't song song b~ng
nhieu each:
• DQ l~eh chuan s (standard deviation)

s> 1L:~~~ (3.2)

N - 1 goi la b~e tl,t do, thuong dUQe ky hieu la K hoac f.

• Phuong sai 52 (variance)
Phuong sai la binh phuong cua dC)l~eh chuan

(3.3)
Ne'u trong mC)t h~ hay mC)t phep tinh e6 n ngu6n sai 56 dQc l~p (m6i
ngu6n e6 b~e tl,t do fj) thi phudng sai tang St21a :

8
2
= ,hS12 + 128; + + Ins;
1 h+/2+ +ln

(ml -1)s; + (m2 -l)s; + + (mn -l)s;

2
SI =~~~~~~~~------~~~~ (3.4)
ml +m2 + +mn-n
voi m! la s6 phep thi't song song (tng voi m6i ngu6n.
MAu 56 eua (3.4) la 56 b~e tl,1 do ft eua h~. Ne'u trong h~ nay 56 phep thi't
song song mj eua cae ngu6n co cung tr! s6 :
m1 = m2 = ..... = mn = m t h1' f eua Phudng sal. t ong
t ? K St2
f = n(m - 1) (3.5)
t

va

j=1
=--- (3.6)
n(m -1) n

36
 N gUdi ta con dung mQt cong thuc khac d~ tinh phuong sai S2 thay cho
cong thuc (3.3):

LX~ _ (Lx;Y
S2 = I N (3.7)
N-l
• DQl~ch chuan tuong d6i RSD (relative standard deviation)
s
RSD= = (3.8)
x
RSD cho ta khai niem ro han v~ dQl~ch chuan vi no dU<;1c
so sanh vdi gia
x
tri trung binh cua t~p du lieu, RSD co tfi~ tinh thea phAn tram. Gia tri RSD
% con goi la h~ sO'bien sai CV (coefficient of variation).

1.2. D(>dung (accuracy)

DQdung danh gia su phu hop cua ke't qua thuc nghiem so vdi gia tri thuc
(true value) hoac duoc coi la thuc (accepted value). 'DQ dung dU<;1c
bi~u di~n
dudi dang sai sO':
• Sai sO'tuyet d6i E:
Ne'u gia tr] thuc la x, thi sai sO'tuyet d6i E :
E=x-~ (3.9)

E
r
= x-_x, xlOO (3.10)
x
Nguoi ta thuong dung E, vi cho khai niem ro rang han v~ dQ18ncua sai sO'.
DQ dung noi len st;t phu hop eua ke't qua phan tich x voi gia tri tht;tc
(hoi[lcdU<;1c
coi 1a thl,ic), con dQchinh xac th~ hi~n st;tphu h<;1pgiua cac du li~u
Xi voi nhau. Hinh 3.1 minh ho~ st;tkhac nhau giua hai khai ni~m d6 :

(a) d~t ket qua dung nhung kem chinh xac.

(b) d~t dQchinh xac rat cao nhung khong dung Him.
(c) d~t dtiQCca dQchinh xac cao va tinh dung cao.
(d) d~t ke't qua vita kem chinh xac vita khong dung.

37
 Hlnh 3.1. Minh hoa d9 dung va d9 I~p lai

BAng thuc nghiem ta co th~ xac dinh dQchinh xac nhung neu khong biet
gia tri thuc (rna thuc te thuong nhu vay) ta khong th~ danh gia dUQcdQdung.
Ghi chu: Hien nay trong cac phong thi nghiem thuc hien theo tieu chuan
ISO 17025, khai niem dQ chinh xac duoc hi~u la bao g6m ca dQ dung va dQ
churn (accuracy = trueness + precision).

2. cAc LO~ SAl s6 (CUA DU LI~U THVC NGHI~M )

Co 3 loai sai s6 tac dQnglen du li~u thuc nghiern:
Sai st;' h~ th6ng (hay sai 86 xac dinh): day la nhimg sai 86 do nhimg
nguyen nhan c6 dinh gay ra nhu do phuong phap, do thuoc thl:i hoac do dung
x
cu... Vi v~y no lam gia trl trung binh l~ch khoi gia tr] thuc x, (v~ phia am
ho~c dUdng). Vi d\l trudng hQp (b) va (d) d tren hinh 3.1. Sai s6 h~ th6ng anh
hUdng den dQdung cua s6Ii~u.
Sai s6' ngdu nhien (hay sai 86 khong xac dlnh): la nhung sai 86 gay ra bdi
nhung nguyen nhan khong c6 dlnh, khong biet truoc khong theo qui lu~t, lam
cho cac 861i~u dao dQnghai ben gia trl trung binh. Vi d\l trudng hQp (a) va {d)
d hinh 3.1. Sai s6 ng~u nhien tac dQng den dQchinh xac va co th~ anh hUdng
den ca dQdung.
Sai s6' th6 (outlier): it g~p hdn, thudng xay ra cho mQt dil li~u, lam no bi
tach xa khoi t~p hQp cac dil li~u con l~i, trd thanh mQt dil li~u ngo~i lai. Khi
xl:ily th6ng ke ngudi ta thudng lo~i bo 8ai 86tho truOc r6i mqi tinh toan den
cac d~i IUQngth6ng ke.

38

--.--------~- .-~~~~-
2.1. Sai s6 h~ th6ng (systematic errors)
V~nguyen t~c sai so h~ thong la sai so gay ra bdi cac nguyen nhan co th€
xdc dinh. duac. va vi vay co th~ hieu. chinh duoc.

2.1.1. Nguon go'c cua sai so' hf th{{ng

Ba nguyen nhan chfnh gay .ra sai so h~ thong cua du lieu:
a. Do df:tng cu:
_ Dung C1,lthuy tinh dong do th~ tich (pipet, buret, binh dinh muc) co th~
co th~ tich sai vdi th~ tich danh dinh (do che' tao, do b~n ben trong, do
sfly nong, do nhiet dQthi nghiem khac nhiet dQhie chuan hoa hay dinh
co dung C1,l).
_ Co thiet bi do chua du<;IChieu chinh hoac do tai sit dung lau cac linh kien
giam chat luong .....
CAndinh ky ki~m tra va hieu chusn thie't bi d~ phat hien va loai tril sai
so nay.
b. Do phuang pluip:
Nguyen nhan nay c6 th~ b~t ngudn tu:
_ D~c di~m cua phan itng: phan ung khong hoan toan, xay ra phan itng ph1,l...
_ Do hoa chflt,thuoCthit thuoCthit khong d~chi~u, hoa chflt khong 6n dinh···
Sai so do phudng phap thudng kh6 phdt h~n va la nguyen nhan quan
tr9ng nhrit gay nen sai so h~ thong.
c. Do cd nhan:
Nhi~u phep do trong phan tich doi hoi slt quan sat va quye't dinh cua ky
thu~t vien nhu: vi tri cua kim, cua mltc nudc giua 2 v~ch, slt chuy~n mau cua
chi thi, slt hoa tan he't cua ke't tua ... Vi v~y sai so do ngudi thltc hi~n 1a di~u
tflt yeu khong th~ tranh dU<;Ic. D~ giam thi~u sai so nay cAnthao tac cAnth~n.

2.1.2. Tac di}ng cua sai s6' hf th6ng den kef; qua phan tich
Sai so h~ thong c6 th~ 1a sai so khong d6i hay sai so ty 1~.
• Sai so' khong do'i: 1a sai so c6 tri s6 khong d6i, khong ph1,lthuQc vao lu<;lng
mAu.Vi d1,lkhi rita tua trong phan tich kh6i 1U<;Ing, ne'u dung 200m1nudc se
lam mfft O,5mgtua tan. Ne'u lU<;Ing tua 1a 500mg thi sai so -0,1%, ne'u 1U<;lng
tua 1a 50mg thi sai s6 la -1%. Nhu v~y ne'u lU<;Ing mAu cang Wn thi sai s6
khong d6i cang it anh hUdng de'n ke't qua phan tich (sai s6 % ph1,lthuQc vao
lU<;Ing
mAu).
• Sai so' ty l~:·sai s6 nay thay d6i ty l~ vdi 1u<;Ing
mAu. Vi d1,lsai s6 do t~p c6
trong mAu nhu dinh lu<;IngCu(II) bAng ph an ung vdi KI d~ giru. ph6ng iod.
Trong mAu co t~p chfft la Fe(III), n6 cling phan ung vdi KI d~ giai ph6ng

39
 iod. Nhu v~y luong iod giai ph6ng la thudc do t6ng cua Cu(II) va Fe(III)
trong m~u. Neu luong m~u tang len g~p doi, 111<;fng
iod duoc giai phong cling
tang len g~p doi. Nhu v~y ty 1~ % cua Cu(II) trong mAu khong phu thuoc
(dQclap) vao hrong mAu.

2.1.3.Pluit hi~n va Ioai tru sai so' h~ thong

Phat hien va 10~itrit sai s5 h~ th5ng la con-gviec r8:t kh6 khan. D~ giam
thi~u sai s5 nay, nguci ta thuong dung 4 each sau day:
1. Phan tich. mciu chudn: mAu chuan la mAu rna thanh ph~n c~n xac dinh
da biet ro nang dQ. Phan tich mAu chuAn d~ danh gia dQ dung cua
phuong phap,
2. Phan. tich. d9Cli),p:nguoi ta phan tich mAub!ng 2 phuong phap: phuong
phap dang khao sat va phtidng phap dQcl~p va so sanh d5i chieu hai
ket qua thu dti<;fc.Thtidng phtidng phap dQcl~p khac xa phtidng philp
dang khao sat v~ nguyen tAcoVi d\l c6 th~ dung phtidng phap do quang
d~ ki~m tra phl1dngphap chuAn dQdo the chAng h~n. Cach chQn nay se
giam thi~u kha nang m~u phan tich c6 anh htidng nhti nhau den ca 2
phtidng phap. -
3. Ph(i,n tich mdu trdng: phan tich m~u trAng giup ta danh gia sai s5 do
d\lng C\lcling nhl1 t~p ch8:tc6 m~t trong thu5c thlt.
4. Thay df/i llifJng mdu: nhti tren da trinh bay sai s5 khong d6i c6 th~ dl1<;fC
phat hi~n b!ng cach thay d6i lti<;fngm~u dung cho phan tich.

2.2. Sai s6 ng§:u nhien (random errors)

Sai s5 ngAu nhien bAtnguan tit nhung bien d6i nhi) khong ki~m soat dl1<;fc
trong qua trinh phan tich m~u. Toan th5ng ke 1a mon hQcnghien cuu v~ cae
bien ngAu nhien. Vi v~y tac dQngclla cac bien nay (gay ra sai s5 ng~u nhien)
den du li~u th\lc nghi~m dl1<;fc
xlt 1ythea cac quy lu~t clla toan th6ng ke.
Cac d~i 111<;fng
ng~u nhien trong HPT thl1dng tuan theo phan b5 chuAn.
Phan b6 nay cung voi cac d~i 111<;fng th5ng ke da dl1<;fcnghien cuu ky d giao
trinh toan th5ng ke. Vi v~y d day chi t6m tAt l~i cac cong thuc tinh toan thong
qua cac vi d\l C\lth~. -

3. xU LY THONG KE cAc DU LItU THljC NGHItM

Ngl1di ta thl1dng xlt 1y th5ng ke du 1i~u th\lC nghi~m gam nhung nQi
dung sau:
- Lo~i bi) cac du 1i~ungo~i lai.
- Xac dinh khoang tin c~y.
- Ngoai ra trong cac trl1dng h<;fpcAnthiet c6 th~ phai ki~m tra cac gia thiet
th6ng ke. D6 13.:

40
 - So sanh d9 chinh xac cua 2 hay nhieu phuong phap.
- So sanh 2 hay nhieu gia trj trung binh.
Gia sa t~p du lieu thuc nghiem thu duqc tit N thi nghiem co gia tri Xi' gia
tri trung binh X va phuong sai S2.
3.1. Loai bo dfi li~u ngoai lai

3.1.1. Chudn Q
Chu~n nay dung cho N ::;10, g6m cac giai doan sau:
- Slip xep cac du lieu tang dan x., X2,· .. Xn ,

- Tinh chuan Qtn d~ ki~m tra du lieu nghi ngd Xmax theo cong thuc

(3.11)

(lJ day x, = Xmin; x, = xmax)'

Ne'uc~nki~mtra du lieu nghi ngd x1thl ta s6 ciia congthuc tren se la X2 - Xl'

_ So sanh gia tri Qtn vdi gia trj Q tdi han (bang 3.1) vdi d9 tin cay da cho:
90% , 96% va 99%
Vi du: cho 5 du lieu thuc nghiem:
55,95 56,00 56,04 56,08 56,23
Ki~m tra du li~u nghi ngd 56,23

Q == 56,23 - 56,08
In 56,23 - 55,95
= °'
54

Theo bang 3.1 vdi N = 5, d9 tin c~y 96% thi Q = 0,73

Qtn < Q: kh6ng 10~ibo du li~u 56,23.
Bang 3.1. Gia tri ella ehu§n Q (fng vdi n
f>Q tin c~y
56 Ianthi nghi~m 99%
90% 96%
0,99
3 0,94
.0,98 0,93
4 0,76 0,85
5 0,64 0,73 0,82
6 0,56 0,64 0,74
7 0,51 0,59 0,68
8 0,47 0,54 0,63
9 . 0,44 0,51 0,60
10 0,41 0,48 0,57

41

~ ~----~---------------------
 .~---....:.- --_._-_ _. ..

3.1.2. Chudn y
Chuan nay dung trong trtrong hop t~p du lieu dii co va s. Danh gia du x
li~u nghi ngd Xmax hoac xmin co thuoc vao t~p du lieu nay khong b&ng each tinh
dai luong' Vtn hoac v' tn:

X -xmin I Xmax -x
y =-====- y =~=== (3.12)
In ~N-l' In ~N -1
s -- s --
N N
Trong do: v va v' la phan b6 chi phu thuQc vao so' b~c tl;Ldo f = N - 2.
So sanh gia trj Vtn hoac v'tn voi gia tri v tdi han dii cho d bang 3.2. Chuan
nay co th~ ap dung khi N > 10.
Vi du: Dinh luong alcaloid trong mQt dU<;1C lieu, tu 12 thf nghiem thu
dl1Qc·trjso' trung binh ham luong 0,85% voi s = 0,02. Trj so' Cl;LC
dai trong s612
thfnghiem do la 0,92% li~u co phai la du li~u ngoai lai khong?
y = 0,92- 0,85 = 3 65
In 002 [iT ,
, V12
Tra bang 3.2 cho f = 12 -2 = 10 ta co v' = 2,387 (dQtin cay 95%).
v'tn> v': c~n lo;;tibo gia trj 0,92% khoi t~p du li~u nay.
Bang 3.2. Gia tri chu§n v (v') chu§n (tng voi 86 b~c til do f

£)Q tin c,y £)Q tin c,y

f f
90% 95% 99% 90% 95% 99%
1 1,406 1,412 1,41,4 13 2,326 2,493 2,800
2 1,645 1,689 1,723 14 2,354 2,523 2,837
3 1,791 1,869 1,955 15 2,380 2,551 2,871
4 1,894 1,996 2,130 16 2,404 2,577 2,903
5 1,974 2,093 2,265 17 2,426 2,600 2,932
6 2,041 2,172 2,374 18 2,447 2,623 2,959
7 2,097 2,237 2,464 19 2,467 2,644 2,984
8 2,146 2,?94 2,540 20 2,486 2,664 3,008
9 2,190 2,343 2,606 21 2,504 2,683 3,030
to 2,229 2,387 2,663 22 2,520 2,701 3,051
11 2,264 2,426 2,714 23 2,537 2,717 3,071
12 2,297 2,461 2,759

42

--.~----.
3.2. Xac djnh khoang tin c~y (confidence interval)
Khoang tin cay cho t~p dil lieu la:
- txs - (3.13)
p=x± ..IN=x±&

Trong do: t la chuan Student, phu thuoc khong chi vao dQ tin c~y rna
ca vao s6 dil lieu thuc nghiem N. Neu s6 thf nghiem N tang d§.n de'n vo cung
thi cac dai luong th6ng ke ciia mAu cung dAn de'n dai luong cua dam dong
(quan th~):
x ---+ J.l , S ---+ cr.Gia tr] cua t chi con phu thuoc vao dQtin cay.
Tit (3.13) co th~ tinh duqc sai s6 tuong d6i:
. A'Of.
Sat so -10 = --=-
&
x
x 100
(3.14)
Vi du: Phan tich ham luong Al203 trong m§.u 5 IAn ta thu duqc ke't qua
phan tram sau: 2,25; 21,9; 2,11; 2,38 va 2,32. V~y ham hrong Al203 n&m trong
khoang tin c~y nao? .
Ta thuc hien cac budc sau day:
1. Ki~m tra theo chuan Q: khong Ioai bi) dil lieu nao,
2. Tinh x: x = 2,25
L(Xj -2,25)2
3. Tinh dQl~ch chu~n s: s= =011
5-1 '
4. Tra bang t (tng voi dQtin c~y 0,95 va n = 5: t = 2,78
co= 2,78 x 0,11 = 0 14
5. T in h E: ".J5'
Ham luqng Al203 trong m§.u 1a: 2,25 ± 0,14
Neu khong co sai s6 h~ th6ng thi voi xae sua't 95% gia tri J.l nAm ti'ong
khoang 2,11 de'n 2,39 (%).
3.3. So sanh dq chinh xac clla hai hay nhi~u ke't qua th1!cnghi~m
D~ danh gia dQ chinh xae ella 2 ke't qua thuQC 2 dAy thi nghi~m ho~c
thuQc 2 phudng phap khac nhau ngl1di ta dung chu~n F, d6i voi n ke't qua
ngl1di ta dung chu~n Bartlett.
3.3.1. Chutin F (Fisher)
Gia s11co 2 ke't qua thu duqc tit hai day thi nghi~m ho~c tit 2 phudng
phap voi s6lAn n1 va n2, de?l~ch chuAn tudng (tng Sl va 82, D~ so sanh de?chinh
xac, ta so sanh 2 phudng sai:

43
 (3.15)

Trang do: s/ i> s/, vi v~y Ftn luon Idn hen 1.

So sanh gia trj. Ftn vdi gill tr] F vdi dQ tin c~y 95% (bang 3.3) va so bac tl,1
do f1 = n1 -1 va f2 = n2 - 1. Neu:
- Ftn < F : dQ chinh xac cua 2 ke't qua khac khong co y nghia thong ke.
- Ftn > F: dQ chinh xac cua 2 ke't qua khac nhau co y nghia thong ke.

Bing 3.3. Gis t~ F v(JioQtin c~y 95%

S,C 11/do S.c til do (til so)

(miu so) 2 3 4 5 6 12 20 ac:
2 19,00 19,16 19,25 19,30 19,33 19,41 19,45 19,50
3 9;55 9,28 9,12 9,01 8,94 8,74 8,66 8,53
4 6,94 6,59 6,39 6,26 6,16 5,91 5,80 5,63
5 5,79 5,41 5,19 5,05 4,95 4,68 4,56 4,36
6 5,14 4,76 4,53 4,39 4,28 4,00 3,87 3,67
12 3,89 3,49 3,26 3,14 3,00 2,69 2,54 2,30
20 3,29 3,40 2,87 2,71 2,60 2,28 2,12 1,84
ac: 3,00 2,60 2,37 2,21 2,10 1,75 1,57 1.00

3.3.2. Chu6n Bartlett

Gia sit co n ket qua thu dU<;Ic tit n day thf nghiem hoac tit n phuong phap
voi 'dQ 'l~eh chuan tuong ung Sl' S2' .•.•• , Sn. D~ so sanh dQ chinh xac cua n ke't
qua nay, ngudi ta tinh:
n
2 ItSI
2 2
+ f2S2 + + fnsn
2 Lh
. i-I
Si2
S - -~--
-> It +f2+······+fll - f
(3.16)

B = 2,303(/lg 8; - t,J; 18S;J

C=I+ 1 (n2:-1--
1 IJ
. 3(n -1) ;=1 J; f
Bartlett dii chtrng minh rang ty so BI C co phan bo x2 v(Ji so b~c t1;ldo
f=(n-1) neu t~t ca fj > 2.
So sanh gia trj BlC voi gia tri X2 (dQ tin c~y 95%), ne'u :

44
 -... -~'-- _ ~
.. ..•..... .. _ _-------
..

BtC ~ X2 su khac nhau giua cac phuong sai khong c6 y nghia th6ng ke,
BtC > X2 s\1 khac nhau giua cac phuong sai c6 y nghfa th6ng ke (khong
dang nhat),
Vi C luon luon > 1 cho nen neu B ~ X2 chap nhan gia thie't Ho: cac phuong
sai S2j khac nhau khong c6 y nghia th6ng ke.
Neu B > X2 c~n tinh C va ty so' BtC.

Bang 3.4. Gia trj "I: va t (tng vOi 56 bac til do f

Gia trj t, d9 tin c~y l ,d9 tin c~y
Gia trj ..
f
95% 99% 95% 99%

1 12,7 63,7 3,8 6,6

2 4,3 9,92 6,0 9,2

3 3,18 5,84 7,8 11,3

4 2,78 4,60 9,5 13,3

5 2,57 4,03 11,1 15,1

6 2,45 3,71 12,6 16,8

7 2,36 3,50 14,1 18,5

8 2,31 3,36 15,5 20,1

9 2,26 3,25 16,9 21,7

10 2,23 3,17 18,3 23,2

11 2,20 3,06 19,7 24,7

12 2,18 3,01 21,0 26,2

Vi du: NgUdita digu ch4 mQthop chilt vo co thong qua ke't tinh d 4 nhiet
dQkhac nhau: TI, T2, T3, T4 ung vdi 4 phuong sai si~}lan tich 8\1dang nhilt
cua 4 phuong sai dUQctom tl'it d bang sau:

Nhi~t d9 512 f, f,.5,2 Igs/ f,lgs,2 11f,

1,72 5 8,60 0,2355 1,177 0,200

T1
1,60 4 6,40 0,2041 0,816 0,250
T2
1,97 6 11,82 0,2945 1,767 0,167
T3
2,37 8 18,96 0,3747 2,995 0,125
T4
L 23 45,78 6,755 0,742

4
f = If: =23;
J
2 _ 45,78 _ 1 99
s ----
y 23 '
=> 19s~ = 0,2889
f 19s~ = 23 x 0,2889 = 6,874

B = 2,303(6,874 - 6,755) = 0,278

45

-~--------- ....-_-- ...-

 .. ~ .__ _._._ _--_
..

Tra bang 3.4 vdi xac sua't P = 95% va f =3: x2 = 7,8

Gia tr] B < x2 nen khong' caln tinh C. Dua vao chuan Bartlett ta chap
nhan 4 phircng sai ken d6ng nhat. Dieu do co nghia 13.qua trinh ket tinh
khong phu thuQc vao 4"nhi~t dQtren,

3.3.3. Chudn C6>ChTaTJ

Neu cac phuong sai Gil ehon (tng voi so thf :nghi~m nhu nhau: m, = m2=
..... = fin = m, nguf1i ta dung chuan Cochran -d~danh gia tinh d6ng nhat cua
phuong sai t.h6ng qua dai htQb.g G

(3.17)

Phan bo tri so ng~u nhien G chi phu thuec vao so phuong sai n va so b~c
tl,t do eua m6i phirong sal. f == m -l.
So sanh Gtn voi,gia tri G tra (1 bang 3.5. Neu Gtn < G ta chap nhan gia
thiet Ho: cac phusng sai <Mng nhat.

Bing 3.5. Gia tri cua G (lng vbi f va n (P = 95%)

I~
.2
1

9g85
2

9750
3

9392
4

9057
5

8772
6

8534
7

8382 8159
8 9

8010.
10

7880.
3 9669 8709 7977 7.457 70.71 6771 6530. 6333 6167 60.25
4 9065 7679 6841 6287 5895 5598 5365 5175 50.17 4884
-
5 8412 6839 5981 5441 50.65 4783 4564 4387 4241 4118
6 780.8 6161 5321 480.3 4447 4184 3980. 3817 3568 3135
7 7271 5612 480.0. 430.7 3974 3726 3535 3384 3154 2756
8 9798 5157 4377 3910. 3595 3362 3185 30.43 2829 2462
"

9 6385 I .-4775 40.27 3584 3286 3067 290.1 2768 2568 2226
10 60.20 4450. 3733 3311 30.29 2823 2Q66 2541 2353 20.32
11 5410. 3924 3264 2880. 2624 2439 2299 2187 20.20. 1737

Luu y: Gia tri ham G luon luon < 1, vi v~y trong bang cho cac so g6m 4
chu so sau dau phfty.
3.4. So sanh hai hay nhi~u gia·tr! trung binb
D~ so sanh 2 tri so trung binh nglidi ta"dung chu~n t, so sanh n gia trj
trung binh dung chuAn·Duncan.

46
 3.4.1. Chucln t (Student)
Gia 511dinh luong hoat chat trong mQt mfru bAng 2 phuong phap co ket
x
qua Xl va 2 , vdi 50'IAn thuc nghiem Nl, N2 va dQI~eh chuan 51,52, CAn danh
gia xem hai ket qua khac nhau co y nghia thdng' ke hay khong, ta thuc hien
cac budc sau:
Trude het 50 sanh dQchfnh xac ella 2 phuong phap theo chuan F (dQtin
. c~y 95%):
• Neu Ftn ~ F': dQl~ch chuan 51va 52thuoc cung 1 t~p hop, tinh dQl~ch chuan
chung theo eong thuc:

Sd = (N, -1)s,' +(N, -1)s; x

NI +N2 -2
J 1 + 1
NI N2
(3.18)

va E =t. 5d
Gia tri tung vdi dQtin cay 99% va f= N, + N2 - 2 (bang 3.4).
So sanh gia tr] cua E vdi I Xc x 2 ~ neu:
I Xc x2 I shai ket qua trung binh Xl va X2 khac nhau khong co
E : y
nghia thong' ke, chung cung dai di~n cho mQt gia tri tht;te,
Xc x2 I > E : hai ket qua trung binh khac nhau co y nghia th6ng ke .
• Neu Ftn> F' : hai phudng phap co dQehinh xae khae nhau co y nghia th6ng
ke. Trong trudng hQp nay hay tinh:
S2
V =_1
I N
I

Tra bang tim gia tri ella t1 voi £1= Nl - 1 va ella t2 voi £2= N2 - 1 voi
P=99%. Tinh gia tri T theo cong thuc:

T = viti + vzt2 (3.19)

~VI +V2

So 5anh gia tri T voi I x x2 I

1-

Xc x2 I ~ T: hai ket qua phu hQp nhau,

Xc x2 I > T: hai ket qua khong phu hQp nhau.
Ghi chu: MQt 50'tai li~u dung ehu~n t 50 5anh 2 tri 50'trung binh voi dQ
tin c~y 95% (khong dung 99%):
- D~ chffp nh~n gia thiet Ho, dung chu~n t mQt phia (to,9J,
- D~ bac bi) gia thiet Ro, dung 'chuftn thai phia (to,97J·

47
3.4.2. Chu·iln Duncan
D~ so sanh nhieu gi€t tri trung binh Xi' nguci ta dung ph an b6 t nho
chuan Duncan. Gia Stl d.n so sanh k gia tri tl'ung binh Xl' X2, ..... Xk vdi cac
phuong sai tuong' ung s/, s/, ....., Sk2 tlJ,uge cung m§t t9-P h{fp {ung vdi phuong
sai thuc nghiern 5/). Viec-so.sanh duoc thuc hien theo cac bUGCsau:
- Slip ~ep k trj so trung binhtheo thli t-.;t tang dAn,
Xac dinh sai s6 dQI~p lai Sx cua C{lC kit qua. ffiIg voi so' b~c t-.;t do fx
fx = f~-+ f2 + ......+ fk
- Tinh sai s6: s.~N (3.20)

- Tra gi3. tr] hang {H) cua p ttl bang Duncan trng vdi P = 95% va Un = fx•
- Nhan gia tri H tuong ling vdi sai s'Otrung binh va so sanh hieu tung c~p
hilt dAu ttl ,gia tri Xmax va xmin'
vdi tri s6thu gU<;Ic

-Bang 3.6. Gia tri'h~ng ella chuan Duncan (P = 95%)

I~ 8 3,26
2 3

3,3Q 3,47
4 5

3,52'
Ei

3,55
7

3,56
8

3,56
9 3,20 3,34 3,41 3,47 3,50 3,52 3,52
10 3,15 3,30 3,37 3,43 3,46 3,47 3,47
11 3,11 3,27 3,35 3,39 3,43 3,44 3;45
12 3,08 3,23 3,33 3,36 3,40 3,42 3,44
13 3,06 3,21 3,30 3,35 3,38 3,41 3,42
14 3,03 3,18 3,27 3,33 3,37 3,39 3,41
15 3,01 3,16 3,25 3,31
- 3,36 3,38 3,40
16 3,00 3,15 3,23 3,30 3,34 3,37 3,39
17 2,98 3,13 3,22 3,28 3,33 3,36 3,38
18 2,97 3,12 3,21 3,27 3,32 3,35 3,37

Vi dl:l: Dinh Iu<;Ingty l~ hOliltcha't ttl 4 m~u nguyen li~u hoa d1i<;lC
(m8i
mAu lam 5 IAn) thu dUQcket qua trung binh sau day (phttcJng sai s/ = 4,41).
Xj (%) 95,1 87,8 91,2 93,5
80' thf nghi~m 1 2 3 4
- S&pxep ket qua trung binh theo thli t-.;t tang dAn:
87,8 91,2 93,5 95,1
(2) (3) (4) (1)

48
 - Sai so trung binh: s- = ,J4,41 = 105
x 4 '
- Tra bang Duncan vdi muc y nghia 0,05 va nD= 16
p 234
h~ng(H) 3,00 3,15 3,23
H. s ~ 3,15 3,31 3,39
- So sanh tung cap:
(1) - (2) = 95,1 - 87,8 = 7,3 > 3,39: khac nhau co y nghia
(1) - (3) = 95,1 - 91,2 = 3,9> 3,31: khac nhau co y nghia
(1) - (4) = 95,1 - 93,5 = 1,6 < 3,15: khac nhau khong co y nghia
(4) - (2) = 93,5 - 87,8 = 5,7> 3,31: khac nhau co y nghla
(4) - (3) = 93,5 - 91,2 = 2,3 < 3,15: khac nhau khong co y nghia
(3) - (2) = 91,2 - 87,8 = 3,4> 3,15: khac nhau co y nghia
Ngoai chuan Duncan, d~ so sanh nhieu tri s6 trung binh con co cac chuan
khac nhu: chuan LSD cua Fisher, chuan Scheffe, chuan. Neuman, Keuls,
Dunnett. M6i chuan co d~c di~m rieng. Co th~ tim hi~u them cac chuan nay
trong cac tai lieu thong' ke chuyen khao.
Ghi chit:
Xiily thong ke du lieu khong don thuan lam mQtbai toano D~ di de'n mQt
ke't luan thong ke: loai bo 1 s6li~u do, chap nhan 2 phuong sai thuoc cung mQt
t~p hop, ke't luan 2 tri s6 trung binh khac nhau ... cAnxem xet de'n cac d~c di~m
Cllamftu clla thong s6 cAndo, clla digu ki~n thl;iChi~n phep do. Co nhli the'moi
dlia de'n mQtke't lu~n tin c~y. M~t khac ke't lu~n th6ng ke khong d~t de'n dQtin
c~y 100%vi v~y trong toan th6ng ke nglidi ta co khai ni~m sai lAmlo~i I va sai
lAm10l?-i II. Hai 10l?-i
sai lAmnay luon co m~t trong mQtke't lu~n th6ng ke.
3.5. XH sai so h~ thong eua phtidng phap
Trong hoa phan tich d~ danh gia sai s6 h~ th6ng clla mQt phlidng phap,
nglidi ta thlidng phan tich mQt mftu chuftn (standard sample) trong do co
thanh phAn dinh lliqng da bie't chiic chiin, vi d\1gia tri tht;!cdo la ).1. Gia tri xac
dinh b~ng tht;!cnghi~m la x.
Dt;!avao chuftn t nglidi ta xem xet hi~u I x-
).1 I
co phai la bie'n ngftu nhien khong:

Neu IX -,ul < .IN: st;!sai khac nhau giua gia tri do dliqc x va ).1 khong co y

nghia, phlidng phap khong co sai so h~ thong.

Neu I~-,ul > .IN: phlidng phap co sai so h~ th6ng.

49
 - -~-~-~--~----~-~~~--.---~------_..._- ------

Vi du: MQt m~u thli co ham hrcng hoat chat da biet la 0,123%. Dung mQt
phuong phap mdi dinh h1qn~ .rn~ll thl1 nay cho ket qua:
x::::: 0,116% vdi s::::: 0,0032 ; N::::: 4

.s: = 3,8 x 0,0032 :::0,0061 (vdi P :::::

95%)
-IN J4
I x - Il I = 0,116 - 0,123 :::::0,007
I X - Il I > 0,0061. Phuong phap mdi co sai so h~ thong (voi xac suat
dung 95%).

4. CACHTRiNH BAy cAc ntr LI~U PHA.Nrtcn

Cac du lieu phan tich c~n duoc trinh bay sao cho nglidi d9C danh gia duoc
dQtin c~y cua chung. Co nhieu each trinh bay du lieu:
- Ghi ro khoangtin cay: 10,5 ± 0,2.
- Ghi ro dQlech chu-An(SD) hose dQl~ch chuan tuong doi {RSD).
- Dung chu s6 co nghia.
TruOc khi trinh bay khai niem chu sO co nghia ta xem xet each lam tron s6.

4.1. Cach lam troD so

Qui tAc lam tron so:
Neu chu so cudi cung la:
chu so 1- 4: bo di,
chu s6 6 - 9: bo di va them 1 vao chu so dung trudc no,
chu so 5: lam tron thanh ~o chAn g~n nnat.
Vi dl:l: 61,55 thanh 61,6 (them 5).
51,45 thanh 51,4 (bdt 5).

4.2. Ch fi so co nghia
MQt du li~u phan tich thu du<}ctit do luang t"'l/c tiep ho~c tinh toan
gitin tiep phai du<}cghi theo quy tAc ve chu·s6 co nghia: mqt con s({phai dU{1c
ghi sao cho chi mqt chft s6~cu6Lcitng lo' con nghi ngd, m9i chft's6' con l{Lilo' ch&c
ch&n. Nhu v~y du li~u ph an tich phai du<}ctrinh bay sao cho philn anh duqc dQ
tin c~y clla phep do.
D~ la'y dung chu 56 co nghia d.n luu y 2 di~m:
- Qui tAc xac dinh so chu so co nghia clla mQt s6 da cho.
- Cach la'y chu so co nghia khi tinh tom ho~c do ludng.

50
4.2.1. Qui t6c xac djnh so'chit so'co nghia
Trong mQt s6 da cho viet theo chir s6 co nghta thi:
- Cac chu s6 khac khong deu co y nghia: 124,5 gam 4 chft s6 co nghia.
- Chu s6 khong nam giua 2 s6 hoac nam ben phai chft s6 khac khong deu
co nghia:
1204,5 : 5 chu s6 co nghia; .
124,50: 5 chfi s6 co nghia;
_ Chu s6 khong nam ben trai cac chti s6 khac khong deu khong co nghia.:
0,00531 : 3 chfi s6 co nghia.

4.2.2. Cach. Ifiy chit so' co nghia khi tinh totin

1. Khi nhan, chia hai hoac nhieu s6, ket qua cu6i cling se duoc him tron
bang s6 co it chir s6 co nghia nhat, vi du:
4,3 x 0,882 = 3,7926 lam tron thanh 3,8
..
0,900/ 0,2250 = 4 phai viet la 4,00
2. Dap s6 cua phep cong hoac trir se co cling s6 chir s6 d ben phai cua dau
thap phan co s6 chu s6 co nghia it nhat. Vi d\l:
24,992 + 3,2 = 28,192 lam tron thanh 28,2
75,2490 - 0,1041 = 75,1449 giu nguyen 75,1449
75,2490 - 0,40 = 74,8490 lam tron thanh 74,85
3. Khi phep tinh phai qua nhieu bucic,chi lam tron ket qua cu6i cling,
khong lam tron cac buoc trung gian.
(3,22 - 3,034) x 5,61
lam tron trl.tOC: 1,0651 thanh 1,06 (sai),
lam tron sau: 1,04346 thanh 1,04 (dung).
4. Khi lay logarit m9t s6 (vi d\l nang de?H+ chuYE}nthanh sang pH, d9
truyen qua T% sang d9 hap th\l) s6 chu s6 ben phai dau th~p phan phai bAng
86 chu 86 co nghia d s6 ban dftu. Vi d\l:
[H+]= 4,9.10-6M ~ pH = 5,31
[H+]= 4,98.10-6 M ~ pH = 5,303
Ngu<;jcIf:\i,khi chuYE}n
tit logarit sang s6 tl,tnhien, ket qua 8e co s6 chu s6
co nghia bAng86 chu s6 sau dau th~p phan.
4.2.3. Cach lay chit so' co nghia litc do luang
Luc can, do thE}tich ho~c dQcd~ li~u tren may cftn lay dung s6 chu s6 co
nghia. Vi dW

51
 - can 90 mg tren can phan tich (sai so ± 0,2 mg), diI lieu duoc ghi 90,Omg
ho~c 0,0900g (3 chu s6 co nghia). Neu can ,tren can phan tfch {sai s6
±O,{)1.mg),du lieu duqc ghi 90,00 mg hoac 0,09.QOOg
(4 chu s6~6 nghia),
- Tren buret 25 ml co chia vach den 0,1 fill thi d\la vao day m~t congcua
dung dich ~~m giita 20,3 va 26,4, ng}tdi doc c6 th~ uOc hrong them: 20,34
ho~c 20;35 (c6 4 chu s6 c6 nghia).
- Khi do dQhap thu tren may quang ph6 UV~VlSthe h~ cft chi c6 t6i da 3
chu so' co nghia: 0;945 hoac 6,140~ Vdi may tlfe h~ moi c6 4 chir s6 co
nghia: 0,9450 hoac 0,1400.

... ., " " A

CAU HOI VA SAl T~P

3.1. Giai thfch 81,1 khac nhau gifta:
- DQdung va dQchfnh xac,
.- Sai so'h~ th6ng va sai s6 ngAu nhien,
- Sai so'tuyet d6i va sai s6tudng d6i,
- Khoang tin c~y va dQtin cay,
- s va cr.
3.2. Ngudn g6c cua sai s6h~ th6ng. Cho vi dv.minh hQa.
3.3. Trinh hay each dang gia sai so'h~ th6ng cua m-Qtphudng phap. _
3.4. So sanh chuAn Q vdi chu!n v. Cach sit d\lng.
8.5. MQtsinh vien can mQt mAu d~ pha: thuOc thit tren can ph an tich kh6i
IUc;lngla 1,2435g. Nhung h?n cung nh,6m can l~i mAu d6 eho ket qua
1,2437g. Day la sai so' gi ? Giai thieh.
8.6. Ki~m tra m~y quang ph6 UV - VIS thong qua do 8 l~n tren 1 mAu
thu dUQcket qua: 0,855; 0,836; 0,848; 0,870; 0,859; 0,841; 0,861 va
0,852. Theo tieu ehuAn eua nha san xuat, dQchinh xae khi do dQhap
thu tren may nay c6 RSn -khong qua 1%.'Thie't hi do co d?t tieu
chuAn khong?
3.7. Lam 3 thi n:ghi~mA, B, c::: thu dUQccac ket qua sau:
ABC
2,4 0,0902 69,65
2,1 0,0884 69,63
2,1 0,0886 69,64
2,3 0,1000 69,21
1,5

52

- --------------_------- ---------------------- --
Tinh tri gia trung binh X va dQl~eh chuan eho m6i thi nghiem.
3.8. Tinh khoang tin e~y (P = 95%) eho 3 thf nghiem d bai 3.7.
3.9. Cac du lieu cuoi cling d bai 3.7 co th~ co sai so tho. Dung chuan Q d~
xac dinh xem loai bo du lieu nao ?
3.10. MQtky thuat vien khac lam lai ba Iftn thi nghiem Cd bai 3.7 co 3
du lieu sau: 69,94; 69,92 va 69,80 (XE)'
Thi':iki~m tra 2 ke't qua tren co khac nhau khong?
3.11. So sanh dQehinh xac cua ke't qua 2 mAu X, va X2 thu dU9c tit 2
phong thi nghiem A va B

Miu PhongA Phong B

s f s f

Xl 0,10 6 0,12 12

X2 0,05 20 0,07 6

3.12. Bon ky thuat vien phan tich hoat ehfft trong cung mQtnguyen lieu
thu dU<;lCdu lieu d bang sau. Hay ki~m tra sl,i dang nhat cua
phuong sai theo chuan Bartlett ..

KTV A B C D

N 3 3 3 5
52 3,6 4,7 2,9 8,3

53
 Chlidng4

- .. ..
CAN SANG HOA.HOC TRONG DUNG DICH '

1. CAN BANG HOA HQC - HO~T DQ

Ta xet mQtph an ung thuan nghjch:
mA+nB ~.pe+qD (4.1)
Trong qua trinh phan itng, t6c dQeua phan ung theo chitu thu~n - phan
(tng giila cac ti~u phan A va B - giam d~n, con t6c dQ phan tmg theo ch..eu
nghich - phan ung giila e va D - tang dftn. Khi t6c dQphan tmg theo chi~u
thuan bltng t6c dQphan ung theo chieu nghjeh thi phan UJlgdat tCsitrang .thai
can b~ng. Dola tr'ang thai can b~ng dQng. H~ng 86can bAngK cua h~ la: .

..(4.2)

Day la biiu thr1e todn hoc eua dinh. lli~t tdc dl:lng kheii llL(/ng. HAng sO' can
bltng K cho ta bie't ehiiu va mac al) hoan toan. eua pluin. r1ng.

1.1.Ho~t d9
Trong phan ung (4.1), A, B, e, D la phan tit trung hoa di~n,..h~ng sO' K
chi ph\l thuQc vao nhi~t dQ.Ne'u A, B, e, D la nhilng ion, tac~n·tinh de'n h;lC
tl1dngtac tinh di~n cua chung, nen trong bi~u thuc (4.2) phai thay nang dQcan
bAng [A], [B], [e], [D]bAngho~t dQtl1dng(lng.

54

_-----
..- ...
 Hoat dQa cua mQtion duoc xac dinh bang h~ thuc:
a=f.C (4.3)

trong do: C Ia nong dQmol ion,

• f la h~ s5 hoat dQ.
Theo thuyet tuong tac tinh di~n cua Debye _ Huckel, h~ s5 f phu thuoc
• vao dien tich cua ion do, n6ng d9 va dien tieh ella tll't ca. cac ion co m~t trong
dung dich, Ne'u dung dich co n6ng d9 cao, h~ s5 f eon phu thuoc ca V8.0 ban
chat cua ion.
• each tinh hf sfi hoqt. d9 f:
D~ tinh h~ s5 hoat dQf, trudc het d.n xac dinh luc ion I cua dung dich.
1= 0,5 [ C1Z12 + C2Z22 + ...] = 0,5 L C, Zj2. (4.4)
Dl;iaV8.0 phuong trinh Debye - Hiickel d~ tinh h~ s5 f :

-1 f = 0,5.2;2.-!i (4.5)
g i 1+ r.O,33.108 •.JI·
Trong do:
Zj: dien tich cac ion c~n tinh f,
r : ban kinh trung binh cua ion solvat hoa da cho, trong dung
dich nude r ~ 3.10.8cm. Cho nen:

-1 f = 0,5.2;2.-!i (4.6)
g i 1+.JI
Do khong th~ xac dinh bang' thuc nghi~m gia tri fj clla cac ion nen ngtidi
ta thay h~ s5 ho~t dQtrong phtidng trinh (4.6) b~ng h~ s5 ho~t dQtrung binh
cho cac ion co di~n tich ± 1, ± 2, ... (fz±) Bi~u thuc nay chi dung cho dung dich
ion I > 0,2 (tuc 18. dung dich co n6ng dQcao hdn)
ntiOckhi Il;iCion:::;0,2. Neu 1l;iC
ta d.n dieu chinh b~ng mQts5 h~ng:
?.JI (4.7)
-lg f z_+ = 0,5.z;- Ir +
1+",1
AI
•
Trong do: A 18. h~ s5 thay d6i thee ban chll't ion.
B~ng tht;tc nghi~m, voi dung dich co n6ng dQtrung binh (0,20 < I < 0,5)
Davies da thu dti<;jcbi~u thuc tinh h~ s5 ho~t dQfz± ( I z I :::;3) nhti sau:

-lgf
z_
?(
+ = A.2;- -!i ,-;-0,21 )
1+",1
(4.8)

Trong dung dieh ntioc, d nhi~t dQphong A = 0,5; dung n6ng dQmol ion d~
tinh ll;iCion I.
55
 Ghi chu:
- Khi luc ion I < 0,02, nguoi ta tinh h~ so f theo phuong trinh gioi han
Debye - Hiickel:

-lgf z_+ =0,5.z;.Jj •

- Khi dua h~ so fi vao bi~u thuc (4.2), ta c6:

•
. [cy .[D]q f~.fZ
K= . =K .f (4.9)
[At .[B)" m.'11 C ±
fA 1B

Trong d6:
Kc la h~ng so can b~ng nang dQ,
f± la tr] so danh gia tac dQng cua hrc tuong tac tinh di~n len h&ng so
can bang,
K lit hang' so can bang nhiet dQnghoc,
Trang thuc te'tinh toan nang dQcan bAng clla cac ti~u phan trong h6a
phan tich, nguci ta thuong dung hAng so can b~ng Re, bo qua tac dQng cua
tuong tac tlnh di~n - titc la chap nhan f± ==1. Ke't qua tinh toan theo each nay
c6 sai so chap nhan du<;tcchi khi dung dich c6 nang dQthap (dung dich loang).
vi ao i.
Tinh hoat dQcua cac ion trong dung dich c6 2 mudi hoa tan KC11,OO.10·3
M va MgS04 1,00. 10.3 M.
- Tinh luc ion I:
1==0,5 (2 x 1,00. 10.3 + 2 X 22. 10.3) ==5. 10.3
- Tinh f:

Igt±1 = -0,5.l..JS. 10-3 == -0,035 ~ f±1 == 0,92

Igt±2 = -0,S.22 •.JS.1O-3 == -0,14 ~ ti2 == 0,72

Tinh ho~t dQ:

a K + = aCI- = 0,92.1.10 -3 = 0,92.10 -3M

aMg2+ = aS042-:: 0,72.1.10

-3 ==0,72.10 -3M
.

Vi dl,l 2: Tinh ho~t dQclla cac ion trong dung dich CaC12 0,1 M.
1= 0,5 (22 x 0,1 + 12x 0,2) ==0,30

56
 Vi I > 0,20 nen tinh h~ 86 f theo phuong trinh Davies:

1gt±2 = -0,5.2 2{ 1+.J0,3-o,2.0,3

.JO,3 ) = -0,598 ~ h2 = 0,252
..
19f±l :: -0,5.12 .( .JO,3
tx:
1+,,0,3
J = -0,149 ~
0,2.0,3 t±l = 0,71

a Co 2+::::: 0,252.0,1= 2,52.10-2 M

1.2. Sl;1'phan ly trong dung djch - lien hep ion

Qua trinh hoa tan va phan ly cua mot cha"tAB trong nude co th~ bi~u
dien theo 2 budc:
AB + (m + n) H20 -=- A(H20)n B+(H20)m~ A(H20)n' + B(H20)m+
- Buoc th{1nhat cac ti~u phan trong AB duoc hydrat hoa, chuyen chung
thanh C?P ion A(H20)n B+(H20)m'
- Budc thu hai, cac cap ion nay phan ly thanh cac ion hydrat Hoa chuyen
d9ng tu do trong dung dich,
Trong truong hop t6ng quat, khi hoa tan m9t chat trong dung m6i co kha
nang solvat hoa AB thi:
- V(Jidung m6i proton:
HS+AB ~
- V(Jicac base Lewis:

Qua trrnh: ion hoa phan ly

Kha nang solvat hoa cua dung m6i (lien ket hydro, tuong tac dipole...)
quyet dinh qua trinh ion hoa tao ra cap ion. Hang s6 dien m6i cua dung m6i se
quyet dinh qua trinh ph an ly tao ra cac ion. NUdCla chat luang tinh solvat hoa
manh lai CO hllng s6 di~n m6i 8 ldn (8 = 78) nen nhieu cha't lien ket ion ho~c
phan C\IChoa tan nhanh chuy~n thanh cac ion. Trong cac dung m6i huu cd khac
nhu alcol, cac acid ho~c amin, amid... hai qua trinh nay th~ hi~n ra't ro r~t.
Vi dl:t: Trong dung m6i acid acetic - la m9t dung m6i proton th6ng qua
lien ket hydro t~o ra nhieu c~p ion, nhung do hllng s68 be (8 = 6,2) nen chi co
s6 it c~p ion chuy~n thanh ion t~ do. Trong dung moi nay, cac chat hoa tan t6n
t~i chu yeu dUdid~ng c~p ion.

57
 ~~~.
~_. ~----.-.---.------
~_- -- .. ~.... .---~.~

• Thuye''tlien hflp ion Bjerrum:

Nam 1926 khi nghien cuu qua trinh solvat h6a va phan ly cua cac chat
trong dung dich, Bjerrum da neu ra thuye't lien hop ion: H'ai ion solvat hoa
dien tich trai dau khi chuyen dQng nhiet trong dung <lich. se tien .lai gAn nhau
de'n mQt khoang each d~c kung q, dudi tac dQng cua luc nut tinh di~n se tao
thanh mQt ti~u ph an dQngh9CdQcl~p chuyen dQng tl,t do. Ti~u phan dQng.hoc
dola c~p ion. D6i vdi cac cl;lat phan ly d6i xung (1-1, 2 - 2...) di~n tfch c~p ion
.b~ng khong, Vai cac chat phan ly khong d6i xung (1 - 2, 2 - 3...) dien tich cap
ion nho hen di~n tich cua cac ion ban dAu. Qua trinh tao c~p ion phu thuQc vao
di~n tich ion, nhiet dQva h~ng so' di~n moi. Co th~ tinh dUQch~ng so'lien hqp
t~o c~p ion Ka:
A + B+ -=-- AB+

(4.10)

Kd la h~ng so'phan ly clla c~p AB+. Gia tri Ka ella cac chat dUQcxac dinh
b~ng phudng phap thl,tc nghi~m (bang 4.1).

Bing 4.1: Gia trj IgK. = pKd ella m('>ts6 chat

Mg2+ Ca2+ Ba2+ Cd2+
~ n
Nitrat - 0,30 0,90 0,40
Sulfat 2,2 2,3 - 2,3
Oxalat 3,4 2,5 1,7 3,3
Malonat 2,8 3,0 2,3 3,9
Acetat 0,80 0,80 0,40 -
Ne'u nang dQchat hoa tan tang len; qua trinh lien hQpkhong chi dung l~i
b c~p ion (ion pairs) rna t~o ra ion ch~p ba (ion triples) ho~c ion ch~p b6n (ion
quadruples).
Dieu cAn luu y la thuye't lien hQp Bjerrum dl,ta vao ll,tcion tudng tac tinh
di~n d~ lUQnggia lien hQpclla cac ion trai dau. Ngoai ra con co d~ng lien hQpclla
cac ion clmg dau nhd cac tudng tac hoa h9c dQcl~p vai di~n tich clla chung.
1.3. Ph an lo~i can bAng hoa hQc
Dl,ta vao ban chat clla cae ph an ung hoa h9C trong dung dich nglidi ta
thudng chia cac can b~ng ra lam 41o~i:
- Can b~ng acid base: qua trinh cho nh~n proton,
- Can b~ng oxy hoa khtt: qua trinh cho nh~n electron,
- Can b~ng t~o phuc: qua trinh t~o phuc chat giua ion kim lo~i va ph6i ttt,

58
 - Can bang ket tua hoa tan: phan ung tao thanh chat it tan trong dung dich.
Dung d goc d9 tinh toan can bang, nguoi ta co th~ xep chung thanh 3
nhom tren co sd cho nhan cac loai ti~u phan:
Cho nhan proton:
An+nH+ ~ HnA tao ra cac cap acid base
- Cho nhan electron:
ox+ne ~ Kh tao ra c~p oxy hoa khii
- Cho nhan ti~u phan (phan tit hoac ion):
M+nL~ MLn Tao phuc chat
M+nX ~MXn"!" Tao ket tua
Cac can bang nay se cho cac hang s6 can bang tuong tmg:
Hang s6 proton hoa (hoac cQngproton) Ka:
[HilA]
K = -"'---'''---''-
a [A-n].[H+]"

HAng s60xy hoa khit K,.:

K '" [Kh]
r [oxJ.[ey

HAngs6 tao phuc J3n :

[MLn]
", '" [M].[L]"
Hang s6 tao ke't tua K,:
K "" [.MXII]
p [M].[X]"
Do MXn khong tan, hoat dQella chung duoc chap nhan bang 1. Vi vay d~
dac trung cho dQtan cua chat it tan nguoi ta dung hAng so Ks (con g<?ila tich
so tan):

K =-1 = [M].[X] " (4.11)

s Kp
DVa vao cac hAng s6 can bang nay co th~ tinh dUQchAng s6 can bAngclla
phan ung cho nh~n proton, electron ho~c ti~u phan.
Trong cac ph~n tie'p theo, chung ta gioi h~n vi~c khao sat trong dung
dich loang (d.do.h~ s6 ho~t dQf:::; 1, va tri s6 ho~t d9 bAng n6ng dQ)thea quan
ni~m truyen th6ng ve 4 lo~i can bAngda neu.

59
 --_ _--

,2. CAN BANG ,ACID - BASE

Khai niem acid va base da co tit the ky 17, nhung mai den cu6i the ky 19
moi xu~t hien thuyet acid va base ciia Arrhenius. Vao nhilng nam ~~u ~he ky
20, chtmg ta co them thuyet Bronsted - Lowry, thuye't Lewis d~ hoan thien
them cac khai niern nay. D~ nghien ciru can bang dung dich trong hoa phan
. tich thuyet acid - base cua Bronsted - Lowry duoc coi la thfch hop hon ca.

2.1. MQt so khiti ni~m

Theo thuyet Bronsted va Lowry: Acid la nhung ch~t c6 kha nang 'cho
proton, base la nhimg chat co kha nang nhan proton.
Acid ............. Base + H+
M9t acid sau khi cho mQt proton tao ra mQt base lien hop vdl no. Nguoi ta
goi do la mQt ciip acid-base lien hCJp. Ban than proton H+ khong t6n tai tl,1do,
mQt acid muon cho proton thi phai co'mQt base nhan proton d6. Base do c6th~
13. phan tti dung moi, .
Yi du:
- Voi mQt base B hoa tan trong nude:
B + H2O --- OH' + BH+
base acid base acid
- Voi mQt acid HA:
HA + H2O '__""H3O+ + A'
acid base acid base

2.1.L Sf! phan ly cua dung moi

Tfnh ch~t acid base clla mQt ch~t th~ hi~n qua phan ung acid - base voi
phan tti dung moi. Trong tntong hc;fPmQt dung moi proton HS, ta c6:
B+HS --- S'+BH+
HA+HS ---
Phan tit dung moi la luang tinh: vita c6 kha nang cho proton (tinh acid),
vita c6 kha nang nh~n proton (tinh base). Hi~n tuc;fngnay ta,o ra ph an ung tl,1
phan ly clla dung moi:
H20 + H20 __.. H30+ + OH'
HS + HS --- H2S++ S-
Day la phan ung can bAng duc;fcd~c trung bAng hAng s6tl,1 phan ly (hAng
sO' ion hoa) Ks:

60
 (4.12a)

K' = [H30+].[OH-] ~ K = [H O+].[OH-] (4. 12b)

n [H20f n 3

Nguoi ta thuong dung pKs :::- 19 K,

De'n day co th~ rut ra 3 di~m chu ye'u sau:
1. HsO+ (H2S+) 18.acid lien hop ella phan tit dung moi, 18.aeid manh nh~t
trong dung moi H20 (HS); OH' (S") la base lien hop ella dung moi, la
base manh nhat trong dung moi H20 (HS).
2. Tinh acid lien quan den ion H+ solvat hoa bdi ph an tit dung moi. D~
d~c trung tinh acid cua dung dich, ngay tit 1909 Sorensen da dg nghi
dung thang pH.
+
pH = -lga + ~ Ig[H2S ]
H

- Moi truong aeid: [H2S+]> [S"],

- Mci truong kiem: [H2S+] < [So],

- Mei truong trung tinh: [H2S+] = [So] =.!.. JK"; .

2
3. MQt ti~u phan th~ hien tinh acid base co th~ la mQt cation, mQt anion
hoac ph an tit va ti~u phan do th~ hien tinh acid (cho proton) hoac tinh
base (nhan proton) la tuy thuoc vao tuong quan cho nhan proton ella
dung moi. Vi du: acid acetic trong nude la met acid:
CHsCOOH + H20 ~ HsO+ + CHsCOO-
nhung trong hydrofluorid long, no lai Ia mot base:
CH3COOH + H2F2 HFz- + CH3COOH2+
2.1.2. H6,ng sf>'din b6,ng cua cijp acid - base lien hlJp
Ta xet acid HA trong dung moi proton HS:
HA + HS ~ H2S+ + A -
HAng so can bAng cho c~p HAl A:
k = [H2S-t].[A-] (4.13)
a [HA]
ka bi~u thi sue acid cua HA: ka cang l(jn, acid phan ly cang nhieu, thi acid
do cang m~nh.

61
 Neu base A trong dung moi HS:
A '+ HS ...,....._.. . HA:r S -
HAng 86 Call bang kb bi@uthi strc ella base A:
k = {HA].[S-]
(4.14)
b [A-]

k, cang ldn, base A cang manh.

Nhan 2 hAng s6 ta co:
k, . kb == [H2S+] . [S·] == K, (4.15a)
Voi dung dich m.toc ta co:
pk, + pkb,== pKn (4.15b)
Nhu vay, trong mQt dung moi dii cho, d6i vdi mQt c~p acid - base lien hQP,
ne'u dang acid cang manh thi dang base lien hop vdi no cang yeu va nguoc lai,
Theo (4.15a), neu biet hAng soka, ta se tfnh dUQchAng s6kb va nguoc lai.
Dua vao cac hAng so' cua ci;lp acid - base lien hop co th~ thie't l~p mQt
thang acid trong dung mdi HS. Thang nay dUQcgidi han boi hang s6 cua 2 c~p
acid· base cua dung moi:
Voi;H20: 2 c~p H30+/ H20 va H20/ OH·.
. Voi HS: 2 c~p H2S+/ HS 'va HS/ S·.
Ta chap nhan dung dich co n6ng dQ 1M tro xu6ng. Thang acid thay d6i
thee pKs 0 nhi~t dQdii cho. Vi dV:
~Nttoc: 0 + 14 (25°C)
- NH3: 0 + 27,7 (- BOaC)
- C2H50H: 0 + 19 (25°C)
- H2F2: 0 + 13,7 (OOe).
• Co nhung acid chua nhieu ci;lp.acid - base lien hQp trong ph an ti':t.Vi dV:
acid oxalic, acid phosphoric ...
H3P04 co ba c~p acid base lien hQp la:
HaPO./ H2P04'; H2P04'/ HPO/'; HP042./ PO/',
M6i c~p acid - base lien h<;1pco mQt h~ng s6 can bang tttdng ung,

2.1.0. Hdng 86 can bdng cua phan. itng acid - base

Phan :(tng acid base la mQt phan (:Lng'giua 2 c~p acid - base lien hQp. Vi
dv HAl A va BH+I B:

62
 HA + B A
Nong de?:
- Ban dAu: o o
- <) can bang: C C
Hang s6 can bang cua ph an tmg:

(4.16)

Neu ta coi phan tmg' hoan toan khi CI s dat 100 trd len thi K ~ 104• Nhu vay:

kka(HA) >
- 104 ~ Pk a(BH+) > k
- P a(HA)+
4
a(BH+)

2.2. Tinh [HsO+] va p'H ciia dung djch nU<1c

Tinh pH ella dung dich dU<;1c dua tren cac h~ng s6 can bang, phuong trinh
bao toan khoi luong va phuong trinh trung hoa dien, Trong nhieu truong hop, d~
tfnh dU<;1C
n6ng de?can bAng [H30+]cAnphai giru. me?tphuong trinh bac cao (bac 3,
bac 4 hoac cao hen). NgUdi ta sit dung phuong phap lap Newton cho bai toan nay
(xem phu luc 1). Tuy nhien co th~ sit dung each tinh gAn dung cho tirng truong
hop cu th~. Tu day, d~ cho don gian ta dung ky hieu: h = [H30+];oh = [OHl
2.2.1. pH cua dung dich. acid mqnli va base mqnh.
Cac acid manh nhu: HCI, HN03, HCI04; cac base manh nhu NaOH, KOH
thudng phan 1y gAn nhu hoan toan trong miac. Co th~ d~ dang suy ra h:::::Ca
cho cac dung dich acid m~nh va h :::::
Knl Cb cho cac dung dich base m~nh. Tuy
nhien, co trudng hqp cAn phai k~ den s1;'lphan 1y clla nuac. Ta xem xet C\l th~
tung trudng hqp:
a. pH eua dung djch acid mfJ,nh HA:
Trong dung dich nay co hai can b~ng:
HA + H20 ~ H30+ + A- (a)
(b)

Phuong trinh trung hoa di~n (c)

Do acid m~nh ph an 1yhoan toan nen [A] =CA, do do:
h = CA + ~/ ;=.h --,
ho~c I h 2 - CA' h - Kn = 0 (4.17)

Th1;'lCte co th~ si't d\lng tuy trudng h<;1p:

_ Neu CA = 10-6M, khi bo qua ~h ta co h :::::10-6 va pH = 6; oh se 1a 10-s. Sai
s6 tinh toan 1a:

63

~ -~-~~----------------------~--------
 10-8
--xlOO::: 1%
10-6
- Neu CA cang IOn; sai SO tuong dOi cang nho.
- Khi CA ~ lO·7M d,n dungphucag' trrnh (4.17).
Vi du: ne'u CA = lO,7M: thi h2 - 10.7 . h - 10.14 = O.
Giai phuongtrinh nay ta co h = 1,26. 1(1·7 ~ pH = 6,79.
b. pH cua dung dich. base manh. BOH
Trong dung dich I:!,1,iOC m~t base manh BOH hoa tan n6ng dQ CB' Ta cling
co hai can bang:
BOH ~ B" + OH-
H20 + H20 ~ HsO++ OH-
Phuong trinh bao to an di~n tfch:
[B+] + [HsO+] = [OH-]
h + CB = le,/ h
(4.18)
Day la phuong trinh t5ng quat tinh n6ng dQh cua dung dich base manh,
Tuy nhien viec su
dung tuy truc,ng hop.
- Neu CB ~ 10·6M, ta bo qua h canh CB' Nhu v~y oh =C B ~ h = ~I CB
pH = p~ + logCB
- Ne'u CB ~ lO·7M, ta 811 dung phuong trlnh (4.18).
Vi du: CB= lO·7M thi 'giai phuong trinh: h2 + 10.7 • h - 10.14 =0
ta se co h =6,28. 10.8 ~ pH = 7,21.
2.2.2. pH cua dung dich. c6 mpt c¥p acid-base lien hflp
MQt c{lp acid-base lien hop HAJ A~ hoa tan trong nUoc nhu CHaCOOHI
C.HaCOO·,NH/I NRc' 6 day d~ng acid' ho~c base eua c~p thu®g xu at phat ttt
mQt mu6iphan ly hoan toan trong nude nhu NaCHJCOO, NH4Cl. Ta hay thie't
l*p cong thuc tinh pH. cho dung dich nay vesi acid HA c6 n6ng dQ CA va mQt
mu6i phan ly hoan wan B+A n6ng dQCB'
Trong dung dich c6 3 can bAng:
H20 + HA --- A- + HaO+
H20 + H20 - HsO++ OH-
BA~ B++A-
Cs CB CB

64

-----_-----~ _-
·. -- _._ _------ .. - ---- __ --~-----
..

HAng s6 ella acid HA:

k JH,o'
a [HA
~t_. [H 0+] = k [HA]
3 a [A-]
(a)

Phuong trmh bao toan khdi IU<;1ng:

[HAl + [A-] = cA + cB (b)

Phuong trinh trung hoa dien:

[HaO+]+[B+]=[OH-] + [A-]
[HaO+]+CB =[OH-] + [A-] (c)

Tu (c) BUY ra: [A-] = CB + [HaO+]- [OH-] (d)

. Tu (b) va (d) suy ra: [HAl = CA - [HaO+]+ [OH-] (e)

Thay (d) va (e) vao (a) ta co:

h = k . CA - h + oh
a CD +h-oh (4.19)
Day la cong thuc t5ng quat tinh h ella mQt c~p acid-base lien hop trong
dung dich nude. Trong thuc hanh co th~ tinh gAn dung trong mQt s6 truong' hop:
1. Trong dung dich acid: h » oh nen:

h =ka•CA -h ~h2 +(CB +ka)h-kaCA =0

CB +h
2. Trong dung dich base: oh» h, ta co:

h = ka. CA +oh = k CA +KJh

CB -oh a CB -K n Ih
Sau khi tri~n khai, cong thuc cu6i cung la:
CBh2- (K, + kaCJ h - kaKn = 0
Trong 2 truong hop tren, giai phuong trinh b~c hai ta thu duoc gia tri
cua h.
3. Thuong g~p nhat trong thuc te', la dung dich e6 h va oh nho hen nhieu
so yoi nang dQ CA va CB nen phuong trinh (4.19) du<;1C don gian h6a:

h == kit. CA
-CB
hoac: C
pH = pka + 19 cB (4.20)
A

65

-. ---_._-----_-----
 Vi du. 1: Tinh pH CUB,dung dich acid acetic va natri acetat eung n6ng de?O,lM
Til cong thuc (4.20):

_pH == 4 75 +lg 0,1 == 475

, 0,1'

Ne'u them O,Olmol HCI vao 1 lit dung dich nay thi:
H+ + CHgCOO' _.... CHaCOOH
nen n6ng de?can bAng:
[CH3COOH] = 0,1 + 0,01 == 0,11
{CH3COO'] ::: 0,1- 0,01 = 0,09
va pH dung dich. se 13::
009
PH = 4,75 + 19-'011'
- = 4 66
,
Nhu vay: Khi them 0,01 mol HCI vao 1 lit dung djch tren, pH cua no chi
giam 0,09 don vi _pH. Neu them 0,01 mol HCI vao 1 lit nude thi pH se giam til
7 xu6ng 2 - tuc la giam 5 don vi pH. Vi v~y dung dich tren 18.dung dich d~m.
Vi du 2: 'I'inh pH dung dich han hop NHs O,lM va NH4Cl O,lM.
Til cong thuc (4.15b) ta co:
pka= 14 - pk, = 14 - 4,75 = 9,25
Til cong thirc (4.20) ta tmh duoc:

pH = 9,25 + lg 0,1 = 9,25

0,1
Ng116i ta co th§ dung cong thirc (4.19) d§ tfnh pH cua me?t ~odung dich
acid base sau:
a. Dung dich. acid ye'u.:
- Trong truong' hop nay CB =0 va h » oh nen:

h == ka' CA - h ~ h2 + kah - kaCA == 0 (4.21a)

h
- Neu CA » h thi:

h = k CA Q• --:, h = Jk"CA
h
1 1
pH = "2 pka - 2 19C A (4.21b)

66

--- - - - _- ~--------- ----------------------- --

 Vi du 1: Tinh pH ella dung dich acid salicylic 10-3M. Bie't pk, cua nola 3.
Do pk, cua acid tuong dO'ildn nen dung cong thuc (4.21a):
h2 + 10-3 h . 10-3• 10-3 0 =
Giai phuong trinh b~c 2 nay ta co: h = 6,2 . 10-4

pH = . lg h = 3,21
Vi dl;t 2: Tinh pH cua dung dich acid acetic O,lM.
1
pH == 2(4,75 -lgO,l) = 2,87
Vi di; 3: Tinh pH ella dung dich NH4CI O,lM. Biet NH3 co pk, = 4,75
1 1
pH = 2(14-4,75)- 21g0,1 = 5,13

b. Dung dick base yiu:

- Trang cong thuc (4.19), CA = 0, oh » h nen:

h = ka' oh
CB -oh
Thay oh = Kul h, xtip xep lai ta co:
CB h
2
- K, . h - kaKn = ° (4.22a)

1 1 1
pH = -(pK" + pka + IgCB) = 7 +- pka +-lgCB (4.22b)
2 2 2
Vi du: Tinh pH ella dung dich KCN O,OlM biet HCN eo pk, = 9,2.
Ion eN- Iii base lien hop ella HCN. Theo (4.22b) :

pH = 7 +~.9,2+~(-2) = 10,6
Neu dung dich KCN eo n6ng d<}O,OOOlM (10-4M) ta cAn dung cong thuc
(4.22a), vi n6ng d9 CB ~ oh nen :
10-4 • h2 • 10.14 h . 10-23,2 = 0 ~ pH = 9,5

2.2.3. pH cua dung dich. c6 nhie'u cq,p acid - base lien hfJp
Dung dich co nhieu cap acid· base co th~ Iii:

67
 - Cac. acid vo co da chuc nhu H2C03l H2S, Haf04; cac acid huu co nhu acid
oxalic, aeid malonic. acid fumaric, acid citric ...
- Cac base da chuc thudllg 18. cac muoi trung tinh eua acid da chuc nhu
Na2COS, Na3P04, •••
Cae ch6t luang tfnh nhu: rnu6i a-cid eua aeid da chuc: Na-HC03, NaH2P04
hoac cac acid amino
Day hi dung djch co nhieu can bang, viec tinh pH 'rat phuc t~p. Trong
giao trinh nay ta xem xet lnQt s6trudng hop don gwn:
a. Dung dich. cdc acid da chuc:
MQtacid hai chirc H~ hoa tan trong nu&. Trong dung dich nay co 5 can b&ng:
- H&ng s6 can b&ng cua acid I:I2A:
k = {H30 }[HA- ]+

J [H2A]
k _[lf O+}[A j 2-]

2 - [HA -]
- Phuong trinh bao toan kh6i luong:
CA == [H2A] + [HA-] + [A2.]
- Phuong trinh trung hoa di~n: [HaO+]::::[HA-] + 2[A2.] + {OH-]
- Phuong trinh tv ph an ly cua nude: [H(lO+].[OH-] ::: K,
Tu 5 phuong trinh tren voi 5 tin sO'(RA HA-, A2., HaO+' OH-) co th~ dua
ramot phucng trinh co ~n so
h bac 4. Cach giai theo phuong phap l(lp Newton
(xern ph\11\1c 1).
Trong tht;tc te, co th~ l~p cac p,hudng trinh g~n dung cho tung trlidng hQp
~
C\lt he:
Trang dung dieh acid nen co tM bi) qua ion OH·. M~t khac, neu ty sO'
k/k2 kha Ion (> 103), n6ng dQHaO+t1,lOra chu yeu do blioc ph an ly thu nh6t, co
th~ bi) qua ion A2• ben c~nh HA, cho nen:
CA == [H2A] + [HA-]
[HaO+]:::[HA-]
Thay cae gia tri nay V8.0 bi~u thuc k1, ta co:
h2
---=kJ ~h
2
+kJh-kJCA =0
CA -h
Day 18. phudng trinh (4.21a) cho trudng hQp add yeu.

68
 Neu CA» h ta lai co phuong trinh (4.21b).
Vi du: Tinh pH cua dung dich H2COs 1.10·sM.
=
Vi ty s5 k/ k2 ::: 4,45. 10.7/4,7. 10.11 0,95. 104cho nen ta dung cong thuc
(4.21a):
h2 + 4,45 . 10.7 h - 4,45 . 10.10::: 0
h = 4,18 . 10·5~ pH::: 4,38
Neu n6ng dQCA ldn, qua trinh phan ly ra HA-va A2• khong dang k~ so vdi
CA, ta chap nhan CA::;; [H2A]. Tit can b~ng k.:

[HA-} =k, ~A
(a)

va h::: [HA-] + 2[A2.] = [HA-] + 2. k2 [HA-] I h (b)

Dtta gia trj cua [HA-] vao (b) ta c6:

hS - k1CAh - 2k1k2CA = 0 (4.23)
Cac acid htru co vdi mach carbon dai d giua 2 nhom chuc acid thuong co
h~ng s6k1 va k2 gAn nhau va gia tri nho, Neu CA IOnc6 th~ dung phuong trinh
(4.23) d~ tmh gAn dung pH.
Vi du:
- Acid fumaric: k1= 9,6. 10.4 k2::: 4,1. 10.5
- Acid succinic : kl= 6,25. 10.5 k2 = 2,32. 10.6
- Acid malic: kl= 4,0. 10.4 k2 = 8,9. 10.6

b. Dung dich. cac base da chuc

Thuong g(l.pIa cac mu5i trung tinh cua acid da chuc nhu Na2COa, NaaP04 .. •
Trong nude cac mu6i nay phan ly hoan toan tli\ora cae anion. D6 la cac base da
chuc, chUng ket hqp voi proton hinh thanh cac c(l.pacid - base lien hQp.
Vi d1/-:
Na2C03 ~ 2Na+ + COa2. (a)

COa2• + H20"""""'" HCOa'+ OH' (b)

HC03' + H20 ~ H2COa + OH' (c)

HAng s6 can b~ng cho 2 phuong trinh (b) va (c):

HC03 - OH-] = Kn::: 1.10-14 = 213.10-4 ::: K'

CO;- kz 4,7.10-11' 1

[H2COJ[OH-] = Kn = 1.l0-147 = 2,25.10-8 == K~

[HCG; ] k, 4,45.1 0-
69
 Cung voi phuong trinh trung hoa di~n va phuong trinh bao toan kh6i
luqng dUQe thiet l~p nhu truong' hop acid da chirc, ta co th~.tinh dUQcnang'eli? h.
Tuy nhien, trong truong hop nay, hai hl1ng so' can bAng K'/ Kr2 ~ 104 1;1n,
nen pH do phan tmg (b),quyet dinh. Vi v~y, co th~ dung eOr1gthuc (4:22) tinh
pH cho oac dung dich base yeu.
Vi du: Tinh pH cua dung djch Na2COS @,1M.
Vi CB » oh nen ta dung cong thuc (4.22b):

pH::: 7 +!.lg4,7.10-11 +!lglO-J :::11,66

2 2
c. Dung dich. cua cdc cheit luang tinh:
o day cac chat hoa tan trong nude vira co th~ cho va nhan proton - th~
hien ea tinh acid va tmh base. Thudng g~p 2 trudng h,QP:
- Cac m,u6i acid cua acid da chirc nhu: NaHCOa, NaH2P04, KH2P04,
NaHS ...
- Cac acid amino
Ta xem xet tung trudng hop:
1. MUDi acid
Mu6i NaHA eua acid 2 chuc H2A hoa tan va phan ly hoan to an trong
nude. C6 4 can bAng trong dung dich:
NaHA ~ Na+ + HA' (a)
HA-+ HsO+ --="" H20 + H?A (b)
HA-+ H 20 ~ HaO+ + A2. (c)

H20 + H20 -==- HaOT + OH- (d)

Tu 3 phuong trinh (b), (c) va (d), c6 th~ viet nang dQh trong dung djeh la:
h::: [A2.] + [OH~J- [H2A] (e)
Thay hAng so k1 va k2 eua acid H~ vao (e) ta co:
h::: k2[HA- ]~ K" _ h[HA-)
(g)
h h kJ
Neu nang dQ Cm eua muO'iNaHA Mn, nang dQ [HA-] trong dung dich Mn
hdn nhi~u so vai [A2.] va [H2A].Ta chap nh~n [HA-] ~ Cm, phUdpg trinh (g) trO
thanh:

h::: 'k1k2Cm +klKn

(4.24a)
~ kJ +C IIl

70
_ Gia thie't [HA"] ~ Cmkhong du<;lCchap nhan khi co 1 trong 3 tinh huong' sau:
+ Ndng d~ dung dich em, rat be (dung dich loang),
+ Knl k, Ion: phan ung (b) tieu thu nhieu HA-,
+ k21on: phan tmg (c) tao nhieu A2...
- NeuCm» k, vak2Cm» Kn, phuong trinh (4.24a) se la:
(4.24b)
h::: ~klk2
+ Vi du I: Tinh pH cua dung dich NaHCOa 0,10M.
Hay xem xet di~u ki~n d~ sU:dung cong thuc tfnh:
- Hang sO'kl va Cm:kl :::4,45.10 ..7 «0,10
- Tich s6k2. Cm::: 4,7.10-11 • 0,10» 10-14
Vi v~y, tinh h theo cong thuc (4.24b):
h:::: ~4,45.1O-7.4,7.1O-11 :::4,6.10-9 -+ pll > 8,34
+ Vi dl.l2: Tinh pH cua dung dich Na2HP04 1,0.10-3M.
Hang so' phan ly k2 va ka cua HgP04 d~u co HP042-. Tri so' cua chiing la
k2::: 6,34.10-8 va kg::: 4,2.10-13
HAng s6k2« Cm-+ k2 + Cm~ Cm
Tich k3_Cm::: 4,2.10.16 < K,
Nhu vay, c~n dung cong thuc (4.24a) voi mftu s6du<;jcgian uoc:

h::: 6,34.10-8 (4,2.1 0-13 .1,0.10-3 + 10-14)

1,0.10-3

h = 8,1.10-10 -+ pH = 9,09
Ne'u dung cong thuc (4.24b) thi h::: 1,6.10-10
+' Vi dl.l3: Tinh pH cua dung dich NaHzP04 1,0.10-2M.
Acid phosphoric co kl :::7,11.10-3 va k2::: 6,34.10-8
Trong trudng h<;jpnay k1 ~ Cm
k2. Cm::::6,38.10-10 » Ku -+ co th~ gian uoc:

h:::: 6,34.10-8.7,11.10-3.1,0.10-2::: 16.10-5

7,11.10-3 + 1.10 -2 '

pH::: 4,8

71
 2. Dung dicli acid amin.:
Acid amin la nhfing c}l.a'tludng tfnh, trong phan tl':t cua chungco chuc
acid (-COOH) va chuc amin (-NH2) nen c6 kha nang coo va· nhan proton nhu
cac muoi acid. Tuy nhisn, yoi cae acid amin.ndng dg t~u ppan luang tinh luon
b~ng nang dQchat tan. Trong nude, acid amin t6n tai (j dang phan tl':t ludng cue
(zwitterion) .
Vi du: Alanin

Alanin c6 pk, = 2,3 va pk, = 9,7 theo 2 can b~ng sau:

/COOH
+ kJ
CH3-CH-COOH
I .
+ H30 ... "" CH3-CH---NH3 + + H2O (a)

NH2

CH3-CH-COOH + H20
k2 -:COO' +
H30 (b)
CH3-CH", +
I NH2
NH2

A pH
1
pH = -(Pk, + pk2)
2
Day 18.pH dAng di~n cua dung dich acid amino
Vai alanin: pH = .!..(2,3+ 9,7) = 6,0.
2
+ Neu trung hoa het chuc amin trong phan tl':t (bAng each them mgt
duong IUQngacid manh nhu HCI) theo can b~ng (a) ta c6 mgt acid yeu
CH3CH(NH3 +)COOH.
+ Neu trung hoa het chuc acid trong phan tl':t(bang' mQt base manh) theo
can bang (b) ta c6 m(>tbase yeu.

72

-------_--_._---_ _
.. .....
- Vi du 1: Dung dichalanin 0,20M ~ pH = 6,0
+ Trung hoa chuc amin bang' dung dich HCI 0,20M (trQn dgu dang th~
tich ella 2 dung dich). Nang dQacid yeu la 0,1M. Tinh h theo cong thuc
(4.21a):
h2 +Ka h - k, CA = °
h2 + 10.2,3 h - 10.2,3 .0,1 = °
h = 2. 10. 2~ pH == 1,7
+ Neu trung hoa het chuc acid bang each trQn dang th~ tich dung dich
alanin 0,20M vdi dung dich NaOH 0,20M ta c6 dung dich base yeu
O,10M vdi pk, =9,7.
Tinh pH dung dich thea cong thuc (4.22b):
1
pH = 7.+-.9,7
2
+lgO,l = 11,36.

- Vi du 2: Tinh pH cua dung dich acid aspartic 0,50M.

Biet pk, =1,9; pk, = 3,6; pk, = 9,6
r---coo:- ;..! .... f----I-;;:~~~::~~~:~
i
pk2 Hooe~' ! NH3+! ! " , : .J

;
t
Nh6m acid d macli
~:.:.:.::::~----,

!
nluinh. cua acid amin
, , :

pH
AH3+
+ Trong nude acid aspartic tan tai d dang AH/, pH cua dung dich lit:
1
pH = 2 (pk, + pk2) = 2,7

+ Neu cho them mQt duong IUQngHCI vao dung dich nude cua acid nay
ta se co m9t acid 2 chuc:
AH/ + HCI ~ AH3+Cl

73
 Bo qua pk2, ta tinh pH ella dung dich mQt acid yeu:
1
pH = 2 (pk, -lgC) = 1,1
2.2.4.pH cua dung djch hai acid
Hai acid HAl va HA2 n6ng dQtuong (tng CI va C2 trong nude. D~ tmh pH
ella dung dich c6 th~ phanra 3 truong' hop:
1. Hai acid manh:
Neu 2 acid HAl va H~ hoan toan phan ly. Tinh pH ella dung dich duoc
thuc hien nhu trttdng hop 1 acid manh c6 nang d~ C == C1 + C2.
2. Acid manh. HAJ va acid y€u HA2:
Ve nguyen tAc, acid manh HAl quyet dinh pH cua dung dich. Tuy nhien,
ne'u n6ng dQ acid manh C1 xap xi vdi Itt<jng HaO+ sinh ra ti't acid HA2 thi khi
tinh toan pH cAn xem xet de'n ca 2 acid.
- Phuong trinh bao toan khO'iluong:
Cho HAl: HAl + H20 ~ HaO+ + A1- C1 = [AI]
Cho HA2: HA2 + H20 --- HaO+ + A2-
C2 = [HAz] + [A2'] (a)
- Phuong trinh trung hoa di~n
[HaO+] = [OH-] + [A1- ] + [A2-] (b)
Bo qua [OH'] trong dung dich acid, cho nen:
h =C+ C2 - [HAzl
1

[HAz] = C1 + C2 - h (c)
va [ A2-] == h _ C1 (d)
DUa (c) va (d) vao hang sO'ka2ella acid HA2:
k _h.[A;l_ h(h-C,)
(e)
a2 - [H~] _ C. +C2-h
Sau khi sAp xe'p l~i ta c6 phudng trinh b~c 2:
h2 _ (C1 - ka2)h - (C1 + CJka2 = ° (4:25a)
Neu bo qua dU<jc8lj phan ly cua acid ~, chap nh~n HA2 ~ C2dua gia trj
l1-ayvao (e) va sAp xe'p l~i ta c6:
h2 _ Cl h - C2ka2== ° (4.25b)
Vi df:t: Tinh h clla dung djch hoa tan 2 acid: HCI n6ng dQ O,OlOM va acid
salicylic O,lOM. Bie't acid yeu c6 pka2 == 3.

74 .. ,.
 Acid salicylic trong nude n6ng <19 0,1M, pH ella dung djch tinh theo cong
thuc (4.21a) se la: .

Do h sinh ra tu acid salicylic xap xi nang dQcua HCI nen dung cong thuc
(4.25a) d~ tinh pH.
h2 _ 0,90. 10.2h -1,1 . 10.4 == 0 ~ h == 1,59.10'2.
3. Hai acid diu yiu
- Phuong trmh bao to Em khdi luong cho 2 acid:
HAl + H20 -==-""" H30+ + AI- C1 == [HAll + [AI']
HA2 + H20 -==-- H30+ + A2- C2 == (HA2J + [A2']
- Phuong trinh trung hoa di~n
(a)
Trong dung dich acid, bo qua [OH'], cho nen:
h == [AI'] + [A2'] (b)
Neu acid ye'u co th~ bo qua su phan ly nen:
C1 ::::; [HAl] va C2 ::::; [HA2] (c)

Tu 2 h&ng so can bang cua acid ta co:

k == h[A1- ] ~ [A-) = kalel _ (d)

al [HAl] I h·

k == h.[A;] ~ [A-} == ka2C2_ (e)

a2 [HA2] 2 h
Dua (e) va (d) vao (b) ta co:
h2 == kal C1 + ka2 C2
(4.26)
h == [C:C + ka2C2 J

Neu dieu kien (c) d tren khong thoa man, ta phai tinh pH theo phuong
phap phuc tap hon.
Vi du: Tinh h cua dung dich 2 acid hoa tan: acid formic 10.2 M (ka1 ==
1,77.10.4) va acid acetic 10·1M(ka2== 1,75. 10.5).
Hai acid co n6ng d9 Ibn va h&ng so k",be nen dieu ki~n (e) du~c tho a man.
Nang dQh cua dung dich du~c tinh theo cong thuc (4.26):

75
2.2.5. pH eua dung dich hai base
each tinh toan hoan toan tuong tt;l nhu trudng hop 2 acid.

2:3. Giltn d6 phan be)

Gian 0:6 phan b6 trong can bang bi~u thi st;lthay d6i cua phan 156mol cac
ti~'u phan theo pH cua dung dich. MQt acid yeu HA phan ly trong dung dich
mi<1ct6n tai dudi 2 dang HA va A. Phan so' mol F eua m6i dang la:
_ .[A- ] ~ [A - ]
r; - [HA]+[A-] -C- (a)

F.::: .[HA] ;::[HA]_

(b)
I [HA]+[A-] C
HAng so' can bang eua acid HA:

k :::h.[A-] ~ [A-} :::kJHA} (e)

a [HA] h
Dua (c) vao phuong trinh bao to an khol1u<jng:
C = [HAl + [A] = [HAJ . (1 + k/ h)

[HA} = C _ (d)
l+k/h
Thay gia trt eua [A] va [HAl tit (c) va (d) vao (a) va (b) ta c6:

F.::: ka1h _ F. ;:: 1

o 1+ka1h 1 1+ka1h
Vi du: Acid HA c6 k, = 10.5• Tinh gia tri cua Fo va Fl khi pH thay d6i tit 2
den 8, ta thu duoc:

Bang 4.2. Gia trj ham F thay d5i thea pH dung djch
h 2 3 4 5 6 7 8
F1 0,999 0,99 0,90 0,50 0,10 0,01 0,001
Fa 0,001 0,01 0,10 0,50 0,90 0,99 0,999

76
 F 1.00

0.75

0.50

0.25 pH

0.00
2 3 4 5 6 7 8

Hlnh 4.1. 51! bh~nd6i ella ham F theo pH

2.4. Can bAng acid base trong dung moi khan

Trong phan 4.2.1, chung ta da xac dinh r~ng tinh acid base cua m(>tchat
phu thuoc vao tfnh chat cua dung moi rna chat d6 hoa tan. 'I'huong dua vao 3
tinh chat cua dung moi: tfnh acid, tinh base va hang' so
di~n mei e d~ phan
loai cac dung moi khan.

2.4.1. Phiin loai dung moi

Tren co sd 3 tinh chat da neu tren, Bronsted da chia dung moi lam 8
nh6m (bang 4.3).
Bang 4.3. Phan loai dung moi theo Bronsted
Nh6m £)~c di~m Ii: Acid Base Vidy

1 LLtCJngtinh + + + NU'de,methanol

2 Cho proton + + - HCN, H2F2long, HCOOH

3 Nhan proton + . + Formamid, ethanolamin

4 Kh6ng proton + . - DMFA, DMSO, aeetonitril

5 LU'Clngtinh - + + Ethanol, eyelohexanol

6 Cho proton - + . Acid acetic, acid propionic

7 Nhan proton - - + Etylendiamin, pyridin

8 Kh6ng proton - - - Aceton, benzen, cyclohexan,

carbon tetraelorid

Nh/tn. xet:
_ 'I'ac gia phan chia dinh tfnh 3 tinh cha't cua dung moi: khi e > 30 ghi la +;
khi e < 30 ghi Ia -. Con dung moi th€ hi~n tinh acid hay tinh base ro r~t

77
- ------_-_ ---

dlic;1Cdanh dau +; khong ro r~t, ye'u danh dau -. Thuc te' tfnh acid hay
base cua dung moi con phu thuoc vao chat tan. Vi du acid acetic thucng'
Ia dung mbi cho proton d6i vdi cac chat tan trung tinh hay base ye'u.
Nhung khi hoa tan H2S04 vao acid acetic thi dung moi nay thci hien tinh
base: nhan proton.
- Do nhan xet tren, m9t dung moi c6 thci xe'p vao nh6m cho hay nhan
proton, nen m9t s6ta? gia chi phan thanh 2 nh6m chinh:
+ Nh6m t~Q lien ke't hydro: g6m 6 nh6m 1, 2, 3, 5, 6 va 7 cua Bronsted.
+ Nh6m khong proton: 2 phan nh6m:
. Khang proton phan cue: nh6m 4 c6 e cao .
. Khang proton khong' phan cue: nh6m 8 c6 s th~p.
- Ngoai ra, con nhieu kh6a phan loai cho dung moi nhu: tinh acid base
Lewis, d9 d~n dien, 8\1 lien hop ion, ... Tuy nhien cho de'n nay chua c6
IDQtphuong phap thO'ng nh~t tfnh toan dinh htc;1ngblc dQng eua dung moi
len chat tan. Do sl,i thie'u h\lt nay, mQt s6 tac gia dA xay dt;tng cac phuong
trinh tht;tc nghi~m au d\1ng cae hAng 86 v~t ly nhu chi s6 khuc x~ nn,
h~ng s6 e ho~c c!\c th.,ong so' do b~ng tht;tc nghi~m (DN: donor number,
AN: acceptor number) d~ xay dl,tng cac phuong trinh toan hQc danh gia
kha nang solvat h6a cua dung maL

2.4.2.Anh huang cua dung moi den tinh acid - base cua chdt tan
Qua trinh hoa tan v~ phan ly mQt chat trong dung mai dl1Qcphan ra lam
2 bl1C1C:
ion h6a va phan ly. Qua trinh solvat h6a thong qua lien ke't hydro (vC1i
dU]lg moi proton) ho~c tUcJngtac ion - dipol (vC1ibase Lewis).
Vi d\l chat tan la-mQt acid HA thi:
- Trong dung mai HS:
HS+HA
K; (ion h6a) Kd (phan ly)
- Trong dung moi base Lewis:
-S: + HA ....,._.,.,..
Kj (ion h6a) Kd (phan ly)
Nhl1 v~y hi~u (tng ion h6a biit ngu6n tit:
- Lien ke't hydro eua dung mai proton, ho~c
- Khii nang cho electron cua dung moi c6 Unh base (Lewis). C6 th~ n6i gQn
hem hi~u (tng nay bAt ngu6n tit Hnh acid: base cua dung maL
Hi~u (tng phan ly dO.""
hAng 86 di~n -moi quye't dinh. Hai hi~u (tng Day
khong phai luc nao cung di kem vC1inhau. Vi d\1 Nitrobenzen la dung moi c6 E

78
 - -_ ...._-----_._---------- ----

cao (£=::34,8)nhung kha nang ion h6a kern nen trong dung moi nay it cap ion
duoc tao ra va chung chuyen gAn he't sang dang ion. Nguoc lai trong dung moi
tributylphosphat (s =::6,8) nhieu cap ion dU<;1c
tao thanh, nhung chi mQt s6 it
chuyen sang dang ion t\1 do.
D~ d~c trung cho sue acid base cua mQt chat trong dung moi khan nguoi
ta dung hang' s6 phan ly toan phan (overall dissociation constant) K:
Vi du: mQt base B trong acid acetic (AcOH):
B + AcOH BH+AcO' BH+ + AcO-
~

K == [BH+].[AcO-] K;Kd (4.27)

[B] l+K;
Vi du: B la p. dimetylaminoazobenzen, mQt base manh trong AeOH c6:
K, =::0,1 va Kd = 5,0.10-6 ~ K =::4,6.10-7

3. CAN BANG T~O PHUC CHAT

Phuc chat a day dUQcgidi han a nhtmg hop chat cua mQt kim loai M vdi
cac ph6i ti'1L. D6 la cac ion boac phan ti'1c6 kha nang tao lien ket ph6i tri (lien
ket cho nhan) vdi kim loai M.
M+nL MLn
C6 nhieu each phan loai phuc chat.
D\1a vao s6 nguyen ti'1M trong phuc chat, ta ph an ra:
- Phuc don nhan: Ag(NH3)2; HgIl-; ...; MLn
- Phuc da nhan: nhieu kim lOl;lilien ket v(ji nhau va lien ket v(ji pho'i ti'1L:
MmLn'
D\1a vao pho'i ti'1L, c6 th~ ph an ra:
- Phuc thu~n nhat: llolili pho'i til L: MLn·
- Phuc han h<;1p:kim lOl;lilien ket v(ji 2 pho'i til:
M + pX + qY MXpYq
Trong th\1c te thudng g~p phuc han h<;1p,nhat la khi qua trinh t~o phuc
th\1c hi~n trong dung dich c6 n6ng dQ H+ ho~c OR' cao (phuc proton h6a, phuc
hydroxyl MORxLy ... ). Tuy nhien trong giao trinh nay tr<;mgtam nghien cUu la
can bAng phuc ddn nhan MLn.

3.1. Hltng so din bltng t~o phiic

Kim lo~i M tl;lophuc voi ph6i ti'1L:

79
 M+L x, :::[ML]I ([M] [L])
ML+L K2 ::: [ML2]1 ([L] [ML]) .

MLn_1+ L ---- Ku ;:: [MLJI ([L] [MLn_1])

Tit diiy ta cd th~ viet:
_[ML] :::K, [M] [L] :::i3i [M] [L]
[ML21 ;::-K2 [L] {ML] ;:: x, K2 [Ml ILJ2 ::: ~2 [M] [L]2
[MLnl :::Kl K2 •• • Kn[M] [L]n::: I3n [M] [L]n. (4.28)
K, la h~ng sCi bgn cua phue thit i: Ml.,
I3nla hAng sCi bgn to an phan eua phuc MLn:
[ML ] n .

Pn = [M][Lr -= K1K2···Kn = 1}x, (4.29)

Co th~ viet phuong trinh bao toan khdi lUc;1ngcho M va L:

CM ::: [MJ + [ML] + ... + [MLJ
::: [M] + 131 1M] [L] + 132 [M] [LF + '" + s, [M] [L]n
N
CM =[M]+[M]IP;[L)" (4.30)
1

CL ::: [L] + [ML] + 2 [ML2] + ... +n [MLJ

:::ILl + ~l [M] [L] + 2 ~2 [M] [L]2 ...... + n ~n [M] [L]"
N
CL = [L] + [M]~)Pi[L]' (4.31)
I

N la sO'phO'itri cue dai.

3.1.1. Phiin sf) mol eua phite thit i: Fi

Do la phan 86 mol eua phuc MLj so vdi n6ng dQkim loai CM'
F. = [ML;] = PI[M][Lr
I CM [M]+[M]IPJ[L],

Pi[Lr
F; = ----''-:-:N'';;__::_-
(4.32)
1+ L:P;[L),
I

Tr] 86 F, cho kim loai t~ do M:

80
 (4.33)

Nhu vay: Fo + F, + ... + F; =1

D6i vdi phuc don nhan gia tr] cua F, chi phu thuoc vao nang dQcan bang'
cua L va cac h~ng s6t;;to phuc K, khong phu thuec vao nang dQ CM va [M].
Tu phuong trinh (4.32) cung cho th~y neu X8.C dinh ducc [L] se tinh duoc
F, va d~ dang suy ra nang dQcan bang cua cac cau tu phuc MLj• Trong thuc te'
nghien cuu can bang' phuc thudng ng1.idita cho nang dQph6i tu IOn hon nhieu
nang dQ .kim loai (CL» CM)d~ thoa man di~u kien [L] ~ CL• Tu day d~ dang
tfnh Fj• Ne'u di~u kien d6 khong thoa man cac phuong trinh (4.32), (4.33) se la
phuong trinh bac cao vdi [L]. C~n dung phuong phap l~p d~ tinh Fj•
vt ao.
Ion kim lo;;ti M3+ (nang dQ lO·3M) t;;tOphuc voi ion Br' (dung dich KBr
0,10M). Tfnh nang dQcan b~ng va ty l~ % m6i cau tu bie't Igj31= 1,2; Igj32= 1,8;
Igj33= 2,5.
VI CL» CM (~ 100 l~n) nen ta dung phudng trinh (4.32) va (4.33):
3
1+ "L,B;[L]i =1+101•2.10-1 +101•8.10-2 +102•5.10-3 =3,54
1

F3 ::= [MBrJ == 102•5.10-3 ~ 0,09

CM 3,54

F ::= [M3+] ::= _1_::;:: 028

o CM 354
'
'
Tu Fj d~ dang tfnh ra nang dQM va ty l~ % cac phuc:
[MBr] = 0,45 x 10. = 0,45.10.3 M ~
3 45% phuc MBr
[MBrzl = 0,18 x 10. = 0,18. 10. M ~
3 3 18% phuc MBr2
[MBrs] = 0,09 x 10.3 = 0,09. 10.3 M ~ 9% phuc MBrs
[M] = 0,28 X 10.3 ::= 0,28. 10.3 M ~ 28% a d;;tng ion kim lo;;titl,t do.

81
 --------_- -_-----.~--.--~-........- ---------,

8.1.2: Phsin. sir molcho acid ~baee da chuc

B~ th§p.g nhat caeh tinh F cho can b{tllg<pfiu<!va can bli:ng acid • base ta
dung h~ng so proton hoa hoac cong proton:
HA
[HA) I
K=· =:-
[lr}[A-} k
a
Vdi acidda chirc, ·vi d\l tIaP04 ta se co:
1 [HPO;-}
K '" -- "" --"----'--,--
I k3 [H+ } [Pg;- }

I [H2PO;}
K ""--=----~~--
2 k2 [H+ } [HPO;}

H{tng s6 proton h6a K, 'trong can bang' acid - base giong.nhu h~ng s6 tao
phuc trong can b~ng phuc. PiBu luu y la h~ng s6 proton h6a K, la nghich dao
v:e gia tr] va ngucc ve chi 86 voi }altng so phan ly k., Trong truong hop HaP04
ta c6:
1 ...
K = - I '" - :;: 0,2.)8.10 13
I k3 4,2.10-13

I 1 8
K '" -- =: s- :;:.0,158.10-
2 k2 6,34.10-

K"'1.= 1=0141.103
3 kl 7,11.1O-j )

Dungphuong trinh (4.32) va (4.33) d~ aang tinh ham Fi cho cac cau tit d
pH xac dinh,
Vi du: Tinh ham Fj eua H;jP04 trong dung dieh nuoc d pH 2 va pH 8.
f31 ::: K} :::0,238. 1013; f32 ::: K} K2 ::: O,:ne. 1020; Pa ::: K} K2 K3 ::: 0,530. 1022•
- d pH 2: h::: 10.2
Gia tri ella mAu 86 d (4.32) la:
D2 ::: 1 + 0,238. 1013• 10-2+ 0,376. 1020 • 10.4 + 0,530. 1022• 10.6
= 0,906. 10 16

82
 . Phan 85 mol ciia cac cftu trt la:

F. == [PO;-] = _1_ == 111.10-16

o CD'
a 2

F; =[HPO;-] == 0,238.1013.10-2 == 2,63.10-4

to
. Co D2

F, == [H2PO;] ::::0,376.1020.10-4 == 0,415

~ Co D2

F == [H3P04] :::: 0,530.1022.10-6 == 0 585

3 CD'
a 2

a pH 2, HaP04 t6n tai 2 dang ehinh: phan tl1 HaP04 58,5%, va ion HzP04'
41,5%.
- a pH 8:
Gia trt cua m§.u s6 a (4.32) la:
D8 == 1 + 0,238. 1013• 10.8+ 0,376. 1020 • 10.16 + 0,530. 1022• 10.24
== 1 + 0,238. 105+ 0,376. 104 + 0,53 . 10-2 == 0,2756. 105

r: ::::0,2756.10
1 5 :::: 3,62.10-5 F == 0,238.105 == 0 864
I 0,2756.105 '

F == 0,376.104 == 0136 F = 0,53.10-2 =192.10-7

2 0,2756.1 05 ' 3 0,2756.105 '

a pH 8, c6 2 dang chinh: ion HPO/- 86,4% va H2P04' 13,6%.

- Tinh ham F, b cac pH khac nhau (tit 1+14) c6 th~ ve duoc ham phan b6
cua H3P04·

3.2. HAng s6 din bang bi€u kie'n

Hang sO'can bang bi~u kien l3' n - con goi la hdng s6' din bdng ai€u ki~n .
danh gia can bang' tao phuc trong dieu kien co tac dt}ng cua cac phan ling phu
thong qua ham a. Cac phan ling phu c6 th~ la:
Ion kim loai M a
pH xac dinh eo th~ tl,\Ophlic vdi ion OH': M(OH),
M(OH)2'"
Ph6i tli L co th~ cQng proton b pH thap tl,\o ra HL, H2L, ..., HnL.
Ngoai cae ion thudng co trong dung dich nUde nhu H+, OH' con co th~ co
di.e ti~u phan khae t~o phlie voi M ben e~nh phan ling chinh t~o ra MLn·

83
 M + nL

-oir If +H+ II
M(OH)m HnL

Trong phan tich h6a h9C dinh luqng nguoi ta quan tam chfnh la phan
ung tao ra MLn c6 toan hrong khong, tj 1~ hop thuc la 'bao nhieu, Vi vay
Schwarzenbach (1957) dli de :xu~t h~ng s6 can b~ng bi~u kien W. A. Ringbom
(1963) dli phat tri~n va van dung cho phue don nhan.

(4.34)

[M'] va. [L11a. n6ng <;\9can 'b~ng bi~u kie'n cua ion M va ph5i ti:t L. D6 la t~ng
n6ng dQ eua M va L khoog tham gia vao phin ung ~o phirc dia't chfnh MLn.
Vi du: M tao phl1c phu vdi ph6i til: X:
M+pX
ph6i ttt L tao phuc vdi H+hay mQt cation nao d6:

L + qY ~ LYq hLlg s6b~n Yi

C6 th~ vie't ty 1~[M']/ [M] va [L']I [L] nhu sau:
[M'] = [M]+[MX]+[.MX'2]+···+[MXpJ
[M] [M~
== 1 + ()l [Xl + ()2 [X]2 + ... + 5p [X]P

- aM(X) =1+ fb',r[X]j

1

Tit day: [M'] == [M] ctM(X) (4.35)

[L'] [L] + [LY] +[LY2] + '" + [LYq]

-=-------------'--
[L] [L]
== 1+ Y1 [Y} + 12 [Y]2 + .., + Yp [Y}p

= aLM =1+ IyzlY)Z

I

Tit day: [L'] == [L] ctL(Y) (4.36)

84
 Thay (4.35) va (4.36) vao (4.34) ta c6 :

P: ::: PII n (4.37)

a M(X)' a LeY)
Tri so UM(X) va uL(Y)cang len We la qua trinh tao phuc phu cang manh thi
phan trng tao phuc chinh MLn cang ye'u, th~ hien d hAng so f31l'cang nho. D~
phan (tng toan luong e6 th~ dung cho dinh lucng thi hAng so bi~u kien - theo
mQt so tac gia - phai dat toi thi~u 108•
Trong truong hop c6 nhieu phan (tng tao phuc nhu tren, phuong trinh
(4.32) c6 thay d6i: e~n b6 sung vao m~u so cac so hang cua phan (tng phu ben
canh phan ung tao phuc chinh MLn :
(4.38)
F.:::
I N
PiLt
p q
1+ LPJLt + L~lX}j + LrJfT
I I

Vi du: Nguoi ta them luong' nho Ni (NOg)2vao dung dich KSCN 0,10M c6
p'H 7. Ray tinh ty l~ % Niken d dang t~ do, dang phuc vdi phci ttl SCN' va OR'
bie't hAng so b~n ella:
Ni(SCN)a: Igf31::: 1,2 ; Igf32::: 1,6; 19j33 ::: 1,8.
Ni(OR): Igf31::: 4,6.
Ty l~ do thay d6i the' nao khi di~u ehinh pR ella dung dich v~ 9?
Giai: Theo (4.38) ta co :
- Ph an (tng t/ilOph(tc ehinh 13.:
3
1+ LPi[L]i::: 1 + 101,2.10-1+ 101,6.10-2 + 101,8.10-3
I

::: 1 + 1,58 + 0,40 + 0,06 ::: 3,04

- Phan (tng t/ilOphue ph\]. clla Ni2+ voi OR' ([OR] ::: 10.7):
01 [ORO] ::: 104,6.10.7::: 0,004.
M~u so clla phudng trinh (4.38) la:
1 + 1,58 + 0,40 + 0,06 + 0,004
::: 3,044
Ph(tc ehinh phuc ph\].
1
v~y: Fo :::-- ::: 0,328
3,044

85
 F= 1,58 =0519 F ::: 0,40 = 0 131
I 3,044 ' 2 3,044 7

F == 0,06 = 0 020 ·0004

F/'Ii(OH) == 3~.()44=-0';001
3 3,044 ' ,
F, + F2 + Fa :::0,671
- o pH 7: ion N:i 2+ n!m d dang phue vdi SeNoIa 67,1%, 32,8% n~m d dang
tu do viI.Q,l% Q dang pbuc hydroxo.
- o pH 9 ([OH"}= 10- 5):

MAu sO'ciia phuong trlnh (4.38) la:

1 + 101,2. 10-1+101,6 • 10-2 + 101,8; 10-3 + 104,6.10-6
:::1 + 2,04 + 0,40 :::3,44
1
F =-=0,29
o 3,44

2,04
Pi +F2 +F3 =--=0,59
3,44
0,40
FNi(OH) = 344 :::0,12
,
Khi tang pH tit 7 len 9 phuc Ni2+ v{jihydroxyl tang tit 0,1% len 12% trong
khid6 ph an (tng tao phtrc chfnh giam tit 67,1% xu6ng con 59%.

3.S. Phtrc cua'kim Ioal viti EDTA

Trong sO.eac ph6i ttl huu co tao phuc vong cang (chelates) vOiion kim loai
thi nh6m complexon dU<;Ic ung dung r~t rQng rai trong phan tich h6a hQCdinh
IU<;Ing.Nh6m complexon Ie.nhllng d~n xu~t cua acid aminopolyarboxylic.
Vi du:
Acid nitrilotriacetic con goi 18.complexon I, acid ethylendiamintetraacetic
(EDTA) con g9i Ia complexon II:

/CH2COOH
:N,CH2COOH vie't tAt Ie. HaY.
CH2COOH

86
 EDTA kh6 tan trong nuoc. D~ tang de}tan, nguoi ta thudng dung mu6i
dinatri Na2H2Y. Mu6i nay thudng dUQcgQi18.complexon III hay trilon B.
Nh6m complexon tao dUQcphuc bgn vdi hang chuc kim loai. Cae phuc
nay dap (tng cac yeu eftu cua phan (tng dung trong ph an tfch th~ tfch, ChQnen
nguoi ta Btl dung rat phd bien phudng phap chuan dQ tao phuc bAng
complexon.
Phuc complexonat tao thanh theo ph an ang sau :
M'" + Y" ..... My<n-4) (4.39)
Bang 4.4 ghi h~ng so·ben cua phuc eomplexonat kim loai (d~ don gian chi
cho thanh phan phuc, khong ghi di~n tfch).
Bang 4.4. Hang s6 ben cua complexonat kim toal
Kimlo,i Phli'c Ig~ Kimlo,i Phli'c Ig(3

Ag+ AgY 7,32 Mn2• MnY 13,79

A13' AIY 16,13 Ni2' NiY 18,62

Ba2+ BaY 7,76 Pb2+ PbY 18,04

Bi3• BiY 28,2 Sn2• SnY 22,1

Ca2+ CaY 10,7 sr2+ SrY 8,63

Cd2+ CdY 16.46 Th4+ ThY 23,20

Ce3~ CeY 15,98 Ti3+ TiY 21,3

Co2+ CoY 16,31 Ti02+ TiOY 17,3

Co3+ CoY 36,0 V2+ VY 12,7

Cu2+ CuY 18,8 V3+ VY 25,9

Fa2+ FeY 14,33 V02+ VOY 18,77

Fa3+
Hg2•
FeY
. 25,1
21,8
V02+
Zn2•
V02Y
ZnY
18,1
16,50
HgY
Mg2' MgY 8,70 zr ZrY 29,9

Trong thuc te e6 nhieu yeu to' tac dQng den phan irng tao phuc
complexonat. Vi vay, c~n tinh hAng sO'bi~u kien J3'.

3.3.1. Gian d6 phan bo' cua EDTA

EDTA c6 4 chuc acid, voi.4 hflng sO'ph an ly:
pkl == 2,07 pk2 = 2,75
pk3 == 6,24 pk4 = 10,34
D~ tinh ham sO'Fj, ta ehuy~n sang d~ng hAng so' proton h6a.
Ig(31 = 10,34 ; 19132 = 16,58; 19l3a = 19,33 ; 19134 = 21,4.
87

_ ..-_ ----------------------
 Theo phuong trinh
\
(4.32), m§.u sf) D se la:
4
D = 1+ 1:J3; h'
I
= 1 + 1010•34 h + 1016•58 h~ + 1019•33 h3 + 1021•4 h4
Tinh phan s6 mol tung cau til d clrc pH khac nhau:
pH =- 4 ~ h = 10-4
D4 = 1 + 1010•34• 10-4+ 1016•58 • 1{)-8 + 1019,33. 10-12 of:- 1021.4 10-16
= 1 + 106•34 + 108,58 + 107•33 + 105•4
= 1 + 2,19.10 + 6 3,8 .108 + 2,14.107 + 2,51 . 105 RI-4,038.108
Tu day:

r, :::
_1_ = 0,248.10- 8 F.I = 2,19.10 6 ::: 0542.10-2
D4 D4 '
F2 = 3,8.108 ::: 0,941 F; = 2,14.107 =0,53.10-1
D4 D4
F4 = 2,51.105 ::: 0,621.10-3
D4
B~ng each tinh tuong tl,t, c6 th~ thu dl1Qcgia trj F, d cac pH khac nhau va
xay dung dUQcgian d6 ph an bO'cac cau til thea pH trong dung dich.

12 !4
pH

Hinh 4.2. Giim do phan b6 cua EDTA theo pH

3.8.2. Hdng 86' t90 phitc bie'u hien f3'
Dua vao phuong trinh (4.37), ta c6 th~ vie't h~ng sO'I3'cho phuc cua kim
loai M vdi EDTA:

88
 13' = _ _..:_J3 __ (4.40)
cx,M(OH),UY(H)

<X.Y(H)
Iii.ham tao phuc phu ella EDTA vdi proton. Do chinh la mau s6 ella
phuong trinh (4.32) :
aY(H)== 1+ ~1 h + (32h2 + ~3 h3 + ~4 h"
Bang 4.5 trtnh bay gia tri lg aY(H)phu thuoc vao pH ciia dung dich.

Bang 4.5. 51! phu thul?c cua Ig cx.Y(H) vao pH dung dich
pH Ig aY(H) pH Ig av(H) pH Ig aY(H) pH Ig aY(H)
1 17,10 4 8,6 7 3,32 10 0,46
2 13.43 5 6,46 8 2,27 11 0,07
3 10,60 6 4,66 9 1,28 12 0,00

aM(OH)
la ham tao phuc cua kim loai M vdi ion OH' trong dung dich, danh
gia tac dQng cua pH de'n s\i hinh thanh phuc complexonat,
= 1 + 81 oh + 82 oh2 + 83 oh" + ...
aM(OH)
Dua vao tri so 8j va pH cua dung dich co th~ tinh dUQctr] so aM(OH)cua
cac kim loai.
Tac d{lng cua pH de'n s\i tao thanh phuc comp1exonat theo 2 huang nguoc
nhau. Khi pH cua dung dich tang thi:
- Gia tri aY(H)giam, tang kha nang tao phuc cua EDTA: tri so 13' tang.
- Gia tr] <X.M(OH)
tang theo pH, kha nang tao phuc phu voi hydroxyl cang
m~nh, lam giam h~ng can b~ng 13'. so
Ve ly thuye't ton t~i m{lt pH d d6 ham 13' (4.40) C\{C d~i (tuc 1a t6ng
+ 19aL(H)el.jc ti~u). Trong thl.jc te', van de con phuc t~p hdn. Ban than
19aM(oH)
phuc complexonat MY (phudng trinh 4.39) con t~o phite ph\]. khac la phuc h611
hQp MYH ho~c MY(OH) co m~t trong dung dich nuoe.
Vi dl:l:
Tinh 19 13' cua phuc complexonat Fe2+ va Fe3+ d pH 4. Cho bie't cac h~ng
so sau:
voi Fe2+: 19f3(Fe y2.) == 14,3; Ig(3(Fe(OH» = 4,5
vai Fe3+: 19(3(FeY) == 25,1; Ig(3(Fe(OH» = 11; Igl3(Fe(OHh) =21,7
Gidi:
pH =4~ h == 10.4 va oh == 10.10
vai Fe3+: t~o 2 phuc Fe(OH) va Fe(OH)2 nen:

89
 aFe(OH) :::: 1 + lOll . 10.10 + 1021,7• 10.20::::16
Theo bang (4.5) d pH 4:
19ay(m::: 8,6 nen 19 W (FeY'):::: 25,1-1g16 _ 8,6:::: 15,3

aFe(OH) :::: 1+ 1004,5 • 10.10~ 1.

Theo bang (4.5) d pH '4:
19aY(H)::: 8,6 nen 19 J3' (Fey2'):::: 14,3 _·lgl...;. 8;6::: 5,7
Nhu v~y d pH:::: 4 thi !1lgJ3'::::Ig P' (FeY) . Ig 13'(FeYz")::::9,6
co th~ chuan dQ ph an bi~t mu6i 'Fe(III) va Fe(lI) b~ng EDTA: Fe(III) tao
phuc truce, tiep theo Ia Fe(II). Vt.n de con lai Ia tim chi th] phat hien di@m
tuong duong.

3.3.3.Phssc complexonat trong d~m amon

Cac kim loai lri~m th6: Ca2+, Sr2+, Ba2+, Mg2+va Ni2+, Zn2+ thl.1dng·dl.1Qc
a
chuan d9 bAng EDTA moi trl.1dng d~m amon. Trong trl.1dng hop nay. ta dung
phuong trinh (4.40) d~ tfnh rr. o
day co them phuc phu eua: kim loai vdi NHs·
Vi du: Tfnh IgP' cua phuc Ni - EDTA trong dieu kien sau:
- Dung h~ d~m NHs - NH4CI co ty l~ d6ng mol O,lM.
- N6ng dQion kim loai nho hen nhieu n6ng dQd~m.
- HAng sO'ben phuc Ni - EDTA: Igl3(NiY) ::::18,6.
- HAng sO'ben phtrc Ni - NH3 la:
Ig131:::2,75 Ig132:::4,95 Ig133:::6,64
Ig134:::7,79 Ig135::::8,50 Ig136:::8,49.
- HAng sO'ben cua phuc Ni - OH Ia Igl3 (NiOH) ::::4,6.
- HAng sO'phan ly cua NH"OH Ia p~ ::::4,65.
Giai: Dung djch d~m d6ng mol O,lM c6pH IS. 14 - 4,65::: 9,35
nen h ::::4,47. 10.10va oh :::0,224 . 10'"
Tinh 19 P' (NiY) theo cong thuc (4.40):
Igl3'(NiY)::: Igl3(NiY) . IgaN'(NH),OH) .1gaY(H) (a)
Hay tinh gill trj ti:lng ~6 h$ilng:
19J3(NiY) ::: 18,6 (b)

aN1(NH,):::: 1 + 131[NHsl + 132[NHaJ2 + 133[NHsP + 13.[NHa]4

+ 135[NH3]5+ 136 [NHs]6

90
 Thay 6 tr] s613 va {NHal ~ 0,1 ta co:
aNi(NH )=-
3 1,49.10+4 -+ 19 aNi(NH3):: 4,17.

ct.Ni(OH) :::: 1 + 104,6 • 0,224 . 10.4 :: 1,90.

Ham phuc phu ella Ni2+ vdi NHa va OH· la:

(c)
IgaNi(NH3.oH) == 19aNi(NH3) :: 4,17

Theo each tinh nhu da trinh bay d di~m 3.3.2. (trang 91) ta co:
(d)
ay(m ~ 12,2 -+ 19 ct.Y(H) :: 1,09
Thay (b), (c) va (d) vao (a) ta co:
19l3' ::: 18,6 - 4,17 - 1,09 =- 13,34

3.3.4.Phdn itng tqo phitc toan IU(jng va hdng srif3'

o day c~n xac dinh s\1 lien quan giua phan tmg tao complexonat toan
luong (phan ung 4.39) vdi h~ng s6bi~u kie'n 13'.
Phan img tao phuc d6ng mol: dung dich EDTA va dung dich M'" d~u co
nong dQbang nhau 1a C. Sau khi tao phuc M - EDTA, ta co:
[My(n.4)] + [M'"] =- C (a)
[My(n.4)] + [Y'] :: C (b)
[Y'] la tf)ng n6ng dQEDTA khong tham gia vao phuc MY.
Tit (a) va (b) ta co: [M'"] :: [Y'] (c)

Chap nh~n sai so

0,1%, tuc Ia co 99,9% kim lo~i da t~o phuc v(ji EDTA,
tue la:

[M"+]=[Y']= 0,1.C::IO-3C (d)

100
Thay (c) va (d) vao bi€u thuc ella h&ng so 13':
[Myn-4 J 106 C
P':::: [MnT J [Yj ::::(10-3 C/ --C
Thong thudng khi chu€ln dQC ~ 10.2 vi v~y:

P '::::10-
106
2
:::: 108

Voi mQt kim Io~i da cho, taose tim dUQcmQt gia tri aY(H) - tu do Ia pH
dung dich . d~ h~ng s613' ;?: 108• Hinh 4.3 cho ta pH t6i thi~u d~ phan ung t~o

91
 phuc toan htQng (sai so ;5; 0,1%) cua mQt so ion kim loai trong digu kien khong
c6 canh tranh tao phuc.
Tit hinh 4.3 ta thay:
- Kim loai ki~m th6 e~n moi trlidng kigm nhe (pH 9 + lQ)
- Phffn IOn cac ion kim loai cffn mei trudng acid nhe (pH 3 4- 6)
so
- MQt it ion kim loainhu Fe3+, 1n3+ co th~ tao phuc vdi EDTA ngay d mdi
trudng acid manh,

.,
~ .... ".. ~... -

>-

"
l<
24

22

20
i:
~ 18

16 '

14 .

12

JO

0 4 6 8 10 12 14
pH

Hinh 4.3. pH t6i thi~u cho phim (tng tao ph(tc toan IllQng cua m¢t 56 ion kim lo~i vdi EDTA.

4. CAN BANG OXY HOA KHtr

4.1. Djnh nghia
. 4.1.1. Cq,p oxy hoa khit
Chat oxy hoa la chat c6 kha nang nhan electron; chat khu nguec lai co
kha nang cho electron.

92
 MQt chat oxy hoa sau khi nhan electron se trd thanh chat khir. Chat oxy
hoa va chat khil tao thanh c~p oxy hoa khu lien hop.
+ Kh} (4.41a)

Khz n2 e ~ OX2 (4.41b)

o day ta co 2 c~p oxy hoa khu lien hop: ox/ kh, va oxzl khj,
Vi du:
+ ne Dang khu
Dang oxy hoa
2H+ + 2e -- H2
Fe3+ + Ie -- Fe2+
Mn04- + 5e + 8H+ -- .....--- Mn2+ + 4 H2O
Fe(CN)63. + e -- Fe(CN)64•
AgCl-l.-+ e --
-- Ag-l.-+ cr
Ban than electron khong t6n tai tl;i do trong dung dich, cho nen mQt chat
chi th€ hien tinh oxy hoa (hoac khu) khi co m~t cua chat khir (hoac chat oxy
hoa) cho (hoac nhan) electron ciia no.

4.1.2. Phiin. itng oxy h6a khit: do la phan (Lng cho nhan electron giua chat
khu va chat oxy hoa.
OXl +
OX2 +
n} e
n2e
--
---
--
---
KhI
Kh2 x
x n2
nl
n2 Ox} +
Vi du:
n, Khz --
____....
n, Kh, + n, OX2 (4.42)

Khi nhung mQt thanh kim loai Zn? vao dung dich d6ng sulfat se xay ra
phan (tng oxy hoa khli sau:
+

2e
d day Zno dB.cho Cu2+ 2e: kim lo~i Zno dB.khu Cu2+ ho~e ion Cu2+ dB.oxy
hoa Zno, Phan ung xay ra trong dung dich mioe. Tuy nhien co th€ thl;ic hi~n
ph an (tng nay tro~g mQt binh chua 2 di~n cl;icgiua chung co n1ang ngan:
- 0 catod xay ra phan (tng khit:
n2 Ox} + n2 n} e . --=--
- d anod xay ra phan (tng oxy hoa:

-~.. -.-~-----------------
 06 'lll nz electron chuyen tit anod sang catod. Phan ung di~n hoa co can
bAng nhu phan ung oxy hoa khi't:

4.2. The oxy lroa khit

M(jt ch~t cang' d~ cho electron thi tinh khit cang rnanh, va dang lien hop
ella n6 cOtinh oxy hoa cang ye'u. NgUQclai, m~t chat cang d~ nhan electron thi
tfnh oxy 1;6a ciui~ rnanh, va dang lien hop ella no c6 tinh khi't cang ye'u. D~e
difun nay tddugt1;i nhu d c~p acid - base:
Ox + ne Kh (4.43)
base + nH+ - acid
Co th~ viet hAng 56 can bAng ella mQt c~p oxy hoa khi1:

K := aKh (4.44)
r
<;« "

o day at)Ia hoat dQcua electron. Tit day:

pe = - 1gae = -11gK r + -11g-.

aox
(4.45)
n n aKh
Tr] 56 pe cang ldn, hoat dQelectron cang giam, tinh oxy hoa cang rnanh.
'I'hang' pe diroc dung d~ danh gia sue oxy h6a khi1, tUdng tl;t thang pH d~ danh
gia sue acid base clla h~.
. D~ so sanh suc oxy h6a lthi1 ngl10i t'a thuong dung the oxy hoa khi1. The
nay du<;sexae dinh theo phudng trinh Nernst:

E:= Eo + RT In aox (4.46)

nF akh
Trong d6:
E : the' oxy hoa khi1 ella c~p oxl kh (von)
R : hAng 86 khi (8,331 Jun),
F : so' Faraday (96 500 0 ),
T : nhi~t d~ tuy~t dOi (oK),
aox va aKh: ho~t d~ cua dlilng oxy h6a va dQ.ngkhu. cua h~ lien hQp,
Eo : the' oxy h6a khit ehu~n (d6 la gia tri eua E khi aox = aKh)
n :. so electron trong ban phan ung.
Neu dua cac tr! s6vao phudng tririh, ehuy~n Iogarit t~ nhien sang Iogarit
th~p phan thi phudng trinh Nernst d 25°C c6 dQ.ng:

94
 - ~- -
-----~---~ --- ~

E -- E o+--g-
0,0591 ao.• (4.47)
n akll
Tit cac phuong trinh (4.44) -;. (4.47) co th~ rut ra:
E:::::0,059 pe.
Eo :::::0,059 peo (trj s6 peo :::::19~ In).
Nhu v~y danh gia suc oxy hoa khu ella h~ lien hop thong qua the' E hoac
tri s6 pe co gia tri nhu nhau. Tit E co th~ chuyen sang pe va nguoc Iai .
• Khi tinh toan the' oxy hoa khu d.n luu Y lllQt s6 di~m sau day:
_ Trong trudng hop dung dich loang, nguoi ta thuong chap nhan f ~1, cho
nen thay hoat dQ bang' n6ng dQ can bclng trong phuong trinh Nernst d~
tinh the E.
_ Trong ph an ung, neu dang oxy hoa hoac dang khi't la chat rim khong hoa
tan VaGdung dich thi hoat dQcua no coi nhu bfing don vi.
Zn2++ 2e ~

0,0591 [Z 2+]
E == E O.Znh I Z"O + -2- g n

* Ban phan img co su tham gia hoac tao thanh cac khi thoat ra khoi
dung dich thi n6ng de?dU<;le
thay b~ng ap suat rieng phl1n clla chat do.
2H++2e ~ H2t

E -= E + 0,059 19 [H+ ]
~2H·IHl ,
_,
P Hz

* Trong cae ban ph an ung phttc t~p co nhi~u cau tit tham gia, el1n dua
chung VaGtrong phuong trinh Nernst.
a Ox + m H+ + ne ~ b Kh + P H20

E:::: E
O.oxlkh
+ 0,0591
n g
[ox]"[H+
[khr
r
Nuoc la dung llloi, coi la h~ng s6 khong dl..tavao trong phuong trinh.
• Sau day 13.mQt vai vi d\1 minh hqa cach tinh the di~n c\ie va cac dlililU<;lng
trong phuong trinh Nernst.
Vi d¥ 1: Tinh the oxy hoa khi't clla ban ph an ttng
Cd2+ + 2e ~ Cd°-l,. Eo::::: -0,403 V
khi n6ng de?clla Cd2+ 13.0,0100 M

95

-.~~----~-----------------
 E = Eo + O'~~~.lg{Cd2+]
E = ~0,403 + O~0591g0,OlOO= -O,462V
2·
Vi rj.l;l 2: Tfhh the cua di~n cue platin khi nhung di~n cue nay vao dung
dich,KBr 0,0100M bao hoa Brom:
Br2 (I) + 2e ~ 2Br- Eo:: 1,065 V
Dung djch hao hoa hoi Brem n@nchffp nhan hoat dQb~ng don vi.

E = 1065+ 0,0591
, 2 g [Br-
1
r '
= 1183V

. Vi du. 3: MQt sci day bac dUQcnhung vao trong dung dich AgNOs. The
di~n cue do dUQCIa 0,682 V. Tinh n6ng dQcua Ag" trong dung dich biet
Ag" + e ;".__ AgO Eo = 0,800 V
E :: Eo + 0,059 19 [Ag"]
Thay so van ta c6 0,680 = '0,800 + 0,0591g[Ag+]
[Ag+] :: 1,00.10-2 MIL

4.2.1. Do the' oxy h6a khi't E

Cho den hay chua c6 phuong phap xac dinh gia tri tuy~t doi the E cua
IDQtcap Ox/Kh lien hop, rna chi co th~ xac dinh st;i chenh l~ch the thong qua
mach di~n h6a. Vi du mach galvanic sau:

[:·:.·:.:"~:~:~
..~~:~·~M)·:"A~ci"b~~"~~~:::.~:":~~·":.::'
:::::::::.·:.~~:,:::~.~:·~P":·"i~~~)"··I·"·~~:·:=:~:.:::::::] ..:]
Anod Catod

..., .
e

"Ib Yonke

Hinh 4.4. Sa do m¢t mach galvanic

.
Khi dong 1 qua mach (tit catod -? anod) do dUQchi~u ~E gitla the catod
(Ee) va the anod (EJ: .
.6.E == E c - E a (4.48)
 --~----- ------

Phan ung di~n hoa t6ng cQng la:

Hz + 2 AgCI ~ 2Ag(r)+ 2 H+ + 2 Cl
_ Ngudi ta chon the' cua c~p oxy hoa khu 2H+/ H21am chuan va chap nhan
=
E 0, (J dieu kien ap suat rieng phan khi hydro PHI = 1 atm va hoat dQ

aH+ = 1:
E == Eo +0,0591g[H+f == O(V)
PHI

Voi chuan nhiet dQng nay, nguoi ta do E (tuc la do .1.Ecua mach di~n
hoa) ella cac cap ox! kh lien hop khac,
_ Nhimg c~p oxlkh eo the mang dau "+" chi rlng the' ella c~p nay Ion hen the'
ella c~p 2H+/H2• Trong phan tmg, khi H2 se khi:Ldang oxy hoa ella c~p do.
Vi du: C~p Fe3+/ Fe2+ eo Eo = 0,77V eho nen:
2Fe3+ + H2 ~ 2Fe2+ + 2H+
_ Nhtmg e~p oxlkh eo the' mang dau -.» thi dang khi:Lella cap nay se phan
Ung voi ion H+.
Vi du: C~p Zn2+/ Zno eo Eo 0,76 V nen: =-
2H++ Zn ~ Zn2+ + Hz t
vi~cdo the' bang' thuc nghiern khong phai hie nao cung thuc hi~n dU\1c.
Vi v~y, nglidi ta con d-.;tavao phudng phap tinh toan nhi~t dQng hQc d~ xac
dinh Eo·
Trong th\fe te', do tinh 6n dinh va an to~m nglidi ta dung 210liti di~n c\fc so
sanh d~ do the' ox/kh thay cho di~n C\fchydro chu~n.
_ Di~n eve blitc clorid bao hoa:
Ag I AgCI, KCl bao hoa
AgCl (r~n) + e ~ AgO + CI-
1
E == Eo + O.0591g--
. [Cr]
co E == 0,199 V (j 25°C.
- Di~n e\fc calomel bao hoa :
Hg I Hg Cl 2 2, KCl bao hoa
Hg2C12 + 2e 2HgO + 2Cl"

E =E + O,0591g 1 eo E == 0,2444 V d 25°C.

o 2 [Cr]2

97
4.2.2. Thang the< oxy hoa khit tieu chudn
Bimg 4,.6. Than-g th~ oxy h6a khCfrtieu chuan
._
IH ox + ne . Kh C(lpoxIKh Eo(V)
F2+2e·~ 2F- F2/2F' 2,87
CQ3++ e ~ 2Co~+ C03+/ C02+ 1,82
H202 + ZH+ + 2e ~ ·2H2O ;H20i' H2O 1,77
2CIOH + 2H+ + 2e ~ C12 + H2O 2CIOH1C12 1,59
Mn04- +>8H+ + 5e Mn2+ + 4H2O Mn04-/ Mn2+ 1,51
CI2 + 2e ,~ 2Cl' C12/2CI' 1,36
Cr20i' + 14H+ + 6e ~ 2Ct3+ + 7H2O Cr2072./ 2Cr3+ 1,33

ctl
'0
O2 + 4H+ + 4e
Br2 + 2e ~
--
......,..".-

2&'
2H2O Ol.H2O
Bri 2Br'
1,23
..c:: 1,07
.>.
x Fe3+ + e ~ Fe2+ Fe3+/ Fe2+ 0,77
·0
:g- O2 + 2H+ +2e ~ H202 O2/ H202 0,68
O)
c
'g Cu++e ~ Cu? Cu+/ Cuo 0,52
o Cu2+ +e Cu+ Cu2+/ ce- 0,17
84062. + 2e~ 282032• 84062./ 282032. 0,08
2H++2e ~ H2 2H+/ H2 0
Pb2+ + 2e Pho Ph2+/ Pho -0,13
Nill+ + 2e ~ Ni? Ni2+/ Nio -0,25
Fe2+ + 2e ~ Feo Fez+/ Feo -0,44
2C02 + 2H+ + 2e ~ H2C204 2C02/ H2C204 -0,49
Zn2+ + 2e
H2 +2e ~
--_,.. Zn?

2H'
. Zn2+/ Zn?
H2/ 2H-
-0,76
·2,25
Mg2+ + 2e Mgo Mg2+/ Mgo ·2,34
Na++e ~ Nao I
Na+/ Nao ·2,71

Dua vao the' chuan Eo, ngudi ta thie't l~p thang the oxlkh trong dung m8i
la nude, thl1dng d pH ;::0 (bang 4.6). Tit thang nay c6 th~ rut ra:
- Ghat .oxyhoa manh nhat co the' cao nhat, con chat khu manh nhat co the'
thap nhat.
- Nhilng chat nam d giita thang co th~ Ia chat oxy hoa trong h~ nay va chat
khli trong h~ khac.
Vi dl:l: C~p i2/ 21' co Eo = O,54V
98
 Dang I' co th~ phan ung vci dang oxy hoa cua cap co the cao hen 0,54V
=
nhu: Br2 (Br/ 2Br' co Eo 1,07 V) hoac Fe3+. Nguoc lai, 12 co th~ oxy hoa dang
khn cua cap co the nho hen 0,54V.
Thang the oxlkh bi giOi han bdi the 2 e~p oxlkh cua nuOc:2H+,!fI2 va O:!H20.

(4.49)

(4.50)

Dung vg m~t nhiet d~ng hoc: nhfing eh(t khn co the'thffp hon the' cua c~p
2H+/ H2 (the mang dau ".") cAn khl:i H20 d~ tao ra c~p khac b~n vimg. M~t
khac, nhfing chat oxy hoa co the' cao hon the cua c~p Oi H20 (IOnhen 1,23V)
can oxy hoa nuoc d~ tao ra c~p khac b~n vfing. Nhfing c~p oxlKh co the'tit 0-;-
1,23V bgn viing trong nude (Hinh 4.5).
E
V ung gidi phong
oxy
1.23
+1

Vung6ndinh
o nhi¢t dqng

VLtng gidi phong H2

-1
o 4 8 12 pH

Hinh 4.5. SI,I'thay d6i Eo' theo pH ella 2 cap 2WI Hz va O2/ H20

4.3. Cac yeu t6 anh hudng . The bi~u kien

Trong dung dich, d~ng oxy hoa va d~ng khl:i co th~ tham gia vao cac
phan (tng khae nhau nhu: phan (tng acid-base, phlm (tng t~o phuc, ph an \:tng
ket tua. Trong nhung di~u ki~n C\1 th~ ngt:idi ta dung d~i lUQngthe oxy hoa
khit bi~u kien d~ d~c trung cha cUdng dQ cua c~p va xet chieu phan (tng.

99
4.3.1..Ank huong eua. pH dung djch
Khi ion H+ tharn gia vao qua trinh (lXY hoa }<hi1 thi the oxy hoa ,kh-ilphu
thuQc vao'pH cua dung dieh. Cac gia tr] the' OXY hoa kb.i1 chuan Eo ghi trong'
esc tai 1i~u la the
ch~n glJCJcx!l>cdinh khi hoat dQ cua ion H+~.bii.ng1, pH =0.
Tu gia tri Eo nay co th~,tinh dU{jethe' chU-An(J cae pH khac nhau. Dola the oxy
h6a·khi't chuan 'bi~u }den Eo',
Vi dlf J: Doi voi him phlm un.g;
Cr..2() 72- + 6e + ViH+ '. 2Cr8+ + 7H20

E == Eo.,"1
C Ol-IC)'
7 r
+
0059
-'-lg
6 rr
Ier2[07 IH+
2-

. Cr 3+
neu [Cr20l1 = [Crt] :::1 thi
-Eo' ::: Eo + (0~0$9/ 6 )lgfH+jl4
E?0 :::: Eo""'O,14pH.
Nhu vay, khi tang pH the' Eo' giam, tinh oxy hoa cua c~p Cr20l se giam
va nguoc Iai,
. Vi dTf: 2: Tinh ~~€0:1 ho~ khit cua c~p A~043·tAsQ3S.trong moi trudng
NaHC03 co pH ::::8 blet the chuan Eo = + 0,57 V (0 pH :::0).
Voi c~p nay ta c6 :
AsO/' + 2H+ + 2e '"'I( .... As033. + H20
(j pH:::: 0, As043. phan ung dUQcvoi 1-:
AsO 43· + 2I- + 2H+"""'- As033• + 1,2+ H20
The' cua.c!ilp AsOtt ASOS3.pht;1 thuQc vao pH:

E==E
o
-1- 0,059(1~fH+]2 +1 490]-
2 l:n g. ASO:-
J
-1' E 0' -- E 0 +-2-
. 0,059} [H + 12
g J

~ ,0059 .
v pH ::::8 thi Eo = 0;57 ....~(-8.2) =.+O,l1V
2
. Nhu v~y khi pH cang ~ngthl the"chuftu bi~ukien.cEmg giam; ngrua la kha
nang khit cila d~ng AS033 .. cat\g tmg. Chinh vi v~y, (J moi trUdng pH ::: 8 ion
As0a 3· c6 th~ khit duQC iod, phan ting e&chi~u ngliQc If,livdi phin ting a pH ::::0:

100
 AS033. + 12 + H20 == AsO/' + 2r + 2H+
C&nluu y r~ng trong nhi~u phan ung khong co sl,i tham gia true tiep ella
ion H+ hoac OH- nen chung khong dUQcdua vao phuong trinh Nernst. Nhung
dang oxy hoa va (hoac) dang khil cua c~p co th~ la cac base yeu va (hoac) acid
yeu, nen n6ng d9 can b~ng cua chiing trong dung dich lai phu thuec vao pH.
Chinh vi vf!.ythe ella c~p lai thay d6i theo pH cua dung dich .
Vi du. 3: Tinh the oxy hoa khii cua dung dich Na28 n6ng d9 CT:
Trong dung dich 82- la chat khii, vdi ban phan img:
SO + 2e ~ 82• Eo == 0,500
thi E == Eo + (0,0591 2) 19 (11 [82.])
Trong dung dich S2-1~i co ph an ung voi H+
82'+H+ ~ H8-
H8-+ H+ ~ H28
Neu trong moi truong' cang nhieu HI-thi n6ng d9 ion 82• cang it, kha nang
khii cua ion 82- cang giam. Co th~ viet gia tri ham F0 cho ion 82.:
1 [82-]
Fo= =--
1+ Klh + KJKzh2 Cr

Cho nen: [82.] == Fo. CT.dua tri sO' nay vao phudng trinh Nernst:

Eo + 0,059 10- 1
E :::::
2 b Cr.Fo
E::::: E _ 0,0591gF. + 0,0591g_1
o 2 0 2 Cr

E'o
4.8.2.rinh huang eua SI! tq,o phitc
Cae dE,lngoxy hoa va dlilng khil clla c~p co th~ t~o phuc v(ji m9t phoi til X
nao do trong dung dich. Ket qua la nang d9 cua cac dE,lngnay giam, dua den
the oxy hoa khil thay d6i.
Ta khao sat trudng hQp tang quat cho m9t e~p oxy hoa khu:
Mm+ + ne ~ M(m-n)+

Mox+ne ~ Mkh
Gia sii dE,lngoxy hoa Mm+ t~o phuc v(ji phffi tit X co m~t trong dung dich .

101
 M+X MX
_ [MX]
K, - [M][X]

[MX2J
K2 = [XXMX]

voi

D~ don gian, khong ghi di~n.tfeh cua ph9'i ttt va eua ion trung tam.
Phan so mol Fo cho ion kim loai tt;t do:
[A1J I
Fo = C1'.M = 1+ Pt[X]+ P2[xf + ... + pAx]"

Thay cac gia tri vao phuong trinh Nernst

E = Eo + 0,059 19[M oJ
n [MkhJ
E = Eo+ 0,059 19Cr. M .Fo
n [MkhJ
E -- E 0+ 0,059
n
1g F0 + 0,059 19··CT. M
1- n [Mkh]
E'o: the'oxy hod khit chudn bilu kiln
Neu phuc cang ben va n&ng d§ phci ttt cang Ion thi gift tri Fa cang be, E'a
cang nho so v6i Eo. Dieu d6 e6 nghla 1a dang Max co tfnh oxy hoa cang yeu, con
dang Mkh e6 tinh khit cang manh.
Vi du: Tinh the oiia e~p Fe3+/ Fe2+ trong hai trttong hop:
a. Khi ty s6 (Fe3+JI [Fe2+] = 103

b. Khi them mgt luong' NaF vao dung dich tren d~ nang d§ [F-] =10-2M.
=
Cho biet: Eo.Fe'+IFeh O,771V;

hAng s6ben cua phuc FeF31a: 1~~1= 5,2; 19 f32 = 9,2 ; 19f33 = 12,0.

102
Giai.~
a. Khi chua them NaF thi :
E = 0,771 + 0,059lg 103 = 0,947 V
b. Khi them NaF d~ co [F-] :::10-2Mthi:
Thay [L] ::::[F-] ::::10-2 trong phuong trinh (4.35) ta co:
aFe"(r)-::: 1 + 105,2.10.2 + 109•2.10.4+ 1012.10.6::: 1,16 .106

nen: E ::: 0,771 + 0,059lg103 + 0,059 Igl,16. 106::: 0,589 V

Nhu vay do eo m~t cua F- trong dung dich, phuc FeF 3 tao thanh lam the'
oxy hoa khi':lcua h~ giam tit 0,947 V xuO'ngeon 0,589 V. Kha nang oxy hoa cua
Fe3+ do v~y bi giam di, con kha nang khi':lcua Fe2+ thi nguoc lai, du<;1etang len.
Neu trudng hop pho].til X tao phuc voi ea hai dang Molt va Mkh, tuy theo dQ
ben cua die phuc tao thanh ma the oxy hoa khi':lciia e~p se tang len hoac giam di.

4.8.3. Anh huang cua sf! too th.anh. ktt tua

Tuong tu nhu truong hop tao phuc, dang oxy hoa Mox hoac dang khit Mkh
tao thanh hop chfft it tan vdi mQt ehfft Y nao do. K€t qua la n6ng dQ eua Mox
ho~e Mkh giam, keo thee slt thay d6i the di~n cv.eeua e~p .
Gia au dQ.ngMkh tQ.oke't tua voi Y:
Mkh + mY ~ MkhYm..!,
v~i h&ng 86 T ::: [Mkh][y]m. Til day ta eo:
T
[MkhJ:::: [YJffi
E :::::
E + 0,059 1 [M oJ
0, Mox/Mkh n g [M khJ

E :::::
E ~ 0,059 1 _2_ 0,059 1 [M 1
0, Mox/Mkh n g [yJ ffi + n g ox_!

E'o: the' oxy hoa khu chudn bilu kiln

Nhu v~y neu d~ng khu eua e~p t~o hqp chat it tan thl khi ke't tua c6 T
cang nhc, n6ng dQ thu6e thu Y cang Ion thi the oxy h6a khu cang tang. Neu
ke't tua xay ra voi dQ.ngoxy h6a MOl( thl d~ dang suy ra the' oxy hoa eua c~p se
giam di, tinh khi':leua h~ tang len.
Vi d¥: Tinh the ehutln bi~u kien eua c~p 'Cu2+/ Cu+ khi them ion r tliJ,O
ket
tua CuI vdi T = 10-12• Biet EO,cu2+lcu'= 0,17, n6ng dQ [r]::: 1 MIL
. 103
 Hai ban phan tmg:
Cu+2,+ e ~ Cut
cu++r ~ CuI~
Cl.lI~
Phan (tng oxy hoa khir: khi khong co ke't tua CuI thi the ()xy hoa khd eua
h~ 1a:

Khi co I' ket tua tao thanh va [Cut] [1] = 10-12~ [Cut] = 10-12
nen: E'o = Eo - 0,059 19 (10-12/1) = 0,86 V
8\1 eo m~lt cua I" tao ket tua CuI lam cho kha nang oxy hoa eua Cu2+ tang
len nhieu: The Eo tit 0, 17V tang len 0,82V.
4.3.4. Ke't luq,n
The oxy hoa khd cua h~ chiu anh hUdng eua nhieu ye'u to' nhu: pH cua
dung dich, ph an ung tao phtrc, phan ung tao ket tua ... Tat cil nhttng yeu to' do
true tiep hoac gian tiep Him thay d6i nang dQcua dang oxy hoa va (hoac) dang
khd thuQc h~ lien hop d~n den thay d6i the ox/kh. Danh gia nhfmg tac dQng
nay thong qua tri so' th~ bi~u kien E'o giup ta xem xet chieu phan ang va mue
dQhoan toan eua phan ang oxy hoa khd.
4.4. Hing se; can bAng cua ph an ling oxy h6a khit
Gia sd ta co ph an (tng oxy hoa khti:
a OX1 + b Khz .~ a Kh1 + b OX2 (4 ..51)
. HAng 86 can bAng eua phan ang la:

K = [kh1f[ox2 t (4.52)
[oxl]Q[kh2t
voi 2 ban phan ung sau:
a Ox! + ne ~ a Khl
b OX2 + ne~ b Kh2
The can bAng cho ea hai c~p:

E = E + 0,0591 [OXIJ
I 0,1 n g [khl r
E =E + 0,0591 [ox2f
2 0,2 n g [kh2f

104
 Khi phan tmg dat toi can bang thi El = E2 cho nen:

E + 0,059 I [ox, ]" =:: E + 0,059 1 [OX2 j

0,1 n g [khJa 0,2 n g [kh2 f
E
0,1
_E
0,2
:::0,059 1 [khl Y [OX2
n g [OXI ]'1 [k1l2
rf
Bi~u thuc sau Ig chmh IS.h~ng s6 K (4.52) nen:

19K ::: n(E0,1 -E )

0,2 (4.53)
0,059
Nhu v~y khi hieu s6 ~Eo =:: EO•1 - EO,2 cang ldn thi h~ng s6 can bang' K
cang Ion, phan ung di~n ra cang hoan toano Ta c6 th~ tinh duoc gia tri ~Eo tOl
thi~u d6 phan tmg x~y ra toan hiQng (voi sai s60,1%).
Vi du: Tinh 6.Eo cftn thiet d~ phan img' xay ra to an luong' vdi h~ c6 n =:: 1
(cho nhan le).

K :::[k/~] [OX2 ]
[oxl][kh2]

K . =:: 1000.1000 = 106

nun 1.1

19K=--=6
ss, ~ ~Eo= 0,354 V
0,059
Neu s6 electron cho nhan IS.hai trd len thi hieu di~n the' ~Eo con nho hem
(bang 4.7).
Bang 4.7. Hi~u ~Eo c~n thi~t d~ phim (tng xay ra toan ilfQng
n
AEo = EO•1 - EO•2 (V)
cho c~p ox,, kh1 cho c~p oxi kh2
1 1 0,354
1 2 0,2655

2 2 0,177

2 3 0,1475

Tit cong thuc 4.53 ta thay h~ng s6 can bAng cua phan ung oxy h6a khu
kh6ng ph\! thuQc vilo n6ng dq cae chat rna chi ph\! thuQc vao the' oxy hoa khit
chugn Eo - Rai c~p c6 Eo cang khac nhau phan ung cang toan lu:qng.

105
....
4.5. D~c di~m cua pban (tng oxy boa kbi:i
Trong phan ung acid-base c6 qua trinh cho nhan proton, tao ra c~p acid-
base lien hop: base, + H ----.....acid. MQt each tuang t1;t, dang oxy hoa nh~
electron bien thanh dang khit, tao ra c~p oxy n6a khl) lien hQP. Tuy vay hai
ph an ung nay c6 nhfmg di~m khac nhau:
a
- Trude het, nhu dij trinh bay tren, phan ung' oxy hoa. khit tuc IS. qua
trinh cho, nhan electron co th~ thuc hien trong cac dung dich rieng reo
Con qua trinh chuyen proton tit acid sang base chi dlli(ifC thuc hi~n 'true
tiep trong mQt dung dich, proton khong th~ chuy~n tit chat cho sang chat
nhan thong qua mgt day dAn nhu electron trong phan (tng oxy hoa khit.
- Th(t hai, sl,t khac nhau v~ toe dg ph an (tng. Phan (tUg acid- base thuong
xay ra nhanh, thuang 18. t(tc thai. Ph an ung' oxy hea thttdng cham. Cac
phuong phap chudn dQ dl,ta vao phan Ung nay thuang doi hoi tang nhi~t
dQ, them xuc tac ho~c cho thua thu6c thi1 t6i chudn dQ ngtt<;jc.Ly do la
ph an {tng oxy hoa khit xay ra qua nhi~u ~ai do~n. Qua trinh chuy~n
electron 18. mQt trong chu6i cac giai do~n (phS. va lien ket, proton hoa, sfip
xep ls;licac phan ti1...)
- Th(t ba, hi~u the chudn cua hai c~p lien p.<;jpchi cho ta biet kha nang
phan (tng, con thl,tc te phan 'ling co xay ra hay khong con ph1,1thugc vao
nhieu dieu ki~n khac. Vi d1,1,a nhi~t dg thttdng c~p 2H+/ H2 khong phan
(tng voi voi c~p O2 + 4H+, m~c d~u tri so ~E cua chung de'n 1,23 V. Trang
khi d6, a nhi~t dQ thttdng oxy d~ oxy hoa ion Fe2+, tuy hi~u cua hai the'
chudn O2 + 4H+/ 2H20 va Fe3+/ Fe2+ chi la 0,46 V.
- Cuoi cung, sl,tkhac nhau lien .quan de'h dung moi ntt&. Phan (tng acid-
base c6 sl,t tham gia cua nuoc. Ban than nttoc n6i rieng va phan ti1 dung
moi n6i chung 18. san phAm cua PhB,D {tug acid- base, c6 th~ eM ho~c
nh~n proton. Trong phan (tng OXY hoa khi1, ne'u phan tit nuoc tham gia
V8.0 phan (tng:
2H20 + 2e ~ 20H- + H2
2H20 ~ O2 + 4H+ + 4e
se giai ph6ng ra khi H2 va O2 thoat ra khoi dung djch. Cho nen trong cac
ph an (tng nay ng1iai ta tim cach tranh qua trinh OXY h6a ho~c khit nttoc.

cAu H61 vA sAt T~P

4.1. Phan bi~t ho~t d~ va h~ s6.ho~t dQ.
4.2. Phdn bi~t hAng so' cdn bAn·gnhi~t dQng hQc K va hAng so can b&ng
n6ng dQ Kc. .

106
4.3. Cap ion AB+ va phan tit chat tan AB co gi khac nhau khong?
4.4. Giai thich thuye't lien hcp Bjerrum. Tac dQng cua dung moi len qua
trinh lien hep ion.
4.5. Giai thich s\l tuong d6ng trong bi~u thuc hang s6 can bang cua phan
ung acid· base, oxy hoa khli, tao phuc va ke't tua.
4.6. MQt dung dich nude co HN02 0,120M va NaCI 0,050M hoa tan. Hay
dung hoat dQ tfnh toan pH cua dung dich nay, bie't hang s6 K cua
HN02 la 5.10'4. .
4.7. MQt eha't AB hoa tan trong nude co h&~g so1iE~nhop K, la 105• Hay
tinh ty 1~% co mattrong nude d dang khong phan ly ung v6i 3 n6ng
dQ 10-1M, 1o-3M va 10-6M (bi) qua h~ so hoat dQf).
4.8. MQt chat XY ph an ly trong nude dudi dang hydrat hoa X+va Y. 0
n6ng dQ 12mM, ty l~ dang phan ly la 19%. Hay tinh (bi) qua h~ s6 f):
- HAng s6 phan ly K, cua XY.
_0 n6ng dQnao se co ffi9t nuad dliing phan tit XY.
_0 n6ng dQ 1M d~ng phan tu chie'm bao nhieu %.
4.9. Hoa tan KCI trong acetonitril va trong acid acetic khan n6ng d9
O,lOM. HAng s6lien hqp ion IgKa tttdng ung 1a 1,2 va 6,9. Tinh ty l~
% c~p ion trong dung moL Giai thich ke't qua thu dttqc.

Can b~ng acid base R

4.10. Tinh pH cua dung dich cac chat co n6ng dQ0,060M:

a. Hydrosulfid c. Natri sulfid
b. Acid malonic d. Ethylendiamin
4.11. Tinh pH eua dung dich cac chat co n6ng d9 O,040M:
a. Natri hydrosulfid
b. Natri hydrooxalat
c. Natri sulfid
d. Ethylendiamin hydroclorid (NH2C2H4NHaCI)
4.12. Tinh pH cua dung dich co hai cha't hoa tan:
a. HCI 0,010M va acid picric 0,020M
h. HCI O,OlOMva acid benzoic 0,020M
c. NaOH 0,010M va Na2COS 0,10M
d. NaOH O,OlOMva NH;3 O,10M.

107
 801

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fl ~~11Uqotp .sunp .8uO.IllVm 90 Uit[d ny!l :>lPoqo '.!J !.Il ~!.8 t[uJl A~H "SF"
'g'O'[ ::: &l'(d 6'8 ::: Cll'(d (;'(; ::: ll'(d

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Hd t{uJ.1 '&1""
 ep chanh qua, 150g saccharose va m:lOc khoang c6 CO2, Tinh pH
cua nude chanh, biet:
- Nude ep chanh qua c6 n6ng dQacid citric O,120M;
- CO2 hoa tan trong nude khoang 251l1M;
- Hang s6 cua acid citric: pk, :::3,1; pk2 = 5,9; pk, :::6,4.
va cua H2COa: pK\ ::::2,2; pK'2 = 10,3.
*4.20. Mau c6 pH ~ 7,4. Hai thanh phan ehinh 5n dinh pH ciia mau la ion
HCOs" va CO2, Nguoi ta do pH va CO2 hoa tan trong mau cua 3
benh nhan:

Benh nhan A B C
pfl mau 7,35 7,20 7,52
CO2, MaD (mM) 1,40 1,20 1,30
Tinh nong dQCO2 toan phan (nam trong ea dang phan tu va dang ion)
va n6ng dQ HC03•• Biet hang s6 phan ly cua R2C03 d 37°C la pk, :::
6,10; pk2::: 10,1.
c6 pH = 2,73.
*4.21. Dung dich acid HNOz nong dQ 1~OO.lO"2M
a. Tinh hang s6 phan ly K, eua HN02•
b. Neu clin dung dich cua acid nay co pH::: 3 thi n6ng dQcua no se
la bao nhieu?
c. Clin bao nhieu ml dung dieh NaOH 0,010M d~ trung hoa 100 ml
dung dich HN02 pH ::::3.
Can biing t~o phitc
4.22. Viet phuong trinh h6a hQc va hang so din b&ng tung nae eua:
Ni(SCNh, Cd(NH;j)4'
4.23. Hoa tan 1,62 g KCN vao nu6e thanh 550,0 rol. Hay tinh:
a. Nong dQmol ena KCN.
b. DQ ehu~n cua dung dieh nay theo ion Ag+ (phan -ang t~o thanh
Ag(CN)z): mg Ag+!ml.
c. DQchu:1n theo CU20: mg Cu20! ml (tlll-oCu(CNh)·

Cho biet MKcN = 65; MAg= 108; M cup ::::143.

4.24. Mqt dung dieh EDTA c6 dQchu:1n 1,08 mg CaO! ml. Hay tinh n6ng
dQeua dung dieh nay thanh:
a. Nong dQ mol.

109

- __ ----_----~--------------
 on
:(01:H o~oq
.HO '+H w~ql uyo n,~u) n'BS 8U1) u~qd qUPl 8uP1\qd o~o 8u~q u~O °88°"
1,.lQll u9Q AXO ~uvq u110
'6'11 = e~.81 <:;'6= 1:~.81
<;'9 = t~.81 :on,qd OBl,9s .8u~q E 90 G.tI9.!1on,qd :8'~ = (NOS8.!1)9.8T
:.8~.I l,~!q+g(NOS)9.!1o1,lqdu~ nvw l,W w~I yP ..!l TOWn~!t{U osq AVO
qoW .8unp O~A w~ql tryO 'W 9'g-01QP .8u9u m nyp lyq oJ).qd 'Btp <;?P
n~oo op oonp +$1q UVt{U ~ql 90 ~ql OBl +1:(NOS)9.!1oJ).qd 'WOI'O ~I
NOS)! gp .8u9u ~A Wg.01 ~1 +f:9.tIgp .8u9u oonu qoW .8unp 19W .8u0.IJ. ·~8°".
'9 ~A V '<:;'1= U ~A WIO'O = 0 :u~P{ n~rp p. %66 :n?1qlWl oJ).qd qu~ql
OBl yp n~1qu osq ~I ny!ql t9l u~ 5Js .8u~H .u~ oJ).qd OBlf}S .8u~q 1I}A
+Il']W ....-- ']U + +W
:.8uJ).u~qd u\lo oJ).ql dpq ~I ~l 09ql '] onqd OBl P.l 1,CJqdw~ql
'Bl Wn.8u '0 gp .8u9u U'Bl uQq +W !BOIwPY u0190 oQ1\UqO!P .8unp 19W '18 0" •

.+1:(NOS)a.tIoJ).qd'B\lo~ ,9s .8~q qtIJJ.

·W".0I'09'9 = [+e9.!{1~I oPnp op op ttl +e9.!{u01 gp .8u9N 'A\lU qoW.8unp
100 001 O~A xosa 1000 01'0 w~t{.L 'WOl'O +e9.!{wnw qoW .8unp 19W °OS°Ji'.
'WOlO'O vJ.a~ 1I}AWOOT 1:(GON)'Bgt9nW '0

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'WI0'0 9P .8u9u .8uQ-ovJ.a~ !QA1:(BON)ug !,CJnw''B
;u¥I u9J:l ulwn.8u !qJ{ ·zX'Bg VA .,.x '...c:'Bg:P.l n,o o~o gp .8u9u qUJJ. °6~0"
'LE = 99.81 l.~!q WOT'O 9(NO)9'!{'')I 'q
'OZ = ll~.8t l,~N WOI'O 6(NO).8YC:)l''B
::>J).qd.8:U0.llop ttl .NO u01 'B'9-0.8u~q u~o gp .8u9u qUJJ. °8~0"
'n '0 6 'q L ''B
:Hd & p. vJ..a~ 1I}A+1:.ISo1)qd 'B'9-0,~ .8{qUJJ.. °L~°Ji'
'OT '0 8 'q 9 ''B
:Hd & p. V.La~ WA +lluW o1,lqd 'Bl,.10,g U_~!J{ny1Et,9s .8u~q qUJJ. °9~'"
'%&'0 VI
A~u wnw 'B\lo np wy gp l,~N qO!P .8unp 'Bl,.10tow: gp .8u9u qUJJ. 'qO!P
.8unp :iJI 000'1 qu~t{l (01:H<:;'X<:Hll'BN)III uoxaldwoo .8 &98'& U'Bl 'BQH ·S~·"
'L '691 ::: (o'a.:/ Jf :Ov = 03WW :99 = OllOW:(;6<;= vJ.QS'W ;l~!q oql)

'100 loza.!{ uynqo gO '0

'lUI IO.8W .800 u~nqo gO 'q
 a. Fe2+ + U022+ ~ Fes+ + U4+
b. Cr20/- + 1" ---7 Ia' + Crs+
C. H202 + Ce4+ ---7 O2 + Ce3+
d. 103' + I' ~ I 2, (rAn)
4.34. Chi ro chflt OXY hoa va chat khii b phia trai cua m6i phuong trinh
phan img b 4.33. Viet phuong trinh can bAng cho m6i ban phan tmg.
4.35. Tinh hang s6 can bAng K cho m6i phan ung b 4.33.
4.36. Viet ban phan ung eua cap oxy hoa khii va bi~u thuc cua the E.
Tfnh gia tr] ciia E so vClidi~n cue hydro chuan (SHE) va di~n cue
calomel bao hoa (SCE):
a. C03+ (0,10M)! C02+ (O,OlM); Eo = 1,82 V.
b. Mn04' (0,50M)! Mn2+ (ImM) b pH = 0; Eo = 1,51 V.
e. H + (pH = 7)! H2 (p = 10. bar);
4 Eo == 0
d. Hg/ Hg2C12, [Cn == O,IM; Eo == 0,280V.
e. CH3COOH (0,10M)1 C2H50H (0,020M); Eo = 0,040 V.
4.37. Can bAng cac phuong trinh phan (tng sau (viet cac ban phan (tng d~
xac dinh h~ s6 cho cac chat): .
a. KMn04 + CSHS02 + H2804 ~ MnS04 + CsH402 + K2S04 + H20
b. CUC204 + KIOs + HCI + KI ~ CuI + CO2 + KCI + H20
c. HIOa + FeI2 + HCI ~ FeCl3 + ICI + H20
d. CuSCN + KI03 + HCI ~ CUS04 + KCI + HCN +ICI + H20
4.38. Tra the Eo, du bao chieu va can bang' cua cac phan ung sau:
a. H2C204 + KMn04
h. O2 + KBr
c. Br2 + O2
d. 12 + 82°32.
Tfnh hAng s6 can b~ng K (neu co) cho phan ung.
4.39. Ngttdi ta cho khi Clo S\lC qua 3 binh n6i tiep nhau, m6i binh d~g 1
chat: NaF, KBr va NaI. Viet phan iing va tinh hfulg so can bfug ciia
phan ungdo.
4.40. Co th~ oxy hoa Br' va I' b~ng ion Cu2+, cho biet Eo cua:
Bri Br' 1,06; 121l' 0,54;
Cu2+1 Cu 0,34; Cu+/ Cu 0,52;
Tich so tan: CuBr 10·9;OuI 10.12•
Til1h hAng so can bAng K.
111
 ----~----'--~~--- ...

ChUdng 5

CAN SANG HOA TAN KETTUA

1. D'_' CUdNG

Trong chudng 4 (fa nghien cuu 3 loai can bAng:acid-base, tao phtrc va oxy
h6a khtt di~n ra trong mQt pha: dung dich nude. D6 18.cac can bAng d6ng th~
cua cac phan ung h6a hoc. o chuang 5 nay se khao sat can bAng di th~: can
bAnggifta 2 pha:
- Cali bAngIOng-khf: mQtchat kht hoa tan trong pha long.
- Can bAnglong- rain: mQtchdt rAn it tan trong pha long tao nen can bAng
gifts,2 pha.
- Can bAnglong- long: hai ch6t long khong hoa tan vao nhau, d d6 c6 ch6t
tan cAnbAng gifLa 2 pha.
Hoa tan 18.mQtdQngtac cAnthi6t trong phan tich. Ngtiai ta thuang danh
gia dQtan mQtchat nhu sau:
- Hoa tan tit p,lM trd len: ch6t d~ tan.
- Hoa tan dttoi 10-6 M: ch6t it tan.
MQt s6 can bAng phuc V\l tr1;LC ti6p cho Xd If mlu nhu: chi6t long-long,
chi6t pha rin, can b~ng qua mang, se dtt~ trlp.h bay C\l th~ lJ h6a phall tich II.
d day khao. sat chu y6u v~ dQtan cua cae ch6t trong nttoc, ti6p d6 xac dinh
di~u ki~n k6t tua toan Itt<ffigdUngtrong phan tich kh011uQng.

112

+----~---------------- ~~-
2. DC) TAN CUA CHAT KHI
MQt khi G dua VaGdung n'loi nude se dUQchydrat hoa tao nsn can bAng
hoa tan l(mg khi:
G (khi) =~ G (nude)
HAng s6 Henry (KH) danh gia dQ tan (n6ng dQ M) d ap suat rieng phan
(P G) ella khf G d nhiet dQxac dinh.
_ [G] (5.1)
K H-
PG
Trong do [G] la n6ng dQM ella chat khi va Po 18.ap suat rieng phan (bar).
Nhiet dQcang tang, KH cang giam. N~u dung dich dUQcdun soi khi G se
thoat he't ra ngoai,
DQ tan d 25°C cua ba khi co m~t trong khong khf: oxy, nito va carbonic
trinh bay d bang 5.1.
dU<;Ic
Bang 5.1. £)Q tan trong rurcc (J 25°C cua khf oxy, nlto va carbonic.
Khi O2 N2 CO2

89 tan (M) b 1 atm 2,6.10-4 4.9.10.4 1.0.10.5

KH (mol·l.bar) 1.25.10.3 5.32.10.4 3.32.10.5

DQtan cua mQt khi co th~ phu thucc vao dieu kien cua moi truong' va d~c
di~m ella chinh khi do. .
Vi du: Khi khi H2S hoa tan trong nude.

k ::::[H30+].[HS-] :::_1
I H2S K2

DQtan rieng ella khi H2S la:

So ::::[H2S]= KH·PH2S (a)

pH clla dung dich lam thay d8i dQtan cua khf H2S. DQtan toan ph~n (dQ
tan bi~u kie'n, Sf) tuy thuQc VaGgia tri ham exS(H):
S' ::::[H2S] +[HS'] +[S2']
(b)

113
 --- -------.----~----.~--~- ---'---

Vi K K == [H2S] ~ [S2-1 == [H2S]

I 2 . h2[S2-] J KIK2h2

Cho nen tit (a) va (b):

S'=[H S].1+:K1·h +K1X~h2
. 2 KIK2h2

SO.aS(H)
S'= (5.2)
h2KIK2

Dq tan bi~u kie'n S' phu thuoc vao pJf eua dung dich, S' tang thea pH.
Khi nhiet dQ tang, d{itan giam.
Vi du:
Tfnh <1Q tan (mg/l) eua O2 d. ap suat khi quy~n khi nhiet dQ 5°Cva 60°C
bi@'t:
- Phan -s6 mol eua oxy la 0,20.
- Hang so'KH a 5°e 18.1,94.10.3; a 60°C 18.:8,64.10.4
Giai:
- Tit phan s6 mol 021a 0,20 tfnh ra ap suat rieng phAn Pox
Pox:::: 0,20.1,013 = 0,203 bar
(1,013 lit h~ s6 chuy~n d6i ap suat tit atm sang bar)
- Tit cong' thuc (5.1) ta e6:
80 (5 a, = KH·Po)C = 1,94.10.3• Q,203.32 = 12,6 mg/l.
80(60°'= KH.Pox = 8,64.10.4.0,203.32 = 5,61 mg/l.

. .
3. DO TAN (J DANG PHAN Tit
Nhi~u hQp eh~t, nhat 18.hop chat huu co thudng tan khong nhieu trong
nude (bang 5.2)

Bang 5.2. £)9 tan So (J 25°C trong mtC1c

HC1P chat H4Y (EDTA) lod Oxln (HOX)

D¢ tan (M) 3,0.10'4 1,26.10.3 1,0.10.3

EDTA va oxin (8 hydroxy quinolin) it tan trong nude. Dua VaG tinh ch~t
acid-base c6 th~ lam tang d9 tan cua chting.
Vi du: Oxin c6 2 hAng s6 acid: 19K2:::: 5; IgK1:::: 9,9

114
 ox ._.
I
9,9 pH

K = (H20X+] = 105 (a)

2 h.[HOX]

K = [HOX] =109,9 (b)

I h.[OX-]
Phuong trinh bao toan kh6i lucng cua HOX chinh la dQtan bi~u kie'n S'
ciia no. Dua (a) va (b) vao phuong trinh ta co:
S'= [OX,] + [HOX] + [ H20X+]= [HOX] ( lIK1h+ 1 + K2h)
(5.3)

=
Voi dQtan So 1.10.3 M ~ IgSo== -3 ta co th~ tmh d~ dang tri s6dQ tan
S' theo pH cua dung dich (bang 5.3)
Bang 5.3. £>9 tan S' thay d6i theo pH cua dung djeh

pH 1 2 3 4 5 6 8 10 12 14

Ig S' +1 0 -1 -1,96 -2,7 -3 -3 -2,96 -1 +1

IgS'
2
1
0
-1
-2
-3
-4
pH
-5
0 ")
~ 4 6 8 10 12 14

Hinh 5.1. SI! thay d6i cua IgS' theo pH cua dung dich

Tit hinh 5.1, ta thay ro dQtan cua HOX thay d5i theo pH, tao ra 3 vung
ro r~t:
- pH<3: HOX tan nhieu, nam dudi dang cation H20X+

115
 - pH> 11,9: HOX hoa tan, t6n tai ~huye'u d dang anion OX'
- 5~ pH SIO: Hoa tan it -nam dliOi-da.ng phan ttl (khoang ImM).
Neu mu6n co dung. dich HOX 0,1 M thi pH dung dich p'hiH ~3 hoac ~1l,9.

4. DQ TAN·oUA MUC)! f)I~N LI iT TAN

Nhigu hop chat it tan trong nude. D~ d(lc tr\.tlig cho d9 tan eua cac mu6i
nay nglidi ta thl1dng dung h&ng sO' can bAng-Kg con goi la tich .so tan (TA .. B~ )
cua chat di~n li it tan. Tu TAmB• cua hep chat AmBn c6 th~ ttnh dl1<;se
dl) tan
cua n6 trong nude:
AmBn" .... rnAn- + nB m+

S mS nS
Do d9 tan She, ta chap nhan h~ s6hoa.t d9 trung binh ~l eho nen:

s =
m "<n n
(5.4)

Vi du l:
Tinh dQ tan cua Ca3(P04h trong nude, biet tich so tan cua n6 d 20°C IS.
3,16.10.33

Vi dl;l2
Tfnh dQ tan eua CaS04 biet tich so' tan eua n6 d 20°C IS.0,260.10.4
S = ~O,26.10-4 = 0,51.10- M
2

Vi dl) tan kha len .nen d.n tfnh den h~ sO'hoat dl) trung binh f2± theo
phl1dng trinh Debye-Hiickel.
I:::: 0,5. L Cj• Zj2= 0,5 (0,51.10'2.22+0,51.10.2.22) = 2,04.10.2

.1 f = - 0,5.Z j.fj = _ ° 252

2
g2± 1+.fi '

~ f2±;::: 0,560

116
 s':::::: Tcaso! 0,260.10-4 = 0,830.10-2 M
f2~ == 0,5602
Trong truong' hop cua CaSO 4' ne'u tfnh de'n h~ 56 hoat dQ trung binh thi
dQtan tang hon 1,5 IAn.
Trong thuc te' dQtan cua cac chat it tan chiu anh hudng cua nhieu ye'u to'.
Sau d&y chung ta khao sat cu th~ hon thong qua nhfing vi du cu th~.

4.1. Anh hu'dng cua h;ic ion

Khi dua mot chat di~n li vao dung dich c6 can bang' ke't tua hoa tan va
cac chat nay khong c6 ph an ung h6a hoc vdi ion tao nen ket tua, rna chi lam
tang luc ion cua dung djch, thi dQtan tang len. Nguyen nhan lam tang dQtan.
1a do h~ 80 hoat d9 trung binh giam xuong.
Vi du:
Trong dung dich KNOa 0,01 M dQtan cua AgCI tang khoang 12%, con cua
BaS04 tang khoang 70% (vi hoat d9 trung binh f2± giam nhieu hen so v8i f1J
4.2. Anh hu'dng cua ion cung ten
Neu dua rn9t ion cung ten vdi ke't tua vao dung dich c6 c&n b~ng ket tua
hoa tan thl can b~ng chuy~n dich ve phia t~o ket tua:
,l-AmBn mAn. + nB m+
S\i chuy~n dich d6 dam bao cho tich so tan khong d6i. Vi v~y, dQtan cua
AmBn se giam.
Vi du: Ket tua AgCl c6 TAgc]=1,82.10'lo dQtan S se la:
S ;:: ~1,82.1O-IO == 1,35.10.5
HCl d~ c6 [Cl']= 10.2 M thi:
S;:: (Ag+]=1,32.10.10/10.2;:: 1,82.10.8 M

D o~ t an eua
., Ag CI d-a glam
.• d'1 1.35.10-
. 85 :::::742 1"
an
. 1,82.10-
Ne'u ion cling t¬ iin
t~o ph(tc du:qcv8i ket tua thl dQtan eua ket tua se tang
len (xem phAn anh hUdng cua s\i tf;\Oph(tc).
4.3. Anh hddn,g cua pH dung dich
D9 tan cua ket tua AmBnse tang len neu nhU:cac ion eua ket tua An" Bm+
phan (tng vdi cac ion H+ va OH' trong dung dich. Vi d\l:
- Ion H+ t~o voi ion An. thanh cac acid HA, H~, ..., HnA v8i cac h~ng so
eQng proton K1, ~, ..... , Kn tudng (tng.

117
 ..".Ion OR- ket hop Bm+tao thanh phuc hydroxo: B(OH), B(OH)2' .... ' B(OH)p
VOlhii~g 56 b~n PI' l32, Pp tt.1Ung tmg ( 0 -.day psm). Do tae dQng cu a 2
nhom phan ling tren nen tcll1g 116ngdQ cua cac dang ion va phan t.\:i hoa
tan .trong dung dich lien quan -den 2 ion An- va B?" tang l~n.Danh gia
anh hlidng nay th.&ng qua ham tao -pnan ung phu c: '
aA(H) '= 1 +,K1h + K1.K2.h'.l+ + K1.K2 ...... Kn.hn
UU(OH) = 1 + P'loh + f320h 2 + + 13vohP
'rich ,so tan b1~ukien T' ~.se'la:
T '=[A,i.]m
, A(H) • [B1Jl1'~. n ""n
,_;m,
...... v. B(OH-) , (5.5)
Kit hQP (5.4) lIa (5.5) ta cO d~ tan bi~u kien 8" la:

S '-s~
-
lIt+n aNI
'A(H)'
anB(Ofr) (5.6)'

Tfch 56 arne.un A danh gia tac d9ng cua pH den dQ tan etta ke't tua A~Bn'
=
Neu An- khong co phan (tng voi H+ thi UA 1; B?" khong co phan (tng voi OH'
ihi aB = l.
Vi dl!- 1: Tfnh -dQtan cua calci oxalat trong dung djeh pH 4, biet =
TCaCz04 = 2,3.10-9; H2C204 co]gKl = 4,2,7 va 19K = 1,25,
2

o day ta eo 3 can bAng:

..j.. CaC204

C20 42· +,'H+ ...

HC204' + H+ .::;;;:::i:~
Tinb a eua acid oxalic:

aCP4(H) :;; 1+ K1h + K1~h2

= 1 + 10 4•27 10.4 + 105•52.h-a ~ 10°,46
23 10-910°.46
Thay vao (5.6) ta eo: S'= "-"2 ' ==8,1.1O-'M
1~.1
Vi dl!- 2: Tinh dQ,tan cua .cuS trong nude b±et tich s6 tal} cua no la 6,3.10.36
va H28 co 19 Kl == 12,89 va 19~ := 7.D;:phjtC Hydroxo eua Cu2+ eo:
19 Pi :: 7,0; 19 P2 :;;13,68; Ig Pa ::.::~7,0 va.}g P4 == 18,5;
Do dQ tan eua 'CuS r~t be n~n n6ng d9 eua ion Cu2+ va 82• khong du d~
thay d6i pH dung dich, nen ch~p nh~n pH = 7.
<Xcu{OH):: 1 + 107x10-7 +.l(J13.68.10:14 + 1017.10.21 + 1018,5.10-28 10°·39 =
<XS{H) = 1.10 12 ,89,10-7 + 1019.&9,10-14 :: 106,19

118

---'--------~--- ..--- -,----~ ~~

 DQtan cua muo'i CuS la:
S':::: (6,36 . 10.36.10°,39.106,19)°,5:::: 10·14,36M
Neu khong k~ den acu va as
S ::::(6,36 . 10'36)0,5::::10,17,6M.

S > 103 nhu vay

S' .,do tan co tinh den (J., da tang them tren 1000 IAn.

4.4. Anh hudng ciia s1:J.tao phirc

Qua trinh tao phuc c6 th~ lam tang dQ tan cua ket tua trong dung dich.
Thuong g~p 2 truong hop: .
- Tao phuc v{ji chat Ia,
- Tao phuc vdi ion cua ke't tua.
Ta hay xet tung truong hop
4.4.1. TC!o phitc viii chat IC!
V{ji ke't tua MmAn
mM+nA
MQt ion dua tu ngoai tao phuc vdi cation kim loai: ML, ML2, .... MLp• Neu
A co phan ung phu thi dQ tan cua .MmAnduoc tinh nhu cong' thuc (5.6). Di~u
quan trong la cAn biet nang dQcan bang cua cac pho'i tit d~ tinh duoc c.
Vi dz.t 1: Tinh dQtan cua AgCl va AgI trong dung dich amoniac 3,3M.
Trong dung dich co cac can b~ng sau:
~AgX Ag+ + X-
Ag++ NHa.:;;==:::!: [Ag(NHa)j+
[Ag(NHs)r + NHa .:;;=~ [Ag(NH3ht

Ig 131 = 3,3; 19132 :::: 7,1

N5ng dQamoniac rai cao, cao hdn nhi~u nang dQ[Ag+]n€mta coi [NH31::::3,3 M
(lAg(NHl) = 1 + Pl[NH3] + P2(NHa]2
= 1 + 103,3. 3,3 + 107,1. 3,32:::: 108,1
SAgC}::::(1,8.10-10, 108,1) 0,5 = 1,5.10- M.
1

SAgl = (10-16. 108,1) 0,5 :::: 1,1.10 ..4 M.

DQ tan eua Agel Wn gap tren 1000 IAn dQ tan eua AgI trong dung djeh
amoniac 3,3 M.

119
1.4.2. Tqo phitc vai ion cua ket tria
.Nhieu thu6c thu ke't tua, hie cho du lam ke't tua tan ra. Vi du:
- Cac hydroxyd luang tinh nhu Al(OH)a, Zn(OH)2
,J.,Al(OH)a + OH- -7 AI(OH)4-
- Cac halogenid
Hg2+ + 2r -7 HgI2,J.,
J,HgI2 + 21- -7 HgI42-
Nhu v~y khi cho thtl0C thl1 tao ket tua 'lao dung dich, n6ng dQ ion dli<;!e
ke't tua se giam d~n rdi d~t cue ti~u. Neu them tiep thuoe thu ~Q tan etta ion
nay lai tang len. Minh hoa eho ke't luan -nay thong qua vi du tfnh dQ tan cua
tua AgCI khi cho du ion CI-.
Vi du. 2: Tim bi~u thuc mo ta
sl;lphn thuoc dQtan S eua ke't tua AgCI vao
n6ng dQmuoi KCI e6 m~t trong dung dich.
Cac can b~ng e6 m~t trong dung dich:
AgCl.d.n AgCldd
A +lfcr]
x,» f g II == 3,9.10-4
[AgCltld]

K = [AgCl;] :: 2.10-5
1 ~Cl-]

K K - [AgCl;-] - ? 10-5
1 2 - [cr Y -_.
DQtan S cua Agel 11\:
S ::::[AgCI(dd)]+ [Ag+]+ [AgC12-] + [AgCl/'J (5.7)
Ta tinh cae thanh ph~n cua S:

[A Cl ] = TAgC1 = 1,82.10-10 == 47.10-7

g dd Kd ,3,9.10-4 '

[Ad= ~~Il
[AgCl2-] :::: KI[Cn
[AgCI32.] :::: K1K2[Cn2
Thay cac gia trj tren vao (5.7):

120
 (5.8)
s= T;:I +~f-I]+KJCr]+K1K2[Crr

Khi cho KCl du IOn d~ [Cn ~ CKel' thi:

TAgCI TAgC1, K C K K c2
S :::--+--,- I KCI + I 2 KCI
(5.9)
s, CKCI
D~ tim cue ti~u ta lay dao ham dSI dC va cho b~ng 0:
dS TAgC1
-=O=--,-+K, +2K1K1C
dC C-
2K1K2C 3 + KiC 2 -TAgC1 = 0 (5.10)
Thay the' gia tri K, va TAgC1 vao ta c6 mQt phudng trmh b~c 3 cua C. Dung
phuong phap l~p d~ tim gia tri C ung vdi Smin' Gia tri thu dllQC la
C :::3,00.lO-3M. Khi bie't C d~ dang tfnh ducc n6ng de')cac thanh phftn khac:
[Ag+]= 1,82. 10-10 13,00.10-3::: 6,1. 10-8
[AgCI2-] ::: 2. 10-5• 3,00.10-3::: 6,0. 10-8
[AgCls2.] ::: 2.10-5• (3,00.10-S)2::: 1,8.10-10
De')tan t6i thi&u Smin tmg vdi C :::3,00. lO-3M la:
Smin::: 4,7.10-7 + 6,1.10-8 + 6,00.10-8 + 1,8.10-10::: 5,9.10-7M
Khi cho C mot tri s5 xac dinh c6 th& d~ dang tfnh dllQC de')tan S cua ke't
tua AgCI va n6ng dQ din b~ng cua cac cflu til trong dung dich (hinh 5.2).
Nong dQ

,.....
c
.2
e
.(0
c
:g-
O>
C

-
"0
C

19 CM
Hinh 5.2. NOng oQ can bang cua cac cau tii trong dung dich

121
 ----~ ----~
...

4.5. Anh huling cua phan (tng oxy hoa khi'i

Khi k6t tua co hang s6 Ks thap thuong rat kho lam .tang dQ tan ella
chung thong qua ph an
tmg acid-base hoac tao phuc. Trang tFudIlg hop nay,
nguol ta Ontong dung pl)an ling oxy hoa khu.
Vi du:
Cac k6t tua sulfid kim loai nhu HgS, CuS, PbS du<)choa tan bang each
dun nong voi HNOa:
3CuS.J, + 8 HN03 2NO t + 3S + 3Cu(NOa)2 + 4. ~O
HNO~ da oxy hoa S2. thanh So lam chuyen dich can h~ng, k6t tua CuS
dUQcchuyen thanh CU(NOa)2 hoa tan.
.. ... ,.....,
s. str HINH THANH KET TUA
5.1. Qua trinh ke't tua
Chung ta khao sat qua trinh ket tua cua mQt muffi don .gian AB tit cac
ion A va B+trong dung dich, Cae ion nay co dUdng ktnh co vai angstrom (lA ==
O,lnm). Khi tich so cac ion vuqt,gu,a tfch s6 tan TAB,A va B+ lien k€t tao ra
mang tinh th~ IOn dAn va lAng xuong day binh do trQng hjc. Nhu vf}.ycac ion co
kich thuoc lO,scm IOn dAn len vUQt qua kfch thuoc hl;lt keo t.~o Ta ket tua c8
, tren 10·4cm.
Ion (dd) ;;r=:=::!::: Hl;lt keo Ket tua
(lO,sem) (lO·7-10·4cm) (>10.4 cm)
St,t thay d6i kfeh thuoc 'nay dUQcxac dinh bdi t6e dQ eua 2 qua trinh, sl,t
hinh thanh mAm tinh th~ va sl,t IOnlen Clla mAm.
Mam tinh th~ t~o ra dau tien co kich thuoc r~t nho. Thdigian hinh thanh
mAm ph\1 thuqc vao him ch~t aua ket tua.
Vi dl:l~'
Tua Agel, mam t~o ngay khi eho Ag;' vao dung di{)hchua ion Ct, vai tua
BaS04 thi ;tlgttQc l/ili,mAm tf,lO ra r~t ch~m m~c du 2 tua nay co T xap xi nhau.
Mam tl;lora dAu tien tra thanh trung tam d~ cac ion trong dung dieh tiep t\lc
ke't tua tren h~ m~t, bien mAm thanh hl;lt to co ca'u true m~ng tinh th~ 3 ehi~u.
Weimann (1923) Ian dAu tien nghien cuu anh hudI).g cua thu6c thi:l len
t6c dQ ke't tua va kich thuoe hl;lt. Tae gia da dua ra khai ni~m ai? qua bao hoa
tl1dng aot. D~i lUQngnay dUQctinh theo eong thuc:

A
01::: Q-S
DQ qua'h- ao h'oa tuong d"" S (511)
.

Tl'ong d6: Q: n6ng dQ toan phan (molll) cua cac thuoc thtl trQn vao nhau
trong dung dich.
S: dQtan eua tua sau khi can b~ng.

122
 Khi hinh thanh ket tua, m6i l~n cho thudc thi'i vao dung dich se gay ra
trang thai qua bao hoa tuc thei (nghia la Q > S). Neu dQqua bao hoa cang Ion,
s6mAm tao ra cang nhieu, ke't tua co xu hudngtao thanh ha: keo, Ne'u thong
so' nay cang be, sO mam tao ra cang it nen cac mam cang co xu huang ph at
tri~n thanh hat ldn, tao tila tinh thi. Thuc te day la mgt qua trinh phuc tap.
Thong 56 dQqua bao hoa mang tinh chat dinh tinh. 'I'ac gia ke't luan rfmg: ke't
tua eo tieh so' tan cang be cang d~ tao ra hat keo.

5.2. Hai loai ket tua

Nhu tren da noi, ne'u eho thuec thi't nhieu vao dung dich, cac mam tinh
th~ tao ra 6 Q.t,ehua kip IOn len thimh hQ.tto da t~p h<jpngay thanh ke't tua.
Do qua trinh t~p h<jp qua nhanh, cac ion du<;!csap xep mQt cach h6n dgn,
khong dinh hliang. Dieu nay dftn den k€t tua khong co hlnh d~ng nhat dinh,
nen g9i la ktt tila vo dtnh hinh. Lo~i tua nay thudng dUQch1nh thanh khi ket
tua co dQ tan nho (S nho nen dQ qua bao hoa clla dung dich qua Ion). Tua
sulfid va hydroxyd cua cac kim lo~i n~ng thuQc lo~i nay.
Co trudng hQp eho thu6c thi't vao dung dich, cac m~m du<jct~o ra ttt ttt.
Cac m~m nay co cd hQi phat tri~n thanh h~t to. Cac ion dUQcs&p d~t tren
m~m tinh th~ co hinh dQ.ngxac dinh. Vi v~y dll<jCgqi la ke/; tua tinh the'.
Tuy nhien, ranh giai giua 2 IOQ.iket tua khong ro rang. Ben c~nh yeu to'
bim chf(t cua chat ket tlia, s;;t hinh thanh dQ.ngtiia nay hay dQ.ngtua khac con
phv. thuQc ca vao dieu ki~n ket tua .•D~ co ket tua hQ.t to ngudi ta ch9n dieu
ki~n sao eho dq qua baD hoa la c;;tc tieu (tUc la tang S va giam Q). Cv.th~ la:
- Tien hanh ket tua tit dung dich loang.
- Cho thuoc th-li ke't tua vao dung dich ttt ttt va khuay deu dung dieh d~
lam giam dq qua bao hoa C\1CbQ.
- Ket tua d pH thap nhat co th~ va dun nong vai mv.c dich tang dg tan S.
- Ket tua trong moi trudng d6ng th~ tQ.odieu ki~n Ii ttidng lam giam dQ
qu~ bao hoa cua dung dich. Trong trtidng h<jp nay thu6c thu khong cho
thang vao dung dich ma tQ.othanh tit ttt ngay trong lOng dung dich nhd
phan ung hoa hqc d6ng th~. Dieu nay tranh du<;!ehi~n tu<;!ngdu thu6c
thu luon t6n t;;ti trong phlidng phap ket tua thong thudng. Nhd ket tua
trong moi trudng d6ng th~, dg qua bao hoa rat thap nen co th~ thu duc;!c
ke't tua tinh th~ co cau truc hoan chinh ngay ca vdi nhung ke't tua von 1a
tua vo dinh hinh nhu hydroxyd kim lo;;ti.
Vi d~[,:
D~ ket tua dbng th~ hydroxyd, ngtidi ta sit dv.ngphan ting thuy phau eua ure:
CO(NH2)2 + H20 --j. CO2 + 2NHs
NH3 sinh ra lam tang tit tit pH dung dich, tQ.oket tua hydroxyd kim loQ.i.
NgUdi ta con dung mgt s6thu6c thu khac nhu: diethyl oxalat (C2H5)2C204;
trimethyl phosppat (CHs)sP04 d~ ket tua nhieu ion kim loQ.i.

123
5.3. Keo va pepti hoa

Keo 19.nhung ti~u phap. co kfch thudc khoang 10-7 ~ 10-4cm, nam trung
gian giila ion va ket tua_ Dung dich keo lEi trang thai trung gian giila dung
dich that va h6n dieh. Trongi.thftng .dieu ki~n nh~t.dj.:nh n:1Qtdung dich c6 th~
chuyen tu trang thai nay sang tr~ng thai khac. Troirg tlll;tc te khong co ranh
gidi ch~t che gitta 3 trang thai nay.

5.3.1. Sf! hinh th.anh. dung-dich. keo

Khao sat trttang hop tao dung djch keo AgCl.
Khi ta cho tung giot. AgNOs vao dung dich Nafll, cac hat keo dau tien
xuat hien, d6 Ia cac vi tinh the' (AgCI)m'Neu hl<;fngAgNOa cho VaGtuong duong
vdi IUQngNaCI trong dung dich, ta se c6 tua tlnh th~. N6u treng dung dich co
thira ion Ag" ho~c ion CI- thi cac vi tinh th~ ban diu se hf(p phu uu ti~n chung
tao ra nhting ldp ion hap phu, con gQila top 8(1 cap. LOp nay se hut cac'ion trai
dl1u trong dung dich de t~o ra ldp ion doi hl1p ph\1 goi IS. lilp th(t dip, DUdng
nhien ldp thu cap ket hQp vdi nhan (tuc vi tinh th~ dAu tien) lOng leo hdn
nhieu so vdi ldp sd cl1p. Hai ldp nAy t~o ra ItJp di~rt kep bao quanh nhan tao
thimh tilu phan keo. Cac tilu phan keo mang di~n tich cling dau nen dAy
nhau, ngan can cac ti~u phan keo ket hQp voi nhau t~o thanh h~t ldn. .
Muon cac ti~u phan keo dong t\). (coagulation) c~n lam m~t di~n tich cua
ldp sdcap.
Sd d5 ti~u phan keo cho hai trtldng hQp :
- Khi dtl CI-
[(AgCI)m nC!' (n-x) Na+r-
nhan ldp sd cap Idp th(1 cl1p
- Khi du Ag+
[(AgCI)m nAg+ (n-x) NOa']x+
nhan lOp sd c~p ldp thu cap
Tinh chat cua dung dich keo:
- La h~ khong d6ng nhat (khac voi dung dich th~t.la mQt h~ d5ng nhl1t).
Tuy v~y cac ti~u phan dUQcphan tan kha 'nhc) kh~ng nhin thay bAng miit
thtlang ho~c kinh hi~n vi thong thlidng. Khi phan tich bAng huyuh
quang, se th~y ro cac ti~u phan khue"ch tan.
- Chua cac h~t nhc) c6 di~n tich cling dau, d~y nhau, nen khong bi lAng khi
Iitam va lQt qua gil1yIQcthtlang.
TU 2 tinh ch~t nay, chung ta th~y:
- D~ chuy~n dung dich keo sang tr~ng thai tua Wc Ia lam dong t\1 keo, d.n
phai cho them VaGdung dich keo cac chat di~n··li thich hQp nhtl: Hel,

124
 _
... .. _- _-_.--_
... .. _-------- -----

NH4N03 .... d~ trung i}oa di~n tfch cua ti~u phan keo. M~t khac cAn dun
nang dung dich d~ tang to'c d9 di chuyen cac hat keo, lam cluing va cham
nhau nhieu va manh tao thanh hat km han va l~ng xuong-.
_ Neu muon duy tri dung dich keo ben vung cAn cho them cac ch~t bao v~.
Cac chat nay duy tri dien tich ti~u phan keo ngan can qua trinh dong tu.

5.8.2. Pepti h6a

Pepti h6a 18.qua trinh chuy~n dung dich keo da dong tu tra ve trang thai
phan tan ban dAu. Hien tuong nay thuong xay ra khi nguoi ta rila keo dang tu
bang' nude. Rila tua khong chi loai chat bAn ma con loai ca cac chat di~n li da
tao nen su dong t\l keo. Nhu v~y rila tua d~ lam giarn tap chat nhung d6ng
thoi c6 th~ lam mat di mC)tph An ket tua.
D& giai quyet van de nay ngudi ta thudng rila tna bAng dung dich cac
chat di~n Ii bay hal. Cac chat nay c6 th~ dUQclo~i khoi ket tua bAng say khO.
a
Vi d\l rila tna AgCl b~ng dung dich HN03 loang, khi say kho 110°C acid nay
bay hai het.

5.4. 811 nhi~m bin cua ke't tua

Dieu quan tam cna ngudi lam phan tich la tach dUQCket tna dUdi d~ng
tinh khiet. s~ hinh thanh k6t tua luan keo theo mC)t sO'tfilP chat liim tna
nhi~m bAn. Vi v~y d.n ki~m soat dieu ki~n ket tua d~ lOfilitru ho~c giam thi~u
t~p chflt. DC)tinh khi€t cua ket tna ph\l thuQc VaG2 hi~n tttQng sau: cQng k€t
(co-precipitation) va ket tua theo (post~precipitation).
5.4.1.C9ng he!
CQng ket la hi~n tUQng ket tua cung vdi ket tua chinh. Co nhieu nguyen
nhan d~n d6n s~ cQng keto
81/ hap phl! b€ miJ,t:
Cac t~p chat dUQCM(p ph\l tren be m~t k€t ttla. Thtidng trong qua trinh
hinh thanh ket tua, khi ket tua tfilothanh, cac ion ho~c phfm ttt tren be m~t
ket tlia con co nhfing lien ket t~ do nen se lien k6t vdi ion va phan tit hoa tan
trong dung dtch.
a
Vi d\].khi cho AgN03 VaGdung dich NaCl, ket tua Agel tfilO thanh trong
moi trudng du NaCl nen tua se hap ph\! tiu ben ion Cl' trong dung dtch. Ket
tua tfilora cac hfilt mang di~n tich am.
Co nhieu yeu to' anh hUdng den qua trinh hap ph\l:
_ Anh huang cua di~n tich be m~t: ltiQng chat dUQChap ph\l ti 1~thu~n vdi
di~n tich be m~t. Tinh th~ cang be, di~n tich be m~t cang Mn, 1uQngchat
bi hap ph\]. cang nhieu.
_ Anh huang cua nhi~t dQ: hap ph\]. 1a qua trinh tda nhi~t nen nhi~t dQ
cang cao thi sl.;i hap ph\l be m~t cang giam.

125
 ._ . ....;..-.;._,.'---_._--

- Anh huang cua n6ng dQ: hap phu la qua trinh can b!ng dQng. Cac ti~u
ph an bi hap phu I~n b~ m~t cua ke't tua co th~ tan trd lai V8.0 dung dich
tuc la co th~ giai h~p phu, St;l chuyen dich can bang .nay phu thuec V8.O
n6ng dQ.Vi du ket tua AgCI:
AgCl (rl1n) + nAg+ AgCl d.n.nAg+
Neu tang n6ng dQ'ion Ag" trong dung dich, qua trinh hap phu tang. Neu
giam n6ng dQ ion Ag" trong dung dich thi IUQng ion Ag+ bi h~p phu tren be
m~t tua giam di (do hoa tan vao dung dich).
- Anh huang cua ban chat ket tua: h~p phu b~ m~t IS:qua trinh hap phu
chon 19C, uu tien truClc het Ia cac ion tao nen ket tua co Irl~t trong dung
dich. Vi du trong dung dich co ion Cl', I', NOs' thi ket tua AgCI h~p ph\l
UUti~n ion Cl". .
C9ng ktt n9i:
CQng ket nQi 18.hi~n tt;ldng lam nhi~m bAn d trong cac h;;tt ket tua. Ngltdi
ta phiin bi~t co 2 Io;;ticQng ket nQi:
- C9ng ket d6ng hinh: hi~n tUQng nay chi xay ra khi vi tri ion trong m~ng
tinh th~ ket tua bi thay the bdi ion khae. Vi d\l slJ cQng ket dang hinh cua
ion Pb2+ vao tua tinh th~ BaS04•
2-
Ba2+ SO!- Ba2+ 804

SO!- Ba2+ S042- Ba2+

Ba2+ SO!- @) 804

2-

S04
2-
Ba2+ S042- Ba2+

Thudng cae ion kim lo;;ti co di~n tich bang nhau va dUdng kinh xap xi
nhau d~ thay the cho nhau trong mlilng tinh th~. Cac bi~n phap neu tr~n
khong th~ IOlilitrit dUQccQng ket dang hinh. Bi~n phap duy nhat dUa I~i ket
qua t6t 18.hoa tan tua sau do ket tua 11ili(tuc 18.pha mlilng tinh th~ CO eQng ket
d6ng hinh).
C9ng ktt hap lrtu: day 1a qua trinh tlilPchat dUQCgiu trong qua. trinh lCIn
l~n cua hlilt ket tlia. 0 day tlilPchat cQng ke't va phan bo khong deu; chli
yeu t~p trung d ch6 khuyet cua mf,lngtinh th~.

5.4.2. KIt tua theo

Day 18.hi~n tUQng tf,lP chat bi ke't tiia tlieo sau khi ket ilia chinh dB.tlilo
thanh va ngam tiep trong dung dich ban dAu. Vi v~y mu6n tr{mh hi~n tUQng
n8.y, ngudi ta tach ngay ket tua tliloth8.nh ra khoi dung djch.

126
 Vi du:
ZnS khong th~ tao thanh trong dung dich co nang dQH+ Ion (khoang 0,1·
0,2M). Nhung neu co tua HgS hoac CuS ngam lau trong dung dich chua Zn2+
thi ZnS se ke't tua theo. Nguyen nhan la ket tua HgS hap phu cac ion S2. len
b€ m~t cua no. N6ng dl?ion S2.tren bg m~t tua HgS tang nen tich s6 [Zn2+][S2.]
vuot qua T ZnS nen tua ZnS tao thanh tren b€ m~t tua HgS.
Tom lai, cl?ng ket va ket tua theo 1a nhfing hien tucng thuong di kem vdi
qua trinh tao ket tua do nhieu nguyen nhan khac nhau. 'I'uy truong hop cu
th~, ap dung nhftng bien phap thfch hop nham giam den mac t6i da sai s6 do
chung gay ra. •

II> ., , " Ito

CAU HOI VA SAl T~P

5.1. Giai thich 8\1 hinh thanh hai loai ket tua: tua tinh th~ va tua vo dinh
hinh.
5.2. Tinh chat cua dung dich keo. Y nghia th\1e te cua hi~n tuqng dong tt;t
va pepti hoa.
5.a. Phan bi~t qua trinh cl?ng ket va ket tua theo. C~n lam gi d~ tranh
nhi~m bgn ket tua do hi~n tuqng cl?ng ket va ket tua theo.
5.4. Khi CO2 trong khi quy~:rt can bang voi nuoe co dQ tan trong nuoc
1,0.10.5 M.
a. Tinh pH 'cua dung dich nuoc bao hoa CO2 va nang dl? toan phAn
eua CO2 (dQtan S eua CO~ cho IgKl ::::10,3 va IgK2 ::::6,4.
b. Ve ham 19S theo pH cua dung djch (0-14).
c. Ml?t dung dich nuoc co pH==7va nang dQ RCOa"::: 1,15 mEll, dung
dich nay co (j trl;lng thai can bang khong?
5.5. Tinh dQtan S (mol/l va mg/l) cho 3 chat sau:
a. CaC03: M=100 va Tcaco, ~ 8,7.10.9

b. Fe(OH)3: M =107 va TFe(OH») = 1,1.10.36

c. Ag2Cr04: M=332 va T Ag2Cr04 = 10.12

5.6. Tinh tich s6 tan cua cac chat sa u cho biet M va S (gil)
a. MgF2: M = 62 va S::: 8,7.10.3 gIl
b. Ag(OR): M :::'"125va S::: 1,7.10.2 gil
M = 97,6 va S::: 9,7.10.6 gil

127
 5.7. Tinh tfch so'tan cua cac chat sau cho biet dQtan S (M)
a. AlP04: S == 7,62.10·10M
b. AgSPO.1 S == 4,68.10·6M
c. NaU02As04: S = 5,06.10.8 M
5.8. Tinh n6ng dQion I: trong dung dich bao hoa cua:
a. AgI: TAgI = 1,0.10'16
b. PbI2: Tpb1z = 7,1.10'9

c. BiI3:
5.9. Tinh n6ng dQion Pb2+cdn thiet d~:
a. B~t ddu ket tua PbS04 tu dung dich co nang dQ SOl 0,05M
b. Lam giam n6ng dQion SOl' xu6ng eon 1,0.10.6 biet TpbSq =1,6.10.8

5.10. Tinh nang dQion Cu2+c6 trong cac dung dich

a. Dung dich nude bao hoa Cu(IOa) biet T=7,4.10·8
b. Dung dich CuC12 0,10 M bao hoa Cu(IOsh
c. Dung dich KIOa 0,10 M bao hoa.Cu(IOa)2
d. Dung dich CuC121,0.10} M bao hoa Cu(IOah
5.11. Tich so' tan cua CdCOgla 2,5.10'14.Tinh toan dQtan cua CdeOa
a. Trong nude
b. Trong dung dich co nang dQC032·19. O,10M
c. Trong dung dich c6 pH=8
5.12. Tinh dQtan cua MnS (T=3.10·13) trong 2 dung dich d~m:
a. pH=5
b. pH=8
5.13. N6ng d9 OH' can phai la bao nhieu d~ hoa tan O,200g Pb(OH)2
trong 200ml dung dich? Biet:
Pb(OH)2 (riin) +OH Pb(OH)3 (dd) co k=5,O.10-2
* 5.14. Trong dung dich nude Zn(OH)2 co 2 can bang:
.J,Zn(OH)2 Zn2+ +20H' co Ks = [Zn2+].[OH·]2=10.17
tZn(OH)2 + 4H20 . Zn(OH)42+ + 2HgO+
co Ks'=[Zn(OH)4].[HaO+]2=10·29

128

'~',,'\
."M-- i ....
-
 a. Tinh dQ tan toan phan eua Zn2+ phu thuQc vao pH. Ve d6 thi 19S -
pH (0-14)
b. Xac dinh dQtan t6i thi~u S min d pH nao?
* 5.15. Mui cua khf HzS nhan bie't dtt<1c d miic 1 ppm trong khong khf
(tuong ung vdi ap sua't rieng phan cua n6 la PH2S 210.6 bar) va
a
chiu dung duoc mire ~ 10ppm (PH2S ~10·5bar). MQt dAm lAy nude
man c6 bun chua FeS. 0 pH nao cua him ta ngiii thAy mui cua
HzS? Cho biet:
TFeS = 10.16•4
HzS eo 19K1=13;19K2=7 (lAy trim)
H~ng sC)KH = 0,1 cho khi H S
2

H~ng sC)tao phuc Fe(OH)+ 19lh= 4,5

129
.--.-~--~-.---.~~---.---- . ...... _ .. - ---

PHAN2

::PHAN·,-:fCH4fOA·HOC IlINH LLIONG

. •• ....- -~,
!•

Chlidng6

PHAN TicH KHOI LlIQNG

1. NQI DUNG vA PHAN LO~I

Phan tfch kh6i luqng (con g9i 180phuong phap can) 180phuong phap xac
dinh ham lUcJngcac chat dua vao kh6i hrong cua san ph~m dang tinh khiet, a
chua thanh pluin cua chftt cAn phan tich duoc tach ra khoi cac chat khac co
trong m~u.
Qua trrnh' tach co tbti duqc thuc hien theo nhieu each khac nhau, co khi
phai qua nhung bi~n. ~5i lY,·h9C,hoa h9C cAn thie't. Vi~c phan loai phuong phap
chu ye'u dua tr~n phuong' phap tach nay.

1.1. Ph'u'dng philp ket cia

. Th~c hi~n biing each: Cho thu6c thii ke't tua vao dung dich c6 chua chat
cAn xacdinh d~ tao ra ket tua hoan toan vdi chat cAn ph an tfch. Tach ket tua
ra khoi dung dich, rt1a, scJ.y(hoac nung) de'n khO'i luong khong d5i. Tit khO'i
lUQngnay Hnh rahamluQng chat cAn xac dinh.
D~fig ke't tua t~o thanh sau ph an ung ket tua g9i 180dr;mg tlla. D~ng tua
cu6i cung aau khi say (h~e nung) den khO'i lu<jng khong d5i g9i 18.d{tng can.
D~ng tua va d~ng can co th~ gi6ng nhau nhung cling co th~ khac nhau. Vi d\l:

1.1.1.Dinn lUfing Na2S04

BaC12 + Na2S04 = BaS04 t+ NaCl

(Di,Ul8 tua)

130
 to
BaS04 .. BaS04 t
(Dang can)

1.1.2·.Dinh htfJng CaC12

CaC12 +. (NH4hC204 = CaC204 t+ 2~Cl

(Dang tua)

CaO t+ CO2 + CO
(Dang can)

1.1.3. Dinh lU(jng Fes+

3 NaOH + Fe3+ = Fe(OHht + 3Na+

(Dang tua)

to
Fe(OHh ---' ......Fe203 t + 3H20
(Dang can)

1.2. Phuong phap bay hoi

o day, mot hay nhieu hop phan cua m§.u duoc lam cho bay hoi.

1.2.1. Phuong phap true tie'p

Cha't d.n xac dinh dUQccan sau khi lam bay hoi mftu.
Vi du:
- Xac dinh ham luong CO2 trong mudi carbonat, ta cho mudi do ph an tmg
voi acid d~ giai phong CO2, Khf CO2 nay dUQCha'p thu vao binh dung
CO2, Sl.1 tang khdi Iuong cua binh nay trudc va sau khi lam hap thu la
khdi luong CO2 de. giai phong.
- Xac dinh ham luong chat ran toan phan (total solids - TS) cua nuoc tu
nhien: lam boc hoi mQt th~ tfch nude xac dinh trong c5c de. biet kh6'i
luong, can con lai trong coc duoc sa'y kho. Tit khdi lUQngtang len cua coc
ta tinh dUQcham lUQngTS cua nudc.
- Xac dinh lUQngb\li co trong khong khi: nglidi ta cho mQt th~ tich khong
khi xac dinh qua ph~u lQcde. biet khO'ihlQng, sau do can ph~u lQc,ta tinh
dUQcham lUQngb\li c6 trong khong khi.
1.2.2. Phuong phap gian tiip
o day, ta xac dinh lUQngcha't trlioc khi bay hoi va hiQng cl)n con l'ili sau
khi bay hoi d~ suy ra khO'ilUQngchat da. bay hdi.

131

.--.~---.-.----~---------------
 Vidl;l
- .Xac dinh d9 flm cua m~u thuoc, DUQed'i~n Vi~t Nam cung nhu met so
mroc dung phuong ph ap bay hoi va goi la Ugiam khoillt{Jng do say kh6".
- V(li1;huoc kh6 hi nhiet phan hily: thuOl3:gsay a 100·1050C .
- Vdi-thuoc de hi nhiet phan huy: 18.m MO (j nhiet dQ thuong' trong binh
but ~m co P205 hay H2S04 d~.
, I A'" ?

2. eACH TINH· KET QUA

2.1. Trong phlidng pJuip bay hoi

Khi xac dinh nude ke't tinh va nude hut ftm cua chat phan tich ta co c6ng
'thuc:

%H20 == 1»1 -m2 .100 (6.1)

1»1

Trong do: m, khoi hiQng mftu phan tieh truce khi say
m, khoi luong' mAu ph an tieh sau khi say kh6

2.2. Trong phudng phap ke't tua

2.2.1. rna« s6'chuyen F
Trong phan tich khoi Iudng d~ thuan IQi cho viec tinh ke't qua, ngttdi ta
thuong si1 dung thira so chuyen F (con gQi la h~ s6~chuyln F). Do la ty so gifta
phan ti1 gam hay ion gam (nhan voi h~ so tUdng ung eua chat cAn xac djnh) va
phan ttl gam d~ng can. a
Vidl;l:

- Trong dinh lU<;fngNa2S04 a tren F = M NlI,SO.

M 8aS0 4

- Trong dinh hi<;fngCaC12: F = M C"C/~

MCIlO

- Trong djnh lUQng Fe3+: F = 2Fe

Fe203
Thua so chuy~n F cho ta bie't ung voi 19 d~ng can co bao nhieu gam chat
cAn xac djnh.

2.2~2.each tinh ket qud

Tu thua so chuy~n F ta de dang tinh dt1<;fc
ham It1<;fng
chat cAn phan tich.
Vi dl;l: Gia sit. khoi luqng cua mAu cAn xac dinh 18.a(g)

132
 Kh6i luong dang can la P(g)
Khoi hrong eh~t A nguyen ch~t e6 trong mftu la: m == P.F (g). Do d6:

%A = P.P .100 (6.2)

a
Cac loai n6ng d9 khac diroc tinh hoac suy luan tuong tt;l dua vao khai
niem n6ng d9 va cac moi lien quan ciia chung,

3. cAc DQNG TAc CO BAN CUA PHUONG PHAp KET TUA

3.1. Hoa tan mau phan rich

Neu mjiu phan tich 0 dang dung dich khong cAn giai doan nay. Nhung
neu la m~u r&n thi hoa tan la 'giai doan rit quan trong vi c6 ho~ tan duqc mftu
phan tich thi mdi chon dUQcthudc tha thieh hop d~ ke't tua hoan toan duoc
chat cAnxac dinh.
• Khi hoa tan m9t ch~t cAn luu y tOi r~t nhieu ye'u to': Ban chat cua chat
can hoa tan (cau tao cua chat d6), nhiet d9, moi truang ... C6 chat d~ tan trong
nude, c6 chat chi tan trong dung dich acid, dung dich kiem, hay tan do t~o
phac, nhieu chat kh6 tan hon phai cAn de'n phan ang oxy h6a khil (vi d\l: hoa
tan CuS b~ng HN03 c6 tinh oxy h6a: CuS + HN03 ~ Cu2+ + S + NO + H20);
d6i khi phai chuy~n sang d~ng d~ hoa tan hdn (vi d\l: BaS04 rat kh6 hoa tan,
nhung ta cho BaS04 tac d\lng voi dung dich bao hoa Na2C03se chuy~n thanh
tua BaC03 d~ hoa tan hon).
CAn luu y trong khi hoa tan khong dUQcdua vao dung dich nhftng chat
lam anh huong de'n phan ling ke't tua sau nay.

3.2. Ke't tua

Day la mQt dQngtac rat quan trQng, doi hoi phai dap ling dAydu cac yeu
cAu doi voj d~ng tua, d:;mgcan, d6i vdi thuoc tha d~ ke't tua va cac ye'u to' anh
hUdng den qua trinh ke't tiia.

3.2.1. Cac yeu cau dfli v(Jidgng tua va dq,ng can

V £Ii dg,ng tila:
_ Tua phai co dQtan nho (d~ ket tua hOftl1toan chat cAnxac dinh).
_ Tua phai d~ lQc,d~ rila (tua hnh th~ thu~n lQi hdn bdi d~ thao tac hdn
tua vo dinh hinh).
_ Tua phai chuy~n sang d~ng can m9t cach d~ dang va hoan toano
Vdi dg,ng can:
_ Tua phai c6 thanh phAn dung v(ji cong thtlc h6a h9C(c6 nhu v~y moi tinh
dUQcket qua, thua so'chuy~n F moi co y nghla).

133
 - Tua phai ben vitng.
- Neu m(>t chat xac dinh co th~ co nhieu dang can, nen chon dang .can nao
co thua so chu~~n F cang .nho clurg t6t. Vi du: .D~ xac dinh Cr = 52 trong
mku co th~ co hai dang can:
Cr203 co F, :::2Cr/Crz03;:;: 2.52/152 ~ '0,7
BaCrO'1 co Fz = Crl BaCl'04 :::521 254,4 .:::::
0,2
Gia 8ti trong <IUatrinh lam deu mat Irng dang can, th! khi tmh ~t qua ne'u
dung Crz03 lam dang can se mlft O,7mg, een neu dung BaCr04 chi ma"t O,2mg.
3.~.2.Cae yeu Cart do'i viii thuoc thit de'tCfo ku tila
- Thu6c thu d.n phai tao cac .tua tudng ling vdi cac yeu c~u cua dang tua
va dang can.
- Thuoc thu phai co tinh chon IQceao.
- Thu6c thu phai d~ loai b6 khi lee, ri1a...
3.2.3. Ch<;mcae diiu kifn ktt tua
Vdi tila tinh,thl
Sl,itlilothanh tua tinh th~ gam 2 giai qO[;ln:Hiiih thanh cac mAm tinh th~
va s\i Mn len eua m~m. Trong phan Hch kh6i hiQng dn lam ch~m giai dOliln
dAu va tang eUdng giai do~n sau b~ng each:
- Ket tua trong dieu ki~n dung dich loang, n6ng ...
- Cho thu6e thi1 ttt itt va khuay deu.
- Doi khi lue dAu them vao dung dieh mQt eMit lam tang dQtan eua tua, sau
d6 eho ihuoc thti hidng ling lam giam de?tan cua tua. Vi dl,l:'Khi ket tua
Ca2+ bilng C20l, hic dAu tie~ h8.'l1'htrong :moitrudng acid nh~ (d~ tang dQ
tan eua CaC204) sau d6 eho them NHPH (d~ giant dQtan eua CaC204).
- Lam mu6i tua.: d~ tua tiep xue lau vOl dung d!ch, cac tua be se tan ra, cae
tim ldn se to len.
Voi tila v6 dink kinh:
Tlla va dinh hinh dl1QC tlilothanh do sl,i dong tv cac dung d!ch keo .Vi v~y
e~n tifo dieu ki~n thu~n IQicho keo dong t\1 va ngan can qua trinh, pepti hoa.
Do v~y khi ket tua cAn:
- Co m;iit cua chat di~n ly mlilnh trong dung dich
- Dun nong dung djeh.
- Ke't tua tu dung dich d~e tlla se it x6p va l~ng nhanh hdn, nhtihg sl,i hap
phl,l chat bfln ding nhieu l1dn. D~,khiie phl,lc, tniac khi 19c eho them m!Oe
nang vao va khuay mlilnh d~ giai hKp phl,l cae chat bAn.

134
 --------

- Loc ngay, khong lam much tua d~ tranh hap phu.

3.3. LQC tua

Co thJ loc tua qua giay loc hoac pheu x6p.
" Giay loc:
Giay loc la loai giay d~e biet co d9 min thieh hQP. Thuong dung loai giay
loc khong tro, nghia la sau khi nung, kh6i luong tro con lai khong dang k~. Co
nhieu loai gifty loc khong tro duoc danh dau bang' mau siic h9P dung:
_ Giay bang xanhr.Rat min, chay cham, dung d~ loc cac tua tinh th~ nho.
_ Giay bang trang, bang vang: D9 min vita phai, t6c d9 chay trung binh.
_ Giay bang do: L6 to, chay nhanh, dung d~ loc cac tua vo dinh hinh.
Khi nung giay loc chay thanh than. Than tao thanh co th~ khtt m9t so'
chat khi nung. Trong truong hop nay, cAn dung pheu loc x6p thay cho giay loc.
Phiu loc x(/p (phiu x6p):
Lop xop min thay cho giay l<?cdUQcgl1n ngay vao day ph~u. Ph~u xop
dUQcdanh s61, 2, 3... so' eang tang, ph~u cang min.

3.4. Rita tiia

Dung dick rita tila (dick rita):
Yeu d.u phai ch<?ndich rtta tua co tinh chat lam giam d9 tan cua ke't tua,
chong l~i hi~n tUQngpepti hoa, ngan can qua trinh thuy phan, phai d~ lOE;li be,
khi sfiy ho~c khi nung.
Dich rda co th~ la chinh bim than thu6c thtt ket tua, la dung dich loang
cua chat di~n ly (vi dl,l NH4NOa), la dung dich acid ho~c base d~ ch6ng thuy
phan, ho~c cung co th~ la nuoc cat.
Crickrita:
Voi cling m9t th& Heh dich rtta t6i da eho phep thi rih lam nhieu IAn t6t
hdn 113. raa it Hin. Ret lu$.n nay dLiQCrut ra tit cong thuc:

An == Ao( Vo JIl (6.3)

V +Vo
Trong do: Ao: LuQng chat blln co ban dAu
An: lUQngchat bftn con IE;lisau n IAn raa
V: Th~ tich dich rua dung cho m6i IAn
Vo:Th~ tich dich rtta con IE;lisau m6i IAn
n: sO' IAn rua

135
 - ------- ----------------------_-"--_ ............... -------'-'--

Vi du: C6 100mI dieh rira, neu Vo ::: 1ml

Ri'ia 5 liln (V¢' 20ml) ~ As ::::Ao(1I21)5
Rua 10 It1n (V= 10ml) --~ AlO =Ao(1/11Yo
R6 rang AlO< A5: Voi 100mI dich rt1a, -chia lam 10 lan, luong chat b~n con •
lai it hen nhieu so vdi trudng hop rita 5_lAn. Ml}t khac, tit coug thirc ta thAy
ne'u Vo nho th! An cang nho. Do -d6 khi rita me;~lAn phili eho -dich rl'ia chay ki~t
mdi ch6ng 8.\1<:*.

8-.5. Say va nung-tiia

CiAy loc va tua da rlta sach phai dfi chay th~tki~t nude rai mdi c~n th~n
lfty ra khoi ph~u, g~p lai va d~t VaG trong chen nung da .nung de'n khO'i ht<;lng
kh6ng d8i. Ne'u chen co n~p ph:li ~y hd mgt ~hut -d~ kpi CQ lei thoat. :Mdldffu
-crin :dfi d nhiet dQthap d~-say cho kh6, giai 4o~n ~ay' khong du<;1C d~ nude va
tqa b~n lung tung ra .thanh chen. Khi tua dB.kh6, khong con giQt nude bam d
thanh chen thi t~ng nhi~t d-9d~ giay IQc chay thanh than (khong <t~giay 19c
chfly bung thanh ng~m rita). Cuoi ctilng nung tua d nhi~t a~thich hqp (khoang
15-30 phut) de'n khoi lU<;lngkhong ddi (khi gia tri hai IAn can ke'tie'p nhau sai
khac duoi O,5m.g).
CAn nho rAng mQt so' trl1dng h<;lptuy theo nhi~t dQ nung ma tua san
- ph~m cu6i cung (df,tngcan) co thanh ph~n hoa hQc khac nhau. Vi d\1 khi nung
CaC204·H20:
300-4000C
... CaCiO 4 + H20
(Dltng can)

-----.... CaC03 + CO + H20

(DE;l.ngcan)

CaO + CO2
(D~ng can)
3.6. Can
Truoc khi can, c~n cho k.et tua d~ng can vao binh hut Am khoang 20 phut
d~ dua ve nhi~t dQphong. Day la giai do~n clloi cung nhullg rat quan tr~mg d~
xac dinh kh6i lU<;lngcua tUa d d~ng can. Phai can tI'en can ph an tich co dQ
chinh xac ± O,OOOlg.
, ,.." .,,,.' --_.,
4. CAC THUOC THtJ' KET TUA
4.1. ThuO'c thit ke't tua vO-'cd
Bang 6.1 thong ke ca-cthuO'c thu. CQt 1 hi cac thuoc tptt VO cd dung d~
k6t tua cac ion trong cQt 2. Gac h<;lpchat trong ngo~c la df,tng can tudng (tng
voi ion do.

136

--- ------------------------------------------
 Bang 6.1. Thuoc thii vo CCI
Thtiocthti Nguyento dn xac djnh
NH3 (dung dich) Be (BeO). AI (AI203). Se (Se203). Fe (Fe203)' Zr (Zr02). Sn (Sn02)
.. _-_
... _ _----_._--,---------
... .. --,-,_.-----,--,--,--,------,,---"-------,.,_._--,--------------'-_-._-'
H2S04 Cd, Sn, Pb, Ba (d1l6i d~ng sulfat)
Mg (Mg2P207), AI (AIP04). Mn (Mn2P207),
• .~ _ ~, _ ..•..
_._~.__..
Zn (Zn
__ .._ .•_.__ •__ N-.- "_._"
2P207), Cd (Cd2P207), Bi (BiP04)
..__.._· _.·_·..•__ •.•
__._···
..··__···_
.._,..-·,·.__. _ _._ __ _ __ .._,.. __ . _

._-_ _. __ -
H2PtCI
.....
6
.... ...._ ..,---,......
K(K2PtCls). Rb. Cs (M2PtCI6)
_-_._--- ----.-----,.----- .....-.....--.-..-..----.--, ...... --.~---....-.-- ...-....... _ __ __ __ .._ _--_ .._._
....... . ........ .......... _ .... ...
,_._H2C20~
..,.. .._ .._ ..__ ._ ....._._~......_~_. __ .__...._.... Ca (CaO).
_.~._ ..__ ' ' ... Sr .._(SrO).
.__ ... Th ._........
(Th02) h_... _.._. ..._~_._ ...._~ __ ......._ .. '_-
AgN03 CI (AgCI), Br (AgBr), I (Agl)
.. "-...."".,,,,,,,,,,-,,.,,,,_._..,._--,_..._,,--,,--,."'-_.,,- ._,,_ .._"--,---,,--,,-,-,,----------"'-------------'---'---_. __ ._-----
Bang 6_2. Cho m(Jt 86 thu6e thu vo co mang tinh khl1 dung d~ chuyen
cac chat xac dinh ve dang nguyen t6 (dang can).
Bang 6.2. M¢t so chat khLtdung cho phan trch khoi 11IQng
Chatkhti Chatc4n X3C djnh
S02 Se, Au
H2NOH Se
SnCI2 Hg
H2C204 Au
Elif)lnphan Co, Ni, Cu, Zn, Ag. Sn, Sb, Cd, Bi

4.2. 'I'huoc thi'i ke't tua htru cd

MQt 80 thuoc thir hiiu co dU<;1C dung d~ ket tua nhieu chat vo co trong
phan tich khdi luong. Phan IOn cac thu6c thi1 nay tao hop chat ehelat it tan
trong nude vdi cac cation kim loai (bang 6.3).

4,2.1. tr« diem

- 'I'ao chelat ben vung vdi kim loai cho nen ket tua toan Iuong.
- Kh6i luong phan tu km nen vdi mQt luong it cua kim loai tao thanh khoi
lUQngldn ket tua.
.. - Nhieu thuoc th1'.thuu cd kha chQn lQc,chi ket tua v(ii mQt hay mQt sO'ion .
Khi chQn pH thieh h<;1pva them ch~t "che", tinh chQn lQcUmg len nhieu.
- Ket tua t~o thanh voi thuoe th1'.thuu cd thudng d~ xu ly hie lQc,rua.

4.2.2. Nhli!1C die"m

- DQtan eua nhieu thuoe thi1 huu cd trong nUdCrat thap gay kh6 khiin cho
qua trinh ket tua.

137
 -~-- -~.--.~-------~-----.-----'--

- Nhieu ket tua tao thanh khong cho ta mc}tdang can tOt vi chiing khoDb
6n dinh hie say kho. MQt 86 hi phan huy truce khi say den 'kh6i luong
khong d6i.
- MQt s61dn ket tua so nude n6i l¬ mbe mat, bam vao thanh thus tinh gay
kh6 khan cho viec tach tua khoi dung dich, •
Bang 6:3. MQl so thuoc thu ket tua -hilU co
Thuocthlt Chelat v~i .kim19'; .irng d')hg
H3C-c= N_,.OH
I H3C-C=N- MIn
H3C-C=N-OH
H:p-6=N/OH
Dimetylglioxim

8- Hydroxyquinolin
W O-Mln
Kat tua vaj nhj~u kim Io~i.Tach bang
each kj~m soat pH

£>!nh klc;1ngCo2t khi c6 m~t Ni2+ voj

Ittc;1ngleln

exNitroso p naphtol

O-~~,NO
ONH~ Tach cac ion (tach Fe va Ti -khoi AI)

Cupferron

HO
~~4f-rH2 I 1.1 Kat tua va djnh IlIt;1ng cac kim IOc;Ji
~ HO SH ro-~-C-rH2 nhom H2S .
Thionalid M/n- S

O)-COOH f)!oh..tl1Qngce. Cu, zn.u

Acid quinaldic

Ngoai ra trong dinh htQng cac ch~t hfru co nguoi ta con d.img nhieu thu6c
thu vo co hoac huu cd. Vi d\l:
- Acid silicotungstic cho djnh luQng mQt s6.alcaloid.
- Acid picric cho dinh luQng piperazin citrat ...
NQidung C\lth~ xem phAn ung d\lng.

138
 5. DANH GIA PHUONG PHAp PHAN rtca KHOI LU'QNG
Phan tich kho'i luong, cling nhu cac phucng phap phan tich th8 tich va
dung C1,l. co nhirng mat manh va m~t ye'u cua no. Chung ta danh gia phuong
phap nay thong qua m9t so tieu chi sau.
•
5.1. Phan t ich khoi ltiqng 18.mQt phuong phap phan t ich tn;t'c tie'p
Nhu da trmh hay (i muc 1.3.3, trong ph an tich kh6i luong khong c~n
chuan d6i chien. Dua vao khoi luong mAu da dung va khoi hrong ke't tua, tren
co sd phan ling hop thuc co th& tinh dU<;1c
ham luong chat c~n dinh luong trong
mftu. Nho do ke't qua phan tich noi chung co dQl~p lai tot, dQtin cay cao co th&
dung lam chuan d&danh gia cac phuong phap khac. Day chinh la uu di8m cua
phuong phap.
5.2. DQ nh~y eua phlidng phap
Trong phtlong phap khoi luqng, tht;lc te'dQ nhlilYhi gioi h~n lien quan den
kha nang tach mQt luqng nho ke't tua tit m<)t th& tich kha IOn cua mftu thii
chua nhi€u thfmh phftn khac. Ket tua hi mat do nhieu nguyen nhan:
- Do d9 tan cua ket tua,
- Keo tl,l kho khan do lUQngtua it,
- Do qua trinh 19Criia tua.
Do nhung nguyen nhan nay, nen ngudi ta thudng dung phudng phap
phal1 tich kh6i ltrqng cho cac thanh ph~n co n6ng d<)trong mftu tren 1%.
5.3. Tinh d~e hi~u
Ph an tich kh6i h.iQng dl,ia vao thuoc thii t~o ket tua. Thttdng thu6c thii
nay dung cho m9t nhom ion, nen cac ion trong cung m<)tnhom se can trd nhau
khi phan tich hling ket tlia. Vi v~y dung ve tinh d~c hi~u, phudng phap khoi
lUQngye'u hon cac phuong phap khac.
5.4. Dq dung
D<)dtmg ella phuong phap khoi htQng thay d6i tuy thuQc vao ban chat va
dieu ki¢n kElttua nhu: DQtan, d6ng tua, keo tl,l ciing nhu thanh phftn hoa h9c
cua d~ng can. Vi dl,l: Xac dinh s&t trong mftu phtm tich khong chua cac kim
lo~i n~ng co th~ chi ph~m sai 861-2%. Cling dinh luqng s&t nhung trong mAu
nhieu thanh phftn nhat la kim lo~i n~ng, sai s6 tang len nhieu do tua hj nhi~m
hfrn phai raa nhieu, mat tua s&t.
Nhin chung VOl mftu adn gian chi(t phan tich chua 1% trd len, phuong
phap phal1 tich kh6i lU<;lngco sai s6 thi(p hdn cac phuong phap khac khoang 1-
2~·o.Ve mQ,t thdi gian thao tac, vOi ll1<)tmftu ph an tich dung phuong phap khoi
hiQng kh6ng chiic chiin ati. cAn dai hdn cac phuong phap khac. Nhung khi s6
mtiu tang len cac qua trinh tua, i<?C, rU:a... se tieu t6n nhieu thdi gian. Trong
trudng h<;1pnay cac phudng phap chuftn aQ to ra uu vi~t hon.

139

- -----~ ---- ------------------~

. 6. MQT s6 lING DVNG CUA PHAN TtCH KH()I Ll1QNG
6.1. Xae djnh nu'oc ket tinh va nu'oc hUt .~m
• Duoc di~n Vi~t Nam co tieu chuan "giam khaT, lUring do sfiy kh6" trong
cac chuyen luan d~ xac dinh nude hut ~m..ho~c ea
m:toc ket .tinh va nude •
hut Am. Day la ph~ong phap phan tich khoi IU<;Ingtheo each lam bay hoi
gian tiep: Can IDQtlUQngnhat djnh m~-u thuec dem say ho~c lam kho d
binh.hut a:m d~ loai ho nude. Sau do can Iai mAu thuO'c suy ra ham IUQng
nude da mat di thee cong thuc 6.1. Vi d¥: Xac dinh "giam khoi luong do
say kho" cua cafein (1,3,7 . trimetyl xantin monohydrat) co cong thuc
=
CSHlO02N4.H20 212,21 dUQclam nhu sau:
Lay mQt chen can co nclp da say kho trong tu cho den khi co kh6i luong
khong d6i. D6 vao chen can mQt luong cafein (khoang 0,5g) sau do dem
can chinh xac (tu do xac dinh dUQckhoi hlQng mAu -cafein tn-toe khi say).
Md nclp chen can va d~t ca chen va nclp vao trong tu say va say d 100-
105°C trong khQang 30 phut. Sau do dung c~p lay chen va ncip d~ vao
hinh hut lim khoang 20 phut. D~y nAp chen can va xac dinh 4ti khoi
h1Qng. Can say chen can den kh6i lUQng khong d6i. Ap <!\lng cong thuc
6.1 tinh dUQc% thea mAu cafein.
Tinh theo dung cong thuc thi ham luQng nuoc ke't tinh trong cafein la
8,48%, nhung vi ngoai nuoc ke't tinh con co nudc hut Am. Cho nen BUQc
di~n Vi~t Nam cho phep % nuoe trong cafein toi da la 9%.
• Luu y d.ng, phuong phap tren chi ap d\lng cho nhung chat kh.i dem say
thi nuoc hi bay hoi, con cac thanh phfin khac khong d6i (khong hi bay hoi,
phan huy, khong bi oxy hoa, thuy phan ...) .
Trong trudng hQp ngani nuoc bay hoi, cac thanh ph&n khac hi bien·d6i ,vi
d\l NaHCOa khi say d 270· 300°C hi ph an huy nhu sau:
2 NaHCOa ~ Na2COS + CO2 + H20
Do do khO'ilUQngmat di khong chi co nuoc ma con c6 CO2, do do ta phai
dung phuong phap khac.

6.2. Djnh hiC!ngacid sulfuric va sulfat boa tan

6.2.1. Nguyen tdc

D:t;tatren phan (tng:
H2S04 + BaC12 = BaS04-1. +HCl

6.2.2. Die'u ki~n k€t tua

- BaS04 th\lC te' khong tan trong nuoe, nhung tan mQt it trong aeid d~c vi
the nen ket tua trong moi trudng acid nh~.

140
 - o nhiet dQthuong vdi ncSngdQvua phai ke't tiia BaSO 4 d dang hat rat nh6
d~ lot qua giay lQC.Cho nen thuc hien ket tiia trong dung dich loang,
nong va lam rnudi d~ thu duoc ket tua hat to hon.

.. - Tiia BaS04 hay hap phu mQt s6 chat (nhat Ii! khi dung dich co n6ng d9
tuong doi) do do phai luu y tranh hien tuong' nay.
- o 1400°C ket tiia bi phan huy theo phuong trinh:
BaS04 -4 BaO + S02
Do do nhiet dQnung khong qua BOO-900°C
- BaS04 d~ bi carbon (do giay IQechay) kh\:i thea phuong trinh:
BaSO" + 2C ~ BaS + 2C02
Sau do, BaS bi oxy hoa bdi oxy khong khi:
BaS + 02~ BaS04

6.2.3. Kj thugt dinh. lut;1ng

Lay chinh xac m{lt luong sulfat (khoang 0,12 - 0,20g) eho vao eoe to, them
200ml nude, 0,5ml HCI d~c (neu dung dich phan tich la H2S04 thi khong cho
HCI nita). Dun soi dung dich tren bep co lot Iuai amiant, vua khuay vua them
tung giQt dung djch BaClz (0,3 - 0,5N) eho den khi du khoang 15% so vai hiQng
sulfat dem dinh IUQng.Dun soi dung dich va tua (khong qua 10 phut), d~ Hing,
ki~m tra xem tua hoan tOEmchua. Dun cach thuy tiep khoang 1 giC1.D~ lAng,
sau do g~n miac trong d tren tua qua ph~u IQcco giay lQckhong tro. Rtta g~n
tua vai IAn b&ng nuac ca't ngu{li. Sat! chuy~n hoan toan tua sang giay IQc,rtta
tiep vai Mn tren giay lQcb&ng dung dich NH4N03 1%. Dem eEl ph~u co gia'y IQc
va tua say d 100-150°C khoang 30 phut. Khi giay con hoi Am, nhac gifiy lQcra
kh6i ph~u, g~p l~i d~t vao chen nung da nung den khoi IUQngkhong d6i (chen
da biet khoi lUQng).D~t chen nghi€mg d bep di~n va dot cho giay lQcdot thanh
than (kh6ng cho chay thanh ngQn !ita). Dem nung chen co tiia trong 10 nung d
600 - 700°C khoang 30 phut. Dung c~p dua chen nung vao binh hut ftm d~
khoang 20-30 phut. Can xac dinh khoi lUQngtren can ph an tich. L~p l~i thao
tac nay cho den khi khoi lUQngchen va tua khong d6i. Tinh kat qua:
2- Kh6i luqng d<;lngcan. 0,4116
% S04 = " _ ., x 100
Khot h.rqng mau thu
Trongdo F = SOt/BaSO,! = 96,06/233,10 = 0,4116
6.3. Dinh IU'cJngdung dich NaCl

6.3.1. Nguyen t&c

Dl;ia tren phan (tng ket tua

141
 AgN03 + NaCl= AgGI..!,+ NaNOa
(Dang tua)
Sau khi loc Ia'y ket tua, raa, sfiy ta thu diroc dang din AgCl.

6.3.2. Kj thug,t djnh IUfjng

Lay mQt th~ tich chinh xac dung dieh cAn dinh lueng (tudng (tng khoang
0,15g NaCI) vao c6c, them nude den \khoa~g 70ml, them tiep Ifiml HNOa 2N,
Dung diia thuy tinh vita khuay manh, vita them tit tit khoang 50ml AgN03
0,IN (du khoang 18% so vdi luong' Cr). Dem dun each thuy va khuay deu
khoang 19id. Sau d6 d~ lAng ch6 t6i khoang' 3-5 gio. Ki~m tra xem tua hoan
to an chua,
Chuan bi s~n mQt ph~u loc x6p so 3 hay so 4: Rita bAng dung dich HNOa
loang, n6ng (2-3ml HN03 2N/100ml), sau d6 rita. lai bAng nude n6ng, say d
130°C den kh6i Iuong khong d5i, xac dinh chinh xac khdi luong ph~u loc xop.
La.p ph~u loc x6p da chuan bi tren vao binh hut chan khong va IQctua.
D~u tien rot ph~n nuoc trong tit c6c co ket tua AgCl vao ph~u IQc,rita viii l&n
bAng dung dich rita HNOaloang, n6ng (dung khi rtta ph~u IQC).Cu6i cung cho
ket tua vilo ph~u IQc,rtta tiep tua b~ng HNOa loang, sau bAng nudc cat. Say
ph~u lQc d 130°C trong khoang 2 gid, d~ nguQi d binh hut Am. Can xac dinh
khoi htQng chinh xac cua ph~u lQcxop co tua AgCI (nho say l~p l~i cho den khi
kh6i IUQng khong d6i). Tit do tinh ket quit Vi d\l co th~ tiIih sO gam Cl" c6
trong 11it dung djch dem djnh IUQngnhu sau:

P gil= K.h6i lU<1llgd~ng can AgCl thu duqc

The dch dung dich dem dinh lU<1llg x 0,2473 x 100
Trong do F = Cl"/AgCl=35,5/143,32 = 0,2473

6.3.3. Chu y
- Tua AgCI khong ben, d~ ra anh sang bj phan huy thEmh Ag (luc dAu tua
trAng --t tim --t den dAn).Vi v~y khong nen d~ lau tua (j-anh sang khuech
tan ho~c tiep xuc tr\1c tiep voi anh sang, tot nhat nen bQc c6c dl,'lngtua
b~ng mQt to giay den.
- Neu khong co ph~u IQcxop so' 3 hay 56 4 co th~ lam nhu sau: Lay 2 giay
IQcco cung dQ min, gap lam tu, mQt giay lQcdem c:it phAn nhQn cua giay
sau khoang lcm, sau do dem can kh6i lUQngtitng giay. Ghlstt:
+ Giay lQccAt goc can dUQc
+ Giay IQckhong cAt goc can dUQc m2 gam.
Sau do dem 16ng 2 giay IQcvao nhau (gi~y IQccAt goc d~t ngoai) r6i d~t
tren pheu lQcd~ IQClay tua. Khi say ket tua d~ng can ta say ca 2 giay. Gia sl:J.
IAn can sau khi say:

142

-----------_._---_---
 + Giay 19Cd.t goo can duoc m, gam
+ Giay 19Ckh6ng dt goc(c6 tua dang can) duoc m, gam
Khi do kh6i luong dang can AgCl thu duoc = (m 4 + m, . m 2 - m3) gam.

6.4. Djnh hi<Jng thuoc t iem vitamin B,

Vitamin B, (thiamin hydroclorid CI2HCIN40S.HCl) co kha nang tao ket
tua vdi acid silicowolframic, do d6 co th~ dinh IUQngbang phuong phap phan
tich khoi Iuong thea quy trinhsau:
Lay chinh xac mQt IUQng dung dich tiem vitamin BI (tuong ung 0,05g
thiamin hydroclorid) vao c6c, them khoang 50ml nude, 2ml dung dich HCl d~c,
dun sci, cho them lien tuc tung giot va khuay deu dung dich acid
silicowolframic 10% (vua mdi 19ckhoang 4ml). Tiep tuc dun soi trong 4 phiit, 19C
nang qua pheu thuy tinh x6p sO'4 (da xac dinh kh6i Iuong truce) d~ lay tua
silicowolframat. Rita tua vdi 50ml h6n hop dang soi g6m 1 th~ tich acid HCl d~c
va 19 th~ tich dung dich acid silicowolframic O,2%(mlV). Sau d6 rita tiep 2 l~n
bAng aceton (m6i Mn 5ml). Say kho tua d 100·105°C trong 1 gid, d~ nguQi 10
phut d binh hut Am (chua dung dich H2S04 38% (mN) trong 2gid r6i can. L~p
l~i thao tac nay cho den khi dUQckh6i IUQngkh6ng d6i. Tinh ket qua. Luu y
thua sO'chuy~n F = 0,1929 (lg d~ng can tUdng ung 0,1929g C12HCIN40S. HCl).

cAu HOI vA BAI T~P

6.1. Trinh bay nQi dung va cach ph an lo~i cua phudng phap phan tich
kh6i IUQng.
6.2. Giai thich cac dQngtac cd ban cua phudng phap ph an tich kh6i lU<jng.
6.3. Minh h9a kha nang sit d\1ng mQt s6 thu6c thu thudng dung trong
phtm tich kh6i hi<;lng.
6.4. Danh gia Uu nhu<;Icdi~m cua phudng phap phan tich kh6i hiQng.
6.5. Khi xac dinh Cr trong m§.u phan tich bAng phudng phap phal1 tieh
khoi IU<;Ing,c6 th~ dung 2 d~ng can Cr20a va BaCr04• Hay cho biet
dung d~ng nao t6t han.
6.6. D~ xac dinh SO/' c6 trong 100mI dung djch phan tich ngudi ta cho
vao d6 mQt IU<;IngBaCl2 du. L9C, rita s~ch, nung ket tua den kh6i
h1Qng khong d6i can dU<;Ic0,3029g. Tinh n6ng dQ gil eua SOl trong
dung dich.
6.7. Lay 0,4000g h6n h<;lpg6m (MgS04, NaCl, Na2S04) hoa tan trong
nuoe, tien himh ket tua hoan to~m Mg2+duoi d~ng MgNH4P04. Nung
d nhi~t dQcao den kh6i lUQngkhong d6i thu dU:QcO,2342g Mg2P207'
Tinh % MgSO 4 tinh khiet c6 trong h6n hQp.

143
 -_ ............ _----- ~-. _._ ...

Cho Mg = 24, S = 32, 0 =16, P = 31

6.8. Boa tan 1,1245g m~u thuoc c6 chua Fe sau c;i6lam ke't tua dtloi dang
Fe(OH)3 bang dung dich NaOH. Loc, nia ket tua va nung tua d' nhiet
dQ800°C d~ chuyen thanh Fe203, khOlltl<;1ngthu duQC13.0.S412g..Tinh
% Fe trong m~u thtt.
6.9. Can 1,053g h6n h<;1pgam (Ca'Cl, + Ca(NOa)'2) dem hoa tan va cho
phan (tng ke't tiia vdi dung dich H2~204 du d~ thu -duoc ket tua
CaC204• LQc, rtta ke't tua, lam kho va nung den kh61luqng lthong:d5i
thu duoc O,3872g CaO. Tinh % m6i muO'itrong h6n hQP.

144
 -- ------------------

Chuang 7

. CUONG VE PHUONG PHAP CHUAN eo.

",' , ~,jIIt,

eAI

1'\ .J , , ","'I '"

1. NGUYEN TAC CUA PHUONG PHAP CHUAN DQ

1.1. Nguyen tAc

Phuong phap chuan dQla phuong phap xac dinh ham luong cac chat dua
tren viec do th~ tich dung dich thu6c thu dB.biet n6ng dQchinh xac duoc them
til til vao dung dich can dinh luong cho den khi phan ung vua du vdi toan be?
luong chat cfin xac dinh, Til th~ tich dB.dung cua thuoc thir, nguoi ta se tinh
ra duoc luong chat can phan tfch. Dung dich thuoc thu duoc goi la dung dicb
chudn.
Qua trinh them tit tit dung dich chuan bang buret vao dung dich cua
chat cl1n dinh hrong goi la si: chudn dq. Cling c6 khi nguoi ta lam nguoc lai:
dung dich can dinh luong duoc rot vao buret.
Thai di~m tai do ta ket thuc chuan dQgoi la diem kef; thuc. Can thdi di~m
rna thu6c thu ph an ung vita du v{ji chfft dn dinh lU<;JnggQi la diem tztdng
aztdng. Thong thudng 2 di~m nay khong trung nhau, nghla 18.lU<;lng thu6c thit
dB.tieu th\l khong tUdng duong v{jilU<;Jng chat cfin xac dinh. Vi v~y, phuong
phap chuAn dQmiic sai sO'.
D~ nh~n biet di~m ttiong duong, ngudi ta thudng su d\lng nhung chat co
kha nang gay ra cac bien d6i d~ quan sat bang m&t nhu: s1.1d6i mau, st,i ket
tua ... xay ra rat gfin di~m tuong duong. Nhung chat do dU<;lc
gQila chat chi tht.

145
1.2. Yeu Call cua phan iing hoa h9C dung trong chuan de?

Nhtrng phan ung' h6a h9C dung trong phuong phap chuan dQ d.n thoa
man cac yeu d.u sau:
1. ThuOc thti dB.chon phai phan ung hoan toan vdi chat efin dinh luong theo
l1'lQtphuong trinh phan img, nghia Ia theo mQt ty l~ hop thuc xac dinh.
2. Phan ung 'Pliai di~n ra nhanh. V(ji cac phan tmg cham, d.n lam tang
t6c dQcua chung bang each: dun n6ng, them chat xuc tac thfch hop,
3. Phan (thg phai chon 19C,nghta la thu6c thti chi tac dung voi chat cAn
dinh IU<;Jng,khfmg phan tmg vdi bat ky chat .nao khac (khong c6 phan
(tng phu).
4. Phai c6 chi thi thfch hop d~ xac djnh di~m tuong dUdng eua phan ung
chudn dQv(ji sai sO'chap nh~n dUQC.
.I> . " ,,~

2. CAe PHlJ'ONG PHAP XAC DINH DIEM TUONG DUONG

2.1.Dii~ tu'~.ngdlidng
Nhu tr~n dB.trinh bay, trong qua trinh ehu~n de?di~m tudng dUdng ung
v{:jithdi di~m lu<)ng thu6c thti cho vao phan ung vita du voi toan be?luQng chat
c~n dinh lu<)ng.Noi cach khac, khi sO'mol dtidng hl<)ngthu6c thti cho vao b~ng
sO'mol dUdng h:lQng chat cAn xac dinh, thi ta n6i h~ d~t toi di~m tUdng duong.
Vi dlJ: Trong chu~n de?HCl b~ng NaOH

HCl + NaOH = NaCl + H20

khis6 mol dUdng lUQngcua NaOH dB.dung bAng sO'mol dudng lu<)ng cua
HCl, trong dung dich chi co NaCl va H20, pH cua dung dich b~ng 7 ung voi
di~m tUdng chidng.

2.2. Di~m ket thue

Trong phlm ilng chu~n de?HCI d tren, ta dUng chi thi d~ phat hi~n di~m
tUdng duong d pH bAng 7. Luc ta ngiing chuAn de?g9i la di~m ke't thuc. Ne'u
dUng chi thi la ·phenolphtalein thi khi chithi chuy~n mau pH b~ng 9, ta ke't
thuc dinh h:tQngsau di~m tUdng dUdng (ne'u NaOH d tren buret). 81,isai khac
giua di~m tuong dudng va di~m ke't thuc gay ra me?tsai sO'h~ th6ng g9i Ia sai
se/chi thj. Vi v~y, cAn ch9n chi thi sao cho sai sO'chi thi n~m trong ph~m vi cho
phep va sai sO'nay dmg nha cang t6t.

2.3. Cae phu'dng phap xac dinh di~m tlidng dlidng

Trohg th¥c hanh co 2 nh6m chi thi dUQcdung d~ xac dinh di~m tUdng
dUdng eua phan (ip.gchuAn de?la.: dung chat chi thi hoa h9c va. dUng thie't hi do
ludng.

146
"

2.3.1. Chat chi thi hoa h9c

Do la cac chat dugc cho vao dung dich phan tmg. Khi phan trng de'n glin
di~m tuong duong thi trong dung dich co sl;lbien d6i dQt ngQt nao do nhu: bien
d6i pH, bien d6i v~ the oxy hoa khtt ... lam eho chi thi d6i mau, lam mat mau
hoac xuat hien ket tua. Nguoi ta thuong dung mQtsO'loai chi thi sau:
- Chi th] mau: co th~ dung chi thi don (mQtchat) hoac chi thi h6n hop (g6m
2 den 3 chat). Cach dung cung thay d6i: co th~ cho vao binh chuan dQ(chi
thi nQi) hoac d~ ngoai lay dung dich phan {lng cho tac dung vdi chi th]
(chi thi ngoai).
- Chi thi due: tao ket tua.
- Chi thi huynh. quang: phat sang hoac tAt sang.
- Co truong hop khong clin dung chi thi vi ban than dung djch chuan la chi
thi. Vi d\l voi dung dich chu~n permanganat khi qua di~m tUdng dUdng,
1 giQtthu6c thtt thua se lam dung dich co mau h6ng nh~t eua KMn04'

2.3.2. Thiet bi do luilng

T~i Ian c~n di~m tUdng dudng, trong dung dich co th~ co sv bien d6i dQt
ngQt cua ffiQt tinh chat v~t If nao do nhu: dQhap th\l anh sang, di~n the, dQ
d~n di~n, cUdng dQdong di~n... Do do co th~ dung cac thiet bi do IUdngd~ xac
dinh di~m tUdng dUdng. Dola cae phudng phap:
- Chudn d9 do the':co buoc nhay the (J di~m tUdng dUdng
- Chudn d9 ampe: co buoc nhay cUdng dQdong di~n d di~m tUdng dUdng.
- Chudn d9 d9 dan: co huoc nhay dQd!n di~n d di~m tUdng dUdng.
- Chudn d9 do quang: co buoc nhay dQhap th\l h{lcx~ d di~m tUdng dUdng.
Ngay nay, voi sl;lket hQp cua cong ngh~ va tin hQc,nhigu hang san xuat
thiet bi do ludng. nhU Metrohm, Radiometer ... da cho ra ddi cac may chu~n dQ
hoan hao. Qua trinh chu~n dQdUQcthljC hi~n hoan toan tt.i dQng (bao g6m ca.
vi~c xtt If sO'li~u va thong bao ket qua).

..
3. PH.AN LOAI cAc PHUONG PHAp CHUAN DO.
Thudng nguai ta phan lo~i citc phudng phap chufin dQtheo ban chat cua
ph an {lng chufin dQ. ..

3.1. ChuAn d9 trung hoa

Phudng phap chu~n dQnay dlja tren phan ung giua cac acid va base.

3.2. ChuAn d9 t~o phiic

Dl;latren ph an {lng t~o phuc chat giua chat cAndinh IUQngvoi thu6c thtt.
PhUdng phap nay dugc dung d~ dinh lugng hAu het cac cation kim lo~i va mQt
so' anion. Thu6c thti ph6 bien nhat co ten chung Ia eomplexon.

147

-- --- .. _--------------------
 3.3. Chuin d_Qoxy hoa }thit'

Phuong phap nay dua tren. phan (tp.g cho nhan electron giua mQt cha't
khu va mqt chat oxy 1)00. Nhieu thu6"c thu duoc dung d~ dinh htc;lnghAu he't
cac chat vo co va mQt sf) chat.huu co.
3.4. Chu&n dQ ket t-i'Ia

Phuong phap nay d\ia tt_en phan ung tao ke't tua gitra thu6c thu' va chat
dn dinh luong. Tuy soluQng die phan (tng tao ke't tua kha Ion nhung da sO'
cac phan itng do hoae di~n ra cham hoac khong co chi thi thich hop nen viec ap
d\ll1,l; phuongphap nay bi han che.

4. cAe KY THU~T CHUAN DO

4.1. ChuAn dQ tryc tie'p

D6 la truong hop cho thh6c thtt va chat cAn dinh luong phan ung vdi
nhau vottadu. Dl,1avao th~ tlch· va n5ng dQ cua dung dich thu6c thii d~ tinh
toim lu~ng chat c~n dinh llic;lng.
Vi dy,: D~ d~hh lli9ng mQt·dUl).g djch NaCI b~ng phliong phap Mohr,
ngl.idi ta cho dung dich cha't chufln d9 AgN03 van dung dich cho de'n khi chi thi
chuy~n mau.

4.2. ChUlln d? ngli(lc (chuAn dQ thiiatrii)

Them m9t th~ tich chinh xac va du dung dich chuftn va~ dung dich cha't
c~n dinh lUc;lng.Sau do xac dinh ltic;lngdu eua thu6c thii b~ng m9t thu6c thii
khac thieh hc;lP.D\ia van th~ Hch va n6n:g dQ eua hai thu6c thu ds. dung eung
voi phan (tng chua:n dQd~ tfnh lli<;1ngchat c~n dinh IU<;1ng.
Vid¥: D~ dinh llic;lIlgelarid, ngUdita cho du AgN03 d~ ke't tua hoan toan AgCI:
AgN03 (du) +-CI" '.~' AgCl + N03"
Sau do chuAn dQphAn du cua AgN03 b~ng KSCN
AgN03 (con lai) + SeN' ~ AgSCN + N03:
Ky thu~t nay thl1dng dVQc;dung cho cae phan (tng chuAn dQdi~Ii ra ch~m
ho(lc khortg co chi thi thich hqp.
4~.Chu~ndQthayth€
Cho cha't cAn dinh luq,ng X tac dl:1ngvoi mQtthu6c thii R thich h<;1pd~ t~o
• • 0

ra san pham P:
X+R ~ P (7.1)
Sau do chu[\n dQPMng mQt thuoc thii khac R'. D\ia van th~ tich va n6ng
dQeua R' d~ tinh h.tQngcha't X.

148
 ._------------""- ~ _._- _._ ..

Vi du: D~ dinh hrong K2Cr207, ngudi ta cho hop chat nay tac dung vdi KI
du d~ giai phong mQt luong tuong duong iod. Dinh luong iod giai phong bang'
Na2S203' o day dinh Iuong K2Cr207 dl1Qcthay the b&ng dinh luong iod.

5. cACH PHA CHE DUNG DICH CHUAN

Phuong phap chuan dQ - con duoc goi la phuong phap hop thuc - thuoc
nhom phuong phap tuyet dO'idung eh~t chuan. Do la co sd xac dinh tinh lien
thong cua phuong phap nay. Trude khi thao luan vg each pha ehe dung dich
chuan, ta xem xet yeu eftu cua mQt chat chudn. - con goi la chat gac - dung
trong phuong phap chuan dQ.

5.1. ChB:tg6c
MQt ch~t duoc dung lam ch~t goc trong phuong phap chuan dQ cftn dap
Ung dUQC4 yeu cftu sau:
1. Chat do phai thuoc loai phan tfch hoac tinh khiet hoa h<;>e,lUQngtl;tp
chat co mq.t trong no phl3.iduoi 0,1%.
2. Thanh phftn hoa h<;>c
ung voi mQt cong thuc xac dinh k~ ca ham luQng
nuCicket tinh.
3. Chat gO'cva dung dich pha che tit no (dung dtch gac) phai ben vung.
4. Khoi lUQng mol phan tii cua chat do cftn du lOn, cang IOn dmg t6t d~
giam sai sO'khi pha che dung dich g6c.

5.2. Pha che dung dich g6c

Dung dich g6c dUQcpha ehe tit ch~t g6e. Can mQt luqng chinh xac chat g6c
tren can phan tich, hoa tan va dinh mue thanh th~ tich dung dich xac dinh.
Vi dl!: D~ pha che dung dich goc Na2C03 O,lM ta cftn can 106,000xO,1 =
10,6000g chat do hoa tan va dinh muc thanh 1 lit dung dich.

5.3. Dung dich chuii'n

Ne'u dung dung dich gee dem chufrn d9 thi dung dich gee do la dung dich
chuftn.
Neu chat da chQn eho ehu~n dt? kh6ng thoa man 4 yeu cftu eua chat gee
da neu - We la ta khong co chat g6c - thi truoe het ta pha mQt dung dich co
n6ng dQ gc1ndung, sau do dung dung dich goc hay mqt dung dich chuAn khac
thich hQp d~ xac dinh ll;tin6ng dq.
Vi dl;l;NaOH d~ hut nuClc,d~ bi carbonat hoa, khong th~ la chat gee. D~
pha dung dich chu~n NaOH ta can mqt luQng xut, lo~i bo lOp cacbonat d ngoai
va hoa tan thanh dung dich co, n6ng dq g§.n dung. Dung dung dich goc acid
oxalic (H2CZ04.2HzO) d~ xae dinh ll;ti n6ng dQ cua dung dich NaOH vita dUQe
pha ehe.

149
 ~ ~ "..~ ? ... ,. ,•.?_ .....
6. eACH TINH KEj QUA TRONG PHI1(jNG PHAP CHUAN DQ

6.1. Quy t~c churig

Trong phuong phap th~ tfch, ta ke't thuc chu~n dQtai Ian can di~m tuong
duong, (j do sO'mol duong' luong (hay so
milimol duong' luong) thuoo thl1 bang
so mol duong Iuong' (hay so milimol duong hiQIlg)cb.at can xac dinh.

6~~.Tinh 'ke't qua theo nang de? dlidng lu'gng. thuoc thi't
C62 trudng' hop thtidng g~p:
- La'y VB 1111dung d!ch chat B c6 n6ng ..dQ NB dem ehuan dQ tai di~m ket
thuc het VA rnl dung -dich chat A co n6ng dQN A' ta co:
VANA = VaNB (7.2)
d day chat Ela chat cAn <Will ltiQngva chat A la chat d~ pha dung dich chuan.
Tit cong thuc tren, ta tinh duoc n6ng d9 duong .Iuong chat cAn xac dinh
- NAVA
N.B---
VB
P gIl =NBEB (EB: kh6i luong duong luong chat B)
Tit day ta tinh dti<;lC

P gl I = N",VA E (7.3)
VB B

Ta cung co th~ tinh cac n6ng d9 CM, C% (kl/ tt) bang cac lien h~ da hiet.
- Can a gam chat A hoa tan thanh dung dich ;r6.ichuAn d9 het VB mi dung
dich chat B c6 n6ng d('lN B , ta c6:

(EA: kh6i hi<;lngdUdng lti<;lngchat A)

d day, chat A la chat goc tinh khiet va chat B Ia dung dich cAn dinh
hi<;lng.Tit do ta rut ra:
- a.lOOO
N s- (7.4)
EAYB

Khi hiet NB d~ dang tinh dU<;Ie

cae n6ng d9 CM'P gIl, C% (kl/tt)
Trong trudng h<;lpta, can m gam nl9t mAu thl1 cAn xac dinh h<;lpchat tinh
khi€t va dinh lU<;lnghet VA mi dung dich chuAn co n6ng dQ NA, ta tinh ham
h.t<;lngh<;lp·chat tinh khiet B thea C% (kll kl): .

150
 C% (kIf kl) = N AVAE B 100 (7.5)
1000 m
(Eg: khdi Iuong duong IUQngchat tinh khiet B)
j
Nhimg each tinh tren day ap dung khi chuan d(>true tiep hay chuan d(>
the, con khi chuan d(>nguoc ta tinh nhu sau:
Gia S11!flYVB ml chat can dinh IUQngB them VA ml dung dich chuan A
co n6ng dQ NA, (dung dich chuan A cho thua), chuan dQchat A con lai het Vc
ml dung dich chuan C co nong' d(>Ne. Nhu v~y, chat A phan ung vdi 2 cha't B
va C sO' milimol duong IUQngchat A phai b~ng t6ng s6 milimol duong IUQng
cua ca 2 chat B va C:
NAVA= NBVB+NeVe
hay NBVB = NAVA-NeVe

- NAVA-NeVe (7.6)
NB-
VB
Khi tinh C% (kll kl), ding ly luan tuong tu, ta co
C% (kIf kl) = (NAVA - NeVe)E B 100 (7.7)
1000 m

6.3. Tinh ke't qua theo de?chuan cua thufic thi'i

Ta dii biet, dQ chuan T cua mQt dung dich bi~u thi IUQng cha't do tinh
bang s6 gam chua trong 1ml dung dich; co 2 truong hop:
• Neu co m gam mAu thir, c~n xac dinh hop chat tinh khiet va dinh luQng
het VAml thu6c thi'i co d(>chu~n TA, lUQngchat A tham gia ph an Ullg la
TAVA-Ta tinh dUQcham lUQnghQp chat tinh khiet B theo C% (kIf kl):

(7.8)

EA: kh6i lUQngmol dUdng lUQngchat chu~n A,

EB: kh6i lUQngmol du<1nglUQngchat tinh khiet B.
• Neu lay VB ml m(>t dung dich va dinh lUQng het VAml thu6c th11 co d(>
chu~n TA, ket qua dUQCtinh ra P gfl theo cong thuc:

(7.9)

151
6.~. H~ so hj~u chinh

Trong qua trinh tien hanh dinh hi<;lng,ta con dung h~. s6 hi~u chinh 4~
tfnh ket qua. H~- so hieu chinh chung to n6ng d~ thuc cua dung dich Idn hon
hay linD hen n6ng dQ ly tbuy€t bao nhieu IAn.

K ==
C
hay K ==
T
_0_
___!!!_ (7.10)
Gil' ~I

• Vi du: M9t dung dich NaOR 0, l012 N 06 th~ viet Ia NaOH O,l;OOON
K = 0,1012 = ID12
0,1000 '

Tinh h~ sO'hieu chinh khi pha cac dung dich chuan theo m9t trong hai
phuong phap sau day:
1. N6u ctin. mot luang chelt g{/c, tinh K theo cong thuc:

K = _!!_ (7.11)
TV
a : luong can ch8\'tgO'c,
T: dQchuan 1ythuyet cua dd tfnh theo chat goc,
V : th~ tich dung dich cAn dinh IU<;Ing
Trang cong .thue nay aN chfnh la T thuc (Tth), con T chfnh 18.TIt, ta lai co
cong thuc 7.10.
2. Neu la'y me?tth~ tich dung dich gfic, tJnh theo

K=Vo K (7.12)
V D

V 0 : th~ tich dung djch goc,

V: th~ tich clung d~ch cAn dinh luting,
Ko : h~ 'SO'hi~u chl'nh cua chfnh dung- dich goc.
Trong th\ic hanh phan tich, dung h~ so hi~u chinh c6 nhieu l<;1iich.Th~t
v~y, khi pha dung djch gO'ctit ffie?tchatgO'c, bao gid ciing phai tinh toan tntoc
h.1qngly thuyet (alt) cua chat g,6c.Khi can vi ly do nao do c6 th~ lli<;lngcan tht,tc
te' (ath) chi xap xl' b&ng alt' ta tfnh dUQcK nhtt sau:

va c6 th~ tinh nhanh n6ng de?th\lc 'dung dich goc:

Nth = Nit .K (7.13)

152

._. - .._-.----~---.~----------
 Ta biet dng cac dung dich chuan sau m(>t thoi gian bao quan, do nhieu
yeu t6 anh hudng, n6ng d(> bi thay d6i di. Mdi khi su dung lai, c~n ki~m tra
n6ng de), hie do khong nhat thiet phai dieu chinh cho dung 0, IN rna co th~ ghi
n6ng de) ly thuyet kern thea K, vi du: Hel 0, IN, K 0,998. = .
6.5. M{lt so di~m c~n Iuu y khi lam vi~c vdi cac dung djch chudn
• Dung cu dong do thong thuong duoc san xuflt vdi dung tich xac dinh d
nhiet d(>nhat dinh. Nhung do ky thuat san xuat, do thdi tiet nen khong
tranh khoi co sai lech. Vi vay c~n phai ki~m tra dung tich cac dung cu do
truce khi tien hanh dinh luong, Mu6n ki~m tra, ta can m(>t dung tich
nhat dinh nude cflt da ghi tren d\lng C1,l,b6 sung m(>t s6 hi~u chinh da
tinh sAn d nhi~t de)tUelng ung, tit do co th~ tinh dU<;1C dung tich th\1e cua
d\lng C1,l.Cac yeu to' anh hUdng, cac s6 hi~u chlnh tUelngung va eaeh hi~u
chinh cae IOf:l.id\lng C\l thong d\lng da dU<;1Cgioi thi~u chi tiet trong tai
li~mth\1c hanh.
• Tflt ca
cac eong thuc da nim d cac m\lc tren deu co th~ dung voi h~ so hi~u
chinh K neu n6ng de)khong dung thea ly thuyet, vi d\l:
(7.14)
• Khi tinh ket qua dUelng IU<;1ngtrong cae chuyen lu~n eua Dti<;1C di~n,
thudng ngudi ta ghi ro 1 ml dung dich chu~n A 0, IN ung voi b gam ch~t
c~n xac dinh. Loi tinh do cho ta ket qua tr\1C tiep, deln gian nhung luon
nho r~ng khi dung dich chu~n eo h~ so' hi~u chinh K, ta dn nhan ket
qua voi K.

6.6. M{lt so vi d\l

Vi dl,ll:
Tinh n6ng de)ph~n tram natri tetraborat (Na2B407.10H20) co trong m~u
borat dem thl1, biet d.ng khi dinh lti<;1ng0,2298g borat da tieu th1,lhet 10,6ml
HClO,1060N
Giai: m = 0,2298g
M 381,42
EB =ENalB.O,IOfllO =2= 2 =190,71
NA == 0,1060
VA == 10,6
C% = N.l'AE/i 100 = 0,1060.10,6.190,71 100 == 93,3%
1000 m 1000 0,2298
Vi d~(,__2:
Tinh lti<;1ngH2S04 nguyen chflt co trong 1 lit dung dich acid sulfuric, biet
ding dem d!nh luqng 25,OOml dung dich nay tieu th\l het 21,7ml NaOH
O,1012N.

153
 Giiii:

VB= 25,00 ml VA= 21,7 ml

EB =A9,{)4 NA= 0,1012

P gIL ::: VANAES

-,- ,-,g - 4-3'1- IL'
-- 21,7.~O,1.r0i12.49.,04
VB 25 '

Vi du. 3:
"I'a pha dung dich natri tetraborat xap xi O,IN bAng Call chtnh xac
18,.8392g hoa trong 1 lit nude, Sau d6 dung dung dieh nay d~ dinh lu<)ng 1
dung dich ReI va thu du<)c ket qua-IS. 24,9 ml natri tetraborat tuong ung 25.2
miReL
Tinh h~ s6 hieu chinh Kborat va n6ng dQduong luong NHcl•
Giai:
E Na,8p,.lOHlO :=190,71
- Tinh KbGrat, ta biet: K
borat
= all!
alJ
= 18,8392
19,.07l{)
= °
,
9879

- Tinh NHCI' ta biet: VA'=- 24,8 ml.va VB= 25,2 ml

N HCI = .N A KAVA = 0,lxO,9879x24,9 = 0,0977
VB 25,2
Vi du. 4:
Can chinh xac O,7500g dil vdi, cho.tac dung vdi 100,Oml HCI 0,1 N, dinh
lUQng 'acid thua b~ng 20,Ooml dung dich NaOH c6 n6ng dQ duong luong
0,I054N. Tinh ph~n tram CaO c6 trong da voi.
Gitii:
56
Ec a0 =-:= 28 m > 0,7500 g
2 '
VA:;: 100,0 ml ;
v; :::20,00 ml; Nc = 0,1054
x = (NAVA - NcV,dEg 100
1000 m
X _ (N HCIVHCI - N Hq.{)HVNaOH)ECDO 100
CaO - 1000. m
X = (0,1.100- 0~1~051.20)28 100 = 795%
CaO 1000 0,1500'

154
 ..... ') " " A

CAU HOI VA SAl T~P

7.1. Phan biet di~m tuong duong va di~m ke't thuc, dung dich goe va
dung dich chuan.
7.2. Gild thich vai tro cua chat goe trong phuong phap chuan dQ, cac yeu
c&ud.n dap img ella mQt chit goe.
7.3. Trinh bay each hieu chinh dung tich mot binh dinh muc 100,Oml va
mot pipet 25,0 ml.
7.4. Giai thich qui tiie chung cua viec tinh toan ke't qua trong phuong
phap dinh luong.
7.5. Tinh ndng dQ mol cua dung dich KOH neu 0,5480 g chat g6C kali
hydrophtalat (KHCgH40J phan img vua du vdi 25,41ml dung dich KOH.
7.6. Chat goc tris-(hydroxymetyl) amino methan thuong viet tiit THAM
hoac TRIS (M=121,14) duoc dung d~ chuan h6a HCI theo phan ung.
(HOCH2)3CNH2+HCl -+ (HOCH)3CNH3+CI-
0,4922 g THAM c§.n dung d~ chuan 23,45 ml dung dich HCI. Tinh
CN ella HCI.
7.7. MQt mau X chua Ba(OH)2' Nguoi ta can 0,8772g mjiu X dem hoa tan
va chuan bang dung dich HCI 0,1057N he't 35,78ml. Tinh ham luong
cua Ba(OHh trong m~u X.
7.8. Tinh ham luong % ella ~HP04 trong m§.u khi 46,79ml dung dieh
Ca(OH)20,04223M da trung hoa dU<;le
0,9073g mAu theo phuong trinh:
2K2HPO<j+ Ca(OH)2 -+ Ca(K2P04)Z + 2H20
7.9. MQt mftu chat huu eo c6 chua Hg(II). D~ xae dinh ham IUQngHg(II)
trong m~u, ngudi ta vo co hoa m~u b~ng HNOs' Sau khi xi'1ly (pha
loang), ehu~n dQHg2+b~ng ph an ung:
Hg2+ + 2SCN- -+ Hg(SCN)2
Lu'<;lngm§.u da ifiy 3,776g va dung het 21,30ml dung dieh NH4SCN
0, 1144M. Tinh ham lu'<;lngHg(II) trong m~u.
7.10. Ngudi ta d.n xae dinh ham lU<;lng(NH4hC204 trong mQt mAu thi'1.
Qui trinh dinh lUQngnhu sau:
Can 0,4755g mftu hoa tan vao nUDeva eho KOH vao d~ ehuy~n NH/
thanh NHa·
Lu<;lng NH~1giai phong dUQCcat vao 50,00ml dung djeh H2S04
0,5035M. Ph&n H2S04 du dUQcehu~n dQ l~i vDi dd NaOH 0,1214M
het 11,13ml. Hay tinh:
a. Ham lu<;lng% eua N ( M:::14)trong -in~u.
b. Ham lu<;lng% ella (NH4)2C204 (M=124,1) trong m~u.

155
 991

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 ------------~--~-~--__,,-

Chirong B
~ ,.
.
CHUAN £)0 ACID - BASE

1. NGUYEN TAC
Chudn dC)acid-base la phuong phap dua tren phan ling cho nhan proton
giua acid va base (phan ling trung hoa):
Acid (1) + base (2) == Base (1) + Acid (2)
Cac phan ling dung trong phuong phap nay phai thoa man cac yeu c~u
cua phan ung dung trong phan tich th~ tich.
Trong qua trinh chuan dC),n6ng dC)cac ion H+va OH' thay d5i tuc la pH
cua dung dich thay d5i. Tai di~m tuong duong co su bien d5i d<)tng<)tcua pH
va ta thu duoc mQt dung dich co pH nhat dinh (j vung acid, trung tfnh, hoac
kiem. Thuong khi dat di~m wong duong khong co nhfing bien d5i co th~ quan
sat duoc, Vi v~y nguoi ta phai cho them vao dung dich dinh hrong nhung chat
goi la chat chi thi co mau stic thay d6i d Ian can di~m tuong duong d~ nhan ra
duoc va ket thuc qua trinh chuiln dC).

2. CHAT CHi THJ TRONG CHUAN DQ ACID· .BASE

2.1. Khai ni~m

Chat chi thi trong chuiln dC)acid-base 13. nhfing chat co mau stic thay d6i
theo st;ibien d5i pH ella dung dich, duqc gqi 1a chat chi thi acid - base hay chat
chi thi pH. Chung thudng la nhung chat huu co co tinh acid base, trong do
dlilngdlilngacid va dlilngbase lien hqp co mau khac nhau ph\! thuQc vao cau
tiuc phan tlt ella chung. Khi pH ella dung dich bien d5i, cau true phan tlt ella
chung se bien d6i theo, d~n den mau thay d5i.
Neu ky hi~u dlilngacid cua chat chi tht la HInd, dlilngbase lien hQpvoi n6
la Ind- , trong dung dich co d.n b~ng sau:

157
 ---~~--

hay: . HInd
-- Ind" + H30+
Ind- +H+

Khi pH thay d6i thi 'can bang (a). se chuyen dich v~ phia phai_h~_(lct.rai,
chat chi thi se t6n tai ch:iiyeu d110imQt trong hai dang nen dung. dich se co
mau cua dang acid (HInd) hay c:iladang base (Ind"),
Vi du: s\l d6i mau cua 2 chit chi thj sau day:
Da cam methyl (Heliantin):

(dang acid: rnau da cam) (dang base: mau yang)

Phenolphtalein

HO~

(A~
~OH
°u~ ~ DOH
I .Q

u
k _00· + H,O
C

(roo-
(dang acid: khong mau) (dang base: mau h6ng)

2.2. Khoang' pH d5i mau cua chat chi th] aeid » base
MeJichat chi thi acid - base thuong' co IDQtkhoang pH d6i mau, ta co th~
tfnh du<:,ckhoang pH do. Tli can bAng (a) ta co: Hang s6 can bAng cua HInd la:

k HInd JHrJ/rL[H
HInd 3
O+]=k HInd
H1ndl
\ Ind"

hay: pH = pk HInd -lg~ 1fndJ (8.1)

Bi~u thuc (8.1) cho tha'y: vdi 1 chi thi da cho, pH thay d5i, theo ty s6
~. Vi hai dang HInd va Ind' co mau sA~khac nhau nen ty' s6 nay quyet
~. ,

dinh mau sAccua chi thi

Th\lC te' cho thay rAng voi da 86 cae chat chi thi, bAng mAt thuong ngttoi
ta chi co th~ phan bi~t du<:,csl;Ld6i mau khi ty .1~ D:;~llJ trong khoang l~ -:-10
nghia la nguai ta chi nh~n du<:,cmau cua dlilngco n6ng dQgap khoang 10 IAn
n6ng dQdlilngkia:

158

~--~--~----------- -----,,-- -
 = - I : ch at
~, cI'11thi1co, mau ' In d".
, d ang
10 ..'

~::::10: chat chi thi c6 mau dang HInd.

Thay cac ty l~ nay vao (8.1) ta c6:

pH = pkHInd± 1 -+ pkHInd +1
-1 S pH S pkH1nd (8.2)
D6 chinh la khoang pH chuydn mau cua chat chi thi acid - base. Nguoi ta
con dung khai niem chi s5 pT cua chat chi thi acid - base d~ chi pH tai d6 chat
chi thi d6i mau ro nhat d~ ket thuc chuan dQ.Ta thuong thay gia tri pT trung
vdi gia tri pkHlndcua chat chi thi.
Tuy nhien, do milt nguci co nhay cam
khong gi5ng nhau vdi cac mau nen
khoang d6i mau cua cac chi thi thuong hep hon, ttrc la ty so n5ng dQ 2 dang
mau nho hon 10 l~n va gia trj pkHIndc6 th~ khong nam chinh gitra khoang pH
d6i mau.
Doi v{:jiIOf,lichat chl thi c6 mQt mau, vi d\l phenolphtalein df,lng acid
(HInd) khong mau, df,lngbase (Ind') co mau hang thi mau cua dung dich se"do
nang dQ df,lng Ind- quyet dinh. Neu Co la nang dQban d~u cua chi thL C la
nang dQcua Ind- c~n df,ltt{:jid~ nh~n ra mau cua no. Khi do pH cua dung dich
,
d~ mau cua Ind- xuat hi~n la: pH == pkHllld -lg
c-c
C
0 c6 nghia la pH cua
khoang d6i mau ph\l thuQc vao nang dQchat chi tht. Vi d\l v{:jiphenolphtalein
neu trong dung dich phenolphtalein bao hoa chi c~n pH = 8 mau h6ng da xuat
hi~n, con neu d n6ng dQloang hdn 10 l~n thi pH = 9 mau h6ng moi xuat hi~n.

2.3. Yeu ciiu chung d6i vOi chat chi thj acid ~base
- Tan duqc trong nuoc ho~c trong c6n,
- Ben vung trong dieu ki~n thong thtidng (it chiu tac dQng cua oxy, khi
carbonic, nhi~t dQ,... cua m6i trudng).
- 6 nang dQnho (10-5 -;- 10-4 M) mau da phai xuat hi~n kha ro,
- Mau_phai chuy~n nhanh, ro trong mQtkhoang pH kha h~p,
Khoang pH chuy~n mau cua chat chl thi phai g~n ho<rtcchua gia tri pH d
di~m tudng dtwng cua phan ung chu~n dC),it nhat n6 phai nAm trong
buoc nhay cua pH d sat di~m tudng dudng (la khoang pH ung voi thdi
di~m dinh luqng con thieu ho~c thua ± 0,1% luqng acid hay base dem
dinh h:i<;lng).Dieu nay ta 5e xet ky trong ph~n chqn chat chi thi eua
chu~n dQacid - base.
Duai day la khoang pH d6i mau- Clla mQt 56 chat chi tht thudng dung
trong chu~n dQacid-base:

159
 Bang 8.1. M9t s6 chi th] acid-base

£)~c Mf.tu Khoang

Nong dQ Dung tinh pH
chi thj (%) moi chat D~ng O~ng chuyin
chi tbi acid base mau
.~
Yang alizarin 0,1 mtac acid vang Um 10,1-12,0
Thymolphtalein 0,1 con 90% acid kMng xanh 9,3 - 10,5
~.
\
Phenolphtalein 0,1 va 1 con 90% acid khOng hong 8,0 - 10,0
_,
" 0,05 con 20% acid khOng hong 7,4 - 9,0
£)0 trung tinh 0,1 con 60% base do vang 6,8 - 8,0
g~ch
.£)0 phenol 0,1 con 20% acid vang do 6,4 - 8,0
Xanh bromothymol 0,05 con 20% acid vang xanh 6,0 - 7,6
Quy 1,0 mtac acid do xanh 5,0 - 8,0
£)0 methyl 0,1 va 0,2 con 60% base do vang 4,2 - 6,2
LI:JCbromocrezol 0,02 c6n 20% acid vang xanh 4,0 - 5,4

Oa cam methyl 0,1 m/ac base h6ng va.ng 3,1 - 4,4

Xanh bromophenol 0,1 ruroc acid vang nau 3,0 - 4,6
Tropeolin 00 0,1 va 0,01 m/ac base. do vang 1',4 ':3,2

Ghi chu:
- Khi Stl dung cac cha't chi thi cAn luu y cac yeu to' anh htt{1ngfien s1,1thay
d6i mau cua chat chi thi nhu: 81,1co m~t cua cac ion treng dung dich,
nhiet dQ, dung moi ...Vi du dung moi ruou hay aceton (co hAng s6 di~n
moi nho han nude) lam cho acid va base it phan 1y han nen anh hudng
den khoang pH d6i mau cua chat chi thi,
- Trong nhieu truong' hop ngudi ta dung han hop cac chat chi thi d~ quan
sat s1,1d6i mau cua chat chi thi ra han. Co th~ cung them VaGvci cha't chi
thi m9t cha't mau khac khong nh;;ty voi s1,1thay d5i pH nhung cha:t nay
h(,1pvdi mau clla chat chi thi thanh m9t mau d~ nh~n han. Cling co th~
ket h<Jphai cha't chi thi co pkHlnd g~n nhau thanh mQt mau de nh~n va
a
chung d5i mau khoang pH trung gian clla hai chi thi d6.
- Chi thi v~n nang 1a han h(,1pgam nhi~u chi thi rna mall sl'ic cua no thay
d6i thea cac gia trj pH khac nhau. C6 nhi~u cong thuc d~ pha chi thi v~n
nang, dttdi day 1a m9t vi d\l:
Phenolphtalein : 1 ph An
Do methyl : 2 ph~n
Vang methyl : 3 ph~n

160
 Xanh bromothymol : 4 phan
Xanh thymol : 5 phan
H6n hop nay cho mau do d pH =2, da cam d pH 4, yang d pH = 6, luc d =
pH = 8, xanh lam d pH = 10. Nguoi ta thuong dung giay tftm chi thi van nang.
Khi thi'i ta chi c:in nho 1 giot dung dich c:in thi'i len giay va d6i chieu mau tren
giay vdi thang mau m:1u (da ghi chu pH) d~ bie't duoc pH cua dung dich. Dudi
day la m<)tso' chi thi h6n hop:

chi thj hemhQp hal thanh ph~n Trl so ~----------~--~--------~

Milu
(TyI~ 1 : 1) pT Mol tntong acid Mol tnJong klem

Da cam methyl 0,1% trong mrCle va 4,1 tim luc

Indigoeaemin 0,25% trong nt/Cle
..................................................................................................................................................................................................................................................................................................
£>0 methyl 0,1% trong e6n va
5,4 do tim h:IC
Xanh methyl 0,1% trong e6n
.................................................................................................................................................................................................................................................................................................
£>6 trung tinh 0,1 % trong eon va
7,0 tim xanh h,,IC
Xanh methyl 0,1% trong e6n
..................................................................................................................................................................................................................................................................................................
Naphthobenzein 0,1% trong c6n va 8,9 h6ng nhat tim
Phenolphtalein 0,1% trong con
............................................................................................................................................................................................................................................................... u .

Xanh thymol 1% trong con 50% va 9,0 vang tim

Phenolphtalein 0,1% trong con 50%

D~ chon chi thi thich hop cho chuan dQ acid - base, nguoi ta thuong
xuyen dl,ing duong bi~u di~n sl,i thay d6i pH trong qua trinh chu~n dQ theo
lU<;ingdung dich chuftn cho vao d~ ph at hi~n di~m tlidng dlidng.

3. KHAO SAT cAe DlJdNG BlED nI:EN DJNH LlJQNG

Tri so pH thay d6i trong qua trinh chu~n dQtuy thu<)c vEtoacid ho?c base·
din d!nh hi<;ingva dung dich chu&n.
Dudi day chung ta se xet trong m<)tso' trudng h<;ipC\1 th~. Trong khi khil.O
sat, d~ ddn gian cho vi~c tinh toan, ta bo qua anh hlidng clla sl,i pha loang va
clla ho~t 09·
3.1. Khiw sat dlidng bi~u di~n dinh llicJngmc?tacid m~nh b{tngbase m~nh
Vi d,!-: Dinh hi<;ingHCl O,IN bAng NaOH 0,1 N.

3.1.1. Khao sat sl/ bfen deli pH trong qua trinh dinh lz.tf/ng:
_ Trude khi dinh lu<;ing:dung dich Hel O,IN 13.dung dich acid m~nh, cho nen
h = 10-1 ---j. pH = 1.

161
 (;91

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Hd "B1]-olQ:8UlQP !9P U,~!q its 90 (%1'0 =1= ,Qs ~"BSWA 2uJ). HO"BN %1'0 "B~~n
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itf/. PI;) UOtp pa l~X ufJ'lfN °8'1"e

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--------------------- 8
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~Up;nl ;np HO"BN (>p.3u9u oaql qotp ~unp "B1]-o Hd qun u~u oq:) ';np HO"BN
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'L = Hd u~u ot{o 'Ol:H 'lO"BN90 u<p !qo t{0!P ~unp :~up;np .5up;nl w~~p !-B.£ -
001
'v = H d
,q •
~ ~_Ol= 1_01x 1'0 = '1 u~u oq:> .o'UP;nl
t{utp opnp "Bntp IOH %'['0 uQo ~I "B!q~u %6'66 opnp ~up;nl t{utl> uty!P !R'll P.
itp JA '.5u6rq UU!P ;)o;np "B;ntplOH "B1]-0
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 do methyl (4,2 + 6,2), da cam methyl (3,1 + 4,4) va xanh bromothymol (6
+7,6). Cho nen neu dung cae chat chi thi nay sai s6 chi thi mile phai nam
trong pham vi s ± 0,1%.
Bang 8.2. SI! thay d6i pH khi chuan d(> HCI 0,1 N bang NaOH 0,1 N

% NaOH Tinh chat Cong th(tc tinh h pH Ghi chu

cho vao dung dlch
1
0
2
90
Acid mann h= CA
3
99
4
99,9
h ::: oh = 10-1 7 Bl(oc nhay pH
100 Trung tfnh
10
100,1
10-14
Base mann h=-- 11
101 oh
12
110

_ Neu khao sat vdi cac dung dich nhu tren nhung d cac n5ng dQkhac nhau:
C1=lN, C2 = O,IN, C, =O,OIN (bang 8.3 va hinh 8.2). Ta thay n5ng dQ
cang cao budc nhay cang dai. Trong thuc te nguci ta hay dung n5ng dQ
0, IN vi khi chuan dQcho budc nhay pH thich hop vdi nhieu chi thi. Neu
n5ng dQloang O,OIN budc nhay ngan lai chi con 5 + 9 khi do dung da cam
methyl se mac sai s6> ± 0,1%. Con khi dung n5ng dQ cao hon O,IN, pH
chiu anh hudng nhieu cua h~ s6 hoat dQ.
Bang 8.3. SI! thay d6i pH khi chuan d(> HCI bang NaOH d cac n6ng d(> khac nhau

pH
% NaOH %HCI Ghi chu
cho vilo con l<;Ii C1= 1N C2=O,1N C3= O,01N

100 0 1 2
0
10 1 2 3
90
1 2 3 4
99
0,1 3 4 5
99,9
Bl(oc nhay
0 7 7 7 pH
100
100,1 11 10 9

12 11 10
101
13 12 11
110

163

--- --------- -----------------

 pH
14

13 IN
12 O,IN
II O,OlN
10 ---------------------
9 Phenolphtalein
8 ---------____________
_ _

6
5

Da cam methyl
-------~------------

%NaOH
96 98 100 102 104 106 108 110

Hinh 8.2. DVong bh~udi~n oinh IVc;1ngHel b~ng NaOH voi n6ng 0(>khac nhau

3.2. Khao sat dliang bi€u di~n djnh higng m(>t so acid yeu bAng m<}t
base marih
Vi du: Dinh lucng' CHaCOOH 0,1N (co k, = 1,75. 10-5) bang NaOH O,lN.

3.2.1. Kluio sat S,! thay d{ii pH trong qua trinh djnh 1ztlJng
- Trude khi dinh Iudng: Dung dich CHaCOOH O,lN Iii dung dich acid yeu;
tinh [H30+] va pH dung dich theo cdng thirc (4.2lb): pH 2,86. =
- Truce di~m tuong .ducng: khi cho NaOH vao, co phan ung:
NaOH + CHaCOOH = CH COONa3 + H20
Trude di~m tuong duong, dung dich gam CHaCOOH con lai chua dinh hrong,
CHaCO-ONa, H20. Day 13. dung dich cua cap acid-base lien hop
CHaCOOH/CH3COO- cho nen ta tinh pH theo cong' thirc (4.20) pH = pk; + Ig ~H •

A
Vi du khi dinh luong dUQc99,9% nghla 13.con 0,1% CHaCOOH chua duoc dinh
IVQng. Tuc la Cui CA b&ng 99,91 o.i- 1000 ~ pH::: 7,73.
- Tai di~m tuong duong: dung dich chi co H20, CH3COONa. Ta tinh pH
cua dung dich base yeu CH3COONa theo cong' thuc (4.22b):
pH -= 7 +± pk" +±lgCs vai Cn ::: 0,1 ~ pH = 8,87.
- Sau di~m tUdng dudng: dung dich chua CHaCOONa, H20 va NaOH du.
Ta ap d\lng cong thuc tinh pH cua dung dich base m~nh (NaOH du). Gia
si't NaOH dv 0,1%, khi do oh::: 10-4 ~ pH =10.

164
 Cac k6t qua dUQc t~p hop ij bang 8.4.

Bang 8.4. Slfthay d6i pH khi dinh 11IQng CH3COOH 0,1N bang NaOH O,1N

% NaOH Tinh chat Cong thtrc tinh pH pH Ghi chu

them vao dung dlch

1 1
0 Acid yeu pH == - pka--lgCA 2,86
2 2
50 4,73

90 C 5,73

99
C~p acid-base lien hop pH = pka +lg CB 6,73
A
99,9 7,73

100 Base yeu pH = 7+-1 pk, +-lgC

1
8 8,87 bltac nhay pH
2 2
100,1 10

101 Base mann

pH = 14 + Ig Cs 11

110 12

3.2.2. Ve duiJng bilu diin: (hinh 8.3)

pH
14
13
12

II

10 ---------------------- -------------------
9 Phenolphtalein
8 --------------------- -------------------
7

6
5
4
-------------------------------------------
Da cam methyl
3 -------------------------------------------

2
1
% NaOH
o
90 92 94 96 98 100 102 104 106 108 110

Hinh 8.3. £>l1<Jng

bi~u dien dinh lL(c;mgCH3COOH 0,1 N bang NaOH 0,1 N.

165
 . .
3.2.3. Nluin xet va chon chi thi.
- o tJ'Ltocd~m tuong duong, ung vo.i- vung d~m nen pH bien d6i cham. d
g~n di~m ttttlng duong. co bu6c nhay pH (7,'13 -;-10). So vdi trudng hop
dinh hrong acid manh b~E,g base manh ta thay budc nhay bi rut ~gAn d
vung acid, hdi'vi dQdai cua:buoc nhay phu thuQc vao hang' so k, cua acid.
Acid cang ye'u (k, cang nbo) buoc nhay cang ng~n. Thuc te' khi acid qua
yeu (k, < 10-8) thi gAnnhu khong ,cobUDenhay, khong dinh hrdng duoc.
- Chon chi thi cung .nhu trudng hgp 4a. xet tren: trong dinh hrong nay vdi
sai so ~ ± 0,1% ta co th~ dung chi thi phenolphtalein, khong dung dU<;1C
chi thi cia cam methyl, vi pH chuyen mau n~m ngoai buoc nhay pH cua
chuftn d§.
- Tudng tt,t nhu ttudng h<;1pda xet, baoe nhay cua pH ciing ph\] thuQc nang
d~: n6ng dQ dmg IOn htidc nhay cang dai, nang dQ cang loang buoc nhay
cang n-glln.

3.3. Dillh ht~ng mqt base yeu bing mqtacid mlilnh

Vi dip Dinh lU<;1hgNH3 O,IN (c:o.kb =1,7.10-5) b~ng HC} O,lN.
8..8.1. Khao s.6t s,! thay do'i pH trong qua trinh dinh lUling
- Truoe khi dinh IU<;1ng: day la dung d!ch base yeu, tinh pH theo cong thuc
(4.22b), ta co: pH := 11,1.
- TruDe -di~m tuong dtiong: cho HCl v.ao se co phan ung:
HCI + NH3 := NH4CJ
<) truoc di&m tUdng du,ong ta co c~p acid-base lien h<;1pNH/I NH3, tinh
pH theo {!ongth'uc (4.20).
Gia Sl1 dinh lti<;1ngdtic;le99,-9%. Ta co 'CB con I~i 0,1% va CA dU<;1C
t~o thanh
99,9%. Do v~y
01
pH = 9,25+ 19_,_ ~ 9,25 -lg 1000 = 6,25
99,9
- TliI-idi~m t'lfong dUdng: co acid yeu NH/, tinh pH thea cong thuc (4.2Ib):

PH =!pk
2· a
-!lgC
2 A
=51
,

- Sau di~m tlidng dl1dng: dung dich dti acid mlil-nhHC!. Gia su du 0,1%. Ta
co: CHC1du = 10~~x 0,1= 10--4~ pH = . IgC Hc1 du = 4.
trinh bay d blmg 8.5.
Du .li~u dli<;1C

166
 Bang 8.5. Slf thay d6i pH khi djnh hJ<if1gNH3 0,1 N bang HCI 0,1 N

% Hel cho vao % NH3 con 1,1 pH Ghl chu

0 100 11,12
50 50 9,25
90 10 8,25
99 1 7,25
99,9 0,1 6,25
5,1 BLtoc nhay pH
100
100,1 4
101 3
110 2

9.3.2. Ve duilng bie"u diin: (hinh 8.4).

pH
12

II
10 ------------------------------------------
9

3
2

%HCI
o

Hinh 8.4. Duong bi~u dien djnh 111QngNH3 0,1 N bang HCI 0,1N

3.3.3. Nhij,n xet va chon chi thi

Luc d~u pH thay d6i cham (do tao cap acid - base lien hop co kha nang
d~m). BuClcnhay pH tu 6,25 -:-4 voi sai 56 ± 0,1%. Do d6 c6 th~ chon chi thi la
do methyl co p'H chuyen mau 4,2 -:-6,2 hoac da cam methyl co pH chuyen mau
3,3 -:-4,4. Khong dung chi thi phenolphtalein, vi vung chuyen mau cua no nam
ngoai buoc nhay pH.

3.4. Djnh higng mqt acid trung binh bAng mqt base yeu
Vi du:
Dinh Iuong CH2CI-COOH 0, IN (co pkui :::; 2,9) bAng dung dich NH3 0, IN
(co pka2 :::::9,25).

167
3.4.1. Khdo sat sl! thay d6i pH trong'qua trinh djnh lu?ng
- Trude khi dinh luong: day Iii dung dich acid trung binh, ta co"th~ tinh pH
g§.n dung theo acid yeu:
11.
pH;::: 2 pK(1 -2"lgCA·;::;; 2

- Trude di~m ttrung duong: co.phan (tng dinh hiQng:

NHa + CHzel-COOH = CH2Cl~COONH4
o day, ta co c~p acid-base lien hop CI-J2Cl·COOHI CH2CI-COO', Gia sli
dinh hiqng dUQe99,9%. Ta co acid con lai 0,1%. Do do:

pH ;::pK A +.19CH = 2,9 + 1999,9 ;::;;

5,9
CA 0,1
~ 'I'ai di~m tuong' duong, ta cO h6n hop hai c~p acid-base lien hop CH2CI-
COOHI CH201-COO' va NH,tINH3' Do do:

P H ~ }_J)k + .!.pk
2 r: o( 2 02
=: 607
'

- Sau di~m tuong duong: ta tinb pH cua cap acid-base lienhop NH/I NHa.
Gia sli du 0, + % ta co:

pH =: pk, + 19 CH =: 9,25 + 19~ ~ 6,25

CA 99,9
Cac ket qua duqc t~p hop d bang B.6.

Bang 8.6. SI! thay doi pH khi djnhJU'<;Jng CH2CI-COOH 0, tN bang NH3 0,1 N

0/. NH3cho vao % acld ,?on l~i pH 'Ghi chu

0 100 2

50 50 2,9

90 10 3,9

99 1 4,9

99,9 0,1 5,9

100 0 6.07
Buoc nhay pH

100.1 6,25

101 7,25
110 8,25

H38
3.4.2. Vi dUdng su« diin: (hinh 8.5)
pH
13 ]
12

11
10
9
8
1

4
3
2

%NH3cho vao
o
90 92 94 96 98 100 102 104 106 108 110

Hinh 8.5. Duong bieu di€in djnh IUQngCH2CI-COOH 0,1N b~mgNH3 0,1N

3.4.3. Nhgn xet va chon chi th]

Vdi sai so ± 0,1% hUGCnhay khong ro (pH chuyen tll 5,9 -? 6,25); VGisai
so ± 1% buoc nhay tll 4,9 -? 7,25 co th~ dung chi thi do bromophenol co pH
chuyen mau 5,2 -;-6,8 (mau chuyen tll yang sang do).
.
3.5. Djnh higng mQt acid ye'u bAng mQt base ye'u hay ngli<JcIai
Kh6ng co ling dung trong thuc te' ph an tfch vi tai Ian can di~m tuong
duong pH bien d6i qua it (khong co bUGCnhay) cho nen khong chon dUQcchi
thi d~ xac dinh di~m tuong duong. Phai tim each dinh luong khac,

3.6. Di~u kien djnh higng r ieng biet mQt acid (hay base) trong h6n hop
hai acid (hay base)
Gia sli. co han hop hai acid HAl va HA2co n6ng dQxap xi nhau va bang C,
hang so ka1> ka2• Ta chuan dQhan hQp nay b~ng NaOH. Hay tim di~u ki~n d~
co th~ xac dinh rieng dUQcacid HAl VGisai so khong qua 1%.
Khi dinh lUQngco cac phan ling sau co th~ xay ra :
HAl + NaOH = NaA l + H20 (1)
HA2 + NaOH = NaA 2 + H20 (2)
Vi ka1>ka2nen hic dfiu chi co (1) xay ra, con (2) coi nhu kh6ng xay ra,
nhung ve sau thi ca 2 phan ling xay ra dang thdi, nen pH eua dung dich phai
la ket qua eua ea 2 phan ling.

169
 (a)

(b)

Muon sai so'khong qua 1% thi [AI-] = 99%C; [HAd :;:;-l%C;{An::;: l%C;
[HA21 = 99%C. Thay cac tr] so nay vao (a) va (b) ta co:
pkal-:-pka2 :;:;4

hay ~=l04 .
(S.3a)
kn2
T11(1ngtl;{ muO'n dinh lu~ng rieng HAl vdi sai 's6 khQng qua 0,1% thi:

kat = 106
(~.3b)
ka2
3.7. Djnh lli«;lngmC}tda acid

3.7.1. Vi du djnh Ilt!Jng HaPOfJO,lN bdn,g NaOH Q,lN

HaPO 4 IAda acid c6,3 h&ng so J)han ly tuong tmg:
H3P04 + H20 ____"._H30+ + H2P04- COk, =7,6.10-3 (p k, == 2,1)
H2P04- + H20 -- H30+ + HPO/-:co k2= 6,2.10-8 (p k2= 7,2)
HPO/-+ ~O ...--- HaO+ + P04a-c6 k3= 4,4.10-12 (p ka= 12,4)
Ta th~y ~pk > 4 nen c6 tMdinh h.tc;m,griengbi~ tUng chuc acid vOisai sO'±l%.
FJjnh lIi(Jng acid 1:
- Trude khi them NaOH: tinh p'H ciia dung dich acid da chirc thea acid 1:
h = ~kl'C; khi dinhluong chua den t11C1ngdtrong 1 ta tfnh

h =k [H)P04J
I [H2PO;]

- Tai di~m tuong dttC1ng1: ta co h = ~kl.k2

Dinh. lUC/ngacid 2:

- Trude di~m tuong duong: ta tfnh h=k2• H2P~;

lfPq-
- T~i di~m tuong dutmg: ta co h = .J k2 .k3

170
 Dinh. lltflng acid 3:

kykn
- Tai di~m tuong duong 3: ta co h
= [PO:-]
Ta co bang torn uit 8.7 va duong bi~u di~n dinh luong d hinh 8.6.

Bang 8.7. SI/thay doi pH khi d!nh Il!~ng H3P04 0.1N bang NaOH 0.1N

Dlnh htqng acid 1 £)lnh htqng acid 2 £)jnh hrqng acid 3

% NaOH % acid %NaOH % acid %NaOH % acid

pH pH pH
them vao con them vao con thim vao con

0 100 1,5 1 99 5,2 1 99 10

50 50 2,1 50 50 7,2 50 50 12,4

90 10 3,1 90 10 8,2 100 0 12,7

99 1 4,1 99 1 9,2

100 0 4,6 100 0 9,6

14 pH G
F _---
12

10
: PO/·+H30+:;:::=eHP042• + OR
8 1 1
PH:::;-pk, + -pk,
" - '? .
6
1 1
4 P H:::; -pk, +-pk,
2 - 2 .

2 A: H3P04 + H20:;:::=eH30+ + H2PO/·

%NaOH
A
0
0 50 100 150 200 250 300

Hlnh 8.6. f)l!dng bieu dien dinh Il!~ng H3P04 0.1N bang NaOH 0.1 N
Nluin. xet va chon
chi tht
_ Buoc nhay ella acid 1 vdi sai 86 ± 1%,pH tit 4, 1 ~ 5,2 co th~ dung chi thi
da cam methyl, do methyl hay luc bromocrezol lam chi thi.

171
 - Budc nhay cua acid 2 vdi sai so ± 1% 'l)H tu 9,2 ~ 10 ta dung chi thi
phenolphtalein,
- Acid 3 gua yeu khong co buoc nhay, trong thuc te khong th~ dung chi ·:th!
d~ xae dinh di~m tuong duong 3. .
3.7.2.Djnh IllflngHjJCJ04 O,lN bdng NaOfifO,lN
H2C2041a da acid co 2 h~ag so phln ly tL'Wng ling:
H2Ci04+ H20 __ HaO+ + HC2@4- co kl =5,36. 10-2 (pk, ::::1,25)
HG204- + H20 ~ HaO+ + C20/-eo k2=5,42 ..10-5 (pk2= 4,27)
Ta thKy kl va k2• khong Ian hdn nhau nhigu do dO khong' th~ dinh luong
rieng bi~t tung.chuc acid v~i sai 86 ± 1%. .
Dinh. IltC/ftg.acid 1:
Tntoc khi them NaOH, ta tinh pH cua dung dich theo add 1 (tjnh theo
acid trung birth). Den di~m t\Jon~ ~(jng 1co th€'tinh pH theo cOng thue :
11'
pH=-pk, +-l'k2 =2,76 '.
2 2
Dinh: luang acid 2:
Tinh pH ella c~p acid - base lien hQP.HC204-/ C20/-:

- Tai. di~m tuong' dirong' 2: ta co Na,2C204va'tinh pH bing eang thtrc:

1 1
pf/=7+-pk2 +-lgC8 =8,4
2 2
- Sau di~m tuong dUdng 2: dung dich co du kiem m~nh NaOH, du 1% co
pH =: 10. Tinh toan c\l th~ se tha'y buac nhay pH 0 tttdng dlidng 1 giin
nhu khong cO (khoang pH tu 2,1 ~ 3,3 do-lue do ca eh(tc acid 1 va chlie
acid 2 deu phim (tng), chi co bud<!nhay b di~m tudng dUdng 2 (hic do di 2
chuc.acid deu dtiQc dinh IU<;1ngvai wac nhay pH khoang tit 6,5 -) 10). Do
v~y) khi chuftn dQH2G204 b~ng NaOH ngl1di ta chi chufln dQ nae 2 (dinh
luQng t8ng cQng ca 2 ch(tc acid) va dung chi thi la phenolpll.talein co
khoang pH chuy¬ nmau tit 8 ~ 10.
3.8~Dinh hi<;1ng mqt da base
Vi d\l dinhluQng Na2COa O,lN b~ng Hel, Q,lN.
Trong nuac, Na2C03 =: 2Na+ + C032- vi the' COl- la mg.t da base tUdng
ling vai da acid H2COa (co kl == 4,45.10-7 va k2:::: 4,7.10-11). Nhu ,,~y, ~pk::::;4 dD
d6 cling co th~)'~inh lUQngrieng tung base v.(fi sai s6 + 1 %.

172
 Phuong trinh dinh IUQng:
COa2- + H30+::::HCOa- + H20
HC03- + H30+ ::::H2C03 + H20
Ta co ket qua t6m tilt d bang 8.8 va duong bi~u di~n dinh IUQngd hinh 8.7.

Bang S.S. D!nh IU9ng Na2C03 0,1N bang Hel 0,1 N

%HCI Thanh phan

Base Cong thli'c h pH Ghi chu
them vao dung dich

0 h=l,·k"ell 11,5 C032-

C032-
10 11,2
h:::: k2·C,4
50 10,2 HC03-' CO/-
Cn
90 9,2
Di~m tlfc1ng
100 h = ~kJ.k2 8,4
HC03- dlfc1ng 1

10 7,5
50 h = k1,CA 6,5
H2C03/HC03 -
HC03~ 90 CB 5,5
99 4,5
Diem tlfdng
100 It == ~kl.C4 3,8 H2C03
dlfc1ng2

101 h =CHC1 dlf 3,0 H3O'

pH 12

10

8
C03' + HC03' I
Phenol phtalein I
6

4
3
2

%NaOH
o+-------~------~------~--~--~------~
o 50 100 150 200 250

Hinh 8.7. Duong bi~u dj~n dinh ILfQngdung dich Na2C03 0,1N bang HCI 0,1N

173
 Ta nhan thay: di~m tuong duong 1 nam trong khoang d6i mau cua chi thi
phenolphtalein nhung budc nhay 6 day khong' ro nen dinh blQng khong duoc
chinh xac, .coth€ mac sai sf) ± 10%, d~ khac phuc ta hen dung m~t blnh mAu
(chua NaHG03 co them chi thi phenophtalein) a~so sanh,
Di~m j;udng duong' 2 co budc nhay tu 4,5 ~3 voi sai so ± 1% co th~ .dung
chi thi da cam methyl.

4. TINH SAl $6 CHi THl

Trong phan 8.3 da trinh bay each chon chi thj cho mQt phep chulln dQ
acid· base dua vao khoang' d6i mau cua chi th] va budc nhay pH tren dUdng
cong dinh luong. Ben canh do, con each thu hai - it ph6 bie'n hon - chon chi thi
dua vao tfnh sai s6 chi thi.

4.1. Cac Ioai sai so chi th]

o phan tren ta da:goi gia tr] pH hic ket thuc chuAn dQIS.pT va mQtcach
gAn dung coi pT = pkH1nd• Do v~ sai 56 eua chi thi gay ra 1ft do .~ia trt pT
khong kung voi pH cua dung dich d di~m tuong dttdng (PHTD), cho nen khi ket
thnc chu~n d(>dung dich se co dtt mQtluqng acid ho~c base nao do.
- Ne'u acid d1.fIS.acid m~nh, trong dung djch se tan ~i chu ye'u 1a HaO+
(viet g9n la H+)ta g9i sai so chi thi gay ra IS.sai so H+ hay sai s6 hydro.
Neu acid dtt la acid yeu HA it phan ly, trong dung dich se t6n t/ilichu yeu
Ia acid ye'u it phan Iy HA, ta g9i sai so gay ra trong trudng h<;lpnay la sai
so HA hay sai so acid.
- Tttong tl;t, neu base dtt la base m~nh, ta g9i sai so gay ra trong trudng
hqp nay la sai so OH- hay sai so hydroxyl. Ne'u base du la base yeu it
phan ly B, ta gQisai so gay ra trong trudng hqp nay la sai so base B.
Sai so cua chi thi thu(1ng duqc tinh duoi d~ng % nhtt sau:
mEH+(ho~c RA, OB-, B) chua d!fih luqng dugc ho~c du xlOO
SS H+(%) = -----------------
mEH+(ho~c RA, OB-, B) dem dinh luqng
(ho~c HA, OR·, B) (8.4)
(6 day mE la milimol duong Ittqng)
Sai so chi thi thuQc lo~i sai so h~ thong.

4.2. Cach tinh cac lo~i sai s6

4.2.1. Sai sCihydro

GQith€ tfch acid m~nh (ho~c base) cAnchuftn dQ18.V, nang dQ1a N, dUQc
chuftn dQbang m(>tbase (ho~c acid m~nh), dung chi thi mau .co pT < pHTD .
Th€ tich dung dich Inc ket thnc dinh lUQngla VT (ml) thi: .
- 86 milimol dUdng luc;1ngacid m~h (ho~c base) dem dinJ:lluQng 18.V.N,

174

------------.----~---------
 - S6 milimol duong luong' H30+ (hay H+) chua duqc dinh hrong hoac du la
[H30+].VT = 10-pT .VT·
Do do ta co cong thuc tinh sai s6 hydro:

SSH+ (%) == lO-PT.vr .100 (8.5)

N.V

4.2.2. Sai s6' hydroxyl

L3:'yV ml base rnanh (hoac acid) c6 n6ng dQN dem chuan bang' acid (hoac
base manh) vdi chi thi co pT > pHTD• Th~ tich dung dich hie ket thuc chuan dQ
lit VT(ml).
Tinh tuong tt;t nhu tren, nhung Iuu y oh = 10-14/ h = 10- (14 - pT), ta c6 cong
thuc tfnh sai s6 hydroxyl:
10 -(I4-PT) V
SSow(%) == . T .100 (8.6)
N.V

4.2.3. Sai so' acid HA

Lay V ml acid yeu (hoac base) n6ng dQ N dern chuan dQbAng base (hoac
acid yeu) vdi chi thi co pT < pH TO'Th~ tinh khi ket thuc chuan dQ lit VT (ml).
Khi 3:'y:
- se milimol duong luong acid yeu HA chua dUQcdinh hrong hoac du lit
[HAl,VT' .
- se milimol duong IUQngHA (hoac base) dem dinh IUQnglit:
V.N = ([HAl + [A-n.V T•

M~t khac k =h.[A-]~.!:_.

II [HA] k"
~rAl
A-
II _ [HA]
~ k" +11-lHA]+[A-]
Do d6 ta co cong thuc tinh sai s6'acid HA:

SS(%) = [HA}Vr xlOO=_h_xlOO

([HA] + [A- ])Vr k(l + II (8.7)
lO-flT
= lO-pka + 10-pT xlOO
-

. 4.2.4. Sal sfI base B

Lay V ml base yeu (holitcacid) n6ng dQ N dem chuEtn dQ bAng acid (ho~c
base yeu) voi chi thi co pT > pHTD.Th~ tich khi kat thuc chufln dQ la VT(ml).

175
 Tinh tueng tu tven, nhung cling luu y oh = 10- 14/ h ::::10 - (14- pT).Ta duoc
cong thuc tinh sai so base B :
10-(14-PT)
SS(%) = (8.8)
lO-pkb + 1O-(14-PT) x 100

4.3. Ap dung cite cong thUc tren d~ chon chi th]

Truce het phai xac dinh xem .trtjdng hop chuan dq .mac sai so gi. Muon
v~y ta phai tinh pHTOsau do so sanh vOi p'I'.
- Khi p'I' > pHTDthi dung dich hie ket thiic dinh IUQng·du base. Neu base Ia
manh ta tinh sai so OH-, neu base yeu 18. tinh sai 86 base B.
- Khi tinh p'I' < pHTOthi dung dich co du acid, neu acid du manh ta tinh
sai so H+, neu acid du lEI.yeu ta tinh sai s6·acid HA.

Vi dl! 1: Tinh sai so' chi thi khi dinh luong NaOH O,IN bang Hel O,IN
vdi chi thi da cam methyl co pT = 4 va voi chi th] phenolphtalein co p'I' = 9.
Guii:

Phan ung chuan dq: NaOH + HCl = NaCl + H 0 2

Tinh pH a di~m tuong duong,

Dung dich co NaCl, H20 tai tudng dUdng do do co pHTD 7. =
- Vdi chi thi da cam methyl pT = 4 < pHTD: dung dich co du acid ml;lnh
HCI, ta tinh sai so hydro theo cong thuc (8.5):

SS(%) = 1O-4.Vr x 100 = 10-4.2 x 100 = 0 2%

1O-1.v 10-1 ' -
(vi cung n6ng dq nen VT 2V) =
- Vdi phenolphtalein co pT = 9 > pHTD: dung dich co du base m~nh NaOH,
v~y tinh sai so OH- theo cong thuc (8;6)
10 _(14-9) V 10-5 2
SS(%) = .T X 100 = --'-x 100 = 0 02%
1O-1.v 10-1 '

Nhu v~y co th~ dung dUQcca. 2 chi thi.

Vi dl! 2: Tinh sai so' chi thi khi dinh lUQngCHaCOOH O,lN bl1ng NaOH
0,1N vdi chi thi da cam methyl, co pT :::4 va vdi phenolphtalein co pT :::9.
.Gidi: Ta tinh pHTDella phep ehuAn dQ.
CH3COOH ;.:NaOH = CHaCOONa + H 0 2

=
pHTD 8,87 (tinh theo bang 8.4).

176
 =
- Vdi da cam methyl pT 4 < pHTD, dung dich con CHaCOOH chua duoc
dinh Iuong, vay sai s6 acid ye'u HA, duc;1c
tmh theo c6ng thuc (8.7):

SSHA%) = 10-4 1~:_4.73x 100 ~ 84%

Sai so qua ldn, kh6ng dung chi thi da cam methyl dU<jc.
- Vdi phenolphtalein pT = 9 > pHTD, dung dieh du NaOH, tfnh sai s60H-,
ta dU<jcSSOH- (%) = 0,02%. Sai s6 nho, nen co th~ dung chi thi
phenolph talein.
~ ~ A'

5. CHUAN DQ ACID·BASE TRONG MOl TRUONG KHAN

Trong thuc te' co nhieu acid hoac base la cac hop chat hfiu co khong tan
trong nude hoac th~ hien tinh acid hoac base qua ye'u (k < 10-8). Trong nhung
truong hop nay khong th~ tie'n hanh dinh luong thea phuong phap acid-base
trong m6i trudng' nude duoc. D~ khac phuc dieu nay, nguoi ta tim each sit dung
dung moi kh6ng nude eon goi la moi truong khan. Nhieu truong hop cho ke't
qua tin cay kh6ng thua kern so vdi tie'n hanh trong m6i trudng nude. Co sd cua
van de nay Ia dua tren st;ltac dQng ella dung moi de'n tinh acid va base ella
chat tan rna ta da de c~p den d phAn can b~ng acid - base.
Trong dung moi proton thi se c6 qua trinh cho 'ho~c nh~n proton giua
dung moi va ch6t tan tlilothanh proton solvat hoa, vi d\l voi acid HA trong
dung moi proton HS:
HA + HS ~ H2S+ + A- (ho~e c~p ion H2S+A-)

Voi base B trong dung moi HS ta co:

B + HS ~ HB++ S- (ho~c c~p ion HB+S-)
Khi chUlln dQacid HA b~ng mQtbase B trong dung m6i proton HS se xay
ra phan ling:
H2S+A- + B -7 BH+A-+ HS
TUdng tl,t nhl1 phim ling trung hoa trong nuoc, d day phan (lng tlilora
mu6i va dung moi HS.

5.1. Dinh higng cae base ye'u

Ngudi ta chQn cac dung moi proton hoa tan dU<jccac base ye'u d6. Dung
dich chu~n thudng dung la dung dich acid mlilnh (pha trong dung moi khong
c6 tinh base). Vi d\l cac base yeu nhl1 pyridin, anilin, cac alcaloid, cac amin,
piperazin ... Khi hoa tan trong acid acetic bang se trd thanh mQtbase tudng d6i
m~nh, c6.th~ du<jcchu~n dQb~ng dung dich chu~n acid percloric voi chi thi
tim tinh th~. Vdi nhung chat c6 tinh base qua yeu nhu cafein thi phai dung
dung moi co tinh acid m~nh hdn nhl1 anhydrid acetic. D6i khi ngl1di ta dung

177
han hop dung moi acid vdi cloroform hoac dung moi tro khac, nhu: acid acetic
+ cloroform, acid acetic + carbon tetraclorid, anhydrid acetic + benzen ... d8
quan sat duoc ro su d6i mau cua chi thi.

5.2. Djnh ltif1ng-cac acid ye'u

Ta chon cac dung moi c6 tfnh base hoa tan d.u<jecac acid ye'u nay. Dung
dich chuan thuong dung la dung dich kiem. Vi du sulfafurazol co th8 dUQc
dinh hrong b~ng natri methyl at (NaOCHa) trong dung moi Ia dimethyl
formamid vdi chi thi la xanh thymol.
Nguoi ta con dinh luong cac acid yeu trong nhimg dung moi luang tinh
ket hop dung moi tro, vi du dinh IUQngacid benzoic trong dung moi methanol
+ aceton.
5.3. Djnh ltif1ng cac han hf1p acid hay base
Khi dinh luong cac han hop acid (hoac han hop base) ngudi ta thuong
khong dung dung moi co tinh base manh (hoac tinh acid manh) vi trong cac
dung moi d6, cuong dQ acid (hoac base) bi san bang' nhu nhau va do d6 kh6ng
dinh Iuong phan biet duoc. Nguoi ta thudng ch(;mnhung dung moi c6 tinh acid
(ho~c base) sao cho n6 c6 th8 phlln hoa cudng dQ cac base (ho~c acid) tl;lo dieu
ki~n d8 cac hllng so phlln ly clla cac base (ho~c acid) khac nhau 2: 104 lAn, khi
d6 c6 th8 dinh IUQng phlln bi~t dUQc.Vi d\l han hQp cafein + natribenzoat
kh6ng th8 dinh lUQngphlln bi~t trong moi trudng nuoc, nhung trong dung moi
han hQp : anhydrid acetic + benzen thi suc base clla chung trd nen khac nhau
rat nhieu nen c6 th~ djnh lUQngphlln bi~t dUQc.

6. MQT s6 UNG DVNG DJNH Ll1QNG BANG PHl1dNG plfAp ACID-BASE

6.1. Pha che cae dung djch g6c va dung djch chudn
Nhung dung dich chufin thudng dung trong phudng phap acid-base:
- Dung dich HCI va H2S04 d~ dinh IUQngcac base.
- Dung dich NaOH va KOH d~ dinh luQng cac acid.
Ta khong th~ pha nhung dung dich nay bAng cach can chinh xac vi chung
kh6ng dUQctinh khiet ho~c thanh phAn khong th~t 6n dinh. Vi d\l: H2SO,j d~c
rat d~ hut nuac, NaOH d~ hut nuoc va thudng chua Na2COa do hap thl} CO2
clla khi trdi. Do d6 phai xac dinh nang dQclla chung bang nhung dung dich goc
duqc pha tit cac chat goc. Nhung chat goc co uu di~m la kha ben d ngoai khong
khi va trong dung dich, sau khi tinh che no dl;ltyeu c~u ve dQtinh khiet va c6
thanh ph~n dung cong thuc hoa hQc. Cac chat goc thudng dung la:
- HCl dllng phi, acid oxalic d~ xac djnh nang dQdUdng h:iqngdung djch kiem.
- Natri borat, natri carbonat d~ xac dinh nang dQdUdng lU<;Ingdung djch acid.

178
.,.
6.1.1. Pha dung dich. acid oxalic gdc
• Tinh che' acid oxalic:
Hoa tan 500g acid oxalic vdi 1 luong HCI 3-4N soi. LQc qua pheu
Buchner: calci tap trong acid va dUQcloai di, Ru:a tinh th~ nhieu IAn bang HCI
loang. Ke't tinh lai trong nude d~ loai clorid. Cho vao binh hut Am co H2S04
dac, acid oxalic mat nude ke't tinh trd thanh b9t. D~ b9t nay hydrat hoa lai
ngoai khong khf hay trong binh hut Am e6 natri bromid chay nude, D~ tdi khi
acid c6 kh6i luong khong dc3i,ung vdi cong thirc H2C204.2H20 b~n vfing trong
dieu kien dQAm tli 5-95%.
• H2C204.2H20 duoc dung lam g5c d~ pha dung dich acid oxalic g6c. Kh6i
IUQngduong luong cua acid oxalic:

E = MH zCP4,2HaO == 63 035
H2C204,2H10 2 '
ta c6 th~ pha cac dung dich co n6ng dQthea yeu cAu.
Vi dIp Mu6n pha 1 lft dung dieh acid oxalic O,lN ta can chinh xac
6,3035g H2C204• 2H20 va hoa tan trong nude du 11ft.

6.1.2. Pha dung dich. Na2COS gfic

• Di~u ehe natri carbonat khan tinh khiet:
Natri carbonat thuong co IAn cr, SO/-, NaHC03 ... Cho nen muon dieu
che' natri carbonat tinh khiet nguoi ta thudng xU:ly tuy truong hQp:
- Neu co Na2C03 khan tinh khiet phan tich thi ta dem nung tli 30 phut
den 1 gid d 270°C- 300°C. Sau do d~ nguQi trong binh hut flm.
- Neu c6 mu6i NaHC03, lay khoang 30- 35 g NaHCOa hoa tan trong 300-
350ml nudc, IQc.Co nude IQcWi khi xuat hi~n tinh th~. D~ nguQi, IQClay
tinh th~ va rua vai Mn b&ng nudc ca't nguQi, say kho ta dUQcNaHC03
tinh khiet. Lay 10 g NaHC03 nay cho vao chen sli hay chen bl;tch kim
dem nung cach d.t giu d nhi~t de?270- 300°C trong 1 gid, ta co phan ling:
2 NaHCOa ~ Na2C03 + CO2 + H20
Sau d6 d~ nguQi trong binh hut Am. Chu y khong d~ nhi~t de?tren 300°C
vi Na2COS se bi phan hUy (Na2C03 + H20 -+ 2NaOH + CO2),
• Na2COa khan dUQc dung lam g6c, trudc khi su dl,mg cAn say 180- 200°C
trong 2 gid d~ dUc3ihet nudc vi Na2COa d~ hut Am trong khong khi tl;tO
thanh Na2COs.I0H20.

Tit E Na2CO, -- M Na2CO,

2 = 52,997 ta c6 th~ tinh toan pha dUQcdung di.ch g6c
co n6ng dQtheo YE!u cAu.

179
 Vi du: Pha 1 lit dung dich Na2C03 0,1N ta can 5,2997 gam Na2C03 goc
pha trong nudccho du 1 lit.

6.1.3. Plea-dung dich. natri borat

• Tinh che natri borat:
Uy 23 gam natri borat hoa tan trong 50ml nude nong 60°C (d nhiet dQ
eao hon se tao thanh tinh th~ co 5 H20). LQCdung dich con nong, Nude loc d~
nguQi va khuay lien tuc se co Na2B407.10H20 lAng xuong. LQc,ep tinh th~ gifta
2 td giay IQC,sau do d~ kho trong khong khi. Bao quan trong 19thuy tinh nut
nham .
• NaiB407.10H20 dung lam chat g6c.
M
, Na2B407.lOH20
re E Na2B407.10H20 = 2 = 190,71
Ta d~ dang tinh dUQckhoi hrong d.n thiet d~ pha cac dung dich goc co
nang dQtheoyeu cAu.
Vi dl:l: Pha1 lit dung dich natri borat 0,1N ta can 19,071 gam
Na2B407.10H20 rBi hoa tan (lAcky) trong nude cho du 1 lit.
Natri borat it tan trong nude nen khi pha phai lAcky va dung dich chuan
cua no khong nen co n6ng dQcao hon 0,25N.

6.1.4. Pha dung dich chudn HCI O,lN tit HCI dij,c
HCI a~c thudng co nang dQtit 35- 38%, khoi IUQngrieng 1,174 - 1,188 va
khong thoa man yeu cAu cua chat g6c. Do do d~ pha dUQcdung dich chu~n HCI
0,1N tit HCI d~c ta phai qua 2 budc: ,
1. Pha dung dich HCI co nang dQxap Xl 0,1N:
Gia slt cAn pha 1 lit dung dich HCI xap Xl O,lN, ta phai tinh IUQngHCI
d~c cAn lay tit EHC1 = MHC1= 36,5.
IU<;jngHCI cAn pha 1 lit dung dich n6ng dQ0,1N Ia: 3,65g. Biet HCI d~c co
nang dQ 38%, d = 1,188. Do do th~ tich HCI d~c cAn la:
(3,65 x 100)/(1,188 x 38) = 8ml.
Ta chi vi~c dong b~ng 6ng dong 8 ml HCI d~c rBi hoa trong nudc cho du 1
lit, se dUQcdung dich HCl co n6ng dQxap xi 0,1N.
2. Xac dihh n6ng dQcua dung dich HCI da pha che:"
Co th~ dung 2 dung dich goc d~ chuAn dQ:
- Dung dich Na2COa O,IN, phan ung dinh Iu<;sng:
Na2COa + 2HCI = H20 + CO2 + NaCl

180
 - Dung dich natri borat O,lN, phan img dinh hrong:
Na2B401 + 2HCl + 5H20 == 4HaBOa+ 2NaCl
Chi thj mau 18. da cam methyl hay do methyl.

6.1.5. Pha dung dich. chuiin NaOH O,1N tu NaOH

NaOH d~ bi carbonat hoa va hut iim vi the cfing khong tho a man yeu eftu
cua chat goc. D~ pha dung dich chuan NaOH O,lN nguoi ta phai qua 3 buck:
1. Loai carbonat khoi NaOH:
Hoa tan 50 gam NaOH trong 500ml nude dun soi d~ nguoi, them 50ml
sua voi (Ca(OH)2)' D~y kin binh, lAc 1-2 gid, d~ yen vai ngay. Gan lay nude
trong la dung dich NaOH tinh khiet. C~n lit CaCOa va Ca(OH)2 thira (vi
Ca(OHh kh6 tan trong nude nhfft la khi c6 NaOH du),
Neu NaOH l~n' it carbonat c6 th~ loai bang each rda nhanh NaOH 2-3
l~n bang mQt it nude, NaOH con lai coi nhu da loai het Na2COa·
2. Biet ENaOH =MNaOH == 40,0. Tit NaOH dB.loai Na2COa hoac dung dich
NaOH tinh khiet tren, tinh toan d~ pha duoc dung dich NaOH c6 nang dQxffp
xIO,IN.
3. Xac dinh nong dQdung dich xap xi 0,IN dB.pha d tren:
- Bang dung dich HCI 0,IN dua tren phan (tng dinh lUQng:
NaOH + HCI = NaCl + H20
Chi thi la heliantin. Cho tit tit dung dich HCI vao dung dich NaOH cho
Wi khi chuy~n tit mau yang sang do cam.
- B~ng dung dich acid oxalic 0,IN dlja tren phan (tng dinh lUQng:
2NaOH + H2C204 == Na2C204+ 2H20
Chi thi lit phenolphtalein. Nho tit tit NaOH vao dung dich acid cho toi
khi xUllt hi~n mau hang nh::;tt.

6.2. MQt so ap d1;lngdinh lligng trong thl;ic te

6.2.1. Dinh hle!ng dung dich NH40H (hay NHJ
NH40H (hay NHa) la mQtbase yeu nen dung mQt acid m::;tnhnhu HCl d~
dinh lUQngtheo phtidng trinh:
NH40H + HCl == NH4CI + H20
Chi thi mau la do methyl c6 vung pH chuy~n mau tit 4,2 + 6,2 (tit mau do
sang mau yang). Cilng c6 th~ dung chi thi han hQpTashiri (3 giQtdo methyl +
1 giQtxanh methylen) mau se chuy~n tit l\lc (vang + xanh) d pH 6,2 sang mau
tim (do + xanh) d pH 4,2.

181

••
. - - .. --~-.-------
6.2.2. Dinh IUr.Jngh6n h(j_p/tla2COs + NaOH
Nguoi ta chuan dQ h&n hop l?{lng mQt dung dich acid manh nhu HCI.
Phuong trinh phan ling:
NaOH + Hel = NaCl + H20 (1)
Na2COa + HCI :::NaHCOa + NaCl
'4
(2)
NaHCOa + HCI::: CO2 + H20 + NaCl (3)
Khi dung chi thi phenolphtalein (pH chuyen mau tu 8 -;-10) thi luc
chuyen mau toan bQ NaOH (phan ling 1) va 1/2 Na2COa (phan ung 2) dB. duoc
dinh luong. Sau dothem da cam methyl (pH chuyen mau 3,1 + 4,4) va tie'p tuc
den chuyen mau thi se dinh luong n6t 1/2 Na2COa con lai (phan (tng 3).

6.2.3. Dinh IUf/ng acid acetic hay cdc acid hiJu ca yeu khac
D~ dinh Iuong, :UgUdita dung' kiem manh nhu NaOH. Phuong trinh chufuI d{l:
CMaCOOH + NaOH = CHaCOONa + H20
ECHaCOOH = MCHaCOOH = 60,0

Chi thi mau 13.phenolphtalein

6.2.4. Dinh IUf/ne acid octophosphoric HSP04

Nhu d phan 8.3.7.1, ta ~j:1ayr~ng H3P04 co th~ dinh luong nhu mQt mono
acid vdi chi thi chuyen mau d pH 4,6 va nhu mQt diacid vai chi thi chuy~n mau
pH 9,6; con acid 3 yeu qua dinh luQng khong chinh xac.
Khi dinh lUQng nhu m9t mono acid thi E = M. Khi dinh luQng nhu mQt
diacid thi E =MI 2.

6.2:5. Djnh IUf/ng cafein trong moi truiJng khan

Cafein (CsHlO02N4• H20 = 212,21) 180 alcaloid co
tinh base rat yeu khong dinh htQng dUQctrong moi
trudng nuac .. Nhung trong h6n hQp dung moi
ahhydrid acetic + benzen hay anhydrid acetic +
carbon tetraclorid tinh base cua no mf;lnh len va dinh
lUQng dU<;lC b~ng dung djch HCI04 (pha trong dung
moi acid acetic khan). Chi thi la tim tlnh th~:
Cafein
6.2~. Dinh IUf/ng strychnin sullat trong moi truiJng khan
=
Strychnin sulfat «C21H22N202)2.H2S04.H20 857,0) 180 alcaloid co tinh
base tf;lOmu6i trung tinh khong dinh htQng dUQctrong moi trudng nuac. Nhung
trong moi tntdng acid acetic khan co th~ dinh lUQIlgdUQcb.~ng dung dich HCI04
(pha trong dung moi acid acetic khan) theo phudng trinh phlm (tng:
R(NH+)~SO!- + HCI04 ~ RNH+CI04' + RNH+HS04•

182

------------- ------------
 ----- -- - ------- ---~----~

cAu HOI vA BAI T~P

8.1. Chat chi thi va khoang pH chuyen mau cua chat chi thi trong phuong
phap dinh luong acid base?
8.2. Khao sat dadng bi~u di~n dinh hrong va chon chi thi cho cac trirong hop:
a) Giira acid manh vdi base manh va nguoc lai.
b) Giua acid yeu vdi base manh va nguoc lai,
c) Giua base yeu vdi acid manh va nguoc lai.
d) Da acid hoac da base.
8.3. Digu kien dinh luong rieng biet h6n hop 2 acid hoac 2 base?
8.4. Chon chat chi thi bang' each tinh sai s6 chi thi?
8.5. Trinh bay each pha dung dich chuan sau (khi cfin pha gian tiep neu
nguyen d.c, phan ung, each tinh ket qua): HCI, H2S04, NaOH,
Na2C03, CH3COOH, NH40H.
8.6. Nguyen t~c, so luoc each tien hanh, each tinh ket qua trong dinh luong:
Na2COa, Na2C03+ NaOH, Na2C03 + NaHC03, H3P04•
8.7. H6n hop g6m Na2C03 va NaHC03 duoc hoa tan vao nude va dem
chuan dq b~ng dung dich HCI 1M het 12,00 ml voi chi thi
phenolphtalein va 34,00ml voi chi thi da cam methyl. Tinh s6
milimol m6i chat trong h6n hQp.
8.8. Can 0,5000g (NH4hS04 c6 Iftn t~p chat cho vao nuoc thanh dung
dtch. Cho vao dung dich d6 mqt IUQngNaOH du. Dun n6ng dung
dich d~ tach het khi NHa ra khoi dung dich phan (tng va cho hap th\1
vao 50,00 ml dung dich HCI O,200M. Chuftn dq lUQngacid du het
20,OOmidung dich NaOH O,200M.Tinh ham luQng % (NH4)2S04tinh
khiet.
8.9. D&xac dinh P20~ W do trong supephosphat ngudi ta lay 10,00 g mftu
ho3. tan vElO l1U(lC,16.cdeu, pha loang den 500,0 ml. Lay 50,00 ml
dung dich thu dUQc(sau khi da lQc),cho them it nuoc r6i dem dtnh
lUQngb~ng NaOH 0,1002 N voi chi tht da cam methyl het 16,20ml.
Tinh % P205 trong supephosphat.
8.10. Dinh h.iljngh6n hQpA (c6 ch(ta NaOH va Na2C03) lam nhu sau:
1) Lay 50,00 ml dung dtch A, them dung dich BaCl2 den tua hOElll
toano LQc.R-Ltatua. Dinh h:tQngtoan bq nuoc IQcva nuoc r-Ltahet
18,75 ml dung dich HCI O,lOOONvoi chi tht phenolphtalein.
2) Lay 20,00 ml dung dich A, dlnh IUQngb~ng dung dich HCI
O,lOOONhet 12,50 ml voi chi tht phenolphtalein.
Cho HCI = 36,5, NaOH = 40, Na C0 = 2 3 106. Hay:

183
 '_ ..

a) Giai thfch qua trinh dinh hrong tren.

b) Tmh % (.E):LlTT)ella dung dich NaOH ya Na2COatrong han hop.
c) 'I'inh pH tai di~m tuong duong, cua .thf nghiem 2.
8~11.··Chu.ftndQdung djeh acid da chuc H~P04 Q,lM b-&ngNaOH. N6u k6t
thuc dinh IUQ:hgd thdi di~m pH == 7 thi phep ainh IUQngdft duoc bao
nhieu % so vdi khi dinh lu~tlg 'hoan tean 'ca 3 ehtrc acid. Bi€t HaP04
co pk, == 2,15;
pk2 == 7,20; pk, == 12,4. H == 1, 0 == 16, Na =: 2'3, P == 31 va khong k~
d6n sl!- tha-y d6i th~ tich trong qua trinh dinh Iuong.
8.12. Ohuftn de) 20,00 ml dung dich NazCQ3 0, 1M b~ng dung dich HCl
D,JM. Neu dung ehtlftn dQkhi:
- Dung dich e6 pH == 10,2
. Dung dich c6 pH = 6,5.
Hay nhan xet ve phep chuan dQ.d6? (ve %chn dft dUQcdinh lUQng
hoiitcthanh phfin dung dich).
8.13. CAn bao nhieu ml dung dich Hel d~ dinh htQng mqt IuC)ngNaOH c6
l~n 4% Na2COa khi dung chi thi phenolphtaIein. Bi6t rang khi dinh
htqD.g cung mQt Iu<}ngNaOH nhu tren nhung dung chi thi da cam
methyl h6t 25,(')OmlHCl c6 cung n6ng dQ.
8.14. Can 0,500 g.(NH4)2S04 c6lAn t~p ~hat }}oatan VaGnuac. Them VaG
dung dich nay NaOH du. Dun n6ng han hC)pcho NHs thoat ra duC)c
,hap thu holm toan vaG 50,00 ml dung d!ch HCl 0,200 M. Chudn dQ
Hel ciu biIng dung dich NaOH 0;200 M he't 20,00 ml. Tinh %
(NH4)2S04 trongmAu dem dpm hNng.
8.1i. Can 0,3542 g NaiCOa tinh khi6t hoa tan vao nuac va dem dinh
lttQng to~m bQ b~ng dung dich HCI voi chi thi da cam methyl. Tinh
nang dQ N eua He!. Cho Na = 23, C == 12, 0 = 16.

184
 Chuang 9·

eo. TAO
~ A ,

CHUAN . PHUC

1. NGUYEN TAC
Phuong phap dinh 111Qng tao phuc dua tren phan Ung tao phuc ciia cac chat.
Phan ung tao phuc dUQcdung cho dinh 111Qng phai xay ra nhanh, hoan toan, hop
thuc, chon loc cao, nhay va co chat chi thi d~ nhan ra di~m tuong duong. Trong
nhieu ph an ung tao phuc, chi mQt 86 it phan irng dap ung dl1QCcac yeu cau tren.
Vi vay thoi gian d~u phuong phap it dUQcung dung rQng rai. Trong 86 rat nhieu
thuoc thi1 vo co, nguoi ta thuong dung hai chuan dQtao phuc sau:
* Phuong phap bac: dua tren ph an ung' tao phuc giua Ag" va CN"
Ag+ + 2CN"'_"!::' Ag(CN)2"
lit Phuong phap thuy ngan (II): dua tren phan ung' tao phuc giita Hg2+ vdi

cac ion Cl, Br" , I", SCN". Vi d1,l:

Hg2+ + 2 CI" ~ HgC12 +
Hg2+ + 41- ~ Hg142-
Nhl1ng tit nhung nam 40 trd l~i day, sau khi nha hoa hQc
G.Schwarzenbach phat hi~n ra cae chElt hun cd co nhieu nhom carboxyl
(polycarboxylic) t~o phuc ben vung vCiinhieu ion kim lo~i thi phl1dng phap nay
da dl1Qcphat tri~n nhanh, ung d\mg rQng rai vCiiten gQirieng la phl1dng phap
ehmln dQbAng complexon.
">,,

.. .
,," A , ~ ",'

2. CHUAN DO TAO PHUC BANG THUOC THl1 VO cd

2.1. Phuong philp b~c
Trong phtidng phap nay ngudi ta chuAn dQ dung dich kali cyanid bAng
dung dich chuftri b~c nitrat.

:""'.

...... '~'.

.
- "'_
 Trong qua trinh chuan QQ, truce di~m tuong duong, trong dung dich co
du cac ion CN- nen xay ra phan ung tao phuc (phan ling chuan dQ):
(lg 132= 21)
Khi phan ling ket thuc, 1 giot thua AgNOa se cho ket tua bac
dicyanoargentat:
Ag" + Ag(CN)2- ~ Ag[Ag(CNhl.J.. wi TAg(Ag(CN)2i = 4.10-12
Dudi day se khao sat d1.tCtngbi~u di&n dinh htQng -dung dich KCN Q,lM
bing dung dich AgN03 0, IM-.(d~ don gian trong tfnh toan, ta cling bo qua anh
.hUdng cua ho~t d9 va sl!-pha loang).

2.1.1. Khiio .sa.tslJ tha.y- d6'i nang d§ Ag+ trong qua trinh chudn d~
• Trude aie'm tuang duang: chua co phan tmg ket tua, dung diich co
Ag(CN)z- va eN- con chua duoc dinh luong, ta tfnh [Ag"]til cong thuc:

f3 -1021 - [Ag(CN);]
2 - - [Ag+ ICN- f
-) [Ag+ ]= [Ag(CN)~]
/32 [CN- ]-
Khi them 90% luong' bac VaG thi CN- con 10% . Do vfJ-ynang qQcae cfiu tti
se la:
[CN-]= lOxO,l =10-2
100
[A (CN)-]:;:: 90x 0,1 = 4 5.10-2
g 2 100-x 2 '

{A +]= ~,5x10-2 =45.10-19 -) pAg = 18,35

g 1021 X 10-4 '

• T(;,j dilm tzidng dUdng : [Ag+] = x; [CN-] = 2x

va [Ag(CN)2-] ~ 0,112 = 0,05.
d
Do d6: x = [Ag+] = 3 5·1O- fO-21 = 2,3.10-8 (nit ra tit bi~u thue eua hfug sO'13:J

-) pAg = 7,64
Nhung tht;tc te d gAil di~m tudng dUdng, ta phiii tinh den ca pharr ung ket
tua. Neu dIan cfJ-ndi~m ttiG1ngdUdng, ta coi n6ng dQ phuc [Ag(CN)2-]~5.10-2
thi tit bi~u thuc 'tich sO'tan:
TAg[A~(CN)21 = {Ag+][Ag(CN)2'] = 4.10-12

186
 ~ [Ag
+] =[ T
Ag(CN);
r , 4.10-12
5.10--
810-11 ~p A·g= 101
= o. ,

Nhu v~y trong qua trinh dinh luong lAg+] tang d~n va dat tri so 8.10-11
truce, tuc 18.co ket tua xuat hien trudc di~m tuong duong (bang 9.1).

Bang 9.1. 51,(bien obi ella nang 0(>Ag+ trong qua trinh ojnh IlfQng.
% Ag+ cho vao lAg+] pAg

90 5.109 18,3

J
99 5.107 16,3
99,9 5.10-15 14,3
100 8.10-11 10,1 BU(jcnhay
100,1 8.10-11 10,1
101 8.10-11 10,1
110 8.10-11 10,1

2.1.2. DuiJng biiu diin

pAg
10 ---------------------........... _----
Tiia Ag[Ag(CN)21

I[

12 Phtrc
Ag(CN)i
13

14

[6

[7

[8

19
90 92 94 96 98 100 102 104 106 108 110

Hinh 9.1. DlIong bieu di~n dinh 11IQngKeN 0,1M bang AgN03 0.1M

187
2.1.3. Nhlj,n xet
N6ng dQ Ag" tang dAn trong qua trinh chuan d-¢'khi cho 99,9% Ag" vao
thi [Ag"] == 5.10-15• Neu ehufln dq tiep ,0,1% hila thi [Ag"] tiep tuc tang va dat
tri so 8. 10-11• Khi do c6 ket tua xUllt hien va ta ket thuc chuan do mac du
chua den di~rn tudng duong' (di~m 'h1dng duong [Ag"] = 2,3. 10-8). ''l'iep tuc
them Ag" vao, tua tiep tuc tao thanh va [Ag+J g~n nhu khong d6i ([Ag+]
=8.10-11). 'J'ua xuff't"hi~n trU(Jc di~m tuong duong aau khi them 99,9% AgNOa
vao dung dich, saisd chi th] khi chuan dQnay cling khong vuot qua 0,1%.

2.1.4. Chon. chi th]

- Phuong pluip Liebig: Do 1a phuong phap ta da xet treh. Trong truong hop
nay chi th] chinh la thuOc thli (Ag"): ta nhan ra di~m .tuong duong' va ke't
thuc chu~n dQkhi c6 -ket tua Ag[Ag(CN)2] xuat hi~n. N~ll.tkhao sat tren,
ke't tiia xufi't hi~n tniac tUdng dUdng, nhung sai so dinh luqng nhq hdn
0,1%. Trong th\tc te' d~ co ket qua t6t. ngtidi ta thudng dinh luqng rat tit
tit khi g~n de'n di~m tuong dUdng, vi chu~:n dQ'nhanh tna c6 th~ xuat
hi~n som hdn.
- Phlidng phap Deniges: D~ kht1c pht,lc nhuqc di~m ciia phudng phap
Liebig, Deniges dil cai tien dt;la tren cd sd ke't tua Ag[Ag(CN)2] co th~ hoa
tan trong dung dich amoniac, khac 'vai tua AgI. Do d6 Deniges da cho
them vao dung djch dinh lUQngamoniac va KI lam chi:thj. Nh~n ra di~m
tUdng dUdng khi xuat hi~n tiia AgI co mau vang nh~t.
Phlm (Lngchuftn dQ: Ag++ 2CN·.._..b. Ag(CN)2'
Di~m Wdng dUdng: Ag++ I' ~ AgI.J, vang nh~t

2.2. Phtidng phap thuy ngin (II)

MQt s6mu6i hoa tan eua Hg(II) (nhu CN', SCN', CL ..) 1a nhilng ph(Lc
chat, do d6 co th~ dung Hg2+d~ djnh lUqng cac anion nay, theo phudng trinh
t6ng quat:
Hg2++ 2X' ~ HgX2
Dung dich chu~n thu-dng dung 1a Hg(N03)2' Hg(C104)2' HgS04.
Vi dl!- 1: C6 th~ dinh 1uQngC1'bAng Hg2+theo phlm (tug:
Hg2++ 2Cl' ~ HgC12
Khi dljlt de'n di~m tUdng dUdng, ta phat hi~rt mQt 1u<jngHg2+thita bAng
IDC)t. trong hai chi thi sau:
- Voi chi thj la natri nitroprusiat: cho tua triingvoi Hg2+
- Voi chi thj 1a diphenylcacbazon: cho ket tiia mau xanh voiHg2+
Cha y: Ne'u ham luqng Cl' nho, phai them va,o dung djch dinh 1uQng mQt
it c6n d~ giam dQphan ly cua HgC12•

188
 ~-----
·_ .....•. --.--...

Vi dlJ 2: Co th~ dinh luong nhfing muoi Hg2+phan ly manh (nhu Hg(NOsh)
bAng dung dich chuan KSCN vdi chi thi la Fe'".
Phuong pluip dinh. IU,!ng bdng HII+ co uu. die"m:
Co th~ dinh luong thang trong moi truong acid.
_ Nhieu ion gay trd ngai cho phuong phap dinh luong bang bac thea
phuong phap ke't tua (phuong phap Mohr va Volhard) khong co anh
huong gi den su chinh xac khi dinh lucng b~mg Hg(NOg)2 hay Hg(CI04)2'
- HQp chat thuy ngan re hen hop chat bac tuong ung,
Tuy nhien phai luon nhd rAng muci thuy ngan rat dQc, do d6 trong khi
thao tac phai het sue cAn than,
,,0) ,... :,

3. CHUAN DQ BANG COMPLEXON

Phuong phap dinh luong bang complexon dua tren phan ung tao hop
chat nQi phuc cua nhieu ion kim loai vdi mQt 86 thu6c thtc huu cd gQichung la
complexon. Can bAng t~o phuc voi cae thu6c thtc complexon da dUQctrinh bay
ky trong ph&n 4.3. a day chi de c~p de'n eae nQi dung lien quan den chuAn dQ
b&ng eomplexon.
Nhu tren da n6i, tuy theo pH cua dung dich ma EDTA va cae mu6i cua
no t6n t~i d trong dung dich duoi nhieu dli\ng H4Y, HsY-, H2y2-, Hy3-, Y4-. Bdi
v~y phan ung tli\o phue cua EDTA voi cae ion kim IOli\ic6 th~ bi~u di~n bAng
cae phuong trinh khac nhau, tuy theo pH cua dung dich. Nhung c6 di~m
chung la trong phuong trinh phan ung do ty 1~mol giua EDTA va ion kim lOli\i
luon la 1: 1.
Mn++
.
H 2y2-
----
My(n-4)+ 2H+ d pH 4·6
Mn++ Hy3-
----
My(n-4)+ H+ d pH 7·10
Cv th~: Ca2+ + HYs-
Zn2+ + HY3-
--
----
--
----
Cay2- + H+
Zny2- + I-f'
dpH 9
d pH 9
A13++ H 2y2··
------ AIY- + 2H+ d pH 5
Cae phuc chat tli\Othanh duqc gQila cae complexonat. Vi dv cau truc cua
calci complexonat:

Dt;ia vao hinh 4.3 (tr 95) va bang 4.4 (tr 90) ta c6 th~ rut ra 2 k€t lu~n
lien quan den chuAn d9 t~o phuc eomplexon:

189
 1. HAng so,beI,l13'cua cac complexonat kim loai rat khac nhau. Vi vf}.yeo
th~ chon pH eua clung dich.thfch hgp d~ dinh htqng mqt ion kim loai
khi co mat mot hoac mot so ion kim loai khac. Mat khac .co t~ chuan
ctq lien ti€p cac ion' kim 'lol;lic6 m~t bAng each thay d6i pH dung djeh.
2. Do hAng soben 13' khac nhau d~n den S\i canh tranh tao phuc, Vtdu d
pH 11, calci complexonat co.lgK' = 10,7; magnesi eomplexonat eo
IgK' = 3,7 ; nenxay ra ph an u:n,g canh tranh:
Ca2+ + MgY pi(" GaY + Mg2+
....1'.

Nhu v~y neu dung dich co ea Mg2+va Ca2+ thi khi them complexon vao,
phirc CaY tao thanh truce, sau do 18. MgY. M~t khac neu them Ca2+ VaG dd
phuc MgY thi Ca2+ se dfty Mg2+ ra khoi phuc cua no. '
Hay khao sat dUd:p.gGong chuan dq cornplexon, sau do xem xet chi thi
phat hi~Il <ti~mtuong' dttdng eho chuft~ dq nay. .

3.1. DUdng cong chuin dq complexon:

S\i hlnh thanh phuc eomplexonat kim lOl;liMY ph\1-thuqc VaG pH dung
dich. Vi v2}.ychu~l1 dq complexon thudng dUQctien hanh trong dung 'dieh d~m.
Hllng sO'ben bi~u kien 13' eua phue MY dUQctinh theo phudng triM (4.37):
I3'MY = 13M)'I (a.M' ay)
Trong trudng hQp phue eomplexonat:
aM = 11 FO.M va ay = 11 Fo.y .(9.1)
Cho nen:
I3'MY =J3MY.Fo.M• Fo.Y (9.2)
Dva VaG phudng trinh (9.1) ho~c (9.2) d~ tinh nang Aq din bing cua ion
kim lo~i trong qua trinh ehu6n dq.

3.1.1. 'Duang cong ch.:utin d9 ion Ca2+ va M¥f+

1913caY= 10,70; Ig13MgY= 8,70
Ve dUdng cong chaftn dq dd Ca2+ O,01Mho~c Mg2+O,OlM blng dung (:Uch
,complexon III O,OlM trong dd d~m amoni pH 10.D~ th5ng nha't each khao sat
ta khong tinh den s\i thay d6i th~ Heh.
• Trude ctiim tudng aUdng:
- Khi chua them complexon III: [Ca2+] = CCa 2' ::: O,OlM ~ pea = 2,0.
- Khi them 90% eomplexon III: luc;fngCa2+ du la 10% nen:
[Ca2+] = 0,01 x 10% = 0,001~ pCa = 3,0.
- Khi them 99% complexon III: lUQngCa2+ du la 1%:
(Ca2+] = 0,01 x 1%:::0,0001~ pCa :::4,0.

190
 Neu chuan dQ dd Mg2+ trong di~u kien nhu Ca2+, n6ng dQ can bang cua
Mg2+trudc di~m tuong duong ciing co gia tr] nhu cua Ca2+.
• Tai die"m tuong duang: cac ion Ca2+ va Mg2+trong dieu kien chuan dQ d pH
10 khong tao phirc phu nen Fo.M=l. EDTA tao phuc vdi H+, theo bang 4.5 (tr
92), d pH 10 19UY(H) = 0,46 nen:
19l3'caY = 10,70 - 0,46 = 10,24
19l3'MgY = 8,70 - 0,46 = 8,24
Ndng dQ phuc tao thanh Ccompla O,OlM. Do phuc ben, st;iphan ly khong
dang k~ so vdi ndng dQcua no, nen chap nhan [CaY] ~ Ccomp = O,OlM. M~t khac
d di~m tuong duong ta co [Ca2+] = [Y'] nen:
[CaY]
13'caY =
[Ca2+]2
= 10 10.24 ~ pCa = 6 1.
'

Truong' hop chuan dQMg2+:

A' -
I-' MgY -
[MgY]
[Mg2+]2
= 10 8•24 ~ pCa = 5,1.
• Sau diem tuong duong:

[Ca2+]= [CaY] ~ [Ca2+] = 1,0.10-2

jJ'.[YI] jJ'.[Y']
Tr] s6 [Y'] duoc tinh tit n6ng dQphtrc Ccomp va ham uo,Y:

[Y'] = Ccomp .Fo,y = Ccomp / uo.y

- Khi cho du 1% eomplexon:
Ccornp = 0,01 x I%..= I,O.10·~
[Y'] = 1,0.10- .10- = 1,0.10.
4 0,46 4•46

r Ca 2+] = 1,0.10-2
1010.24.10- ..,46
== 10-7,8 ~ pCa = 7,8.
Trong trudng hQp chuAn dQMg2+:
M 2+] _ 1,0.10-2
10.5•8 pMg = 5,8
[ g - 108,24.10-4.46 -
~

- Khi eho du 10% eomplexon thi: pCa = 8,8 va pMg = 6,8.

- Khi eho du 100% complexon thi: pCa = 9,8 va pMg = 7,8.
Bimg 9.1 tom t&t ket qua tinh toan n6ng dQ can bAng eila Ca2+ va Mg2+
trong qua trinh ehu~n dQbAng dd eomplexon III O,OlM. Hinh 9.1 va 9.2 minh
h<;>abuoc nhay pM tren dUdng cong ehu~n dQeua 2 ion kim 10f,li tren.

191
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 OpH9:

Trude aii'm tuang duang:

- Khi them 90% EDTA: luong Zn2+ du la 10% nen:
CZn==0,01 x 10% == 1,0. 10.3
[Zn2+] == CZn'Fo,Zn=.1,0.10·3• 3,68.10.6 == 3,68.10.9 ~ pZn = 8,43
- Khi them 99% EDTA: luong Zn2+ du la 1%:
CZn=0,01 x 1% = 1,0. 10.4
[Zn2+] = 3,68.10.10 ~ pZn == 9,43
Tai ailm tuang duang: chap nhan n6ng dQ phuc ZnY tao thanh 1,0.10·2M,
n6ng ee bi~u kien [Zn2+ '] == [Y'] nen:
[ZnY] = A' = A F F
(Zn'].[Y'] I-' 1-" o,Zn'o,Y

= 3,20.1016.3,68.10.6.5,20.10.2 == 6,12.109
Ttl day ta co:

[Zn']2 = 0,01 = 1,63.10.12 ~ [Zn'] = 1,3.10.6

6,12.109
[Zn2+] :::: [Zn']. Fo,zn::::1,3.10.6.3,68.10.6 =4,78.10.12
~ pZn = 11,32.
Sau tuang duang:
Ndng dq phuc ZnY la O,OlM, chap nhan [ZnY] = O,OlM. Ncng dQ EDTA
du tinh theo 1U:Qngthem VaG sau di~m tuong duong:
- Them du 1% EDTA:
[Y'] == CED'J'A == 0,01.1% == 1,0.10.4

[ZnY]
[Zn'].[Y']
0,01
[Zn'].1,O.1O-4'
= 13' = 6 12.109 ~ °
[Zn'] :::: 163.10.7
,
[Zn2+] = [Zn']. Fo,zn::::0,163.10.7.3,68.10.6 =0,6.10.13
~ pZn:::: 13,22.

193
 - Cho du 10% EDTA thi nang dQ EDTA.tang len:
[Y'] == CEDTA = 0,01.10% = 1,0.10- 3

[Zn'] = 0, 163.10-8 ~ [Zn2+] = 0,-60.10-14

pZn = 14,2.
2. Neu giam nang dQ dd d~m 10 i~n, pH vAn gill nguyen nhung
[NH3]=0,0IM tr] s6 pZn trong qua trinh chuan dQ se thay d6i hdi vi gia tr]
aZn(NH,), se giam di nen Fo,Zn tang len:

4
aZn(NH 3)4 = 1+ LPi.O,Oli = 54,92
1

1,82.10-2

Trude diem tuang duang:

- Khi them 90% EDTA: lUc;1ngZn2+ du la 10% nen:
CZn= 0,01 x 10% = 1,0. 10-3
[Zn2+] = 1,0.10- .1,82.10-
3 2 = 1,82.10-5 ~ pZn = 4,74
- Khi them 99% EDTA: pZn = 5,74
Tai diem tuang dlidng:
I3'znY = 3,20.1016.1,82.10-2. 5,20.10~2= 3,03.1013
Cho nen:

[Zn']2 = 1,0.10-2 = 3 3.10-16 ~ [Zn'] = 1,82.10-8

3,03.1013 '

[Zn2+] = [Zn']. Fozn = 1,82.10-8.1,82.10-2 =3,3.10-10

~ pZn = 9,48.
Sau diem tuang duong:
- Cho du 1% EDTA:

[Zn'] - 1,0.10-2 = 0,33.10-11

- 1,0.10-4.3,03.1013
[Zn2+] = 0,33.10-11• 1,82.10-2 = 0,60.10-13
~ pZn = 13,2.
- Cho du 10% EDTA:
[Zn2+] = 0,60.10-14 ~ pZn = 14,2.

194
 Bang 9.2 tom tAt ke't qua tinh toan pZn trong qua trinh chuan d(>Zn2+
O,OlMb&ngdd complexon III O,OlMtrong d~m amoni pH 9 vdi 2 loai nang d(>
can bang cua NH3.
Bang 9.2. SI! thay 05i ella pZn trong qua trinh chu§n 09 bang eomplexon.
pZn khl pZn khl
% EDTA them vao
[NH3J=O,10M [NH3J=O,01M
0 2,0 2,0
90 8,43 4,74
-
99 9,43 5,74
100 11,3 9,48 Bltoc nhay
101 13,2 13,2
14,2
-
110 14,2

pZn
16

14

12

Hinh 9.3. f)lfdng cong 10

chu§n 09 ion Zn2+

4
90 92 94 96 98 100 102 104 106 108 110

Hinh 9.3 minh hoa duong eong chuan d(>Zn2+ theo ket qua cua bang 9.2.
Tit bang ket qua tren cho thay:
- Chap nhan chuan d(>sai so
1% budc nhay pZn khi [NH3]=0, 1M la gAn4 don
vi, Khi giam n6ng d(>[NH31xuong 10 l~n buoc nhay tang len 7,5 don vi.
- Ncng dQcan bang' cua NH3 cang Ion, buoc nhay tren duong cong chuan
dQ Zn2+ cang ngan, Nguyen nhan la do ham tao phuc phu tang len lam
giam nang dQ [Zn2+] trong qua trinh chuan d(>.Vi vay chi can them vita
du NH3 ngan can qua trinh tao ke't tua kern hydroxyd, kh6ng cAn thua
qua nhieu.

3.2. Chi th] kim loai

Trong chuan dQcomplexon co budc nhay pM, cho nen can co chi thi ion
kim loai d~ phat hien di~m ttidng dtidng. Trong th\ic hanh phan tich c6 2
nhom chi thi:

195
-
- Chi thi mau kim loai: do Ia nhimg chat mau huu co, co kha nang tao wi
ion kim loai nhung phuc chat co mau va trong nhimg dieu ki~n xac dinh,
mau ella phuc vdi mau ella eh~t chi thi t1,1do khac nhau. D1,1aVaGst.;t.thay
d5i mau nay d~ nhan ra di~m tuong duong cua phan ung ehuan dq.
- Phuong phap do the': dung di~n cue chi thj 18.Hg(II) complexonat hoac
Cu(II) complexonat d~ xac dinh bucc nhay the' trong qua trinh chu~n dQ.
8au day se trinh bay cu th~ mQt vai chi thi mau kim-loai thlidng dung.
Con phuong phap chi thi do the'se duoc de c~p trong Hoa phan tfch II .

.3.2.1. M9t so' chi thi mau kim loqi thuong dung
Yeu c&u eua chi thi mau kim loai:
MQt eh~t mau htru co dll<;'C
dung lam chi thj cho chuan de}complexon cAn
dap (tng 3 yeu cAu sau:
1. Phan (tng t~o phue mau eua ion kim lo~i M va chi thj Ind phai thu~n
nghieh va mau ella chi thi d d~ng t1,1do khae vdi mau cua phuc MInd.
M +Ind ~ MInd
2. Phuc complexonat kim lo~i MY phai ben hdn phuc MInd. Nghia la co
th~ xay ra phan ung c~nh tranh t~o phue:
Mlnd+Y ~ MY+lnd
3. 81,1d5i mau eua chj thi phai x~y ra d Ian c~n di~m tlldng dlldng. Noi
cach khac, s1,1d5i mau clla chi thj n~m trong blldCnhay pM.
Cae chj thi mau kim Io~i thlldng dung Ia acid da chue. Cho nen mau eua
chi thi thay d5i theo pH ella dd. Vi v~y khi ehQn chi thj cho chuAn de)me}tkim
l()~i b~ng complexon phai chc;mdd d~m co pH thieh h<;,pd~ phan (tng xAy ra
nhanh, hoan toan va mElUchi thi t1,1do Ind khac vdi mau ella phuc MInd .
• Den eriocrom T (ky hi~u ET):

Day la me}tacid 3 chuc, nhung nhom -803H ph an Iy kha m~nh, thudng

dung d~ng mu6i natri. Trong dd chi thj n~m d d~ng anion vdi co 2 h~ng sO'
proton hoa.
ET3. + H+ ~ HET2. 19K1= 11,5
Mau da cam

196
 19K2 = 6,3
Mau xanh Mau do
HAng s6 tao phuc cua ET vdi mQt s6 kim loai duoc trinh bay d bang 9.3.
D~ so sanh co dua vao bang hang s6 cua complexonat kim loai tuong irng.
ET tao phuc mau do hoac hdng vdi Mg2+,Zn2+, Cd2+. Vi v~y no thuong
duoc dung lam chi thi cho chuan dQ true tiep cac ion do trong dung dich d~m
amoni pH 10. Ngoai ra ET con dung cho chuan dQgian tiep:
- Dinh luong Ni2+,Pb2+bAng each chuan dQnguoc voi muoi Zn2+ d pH 10.
- Dinh luong Ca2+ bAng each them phuc MgY vao dd chuan dQ.

Bang 9.3. Hang 56 tao ph(tc (19P)cua ET

M2+ H~ng so Igp .lgilMY
Sa2+ Sal 3,0 7,76
Ca2+ Cal 5,4 10,70
·Mg2+ Mgl 7,0 8,7.0
Mn2+ MnL 9,6 Mnl2 17,6 13,7.9
Zn2+ Znl 12,9 znt, 20,0 16,50

• Murexid:
Murexid (Md) la mudi amoni cua acid purpuric. Dang muo'i nay t6n tai
ngay ca trong dd acid manh, Murexid la mQt acid 3 chuc -vdi 3 hAng 8&- cQng
proton 18.:
Md4- +H+ HMda-----
----- 19K1= 10,9
HMda. + H+
H2Md2. + H+ ~
---- H2Md2.
H3Md'
Ig~=
IgKa=
9,2
0

H 0 0 H
I I II I
N-C -C-N
/ ~ / \
O=C C-N --C C-O NU._+
\ / \ / ~4
N-C C-N
I II II I
H 0 0 H
L
Mau cua chi thi thay d6i theo pH cua dd:
HMda- ~ H2Md 2- ~ HaMd-
(xanh tim) (tim hoa cil) (do tim)

197
 Murexid t<;lO phuc vdi mQt 56 kim loai:
- 0 pH 12, tao phuc jnau do vdi Ca2+,
- o pH 7 - 9: tao phuc mau da cam vdi Co2+, Cu2+, Ni2+,
- d pH 10 -11,5 (~rn amoni) tao phirc mau do vdi Ag",
Nguoi ta thnong dung Md cho chuan aQ true tiep Ca2+, Cu2+, Ni2+ va Ag"

'Simg '9.4. Hang 56 tao ph(/c (Ig~) ella Murexid

M2+ Hling so Igp IgPMY
Ca2+ CaL 5,0; CaHL 14,5; CaH2L 22,7 10,70
Cu2+ CuH2L 25,1 18,80
Ni2• NiH2L 24,1 18,62

• M9t.s6'chl thi ·khiic:

Ngoai ET va Md la 2 chi thi thuong dung trong nganh duoc, nguoi ta con
dung InQt s6 chi thi khac:
- D~n chat pyridinazo: PAN, PAR
- DAn chat triphenyl metan: tim pyrocatechin, da cam xylenol
Chung deu la nhfrng acid da chuc c6 th~ tao phuc trong khoang pH rat
r~ng vdi nhieu kim loai.

8.2.2. Vung ehuyln mau eua chi thj kim loai

Chi thi ET:
Ham a cua chi thi ET: aET(H) = 1+ 1011,5h +1017,8h2
o p'H 10: UETtH) = 1+ 101,5 +10-2,2 = 32,6
Chi thi nam d 2 dang HET2• (F1=0,969) va ET3- (Fo=0,031). Dung dich c6
mau xanh cua chi thi dang HET2-.
Khi cluuin. d9 Mg2+: Ta c6 cac can bang:

k = [H+].[ET 3-] = 10-11,5

1 [HET2-]

Mg2+ + ET3-~ MgET- vdi P= [MgET-] -107,0

1 [Mg2+][ET3-]

Nhan kl voi 131 ta c6:

[.MgET-].[H+] = 10.11,5.107.0=
10-4•5
[HET~-].[Mg2+]

198

.--------------.----.-~.~-.-
 -- ---- --- ------~--

[M 2+]= [MgET-) .E:

g [HET2-] '10-4,5

Thay h=10-10 va ty 1~[MgET"]I[HET2-] thay d6i tit 0,1· 10 (d~ ph at hien

su d6i mau) ta co:

[MgET-] =
[HET2-]
° ,
1 -+ pMg = 5,5 + 1: mau ella chi thi HET2-

[MgET-] = 10 -+ pMg = 5,5 . 1: mau cua phuc MgET-

[HET2-]
Nhu v~y vung d6i mau ella ET khi chuan dQMg2+d pH lOla:
pMg = 5,5 ±1.
Khi chudn d9 Ca2+: phuc mau ella Ca2+ vdi ET:
Ca2+ + ET3- ~ CaET- Ig~ = 5,4
Voi each tinh tuong tl,i ta co:
pCa = 3,9 ±1.
D6i chieu vung chuyen mau cua chi thi vdi ket qua bang 9.1 ta thay:
- Vdi Mg'": budc nhay tren duong eong chuan dQvdi sai sO'1% la 4 - 5,8 eho
nen co th~ dung ET cho chuan dQnay.
- Voi Ca2+: buoc nhay tren duong' eong chuan dQ la 4 - 7,8_ Trong khi do
vung chuyen mau cua ET la 2,9 - 4,9 nen dung ET cho chuan dQ Ca2+ se
mac sai sO'IOn.
Khi chudn. d9 Zn2+:
Phuc cua chi thi vdi Zn2+ :

Zn2+ + ET3- ~ ZnET- 19~= 12,9

Thuc hien cac phep tinh tuong tu nhu vdi Mg2+,ta co:
pZn = 10,4 ±1.
D6i chieu voi ket qua d bang 9.2 ta thffy:
- Buoc nhay khi [NH3] = O,lOM: 9,43 - 13,2
- Buoe nhay khi [NHa] = 0,01M: 5,74 - 13,2
Trong ea 2 trudng h<Jp,chi thj ET rat phu h<Jpcho ehu~n dQeomplexon.
Chi thj Murexid:
Murexid thudng dung lam chi thj cho chu~n dQ Ca2+ bAng complexon d
pH 12. Ham tl;\Ophuc ph\). a. d pH nay:

199
 UMd(H) = 1+ kl·h + k1.k2.h2+ k1.k2.k3·h3
= 1+ 10.1,1+ 10-3,9 +10'15,9= 1,079
Nhu yf}.yMd tan tai b 2 dang Md4- (Fo=O,927) va Hl\'1d3-(F1=0,073). Khi
chuan d(l Ca2+ bang EDTA vdi chi thi Md ta co 2 can bang:
Ca2+ + Md4- .... ~ CaMd2- 19p = 5,0
lgk, = 10,9
Tfnh tuong tl;1 nhu chi th] 'ET, ta co:
pCa = 6,1 ±l.
.Nhu vf},ychi thi chuy~n til mau do cua phirc CaMd2. sang mau xanh tim
HMd3- cua chi thi, Doi chie'u Val' btrdc nhay pCa b bang 9.1 ta th(y hoan toan
co th~ dung chi thi nay cho chuan d(l Ca2+b~ng complexon.

3.3. Cac ky thu~t ehuAn dq complexon

'Prong chuang 7 (muc 7.4) da gidi thi~u 3 ky thuat chuan dQ: true tie'p,
thira tril va thay the'. Ba ky thuat nay dUQcsic dung rQng rai trong chuan d(l
complexon.

S.3.1. Chuan 49 true tiep

Ky thuat 'nay dUQc Stl dung khi co chi thi thfch hop, Vi du dinh luong
Mg2+, Zn2+ trong dd d~m arnoni vdi chi fhi ET. Khi cho ETDA tu til vao dd
Mg2+hoac .Zn2+,ph(tc MY t~o th~mh. d g~n di~m tuang duang co phan (tng
c~mh tranh t~o ph(tc:
Hy3. + MgET- ~ Mgy2. + HET2-
Chu~n d(l t~o ph(tc ke't thuc khi l1)au chuy~n hAn til mau do (ph(tc
MgET") sang mau xanh (chi thi HETz").

3.8.2. Chufin d9 thufl, tru

Khi khong co chi thi cho chuAn dQtn,tc tie'p, ho~c phan (tng cua EDTA voi
ion kim lo~i di~n ra ch~m, ngudi ta dung ky thu~t chuAn dQ thila tril: Cho
EDTA du vao dd hoa tan ion kim 109-i, phan (tng di~n ra:
Mn++ Hy3. ~ My(n-4)+ H+
Sau khi phan (tng ke't thuc, dinh lUQng EDTA du b~ng dd chuAn Mgz+
ho~c Zn2+ VOl chi thi ET. D~ chuAn d(l nay thanh cong thi phuc MY(n-4) phai ben
hon phuc MgY ho~c ZnY.
ChuAn dQthua tru con dUQcdung d~ phan tfch cac mAu co chua anion t~o
ra hQp chat it tan voi ion cAn dinh hiQng Mn+.LUQngEDTA cho du da ngan can
8\1 hinh thanh ke't tua.

200
 3.3.3. Chuiin dt} thay the'
Ngtroi ta cho du phuc ZnYho~c MgY vao dung dich phan tfch chua M'".
.
Ph an ling canh tranh tao phuc xAY'ra: Zn2+.hoac Mg2+se bi dAy ra khoi phuc
,
cua no:
MgY + M'" ~ MY(n.2)+ Mg2+
ChuAn d<)Mg2+da giai phong bAng dd chujin EDTA. Ky thuat nay thuong
dung khi khong co chi thi phu hop cho chuan d<)true tiep ion M'",

3.4. Ung dung cua chudn de}complexon

Chuan d<)complex on dUQcling dung rQng rai trong phan tich th~ tich d~
dinh luong cation kim loai, m<)ts6 anion va hop chat hiru co.
• Dink luc;mg ion kim loai:
Cac ion hoa tri duong 3 nhu Fe3+,In3+,Bi3+co th~ dUQcchuan d<)bang'
EDTA d pH ~ 1 rna khong bi hAu het ion kim loai M2+can trd nhu Ni2+,Co2+,
Zn2+, Cd2+, Fe2+ ••••
M~t khac, co th~ lua chon pH dd thich hop d~ dinh Iuong m<)ts6 ion khi
co m~t cua cac ion khac. Vi dQ.phuc EDTA cua Zn2+ho~c Cd2+b~n rung hdn
phlic MgY, co th~ chuAn de)Zn2+va Cd2+khi co mi!.t cua Mg2+d pH=7 voi chi
thi ET bdi vi phlic mau Mg2+voi ET khong xuat hi~n d pH nay.
Cu6i cung, trong chuAn d<)complexon doi khi ngudi ta dung chat "che" d~
khoa cac ion can trd. Vi dQ.khi d.n chuAn d<)Mg2, Ca2+trong dd co nhi~u ion
kim lo~i ni!.ng nhu Cu2+, Co2+,Ni2+, Cd2+... nguCsita them du mu6i KCN. Cac
ion nay t~o phuc b~n cyanid khong can trd chuAn de)Mg2, Ca2+bAng EDTA.
• Dink lztc;mgeac anion:
NgUCsita chuAn dQ gian tiep bAng cach chQn me)t thu6c thi't cation thieh
hQp d~ ket tua anion. Vi dQ.dung ion Ba2+d~ dinh h.tQnganion 8042.. Cho thita
Ba2+ ket tua he't 80/'. 8au do th\lc hi~n m<)ttrong 2 cach:
- Xae dinh htQng Ba2+ du sau ph an ling ke't tua.
- Hoa tan Ba804 b{tng EDTA du. Xae dinh EDTA du b{tng Mg2+hoi!.cZn2+
tit do tinh ra hlim lu<;lng8042,.
• Xac dink de; ding eua nude:
D<)cung toan phAn cua nuoe la t6ng mu6i calei va magnesi tan trong
nuoe. Co th~ xac dinh de) cling toan phAn bAng complexon III voi chi thi den
erioeromT.
Lay m~u nuoe eAn dinh lU<;Ing,cho them chi thj den eriocrom T vao. Chi
thi si t~o phlic mau do yang voi mQt ph AnMg2+trong m~u. Khi cho EDTA vao,
EDTA se phan ling voi Ca2+ t1;ldo, saU:do voi Mg2+t1;ldo (vi phuc CaYZ-b~n
hdn phuc Mgy2-), den Ian c~n di~m tUdng dUdng EDTA se pha phlic cua chi thi
voi Mg2+,giai phong ra chi thj t1;ldo co mau xanh.

201

--------_- --------_----------
csu HOI VA BAt T~P
9.1. Ve dUdng cong chuan aQ tao phuc bAngdd AgN03 O,lN vdi cyanid?
:9.2. Trinh bay nhung lqi the cua phuong phap complexon III?
9.3. Gild thtch .3 yeu du doi vdi chi th] mau kim Ioai trong chuan dQ
complexon. 'I'ai sao lai dung d~m .ameni pH 10 'trong chuan de?
Zn2+hoac Mg2+ bang' complexon vdi chi thi ET?
9.4. Trong chuAn de? Zn2+b&ng complexoa trong 4~m .amoni pH 9 budc
,nhay pZn giam khi {NHaltang.-Giai thich tai sao?
9:5. Dung vi du minh hoa 3 ky thuat chuAn d9 complexon. 'I'ai sao nguoi
ta thu'im,g:dung chu,An de?gifm tie'p.
9.6. Hoa tan 1,0236g h6n hop die halogenid bae khan trong 50,00 ml
KCN 0,181N. ChuAn de?eN" du he't 28,14 ml AgN03 O,lOlN. Tinh %
Ag trong han -hop .dem dlnh.ltiQu-g. Cho Ag = i08.
9'.7. MQt dd EDTA co de?chu:1n 1,08!:pg CaO/ml. Hay tinh:
- N6ng de?M
- DQchuAn rug MgO/ml
- DQ chuan mg FezOiml
9.8. Dieu ehe dd EDTA btUilghoa tan 3,853 g muoi Na2F12Y.2H20 trong
nu{jcvua du 1 lit. Tinh n6ng dQM eua dd biet de?fun cUa cha1 tan 0,3%.
9.;9. MQt mAu nttac ti~u 24 gia dtCc;1c
pha loang th~nh 2,000 lit (dd A). Lay
10;00 ml dd A them vua dU d~m pH 10 va chuAn dQ b&ng dd EDTA
0,003474M, .bet 26,81 ml. Lay 10,00 ml dd A, them dd oxalat d~ ket
tua Ca2+duoi d~ng calci oxalat ..Lay ri~ng ket tila hoa tan trong acid
va chuAn'dQ voi dd EDTA d tren, !let 11,6,3 ml:Tinh hiQng Ca2+ va
MgH trong nuac ..ti~u 24 gia.
9.10. MQt mAu phan tich X co muor Ag+ hoa tan. Lay.25,00 ml mAu x
them VElD do phl1c Ni(CN)4 d~ ehuy~n Ag+vao phl1c:
Ni(CN)1 + 2 Ag+~ 2 Ag(CN)2' + Ni2+
Ni2+ giai ph6ng sau phan (lng duc;1cchu:1n di? vCii,ddEDTA 0,02408
M, het 43,77 ml. Tinh n6ng d9 M eua mAu X.
9.11. Tinh h~ng so oon hi~u kien eua phuc EDTA-Mn2+ d 3 tri s6 pH: 7,0;
9,0 Vg 11,0 (H&ng so ben ctra -MnYla 6,2.1013).
9.1.~. Ve duang coIig chuAn de?50,00 ml dd Sr2+ 0,0100 M b&ng dd EDTA
0;0200 M tro~g d~m pH 11,0. Tinh trj s6 pSr sau khi them: 0,00;
10,GO;24,00; 25,00; 25,10; 26,00 va 30,00 ful dd EDTA. Biet phuc
S;rYco hang s6ben 4,3.108• Ye~ cAu tlnh den sl,1thay d6i th~ tich.

202
 Chu'dng 10
..1 ... ",,'
eo• KET TUA
?

CHUAN

" ,J
1. NGUYEN TAC
Chuan d9 ke't tua la phuong phap dinh luong th~ tich dua tren co Sdcua
phan trng tao thanh cac chat ke't tua. Yeu cau cua phan ung dung d~ dinh
IUQngphai xay ra nhanh, nhay, chon loc, hoan toan ... va chon duoc chi thi d~
nhan ra di~m tuong duong.
Trong hoa hoc co nhieu phan irng tao thanh ke't tua, nhung chi co so it
duoc ung dung d~ chuan d9 bdi vi:
- Nhieu ph an ung ket tua xay ra cham nhat la trong cac dung dich loang
an
khong thich hop cho ph ung' chuan d9. ..
- Nhieu ket tua co thanh phan khong 5n dinh do bi nhiem b~n (C9ngket,
tua theo) gay sai s61dn.
- Khong tim dUQcchat chi thi thich hQp.
Bdi v~y trong phan tich, phuong phap dUQcap dl,mg rQng rai nhat la
phuong phap dinh lUQngbAng b~c: D\ia tren co sd cua phan (tng t~o ket tua
giua Ag+ (thudng dung la AgNOa) vdi cac ion X' (halogenid) va CNS'
(thiocyanat). Dudi day khao sat chu ye'u phuong phap nay .
., ,... ",. "
2. KHAO SAT DUONG CONG CHUAN DQ DO B~C
Dinh lliQng dung dich NaCl O,lN bAng AgNOa 0,1 N ( TAgC1 = 10.1°). D~
don gian trong tinh toan, ta bo qua anh huang cua ho~t dQva s\i pha loang.

2.1. Khao sat sl:j.bien d5i nang dQAg+va CI' trong qua trinh dinh hic;1ng
• Trude aii'm tUdng aUdng:

203
 - Trude khi cho AgN03
Dung dich NaCl 0, IN ~ pm = 1 (pCl =- 19[CI'])
- Khi b&t dAu cho AgNOa• ta co phucng trinh phan ung:
Ag" + Cl -".., AgGI..!,
vci TAgC1 = {Ag+].{CI"] ::: 10,10
Trang dung dich co tiia AgCI, va jon cr con chua duoc dinh hrong he't. Ta
tinh nang dQ ion Cl: trong dung -dich theo IU,Qngphan (tng hqp thuc.
Vi du: (5 th(ii odi~JIlthem vao 99,9% AgNOa thi 99,.9% ion cr duoc k~t tua
duei dang AgCI va n6ng d9 ion cr con hili la 0,1%, cho nen trong dung dich
n6ng dQ Cl Ia:

[Cr] = 0,1 x-lO-1 == 10-4 M ~ pCl= 4

100
Tit TAgC1 =[Ag+].[-Cl"]=lO·lo
10-10
~ Ag+ = 10-4 = 10-6 M ~ pAg:= 6 (pAg= -lg[Ag+])

Tt;ti diim tuang dUdng:

Dung dich t6n t~i tua AgCI

do v~y:[Cr] := [Ag+] = ~TAgCI = .JlO-H) = 1()-5

pCI = pAg = 5.
'Sau. die"m t/tung duang:
Trong dung dich t5n tai tiia Agel va Ag" du, Tmh n6ng dQ ion, 'lC!"] trong
dung dich thea htl}ng Ag+ duo
Vi d~:_Khi cho thua 0,1% AgNOa, ta tinh n6ng dQ ion Ag+ du;
Ag+ = G,l .xlO-1 = 10-4 M -+- pAg = 4
100
10-10
Va [Cr] = 10-4 = 10-6 ~ pCI = 6.

St,t thay d6i eua pCl va pAg trong qua trinh chu~n dQ dUQc trinh bay d
bang 10.1 va blnh 10.1.

2.2. DUCJng bi'u di~n dinh hicjng: dUQGtrinh bay a.hinh 10.1
• 0

204
 ------------- -~--_,.....,,-~

Bang 10.1. St,t thay d6i ella pCI va pAg trong qua trinh djnh IU'Qng

% AgN03 them vao pAg pCI Ghichu

0,00 1
90,00 8 2
99,00 7 3
99,90 6 4
100,0 5 5 BltClc nhay
100,1 4 6
101,0 3 7
110,0 2 8

10 ---------------------~----------------------
I
I
9 ---------------------~----------------------
I

8 ---------------------f--------------I
p~1
I
7 ----------------- ---7--- -----------------
I
I
6

5
4
I

3 ------------------ --~- ------------------

I
2 _J".... :":_=
=-::_~_'!'::
__ - - - ~- - - - - - - - - --=:- -:-:-~- _=-=_........ _..J. p Ag
I

I ----------------------~---------------------
I
o I

90 92 94 96 98 100 102 104 106 108 110

Hinh 10.1. Duong eong djnh Ilf<;JngNaCI 0,1 N bang dung djch AgN03 0,1 N

2.3. Nh{in xet

Duong bi~u dien co dang chung tuong h;t cac duong bi~u di~n dinh luong
khac trong chuan dQ th~ tich. a g~n di~m tuong duong vdi sai s6 ± 0,1% co
budc nhay pCI tit 4 den 6 va pAg tit 6 ve 4.

2.3.1. Buac nhily cua duimg bie'u diin ph,! thu9c vao n6ng d9
N6ng dQ cua dung dich can chuan dQ va cua thuoc thli cang cao budc
nhay cua duong cong chuan dQcang dai. Neu n6ng dQdung dich NaCI1N dUQc
chuan bang dung dich AgN03 1M thi budc nhay la 4 don vi (pCl tit 3 len 7),
khong phai 2 don vi nhu trudng hQpn6ng dQO,IN.
Ne'un6ng dQgiam, buOcnhay ngAnl~i,th$.mchi khong con buoc nhay nua.

205
2.3.2. Buac nhiiy ella dliilng bie"u diin ph,! thu§c vao tick s6~t{1,n
TIch so tan cang be, tuc 18.n6ng d9 chat tan cang it thi budc nhay cang
dai. Hinh 10.2 minh hoa 93:C dudng cong chuan d9 cac halogenid, iodat va
-bmmat bang AgNOa•
(A): 1- co tich so tan 18.8,3. 10..,,17
(B): Br- co tich so tan 18. 5,2.10-13
(C): or co tfch so tan 18. 1,8. 10...10
(D): 103- co tich so tan la 3,0. 10-8
(E): BrO;- co tich 56 tan la 5., 7. 10-5

20 40 60 80 100 120

Hinh 10.2. Duong cong chu§n 09 hatogenid. iodat va bromat bang AgN03 O,1M
? ~ . ~ ~

3. CHI THl HOA HQC CHO CHUAN'DQ,DO'B~C

Trong phaong phap do bac d~ phat hi~n di~m tuong duong nglidi ta co
th~ dung chi thi hoa hoc va chi thi di~n hoa, o day ta khao sat chi thi nhom
d~u, con nhom thu hai se duoc trinh bay d hQCphan Hoa phan tich II.
Co 3 phucng phap dung chi thi hoa hoc trong phuong phap do bac,

3.1. Phuong philp Mohr

Trong dinh ludng' ion clorid, bromid b~ng AgNOs ngudi ta dung chi th] 18.
kali cromat. Khi tdi g~n di~m tttdng duong i9n Cr04-2 ket hgp vdi Ag+t~o ra
ket tlia do Ag2Cr04• C~n xac dinh n6ng d9 chat chi thi d~ tlia Ag2Cr04 xuat
hi~n trong bUdCnhay tren dudng cong chu~n d9 (sai s5khong qua ± 0,1%).

206

~----~-------~~~- ---~~--------
 Cac can bang co mat gifia pha d.n g6m 2 ket tua AgCl, Ag2Cr04 va dung.
dich la: [Ag+]{Cn = =
1. 10-l<l TAgC1

= 2.10-12= TAg2CrZ04
[Ag+]2[Cr04-2]
Khi tua Ag2CrO4xuat hien, n6ng dQAg" ling dung vdi ca hai can bang tren:

. [cr] ..= TAgC( = 10-10 = 7.10-5

~[CrO;2] TAxPP, -J2.10-12

a di~m d~u buoc nhay n6ng dQ[Cn = 10-4 nen:

CrO-2] = ( [cr ]) 2 = 10-8 = 2

[ 4 7.10-5 49.10-10

- o dung' di~m tuong duong ten = 10-5 nen:

:.. 10-10
[Cr0
. .
4:7] =='49:10-
., . = 0,02
)0

?? .: ~ -, ~•

- 0 diem sau tuong duong khi thua .0,1%AgN03 thi [Cl"] = 10-6 nen:

[CrO-4 2] = 10-12 = 2.10-4

49.10-10
Nhu vay d~ co tua Ag2CrO4 xuat hien vdi sai s6 ± 0,1%, nong dQ ion
Cr04-2 thay d6i trong pham vi rat rQng tu 2.10-4 den 2M. Trong thuc te thuong
dung chi thi vdi nong dQ 10-2 den 10-3M. Neu dung n6ng dQ cao hen 10-2M
dung dich co mau vang darn kh6 nhin su chuyen mau, Neu dung n6ng dQthap
hon 10-3M kho phat hi~n mau vi ket tua Ag2Cr04 t~o thanh it.
Lltu j:
- Phudng phap nay chi dung lam chi thi cho chu~n dQion cr va Br- d moi
trudng trung tinh hay kiem yeu (pH = 7-10). 6 moi trudng acid ion
CrO4-2 phim ling voi ion H+lam giam dQnh~y cua chi thi:
Cr04-2 + H+ ~ HCr04-
Neu d moi trudng kiem m~nh, tua Ag20 se t~o thanh truoc tua Ag2Cr04•
- Trong chuAn dQionr va SCN- khong th~ dllng Cr04-2lam chi thi vi xay
ra hi~n tu<;lnghap ph\).kho phat hi~n di~m ket thuc phlm ling.

3.2. Phtidng philp Volhard

Co t.h~.xac dinh b~c rat chinh xac d moi trudng acid voi thuoc thi't SCN-
t~o thanh ket tua AgSCN. Ion Fe3+ se 18. chi thi cho ph an ling chu~n dQdo t~o
ra phlic mau do:

207
 Fe3+ + SCN- ~ Fe(SCN)2+vdi K =' [FeCNS2+]. = 14.102
[Fe3+].[CNS-] ,

TAgSCN = 10-12 nen d di~m tttdng duong ta co pSCN == 6. Hay tinh xem cAn
co nang dQ Fe3+ 13. bao nhieu d~ phuc mau do xuat hi~n dung d d:i~m nay.
a d~m tuong duong thi:
[Ag+],= [SeN] + (Fe(SCN)2+]
- Co th~ phat hi~n duqc mau 40 cua phuc Fe(SCN)2+ khi dQ cua no oong
trong dung dich khoang 6A. 10,..6M. Bi~u thuc tich so
tan cUa Ag(SCN) la:
[A~f][SCN-] = 1,1. 10-12
[Ag ='l [~~~:l
=[ SCN-]+ 6;4.10-<

[SCN-]2 + 6,4. 10-6[SCN-] - 3,,1. 10-12= 0

Giai phuong trinh nay ta co lSCN-] = 1, 7. 10~7
- Hang s6 tao phuc cua Fe(SCN)2+la 1,4. 102
Fe(SCN)2+ = 1 4.102
Fe 3+ SCN- ,

~[Fe3+]= 6,;.10-6 7 = 0,27M

1,4.10 .1,7.10-

Ne'u chap nh~n sai f!6 chufln dQ ± 0,1% thi n6ng dQ ion Fe3+ (tinh toan
tueng tt;!nhu tren) dao dQhg tit 0,002 de'n 1,6M.
Trong thuc te' ne'u nang dQ Fe3+ tren O,2M thi tnllu vang cua E.O lam ta
kho nhan st;! d6i mau -cua dung dich chuan d~. Vi v~y ngudi ta tht1dng dung
nQng dQchi th] Fe3+ khoang O,DIM.
Llluy:
- Moi tfudng dinh luqng phai la acid m~nh d~ tranh st!. thuy philn cua
Fe3+, tranh U;lotua Ag20 va giam hi~n t\,1Wlghap ph\)..
- D~ lo~i tru sai s6 do hap- ph\)., Volhard dUng kg thuil-t chufln dQ nguqc:
cho AgNOa dl1 phah (tng voi Cl-, Br- va r trong m~i truCing acid. Djnh
luqng AgN03 du bAng dung djch KSCN vOi chi thj phen s&t amon.
Voi ion cr, mQt kho khan moi xay ra do ke't tua AgSCN it tan hon AgCl
nen co ph an ling:
,J..AgCl + SCN- ~ Ag~CN,J..+ Cl-
[cr] = TAgCl
-=-----=~ 10-10
= _._ = 100
[SCN-] TAgSCN 10-12'

208

_ .... _-_._---
 [ct]
Nhu vay khi co mat tua AgCl thi chi den khi ti so n6ng dQ [SCN] =100

phan ling mdi dat duoc tdi can bang, mot IUQngSCN- duoc dung them dua den
sai so thieu chuan dQ.D~ khac phuc hien tuong nay nguoi ta ap dung mQtso
bien phap:
- Loai bo ket tua AgCI truce khi chuan dQAgN03 du bang' KSCN.
- Them mQtit dung moi htru co, tot nhat la nitrobenzen vao h6n .dich nude
AgCl, ket tua nay dong von lai (J mat phan each nude- dung moi nen
khong phan ling vdi KSCN.

3.3. Phuong phap Fajans

Day la phuong phap dung chi thi hap phu, Do la nhung hop chat hiiu co
bi hap phu tren b~ mat, ket tua. Su hap phu xAy ra g&n di~m tuong duong,
thuong co su thay d6i trong cau tao phan tu d~n den st;lthay d6i mau.
Fajans la ngtidi d&utien phat hi~n ra fluorescein va cae d~n xua't ella no
co th~ dung lam chi thi ha'p phl,leho phudng phap b~c. Co th~ giai thich st;ld6i
mau ella chi thi fluorescein nhu sau:
Trudc di~m ttidng dUdng, lU<JngAgN03 cho vao NaCI con thieu, nen tlla
t~o thanh AgCI se ha'p ph\! ion cr du trong dung dich, vi vf!_ycac h~t ket tila
mang di~n tich am. Sau di~m tUdng dUdng,ion Ag+co du nen dU<Jc ket tila ha'p
phl,l.Vi vf!_y,ket tila mang di~n tich dUdng.
Chi thi fluorescein la mQt acid yeu HFI co mau vang, phat huy-nh quang
m~nh. Trong dung dich chi thi HFI bi phan ly:
HFI ~ H++Fr
Chinh ket tlia SaU di~m tUdng dUdng mang di~n tfeh dUdng ha'p phl,l
anion Fr cua chi thi, lam no chuy~n sang mau h6ng. St;lchuy~n mau nay giup
ta phat hi~n di~m ket thuc cila ehu~n dq.
Trong chu&n dq ion Br- va 1- bilng dung dieh AgN03, chat mau eosin
dU<;lC
dung lam chi thi. Eosin la mqt acid huu cd yeu, phan ly trong dung dich
nude t~o ra anion eosinat E-:
HE ~ H++ E- (mau h6ng)
TUdng tv nhu trudng h<;lpdinh lu<Jngcr, sau di~m tUdng dUdng h~t tua
AgBr ho~c AgI se ha'p phl,l ion Ag+mang di~n tich dUdng. H~t nay hap phl,l
anion E-, ehuy~n mau clla E- til h6ng sang do tim.
D~ co th~ Stl dl,lngchi thi hap phl,l doi hoi ket tlla cling nhu chi thi phai
co nhung d~c tinh sau:
1. Ket tila phai cokieh thudc clla h~t keo til 1- 100m~ha'pph\! toi da chi thi·
2. Ket tua ph:h ha'p phl,lmljtnhdi.c ion eua no d~ mang di~n tich.

209
 3. Muc dg hap phu chat chi thi len he mat ket tua d gftn di~m tuong
duong quyet dinh sai s6 chi thi va kha nang ling dung. cua no. Neu chi thi hi
hap phu manh len he mat ket tua lam eho su d5i mau xay ra qua sdm truce
khi den di~m tuong duong. Nguoc lai, neu chi thi bi hap phu qua yeu di~m ket
thuc chuan dg se duoc phat hien qua muon. Chinh vi vay mQt chi thi chi duoc
xli dung trong mQt 86 truong' hop nh-ii'tdinh. Vi du: eosin chi dung trong chu&n
dQBr- va I", khong th~ dung eho ehuan dQ cr.
4. pH cua dung djch anh hUdng den chuan dQhdi vi cac chi th] hap phu la
cac acid yeu. Dang hoat dgng cua chi th] la ion lien hop cua ch~t mau. 'Nen pH
chu&n dg co lien quan den hitng 86 phan ly cua chi thi, fluorescein co h{tng 86
khoang 10-7, vi v~y trong dung dich acid, n6ng dQanion Fr qua nhc, kh6ng
xay ra 81,1deSimau, pH t6t nhat cho trudng h<;lpnay la 7- 10. Voi eosin, ngu~e
ll(lido chi thi la mQt acid ml(lnh hon nhieu, nen chuftn dg co th~ dU<;lC
thlfc hi~n
d pH ~ 2.
Mgt 86 chi thi hap ph\l thong d\lng duQc neu ra l1 bang 10.3
Bang 10.3. M9t so chi thi M'p ph\) thOng dl:Jng
chi thi Ion dl1<;Jc
chu~n d~ Chat chu~n Oieu ki~n
Diclorofluorescein cr Ag+ pH;: 4
Fluorescein cr Ag+ pH ;: 7- 8
Eosin Br-, r, SCW Ag+ pH =2
Thorin S04- Ba2+ pH = 1,5- 3,5
3.4. (rng d....ng cua chu~n d<)do b~c
Phftn IOn chu&n dg do hl(lcthudng th1,1Chi~n hAng chuftn d'Qngti{;lCthea
phudng phap Volhard. AgN03 d day dU<;ledUJJ,gnhu 18.chat goc. Dung dich
chuftn KSCN dU<;lcchu&n ll(livai dung d!ch AgN03. Bang 10.4 tom t:1t cac ion
co th~ dU<;lcchu&n dg hAng phuong phap do b~c.
Ngoai ra, ngudi ta con dung chuftn dg ,ket tua vai cac thuoc thli khac
nhau nhu Hg2(N03)2' BaC12, Pb(NOJ2' K4Fe(CN)6' Nhat la hi~n nay gia thu6c
thli g6c'AgN03 cao nen ngudi ta co khuynh huong dung Hg2(N03)2 thay the.
Bang 10.4. PhU'dng phap chuan 09 kat tua b~c
Ion dlt<;Jc
chu~n d9 chi thi Ghi chu
Br-, 1-, AS04-3,
Volhard KMng can I09i ket tua cUa b~c
CN-, CNS-
C03-2, Cr04-2, CN-,
Volhard L09i ket tua truac hJC chu~n d9 b~c dv
cr, P04-3, S-2
ket tlia K+vai B(CsHs)4-' cho them Ag+ dv d~ cO
K+ Volhard cai tien AgB~C6H$)4J, va chu~n d() Ag+ dV b~mg KCSN
Br-, cr Mohr, chi th! hap phl,l Chu~n d9 tn!c tiep
Br-, cr, r, Se03-2
Zn+2 ket tlia ZnHg(SCN)4' Iqc, hoa tan trong acid.
Volhard cai tien
Them Ag+ dv va chu~n d(>

210
. -----------------

4. PHt1<1NGPHAp DO THUY NGAN (I)

4.1. Phuong phap djnh luong d':l'a vito dung djch ehuc1n cua mucH Hg22+
Phuong phap nay dung d~ dinh luong mQt so chAt dua vao dung dich
chuan cua mu6i Hg22+(thudngdung Ia HgiNOa)2)'
Khi cho dung dich Hg22+tac dung vdi Cl, Br, L..se tao thanh nhilng tua
it tan Hg2C12, Hg2Br2, Hg212... tuong tl,tnhu ke't tua AgX:
Hg22++ 2 Cl ~ Hg2C12,!..
So vdi phuong phap do bac, phuong phap dinh luong bang' thuy ngan (1)
co mot so uu di~m sau:
- Khong phai dung de'n nhfing hoa chat co bac Ia mQtkim loai qui diit hen
thuy ngan.
- Mu6i thuy ngan (I) it tan hon so vdi mu6i bac tuong ung do do khi dinh
IUQngCI-bang Hg22+budc nhay tren duong cong dinh luong dai hon.
- Co th~ dinh Iuong true tiep bang thuy ngan (I) d moi truong acid, trong
khi dinh lUQngbAngbl;lCphai d moi trudng trung tinh.
Nhu<;Icdi~m cua phudng phap dinh htQngbAngthuy ngan (1) Ia mu6i thuy
ngan dQc.Do do khi lam vi~ phai het suc th~ trQng.

4.2. chi thi thlidng dung

- S&t sulfocyanid Fe(CNSh trong qua trinh dinh lUQng den g~n di~m
tUdng dUdng dung dich se mat mau do Hg22+ du se phan (tng:
=
3Hg22++ 2Fe(CNS)a 3Hg2(CNS)2+Fe3+

- Diphenylcacbazon:
Nhlitnra di~m tudng dUdng do t~o voi Hg22+tua mau xanh.

5. MQT s6 UNG Dl}NG THVC T:E

5.1. Cae dung dieh ehu§:n
Cac dung dich chwln hay dung la NaCl 0,05N, AgN03 0,05N va KCNS
0,05 N. Nhilng dung dich nay dUQcpha til NaCl, AgN03, KCNS. Ca ba chat
nay co th~ dUQChnh che d~ dl;lttieu chu~n chAt g6c:
• Tink eke'NaCl: Pha dung dich NaCl bao hoa khoang (36g/100ml). LQclay
nuoc lQc,sau do them HCI d~c vao d~ ke't tua het NaCl. LQClay NaCl.
Dem rita bAng nuoc cat, sau do sAykho d 270°C, tan thanh bQt va nung
tie'p d 500 - 600°Cde'n khoi lUQngkhong d6i, thu dUQcNaCl tinh khiet.
• Tink eke'AgN03: Hoa tan AgNOa trong nuoc (ti l~ 100g AgN03 cho 45ml
nuoc). LQcqua ph~u IQcthuy tinh (khong dung giay lQc).Lay tinh th~

211
 AgN03 say kh6 d 100°C, sau do say them d 220 - 250°C khoang 15 phut
(kh6ng duoc say qua 250°C d~ tranh AgN03 bi phan huy mot ph~n thanh
AgN02)· AgNOa thu duoc kh6ng .hut flm. nhung phiii d~ trong 19 mau,
tranh anh sang.
• Tinh ehe'KeNS: Hoa tan KCNS trong nucc tll~ 68,5g/100ml nude, Thuc
hien ket tinh lai 2 lAn, lam kh6 trong binh hut Elmld nhiet ~Q thuong, sau
do say d 100-150°C. Cu6i cung say them d 190 - 200°C trong 2 phut. Khi
do KSCN thu du(;jcse tinh khiet va kho. bao quan: cAmtranh anh sang va
cac khoi acid (KCNS kh6ng hut Elmtrong khf qtiy~n co dQ Am dudi 45%).

5.2. Djnh h.igng NaCI theo phuong phap Mohr

Trong m6i truong trung tinh tien hanh chuan dQ NaCI bAng dung dich
chuan AgNOa vdi chi thi la K2Cr04•
Ph an ung chuan dQ: NaCI+ AgN03 ~ AgCl! + NaN03
Nhan ra di~m tuong duong khi du AgN03 se cho ket tua mau nau do
Ag2Cr04:
K2Cr04 + AgN03 ~ Ag2Cr04! + 2 KN03
CAn m6i trudng trung Hnh nen neu dung dich acid phai trung hoa b~ng
NaHC03 hay CaC03 (cho thita CaCOa, dem du5i het CO2, d~ nguQi). Neu dung
dich kiem phai trung hoa b~ng HNOa• Luu y khi pha AgN03 kh6ng du<;jccho
them HNOa•

5.3. Dinh lligng KCNS

Dl,tatren cd sd phan Ung t~o ket tua v& AgN03 theo phUdng trinh phan Ung:
AgN03 + KSCN ~ AgSCN,!. trAng + KNOa
ChI thj la Fe3+ (hay dung Ia phen sAt amoni). Trong chuEln dQriay thudng
d~ dung djch KCNS tren buret, binh non dl,tng AgN03• Nh~n ra di~m tUdng
dudng khi xuat hi~n mau do cua phuc FeSCN2+:
Fe3+ + SCN- ~ Fe(SCN)2+ mau do
Phan ung chufln dQphai tien hanh trong m6i tnidng acid (hay dUng HNOa)

5.4. Dinh llic;tngBr', 1-bAng phlidng phap Volhard •

Djnh lU<;jngtheo phudng phap chuAn dQ ngu<;jc(chuAn dQ thita trit): Cho
AgN03 du chinh xac d~ ket tua het Br' (hay 1') theo phan ung:
AgNOa + I' = Agl! + N03'
Sau do dinh lU<;jngAgN03 du b~ng dung dich chuAn KCNS voi chi thi
Fe3+ . Tinh ket qua dl,ta tren c6ng thuc:
VAg+ NAg+= Vr.Nr. + VCNs.NcNS.

212
 5.5. Djnh ltiqng CI- b~ng phtidng phap Volhard
Tien hanh dinh luong theo phuong phap chuan de?nguoc nhu truong hop
cua Br, I' dtren:cho AgN03du chinh xac d~ ket tua het Cl theo phan ling:
AgN03 + Cl = AgCl! + NOs-
(d11 chinh xac)
Sau khi phan ling xong, dinh IUQngAgN03 du bang dung dich chuan
KCNS voi chi thi Fe3+:
CNS' +Ag+ ~ AgCNS! trang
CNS- +Fe'" ~ FeCNS2-t mau do
Trong truong hop nay, d~ tranh sai s6 ldn, ta phai IQcloai bo ket tiia
AgCI trudc khi chuan de?AgN03 du bAng KSCN. Ki thuat nay duoc thuc hien
bang each cho phan ling (1) xay ra trong binh dinh muc du 100,0 ml, d~ liing,
loc qua 2 lfin giay loc (nude loc phai trong), Lay chinh xac 50,Oml nude loc,
chuan de?Ag" du bang KCNS. Nhu vay ta co cong thirc:
VAg+ NAg+= V1.N1_ + VCNs.NcNS-
Phuong phap nay chi cho ket qua chinh xac khi lc;>c
lo?i bo ket tua AgCl
trtiOCkhi chu~n dQAgNOa du; n6ng dQCNS-,Ag+,Cl xap xi nhau.

5.6. Dinh ltigng Br', I- b~ng phtidng phap Fajans

Thl!c hi~n phan ling ket tua Br-, 1bAng dung dich chu~n AgNOa voi chi
thi hap ph\l la natri eosinat trong moi trudng acid acetic. Ion eosin at K la
base lien hQp cua acid huu co HE, trong dung dich co mau h6ng, khi dinh
lUQngphan ling xay ra:
Ag++ 1-~ AgI!
Sau di~m tuong duong khi du 1 gi<;>t Ag+, cac ti~u phan AgI se hap ph\l
Ag+d tren be m~t se tich di~n duong, cac ion trai dau K se bi hap ph1,lva mau
se chuy~n tit h6ng sang tim, phep dinh lUQngket thuc.

5.7. Dinh ltigng CI-b~ng phtidng phap Fajans

Tuong tt;Lnhu dinh lUQngBr-, 1- d tren, nhung trong trudng hQp nay ta
dinh lUQngCl- bAng dung dich chu~n AgN03 yoi chi thi hap ph1,lla fluorescein
trong moi trudng trung tinh.
Chu~n de?ket thuc khi mau chuy~n tit yang xanh sang h6ng do.

213

---,
 ·--------.-~-----_-----------.,........:._.............. _,............-

csu HOI vA sAl T~P

10.1. Khao sat dl1dng bi~u di~n dinh hrong Cl: b~ng phuong phap do bac,
1'6.2. Nguyen t~c, di~u kien va ung dung cua phuong phap dinh htQng
bftng bac thea phuong phap Mohr.
1.0.3. Nguyen tllc, di~u kien va ung dung cua phuong phap dinh luong
hAng bac theo phuong phap Volhard.
10.4. Nguyen t~e, di~u kien va ung dung cua phuong phap dinh luong ..
bang' bac theo phuong phap Faijans.
10.5. D~ dinh luong KBr trong dung dich co m~t HCl nguoi ta tie'n hanh
nhu sau:
- L~y 20,00 ml dung dich han hop dinh 111c;sng he't 4,50 ml dung
dich NaOH 0,1000 N VCfichi thi phenolphtalein.
- Lffy 20,00 ml dung dich han hop, them vao 25,00ml dung dich
AgNOa 0,1000N. LQcrita ke't tua. Djnh luong' toan bQn110CIQcva
nude rita tua he't 7,00 ml dung dich KCNS 0,1000 N. Hay:
1. Giai thich qui trinh dinh luong tren .
2. Tinh % (kl/tt) ciia KBr trong han hop.
3. Tinh pH eua dung dich han hQp trl1CJekhi dem dinh 111Qng.
10.6. Chulin dQdung dieh NaCl O,lM b~ng AgNOa vCJichi thi K2Cr04 10.2
M. Phep chulin dQ ke't thue khi co ke't tua Ag2Cr04 bllt d~u xuat
hi~n. Hay tinh sai so eua phep ehuAn dQ do.
10.7. Dinh 111c;sng
10,00ml han hC;Sp(HNOa+HCl) he't 17,50 ml dung dich
NaOH O,lOOON.Sau do dinh 111C;Sng tie'p b~ng dung dich AgNOa
0,1000N vCJichi thi K2Cr04 he't 8,50ml. Hay:
1. Giai thieh qua trinh dinh ll1c;sngtren.
2. Tinh n5ng dQP gIl eua HNOa va HCl trong dung dich.
3. Tinh pH cua dung dieh trong qua trinh dinh 111c;sngd thdi di~m
mm eho dl1c;JC
8,25 ml dung dieh NaOH 0,lOONvao 10,00ml han hC;Sp.
10.8. Lay 10,00 ml dung dich NaCI dem dinh 111c;sngb~ng AgNOa O,lOOON
he't 15,78 ml theo phl1dng phap Mohr. Khi ehuAn dQvCfim~u tr~ng
he't 0,08 ml AgN03 tren. Tinh % eua dung dieh AgNOa dem dinh
luc;sng.Cho NaCI=36,5.
10.9. Co bao nhieu gam NaCI chua trong llit dung dieh ne'u lay 25,00 ml
dung dich nay them HNOa d~c va chinh xac 40,00 ml dung dieh
AgNOa 0,1020N r6i them nl1CJevita du 100mI. LQc, rita tua. Lffy
. 50,00 ml nl1CJeIQCva nl1CJcrita tua dem dinh 111c;sng
he't 12,00 ml
dung dieh KCNS 0,098N.
Cho Na=23, Cl=35,5.

214
 10.10. Nfing de)CrO/- trong dung dich NaCl 0,1000N phai nam trong gioi
han nao d~ khi dinh luong b~ng AgN03 sai s6 chi thi khong vuot .
qua 0.1 %? D~ tua xuat hien dung di~m tuong duong. Biet rang
th~ tieh cua h~ tai hie ket thuc dinh Iuong la 30ml, hay tinh s6 ml
K2Cr04 5% phai eho vao h~ hie d~u d~ dam bao dat yeu e~u tren.
10.11. Hoa tan 0,1535 gam h6n hop g6m (KCl + KBr) vao nude va dem
dinh IUQngtoan be)bang' AgN03 0,0500N het 30,25 ml vdi chi thi
K2Cr04• Tinh % KCI va % KBr trong h6n hop,
10.12. Them 50,00 ml AgN03 0,0202N vao 25,00 ml HCI. Chuan de)h6n
hop thu duoc b~ng KCNS 0,0501N het 15,17 ml vdi chi thi Fe3+.
Tinh pH cua dung dich HCI ban d~u .

..

215
 ·-
"- - .- -"------.---~ --~ ~---.-- - -

Chlicmg 11
~ A _ , ?
CHUAH £)Q OXY HOA KHl1

A oJ
1. NGUYEN TAC
Chuan d9 oxy h6a khir la phuong phap phan tfch dua tren phan ung cho
nhan electron giira chat OXY h6a va chat khl1 hoa tan trong dung djch.
M9t s6 chat khong co tinh oxy hoa hoac khl1 nhung co kha nang phan
itng hoan toan vdi chat oxy h6a hay chat khl1 (thuong tao thanh chat ke't tua
hoac phtrc chat) cflng co th~ duc;scdinh luong' bAng phuong phap oxy hoa khl1
theo each giiut tie'p.
Yeu cAucho mQtphan uug dung trong chuAn dQoxy h6a khl1:
- Phan (tUgphai du nhay va xay ra theo chieu cAnthie't,
- Phan ung phai hoan toan va c6 tinh chon IQccao,
- Phan (tng phai xay ra du nhanh,
- Phai chon duc;scchi th] phat hien di~m tuong duong cho phan ung
Chieu eua-mQt phan ung oxy h6a khiJ duc;scdt;tbao dt;tavao the' oxy hoa
khiJ tieu chuAn. Trong can bAng oxy h6a khiJ da dua ra tri s6 .6.Eo t6i thi~u
cua 2 c~p ox)' hoa khti lien hC;Sp d~ cho ph an ung xay ra. Tuy nhien tri s6
.6.Eo chi cho ta bie't kha nang xay ra ph an ung, con tht;tc te' phan ung co xay
ra hay khong, t6c dQnhanh hay ch~m ph\l thuQc vao ca ban chat hoa hQccua
chung cting nhu dieu ki~n C\l th~ cua phan ung. Thudng cac phan ung oxy
hoa khiJ lA mQt qua trinh phuc t:(lP,xay ra nhieu giai do~n trung gian nen t6c
dQpluin ung nhieu khi khotig dap ung duc;scyeu cAu djnh luc;sng.Trong nhung
trudng hQp nay, d~ lam tang t6c dQ phan ung co th~ thl;tc hi~n mQt s6 bi~n
phap sau: -

21t)

., - - ----- "----
 - Tang nhiet d9: Noi chung khi nhiet dQ tang, t6c dQ ph an ling tang theo.
D6i vdi h~ d6ng th~ khi nhiet dQ tang 10° C, t6c dQ phan ling tang len
khoang 2-3 !cin. Vi du phan ling giiIa dung dich ~\1n04 vdi acid oxalic
(H2C204) xay ra cham d nhiet dQthuong. Khi dun nong ph an ung nay xay
ra kha nhanh.
- Tang nong d9: Co truong hop khong th~ dung nhiet dQ d~ lam tang t6c dQ
ph an ling, vi tang nhiet dQ se lam bay hoi chat phan ling (nhu iod), tao
phan ling oxy hoa do oxy cua khong khi, Trong mQt sO'truong hop nguoi
ta tang n6ng dQ cua thuoc th-li d~ lam tang t6c dQ phan ling. Ky thuat
chuan dQnguoc dU<;1C dung d day d~ xac dinh n6ng dQ .
- Dung ehat xue tdc: Cac phan ling oxy hoa khu xay ra qua nhieu giai doan
trung gian. Chfi'txiic tac thuong' lam tang t6c dQcua cac giai do~n trung gian
nay. Vi dl,lion r dU<;1CdUng la xuc tac cho phan ling oxy hoa 82°32. b~ng H202.
Co nhung phan ling ma san ph~m t~o thanh dong vai tro xuc tac cho
chinh ph an ling do. Ion Mn2+ trong chu~n dQb~ng KMn04 1a vi d\l cho xuc tac
ki~u nay.
... ,..?,..,?
2. DU'dNG CONG CHUAN DQ OXY HOA KHU
TUdng t1.;inhu trong chu~n dQ acid-base, trong qua trinh chu~n dQ oxy
h6a kh-li, n6ng dQ clla thuoc th-li va clla chfi't cftn chu~n dQluon thay d6i. Dieu
do d§.n den s1.;ithay d6i the oxy hoa kh-li clla h~. Ta co th~ bi~u di~n s1.;ibien d6i
clla the nay thea th~ tieh thu6c th-li.
Vi d1!: Khao sat dUdng bi~u di~n dinh lu<;1ngmuoi Fe (II) b~ng Mn04-
trong moi trtidng acid (gia thiet h =1). Phudng trinh phan ling:
Mn04- + 5Fe2+ + 8H+ = Mn + + 5Fe + + 4H 0
2 3 2

Trong qua trinh chwln dQ luon t6n t~i trong dung dich hai c/iipoxy hoa
khit: Fe3+/Fe2+ va Mn04-/Mn2+. Vi v~y co th~ tinh the oxy hoa kh-li clla h~ theo
mQt trong hai phuCing trinh sau:
- The cho h~ Fe3+j Fe2+:

(1)
..
- The eho h~ Mn04-j Mn2+:

E = 151+ 0,0591 [MnO; ].h 8

2)
, 5 g [Mn2+]

2.1. Khao sat slf.bien thien ella the oxy hoa khi'i trong qua trinh ehugn d9
2.1.1. Trlide die'm tliang dliang
Trong dung dich con du h~ Fe3+J Fe2+ nen ta Hnh E theo phuCing trinh (1):

217
 ~ -Khi them 50% Mn04- vao dung dich Fe2+ co cung n6ng dQ duong hrong.
Luong Fe2+ dula 50%:
'E~ 0,77 + O,G59lg (50/ 50) = O,77V
- Khi them 90% Mn04-:
E = 0,77 + 0,059olg (90/ 10) = 0,83 V
.;_.'Khi-them 99,9% Mn04-:
=
"E 0;77 + 0,0591g (99,9/ 0,1) :::0,94 V

2.1.2. TC!i dii'm tudng GrlClng

Ta khao sat cong tbuc tang quat tlinh"E cho h~ d tai di~m tuong duong:
- R~ 1: OXl + n.e .,...- kh,
- E 0,0591 [OXl]
E 1 - 0.1 + n] g [~ ] (11.1)

- H~ 2: ox, +.n2e ~ kh2

E - E + 0,0591 [OX2] (11.2)
2 - 0,2 ~ g{k~]
Gia si'1 Eo.l > EO,2 nen phan uug xay ra:
n2 OXt + n, kh, ~ n2 kh, + nj ox,
Tit 2"phllong trim tinh g cho 2 h~ta co:
nlEl = nl EO•l + 0.,059 19( {Qx11Ikh1tI )

~E2 -= ~Eo.2 + 0,059 19([Dx2]{kh2rl )

The a di~mtuong'dUdng E = E2 = Etdnen (cQI;lg tUng ve 2 phuong trinh tren):
t

_ . '. . {ox'Joxd
(nl +~)Eld - nlEo,1 +n2Eo,2 +.0,0591g [~I~] (11.3)

'I'ai di~m tttdng dUtSng,trong dung 'djch s6 Quong lu<_1ng

cua ch~t oxy hoa
bAng s6duong Itt<;lng;cuach~t khl1, cho nen:
nl[oxl] = nll[kha] ---+ [ox.j= naJ n1[kh2]
n,i[khl] = n2[ox2] ---+ [khll == U2 / n1[ox2]
Thay gia tri cua [oxt1 va [khil vao phttdng trinh (11.3) ta dtt<_1C:
Etd = nlEo,1 +n2Eo,2 . (11.4)
nl+n2
Trong trt1~ng h<_1p
nay, MnO.- thuQc h~ I va Fe2+ thuQc h~ II, n1 =5, n2 =1;

218
 _ .. --------------

. E =5.1,51+1.0,77 =139V
Id 5 +1 '

2.1.3. Sau die"mtuong duang

TInh the' cua h~ thea Mn04-1 Mn+2 theo phucng trinh (2)
- Khi thira 0,1 % Mn04-: Gia thie't h

E ~ 151 + 0,0591
, 5 g Mn2+
rno;;
=1

E = 1 51 + 0,059 I 0,1 = 1 48V

, 5 g 100 '

- Khi eho thua 10%Mn04-

E = 151 + 0,059 1 _!Q_ = 1 50V

, 5 g 100 '

Cac ke't qua tfnh toan duoc tang hop d bang 11.1

Bang 11.1. Bien thlen cua the E trong qua trinh chu§n d(>.

% MnO....
- them vao % Fe2+ con lal E (V) Ghi chu

50 50 0,77

90 10 0,83

99 1 0.89

99,9 0,1 0,94

100 1,39 BlIac nhay the

Thlta 0,1 1,48

1,0 1,49

10 1,50

100 1,51

219

---~ -- -------_---------
2.2. Duong bi~u di~n: Hirth 11.1
E

0,8

0;9

1,0
1,1
1,2

1,3
1,4
1,5
1,6

%
90 92 94 96 98 UO T02 104 106 lOS 110

Hinh 11.1. .Bit~udien sl! b~n {men (;ua the E trang qua trinh chu&n o{l

2.3. Nh~n xet

- Duong .b~:u di~n dinh luong nhu tton.g phuong phap acid-base. o gAn
di~m tuong' duong co buac nhay ,the' d9t ngQi;.C6 th~ dung chi th] d~ ph at
hien di~m nay.
- Duong bi~\l di~n khong phu thtaQc vao dQ pha loang dung dich vi trong
phuong trinh dinh tinp the E ty s6 n6ng dQ chat OXY h6a va chat khi't
khon'g thay d5i khi pha loang.
- Tr] s6 birdc nhay the phu thuoc van 'hi~u s6 ~Eo = Eo,! - EO•2' Hieu s6 ~Eo
cang Ion buoc nhay the cang dai (Minh hoa qua hAng s6 can bang Kbang
11.2 va d5 thi tren hinh 11.2)
Hang' 56 can bAngOKtreng bang 11.2 dUQc tinh thea phuong trinh:

1 K = n(EQ,l - EO;2}
g 0,059

Bang 11.2,

£)U'crng Ii Eo (V) HAngso can bang K

A 1,0 8.1016
B 0,8 3.1013
C 0,6 1. 1010
-
D 0,4 6.106
E 0,2 2.103

220
 E

1,0
o 0
EZ -EA K
.>:
8

0,8
A 1.00V
80.BOV
B x 10'6
3 x 10'3 VC

-:
C 0.60V 1 X 10'0
o 0.40V 6 X 106
E 0.20V 2 X 103
0,6 D-

0,4
r:
E -

-~-
0,2

--
o >j<
40,0 80,0 100 %

Hinh 11.2. £)lfClngcong chuan de?vC1ih~ co llEo khac nhau

3. CHi THI TRONG PHudNG PHAp OXY HOA KHU

Nguoi ta co th~ xac dinh di~m ke't thuc cua phan ung chuan de?bang mot
so each sauday:
l. Chuan di? do the: Phuong phap nay theo doi su thay d6i the' E trong
qua trinh chuan de?d~ xac dinh di~m ket thuc phan ung. NQi dung chi
tie't duoc trinh bay chi tie't trong hoc ph lin hoa ph an tich II.
2. Chat oxy hoa hoac chat khir tham gia van phan ung chuan dQco mau,
Trong dung dich co du 1 giot se lam thay d6i mau, Dung dich chuan
KMn04 thuoc loai chi thi nay.
3. Chat chi thi dac biet tao vdi chat oxy hoa hoac chat khir trong phan
ling chuan dQ mQt mau d~c trung. Vi du h5 tinh bQt trong phuong
phap do iod.
4. Chat chi thi co rnau bien d6i theo the' oxy hoa khu cua h~. Day la chi
thi oxy hoa khu dich th1.Jc.

221
 ~- --~ _-- -----~-----~-------...._-
--'---

Ban phan ling tuong ung vdi su d6i man cua chi thi oxy hoa khu thuan
nghich la: - ,
lox + ne ~ Ikh

E E 0;0591
; = o.,+--g- [lox 1 (11.5)
n Ikh

Eo. I la the' chuan cua cap chi thi, tuong tv. nhu chi thi acid-base phu
thuoc vao ty s6 nang dQ[lox] / [Ikhl.
Ty s6 [Ioxl /[Ikhl

0.1 10
Mau ella Ikh Khoangd6i rnau Mau ella lox

Khoang d6i mau ciia chi thi se la:

~E = EO•l ± 0,0591 n (11.6)
Vi gia tri 0;059 V kha nho nen nguoi ta thuong' dua vao gia tr] Eo.I d~
chon chfft chi thi cho mot chuan uQ.Thong thuong' chon gia trj Eo.I narn trong
buoc nhay dUdng cong chuan dQ.Co hai nhorn chi thj oxy hoa khii :

3.1. Nhorn diphe nylamin

Knop (1924) de nghi dung diphenylarnin cho chuan dQ Fe2+ b&ng kali
dicromat. Dang khu cua chi thi Ikh khong mau, d~ng oxy hoa co mau tim d~m.
Khi co m~t cua chat oxy hoa m~nh xay -ra cac phan ling sau:

2 O-N~ -- O-N~mr-O
2W+2e
Diphenylamin Diphenyl benzidin
(KhOng
mau) (KhEmg
mau)

~
0-+00+;=,\
= _ N-I= _ =NH-V + 2e

Diphenyl benzidin (tfm)

Phan ling d~u khong thu~n nghich t~o ra diphenyl benzidin khong mau.
Phan ung sau thu~n nghich t~o ra h~ h.en h<;ip.ion co mau tim. Do dQtan trong
mioc thap, nen phai dJ),ngcl,ungdich diphenylamin trong H2S04 d~c. Hdn nJla
san phAm oxy hoa t~o ke't iua vbi ion tungstat va Hg(II). Vi v~y ng1idita dung
dAn xuat sulfonic. '

222
 Muoi Ba(II) hoac natri ella acid nay dU\1cdung d~ pha dung dich chi thi
vdi dung moi la nude.

Acid diphenylamin sulfonic

3.2.Ferroin
1,10 phenanthrolin tao phuc ben vdi ion Fe(II). Ba phan tit tao lien ket
phoi trf vdi ion Fe(II).
(3 Ph) + Fe2+ ~ Ph.Fe'"
Fe2+ trong phuc d~ bi oxy hoa:
----
.....- Ph3Fea+ + e
Xanh nhat (ferriin)

I
N
2+
3 + Fe
N
I

1, 10 phenanthrolin 1, 10 phenanthrolin Fe(lI)

Chi thi nay duoc dieu ehe theo ty l{l duong luong cua Fe2+ va
phenanthrolin. Dan xuat the ella hop chat nay eho ta cac chi thi oxy h6a khu
tuong tl;i h~ ferroin- ferriin. Bang 1l.3 thong ke mot so' chi thi oxy h6a khu vdi
the chuan EO•l cua chung.

Bang 11.3. M9t 56 chi th] oxy h6a khil

Ten chi th]

Indigo tetrasulfonat Kh6ng rnau Xanh 0,36 Dung dich acid 1M
........................................................................................................................................................................................................... _ .
Xanh methylen Kh6ng rnau Xanh 0,53 Dung dich acid 1M
.............................................................................................................................................................................................................................................................................................
Diphenylamin Kh6ng mau Tim
...................................................................................................................................., " .
Acid diphenylamin sulfonic Kh6ng mau Tim do
................................................................................................................................................................................................. _
0,85 Dung dich acid loang
.
5,6 dimetyl feroin (Eriglaucin A) Xanh 113
..........................................................................................." " .
Ferroin Xanh nhat
.............................................................................................................................................................................................................................................................................................
Nitro terrain Xanh nhat

223
4. PHAN LO~I cAe paU'dNG PlIAp OXY nOA KHU'
Trong phuong _phapchuan dQacid base, thuong ta co th~ thay acid (hay
base) manh nay de dinh hiQng mQt-base (hay acid) khac. Nhung -trong chuan
dQoxy hoa khli, vi di~n the' oxy hoa khti cua cac cap rat khac nha~, m6i cap
khi phan ung lai doi hoi cac dieu kien nnat dinh. Do vay, khcng the ·thay the
tHYti~n chat oxy hoa (hoac chat khti) nay bang m{>t chat oxy hoa (hoac khu)
khac tuong duong ve mat. dien the oxy hoa khu. Mudn thay the phai xern xet
tinh toan tdi ta:t ca cac yeu to', neu thay dap ung du dieu kien cua phan UI).g
mdi duoc .phep th~c hien,
Vi~c phan loai cac phucng phap chuan dq oxy hoa khti thuong' dua tren
cac chat oxy hoa, dung, trong ph~n ang. Chul1.ndQva 'g<;>i
ten theo cae chat OXY
hoa do. Thong- d\mg co cac phudng phap sau: Phlidng phap permanganat,
phlidng'phap iod, phlidng phap brommat, phli<1ngphap brom, phudng phap do
dang, phlidng phap dicromat, phudng p~ap nitrit.
4.1. Phlidng phap permang~nat
La phlidng phap dinh lUQng dVa van khil nang oxy hoa khu cua
permanganat d ca trong moi trudng acid, trung tinh, kiem.
- Trong moi trUdng acid m~nh, Mn04" bi khti den Mn2+:
Mn04" + 5e + 8H+= Mtl2++ 4H20
(Mau hang) (Khong mau)
The' oxy hoa khti tieu chu~n Eo= 1,51V
- Trong moi trUdng trungtinh, kiem, Mn04" bi khti den Mn02
Mn04" + 3e + 2H20 = Mn021+ 40H"
The oxy hQakhu tieu chu~n Eo= O,59V
The oxy hoa khti cua c~p Mn04"' Mri2+(trongmoi trUdng acid) Ion hdn the
oxy hoa khti cua c~p Mn04"' Mn02(trong moi truQng trung tinh, kiem) rat
nhieu. M?t khac, san ph~m oxy hoa trong moi trUdng acid la Mn2+khong mau,
trong moi trlidng trung Hnh, kiem la ket tua Mn02 co mau nau. Vi v~y vi~c
xac dinh di~ltl tUdng dUdngtrong moi trudng acid d~ hdn nhieu. Trong tht;icte,
thudng dinh lU-qngcac chat khti b&ngdUhg·dichKMn04 trong moi trUdng acid,
voi chi thi la chinh dung dich chu~n KMn04"

4.2. Phlidng phap iod

4.2.1. Dij,c diim chung cua phttdng phap

Phudng phap iod d\ia tren the oxy hoa khti cua c?p 12/21":
12 + 2e ~ 21"
The oxy hoa khti tieu chu~n Eo = O,54V(d van kholmg giua cua bang the
oxy hoa khti tieu chufln)

224
 Nhimg ch8:t co Eo< O,54V co th~ bi oxy hoa bdi 12t~ do
- Nhfmg chat oxy hoa co Eo> O,54V co kha nang bi khi't bdi I-
Do vay, co th~ dung phuong phap iod d~ xac dinh eac ch8:t khu, chat oxy
.hoa va ca acid.
Xac dinh. chat khii:
Co th~ xac dinh true tiep cac ch8:t khit bang each cho tac dung vdi 12,
Nhan ra di~m tuong duong dua tren s~ d6i man: Dung dich khong mau (thieu
iod) chuyen sang mau vang nhat (khi co du iod). D~ d8 nhan mau hon, ngtidi
ta dung h6 tinh bQt, iod du se tao vdi h6 tinh bQt mQt chat co mau xanh d~m.
Xac dinh. chat oxy hod:
, Thuong dung phuong phap the: Cho thira KI VaGchat oxy hoa cAn dinh
hrong d moi trudng acid phan tmg se giai phong mQt IU<Jngtuong dUdng 12,
LU<Jng12 giai phong dU<Jcdinh lU<JngbAng dung dich chu~n Na2S203. .

Xac dinh cac acid:

Ngoai cach dinh lU<Jngch8:t oxy hoa va ch8:t khi't, doi khi con dung
phudng phap iod d~ xac dinh acid. Nguyen tiic dinh lU<Jngd~a tren ph an (tng:
103- + 51-+ 6H+ = 3 12 + 3H20
Phan (tng tieu thl,l H+ va giai phong mQt lU<Jngtudng dUdng 12, Dinh
lU<Jng12bang dung dich chu~n Na2S203 tit do cling co th~ suy ra lU<Jngacid
tham gia phan (tng.

4.2.2. Die'u kifn tien hanh dinh llt(jng bdng iod

1. Phudng phap iod thudng dU<Jctien hanh d di~u ki~n thudng, nhi~t dQ
thap, vi khi nhi~t dQtang, 12 co th~ bi thang hoa va dQnh~y cua chi thi h6 tinh
bQt giam.
2. I{hi dinh lU<Jngtn;lc tiep voi 12c~n thl;lc hi~n trong moi trudng trung
tinh ho~c acid yeu. 0 moi trudng ki~m m~nh va carbonat kim lo~i ki~m se xay
ra phan (tng:
12+ 20H- = 10- + 1-+ H20
3. Neu cAn moi trudng ki~m yeu co th~ dung NaHC03, khong nen cho
~H40H vi co th€ t~o thanh I3N la eh8:t d~ gay nB'.
4. Khi ehufln dQ12 bang Na2S203, c~n phai cho h6 tinh bQt VaGhie g~n ket
thuc dinh lU<Jng(Wc la khi do con it iod trong dung dich, dung dich co mau
vang nh~t). Neu lam ngti<Jc11:.li,
tinh b9t se h8:p phl,l m9t ph~n 12 va nha 12 r8:t
ch~m. M~t khac tinh b9t con co th~ khit dU<Jcm9t vai ch8:t oxy hoa m~nh. Do
do dinh lUQIlgse co sai s6 dUdng IOn.
5. Khi dinh hi<Jngcac ehfi't oxy hoa bA.ngphudng phap iod, cAn phlli cho
thita KI d€ phan (tng giua KI va chat oxy hoa xay ra hoan toano M~t khac 12 da

225
 giai ph6ng se d~ dang hoa tan vao dung dich nude c6 du Kl do phan ang t:;1.0
·phuc kern ben 13-:
12 + 1" = 13-
6_ H6n hop dinh h:tQngcAn han ch-e'anh sang chieu vao vi anh sang lam
tang van toc cua ph an lihg oxy hoa 1" thanh 12 bdi oxy khongkhi:
=
41- + O2 + 4H+ 2 12 + 2H20
4.3. Phtiortg ph~p bromat
Dua tren kh~ nang GXyh6a cua BrOa- trong moi trltdng acid:
Br03- + 6H+ + 6e = Br + 3 H 0
2

The oxy hoa khu tieu chuan Eo= 1,45V

Phuong phap nay thlldng dUQcap 'dung d~ dinh 11.1Qng
cac chfit khii nhu
As3+, Sb3+, hydrazin trong moi trudng acid.
Di~m tuong duong diroc xac .dinh dua vao phan uug sau: Br03- du se
phan ung vdi Br c6 trong dung dich giai ph6ng ra Br2 t~ do ,c6mau vang' .nhat:
. Br03- + 5Br- + 6H+ = 3Br2 +' 3H20
Cling c6 th~ dung chi .thi mau hop chat azo nhu do methyl hoac da ca!ll
methyl: Br2 se oxy h6a chi thi nen mau se chuy~n tit do sang vang_ St;ichuyen
mau nay khong thu~n nghich vi chi thi bi ph an huY. Do d6 khi diu.h lUQngc~n
phai cAn th~n khong cho qua thita Br03-' Cling c6 th~ dung chi thi lo~i acid
indigo sulfonic.
4.4. Phuong philp bl'om
Phlldng phap nay d\ia tren kha niulg oxy h6a ciia Br2:
Br2 + 2e::: 2Br-
The oxy h6a khii tieu chuAn Eo = 1,70V
D~ thu dUQcBr2 co n6ng dQxac dtnh, ta cho mQt htQng du KBr phan ung
voi mQt 111Qngxac dinh KBr03 chuftn trong moi tnidng acid theo phudng trinh
ph an ung:
Br03- + 5Br- + eH+ = 3Br2 + 3H20
Sau d6 cho Br2 (dll chfnh xac) .phan ung vOi chfit cAn dinh hiQng. LUQng
Br2 du dUQcxac dinh bAng phudng phap iod (them KI va dinh lUQng 12 giai
ph6ng ra bAng Na2S20a).
Phudng phap brom thudng dung d~ dinh lUQngcac hQp chat huu cd vi cac
chfit huu cd khi tac dl,1llgvOinhi~u chfit oxy h6a khac thudng kern theo cac phan
ung ph\! phuc t~p. Nhtlng khi phan ung vOi Br21~i rfit hQp thuc theo ddng
phlldng trinh phan ung, do do c6 th~ dung g~ dinh luqng. Trong ngahh DUQc,
phudng phap brom dUQcdung ag dinh lu:<;tngcac phenol, cresol, benzonaphtol,
resorcin, anilin, acid salicylic, cac sulfamid, acid aminobenzoic_ ..

226

------ ------_---_.-- -----

4.5. Phuong' phap nitrit
Trong moi trueng acid, nitrit phan ung vdi cac che' pharn nhom amin
thorn (sulfamid, novocain..,) tao thanh hop chl1tdiazoni:

R-NH2 + HONO + HCI , ~ [R-~=NJ + 2H 0 2

cC
D~nhan ra di~mtuong duong cua phan Ungnay, c6 th~ dung 2 loai chi thi:
- Chi thi ngoai: Nitrit du se lam xanh giB:yt~m h6 tinh bQt c6 iodid, do co
phan (tng giai phong 12:
2N02' + 21"+4H+= 2NO + 12+ 2H20
- Chi thi n9i: Thuong dung tropiolin 00 nitrit du se phan (tng vdi chi thi
tao thanh d~n chB:tnitro so hoa c6 mau yang nhat.
Phuong phap dinh Iuong nitrit thuong tien hanh d digu nhiet dQthap
(khoang 10°C).Thuong cho them vai gam nude da vao binh dinh luong.

4.6. Phuong phap dicromat

Dua tren co sd kali dicromat co tinh oxy h6a trong moi truong acid:
Cr2072. + 14 H+ + 6e ~ 2 Cr3+ + 7 H20
vdi Eo = 1,35 V (d pH=O)
Dung dich chuan dicromat rB:tben, c6 th~ acid hoa bang acid H2S04,
HCI04 loang, HCI (voi digu kien n6ng dQHCI duoi 3,5M vi ne'u HCI d~c hcln
nhB:tla khi dun n6ng c6 th~ giai ph6ng CI2). Khi chu~n dQvoi dicromat c6 th~
dung cac chi thi nhu diphenylamin, diphenylbenzidin, natri diphenyIsulfonat.
Dicromat dU<;lcdung d~ chu~n dQnhigu chB:tkhi'1nhu Fe2+,muO'iiodid; c6
th~ djnh hi<;lngn6ng dQion Ba2+,Pb2+theo phuclng phap gian tie'p; djnh lUQng
cac chB:toxy h6a b~ng cach cho phan (tng voi IUQngdu chinh xac Fe2+, sau d6
djnh IU<;lngFe2+ du b~ng K2Cr207; dinh IU<;lngchB:tkhi'1bang cach cho phan
(tng voi Fe3+du, sau d6 chwln dQFe2+ t::;tothanh b~ng K2Cr207•
C6 th~ djnh hiQng ethanol b~ng cach cho tac d\illg voi h.iQngdu chinh
xac K2Cr207 (trong m6i trudng acid va dun n6ng) khi d6 x~y ra phan (tng:
3 C2H50H + 2 Cr2072. + 16 H+= 4 Cr3++ 3 CH3COOH + 11 H20
, .',. ,,~~~6 djnh lU<;lng~~Cr207 ~AU
b~~g d~,ng ~ic~. F~:+ v~i chi thi natri
dlphenyIsulfonat. Trong klem nghl~m dqc chat, da cal hen dlnh lUQngrUQu
theo 2 phuclng phap sau:
- Phltdng phdp Nicloux: oxy h6a rUQubang IUQngdtt chinh xac ~Cr207 d
45°C(trong moi trudng H2S04), Sau d6 chu~n dQ~Cr207 dtt bang cach cho
thua chinh xac Fe2+, dinh lUQngFe2+du bang dung djch chuAn KMn04•

227
 - •. -_- ----J.-. __ 7·_~..,....',..--
__ - .__-,-_. __ ,-__ , ~- __ . __ .......... ...._. ' _

- Phuang phap Cordebard: oxy h6a ruou bAng luong du K20r207 trong moi
trudng acid HN03• Sau do chuan d-QK2Cr207 du bAng phep do iod.

4.7. Phmrng phap Ceri

4.7.1. D¥a tren. tinh oxy hila ella Ce4+ trong moi truilng acid
Ce4+ + e ~ Ce3+
C~p Ce4+/Ce3+c6 di~n thephu thti<}cvao nang dQcua cac acid nhu sau:

Gia tri ditn the cua e,p Cj4"'Ce3+ kht nong dq cae acid
Acid
1N 2N 4N 6N -:eN
HCI04 1,7 1,71 1,75 1,82 1,87
HN03 1,61 1,62 1,61 - 1,56
H2SO4 1,44 1,44 1,43 - 1,42
HCI 1,28 - - - -
S\l phu thuoc dUQcgiiH thich theo co che' taophuc:
- Trong moi trudng H2S04: ion Ce4+tan tai dudi dang [Ce(S04)]H4 cho nen
khi nang dQH2S04 tang tac dung r~t it de'n the' cua c~p Ce4+/Ce3+.
- Trong moi truong' HCI04: ion Ce4+ tan tai dudi 4 dang Ce(OH)3+'
Ce(OH)/+, [HO-Ce-O-Ce-OH]4+va [Ce-O-Ce-OH]5. Nang de>cac ti~u phan
. phuc lien quan chat che vdi HCI04, the' cua c~pCe4+/Ce3+tang.
- Trong moi trudng acid nhe hoac trung tinh, ion Ce4+ nam duoi dang
Ce(OH)4 nen khong con tinh oxy h6a nifa.

4.7.2. Dung djch chutln Ce4+

Thudng pha dung dich chuan Ce(S(:)4)20, IN vi dung dich tnu6i sulfat r~t
ben, khong bi phan huy khi bilO quan ciing nhu khi dun nong, s\l oxy h6a
khong kern theo san ph Am trung gian.
Dung dich Ce4+co matI vang, Ce3+khong mau nen khi chuAn dQcac dung
dich khong mau c6 th~ khong cAn dung them ch~t chi thi. Trong mQt s6trudng
hQp chuAn dQ co th~ dung chi thj 180diphenylamin sulfonat ho~c ph(tc 0-
phenantrolin sAt (II).

4.7.8. Ung dung

- Djnh lUQng tr\ic tie'p cac ch~t vo cd c6 tinh khi':Lnhu: Fe2+, H202, acid
oxalic, As20a, K4[Fe(CN)J, KI ...
- Djnh lUQng cac ch~t huu cd c6 tinh khi':Lnhu cac alcol, polyol, aldehyd,
acid (acid lactic, acid pyruvic). Phan (tng oxy h6a khi':Ldi~n ra ch:~ninen
thudng phai dun n6ng va djnh IUQnggian tie'p (chuAn dQngtiQc: cho phan

228

------------------------- .._._-_._---_-
 ung chat cAn dinh luong vdi hrcng du chinh X{lC Ce4+, dinh lucng' Ce4+ du
bang dung dich ehuan Fe2+).

4.8. Phuong phap do d6ng

MQt s5 dUdng nhu glucose, levulose, galactose, manose, maltose, lactose
trong phan tit cua chung ngoai n chirc ruou con c6 chua chuc aldehyd hay
ceton lam cho dUdngc6 th~ khit duqc thu5c thit Feling (dung dich CuS04 trong
moi truong kiem manh c6 mat mudi kep natri kali tartrat - mu5i Seignette)
cho tna do Cu20.
D5i vdi nhfing duong' khong c6 chuc aldehyd hay ceton t~ do, phai thuj'
phan d~ tao thanh duong khir r6i mdi tie'n hanh phan tmg duoc. Vi du duong'
saccharose thuy phan thanh glucose va fructose:
C12H220n+ H20 = C6H1206+ C6H1206
(saccharose) (glucose) (fructose)
Trong qua trinh phan tmg vdi thuoc thit Feling, san pham cua s~ oxy h6a
cac duong nay la mQthan hop phuc tap cac chat c6 tmh khii nhu formaldehyd,
anhydrid glyceric... phan ung khong hop thuc nen khong xac _dinhduqc E cna
dUdngdem phan ung. Bdi v~y, trong dinh luqng b~ng phep do d6ng phai dung
phudng phap so sanh ho~c dung bang thl,tenghi~m. C6 3 phudng phap:

4.8.1. PhuOng phap Feling

Dinh luqng tr:~e tie'p dung dieh dudng khii b~ng mQt IU<;Ing
chinh xac
dung dich Feling:
CuS04 trong moi trudng kiem m~nh se cho tna CU(OH)2:
CuS04 + 2NaOH = Na2S04 + CU(OH)2-i-
Do s\i c6 m~t ena thu5e thii Seignette nen tna nay tan thanh phuc c6
mau xanh th~m:
/OH HO-CH-COOK /O-CH-COOK
Cu", + I )It- 2H20 + Cu"",- r
o -CIt-COON:
OH HO-CH-COONa

Khi dun soi voi dUdng khi'i, d6ng se bi khii t~o thanh ke't tna Cu20 mau
do. D~a vao mau cna dung dich nh~n ra di~m tudng dUdng: dung dich chuy~n
til xanh sang vang nh~t hay mat mau.

4.8.2. Phuong phap Causse Bonnans

Dinh luqng theo phudng phap Feling kh6 nh~n ra mau (til xanh sang
vang). M~t khac tna mau do Cu20 eang lam cho ta nh~n mau kh6 hdn. Cho
nen, trong phudng phap nay, ngudi ta cho them K3[Fe(CN)6] vao binh dinh
h!<;lngd~ hoa tan ke't tna Cu20. Dinh IU<;lng
se ke't thuc khi chuy~n mau tiI
xanh sang nau xam.

229
4.8.3. Phuong phiip Bertrand
clio glucose (dudng khir) cAn dinh IUQng phan (tng vdi mQt ludng' thita
dung dich Felinh d nhiet dQsoi, thu duoc ke't tua Cu20. LQcH(y rieng tua Cu20
cho phan ung' vdi mQt IUQngthira Fe2(S04)a theo phusng trmh phan ung: .
CU20 + FeiS04)a + H2S04 == 2FeS04 + 2CuS04 + H20
Dinh IUQngFeS04 bAng KMn04, tinh duoc n6ng dQ d6ng (I), dung bang
thuc nghiem 11.4 dUC1iday, tinh ra IUQngglucose co trong miu.
Thuoc thit Feling dung trong phuong phap do dang dUQcpha 'che':rthu sau:
Feling A: D6ng sulfat tinh th~ 35 g
Acid sulfuric d~c 5 ml
Nudc ca't vita dii. 1000 ml
Feling B: Muo'i Seignette 200g
Xut thoi hay vien 150g
NuC1C
ca't vita dii. 1000ml
Bang 11.4. LlIQng glucose tllong (tng vai 11IQngdong trong truro nghi~m Bertrand

LU'qng LU'qng LU'qng LU'qng LU'qng LU'qng LU'qng LU'qng

dong dllCJng dong dllCJng dong dU'bng dong dllbng
(mg) (mg) (mg) (mg) (mg) (mg) (mg) (mg)
20,4 10 64,6 33 105,8 56 144,5 79
22,4 11 66,5 34 107,6 57 146,1 80
24,3 12 68,3 35 109,3 58 147,7 &1
26,3 13 70,1 36 111,1 59 149,3 82
28,3 14 72,0 37 112,8 60 .150,9 83
30,2 15 73,8 38 114,5 61 152,5 84
32,2 16 75,7 39 116,1 62 154,0 85
34,2 17 77,5 40 117,9 63 155,6 86
36,2 18 79,3 41 119,6 64 157,2 87
38,1 19 81,1 42 121,3 65 158,8 88
40,1 20 82,9 43 123,0 66 160,4 89
42,0 21 . 84,7 44 124,7 67 162,0 90
43,9 22 86,4 45 126,4 68 163,6 91
45,8 23 88,2 46 128,1 69 165,2 92
47,7 24 90,0 47 129,8 70 166,7 93
49,6 25 91,8 48 131,4 71 168,3 94
51,5 26 93,6 49 133,1 72 169,9 95
53,4 27 95,4 50 134,7 73 171,5 96
55,3 28 97,1 51 136,3 74 173,1 97
57,2 29 98,9 52 137,9 75 174,6 98
58,1 30 100,6 53 139,6 76 176,2 99
60,9 31 102,3 54 141,2 - 77 177,8 100
62,8 32 104,1 55

230
5. MQT s6 UNG DlJNG DJNH LU'QNG
Phuong phap chuan dQ oxy h6a khtt la mQt trong nhung phuong phap
duoc ung dung kha nhieu trong thuc te'. MQtB6ch~t oxy h6a khtt hay dung d~
pha che' dung dich chuan dirocneu trong hai bang 11.5 va 11.6.

Bang 11.5. MQt s6 chat OXYh6a khlr thuong dung

Chat goc
1,51
................._ -....................... . -.~ ..-......... . _ .
KBr0 3 1,44
............................................................................................................................................................................................................................................................. _ ..
Ce+4 1,44 Na2C204, As203, H2C204·2Hp
................................................................................................................. , , ..
K2Cr207 1,33 K2Cr207
....~
'
_ _. - .
1,24
.......................................................................................................................................................................................................................................................................
0,54
................................................................... .. _ _ ..
0.99 Acid sulfanilic

Bang 11.6. M¢t s6 ch~t khlr thuong dung.

Chat khi'r Chatgoc
Mu6i Mohr 0,77
........................................................................................................................................ _ .
0,56
........................................................................................................................................................................................................................................................................
0,08
..................................................................................... _ ..
Titan (III) 0,10

Dudi day trinh bay mot B6ung dung cu th~

5.1. Phuong phap permanganat
5.1.1. Pha dung dich. chulin KMn04
KMnO4 khong thoa man tieu chuan chat g6c vi thuong l~n Mn02• Do v~y
thuong pha gftn dung, d~ 6n dinh vai ngay, sau d6 xac dinh lai n6ng dQcua n6
bang dung dich chuan H2C204 theo phuong trinh phan trng sau:
2 x 2Mn04- + 8H++ 5e = Mn 2++4H 0 2

5 x C20l -2e = 2C02

Trong phan ung dinh luong nay phai dun n6ng toi 70 - 80°C d~ tang t6c
dQ phan img. M~t khac ion Mn2+ la ch~t xuc tac ph an ung, nen hie d~u khi
chu€ln dQphan ung xay ra ch~m, Bau khi c6 Mn2+tt;\othanh, t6c dQphan ung
tang len lam KMn04 m~t mau nhanh han hic ban d~u.
Vi KMn04 c6 mau tIm, khi hoa tan kh6 nh~n bie't da hoa tan he't hay
chua, cho nen khi pha dung dich cftn dun nang nh4il,khu~y ky, g:,tn(ho~c lQc)
vao lQva d~ 6n dinh 5-7 ngay sau d6 moi xac dinh l?-in6ng dQ. .

231
 (l'BUOJt{l'B.Ilal J.Il'BN)
90tSgUN + I'BN~ = 1:1+ &OgS1:'BN~
:.8u1) tI'~t{d go 'Bl gr JP,A.8U1) u~t{d eOgS1:'BNOtIO Jtffi
80gSgvN u.1}n1p 'pip Bunp D1{d 'l'g'!J

pOI d,qd .3uPlllfd 'g'S

·~U :r}tPI 9P go
l'B0l{ l{UJ8.8uO.Il .8u~p opnu .8UQJ'll{l.8ugl{.L 'w~Jl{u 9 tq .8uvo OP,JlU9l lju1)l{o 'up,l
n.l{J{9P n,~N 'op,J'lulJI 19w 'Bgl{AXO~P (uPq .8~p A'B'q)AXOljw 98
.8tIlp OP,J'lU'Bt,:'-o
A'Bl{1'0uW}! .8w ,g8 .8u~q jl{l n~Jq oonp opnu 'Bt;,ton.t{l{9P 'jl oinn ljuO.I,L'''ouW}!
otmp J;,ll{1I'n.l{1Il{un go A~U oo nu.l{ l~l{O =o 'u~q w~Jl{u tq oonu 0l{0 w~l 'Op,J'lU
ljuO.Il u~l tI'~l{d 'At,:'-l{tI'~t{d jq "'l~A Oill{l 'l~A .8u9P o~x op po nnT.{l~tlD
(~P,TlU D!l3 1,}1[1f 9P 1[uip ~PX) 3p,TlU l1UO.l.1-/)3 n1J1[ 1-,1}1[~quip ~px'''01"!)'
'AXOlIT 9'9 ='I7/t'~Z JP,A.8tI1)A'Bl{1:01:H
lOW'17/1 0l{0~8 ~nl{ u~l{d 1:01:H Ziup):"il
ZiuPJ'lp
lOW ZiuPJ'l1J9tp{ 1 gp op go lOW Z/I 'Bl oqo At;,tqt!Vqd g01:H lOW 1 A)Jt{l'B,L
1:0~/1+ 01:H gOgH
:'o'n 'Bt;,toAt;,tt{tI'~l{d l{UPl .8tIpJ'l"ld~.L
: n'BS nqu l{UJl 1I0'Y:.J
·,,'OJ. A'[l1{ uV1{d iz1 gOgH 1{ajp Bunp 1Jl1 op AXO1Jl})S" lju~q l{uJl oPJ'lP 'AXOqon ~ql
oal{l 9P Ziu9u .8u~p uQo 'Bl W;nZJu'jl{l n~Jq OPJ'lP.8UQJ'll{l9P lju9u OW;) ~~o.8u gOgH
l{ojp .8unp JP,AWG ·gOgH 9P SU9u OPJ'lPl{un '.8u~p ~p touWJI l{OH~ql ~.L
Z
900'L 1= YV = ~6;::H~ A"§PQ

OilH8 + '609 + +gUWZ= +H9 + gOilH9 + .I'ou:w~

:goz:g JP,At ou.t\ni ut;,tQ2uJ) ul;!lfd
go = a6 .. z:go :n.qJf ljqo V'l .
AXOl~tP ~'l.
OgH6 = a6 + +H'17+ .z:(10 :'B<Jt{
:n.t{1ItIuJl90 U~Augl{ AXOl{!lJlgo "'WA60Z:H
, 'Or;H·lIuOTll. 1[-uj(f 'trrg
"
''171 'Z6E =::w =O"H9 ··(l'os)a.!lo(tHN)JI

+ "ooW)!
'O(lH8 + tOSZ:}i+tOSUW6 +E('I70S)6a~9 = I'OSZ:H8+ I'OS<>>!101
:"ouW}! l{O!P.8unp .3u~q 9P u~nqo .8uJ) n~qd U~:I4 gila
OgH9·gfos)ai/gfHN) .I.1[Op{ l,ynw A1J1[ "osai/ l1U0111 ,!u1.U 'g'l'9
 M
o day EI2
?

= -= 126,7 ; ENa2S20a = M =248,19.

2
Vi Na2S20S.5H20 d~ ma't nude ke't tinh, khong thoa man tieu chuan cha't
gO'cnen phai pha g~n dung sau do xac dinh lai n6ng dQ. Khi pha Na2S20S
thuong phai dung nude dun soi d~ nguQi va cho them mQt it Na2COSd~ bao
quan (O.OlgNa2COS cho 100ml dung dich), d~ yen 1-2 ngay r6i mdi xac dinh
lai n6ng dQ.Theo thoi gian, dung dich Na2S20S bi thay d6i n6ng dQdudi anh
hudng cua CO2, O2,,,trong khong khi theo ph an tmg:
Na2S20S+ CO2+ H20 ~ NaHCOa + NaHSOs + S (1)
(2)
CO2lam cho n6ng dQduong IUQngdung dich Na2S20Stang len vi NaHSOs
mdi tao ra tac dung vdi 12thea t11~ga'p doi:
HSOs- + 12+ H20 = HS04- + 2HI
Khi cho Na2COSvao se co tac dung ngan can phan tmg' (1). MQtdung dich
Na2S20a pha dung ky thuat co th~ bao quan duoc 2-3 thang.
, D~ xac dinh lai n6ng dQ Na2S20Sco th~ dung cac chfft g6c nhu K2Cr207
(hay KIOs) dua theo phan trng:
K2Cr207 + 6KI + 14HCI = 312 + 2CrCIs + 8KCI + 7H20

d day EK2Cr207 = ~ = 49,03

KIOa + 5KI + 6HCI = 312+ 3H20 + 6KCI

d day EKIOs = M = 35,67

6
(KIOs trudc khi dung lam g6c dUQctinh che bAng cach ket tinh l~i 3 l~n,
sau do sf{yd 140 - 180°Cden khO'iIUQngkhong d6i).
12 giai phong tu cac phan ling tren dU:<;ic
dinh IU<;ingbAng Na2S20a• Vi d\l,
neu dung a g cha't gO'cK2Cr207 hoa tan, cho tac d\lng voi KI sau do dinh IUQng
het Vml Na2S20S thi:
a .100

5.2.2. Pha dung djch chucin 12 tit 12 tinh khiet thiing hoa
lod thudng m~i thudng IAn C12,Br2, H20. Vi v~y, ngudi ta phai tinh che
lo~i bi) cac t~p bAng cach nhu sau: Nghi~n nhi) 12voi KI va voi sO'ng(ty l~ 10 -
12g 12+ 19 KI + 2g voi sO'ng)sau do cho han h<;ipvao cO'c,d~y c6c b~ng mQt
binh c~u dl,tng nuoc l~nh. Dun nong nh~ day c6c, 12thang hoa se bam vao day

233
 _,. ~~~~_._ -----1

binh, d~y coco Gat C{lC tinh th~ 12 nay vao trong coi ma nae, dem lam kho
trong binh hut ~m co chua CaC12• Iod thu du<;1C la lod tinh khiet thang hoa,
dat tieu ehuan chat goc. Vi 12k}16tan trong nude, do d6 khi pha ehe phai eho
them KI du va 'dung rfit it nude. Sau khi 12tan het mdi them nude cho dii th~
tich yeu cftu.

5.2.3. Djnh ll((jng dung dj,chAs20s1%

• Dung dich c6 As20a 1% truqc day goi la dung dich Fowler. C6 th~ dinh
ludng' As20a trong dung dich nay b&ng dung dich chujin 12theo phuong
trinh phan tmg:
As20a + 212+ 2U20 = AS205 +4 HI
Phan ung chu!n d9 dugc tie;n hanh trong mdi truong' c6 PH = 8 (bang
each cho them NaHCOa vao dung dich djnh' luong).

EAs20a = -M = 49,46
4
• C6 th~ dinh Iuong dung dich Fowler bAng phuong phap bromat dua tren
ph an uug oxy hoa cua Br03' vdi As20a trong moi trudng acid:
2KBrOa + 3As20a = 2KBr + 3As205
Nhan ra di~m tuong duong b&p.gchi thi do methyl: Khi thira 1 giot
KBrOa mau se chuy~n tiI do sang yang (do chi thi bi B1:'2
oxy hoa).

5~2.4.lJinh IU,!ng dung djch glucose dcing trztong 5%

Glucose dli<;1C dinh lugng bling phudng phap iod theo ky thu~t chu!n dQ.
nguqe (thiIa triI): Cho mQtluqng 12 du chinh xac vao dung dich glucose trong
m6i trudng ki~m (dung NaOH) d~ oxy h6a glucose:
12 + 2NaOH = Nal + NaTO+ H20 (1)
CH20H(CHOH)4-CHO+ 10' = CH29H(CHOH)4COOH+ 1- (2)
Sau khi hoan thanh phan ung (2), ta acid h6a m6i trudng b&ngH2S04 d~
can bling (1) chuy~n dich v~ phia trai, ,dinh lUQng12du b&ngdung dich chu~n
Na2S20a• Tinh ra ket qua % glucose nhu sau:

M
- =90,08
2
f la h~ s6 pha loang dung dich glucose truoc khi dinh hl<;1ng.

234
5.2.5. Dinh IUfing H20, bdng phuong phcip iod
Dua tren tinh oxy hoa cua H202 trong moi truong acid, H202 oxy hoa Kl
theo phan ung:
H20z + 2KI + H2S04 = 2H 0 2 + 12+ K2S04
12giai phong ra diroc dinh hrong bAngNa2S20g.

5.3. Phu'dng phap nitrit djnh hif1ng sulfathiazol

Sulfathiazol (hay 2-[p. aminophenylsulfamido]- thiazol) co cong thirc:
= 255,33
C9H902S2Ng

Day la m9t sulfa mid thong dung, co th~ dinh luong dUQcbAng dung dich
NaN02 trong moi truong acid lJ nhiet d9 lO°C vdi chi th] n9i tropeolin 00.
Phuong trinh phan tmg chuan d9:
+
NaN02 H)Ir HONO

+
H +
R-NH2 + HONO • R- N=N + 2IllO

vdi ENaNo, = M =69; Esulfathiazol = M = 255,33

Trong dinh luong nay, dung dich chuan NaN02 thuong pha gAn dung (do
NaN02 khong.dattieu chuan chll't gO'c)sau do xac dinh lai n6ng dQ.Dung chll't
gO'cla acid sulfanilic (E =M = 137,2).

cAu HOI vA sAl T~P

11.1. Khao sat duong bi~u di~n dinh luong H202bang' KMn04 O,IN.
11.2. D~c di~m, digu kien, ling dung cua phuong phap pemanganat.
11.3.D~c di~m, digu kien, ling dung cua phuong phap dinh hrong bAngiod.
11.4. Trinh bay chll't chi thi trong phudng phap dinh lU<;lng
oxy hoa khii.
11.5. Nguyen tiic cua phudng phap dinh lU<;lngbAng bromat, phudng
phap nitrit, phudng phap do d6ng.

235
",. -------- _- ----------- ----'---'---

11.6.1' Lay 5,OOmldung dich H202 pha loang b~ng nude cho du 100,OOml
(duoc ..dung dich A). Lay to,OOm}dung dich Adem dinh lUQngbang
phuong phap iod het 12,50ml dung dich NaJ)20g. M~t khac khi chuan
dQ0,0735 'K2Cr207 tinh khiet theo phirong phap iod het 15,OOmldung
dich Na2S203 tren. Hay: .
a. Giai thfeh va viet uit ca cac phuong trinh phan ilng xay ra trong
cac phep din~ luong tren,
b. Tmh.ndng dQtheo th~ tich oxy cua dung dich H202 ban dliu.
ChoH = 1, 0= 16, S = 32, Na = 23, k-= 39, Cr> 52.
11.7. D~ xac dinli Na2S20a-.5H20 va NazS.9H20 trong mQt miu phan tich,
nguoi ta can 10,OOOgmiu hoa tan vao nude cho <iu 500,OOml(dung
dich A). Sau do lam 2 thf ngJIi~t_n:_
t. 'L~y 25,OOml dung dich A, them vao 50,OOml iod O,1005N. Djnh
Iuong iod du het 12,91ml dung dich Na2~03 O,lOlON.
2. LAy 50,00ml dung dich A, them' ZnS04 den khi ket tua hoan toano
Loc, lay 1/2 dich loc dem chuAn aQ bang dung dich iod O,OIOON
het a,65ml. Hay:
a. Giai thich va viet cac phuong trinh ph an i:ing xay ra.
b. Tinh ty l~ % Na2S203.5H20 va % Na2S.9H20 co trong miu.
Cho biet san phgm phan i:1ngcua miu vCliiod co S4062.va S; H = 1,
0=16, Na = 23, S = 32.
11.8. Hoa tan 1,l20g miu co chua CaO trong dung dich HCl(vita du). Ion
- Ca2+ dUQcket tua bllng 25,OOmldung djeh H2C204. LQe, rita ket tua.
'Lay toan bQ nuClcrl1a -va nuClclc;>cdem dinh 'htQng bAng dung dich
KMn04 O,050N het 8,50m!. M~t khac lay lO,OOm!"dung dich
H2C204 tren dem dinh lUQngbllng dung dich KMn04 O,0500N het .
24,OOml. Hay:
a. Giai thieh va viet cae phudng- trinh phan ung xay ra.
b. Tinh % CaO trong miu. .
.Cho Ca =40,0 = 16.
11.9. 'H2S04 b6c khoi (oleum) g6m H2S04,,S03, S02' D~ xac dinh thanh
ph~n tung cha't, ngudi ta can 2,OOOgoleum va hoa tan vao nuClc
thanh 500,OOml(dung dich A). San do:
1. Lay 50,OOml dung cijch Adem chuAn'dQ bAng ,dung dich NaOH
O,lOONvoi thLthi phenolphtalein he't'42,40ml.
2. Lay lOO,OOmldung dich Adem chugn dQ bllng dung dich iod-
O,lOlON he't 1;·85ml.Hay:
a. Giai thich va vie't cae phudng trinh ph an ung dinh htQng.

2,36

",. _- <_~_._. a! __~o~ __ . _

 ~"--~-----~- ~---------

b. Tinh % tung chfft trong h6n hop oleum tren.

Cho H = 1, 0 = 16, S = 32, 1=127.
11.10. Can chinh xac O,6935g m~u thu6c md kern oxyd, dun nong do d~
phan huy het chA'thfiu co. C~n kho thu dUQchoa tan trong H2S04
loang, sau d6 them nude va ket tua hoan to an dudi dang ZnC204.
Hoa tan ke't tua thu duq~ bang H2S04 loang va dem chuan dQ
bang dung dich KMn04 O,1042N het 32,64ml. Hay:
a. Giai thich va viet cac phuong trinh phan (lng xay ra.
h. Tinh % ZnO trong h6n hop,
Cho Zn = 64,0 = 16.
11.11. Hoa tan O,2856g Na2C204 vao nude, them H2S041oang va 45,12 ml
KMn04• Luong' KMn04 du phan (lng vua du vdi 1,74ml H2C204
O,1032N. Tinh n~ng dQdirong luong' dung dich KMn04•

237
 . ,. A' ~ _

.flAP S9.BAt T~P

Chttdng2
2.2. N6ng dO.mol
a. 0,195 b. 3,13 e. 0,0104i
.d. OrDli607 e. 1,80 f. 2,40
2.3. N6ng dO.dttdng hiQng (N)
a. 0,159 b. 5,16 e. 10,7 d. 9,92
e.O,0492 f. 0,Q121 .g. 0,0428
2.4. Pha cae dd sau:
a, Hail tan ;2,8g KGH vao mrdc, pha l~g dtn 500 ml. LAc;
h.·FIaa tan 2,2g NaCI vao mtck, pha loangde'n 250 ml. Lt\e.
c. Hoa tan 36g glucose vas nude, pha loang de'n 100 ml, ~Ae.
d. Pha Ioang 4,2'ml dd HCI 12M bAng nude thanh 500 ml. Lt\e-.
€. Pha loang 12ml NaOH 2M bang nl10c thanh 100 ml. Lt\e.
f. Pha loang 1,5ml dd H2S04 IBM b~ng nl10e 500 ml, La.c.
2.5. Pha cac dd sau:
a. Hoa tan 6,8g KH2P04 vao nude, .pha Ioang thanh 500ml.
b. Pha loang 1,5ml H2S04 IBM voi nude, thanh 500ml.
c. Hoa tan 7,lg Ba(OHh vao nude, pha J:oang thanh 750ml.
it Hoa tan 1,6g Na2COa vao mtoc, pha leang thanh 200m~.
e. Hoa tan 15 g NaHC03 vao mree, pha loang thanh 700ml.
f. Pha Ioang 1,0 ml HaP04 vao nude, pha loang' thana 300 ml.
2.6. Lay fi.Omlacid acetic 17M va 12,Ognatri aeetat. H?'a tan natri acetat
vao nuOc, them 5 ml aeid acetic, pha loang de'n 500,0 ml. Lt\e deu.
2.7. 156 ml
~.8. 4,4.10.3 va 6,7.10.3
2.9. a. 5p,6 b.1,80
2.10. 3,010
Chddng 3
3.S. RSD·: 1,1% khong d~t tieu chuAn .
3.7. x 2,08 '0,0918 69,53
s 0,35 0,0055 0,22

238
 3.8. 2,08 ± 0,44 0,0918 ± 0,009 ; 69,53 ± 0,35
3.9. vei A: Qtn = 0,67 Qbang = 0,73 ~ giu lai gia tr]
Voi B: Qtn = 0,84 Qbang = 0,85 ~ giu lai gia tr]
Qtn = 0,95 Qbang = 0,85 ~ loai gia tri
0,2152
3.10. F:II = 2 = 8,07
0,0757
F4•2 = 19,25> Ftn : d9 chfnh xac khong khac nhau
- -
XE - XB = 0,354

Theo phuong trinh (3.17) thi E = 0,53 (vdi P = 95%)

xE - xB < E : khac nhau khong co nghia. y
3.11. Voi x.: Ftn = 1,44 F12•6 = 4,00 khac nhau khong co y nghia
Voi x2: Ftn = 1,96 F6•20 = 2,60 khac nhau khong co y nghia
3.12. X2tn = 0,904
Bang 3.4 vdi P = 95% va f= 3 co X2 = 7,8
B6n phuong sai tren d6ng nhat,

Chtidng 4
4.6. 9,4.10.3
Ne'u khong tinh de'n h~ s6ho~t d9 thi [H30+] = 7,8.10.3
4.7.0,99% 9,5% va 91,6%
4.8. K = 5,35.10.4; 1,07mmol.P; 97,7% d dang XY (chi co 2,3% d dang ion)
4.9. Trong acetonitri146,1% Trong acid acetic 99%
Acetonitril co E = 36,2 nen KCl t6n tai ca d dang cap ion va dang di~n ly.
Acid acetic co c = 6,2 nen KCl t6n tai chu yeu d dang cap ion (99%).
4.10. a. 4,23 h. 2,07
c. 12,78 d. 11,35
4.11. a . 9,92 h. 2,95
.. c. 4,56 d. 8,39
4.12. a. 1,54 h. 1,99
c. 12,07 d. 12,01
4.13. a. 2,06 h. 7,20
c. 10,62 d. 2,09 e.2,01

239
 4.14. a. 2,11 h. 7,37
4.15. Tron 442 ml Na2C03 O,30M voi 558 ml-dd HCl O,20M
4.16. Can 50,3 g.
4.17.h. A~1,1 B-;5,5 C~9,7 D ~ 12,2
c. (A+D) -4 8,9 (A + C) ~ 5,5
4:18.
.pH F2 F1 Fo
, 2 0,899 0,10~ 3,94,10-3
.----
a 6 1,82. 10'" 0,204 0;796
10 2,28.10.12 ,2,56.10.5 1,00
2 0,500 . 0,500 1,30.10.5
b
-
6 7,94.10'5 O,7Q4 0,206
10 3,84.10'12 3,84.10·~ '1,00

4.19. 2',57
4.20.
B,nh rihin A B C
pH 7,35 .7,20 7,52
CO2• hi (mM) 1,40 1!20 1,30
He03' (mM) 24,9 15,1 34,2
.-.
CO2 toan ph~n 26,3 16,3 35,5
CO/" (mM) 4,4.10-2 1,9.10'2 9,0.1'0-2

4.21. a. K, = 4,25.10.4 h. C = 3,34,10'~ c. 33,4 ml

4.23. a. 0,0453 M b. 2,44 mg A,g+/ml c. 1,62 mg Cu201 ml
4.24. a. 0,0193M b. 0,776 m~ MgOI ml c. 1,54 mg Fe20.3 Iml
4.25. 0,01032 M
4.26. a. 2,18.109 h. e.s.ro= c. 4,37~1013
4.27: a. ,5,33 h. 7,33 c. 8,54
4.28. a. 1,26.10.7 Mil h. 4,8.10.6 MIl
4.29. •
C~
[Ba2+] rr-J (Bay21

a 1,3.10'5 1,3.10'5 .,.0,01

b 1,8.10'9 0,09 .,.0,01
c 1,8.10'9 9,9.10'3 .,.10.3

240
 4.31.
n 2 6
2,5.109 2,1.1021
13"
4.32. 3,8.10-3 Mil
4.33. a. 2Fe2+ + U02+2 + 4H+ ~ 2Fe3+ + U4+ + 2H20
h. Cr20t +91"+ 14H+ ~ 2Cr3+ +313' + 7H20
c. H202 + 2Ce4+ ~ 2Ce3+ + O2 t + 2H+
d. 103' + 51 . + 6H+ ~ 312 (r) + 3H20
4.35. a. 1,7.10-15 h. 3.1080
c. 4.1025 d. 6,1.1055 (trong dd H2S04 1M)
4.36. a. Co3++ e ~ Co2+ 1,879 V va 1,634 VI SCE
h. Mn04- + 8H+ + 5e ~ Mn2+ + 4H20 1,542 V va 1,297 VI SCE
c. 2H+ + 2e ~ H2 - 0,295 V va - 0,540 VI SCE
d. Hg2C12+ 2e ~ 2Hg + 2Cl" 0,339 V va 0,094 VI SCE
e. CH3COOH + 4H++ 4e ~ C2H50H + H20 0,050 va -0,195VISCE
4.37. a. C6H602 ~ C6H402 + 2H+ + 2e
hydroquinon
2KMn04 +
h. 6 CUC204 + KI03
c. 5HIOa + 4FeI2 + 25HCl
d. 4CuSCN + 7KIOa + 14HCl
4.38. a. 2Mn04 + 6H+ + 5H2C204 ~ 2Mn2+ + 8H20 + 10C02 t
h. Br2 + H202 ~. 2Br - + 2H+ + O2
c. Kh6ng phan ling
d. 2S2032- + 12 ~ I' + S4062.
" e. 2Cr20l + 16H+ + 3C2H50H ~
so
Hang can h~ng 19K:
a. 339 h. 13,2 c. 15,6 d. 262
4.39. Binh dung NaF kh6ng co phan ling
Binh dung KBr : co Br2 giai phong, 19 K = 10,2
Binh dung' KI : co 12 giai phong, 19 K = 27,8

241

- - - -------- -------------------
 ---____.. ........... - -_. ---- - ..

4.40. Vdi Br -: 19K = - 12,5

V,oi1" : 19K = 11,1
Chuang 5.
5.4. a. pH = 5,7 va s = 1,2.10-5 Mil
b. Khong can bAng do dQ tan ella CO2 Ie. s = 2,:3_10-4Mil VJ.iQt qua
trang thai din b~ng co dQtan 1,2.10-5 gAn 20 IAn. CO2,thiia ~ c¬ iin
md chai d€ D;lat·oot·CO2,
5.5. a. 9,33.10-5Mfl va 9,33 mg/l
b. 4,5.10-10 MIl va 0,12pg/l
c. 6,3.10-5 Mil va 20,9 mgll
5.6. Tinh TST cua cac chat
a. 1,1.10-11
b. 1,B.10-8
C. 5,7.10-21
5.7. a. 5,B1.10-19 b. 1,30.10-20 C. 1,3.10-22
5.B. a. 9,1.10-9 b. 2,4.10-3 c. 3,9.10-5
5.9. a. 3,2.10-7M c. 1,6.10-2M
b. 0,100M d. 3,3_10-3M
5.11. a. 1,8.10-6 b. 2,5.10-13 C. 2,3_10-6
5.12. a. 0,70M b. 2.10-3M
5.13. B,3.10~2M
5.14. a. S = [Zn2+] + [Zn(OH)42-]
h. Smin == 2.10-9 M d pH = 10
19S
+4
j
Zn(OH)t
o
-4
-8 •
-12~ ~~

4 8 t2 pH

5.15. pH < B,2 nhan biet H2S

pH2S > 10-5 bar khong chiu dttQcmui ella H2S (tng vdi pH < 7,5

242
 ----- ------~----

Chirong 6
6,5, Dung dang can BaC204
6,6, 1,248 giL
6.7, Phuong trinh khi nung
2MgNH4P04 ~ Mg2P20'l + N2 + H20
% MgS04 = 63,27%
6,8. % Fe = 21,22%
6.9. %CaC12 ='15,88% % Ca(NOa)2 = 84,12%
Chu'dng 7
- 7.5. 0,1056 M
7.6. 0,1733 M
7.7. 36,94 %
7.8. 75,87 %
7.9. 6,47%
7.10, a. 10,85% b. 48,07%
7.11. 0,8517 mg COil
7.12.7,317% (NHJ2CS
7.13.0,2970 M HCI04 0,3258 M NaOH
7.14.0,09151 M
7.15.346 ppm
Chu'dng 8
8.7, 12 mmol Na2COS 10 mmol NaHCOa
8.8, 79,3%
8.9. 11,5%
• 8.10. b. NaOH: 0,15% Na2C030,265%
c. pH = 9,0
8.11. 46%
8.12. Dung d pH = 10,2, dung dich co [HCOa'] = [Cot]
Dung d pH = 6,5 , dung dich co [H2COa] = [HCOa']
8.13. 24,60 ml
8.14.79,3%
8,15. 0,2211N

243
Chirong 9
9.6. 23,18%
9.7. 0,0193 M
0,776 mg MgO I ml
1,54 mg Fe203/ ml
9.8. 0,010321~
9.9. 323,9 mg Ca2+ ; 256,4 .mgM~+
9.10. 0,01032 M
9.11. 1,4.109; 3,3.1011; 2,2.1013•
9.12. o pH 11: P'SrY = 3,66.108
pSr V(ml) .pSr
V (mI)
2,00 25,00 5.37
0.00
2,30 25,10 6,16
10,00
24,00 3.51 26.00 7.16.
24,90 4,57 30 •.99 7.86

Chtrong 10
10.5. 2. %KBr = 0,803%
3. pH = - 19 0,0225 = 1,65
10.6. 1,4.10-2%
10.7. 2. Pgll HN03 = 5,60 Pg/IHCl = 3,10
3. pH = - 19 8,25.10-2= 1,08
10.8. 0,92%
10.9. 4,04 g
10.10. Nong d9 Crot til 2.10-14Mden 2M
Th~ tich K2Cr2045% can lay s 2,3 ml.
10.11. %KBr = 70,68% % KCl::: 29,32%
Chirnng 11
11.6. 2. 141ft oxy
•
11.7. h. %Na2S203"5H20 = 2,8% % Na2S.9HzO = 93,35%
11.8. 2. %CaO = 11,08%
11.9. 2. %802 = 1,5% %803 = 9,5%
11.10. 2. %ZnO = 19,6%
11.11. 0,0985 N

244

_. --~----~...._,__-~--------
 cAe PHV LVC

1. PHUONG PHAp I4.P NEWTON GIAI PHU'ONG TRINH B~C CAO

Trong khi giai cac bai toan can bang, tinh n6ng dQcac ti~u ph an thuong
.dua de'n phai giai mQt phuong trinh b~c cao, vi du bac 3, b~c 4... Phuong phap
l~p Newton thuong duoc dung d~ giai cac phuong trinh nay. Nguyen tilc cua
phucng phap nhu sau:
Gia thie't co phuong trinh bac 3
ax" + bX2+ ex + d = 0 (1)
Y
Gan cho x cac gia tri Xi' thay vao
phuong trinh nay duoc gia tri Yi' Ve d6 Y1 ------------------------------------
th] eua Yitheo Xi' . D6 thi cilt true hoanh
tai di~m X. D61a nghiem cua (1).
Gia tri g~ndung d~u tien x, thay
vao (1) ta duoc y r- Lay dao ham cua (1)
theo x: y' = 3ax2 + 2bx + C
Tinh y I' tmg vdi gia tri x.. D6 chinh
la h~ s6 g6e ella tie'p tuyen vdi dUdng Y2· --------------------
cong tai toa dQ(x., y 1) xeX2
~ ~ __~__________ x
Yl'=Yl'(Xl-X2) (2)
Tit (2) ta e6:
(3)
Tit (3) ta tinh duoc x2 cho vong 2 va tie'p theo la tim dUQcY2,Y2'. Vi~c
tinh toan cu tie'p t\lC eho de'n khi cae gia tri clla X tli\i 2 vong ke'tie'p nhau (Xi
va Xi+1)chenh l~ch nhau duoi 1%. Nhi~u khi cac phudng trinh thu dUQcc6 cac
h~ s6 voi mu am. D~ giai d~ dang hdn c~n d6i bie'n. Vi d\l:
X3+ 2.10-4 X2+ 7.10-lox + 4. 10-16= 0
D~t z = 106Xta dUQc:
Z3+ 200 Z2+ 700 Z + 400 = O.
Vi d\l: giai phudng trinh
316 X4+ 126,3 X3+ 22,1 X2+ X- 0,10 = 0
,
Thay s6 0 a ve' phai b&ng y
- L~y Xl = 0,05 ta tinh dUQcY1= 0,0230
L~y dli\oham clla phudng trinh:
y' = 1264x3 + 378,9x2 + 44,2x + 1

245
 thay x, :;::0,05 van ta co Yl' :;::4,315

- Tinh gia tri X2 theo (3): x2 = 0,05- 0,Q23 == 0,0447

. 4,315

vdi gia tri X2 nay ta tinh ducc: Y2:;:: 0,0014 Y·'::::3846

2 ,

x
3'
= Q 0447 - 0,0014
3846'
,
= ° 0443

Ne'uchap nhan chenh l~ch eCi1%khong c~ntinh toan them.

Gia tri Xi cu6i cung la nghiem g~n dung cua phucng trinh (1).
~ "",.. ." ""
2. HANG SO DI~N LY CUA CAC ACID VA BASE
* ACID
__ A_ceti9 7:..,:5:..:....
,__ 1:.!.:, :..:...1~,-~5 ~ _._. __ ",, ,,__ 1-. _

r- A_r_se_n_i~
___'_ . 6,0. 10-3 __ ._~_!.Q.?.:_1~=~ 3,0.10-12
Benzoic
f---------------. -. 6,14. 10-5
I-,.__ _::_:_:~.~ I___--.-----.--.--.---J.-----
Boric 5,83. 10-10
f------- --,,--
f..-----. --'--'- -.---.-.--,,----- .-----------
Carbonic 4,45.10-7 4,7.10-11
c----.--.--.---------,,------.-------"---.-.-------"""---.".""""".""-.--,,,,.--------.--.
Cloracetic 1,36. 10-3
c--"-.---"--.-------"----- .---- -----_."""C".---.,,"-- ------.-
Citric 7,45.10-4 . 1,73.10-5 4,02.10-7
r--------.------------- '-' ---
---".---
.-..
.."""".--,,.--
r-'--.-----
_,,_ Cya..!!~y~~_. __ ,,________ 6,2 x 1,...:0"_"10 -1-- "".""_"_.,,,,,,. -.---.-,,-.-,,-

"'_. Formic
,, "" ,,__. .,,__ 1-__ 1,77. 10-4
-----.,,-,,- ----.----.-"--c-"-----"""-.
Fumaric
..."._"-"-""""-_.
lodic
__ ._--,,--_.,,,,._-""---,,----
. 9,6. 10-4
1,7. 10-1
----,,- .
4,1. 10-5 .
__
._-"_._-"" ... _,,._.- ---_.""""_._-",,

""---_._-""-".,,-,,-,,-,,--""-.---"""-"_-. -,,"--------""'. ,,_._-"''''"''''-"''''-,,-''"----_._._--"._" .... """.

"_"'__ ~~ctic; ,,__ ,,._. __,, ,, 1,37. 10-4 ._"_"... ,,._,,

__ ", .__ """"" __ ,,

Malic 4,0. 10-4 8,B. 10-6

.""".""".-"'--.---""--.--"'--.-----""....
._"_"_~Ie~ __
Malonic
,.,..
,,"_""
-.-" ...
__._"""_,,.""__"'''''."''_'''''' ..__ _!~ 1
.._,,_
1,40. 10- 3
~=~ ..""'"
---.,,.1-------_._--"-,,._._,,-"" "--'--'-"'-"'-"-'-"-""''''''"'''-''
,,_B!~6..:,,!..q=~.
4,01. 10-6
""."---".".".-,,.-.-.
. ._"_"
"".-----.---."'---,,---,,-- .__ .__ ._."._._----"-"-1-.--'-._-"'""",,,,.,,._-"''''-- ----"-.---.,,.-
Oxalic 5,36. 10-2
."""."'''""."''"''''''''-.-".".".-"".-''"-"".".,,''''''-,,-.-,,''".,,.".""""-"".",,,,""'."'."'.-.-1---".,,----.--.--.-"'.".--
5,42. 10-5
".---"'.-""."'".".""." -,,"'-". ".".-.---"""''''--,,-'''',,."

."-""..."_... Phenic _
_."-"-,,,,.-----,,.,,""'''-'''""""''"'',,'',,''".'''._''''''.--''--
1,00. 10-10
"'._----"'----'" ."-"---""._"""."."."""""".".",,,- ."'-"_.,,._._,,--_._".-
--"._"-"."'.
Phosphoric
__ ."-"_."'-"'''''" ...... "'''.,,,,'''''''''''''',,.,,'''',,.,,'',,.,,''-,,- __
.
7,11. 10-3
._--""---"""._---,,._. 6,34. 10-8
"_."--"",,",,"',,.,,,,""-""""-,,-,,--
4,2. 10-13
."._"._"-""_.",,-".",,,, .
._"'""._~~hthali?.._""",,. "_""""
__"_."..._"_."_ " "_~!..?:_"!Q"~~
__"_"_..._...""_"."."_"~"!~_1_:}T~,,._" ,,_... ""_,,_""_."._
Picric
--""."------"_._"._-""."."._."._._ .."",,_.-
5,1. 10-1
-,,-"- "_.-..._-""... ... ,,,,, "" ""._.".""-" "'--'--'""---'---"""
____ ~ruvi~ .... ,,_._,,_
..._" __ .. ~~~1_0-3_". ,,_.
_"_.__,,_"_._
....
"....
,""..___
. ." " ._"",,
Salicylic 1,05. 10-3
-----=-"_.-"""_ ..
_--"--_._
...
_._.,,-"._,,._-1--" -"_'-"-" -."".-----"" .....
--,,"-.--.- -""'--'-""'-"""""""'"
•
"" ~ucci~I~_"_" . ._."."."_,,, """_ 6,21. 10-5 ".__ 2,32:_~,,~~
."_... __ f..-- "'''"
Sulfurhy'dric
"__ .__ ~" ... I--. 1,0. 10.7 -".".-."._-1,3 .
.__..""--""
...10. 13
"--"-,,---1----"."-_._ ...
"

[-~~--~~~~===
246
 • BASE Hang 56phan Iy
Amoniac 1,76. 10-5
f--.------------------~----..-".-,,---..:.,,-----'-,,-------.-- ..-.-----------.--.-.-.-
Anilin 3,94. 1010
----- -_._--_,._---- ------- _.-
4,0. 10-4
'------_._--_._---". __ .__ ._._._----_._------------_._,,--------_ ..._-_._-----
1- Butylamin
Dimethylamin 5,9. 10-4
.---- -_
Ethanolamin 3,18. 10-5
--.
Ethylamin 4,28. 10-4
~.------- ..--
Ethylendiamin K1 = 8,5. 10- 5

_. ,,-
K2 = 7;1. 10- 8
__
.

Hydrazin 1,3. 10-6

, Hydroxylamin 1,07. 10-8
----_. _._-_._---------_.
Methylamin , 4,8. 10-4
Piperidin 1,3. 10-3
-- .- -.---~---.-----
Pyridin 1,7. 10-9
Trimethylamin 6,25. 10-5

~
3. THE OXY HOA KHl1 CHUAN
. . ~

(<1250C) (k = khi, 1 = long, r = ran)

Nguyen to Mac o~y h6a cao
g6 di,n tl'r Di,n the
Mli'c oxy h6a thap
nh,n + ne (V)
Ag Ag+ +e Ag (r) +- 0,80

As 1--------_._-_. __
As(r) + 3W
._._._-----
+ 3e AsH3
--------------_._,,---- _._-_._-
- 0,54
AS043- + 2W + 2e AS033-+ H2O + 0,559

H3B03 + 3W
B ..~-....-.-.-.-.-.-.------...--,--.-........ -.... ............
+3e
__ _
B (r) + 3H2O
---.......... ...__._._._._._ ...-..._-_._ ...._.._._-_._--_ .. -0,73
_----- -_._--_._---
..... ......_ ... ..__ .
H2B03 + H2O + 3e B (r) + -40W - 0,25
Bi3+ + 3e Bi (r) + 0,39
._-"-_.-._"---,,-_._,,._---_ _- ._--_._---
....._ ... 1----_. __ .__
._--".-
..
_- f---------.---
Bi NaBi03 + 4W + 2e BiO++ Na+ + 2H2O + 1,8
-_.__ --------_. -- --_._------ ----------
BiO+ + 2W + 3e Bi (r) + H2O + 0,320

Br -'
Br2 (I)
-_. __ .
+ 2e
--.
2Br-
--- .- ..
+ 1,07
-----
Br03- + 6W + 6e Br - + 3H2O + 1,4-4

(CN)2 + 2e 2 CN- + 0,27

C (SCNh
,,------,,-_._-_._._---
2 CO2
+ 2e
------ ----_.
+ 2e
__
2SCN-
C2O/-
.-._-----"-,,.- 1--
+ 0,77
-0,50
-_
247
- ......

Nguyen to' Muc oxy h6a cao

so' d~n tll Mac oxy h6a tlJ.ap
Oi~n the
nhfn + ne (V)
Cd Cd2' + 2e .C,d(r) - 0,403
Ce Ce4' +e Ge3+ + 1,71
CI2(k) + 2e ~.__ 2Ci- + 1,36
_-_ .._ ...,----_._---
-..
- ._M__ .._____ .__ ________ H'

2HCIO + 2W + 2e CI2 + 2H 2O + 1,63

CI f----- ..
-.-- ...
-.---------- -----.-- _. ___ .___ ._._
.._c.____ .:.
__ --_"_-,_,--,_,,
C103- +6W + 5e 0,5 CI2+ 3"H2O +1,47
r---'-'-' --t--.---.----
C104- + 8W + 8e cr + 4H2O + 1,35
Cr 2. + 2e .cr (r) - 0;56
t--- .-
Cr02 + 2H2O + 3e Cr (r) + 40W -1,2
--------- --------.--- -_._-----
C~· + 3e Cr 2. - 0,41
Cr
_._-----_._---
Cr 3. + 3e,
------ _._.__Cr._-----_._----
(r) - 0,744
1--_._---'--'
+ 14W + 6e 2 C~· +7H2O + 1,36
_. Cr20/- ----
Cr042- + 2H2O + 3e Cr02-+ 40W - 0,12

-.
Cu 2' +2e Cu (r) + 0,337
.. _
+e Cu'
Cu
Cu2'
._-_ ..._._ .._.'----_._--- _._-- - ....+---
0,153
.....-.-
2 CU(OH)2 + 2e Cu20 + 20W + H2O -0,09
-_. --~
Cu2' + 1- +e Cui (r) + 0,86
Fe2' .+ 2e Fe (r) - 0,440
--
..._ ..._.....__ ..__ ._._..
Fe3' +e Fe2' + 0,771
_._----_
------------------ 1---. ._-.---...-
Fe
---.
Fe (OH)3 (r) +e Fe(OH)2 (r) + OW -0,65 _._-
_.._ .....__ .__FeO/- + 4H2O.__ ._--
..._--_._----_._ ..-.. __ + 3e
1---..
_---_._.
Fe(OH)3
--_._._-_ _ _----_ __ ._..._
...._ .. ....._ ..
+ 50H-..... + 0,60
.__ ._....._ ...._-_ .._ ...__ ._....._._ ...
FeO/- + 8W + 3e Fe3++ 4H2O + 1,9
--'._----_.- - ._-_._--_ .. _-_._--- ---_._ ....._-
Fe(CN)63- +e Fe(CN)64- + 0,36
2H+ + 2e H2 + 0,00
H + 2e 2H O + 1,80
_ H202
_ + 2W
_ __ _ _ .•...-
...........•_.- •... ......_ .. ............_ .•......• .. ... .. _._.--.- _._--_._ .._--_._-_ 2
.._ ....------ ----_ .._-_ .._ ..__ ...
2H' +02 + 2e H202 + 0,68
Hg/+
_._._ .._.__ .._----_. __ .._-f---------
+ 2e ._ .._ ...(I)__ .....•.........._...._._.- ---_._._-_._
--------_2.._Hg + 0,788
.. .._. __ .--
I
_ ...

Hg Hg2+ + 2e Hg (I) + 0,854

--~--.-~ - -.~.-.~-
..

2Hg2+ + 2e Hg22+ + 0,920

12
-----_._ ..
+ 2e 2r
----- _. __ ..__ _-
+ 0,536 .- ._......
2HIO +2H' + 2e 12+2H2O + 1,45
..---.--.
-.~-.--.---~ ---
1
r--------.
HIO+W + 2e
..- ----_ .•._--_. r+H2O
__ ._- -------
+ 1,00

·.____ .____ 10._.M_____

3- + 6W + 5e 0,512 + 3H2O + 1,178
..
103- + 2cr + 6H' +4e ICI2- + 3H2O + 1,24

248
 s6di,n tli £)i~n the
Nguyen to' MlI'c oxy hoa cao
nh~n + ne
Mti'c oxy h6a thap
(V)
. Mn2>
-_._------_._. __ ....._._-_ ..__ .__......._._---_ _-_
+ 2e....-,--- .... ....-._.._-_._._--_.
Mn (r) ....__ __ ..... ..
-1,180 __ _ ..

Mn3+
.._--_ _--_._ _.__ .._ _- +e
_._--_
..__ ..- ._---_
Mn2+
_---_ ..- - 1,51
-----_ .. . _-_
-_ .._-_._._._- ..---_ .._ ..._._- ...__ ..._.__ ... _-_._ ...__ ....__ ....- _ .._...._ ..._--_ ..
Mn4> + 2e Mn2+ __
...... -._-- '-_ ....
+ 1,57
.._- _-_
Mn _ Mn02 (r)+4W
._._.._ _ _ ___ . + 2e . ..___._ __ Mn2+ . + 2HP +
1--------.---1,23

.. ..Mn04- +..
_. ..
_ 8W ...
__
..
_..-.. + 5e
---- .. Mn2+
--.-_..+ 4H20
-,---..--.. + 1,51 .
-.- f--.----__:__
Mn04- + 4W + 3e Mn02+ 2H20 + 1,695
------_ ..__ .._--_._---- -_..... ....... _--_ ...-
Mn04- +e ¥nO/- + 0,564
HN02+ W +e NO (k) + H20 + 0,99
--.----'--- ...
-------- 1---' .J.-.------':._:_-.-=------f--.-----
2HN02+ 6W
+ 6e N2(k) + 4H20 + 1,45
-.--
-------t-------.- .. .
:.....:....:--..::_----+----~--
N03-+ 3W + 2e HN02+ H20 + 0,93
f--.------------ ------- ..
- ...
---.. -------- -------1
---..
N _ .. __
N03-+ 2W
.._--_._-_.-
+e N02+ H20 + 0,81

._
...
N03....
-+ 4W
__..__
...
_..
+ 3e NO (k)..------
+ 2H20 _.--------1
+ 0,85
2N03- + 12H' + 10e N2+ 6HP + 1,24
f--.._--.--- .....
--- - --=-------=----'-----
1-------...
N03- + 7W + 8e NH40H+ 20H- + 0,12
Pb2+ + 2e Pb (r) - 0,126
Pb 1--.--------- ----.------------.-
--- ..
----1

Pb02 (r) + 4W + 2e Pb2++ 2H20 + 1,455

1--" - ---.-...
- ..
--.-. . .....
-- ..-.- --f--
.. ..
-----
PbS04 (r) + 2e Pb (r) + SO/- - 0,350
S (r) ~ + 2e S 2- - 0,55
_- ._
._._.
... --- 1---------.--.--- f-..------
S (r) + HP + 2e HS-+ OH" - 0,51
- ..
----.---.. ------.. ---I----.-.-.---.------f-------- ..
S+2W +2e H2S +0,17
--.--- ....
- ..--..
--.---;...
-t------ ...
-----
...
I-- ...
- ..
--.... ---.---f.-.------..
---.-- ... ----...
-
S/- + 2e 2S 2- - 0,51
S 1---._---_ ..
_._..
_...
_-_..
_------.--- --..
--.-.-
....
-...
---..
--....
-......
--...
----.--- ---.---- ...
-
_. _ _._._-_ ..__ __ __ _ - _--_._----
. S4062-.. ....
+ 2e . . _----_._ _ __ ._ ---_+..__0,08
--_._._._ 2S20/-
..... ..... .. .._-- ... .. ..... ..
SO/- + 4W + 2e H2S03+H20 + 0,60
-------.- --- --- -- ..
- t-..- --.--.---I--..
--- -----.- ..
------- .._ --- ..
---.
S20/- + 2e 2S0/- + 1,1
...........
-- ----.- - -.-- ..-.- ---.--..
-- - - ---_
.___
. ..
_---_._ 1---- ..
_.___
.-..
S20/- + 2e 2S0/- co mat Ag+ + 1,98

........ _ Sb_--_
_._ (r) +__3H' _ - __ - ---_ _- _._--_ .._--_SbH
+ 3e 3 0,50
.._-_ _ __ ._-- -.-------
.. ..
-

Sb (r) + 3H20 + 3e SbH3 + 30H" - 1,3

f------ -.-.-
..- ----- --- -- -- ---'''- ..
-..-..
- -.--- ------- .. -
Sb Sb 3+ +3e Sb(r)
------_._._ ......_._._ .....__ .- ---------- .__ .._ ......_-_. ...._--_ .. ...._--- ...__ ... __
+0,10
...._--- _ _-_
-_Sb(OH}6-
_+ 2W _-_ + 2e Sb02+ 4H20
__ - 0,43
"._. ..__._- -_._---_ ..- -----_ -- _ .. ..-..-..-..-- .._-._----_ _ _ -
Sb205+ 6H' + 4e 2SbO++ 3H20 + 0,581
Sn2+ + 2e Sn (r) - 0,136
Sn
+ 2e + 0,154
Ti02++ 2W + 4e - 0,90
---.-----r---------t-
TiO++ 2W +e Ti 2++ H20 - 0,40
Ti
---t-'--------- -----. -----. --------
Ti02> +e TiO> + 0,1

249
 ----t

096

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-----------_--_._- -_._-- --
 5. HANG s6 T~O 'PHUC
* Pho'i tit' vO eo
,..---
Phoi tl't Cation logK1 . .I~K2 logK3 logK4 logK5 log~
'OH3COO- Ag+ 0,4 ...0,2 _,.
.Cd2+ 1.3 1.0 0;1 -0,4
Cu2+ 2,2 1,1
Hg2+ . log K1K_? := 8,4
Pb2+ 2,7 1,5

NH3 Ag' 3,3 3,8

Cd2' 2.6 2,1 1,4 0,9 -0,3 -1,7
Co2' .2,1 1,6 1,0 0,8 0,2 -0,6
Cu2+ 4,3 3,1 3,0 2,3 -0,5
. Ni2' 2.~ 2,2 1,7 1,2 0,8 0,0
Zn2+ 2,4 2,4 2,5 2,1
Br- Ag+ AgBr(r) + Br - ~ AgBr2- IgK2= - 4,7
AgBr2- + Br" ~ AgBr/- IgK3 = 0,7
Hg2+ 9,0 8,3 ' 1,4 1,3
,
Pb2+ 1 ;2
CI- Ag+ AgCI(r)+ cr AgCI2- log Ks2= - 4,7
AgCI2-+ cr AgC132- log K3 = 0,0
8;3+ 2.4 2,0 1,4 0,4 0,5
Cd2+ 1,5 0,4 0,4
Cu' Cu++ 2cr CuCI2- logK1K2 4,9 =
Fe2+ 0,4 0,0
Fe3+ '1.5 0,6
- -1,0
Hg2+ G.7 6,5 0,9 1,0
Pb2+ 1,6 Pb2++ 3Cr PbCI3- log K1K2K3 1,7 =
Sn2+ 1, '1' 0,6 0,0

CW Ag+ Ag+ + 2CN- Ag(CNh- logK1K2 = 21,1

Cd2+ 5,5 5,1 4,6 3,6
1-Ig2+ 18,0 16,7 3,8 3,0
Ni 2+ Ni2++4CW Ni(CN)4- logK1K2K3K4 22 =
F- A13+ 6,1 5,0 3,8 2,7 1,6 0,5
Fe 3+ 5,3 4,0 2,8

252
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 'A ~
TAl LI~U THAM KHAO

1. Bui Long Bien (1995), Phan tich. hoti h9C dinh. luang, NXB Khoa hoc
ky thuat, Ha NQi.
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255
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