Bài Tập Phân Tích Công Cụ
Bài Tập Phân Tích Công Cụ
Bài Tập Phân Tích Công Cụ
units of M1cm1.
10. One method for the analysis of Fe3+ that can be used with a variety of sample
matrices, is to form the highly colored Fe3+thioglycolic acid complex. The complex
absorbs strongly at 535 nm. Standardizing the method is accomplished using external
standards. A 10.00 ppm Fe3+ working standard is prepared by transferring a 10-mL
aliquot of a 100.0 ppm stock solution of Fe3+ to a 100-mL volumetric flask and
diluting to volume. Calibration standards of 1.00, 2.00, 3.00, 4.00, and 5.00 ppm are
then prepared by transferring appropriate amounts of the 100.0-ppm working solution
into separate 50-mL volumetric flasks, each containing 5 mL of thioglycolic acid, 2
mL of 20% w/v ammonium citrate, and 5 mL of 0.22 M NH3. After diluting to
volume and mixing, the absorbances of the external standards are measured against an
appropriate blank. Samples are prepared for analysis by taking a portion known to
contain approximately 0.1 g of Fe3+, dissolving in a minimum amount of HNO3, and
diluting to volume in a 1-L volumetric flask. A 1.00-mL aliquot of this solution is
transferred to a 50-mL volumetric flask, along with 5 mL of thioglycolic acid, 2 mL of
20% w/v ammonium citrate, and 5 mL of 0.22 M NH3 and diluted to volume. The
absorbance of this solution is used to determine the concentration of Fe3+ in the
sample.
(a) What is an appropriate blank for this procedure?
(b) Ammonium citrate is added to prevent the precipitation of Al3+. What effect would
the presence of trace amount of Fe3+ in the ammonium citrate have on the reported
concentration of iron in the sample?
(c) Why does the procedure call for taking an amount of sample containing
approximately 0.1 grams of Fe3+?
(d) Unbeknownst to the analyst, the 100-mL volumetric flask used to prepare the 10.00
ppm working standard of Fe3+ has a volume that is significantly smaller than 100.0mL.
What effect will this have on the reported concentration of iron in the sample?
11. A spectrophotometric method for the analysis of iron has a linear calibration curve
for standards of 0.00, 5.00, 10.00, 15.00, and 20.00 ppm. An iron ore sample with an
expected iron content of 4060% w/w is to be analyzed by this method. An
approximately 0.5-g sample is taken, dissolved in a minimum of concentrated HCl,
and diluted to 1 L in a volumetric flask using distilled water. A 5.00-mL aliquot is
removed with a pipet. To what volume (10, 25, 50, 100, 250, 500, or 1000 mL) should
it be diluted to minimize the uncertainty in the analysis? Explain.
12. In a recent paper, Lozano-Calero and colleagues describe a new method for the
quantitative analysis of phosphorus in cola beverages.28 The method is based on the
formation
of
an
intensely
blue-colored
phosphomolybdate
complex,
it necessary to ensure that the dissolved gases have been removed? (d) How would
you prepare a blank for this method? (e) The calibration curve reported by the
authors yields a regression line of Abs = 0.02 + 0.72 (ppm P2O5)
A sample of Crystal Pepsi, analyzed as described here, yields an absorbance of 0.565.
What is the concentration of phosphorus, reported as parts per million of P, in the
original sample of Crystal Pepsi?
13. EDTA forms colored complexes with a variety of metal ions that may serve as the
basis for a quantitative spectrophotometric method of analysis. The molar
absorptivities of the EDTA complexes of Cu2+, Co2+, and Ni2+ at three wavelengths
are summarized in the following table (all values of are in M1 cm1)
Using this information, determine (a) the concentration of Cu2+ in a solution that
has an absorbance of 0.338 at a wavelength of 732.0 nm; (b) the concentrations of
Cu2+ and Co2+ in a solution that has an absorbance of 0.453 at a wavelength of
732.0 nm and 0.107 at a wavelength of 462.9 nm; and (c) the concentrations of
Cu2+, Co2+, and Ni2+ in a sample that has an absorbance of 0.423 at a wavelength
of 732.0 nm, 0.184 at a wavelength of 462.9 nm, and 0.291 at a wavelength of 378.7
nm. The pathlength, b, for all measurements is 1.00 cm.
14. The concentration of phenol in a water sample is determined by separating the
phenol from nonvolatile impurities by steam distillation, followed by reacting with
4- aminoantipyrine and K3Fe(CN)6 at pH 7.9 to form a colored antipyrine dye. A
phenol standard with a concentration of 4.00 ppm has an absorbance of 0.424 at a
wavelength of 460 nm using a 1.00-cm cell. A water sample is steam-distilled, and a
50.00-mL aliquot of the distillate is placed in a 100-mL volumetric flask and diluted
to volume with distilled water. The absorbance of this solution is found to be 0.394.
What is the concentration of phenol (in parts per million) in the water sample?
16. In the DPD colorimetric method for the free chlorine residual, which is reported as
parts per million of Cl2, the oxidizing power of free chlorine converts the colorless
amine N,N-diethyl-p-phenylenediamine to a colored dye that absorbs strongly over
the wavelength range of 440580 nm. Analysis of a set of calibration standards gave
the following results
A sample from a public water supply is analyzed to determine the free chlorine residual,
giving an absorbance of 0.113.
What is the free chlorine residual for the sample in parts per million Cl2?
17. Brown and Lin reported a quantitative method for methanol based on its effect on
the visible spectrum of methylene blue.30 In the absence of methanol, the visible
spectrum for methylene blue shows two prominent absorption bands centered at
approximately 610 nm and 660 nm, corresponding to the monomer and dimer,
respectively. In the presence of methanol, the intensity of the dimers absorption
band decreases, and that of the monomer increases. For concentrations of
methanol between 0 and 30% v/v, the ratio of the absorbance at 663 nm, A663, to
that at 610 nm, A610, is a linear function of the amount of methanol. Using the
following standardization data, determine the %v/v methanol in a sample for
which A610 is 0.75 and A663 is 1.07.
18. The concentration of the barbiturate barbital in a blood sample was determined by
extracting 3.00 mL of the blood with 15 mL of CHCl3. The chloroform, which now
contains the barbital, is then extracted with 10.0 mL of 0.045 M NaOH (pH 13).
A 3.00-mL sample of the aqueous extract is placed in a 1.00-cm cell, and an
absorbance of 0.115 is measured. The pH of the sample in the absorption cell is then
adjusted to approximately 10 by adding 0.5 mL of 16% w/v NH4Cl, giving an
absorbance of 0.023. When 3.00 mL of a standard barbital solution with a
concentration of 3.0 mg/100 mL is taken through the same procedure, the
absorbance at pH 13 is 0.295, whereas that at a pH of 10 is 0.002. Report the
concentration of barbital, (milligrams per 100 mL), in the sample.
19. Jones and Thatcher developed a spectrophotometric method for analyzing analgesic
tablets containing aspirin, phenacetin, and caffeine. The sample is dissolved in
CHCl3 and extracted with an aqueous solution of NaHCO3 to remove the aspirin.
After the extraction is complete, the chloroform is then transferred to a 250-mL
volumetric flask and diluted to volume with CHCl3. A 2.00-mL portion of this
solution is diluted to volume in a 200-mL volumetric flask with CHCl3. The
absorbance of the final solution is measured at wavelengths of 250 nm and 275 nm,
at which the absorptivities, in ppm1 cm1, for caffeine and phenacetin are
extracting the aspirin into CHCl3. The combined extracts are diluted to 500 mL in a
volumetric flask. A 20.00-mL portion of the solution is placed in a 100-mL volumetric
flask and diluted to volume with CHCl3. The absorbance of this solution is measured at
277 nm, where the absorptivity of aspirin is 0.00682 ppm1 cm1. An analgesic tablet
treated by this procedure is found to have absorbances of 0.466 at 250 nm, 0.164 at 275
nm, and 0.600 at 277 nm when using a cell with a 1.00-cm pathlength. Report the
milligrams of aspirin, caffeine, and phenacetin in the analgesic tablet.
20. The concentration of SO2 in a sample of air was determined by the p-rosaniline
2
method. The SO2 was collected in a 10.00- mL solution of HgCl42, where it forms
Hg(SO3)2
, by pulling the air through the solution for 75 min at a rate of 1.6
L/min.
After adding p-rosaniline and formaldehyde, the colored solution was diluted to 25 mL
in a volumetric flask. The absorbance was measured at 569 nm in a 1-cm cell, yielding
a value of 0.485. A standard sample was prepared by substituting a 1.00-mL sample of
a standard solution containing the equivalent of 15.00 ppm SO2 for the air sample.
The absorbance of the standard was found to be 0.181. Report the concentration of
SO2 in the air in parts per million. The density of air may be taken as 1.18 g/L.
23. The following table lists the molar absorptivities for the Arsenazo complexes of
copper and barium at selected wavelengths. Determine the optimum wavelengths
for the analysis of a mixture of copper and barium.
595
600
607
611
614
620
11900
15500
18300
19300
19300
17800
7100
7200
7400
6900
7000
7100
626
635
641
645
650
655
658
665
16300
10900
7500
5300
3500
2200
1900
1500
8400
9900
10500
10000
8600
6600
6500
3900
670
1500
2800
680
1800
1500
26. The stoichiometry for a metalligand complex was determined by the method of
continuous variations. A series of solutions was prepared in which the combined
concentrations of the metal and ligand were held constant at 5.15 104 M. The
absorbances of these solutions were measured at a wavelength at which only the
metalligand complex absorbs. Using the following data, determine the formula of the
complex.
Mole fraction M
Mole fraction L
Absorbance
33. Hobbins reported the following calibration data for the flame atomic absorption
analysis for phosphorus.
To determine the purity of a sample of Na2HPO4, a 2,469g sample is dissolved and diluted
to volume in a 100-mL volumetric flask. Analysis of the resulting solution gives an
absorbance of 0.135. What is the purity of the Na2HPO4?
34. Bonert and Pohl reported results for the atomic absorption analysis of several metals
in caustic suspensions produced during the manufacture of soda by the ammoniasoda process. The concentration of Cu was determined by acidifying a 200-mL
sample of the caustic solution with 20 mL of concentrated HNO3, adding 1 mL of
27% w/v H2O2 and boiling for 30 min. The resulting solution was diluted to 500
mL, filtered, and analyzed by flame atomic absorption using matrix-matched
standards. The results for a typical analysis are shown in the following table.
HNO3 and HCl and evaporated to dryness. Finally, the residue was dissolved in 5 mL of
HCl, filtered, diluted to volume in a 50-mL volumetric flask, and analyzed
by atomic absorption using the method of standard additions. The atomic absorption
results are summarized in the following table.
35. Quigley and Vernon report results for the determination of trace metals in sea water
using a graphite furnace atomic absorption spectrophotometer. Calibration was
achieved by the method of standard additions. The trace metals were first separated
from their complex, high-salt matrix by coprecipitating with Fe3+. In a typical
analysis a 5.00-mL portion of 2000-ppm Fe3+ was added to 1.00 L of sea water. The
pH was adjusted to 9 using NH4OH, and the precipitate of Fe(OH)3 allowed to stand
overnight. After isolating and rinsing the precipitate, the Fe(OH)3 and coprecipitated
metals were dissolved in 2 mL of concentrated HNO3 and diluted to volume in a 50mL volumetric flask. To analyze for Mn2+, a 1.00-mL sample of this solution was
diluted to 100 mL in a volumetric flask. The following samples were injected into the
graphite furnace and analyzed
Report the parts per billion of Mn2+ in the sample of sea water.
What is the %w/w Ni in a sample for which the ratio of emission intensity is 1.10
* 103?
Bi dch:
1. Cung cp cc thng tin cn thiu trong bng di y:
Bc sng
Tn s
S sng
Nng lng
(m)
(s-1)
(cm-1)
(J/mol)
4,50.10-9
6,67.1016
2222222
-7
15
2,26.10
1,33.10
44248
-6
13
3,11.10
9,65.10
3215
-7
15
2,76.10
1,09.10
36232
2. Cung cp cc thng tin cn thiu trong bng di y:
Nng cht
Mt quang
truyn qua
4,42.10-17
8,80.10-19
6,39.10-20
7,20.10-19
H s hp thu
Pathlength
phn tch
phn t
(cm)
(M)
(M-1cm-1)
1,4.10-4
0,157
69,7
1120
1,00
-4
7,5. 10
0,563
27,4
750
1,00
2,56.10-4
0,225
59,6
440
2,00
-3
1,55. 10
0,167
68,1
21,5
5,00
-4
8,46.10
0,478
33,3
565
1,00
-3
4,35. 10
0,674
21,2
1550
0,10
-4
1,20. 10
0,0899
81,3
75
10,00
3. truyn qua ca mt dung dch c tm thy l 35%. truyn qua l g nu
mt dung dch c pha long trong mt na?
Bi gii: Ta c: I/Io=0,35 => A ban u = log(Io/I) = log(1/0,35)=0.456
Khi dung dch c pha long mt na th nng gim i mt na, tc
Cs=C/2
M A=.l.C => As=A/2= 0.456/2= 0,228
A=log(Io/I) => T= I/Io= 1/10A = 1/ 100.228= 59,2%
Vy truyn qua khi pha long dung dch i mt na l 59,2%
4. truyn qua ca mt dung dch c tm thy l 85% khi o trong mt m
pathlength l 1cm. truyn qua l g nu pathlength c tng ln n 10 cm?
Bi gii: Ta c: I/Io= 0,85 => A= log(Io/I) = log (1/0.85) = 0.0706
A= .l.C
As= .ls.C => A/ As= l/ls=1/10 => As= 10. A= 10. 0,0706= 0,706
=> I/Io=1/10A=1/100,706= 19,7%
Vy truyn qua khi di cuvet l 10 cm l 19,7%
6. lch ha ca nh lut Beer c th xy ra khi nng ca cht hp th b nh
hng bi v tr ca cn bng phn ng. Xem xt mt axit yu , HA, cho K a l 2.10-5.
Xy dng ng nh chun nh lut Beer ca hp th so vi tng nng ca
HA
B:
Co
Cb:
Co-a
H+
A-
CHA = 2,68.10-6M
=> A= 2000. 2,68.10-6 +500. 7,32. 10-6 = 0,009
Ctot = [HA] + [A] = 3.10-5 => CHA = 3.10-5- CA_
=> (CA_)2 = 2.10-5. (3.10-5- CA_) => CA_ = 1,65. 10-5 M
CHA = 1,35.10-5 M
=> A= 2000. 1,35.10-5 +500. 1,65. 10-5 = 0,035
Ctot = [HA] + [A] = 5.10-5 => CHA = 5.10-5- CA_
=> (CA_)2 = 2.10-5. (5.10-5- CA_) => CA_ = 2,32. 10-5 M
CHA = 2,68.10-5M
=> A= 2000. 2,68.10-5 +500. 2,32. 10-5 = 0,065
Ctot = [HA] + [A] = 9.10-5 => CHA = 9.10-5- CA_
=> (CA_)2 = 2.10-5. (9.10-5- CA_) => CA_ = 3,36. 10-5 M
CHA = 5,64.10-5 M
=> A= 2000. 5,64.10-5 +500. 3,36. 10-5 = 0,130
Ctot = [HA] + [A] = 11.10-5 => CHA = 11.10-5- CA_
=> (CA_)2 = 2.10-5. (11.10-5- CA_) => CA_ = 3,8. 10-5 M
CHA = 7,2.10-5 M
=> A= 2000. 7,2.10-5 +500. 3,8. 10-5 = 0,163
Ctot = [HA] + [A] = 13.10-5 => CHA = 13.10-5- CA_
=> (CA_)2 = 2.10-5. (13.10-5- CA_) => CA_ = 4,2. 10-5 M
CHA = 8,8.10-5 M
=> A= 2000. 8,8.10-5 +500. 8,8. 10-5 = 0,197
(c) HA = 2000 v A- = 500v dung dch c m n pH l 4.50, l=1cm
Ta c A= AHA + AA_ = HA. CHA.l + A_. CA_.l
A= 2000. CHA + 500 . CA_
H+
B:
Co
10-4,5
Cb:
Co-a
a + 10-4,5
A-
6M
=> CHA= 6,38.10-6 M
=> A= 2000. 6,38.10-6 +500. 3,62. 10-6 = 0,014
Ctot = [HA] + [A] = 3.10-5 => CHA = 3.10-5- CA_
=>
9,77.10-6 M
=> CHA= 2,02.10-5 M
=> A= 2000. 2,02.10-5 +500. 9,77. 10-6 = 0,045
5M
=> CHA= 3,5.10-5 M
=> A= 2000. 3,5.10-5 +500. 1,5. 10-5 = 0,078
Ctot = [HA] + [A] = 9.10-5 => CHA = 9.10-5- CA_
=>
2,38.10-5 M
=> CHA= 6,62.10-5 M
=> A= 2000. 6,62.10-5 +500. 2,38. 10-5 = 0,144
Ctot = [HA] + [A] = 11.10-5 => CHA = 11.10-5- CA_
=>
2,72.10-5 M
=> CHA= 8,28.10-5 M
=> A= 2000. 8,28.10-5 +500. 2,72. 10-5 = 0,179
Ctot = [HA] + [A] = 13.10-5 => CHA = 13.10-5- CA_
=>
3,13.10-5 M
=> CHA= 9,87.10-5 M
=> A= 2000. 9,87.10-5 +500. 3,13. 10-5 = 0,213
10. Mt phng php phn tch Fe3+ c th c s dng mt lot cc mu nn,
3+
. Cc hiu ng
3+
trong citrate
amoni l g ?
(C) Ti sao cc th tc xc nh rng mu c cha khong 0,1 g Fe 3 + ?
(D) Khng nh cc nh phn tch, cc bnh nh mc 100 ml dng chun b 10,00 ppm
tiu chun lm vic ca Fe 3 + c mt khi lng nh hn so vi 100,0 mL. Hiu ng g
s c trong nng bo co ca st trong mu?
11. Mt phng php quang ph phn tch cc cht st c mt ng cong hiu chun
tuyn tnh cho cc tiu chun l 0.00, 5.00, 10.00, 15.00, 20.00 vi n v mg Fe / L
(ppm). Mt mu qung st 40-60% w / w c phn tch bng phng php ny. Ly
khong 0,5g mu, ha tan trong mt lng ti thiu HCl m c v pha long trong bnh
462,9
732,0
378,7
Co 2 +
15.8
2.11
3.11
Cu 2 +
2.32
95,2
7.73
Ni 2 +
1.79
3.03
13.5
hp th
0.00
0.000
0.50
0,270
1.00
0,543
1.50
0,813
2.00
1,084
A 663 / A 610
0.0
1,21
5.0
1,29
10.0
1.42
15.0
1,52
20.0
1,62
25.0
1.74
30.0
1,84
Bi gii:
Theo phng php lp
ng chun
Gi phng trnh
h gia nng o v
mt quang A
Gi
caffeine
0,013 0,048
1
C1 l nng ca caffeine
C2 l nng ca phenacetin
20. Nng SO 2 trong mu khng kh c xc nh bng cc phng php prosaniline. SO 2 c thu thp trong 10,00 ml dung dch HgCl 4 2-, n to thnh
Hg(SO3)2 2- , bng cch ht khng kh qua dung dch ny trong 75 pht tc 1,6 L /
pht. Sau khi thm p -rosaniline v formaldehyde, dung dch mu c pha long n 25
ml trong bnh nh mc. Mt quang c o 569 nm trong cuvet 1 cm, t gi tr
0,485. Mt mu chun c chun b bng cch ly 1,00 ml dung dch chun cha
tng ng vi 15,00 ppm SO 2 trong mu khng kh. Mt quang dung dch chun
ny c tm thy l 0,181. Tnh nng SO 2 trong khng kh theo ppm. Mt ca
khng kh l 1,18 g / lt.
Bi gii: Achun=.l.C => = Achun/l.C = 0,181/15= 0,012ppm
Khi A=0,485 ta c C= A/l.= 0,485/0,012= 40,417 ppm
Ta c: Vkk= 120 . 1,18= 120 (l)
mkk= 120. 1,18 = 141,6 g
23. Cc danh mc bng cht hp th phn t sau cho hp Arsenazo ng v bari.
27
Cu (M -1 cm -1 )
Ba (M -1 cm -1 )
595
11900
7100
600
15500
7200
607
18.300
7400
611
19.300
6900
614
19.300
7000
620
17800
7100
626
16.300
8400
635
10900
9900
641
7500
10500
645
5300
10000
650
3500
8600
655
2200
6600
658
1900
6500
665
1500
3900
670
1500
2800
680
1800
1500
1.0
0.0
0,001
0.9
0.1
0,126
0.8
0.2
0,260
0.7
0.3
0,389
0.6
0,4
0,515
0.5
0.5
0,642
0,4
0.6
0,775
0.3
0.7
0,771
0.2
0.8
0,513
0.1
0.9
0,253
0.0
1.0
0.000
33. Hobbins bo co cc d liu hiu chun sau y cho ngn la phn tch hp th
nguyn t s dng pht pho.
mg P / L
Mt quang
2130
0,048
4260
0,110
6400
0,173
8530
0,230
dung dch
mg Cu / L
Mt quang
Trng
0.000
0,007
tiu chun 1
0,200
0,014
tiu chun 2
0,500
0,036
tiu chun 3
1.000
0,072
tiu chun 4
2.000
0,146
mu
0,027
(B) Vic xc nh Cr c thc hin bng cch axit ha mt mu 200 ml dung dch xt
vi 20 ml dung dch HNO tp trung 3 , thm 0,2 g Na2 SO 3 v un si trong 30 pht. Cc
Cr c phn lp t cc mu bng cch thm 20 ml dung dch NH 3 , sn xut mt cht
kt ta bao gm crom cng nh oxit khc. Kt ta c phn lp bng cch lc, ra sch,
v chuyn giao cho mt cc thy tinh. Sau khi axit ha vi 10 ml dung dch HNO 3 , cc
gii php c bc hi n kh. Phn d c ra gii trong mt s kt hp ca
HNO 3 v HCl v bc hi n kh. Cui cng, phn d c ha tan trong 5 ml dung
dch HCl, lc, pha long vi khi lng trong mt th tch bnh 50 ml, v phn tch bng
cch hp th nguyn t s dng cc phng php b sung tiu chun. Cc kt qu hp
th nguyn t c tm tt trong bng di y.
mu
mg Cr thm / L
hp th
trng
0,001
mu
0,045
0,200
0,083
0,500
0,118
1.000
0,192
hp th
0,223
0,294
0,361
nguyn t ngn la. Cc vt liu c phn tch c chun b bng cch nghin,
homogenizing, v sy 103 o C. Mt v d v khong 4 g c chuyn giao cho mt ni
thch anh v un trn mt tm nng char cc cht hu c. Cc mu c lm nng
trong l mp 550 o C trong vi gi. Sau khi lm lnh n nhit phng cn c ha
tan bng cch thm 2 ml dung dch 1: 1 HNO 3 v bc hi n kh. Phn cn li c ra
gii trong 10 ml 1: 9 HNO 3 , lc v pha long n 50 ml trong bnh nh mc. Cc d
liu sau y thu c trong qu trnh phn tch tiu biu cho nng Na trong mt
mu 4,0264 g cm yn mch.
mu
mg Na /
Cng pht x
L
trng
0.00
0.0
tiu chun 1
2.00
90,3
tiu chun 2
4.00
181
tiu chun 3
6.00
272
tiu chun 4
8.00
363
5 tiu chun
10.00
448
mu
238
37. Gluodenis m t vic s dng cc pht x nguyn t ICP phn tch mu bng
ng thau cho Pb v Ni. Cc phn tch cho Pb s dng cc tiu chun bn ngoi chun b
t cc mu ng thau c cha mt lng ch c bit n. Kt qu c th hin trong
bng di y.
% W / w Pb
cng pht x
0.000
0,0100
0,0200
0,0650
0,350
0,700
1.04
2.24
3.15
9.25
Cc% l g w / w Pb trong mu ng cung
4.29 10 4
1,87 10 5
3.20 10 5
1,28 10 6
6.22 10 6
1,26 10 7
1,77 10 7
3,88 10 7
5.61 10 7
1,64 10 8
cp cho mt cng pht x ca 9,25
10 4 ?
Bi gii: Theo phng php lp ng chun
Gi phng trnh y= bx+a l phng trnh tuyn tnh v mi quan h gia nng
o v cng pht x I
Gi
Ta
c:
tng[(xi-xtb)(yi-ytb)]=(0,00-1,6825).(4,29.104-2,97.
107)+(0,01-1,6825).
t l cng pht
Ni
thi
0.000
0,00267
0,0140
0,00154
0,0330
0,00312
0,130
0,120
0,280
0,246
0,280
0,247
0,560
0,533
1.30
1.20
4,82
4.44