Principles of Analytical Chemistry 2010

Chapter-5
Introduction to titrations

Introdu the analyte. The reagent must be a standard solution.

Some Basic Concepts
Titration: is a process in which a standard reagent or titrant is added to a solution of
the analyte (titrand) or vice versa until the reaction between the analyte and the react
is judged to be complete.
Volumetric titrimetry: is a type of titrimetry in which the standard reagent is
measured volumetrically.
Titrant: Usually the standard solution that is located in the burette.
Titrand: usually solution containing the analyte. It is kept in the titration flask during
titration.
Equivalence point: That point in a titration at which of the titrant added is chemically
equivalent to the amount of the analyte in the sample.
Indicator: substance that signal the end point of a given titration by showing some
physical change at around the equivalence point.
End point: The point in the titration when physical change that is associated with the
condition of chemical equivalence occurs.
Titration error: The difference between the titrant volumes needed to reach the
equivalence point and the end point, respectively

Et = Veq – Vep
Where
Veq = theoretical valor actually necessary (at the equivalent point)
Vep = Volume really measured at the end point
Back- titration: is a process in which the excess of a standard solution used to react
with an analyte is determined by titration with a second standard solution. Back
titrations are often required when the rate of reaction between the analyte and reagent
is slow or when the standard solution lacks stability.
Displacement or indirect Titration: Are used when no indicator for an analyte is
available or the direct reaction takes place very slowly.
Example
The amount of NH4+ in a solution can be measured because of the stoichiometric
amount of OH- produced when ammonium react with formaldehyde.
Primary standard: A chemical that possesses such properties as extraordinary purity,
large combining weight, and straightforward stoichiometry. Most Titrimetric methods

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Principles of Analytical Chemistry 2010

require a calibration step involving primary standard.

Important requirements for a primary standard are:
1 High purity. Established methods for confirming purity should be available.
2 Stability toward air.
3 Absence of hydrate water so that the composition of the solid does not change
with variations in relative humidity.
4 Ready availability at modest cost.
5 Reasonable solubility in the titration medium.
6 Reasonable large molar mass so that the relative error associated with
weighing the standard is minimized.
Of course, it’s difficult to find substances that meet all of these properties.
Examples of primary standards are
Na2CO3; KIO3; Na2C2O4;AgNO3

Secondary standard: A substance whose purity has been established and verified by
chemical analysis. After the purity is determined, they substitute primary standards.
Standard solution: A solution in which the concentration of a solute is known with
high reliability.
The ideal standard solution for a Titrimetric method will
 be sufficiently stable so that it is only necessary to determine its
concentration once;
 react rapidly with the analyte so that the time required between additions
of reagent is minimized.
 react more or less completely with the analyte so that satisfactory end
points are realized;
 undergo a selective reaction with the analyte that can be described by a
simple balanced equation.
Standardization: is a process in which concentration of a volumetric solution is
determined by using it to titrate a known mass of a primary or secondary standard or
an exactly known volume of another standard solution.

Buffer solutions: Solutions that tend to resist changes in pH as the result of dilution
or the addition of small amounts of acids or bases.
[H3O+] = Ka Cacid / Cbase
Buffer capacity: The number of moles of strong acid (or strong base) needed to alter
the pH of 1.00 L of a buffer solution by 1.00 unit.
Carbonate error: A systematic error caused by absorption of carbon dioxide by
standard solution of base that will be used in the titration of weak acids.

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Principles of Analytical Chemistry 2010

Calculations in Titrimetry
Most volumetric calculations are based on two pairs of simple equations that are
derived from definitions of the millimole, the mole, and the molar concentration

(Working in groups)
Recall the concept of molar concentration, mol and millimoles and try to
derive the equations given bellow.

amount A (mol, mmol) = mass A (g, mg) / molar mass A (g/mol, mg/mmol)
and
amount A (mol, mmol) = V (L, ml) x CA (mol/L, mmol/ml)
Weight molarity: The concentration of titrant expressed as millimoles per gram.
Example: If the weight Molarity of a solution is 0.1, it means that the solution
contains 0.1 moles of solute per liter of solution.
In diluter aqueus solution Molarity and weight Molarity are numerically identical
(Why?)

Table:-1 Titrimetric methods of analysis

Titrimetric method Analyte Standard reagent

Neutralization An Acid, a base or any

Strong base/strong acid of
substance that can form acidic
titration known concentration
or basic solution
Ions that form slightly soluble
Precipitation titration precipitation (most of the times Precipitating agents
anions)
Complexometric cations other than alkaline Complexing or chelating
titration metals agent
Redox titration Oxidizing/reducing agent Reducing/oxidizing agent

Neutralization Titrimetry
Neutralization reactions forms the bases for one of the different titrimetric methods
called neutralization titration. Neutralization titration involves the use of standard
solutions of strong acids or strong bases for the determination of analytes. The
analytes themselves are either acids, bases or substances that can be converted into
acids or bases by suitable treatments.
Standard solutions of acids are prepared by diluting concentrated hydrochloric,
perchloric, or sulfuric acid. Nitric acid is seldom used because its oxidizing power
results in undesirable side reactions. Standard solutions of bases are ordinarily
prepared from solid sodium and potassium hydroxides. There is one practical

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Principles of Analytical Chemistry 2010

limitation with the use of these hydroxides. When exposed to air the hydroxides
undergo reaction with CO2 forming carbonates.
Titration Curves
Titration curve is a plot of the reagents volume as a function of the reagent or analyte
concentration or as a function of some quantity related to concentration. It helps for
understanding the theoretical basis of end point, sources of titration errors and
selection of proper indicator.

An important characteristic of a titration is that it shows major change in the plotted

property (usually a p-function, in neutralization titrimetry pH) at around the
equivalent point. This result is an important characteristic of titration curve; sharp
change at around the equivalent point, the curves for complex formation, precipitation
and redox titrations will exhibit similar sharpness around the equivalent point.
Indicator selection and end point detection is based on the large change region of the
titration curve. Characteristic titration curves can be plotted for each of the titrimetric
methods. In this section we will deal with titration curves that are commonly
encountered in neutralization titrations. Different types of acids and bases
(monoprotic, diprotic . . .) have their own characteristic
titration curve.
Four different pH expressions are
required to draw a typical titration
curve for neutralization titration.
1 intiatial point pH expression
2 pre-equivalent region pH
expression
3 Equivalent point pH
4 Post equivalent region pH
expression
Titration curves for
titration of strong acids
with strong base
The reaction between strong acid and
strong bases result in the formation of
type I salt. Since type I salt does not
Fig-1 Titration curves
undergo hydrolysis (reaction
ionization water), the equivalence
point pH is simply 7.

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1 Initial pH. Here no any standard base reagent is added and the pH value can
be calculated from the concentration of the acid.
The pH is expressed as the concentration of the acid.
pH =-log [H+]
[H+] = Cacid = Ca
pH = - log Ca
2 Pre-equivalent pH- In the pre-equivalent point region the titration mixture
consists of the product salt and unreacted acid. No enough base is yet added to
completely react with the acid. Thus, the pH is calculated from the unreacted
acid. The amount of the unreacted acid can be found by subtracting the
amount of the base yet added from the original amount of acid.
Number of mole of unreacted acid (Nun) = na - nb
where na is the original number of moles of at the acid and nb is the amount in
mole of the base yet added. Number of mole is calculated from volume and
concentration as n = VC
 nun = na – nb = nH+
= VaCa - VbCb
The molar concentration of hydrogen ion [H+] is given by nH+ divided by the total
volume. The total volume is the volume of the acid plus volume of the base added so
far.
nun v a c a −v b c b
=
 [H+] = v total v a+ v b

 pH = - log
[ v a c a −v b c b
v a +v b ] an expression for pre-equivalent point pH value
3 Equivalent point pH: here all the acid is consumed by equivalent amount of
the standard base. Since the salt formed is type I and does not undergo
hydrolysis, the only source of hydrogen and hydroxide ions is the
outoionization of water.
H2O H+ + OH-
Since one mole of water ionizes to give H+ and OH- one mole each;
[H+] = [OH-]
The ion-product of water is given by kw = 10-14
i.e [H+] [OH-] = 10-14
Since [H+] = [OH-] we can write as
[H+][OH-] = [H+]2 = 10-14
[H+]2 = 10-14

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Principles of Analytical Chemistry 2010

[H+] = √ 10−14
[H+] = 10-7
PH = lop [H+] = lop 10-7 = - (-7) = 7
4 Post equivalent point pH: - After the equivalence point the solution contains.
the salt, the product of the reaction
the excess base, which is added after reaching the equivalence point.
Since there is no hydrogen ion in this region pH is directly calculated from POH.
pH and POH are always related as;

pH + pOH = 14

POH is calculated from the knowledge of [OH-]. But [OH-] = the amount of excess
base.
Excess base (in mole) = nb – na = nOH- where nb is the number of mole of the base
added so far and na is the original number of mole of the acid.

nexcess base = nOH- = nb - na

= cbvb - cava
nOH − c b v b −c a v a
=
[OH-] = v total vb + va
where vb is the volume of the base added so far and v a is the volume of the original
acid.

 POH =
−
−log [OH ]=−log
[ c b v b −c a v a
v b +v a ]
 pH = 14 – pOH = 14 -
( [ −log
c b v b −c a v a
vb+ va ])
 pH = 14 + log
[ c b v b −c a v a
v b +v a ]
Problems
A 50.00 ml aliquot of 0.1000M HCl is titrated with 0.1000M NaOH. Calculate the pH
of the solution after the addition of 0.00, 10.00. 25.00, 40.00, 49.00, 49.90, 50.00,
50.10, 51.00, and 60.00 ml of the base and prepare a titration curve from the data.
Solution: - first we have to know the four region of titration and then we can use the
proper expression for pH at each point. To do this first we have to
determine the equivalent point volume.

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Principles of Analytical Chemistry 2010

From stoichiometry;
HCl + NaOH  NaCl + H2O,
one mole of HCl reacts with 1 mol of NaOH.
i.e nHCl = nNaOH at the equivalence point
 CHClVHCl = CNaOHVNaOH at equivalent point
0.1000M (50.00ml) = 0.1000M (VNaOH) at equivalent point
 The equivalent point volume of NaOH is 50.00ml
Therefore 0.00ml is initial volume
volume < 50ml is pre-equivalent volume
50 ml is equivalent point volume
volume > 50 ml is post equivalent volume
i Initial pH:
pH = - logCa
= - log0.1000
pH = 1.00
ii Pre-equivalent pH

pH = -log,
[ v a v a −v b v b
v a +v b ]
After the addition of 10.00ml of the base

pH = - log
[ 50 .00 ml × 0.1000 M−1000 ml × 0 .100 M
50 .00 ml+10.00 ml ]
pH = - log
[ 50 . 00 mmol −1.000mmol
60. 00 ml ]
= -log
[4 .000 mmol
60. 00 ml ]
= -log (0.06667)
= 1.18
In the same way we can calculate for all other pre-equivalent volumes and we get the
following pH values
Volume of NaOH 25.00 40.00 49.00 49.90
pH 1.48 1.95 3 4.00

iii Equivalent point pH because the salt formed NaCl is type I and does not
undergo hydrolysis equivalent point pH is simply 7.00 (Neutral pH).
iv Post-equivalent pH

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Principles of Analytical Chemistry 2010

pH = 14 + log
[ c b v b −c a v a
v b +v a ]
After the addition of 51.00ml of 0.1000M NaOH;

pH = 14 + log
[ 0 . 1000 M×51 . 00 ml−0 .1000 M×50 . 00 ml
51 . 00 ml+50 . 00 ml ]
pH = 14 + log
[ 5 .100 mmol−5. 000 mmol
101 . 00 ml ]
pH = 14 + log
[ 0 . 100 mmol
101 . 00 ml ]
pH = 14 – 3
pH = 11.00
 In the same way pH = 11.96 at volume of 60.00ml

Final data
NaOH (ml) 0.00 10.0 25.0 40.0 49.0 49.9 50.0 50.1 51.0 60.0
pH 1.00 1.18 1.48 1.95 3.00 4.00 7.00 10.0 11.0 11.9

(Individually)
Sketch the titration curve using the data given above

The titration curve will look similar to those in fig -2;

Fig-2
Titration of a strong acid
with a strong base.
A
50.00 ml of 0.0500M HCl
with 0.1000M NaOH
B
50.00 ml of 0.000500M
HCl with 0.001000M
NaOH.

Observe the influence of

concentration on the gap of
the inflexion zone.

Observe the rapid change in pH with very small increase in the volume of the standard
reagent (NaOH solution). Indicators whose transition range lies outside the inflexion
range will cause significant volume error if used for the above titration.

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 Principles of Analytical Chemistry 2010

Titration curve for the titration of weak acid with strong base
Unlike the titration of strong acid with strong base, the titration of weak base with
strong base forms hydrolysable salt called type II salt. The anions of type II salts
undergo reaction with water (hydrolysis producing OH- ion)
e.g. NaCH3COO  Na+ + CH3COO-
(type II salt)
CH3COO- + H2O CH3COOH + OH-
Therefore the equivalent point pH is not 7.00 but greater than 7.00. Basic salt is
formed in this case.
More over weak acids do not undergo complete dissociation. Thus the initial poit pH
does not depend only on the initial concentration of the weak acid but also on it’s
dissociation constant (Ka). Now let us drive the pH – expression at the four different
stages of titration.
i Initial pH: - calculated from the initial concentration and the dissociation constant
of the weak acid.
 For a weak acid, HA, with dissociation constant Ka
HA H+ + A-

[H+] = √ KaCa where Ca is the initial concentration of the acid.

 pH = -log [H+]

= - log √ KaCa
= - log (KaCa) ½
= - ½ log KaCa
= - ½ (log Ka + log Ca)
= - ½ log Ka – ½ log Ca

pH = ½ PKa – ½ log Ca

NB. PKa = - log Ka

ii Pre-equivalent point pH; In this stage of titration we have excess untitrated weak
acid.
The expression for pH can be derived as follows
- From the dissociation equilibrium, we can write
HA H+ + A-
[ H + ] [ A− ]
Ka = [ HA ]

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Principles of Analytical Chemistry 2010

[ HA ]
 [H+] = Ka [ A− ]
where HA is a weak acid with dissociation constant Ka, at equilibrium.
A- is the anion of the acid.
The concentration of untitrated HA can be calculated as;
V a C a−V b C b
[HA] = V a +V b

 A- ions originate from two sources.

1 The dissociation of the untitrated acid.
2 The dissociation of the salt formed.
The dissociation of the salt formed is assumed to be complete. Thus the amount of A -
ion coming from the slight dissociation of the weak acid is negligible and hence we
take A- from the salt dissociation as an approximation for the total amount of the
anion [A-].
However, the only source of H+ the slight dissociation of the weak acid coming from
the 2nd source. Since the amount of A - ions is equal to the number of mole of the salt
formed which in turn is equal to the number of mole of the base added, we can write
V bCb V bCb
=
[A ] =
- V total V a +V b

Now we can write

Ka [ HA ]
[H+] = [ A− ] = Ka

[ V a Ca −V b Cb
V a +V b ]
V b Cb
[H+] = Ka V a +V b

= Ka
[ V a C a −V b C b
V a +V b ]
[H+] = Ka
[ V a C a −V b C b
V bCb ]
 pH =-log[H+] = - log Ka
[ V a C a −V b C b
V bCb ]
= - log Ka – log
[ V a C a −V b C b
V b Cb ]

pH = pKa – log
[ V a C a −V b C b
V bCb ] 10
 Principles of Analytical Chemistry 2010

iii Equivalent point pH: - At the equivalent point an amount of the standard solution
that completely neutralizes the acid is added. However, free molecules of the
analyte(acid) are formed by hydrolysis of the anion.
A- + H2O HA + OH- (hydrolysis reaction)
An amount of A- hydrolysis to give equal amount of, HA and OH- as can be seen from
the hydrolysis reaction equation
 [HA] = [OH-]
If the extent of hydrolysis is not so appreciable: the amount of A - is almost equals to
the original amount of the acid.
i.e nA- = VaCa = nacid
Since concentration is given as number of moles per total volume
n A+ V a Ca
=
[A-] = V total V a +V b

Remember
[ HA ]
[H+] = Ka [ A− ]
Ka [ OH − ]
V aCa
=Ka [ OH − ]
V a +V b
V aCa [ ]
= V a +V b

But [OH-] = 10-14/[H+]

 [H+] =
Ka ×10−14 V a +V b
[ H+] V a Ca [ ]
[H+]2 = KaKw
[ V a +V b
V aCa ] since Kw = 10-14

[H+] = √ KaKw
[ V a +V b
V aCa ]
 pH = - log
[ H+ ]
=−log √ KaKw
[ V a +V b
V aCa ]
=-½
( log KaKw
[ V a +V b
V aCa ])
= - ½ logKa – ½ log Kw – ½ log
[ V a +V b
V aCa ]

pH = ½ pKa + ½ pKw – ½ log

[ ] V a +V b
V aCa
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 Principles of Analytical Chemistry 2010

equivalence point pH expression

iv Post – equivalence point pH
In this stage of titration the pH is largely governed by the excess standard reagent
(base)
 The amount in mole of the excess base (n excess) is given by the difference between
the total mole of base added (n b) and the original number of mole of the weak acid
(na).
nexc = nb - na => nexc = VbCb - VaCa
 The concentration of the excess base is given by the ratio of the excess number of
mole to the total volume
nexc V b C b −V a C a
=
[base] = [OH-] = V total V a +V b

V b C b−V a C a
 POH = - log [OH-] = log V a +V b

But pH + pOH= 14 ( in any solution)

 pH = 14 - pOH

pH = 14 –
( [
− log
V b C b −V a C a
V a +V b ])
V b C b−V a C a
V a +V b Post equivalent point pH expression.
pH = 14 + log
Problem and solution
HNO2 is among the weak acids and it has dissociation constant, Ka, value of 7.1 x 10 -
4
. Calculate the pH after the addition of 0.00, 5.00, 15.00, 25.00, 40.00, 45.00, 49.00,
49.90, 50.00, 50.01, 50.10, 55.00 and 60.00 ml of 0.1M NaOH in the titration of 50.00
ml of 0.1000M HNO2. Draw the titration.
Solution
First let us define the equivalence point volume of NaOH. Since one mole of NaOH
reacts with one mole of HNO2, their number of mole at the equivalence point becomes
the same.
n HNO =nNaOH
2 at equivalent point
V HNO C HNO 2 =V NaOH C NaOH
2

50.00 ml x 0.1000M = VNaOH x 0.1000M

 VNaOH = 50.00 ml at the equivalent point.
Thus we can classify the different volumes as

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0.00 ml  Initial point volume

volume < 50.00 ml  pre-equivalent point volume
50.00 ml  equivalent point volume
volume > 50.00 ml  post equivalent point volume
We can determine the pH values at each stage by using the respective expression
i Initial pH
pH = ½ pKa – ½ log Ca
= ½ (- log(Ka) – ½ log(Ca))

(−log7. 1×10 −log 0. 1 )

−4

=½
= ½ (3.15 + 1)
pH = 2.08
ii Pre equivalent pH

pH = pKa – log
[ V a C a−V b C b
b b V C ]
Let us calculate for 5.00 ml of the base

pH = 3.15 – log
[ 50 . 00 ml×0 .1000 M−5 . 00 ml×0 .1000 M
5 . 00 M×0 .1000 M ]
= 3.15 – log (9)
= 3.15 – (0.95)
pH = 2.20
Using the same expression we can calculate the other pre-equivalent pH values as;
Volume (ml) 15.00 25.00 40.00 43.00 49.00 49.90 49.99
pH 2.78 3.15 3.75 4.10 4.84 5.49 6.85
iii Equivalent point pH

pH = ½ pKa + ½ pKw- ½ log

[ V a +V b
V aCa ]
pH = ½ (3.15) + ½ (−log 10−14
) - ½ log
(5050 ml+50
ml×0 .1000 M )
ml

= 1.58 + ½ (14) – ½ log

( )100
5
= 1.58 + 7 – (1.30)
pH = 7.93
iv Post equivalence point pH;

pH = 14 + log
[ V b C b −V a C a
V a +V b ]
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Principles of Analytical Chemistry 2010

After the addition of 51.00 ml of the base

pH = 14 + log
(51×0 . 1−50×0 .1
51+50 )
pH = 14 + log
(101 )
0 .1

= 14 + log (9.9 x 10-4)

= 14 – 3
pH = 11

Similarly pH values for the other post equivalent point volumes can be calculated to
yield the following values.
Volume of NaOH (ml) 50.01 50.10 55.00 60.00
pH 9 10 11.68 11.96

(Individually)
Sketch the titration curve using the data from the above problem.

Fig-1 is an example of titration curve that shows the influence of concentration on the
size of the inflexion zone.

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Principles of Analytical Chemistry 2010

Fig-3
Curve for the titration of
acetic acid with sodium
hydroxide.
A
0.1000M acid with 0.1000M
base.
B
0.001000M acid with
0.0010000M base

(Assignment, working in groups)

Derive pH expressions for the titration of a weak base with strong acid.
Sketch the titration curve for the reaction of NH3 and HCl

Selection of Indicators
Indicators are substances used to signal the end-point of a titration. They import an
observable physical change to the titration solution at the end point.
The most used properties are appearance or disappearance of color and change of
color.
Acid-base indicators are weak organic acids or bases whose undissociated forms
differ from their conjugate acid or base form in color.
HIn + H2O In- + H3O+
acid base
color color
or,
In + H2O InH+ + OH-
base acid
color color
Different acid-base indicators have different pH value at which they show color
change. At lower pH values they show their acidic color and at higher pH value they
show basic color. The pH range over which an indicator shows intermediate color is
known as the trAnsition range. The approximate pH transition range of most acid type

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Principles of Analytical Chemistry 2010

indicators is roughly pKa ± 1

Some Important Acid/Base Indicators
TrAnsition Color Indicator
Common Name pKa*
Range, pH Change** Type***
Thymol blue 1.2-2.8 1.65 R-Y 1
Methyl Yellow 2.9-4.0 R-Y 2

Methyl Orange 3.1-4.4 3.46 R-O 2

Bromocresol Green 3.8-5.4 4.66 Y-B 1

Methyl Red 4.2-6.3 5.00 R-Y 2

Bromocresol purple 5.2-6.8 6.12 Y-P 1

Bromothymol blue 6.2-7.6 7.10 B-Y

Phenol Red 6.8-8.4 7.81 Y-R 1

Cresol Purple 7.6-9.2 Y-P 1

Phenolphtalein 8.3-10.0 C-R 1

Thymolphtalein 9.3-10.5 C-B 1

Alizarin Yelow GG 10-12 C-Y `2

(*) At ionic strength of 0.1. For the reaction InH+ + H2O H3O + In
+ -

(**) B = blue; C = colorless; O = Orange; P = Purple; R = Red; Y = Yellow

For better accuracy in titration analysis the proper choice of indicators is important. A
proper indicator for a given titration is the one whose trAnsition range lies in the pH
range where the titration curve for that specific titration shows sharp increment,
because the equivalence point of the titration lies in this region.

(Working in pairs)
Explain why the trAnsition range of an indicator for a given titration
should lie in the pH range where the titration curve shows sharp
increment?

Polyfunctional acids and bases

Polyfunctional acids and bases show more than one inflexion point in every, one for
each proton donated (fig -4)

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Fig-4
Titration of 20.0 ml of
0.1M H2A with
0.100M NaOH.

For H2A
Ka1 = 1.00x10-3 and
Ka2=1.00x10-7.

(Working in groups)
Observe fig-4 and explain why there are two inflexion points?
Give an example of polyprotic acid.
Sketch the titration curve of a Na2CO3, a polyfunctional base, when is titrated
with hydrochloric acid.

Precipitation Titrimetry
The basis for precipitation titrimetry is the formation of ionic compounds of very
limited solubility on the reaction of the analyte with the standard reagent/ titrant.
Standard reagents used in preparation titrimetry are substances that can form
insoluble/slightly soluble precipitate with the analyte. The most widely and commonly
used standard reagent used in precipitate titrimetry is a solution of known
concentration of silver ion (Ag+). This is attributing to the fact that Ag+ forms slightly
soluble salt with many anions. Titrimetric method in which Ag + solution used as a
standard titrant reagent is termed as Argentometric. Argentometric method is
classified in to three major kinds: Mohr’s method, Volhard’s method, and Fajans’s
method

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Principles of Analytical Chemistry 2010

(Brainstorming)
Discuss about the principles behind the three argentometric methods showed
below.

.1 The Mohr method

The Mohr’s method is an argentometric method in which chromate ion is used as an
indicator. The indicator solution is usually prepared by dissolving either sodium
chromate (Na2CrO4) or potassium chromate (K2CrO4) in sufficient water to give
0.01M CrO4-2 solutions.
The titration starts with the addition of the standard Ag + ion solution to the solution
containing the analyte (e.g. X- ion) and the CrO42- indicator. Ag+ forms less soluble
precipitate (AgX) with the analyte. Thus Ag2CrO4- (with a brick red color) will not
form until all the analyte form precipitation. After the complete precipitation of the
analyte (at the equivalent point) the CrO4-2 starts to form silver precipitate. A single
drop of Ag+ reagent will produce a brick red color at the equivalent point which
signals the end-point for the titration. The amount of the analyte is determined from
the amount of the standard reagent used until the end point.

Analyte reaction Ag+ + X- AgX (s)

Indicator reaction 2Ag+ + CrO42- Ag2CrO4 (brick red)

The titration mixture at the equivalent point is simply a saturated solution of AgX.
Applying the solubility product principle to the solution will enable the calculation of
the ionic concentrations. i.e

[Ag+] = [X-] = √ K SP where KSP is the solubility product constant for the
dissociation of AgX.
Eg. For the titration of chloride concentration with silver ion, the mixture at the
equivalent point will be a saturated solution of silver chloride.

[Ag+] = [Cl-] = √ K SP (AgCl)

= √ 1.6×10.50 = 1.26 x 10-5

In order to precipitate Ag2CrO4 from a saturated solution of AgCl, the minimum
concentration of CrO42- ions in the solution must be
[Ag+]2-[CrO42-) = KSP (Ag2CrO4)
K SP ( Ag2 CrO 4 ) 1 .2×10−12
2
= 2
 [CrO4 ] =2- [ Ag+ ] ( 1. 26×10−5 )  6.8 x 10-3M
The Mohr titration must be carried out at pH between 7 and 10 in order to avoid the
adverse side reactions of the chromate ion.

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Principles of Analytical Chemistry 2010

(Working in groups)
Explain why if the Ksp of silver chloride is greater than the Ksp of
K2CrO4, the former precipitate first.

.2 The Volhard Method

The Volhard method is based on the formation of the red-colored [Fe(SCN)] 2+
complex at the equivalent point. The method is used;
1 Directly to determine the amount of silver ion it self
2 By back-titration method in the titration of halide ions (Cl-, Br-, I-)
In the direction method Ferric ion is introduced as an indicator in the form of an
aqueous solution of ferric ammonium alum (FeNH 4 (SO4)212H2O. We may write the
reaction of the analyte and the indicator as follows:

 Analytical reaction: Ag+ + SCN- AgSCN

 Indicator reaction Fe3+ + SCN- [Fe(SCN)]2+ (red colored

complex).
In the initial stages of the titration the analytical reaction is predominant. The
indicator reaction will not start after the equivalent point. A few drops of the
thiocyanate solution added after the equivalent point will initiate the indicator
reaction. The result is that the titration mixture will develop an intense red color. The
formation of the red colored complex [FeSCN]2+ signal the end of the titration.
In its indirect (back titration) method for the determination of halides, an excess of the
standard silver nitrate solution will be added to the analyte solution. After complete
precipitation of the halide ions from the solution the excess silver ion will be titrated
with standard thiocyanate in the presence of Fe3+ ions. The amount of silver ions
solution that is consumed by the halide (analyte) is the difference between the initially
added excess amount and that reacted with the standard thiocyanate solution.

(Working in pairs)
Briefly explain the difference between the direct and the back titration
Volhard method.

Silver chloride (and some other anions) is more soluble than silver thiocyanate. As a
consequence, in chloride determination by back titration Volhard method, the reaction
AgCl(s) + SCN- ↔ AgSCN(s) + Cl-
occur to a significant extent near the end of the back-titration of the excess silver ion.
This error can be circumvented by filtering the silver chloride before undertaking the
back titration.

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3 The Fajans Method

The Fajans method is an argentometric method based on the use of adsorption
indicators. Adsorption indicators are usually organic compounds that tend to be
adsorbed on to the surface of a solid in precipitation titrations. Fluorescein, and eosin
are examples.
The indicator color differs when in solution and when adsorbed on to the precipitate.
Let us consider a case for the titration of chloride solution with silver ion solution in
the presence of fluorescein as an adsorption indicator. Fluorescein is a weak acid and
let us represents it as HIn. In solution it undergoes ionization as;

HIn H+ + In- (yellowish – green)

By the reaction with Ag+ ion, a reddish precipitate of silver fluorosceinate (AgIn)
formed

In- + Ag+ AgIn (red)

When the Ag+ ions are added in a concentration in which the solubility product for
AgCl is exceeded, the formation of AgCl crystals will begin.
In the pre-equivalence region, the solution will contain an excess of Cl - ions than Ag+
ions. As a result the region around the AgCl crystal will be surrounded by Cl- ions.
The negatively charged chloride ions around the AgCl precipitate repeal the
negatively charged In- ions and there will not be adsorption of the indicator on the
precipitate. Thus during the pre-equivalence stage of argentometric titration, the
fluoresceinate ions will remain in the solution and imparts yellowish – green color to
the solution.

After the equivalent point all the Cl- ions will be changed to AgCl and the Ag+ ions
goes up to be in excess. Thus the charge around the AgCl precipitate will be positive
and attract In- ions. The consequence is the adsorption of In- on to the precipitate. This
will result in the formation of reddish color.
This color change signals the end-point of the titration.
The Fajans method should be applied under conditions that favor the formation of
colloidal precipitation than crystal growth. The fine colloidal precipitate with their
larger surface is more efficient adsorbents than the coarse precipitates of equal mass.
Very dilute solutions of both the analyte and the reagent give rise to small quantity of
precipitate of larger particle size and small surface area to volume ratio which in turn
results in less adsorption. Consequently, sharper end-points can not be obtained and
should be avoided in Fajans’s titration.

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.i Applications
The argentometric methods are widely used in halides, mainly Cl-, but also in SCN-,
CO32-, CrO42-, S2-, etc. Indicators usually respond to changes in Ag+ concentration in
the equivalent point. The titration curves are made using
pAg = - log[Ag+] versus of. Electrodes sensitive to silver concentration can be used
for potentiometric titrations.

Fig-5
Effect of titrant
concentration on
titration curves.
A:
50.0 ml of 0.05000M
NaCl with 0.1000M
AgNO3.
B:
50.0 ml of 0.00500M
NaCl with 0.01000M
AgNO3

(Working in groups)
Analize fig -6
Mathematically justify the dependence of the shape and the Ksp of the titrand.
Is it possible titrating I- and Cl- in the same solution? Justify numerically your
Answer.

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Principles of Analytical Chemistry 2010

Fig-6
Effect of reaction
completeness on
titration curves.
For each curve,
50.0 ml of a
0.0500M solution
of the anion was
titrated with
0.10000M AgNO3

 Gravimetric Titrimetry
So far we have looked at two important types of volumetric titrimetry. Gravimetric
titrimetry differs from volumetric titrimetry in that the mass of the standard reagent
(titrant) is measured rather than the volume. Thus, in a weight titration, a balance and
a solution dispenser are substituted for a burette and its markings. With development
of recent sensitive top-loading balances and convenient plastic solution dispensers,
weight titrations can now be performed more easily and more rapidly than volumetric
titrations.
The most convenient unit of concentration for gravimetric titration is the weight
molarity Mw, which is the number of moles of a reagent in one kilogram of solution.
For instance 0.1Mw NaCl contains 0.1 mol of the salt in 1kg of solution. For a solute
A;
no. mol A no . mmol A
=
MWA = no.kg solution no . g solution
The data gathered from gravimetric titration can then be treated by in the same way as
in the volumetric titrimetry.
.i Advantages of gravimetric titrations
In addition to greater speed and convenience, weight titrations offer certain other
advantages over their volumetric counterparts:

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Principles of Analytical Chemistry 2010

1 Calibration of glassware and tedious cleaning to ensure proper drainage is

avoided.
2 Temperature corrections are unnecessary because weight Molarity does not
change with temperature in contrast to volume Molarity. This is particularly
important in titrations that are performed in nonaqueous solutions because of
the high expansion capacity of most organic liquids. The expansions highly
increase the volume of the liquid and alter the volume Molarity but not weight
Molarity.
3 Weight measurements can be made with considerable. Greater precision and
accuracy than can volume measurements. These in turn will results accurate
analysis.
4 Weight titrations are more easily automated than are volumetric titration.

(Group discussion).
Comment the advantages of gravimetric titration. Try to describe how you
would carry out it in practice.
Why they are not still widely used?

Exercises
1 List the characteristics that must meet a Primary Standard.
2 What is the difference between primary and secondary standard.
3 What are the advantages of using Gravimetric Titrimetry? What of using
volumetric?
4 What factors affect end-point sharpness in an acid-base titration?
5 Why are the standard reagents used in neutralization titrations
6 Exactly 50.00 ml of HCl solution required 29.71 ml of 0.01963 M Ba(OH) 2 to
reach the end point with bromocresol green indicator. Calculate the molarity
of the HCl. Ans: 0.02333M
7 Titration of 0.2121 g of pure Na2C2O4 (134 g/mol) required 43.31 ml of
KMnO4. What is the molarity of the KMnO 4 solution? The chemical reaction
is
2MnO4- + 5C2O42- + 16H+ → 2Mn2+ + 10CO2(g) + 8H2O
Ans: 0.01462M
8 A solution of HClO4 was standardized by dissolving 0.3745 g of the primary-
standard-grade HgO in a solution of KBr:
HgO(s) + 4Br- + H2O → HgBr42- + 2OH-
The liberated OH- required 37.79 ml of the acid to be neutralized. Calculate the
molarity of the HClO4.

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Principles of Analytical Chemistry 2010

Ans: 9.151 x 10-2M

9 The thiourea in a 1.455 g sample of organic material was extracted into dilute
H2SO4 solution and titrated with 37.31 ml of 0.009372M Hg2+ via the reaction
4(NH2)2CS + Hg2+ → [(NH2)2CS]4Hg2+
Calculate the percent (NH2)2CS (76.12 g/mol) in the sample.
10 Calculate the hydroxide ion concentration and pH in a 0.01 M sodium
hypochlorite solution. (KaHClO=3x10-8)
Ans:[OH-] = 5.77 x 10-5; pH = 9.76
11 Calculate the pH of
a 0.02 M CH3COOH (Ka = 1.74 x 10-5)
b Saturated (at 20°C) 3.8 x 10-2 M solution of CO2 (Ka = 4.5 x 10-7)
c 0.05 M NH4OH
Ans: a) 3.23 b) 3.88 c) 10.97
12 Figure out the changes in the pH of 1 L a solution containing 10 -5 M NaOH,
which are brought about by addition of a) 0.001 mol of NaOH; b) 0.001 mol
of HCl
Ans: a) Increased in 2 units b) Diminish in 6
13 A solution contains 0.056 mole of NH4OH and 0.1 mole of NH4Cl per litre.
What is the pH of this solution and how will it change on addition of 0.001
mol of a) NaOH b) HCl to 1 litre of solution
Ans: pH = 8.99 a) Increased 0.01 units b) decreased 0.01 units.

14 What will be the color of each indicator in a buffer at pH = 4.6?

Indicator pH range Color Change
Thymol Blue 1.2-2.8 Red – yellow
Methyl Orange 3.0-4.6 pink-yellow
Methyl Red 4.2-6.3 Red-yellow
Phenol Red 6.8-8.0 Yellow-red
15 From table No. 7-2, which acid/base indicator would you select in each of the
following pairs of titration reactants (both at 0.05 M).
a NaOH in acetic acid (Ka = 1.8 x 10-5)
b NaOH and HCl
c NH3 and HCl
Ans: a) Phenolphthalein b) Bromothymol Blue c) Methyl red
16 Calculate the pH of the following mixtures
a 20 mL of HNO3 0.02 M and 20 mL of NaNO3 0.02 M
b 12 mL of NaOH 0.02 M and 12 mL of HCl 0.01 M

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Principles of Analytical Chemistry 2010

c 12 mL of HAc (Ka = 1.8 x 10-5) 0.1 M and 6 mL of KOH 0.1 M

Ans: a) 2.00 b) 11.7 c) 4.74
17 A 50.00 ml aliquot of 0.0500 M NaCN is titrated with 0.1000 M HCl. The
reaction is:
CN- + H3O+ HCN + H2O
Calculate de pH at a) 0.00 b) 10.00 c) 25.00 and d) 26.00 ml acid added.
Ans: a) 10.95 b) 9.38 c) 5.34 d) 2.88
18 In a titration of 50.00 ml of 0.05000M formic acid with 0.1000M KOH, the
titration error must be smaller than ±0.05 ml. What indicator can be chosen to
realize this goal?
Ans: The theoretical pH at 24.95 ml is 6.44; at 25.05 ml is 9.82. Thus, the
indicator should change in the range of pH 6.5 to 9.8. Cresol purple (range: 7.6
to 9.2) would be quite suitable.

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