VO L Lt ,~ E -r R I C

TITRATION

A solution of kn own co1Kcntrnri on is called a standard solution . Such a solution can be

used to find the co nccntrntions of solutions of ot her reagents.
In volumetric analysis, the concentrntion of a solution is found by meas uring the volume of
solution that will rcacr with a known volume of a standard so lution. The procedure of
adding one so lution to another in a measured way unril the reaction is complete is called
titration . Vo lumetric a nal ys is is often referred to as tirrimetric analysis.

ACID-BASE TITRATIONS

A standard solution oi acid can be used to find the concentration of a solution of alkali. A
known vo lumt' of ,dbli is taken by pipette, a suitable indicator is added, and the alkali is
titrated against the standard acid until the equivalence point is reached. The number of
mo les of acid used ctn be calculated and the equation used to give the number of moles of
alkali neutralised .

EXAMPLE 1 Standardising sodium hydroxide solution

Of a solution of sodium hydroxide, 25.0 cm 3 requires 20.0 cm 3 of hydrochloric acid 0 _f
concentration 0.100 mol dm -J for neutralisation . What is the concentration of che sodium
hydroxide solution?

EXAMPLE 2 Standardising hydrochloric acid

Sodium carbonate (anhydrous) is used as a primary standard in volumetric analysis. A
so luti o n of sodium carbonate of concentration 0.100 mol dm - 3 is used to standardise a
solution of hydrochloric acid. 25 .0 cm ·' of the standard solution of sodium carbonate
require 35 .0 cm ·' of the ac id for neutralisation . Calculate the concentration of rhe acid.

EXAMPLE 3 ·
Calculating the percentage of sodium carb onate m
· was h"mg so da crystals
· soda crysta Is are d.1ssoIve d an d ma d e u p to 250 cm 3 of solution.
5.125 g of washing . .A
3
25 .0 cm porrion of the solutton · 35 .8 cm 3 o f O•0500 m ol dm - 3 sulphunc acid for
· requires
neutralisa rion . Calculate rhc percentage of sodium carbonate in the cryS t als .

EXAMPLE 4' Esrimating ammonium salts

A sample containing ammonium sulphate was warmed with 250 cm 3 of 0.800 mo! dm- 3
sodium hydroxide solution. After the evolution of ammonia had ceased, the excess of
sodium hydroxide solution was neutralised by 85 .0 cm 3 of hydrochloric acid of
concentration 0.500 mol dm- 3 • What mass of ammonium sulphate did the sample contain?

OXIDATION-REDUCTION REACTIONS

Oxidation-reduction (or 'redox') reactions involve a transfer of clecrrons. The oxidising

agent accepts electrons, and the reducing agent gives electrons. In working out the equation
for a rcdox rcacrion, a good method is to work out the ' half-reaction equation' for the
oxidising agent and the 'half-reaction equation• for the reducing agent, and then add them
together.

Examples of half-reaction equations

a Iron(fll) salts arc reduced to iron(fl) salts. The equation is

Fe 3 • - - Fe2♦
for the equation ro balance, the charge on the right-hand side (RHS) must equal the charge
on the left-hand side (LHS). This can be done by inserting an electron on the LHS:
FeJt + e- - - Fc 2•
b When chlorine acts as an oxidising agent, it is reduced to chloride ions:
Cl 2 -- 2e1 -

To obtain a balanced half-reaction equation, 2e - must be inserted on the LHS:

Cl 2 + 2c- ___.. 2e1-
 2
c Sulphites can be oxidised to sulphates:
so /- - - so/-
To balance the equation with respect co mass, an extra oxygen acorn is needed on the LHS.
If H 2 0 is introduced on the LHS co supply this oxygen, the equation becomes
so/-+ H 2 O - - So,Z- +2H•
To balance the equatjon with respect to charge, 2e - are needed on the RHS :
SO/- + H 2 0 - - so/- + 2H • + 2e -
d Potassium manganate(V ll) is an oxidising agent. In acid solution, it is reduced to a
manganese(I l) salt:
Mno◄ - +H• - Mn 2'
To balance the equation with respect to mass, SH . are needed co combine with 4 oxygen
atoms:
2
MnO 4 - +8H . - - Mn •+4H 2O
To balance the equation with respect to charge, 5e - are needed on the LHS:
2
MnO 4 -+ SH•+5c- - - Mn •+4H 2 O
It is a good idea co make a final check. Charge on LHS = -1 + 8 - 5 = +2. Charge on
RHS = +2. The equarion is balanced.
e Potassium dichrornate(V l) is an oxidising agent in acid solution, being reduced to a
chrorruurn(ll l) salt:
Cr 2 O /-+ H ' - Cr 3 '
To balance the equarion for mass, 14H• arc needed :
Cr 2O/- + 14H • - - 2CrJ+ + 7 H 2 O
To balance the equation for charge, 6e - are needed on the LHS:
Cr 2 O/- + 14H• + 6e - - 2CrJ. + 7H 2 O

A final check shows that the charge on the LHS = -2 + 14 - 6 = +6 .

Charge on RHS = 2( + 3) = +6 . The equation is balanced.
You may like to practise with the half-reaction equations in Exercise 8.4 .

Using hcJlf-reaction equations to obtain the equation for a redox reaction

S,..~{Q.~
Sodium thiosulphate and iodine
In the reaction between iodine and thiosulphate ions, the two half-reaction equations are
l 1l

2S 2 O/- - S4 0/- +2e- (2]

Adding equations [1] and [2] gil'eS

l 2 +2e-+2S 2 O/- - - 21-.,.s.o/- +2e-

Deleting the 2e · term from both sides of the equation gives

12 + 2s2O/- - - 21- + s.o/-
A check shows that the charges on the LHS and the RHS are both -4.

EXAMPLE2 Potassium manganatc(V Il) and iron(Il) salts

When potassium manganate(V ll) ox idises an iron(ll) salt to an iron(ITI) sa lt, the equations
for the half-react ions are
MnO 4 - +8H'+5e- - Mn 2· +4H 2 O (3]
Fe 2
' - Fe 3 ' + c · (4]
One manganate(V II) ion needs 5 electrons, and one iron(II) ion gives only one.
Equation (4] must therefore be multiplied by 5:
5Fe2+ - SFc 1• + se· (51
Equations (3] and [5] can now be added to give
2
MnO 4 - +SH'+ 5Fc • -- Mn 2 • + 4H 2 O + 5Fe 3 •

EXAMPLE 3 Potassium manganatc(VIJ) and sodium erhanedioare

When potassium manganate(VII) oxidises sodium ethanedioatc , the eq uation for the
manganate(VII) half-reaction is [JJ as in Example 2, and the equation for rhe reduction of
crhaned1oarc is

f6J
 <J11 c 11111111:,111r11l'(VII) ion 11ccd , 5c , n11 d unc crha ncdio a1c ion i-ivcs 2c · . Multiplyin g 3
cq11 :11io11 IJI by 2 1•,ivn

2 Mn O 1 + 16H ' + I0c · - 2M n 1 ' + 8H 2 O

Mu l1iplyin1; cq 11 a1ion 161by .5 give

5C 2 O /· - I0 CO 2 + I0c ·
/\ddi11g the new cq ua1 ion~ 11ivc,

2MnO • · + 16H' + 5C 1 O /· - 2M n 2• + 10CO 2 + 8H 2 O

EXAMPLE 4 l'n1a s\ium dichrr,matc( VI) and iron(U) ~a lt\

l'ora ,~i um di chrorn a tclVI) oxid i~<:~ iron(II) sa lt, 10 iro n( III ) s~lu . The equations for the two
h:,H -n ·aci io n, arc

171
181
O ne di chrnn inte ion wi ll oxidise ,ix imn( ll ) iom:

c,,o/ · + 141-1' + (, f-c 2' - 2C r }· + 6 Fc )· • 7H10

Yn11 may lik e IO fry 1hc problem on hnhncing equa 11o n, in Exerc, 1-e 8.4 befo re going o n 10
1:ick le 1hc m1111 cr ica l problcrm.

OXIDATION NUMBERS

It i, helpful to discu ss o xidation-reduction rcact1om in term\ o f : he cha nge 1n the

oxidation number o f each reactant. In the reaction

copper is oxidised and oxygen is reduced . It is ,a id th~t the ox «.Lm on numbe r ., , , u ppe r
incrca,cs fro m zero to +2 , and the oxi da ti o n number o f ox:-gcn dc,:-cc4~, from 1crr, w - 2.
T he followi ng rules arc fo ll owed in assigning ox ida tion nu m bco:

The oxidation number of an uncombined clement is uro .

2 In ionic compounds, the oxidation number of each clement is th<: ch:.l 'b.c on •t~ 10 11. In
NaCl, the oxi dati o n number of Na = +I, a nd th :1 1 of Cl = - 1.

3 The sum of the oxidati o n numbers of all the clements in a com pound~ z.c10. In AICI ,. the
oxidation numbers arc : Al = +3; C l = -1, so th a t the sum of 1hr o xidanon num be r, "
+3+3 (-l) s 0.

4 T he sum of the ox id ation numbers of all the clemcncs in :in ion i., <""Gilli 10 the ch.irg c un
t he ion . In SO/- , the oxida tion numbers a rc S = +6 , 0 = -2. The sum o f the o x1d,1t1on
numbers fo r a ll the atoms is +6 + 4(-2) = -2, t he sa me :is the ch:irgc on the 50 ,:- 10 n .

5 In a cova lent compound, one clement must be given .1 posiriw oxidation n umber 3nJ di t·
other a negative ox idation number, such thnt the sum of the o xidation nu mbers fo r 3!1 the
arum ~ is zero . The fo ll ow ing clements a lw~ys have the s:i mc oxid a tion num bas in all rh cir
compou nd~. /\ knowledge of their oxidnrion number, helps l b to l s; ign o xid3ti o n num be r,
to 1hc other elcrncm s combined with tht•m:

Na, K 1 I 1-1 + I, cx ,cpt in mctl l hyd ri des

Mg, Ca +l F - I
/\ L +J Cl - I, c-xccp1 in co mp o und s with O .1nd F
0 - l, cx,cpt in pao xiJc, Jnd rnrnpo unds with F

EXAMPLE 1 Wha1 i, rhe nxid :11io11 numbe r of gcr 111 ,1nium in Gt·C l,'

METHOD C hlorin e i, one o f the clemcnl s wi1h J comtant oxi dati o n num ber o f - 1.

(Ox idat io n number of Ge ) + 4( - 1) = 0 .

AHBWER Ox id at ion number of Ge ~ +4 .

EXAMPLE 2 What i, rhc n xida rion number o f man~ancsc in M n 1 O 7 ?

METHOD Oxy1;c n i, one o f th e dem cnlS wit h a comtant oxidation number of - 2.

2(Oxi d a1io n n11111hcr o f Mn) ➔ 7(- 2) e 0.

ANBVIER O x1d;i1io n 1111mhcr of Mn ~ ., 7.

 POTASSIUM MANGANAT E(VII) TITRATIONS .Lf .
When potassium manganate(Vl l) acts as an oxidising agent in acid solution, it is reduced to
a manganesc(II) salt:
MnO 4 -(aq) + 8H•(aq) + 5e- - Mn 2 '(aq) + 4H 1 O(1)
Potassium manganate(VIl) is not sufficiently pure to be used as a primary standard, ·and
solutions of the oxidant are standardised by titration against a primary standard such as
sodium ethanedioate. This reductant can be obtained in a high state of purity as crystals of
formula Na C 0 • 2H 0, which arc neither deliquescent nor efflorescent, and can be
2 2 4 2
weighed out exactly to make a standard solution.
Once it has been standardised, a solution of potassium manganate(Vll) can be used to
titrate reducing agents such as iron(ll) salts. No indicator is needed as the oxidant changes
from purple to colourless at the end-point.
EXAMPLE 1 Standardising potassium manganate(VII) against the prima~y standard, sodium
ethanedioatc
A 25 .0 cm 3 portion of sodium ethanedioate solution of concentration 0.200 mol dm -J is
3
warmed and titrated again.st a solution of potassium manganate(VIl). If 17.2 cm of
potassium manganate(Vl l) are required, what is its concentration?

EXAMPLE 2 Oxidising iron(II ) compounds

Ammonium iron(Il) sulphate crystals have the following formula:
(NH ) 5O • FeSO • nH O . In an experiment to determine n, 8.492 g of the salt were
4 2 4 4 2
dissolved and made up to 250 cm 3 of solution with distilled water and dilute sulphuric
acid . A 25 .0 cm 3 portion of the solution was further acidified and titrated against
potassium manganate(VII) solution of concentration 0.0150 mol dm- 3 • A volume of
22 .5 cm 3 was required.

EXAMPLE 3 Oxidising hydrogen peroxide

A sol_ution of hyd:ogen peroxide was diluted 20.0 times. A 25 .0 cm 3 portion of the diluted
solut10n was acidified and ti~rated against 0.0150 mol dm - 3 potassium manganate(V ll)
solution. 45 .7 cm of the madam were required . Calculate the concentration of the
hydrogen peroxide solution a in mo! dm- 3 and b the 'volume concentration '. (This means
the number of volumes of oxygen obtained from one volume of the solution.)

POTASSIUM DICHROMAT E(VI} TITRATIONS

Pota~sium dichromate(_VI) can be obtained in a high state of purity, and its aqueous
solut10ns are stable. It 1s used as a primary standard. The colour change when
chrom1um(VI) changes to chromium(III ) in the reaction
Cr2O/-(aq) + 14H •(aq) + 6e- - 2Cr 3•(aq) + 7H 2 O(1) ,
is from orange to blue. As it is not possible to see a sharp change in colour, an indicator is
used. Banum N-phenylphen ylamine-4-su lphonate gives a sharp colour change, from blue-
green to violet, when a slight excess of potassium dichromate has been added.
Phosphori~(V) acid_must be present to form a complex with the Fe 3• ions formed during
the ox1dat1on reaction; otherwise Fe 3• ions affect the colour change of the indicator.
Since_dichromate(V I) has a slightly lower redox potential than manganate(VII), it c~n be
used m the presence of chloride ions, without oxidising them to chlorine.

EXAMPLE Determinatio n of the percentage of iron in iron wire

A piece of iron wire of mass 2.225 g was put into a conical flask containing dilute
sulphuric acid . The flask was fitted with a bung carrying a Bunsen valve, to allow the
hydrogen generated to escape but prevent air from entering. The mixture was warmed to
speed up reaction. When all the iron had reacted, the solution was cooled to room
temperature and made up to 250 cm 1 in a graduated flask . With all these precautions, iron
is converted ro Fe 2 • ions only, and no Fe ·\+ ions are formed . 25.0 cm 3 of the solution were
acidified and titrated against a 0.0185 mol dm- 3 solution of potassium dichromate(V l) . The
volume required was 31.0 cm 3. Calculate the percentage of iron in the iron wire.
J .. . 1

SODIUM THIOSULPHATE TITRATIONS

. . . d'd . . and forms sodium tetrathionatc,
Sodium thiosulphate reduces 1odmc to 10 1 e tons,'
Na 1 S4 O ~
2S2O/-(aq) + lz(aq) ____.. 21 -(a q) + s.o/- (aq)
0 . ot used as a primary standard as the water
Sodium thiosulphate, Na2S20J · 5 H2 • t~ n d' h' I hate can be standardised
wntent of the crystals is variable. A solution of so mm _t ~osu(~) or otassium
against a solution of iodine, or a solution of potasSium 10 ate p
dichromate(Vl) or potassium manganate(VII) .

EXAMPLE 1
Standardisation of a sodium thiosulphatc solution, using iodine
. I · f potassium iodide
Iodine has a limited solubility in water. It dissolves m a so unon o
because it forms the very soluble complex ion, l3 - .
l (s) + 1-(aq) ~ ~ 1., -(aq)
1

. d' d .. d 'd · ncl if iodine molecules art·

An equilibrium is set up between 10 me an tn-1o I e ions, a . d'
. . . I' I • cl- . ··arc to form mo re 10 me
removed from solution by a rcacnon, tn-1oc It e ion s issou, . - •h .
th
molecules. A solution of iodine in potassium iodide can therefo re he ntratcd as oui-: It
were a solution of iodine in water.
. . Id cl I · of iodine th,· co lour of
When sufficient of a solution of th1osulphate 1s ac e to a so uuon . · bl _1
I
iodine fades to a pale yellow. Then 2 cm of starch solution arc added to givt· :I u,· ~o our
with the iodine. Addition of thiosulphatc is continued drop by drop. unnl th c uc co our
disappears .
J 835 g of iodine and 6 g of potassium iodide arc dissolved in distilkd w::ncr and mad,· up
;~ 250 cmJ. A 25 .0 cm 3 portion titrated against sodium thiosu_lphatc solution required
.17.7 cmJ of the solution. Calculate the concentration of the th1osulphate solutwn .

EXAMPLE 2 Standardisation of thiosulphace against potassium iodate(\/)

Potassium iodate(Y) is a primary standard . It reacts with iodide ion s in the pr.:sc·ncc of .K,d ·
toform iodine:
10 3-(aq) + 5i-(aq) + 6H '(aq) - 3l 1 (aq) + 3H 1 O(1)
A standard solution of iodine can be prepared by weighing o ut the necessary quant iry of
potassium iodate(V) and making up to a known volume of solution. When a porrion of th1>
solution is added to an excess of potassium iodide in aci d solution, a cakulated amo unt ni
iodine is liberated .
1.015 g of potassium iodate(Y) are dissolved and made up to 250 cm 3. To a 25.0 cm '
portion arc added an excess of potassium iodide a nd dilute sulphuric acid. The solur,on i,
titrated with a solution of sodium thiosulphate, starch so lution being added ne.-ir thc--.· nJ -
point. 29.8 cmJ of thiosulphatc solution are required . Calctilate the concentration ,,r th~
thiosulphate solution.

1'.XAMPLE 3 Estimation of chlorine

Chlorine displaces iodine from iodides. The iodine formed c:rn be found by ritration with a
, t:indard thi os ulphate solution . Chlorate(!) solutions are o ften used :ts a so urce of chlorine
as rhcr liberate chlorine readily on reaction with acid :
CIO ·( aq) + 2H ' (aq) + c J-(aq) - Cl 1 (aq) + H , 0(1)
The amount of chlorine avaibblt: in a domestic bleach which co ntains sodium chl o race(I )
c·an hc found by allowing th!= bleach to rean with :rn iodide solution to form iodine, and
th en titrating with thiosulphatc solution :
CIO-(aq) + 2H '(aq) + 21 -(aq) - l~(aq) + C J- (aq) + H 1 O(1)
A domestic bleach in solution is diluted by pipetting 10.0 cm ·' and making chis volume up
w 250 cm 1• A 25.0 cm-' porti o n of the so lution is added to an excess of potassium iodide
.rnd e1hanoic acid and titrntcd against sodium thiosulphate solution o f concentration
(J.0950 mol dm - 1• using starch as a n indicator. The volume required is 21.3 cm -'. Cakulme
the percentage of nailable chlorine in the blea ch.

EXAMPLE 4 Estimation of coppcr(ll) salts

Copper(lf) ions oxidise iodide ions to iodine. The iodine produced can l:,e titr:ited with
standard thiosulphate so lution, and, fro m the amount of iodine produc<.'d. the
concentration of coppcr(II) ions in the solution can be calcul:itcd.
A samp le of 4.256 g of copper(lf) sulphatc-5-water is d1sso l\'cd a nd m,,de np to 250 cm '. .·\
25 .0 cm J portion is added to an excess of potassium iodide: . The- ioJinc formed r<'q111r cd
l8 .0 cm I of a 0 .0950 mol dm -' solution of sodium thiosu lph ~te for rcdu,ti,,n . C.1k-11l.11.-
thc p<'rccnt:1gc nf copper in the Cr)'st:ils.