End Point Detection with Gran Plot

and
Titration Error

A Dissertation Submitted to Central Department of Chemistry

Tribhuvan University, Kirtipur, Kathmandu, Nepal.

In partial fulfillment of requirements for the degree of

Master of Science in Chemistry

By
Basant Giri

Tribhuvan University
Kirtipur, Kathmandu, Nepal.
2004

1
 TRIBHUVAN UNIVERSITY
INSTITUTE OF SCIENCE AND TECHNOLOGY
CENTRAL DEPARTMENT OF CHEMISTRY
KIRTIPUR, KATHMANDU

The dissertation entitled

End Point Detection with Gran Plot and Titration Error

Submitted by
Basant Giri

has been accepted as a partial fulfillment of the requirements for the

Master's degree in Chemistry

...........................................
External Examiner
........................................................
Supervisor
Professor Dr. R. R. Pradhananga
Head
Central Department of Chemistry

2
 FOREWORD

The entire work presented in this thesis is carried out by Mr.

Basant Giri under my supervision. During the research period he
performed his work sincerely and satisfactorily. Part of this thesis was
presented on the occasion of 22nd symposium conducted by Nepal
Chemical Society in April 2004. No part of this thesis had been submitted
for any other degrees before.

...........................................................
Professor Dr. R. R. Pradhananga
Head
Central Department of Chemistry
T. U. Kirtipur, Kathmandu

3
 ACKNOWLEDGEMENT

I would like to express my sincere gratitude to my respected

supervisor Prof. Dr. Raja Ram Pradhananga, Head, Central
Department of Chemistry, T.U. for his invaluable guidance,
encouragement and laboratory facility throughout my dissertation work.

I also want to thank Dr. S. Shrestha and Mr. L. K. Shrestha for

their help in making ion selective electrodes with other faculty members
and staffs of Central Department of Chemistry for their support to
complete my work. At last I cannot forget to give thank for all my senior,
colleagues and family members.

Basant Giri

4
 ABSTRACT

In classical methods of end point location in potentiometric

titrations, data points near the end point are used. Accurate results would
be obtained by these methods if large number of data points
corresponding to very small change in the volume of titrant added are
used. But electrode potential does not attain constant value quickly near
the end point due to supersaturation, coagulation and adsorption of ions
by the precipitate in case of precipitation titrations. This introduces
uncertainty in the location of end point, and leads to titration error.
Alternative method for the location of end point, Gran plot, which does
not need the value of electrode potential near the end point, has been
examined. Titration errors with Gran plot in the neutralization tritration of
strong acid with strong base have followed the reported trend. Influence
of number of data points taken and spacing between the points have been
examined in the titration of KI, KBr and KCl with AgNO3 using
laboratory made silver/silver halide and silver ion selective electrodes.
Titration errors and end point uncertainties can be minimized by wisely
selecting the number of points before and after the end point, and by
carefully fitting the Gran plot. Accurate end point can be obtained even
using last 40% of data points near the equivalence point before the end
point. The advantages of Gran plot in locating the end point are
discussed.

5
 TABLE OF CONTENTS
Foreword
Acknowledgement
Abstract
1. Introduction 1-15
1.1 Titration 1
1.2 Potnetiometric Titration 2
1.3 Types of Potentiometric Titration 3
1.4 Location of the end point in Potentiometric titration 6
1.5 Theory of Gran Plot 9
1.6 Literature Review 13
1.7 Objectives of the Present Work 15
2. Experimental 16-20
2.1 Preparation of reagents 16
2.2 Fabrication of Working Electrodes 17
2.2.1 Fabrication of Ag-electrode 17
2.2.2 Fabrication of Ag2S Based Ag-ISE 18
2.3 Potentiometric Titration 19
2.3.1 Neutralization Titration 19
2.3.2 Titration of KI with AgNO3 19
2.3.3 Titration of KBr with AgNO3 19
2.3.4 Titration of KCl with AgNO3 20
2.4 Location of End Point 20
3. Results and Discussion 21-28
3.1 Neutralization Titration 21
3.2 Precipitation Titration 23
4. Conclusion 29
References
Appendix
Tables
Figures

6
 1. INTRODUCTION

1.1 Titration

The quantitative chemical analysis in which the amount of

substance to be determined is calculated from the volume of the standard
solution used is known as titration. In titrimetric analysis the standard
solution is called titrant and the substance being titrated is termed as
titrand.

The titrant is usually added from a burette. The point at which the
reaction between the titrant and titrand is just complete is called the
equivalence point or the theoretical or stoichiometric end point. The
completion of reaction is detected by some physical change produced by
the titrant, by the addition of indicator or some other physical
measurements may be used. The point at which the above methods
indicate the completion of the reaction is called end point. In the ideal
titration end point will coincide with the equivalence point. In practice,
however, a very small difference usually occurs. This represents the
titration error. Titration indicators are the auxiliary reagents. They
indicate the end point by changing their colour at the end point. Therefore
choice of indicator is very important. In acid-base titrations, the indicators
are complex organic compounds which are generally weak organic acids
or weak organic bases. The choice of indicator, here, depends on the
nature of acid, base and the pH range of the indicators. In the case of the
neutralization of strong acid - strong base, the indicator having pH range
between limits pH 4.5 and 9.5 should be used. Similarly in case of the
neutralization of weak acid - strong base, the indicator having pH range
between limits pH 8 and 10.5 should be used. But no suitable indicators
are available for neutralization of weak acid-weak base, polyprotic acid-

7
base and with strongly coloured solutions. In argentometric titrations the
visual indicators may be the substances forming coloured precipitate (e.g.
K2CrO4), forming a soluble coloured compound (e.g. KSCN) or
adsorption indicators (e.g. eosin i.e. Tetrabromofluorescein) may be used.
The above mentioned argentometric indicators will give characteristic
colour in presence of silver ions. End point location by such visual
indicators is subjected to titration error. The end point in a titration can
also be located by potentiometric methods.1

1.2 Potentiometric Titration

In potentiometric titration, the end point of titration is determined

by measuring the potential of an indicator electrode as a function of the
volume of titrant added. Beherend2, in 1893 performed potentiometric
titration of chloride, bromide and iodide with mercurous nitrate.

In a simple arrangement for a manual potentiometric titration a

reference electrode (e.g. saturated calomel electrode) is coupled with a
working electrode or indicator electrode, which is reversible with one of
the ions involved in the titration. The emf of the cell containing the initial
solution is determined and emf of the cell after each addition of titrant
solution is also measured. The emf of the cell changes with the addition
of titrant but a rapid and large change of emf takes place near the
equivalence point. Sufficient time should be allowed after each addition
for the indicator electrode to reach a reasonably constant potential (~ 1-2
mV) before the next increment is introduced. In this procedure, we are
concerned with changes in emf of the cell which is due to the change in
concentration of ions reversible to the indicator electrode.1

There are many situations where potentiometric titrations have

advantages over 'classical' visual indicator methods. These include1

8
 1. Where the end point obtained by the indicator is masked, e.g.
if the analyte solution is coloured, turbid or fluorescent.

2. Where there is no suitable indicator or where the colour

change is difficult to ascertain.

3. In the titration of polyprotic acids, mixtures of acids, mixtures

of bases or mixtures of halides.

1.3 Types of Potentiometric Titration

Depending on the type of the reactions involved to which potential

measurement can be applied for end point detection, potentiometric
titrations can be classified into followings.

(a) Acid-Base Titration

An electrode, reversible to hydrogen ion is employed in order to

follow the progress of acid-base reactions, the most commonly used
being the glass electrode, but, regardless of which electrode is chosen, the
potential of the electrode at 250C is given by an equation of the form

E = E0 - 0.0591 log [H+]

or, E = E0 + 0.0591 pH

Where, E0 is a constant potential depending on the experimental

arrangement, the liquid junction potential(s) and reference electrode. If
pH is monitored during the titration, pH at the equivalence point of the
titration of a strong acid with a strong base is always 7 at 250C, regardless
of the concentration of the acid. This is not true for weak acid. In this
case the pH of the equivalence point decreases as the concentration
decreses.3 Satisfactory results are obtained in all acid-base potentiometric
titrations except (a) where either the acid or the base is weak (K<10-8) and

9
solutions are very dilute and (b) where either the acid and the base are
weak1.

Remarkable advantage of the potentiometric method appears in the

titration of polybasic acids or mixture of strong acid and weak acid with a
base. When the ionization constants of the different stages of a polybasic
acids or the different acids in a mixture differ by a factor of at least 1000,
the potentiometric titration yields directly a number of distinct steps for
the various neutralizations.4

(b) Complexometric Titration

Complexometric titration can be followed with an electrode of the

metal where ion is involved in complex formation4. For instance a
number of ion selective electrodes can be used to monitor the titration of
metal ions potentiometrically by EDTA.1 A silver electrode may be used
to follow the titration of cyanide ion with a standard silver solution. The
potential of the silver electrode may be expressed at 250C by3

E = E0 + 0.0591 log [Ag+]

(c) Oxidation - Reduction Titration

Oxidation - reduction titrations involve the transfer of electrons

from the substance being oxidized to the substance being reduced.

Oxidized form + n electrons = reduced form

For such reaction the potential (E) acquired by the indicator electrode at
250C is given by

E = E0 +
0.0591
log
[ox ]
n [red]

10
 The potential is controlled by the ratio of these concentrations.
During the potentiometric titration, the ratio and therefore the potential,
changes more rapidly in the vicinity of the end point of the reaction. It is
possible to titrate two substances by the same titrant provided the
standard potentials of the substances being titrated, and their oxidation or
reduction products, differ by about 0.2 V.1

(d) Precipitation Titration

Precipitation titrations are titrations in which the titration reaction

results in the formation of precipitate. A precipitation titration that
involves insoluble salts of metals such as mercury, silver, lead and copper
may be followed potentiometrically. The indicator electrode may be made
of the metal involved in the reaction, a silver electrode for the titration of
halides for instance, or may be an electrode whose potential is governed
by the concentration of the anion being precipitated.3

The potential of the silver electrode used in the titration of halide

(X-) with silver nitrate will be governed by the appropriate Nernst
equation

EAg+/Ag = E0Ag+/Ag + 0.0591 log [Ag+]

As soon as the enough silver nitrate solution to precipitate some

silver halide has been added, equilbrium is established and the
concentration of silver ion is related to solubility product as follows:

[Ag ] = K[X ]
+ AgX
−

Hence, the electrode potential can be expressed in terms of the

halide ion concentrations as:

EAg+/Ag = E0Ag+/Ag + 0.0591 logKAgX - 0.0591 log[X-]

11
 After the addition of titrant (e.g. AgNO3) concentration of halide
ion decreases which will increases overall potential of the electrode. In
potentiometric titration the electrode potential over most of the titration
range varies gradually, but near the equivalence point the electrode
potential changes very abruptly even by the addition of small amount of
titrant1.

The magnitude of the potential change at the end point depends on

the solubility of the substance being precipitated as well as on the
concentration of the active species involved.1,3 For example the change is
more pronounced for silver iodide than for silver chloride, since the
solubility product of the silver chloride is about 106 larger than the
solubility of the silver iodide.1 It has been found that potential change of
silver electrode for the titration of 0.1M KI with 0.1M AgNO3 is greater
than for the titration of 0.01M KI with 0.01M AgNO3.5

In precipitation based potentiometric titration a number of

components differing in solubility product could be analyzed. For
example mixture of potassium iodide, potassium bromide and potassium
chloride could be titrated with silver nitrate solution using silver electrode
and silver-ISE. Among three halides, the solubility product of iodide is
least (10-16) and of chloride is highest (10-10), silver iodide precipitates
first, then silver bromide and at last silver chloride. But due to co-
precipitation, adsorption the end points in halide mixture contain error.1,3

1.4 Location of the End Point in Potentiometric Titrations

(a) Titration Curve

It is obtained by plotting the successive values of the cell emf on

ordinate and corresponding values of volume of titrant added on the

12
abscissa. This gives a S-shaped curve. The central portion of this curve
which shows the steeply rising portion corresponds to the volume for the
end point of the titration. When there is a small potential change at the
end point like in the titration of weak acid with strong base, titration of
very dilute solution etc, it is difficult to locate end point by this method.

(b) Analytical or Derivative Method

The end point can be more precisely located from the first or
second derivative curves. The first derivative curve involves the plot of
slope of the titration curve (∆E/∆V) against the volume of the titrant
added. Slope indicates the rate of change of emf per unit change in
volume of titrant, which is maximum at the end point.

In second derivative curve we plot the slope of first derivative

curve (∆2E/∆V2) against volume. The point on volume axis where the
curve cuts through zero on the ordinate gives the end point. This point
corresponds to the largest steepest point on titration curve and maximum
slope of the ∆E/∆V curve.

Above mentioned methods need values of potential corresponding

to very small change in volume near the end point for good result. In the
immediate vicinity of the end point the concentration of the original
reactant becomes very small, and it usually becomes impossible for the
ions to control the indicator electrode potential. The cell emf becomes
unstable and indefinite because the indicator electrode is not longer
bathed with sufficient quantities of each electroactive species. Therefore
the above methods may not give satisfactory results. Again also, results
obtained by above methods may be in error if the reaction is not
symmetrical e.g. in titration of silver ions with chromate ions.1,3,6,7

13
 Emf

Volume of Titrant Added (mL)

Figure 1.1: Titration Curve

∆E/∆V

Volume of Titrant Added (mL)

Figure 1.2: First Derivative Curve

2
∆ E/∆V
2

Volume of Titrant Added (mL)

Figure 1.3: Second Derivative Curve

14
(c) Gran Plot

In the analysis by above classical methods, the only data on the

titration curve that were actually used to obtain the accurate end point
were near the end point itself. It would be convenient to use data away
from this region to avoid the tedious of measuring a large number of emf
near end point corresponding to very small change in the volume of
titrant added. Further, a linear function relating the data, the end point
would be better6. In 1952 G. Gran8 proposed a graphical end point
detection method that meets these goals by a numerical manipulation of
titration curves into linear straight lines intersecting at the equivalence
point. This method is based on the fact that the differential curves have
two branches intersecting at the equivalence point. His method resembles
the fact that the amount of titrand decreases linearly with the volume of
titrant added.9 This new method can be applied to acid-base, redox,
complex formation and precipitation potentiometric titrations.

1.5 Theory of Gran Plot

Consider a reaction:

A+ + B-→ AB

Let V0 mL of B- with initial concentration

0
CB
is titrated by adding

VmL of A+ having concentration CA at each time.

The Emf of the cell is given by,

2.303RT
E = E0 − log a B
nF
2.303RT
Or, E = E0 − log γC B
nF

15
 Or, E0 − E =
2.303RT
log γ  B 0
(
 C 0 V − CA V  )

nF  (V0 + V ) 

Or,
nF  C 0 V − CA V 
(E 0 − E) = log γ  B 0
( )

2.303RT  (V0 + V ) 

(V0 + V )10 − nFE / 2.303RT ×10 nFE / 2.303RT = γ (C B 0 V0 − C A V )

0
Or,

Or,
(V0 + V )10 −nFE / 2.303RT ×10 nFE / 2.303RT = γ (C B 0 V0 − C A V )
0

V0 V0

Where E = Emf of the cell at temperature TK

E0 = Standard emf of the cell
n = no. of electrons involved
F = Faradays Constant
aB = Activity of B-
R = Gas Constant
γ = Activity coefficient

0
At equivalence point: C B
V0 = C A Ve

Where Ve is the volume of A+ added at equivalence point.

So,
(V0 + V )10 −nFE / 2.303RT = 10 −nFE / 2.303RT γ C A (Ve − V) . . . . . . . . . 1
0

V0 V0

(V0 + V )
If a plot of 10 − nFE / 2.303RT verses V is made a straight line will be
V0
obtained. At the intercept of the straight line on x-axis:
(V0 + V )
10 − nFE / 2.303RT = 0
V0

i.e. 10 −nFE
0
/ 2.303 RT
γ CA
(Ve − V ) = 0
V0

∴ (Ve - V) = 0

So, Ve = V

16
 This shows that the volume corresponding to the intercept on x-
axis is the equivalence point.

Equation 1 best fits for the data points taken only before the
equivalence point. The end point can also be obtained from the data
(V0 + V )
points after the end point by plotting 10 nFE / 2.303RT against the
V0

volume of titrant added.

Before End Point After End Point

(V0 + V ) 10 ±nFE / 2.303RT

V0

End Point

Volume of Titrant Added V (mL)

Figure 1.4: Gran Plot of Locating End Point

Thus the end point from Gran Plot can be obtained either taking the
points before the end point or taking the points after the end point. It is
obvious that the results obtained from linear curves would be more
accurate than from the non-linear ones. The linear straight lines can be
extrapolated to the volume axis to locate the end point. At the time when
Gran developed this method, semi-log papers should be used for
calculations but those papers were not readily available. This difficulty
decreased the use of Gran Plot. By the development of calculator, later on
computer and using ion selective electrode, use of Gran Plot is increasing.

The advantages of using Gran's method of locating end point are 9,10

17
1) Simplicity of measurement : Fewer titration points need to be taken
and this method do not require large number of readings,
corresponding to very small changes in volume of titrant, in the
region of the equivalence point than with conventional methods.
2) Simplicity of Calculation : The calculations are easy and quick by
the use of computers.
3) Versatility: This method is applicable to all types of potentiometric
titrations e.g. acid-base, redox, complex formation and
precipitation potentiometric titrations.
4) Precision: Measurements need not be made close to the
equivalence point since this point may be obtained by
extrapolation; therefore, problems associated with incompleteness
of reaction or instability of measurements close to the end point
can be avoided. So results obtained by this method are more
precise and accurate.

18
1.6 Literature Review
The end point in precipitation titrations is being detected by using
indicators from very long time. One of the oldest technique, the Mohr
method, uses K2CrO4 as the indicator substance in the argentometric
titration of halides. The end point in this method is indicated by the
appearance of red colour of Ag2CrO4. The Volhard method involves
basically the titration of silver in acid solution with a standard solution of
potassium thiocyanate, KSCN, using iron (III) as the indicator substance.
At end point a intensely red soluble complex of Fe(SCN)2+ is resulted.
But these indicator methods may contain errors since excess titrant must
be present to develop colour.9 Flurorescein adsorption indicator technique
was developed by Fajans10 and his associates. The end point, in this case,
is indicated by the deep red colour of silver fluoresceinate on the surface
of precipitate.
In potentiometric titrations, potential measurement is taken into
account to locate the end point. In most of the routine laboratory works,
the end point in potentiometric titration is located by conventional
titration curves. If there is small potential change at equivalence point, the
end point is located by first and second derivative curves. But these three
methods of locating end point requires large values of potential near the
end point corresponding to very small change in volume of titrant added
for accurate result. These methods also may contain errors in case of un-
symmetrical reactions.6
In 1950 G. Gran11 proposed a method of transforming the titration
curves by a numerical manipulations into straight lines intersecting at the
equivalence point. That method overcomes the difficulties of previous
methods. Gran's method was based on the fact that the differential curves
have two branches intersecting at the equivalence point. In 1951
Sorensen12 pointed out that graphs very similar to those obtained by Gran

19
were obtained if the antilograithm of the potential/pH was plotted as a
function of the volume of titrant added. Sorensen, however, did not study
reactions other than the titrations of strong and weak acids with strong
bases and the precipitation titration of chloride ions with silver ions. Later
on in 1952 G. Gran8 investigated more fully the possibilities of
Sorenson's method, especially for more complicated titrations such as
ion-combination titrations, including ions of different valencies. Gran
also made correction to dilution effect, which was not made by Sorenson,
and obtained linear graphs. But at that time the Gran's method of locating
end point was not so much popular due to the non-availability of antilog-
paper.

The determination of activity coefficients and junction potentials

using modified Gran plots was done by Rossotti and Rossotti13. They also
studied the potentiometric titrations using Gran plots for all neutralization
reactions.14 They found that their results were favoring the advantages of
Gran's method.

Gran plot does not need values of potentials very near to the end
point and the end point can be obtained by extrapolation of the straight
line. Burden and Euler15 described the results of a theoretical study,
which evaluated titration errors associated with using Gran plots. Their
study suggested that the advantages favoring Gran plots are significantly
influenced by the number of data points chosen, the spacing between the
data and the precision of the data. Later on they proved their theoretical
study by the titration of strong acid with strong base in the paper
"Titration errors inherent in using Gran Plots" published on Analytical
Chemistry.16

20
1.7 Objectives of the Present Work
Gran's method when applied to evaluate the end point, it has been
reported that the titration errors in neutralization titrations depends upon
the number of data points chosen and spacing between the points. No
such reports in literature is available regarding the titrations involving the
precipitation reactions. In fact no systematic studies in the use of Gran
plot in the determination of end points in the argentometric titrations had
been investigated. So the objectives of present work are:

(a) To study systematically the Gran's method of locating end point in

potentiometric titration and to compare with conventional methods
of locating end point.
(b) To analyse the titration errors with the variation of the number of
data points and spacing between the points in Gran Plot.

21
 2. EXPERIMENTAL

2.1 Preparation of Reagents

All the regents were prepared in distilled water using AR and LR

grade reagents.

2.1.1 Silver nitrate solution (0.1 M)

It is prepared by dissolving 4.246 gm of AR grade solid silver

nitrate crystals in 250mL of distilled water.

2.1.2 Potassium iodide solution (0.01 M)

It is prepared by dissolving 1.66gm of LR grade solid potassium

iodide crystals in 1000mL of distilled water.

2.1.3 Potassium bromide solution (0.01 M)

It is prepared by dissolving 1.99gm of LR grade solid potassium

bromide crystals in 1000mL of distilled water.

2.1.4 Potassium chloride solution (0.01 M)

It is prepared by dissolving 0.745gm of LR grade solid potassium

chloride crystals in 1000mL of distilled water.

2.1.5 Stock Sodium Hydroxide Solution (0.1 N)

Sodium hydroxide solution of 0.2N is prepared by dissolving 0.8

gram sodium hydroxide in 100 mL volumetric flask with distilled water.
That solution is standardized by titrating with standard 0.1N oxalic acid
using phenolphthalien indicator. The concentration of above prepared
sodium hydroxide solution was found 0.2 N.

22
2.1.6 Sodium hydroxide solution (0.1N)

It is prepared by diluting 50 mL of 0.2 N stock sodium hydroxide

solution in a 100 mL volumetric flask using distilled water.

2.1.7 Stock hydrochloric acid solution (1 N)

It is prepared by diluting 8.9 mL of 11.3 N hydrochloric acid taken

with graduated pipette in 100 mL volumetric flask using distilled water.

2.1.8 Hydrochloric acid solution (0.01 N approx.)

It is prepared by diluting 1 ml of 1 N stock hydrochloric acid in

100 mL volumetric flask using distilled water.

2.2 Fabrication of working electrodes

2.2.1 Fabrication of Ag-Electrode

About 4cm long silver wire was made from 99.9% pure silver. A
25 cm long copper wire was soldered to the silver wire and inserted into a
15 cm long glass tube in such a way that half part of the silver wire piece
was outside the fire polished end of glass tube. The copper wire soldered
to silver wire was fixed to the glass tube by araldite and air dried for
about 24 hours. The exposed end of the silver wire was dipped in 1:1
nitric acid for short time and rinsed with distilled water, then air dried for
about 24 hours.

Fig. 2.1: Silver Electrode

23
2.2.2 Fabrication of Ag2S based Ag–ISE

The silver sulphide was prepared by passing hydrogen sulphide gas

to an aqueous solution of silver nitrate. The precipitate was washed with
distilled water, and finally with acetone then dried at 1200C in air oven
for two hours. The precipitate was grinded and sieved from Mesh No. 140
size.

About 1.8 gm sieved silver sulphide was used to make pellete

having 2 mm thick and 1.3 cm diameter applying 12×104 N/m2 pressure
in a Perkim Elmer Pellet making assembly. Thus prepared pellet was
again dried at 1800C in air oven and was polished in an emery paper.
Then one side of the pellet was coated with silver using silver conducting
paint.

A copper wire of 25 cm was soldered to a silver disc for electric

contact and inserted into a groove made in a 10 cm long, 1.5 cm diameter
polythene rod with a groove 1.3 cm diameter and 3 mm depth containing
hole of 5 mm diameter. Silver coated silver sulphide pellet was inserted
in such a way that the silver coated membrane came in contact with silver
metal disc. Finally, the pressed pellet membrane was fixed in the groove
by araldite. In this way silver sulphite based Ag-Ion selective electrode
was fabricated in the laboratory. The Ag-ISE fabricated in the laboratory
was characterized by a method followed by Shrestha17 .The electrode was
found to follow Nerstian behaviour within the concentration range of
silver ion from 10-1M to 10-5M with slope 58.7mV per decade change in
silver ion concentration, which is in agreement with previously made
electrodes in the laboratory of Central Department of Chemistry, T.U.17, 18

24
2.3 Potentiometric Titrations
2.3.1 Neutralization Titrations

100 mL of 0.01N (approx.) hydrochloric acid was taken in a 150

mL beaker. This solution was stirred with a Teflon coated bar magnet. A
glass electrode was introduced into the solution. Sodium hydroxide
solution (0.1N) was added from a graduated pipette one milliliter at a
time to the acid solution and corresponding pH of the solution was
measured with Jenway pH meter with Elico glass electrode.

2.3.2 Titration of KI with AgNO3

Six 100 mL samples of 0.01 M potassium iodide solutions were

taken in six 150 mL beakers and solutions were stirred with a Teflon
coated bar magnet. Silver nitrate solution of 0.1M was added by 1 mL
graduated pipette. An Ag-electrode was inserted to the beaker containing
KI solution whereby a thin layer of AgI is believed to be formed on Ag-
metal and Ag/AgI electrode is thus formed. This electrode was then
coupled with a standard calomel electrode. The two half cells were then
connected with NH4NO3 - Agar gel salt bridge and the emf were
measured in OSWA digital potentiometer after each addition of titrant.
The cell for potentiometric titration may be represented as:

Hg/Hg2Cl2, KCl (sat.) // KI, AgI/Ag

2.3.3 Titration of KBr with AgNO3

Six 100mL samples of 0.01M potassium bromide solutions were

taken in six 150mL beakers and solutions were stirred with a Teflon
coated bar magnet. Silver nitrate solution of 0.1M was added by 1mL
graduated pipette. An Ag-electrode was inserted to the beaker containing
KBr solution-whereby a thin layer of AgBr is believed to be formed on

25
Ag-metal and Ag/AgBr electrode is thus formed. This electrode was then
coupled with a standard calomel electrode. The two half cells were than
connected with NH4NO3-Agar gel salt bridge and the emf were measured
in OSWA digital potentiometer after each addition of titrant. The cell for
potentiometric titration may be represented as:

Hg/Hg2Cl2, KCl (sat)// KBr, AgBr/Ag

2.3.4 Titration of KCl with AgNO3

Six 100 mL samples of 0.01 M potassium chloride solutions were

taken in six 150 mL beakers and solutions were stirred with a Teflon
coated bar magnet. Silver nitrate solution of 0.1M was added by 1 mL
graduated pipette. An Ag-electrode was inserted to the beaker containing
KCl solution whereby a thin layer of AgCl is believed to be formed on
Ag-metal and Ag/AgCl electrode is thus formed. This electrode was then
coupled with a standard calomel electrode. The two half cells were than
connected with NH4NO3-Agar gel salt bridge and the emf were measured
in OSWA digital potentiometer after each addition of titrant. The cell for
potentiometric titration may be represented as :

Hg/Hg2Cl2, KCl (sat)//KCl, AgCl/Ag

2.4 Location of End Points

The end points in potentiometric titrations were determined from

classical methods and then from Gran Plots using titration data by
performing linear regression analysis on the Gran equation. The linear
regression analysis and all subsequent calculations were performed on
computer using excel programme.

26
 3. RESULTS AND DISCUSSION

3.1 Neutralization Titration

pH values after addition of each one milliliter sodium hydroxide of

0.1N in the titration of 100mL of 0.01N (approx.) HCl are tabulated on
Table 3.1.

Table 3.1: Titration data for the titration of 100 mL of 0.01N

(approx) HCl with 0.1N NaOH.

S.N. Vol. of NaOH added (mL) pH S.N. Vol. of NaOH added (mL) pH
1. 0 1.89 10. 9 2.90
2. 1 1.91 11. 10 9.06
3. 2 1.95 12 11 10.42
4. 3 1.98 13 12 10.65
5. 4 2.05 14. 13 10.84
6. 5 2.09 15. 14 10.90
7. 6 2.16 16. 15 10.99
8. 7 2.32 17. 16 11.04
9. 8 2.47 18. 17 11.07

Figure 1a represents the titration curve which is obtained by

plotting the pH values against the volume of sodium hydroxide added for
the titration of 100 mL of 0.01 N (approx) HCl with 0.1 N sodium
hydroxide. Figure 1b is the first derivative curve of Figure 1a, where
∆pH/∆V is plotted against the volume of sodium hydroxide added. When
∆pH/∆V is plotted with the initial volume of titrant, a negative error is
found to occur and when ∆pH/∆V is plotted with the final volume of the
titrant added, a positive error is found to occur. Certain author, therefore,
suggested to use average of the initial and final volume of titrant added in

27
x-axis. In Figure 1b the values of ∆pH/∆V are plotted against the average
volume of sodium hydroxide added corresponding to the values of the pH
taken. From both figures more accurate end points would be obtained if
we use more readings close to the end point corresponding to very small
change in volume of titrant added. Figure 1c is the second derivative
curve of Figure 1a, where ∆2pH/∆V2 is plotted against the volume of
sodium hydroxide added.
Figure 2 represents the Gran plot to obtain the end point in
neutralization titration of 100mL of 0.01N (approx.) HCl with 0.1M
NaOH solution. The Gran's function is plotted on y-axis against the
volume of NaOH solution added on x-axis. Two straight lines are
obtained. The first one (Figure 2a) is obtained by taking the values of data
points before the end point and the second line (Figure 2b) is obtained by
taking the values of data points after end the point. On the course of
titration amount of hydrogen ion decreases, this could be reconciled with
the negative slope of first line and amount of hydroxide ion after end
point increases, this could be reconciled with the positive slope of the
second line.
Table 1 gives the values of end point and titration error in the
titration of 100mL of 100 mL of 0.01N (approx.) HCl with 0.1N NaOH
solution with the variation of number of data points and spacing between
the points.
The titration errors are calculated from the deviations of each Gran
plot end point from its stoichiometric end point. The deviation from
equivalence point depend on the error introduced by the instrument (pH
meter), the electrode used and other interfering agents. Large titration
error has been observed when the data points at the very beginning of the
titration (0,1 and 2mL of titrant added) are taken. This trend in titration
error is in agreement with the reported trend16.

28
3.2 Precipitation Titration
The values of emf of the cell after addition of each milliliter of
silver nitrate in the titration of six-trials of potassium iodide are tabulated
on Table 2. The values of cell emf obtained are as expected and the emf
values in each trial agree with each other within experimental error.
During the potentiometric titration silver/silver iodide electrode functions
as a cathode with SCE as anode The negative values observed for emf of
the cell at the beginning are as expected. Iodide ions in the titrand were
removed with the addition of silver ions and the value of emf is
increasing with the addition of each milliliter of silver nitrate solution
which is in accordance with the following Nernst equation for the cell.
RT
Ecell = E0cell - 2.303 log [I-]
F
Figure 3a represents the plot of emf against the volume of silver
nitrate added for the titration of 100 mL of 0.01 M KI with 0.1M silver
nitrate (1st trial). Both Table 2 and Figure 3a show large change in emf
near the end point during the titration. Almost all iodide present in the
titrand combined with silver ions to give silver iodide precipitate and the
end point. The change in emf at the end point can be explained as
follows. At the end point concentration of silver and iodide ions are
nearly equal to 10-8 M which is produced by dissolution of sparingly
soluble silver iodide (Ksp of AgI = 1.5 × 10-16 at 250C)4. If 0.1cc of 0.1M
silver nitrate is added at the end point, the concentration of silver ion
would become nearly 10-4M. Thus the concentration of silver ions is
changed by 104 fold. The sharp change in emf is due to this change in
concentration of silver ion. The change in emf at the end point was found
to be nearly 490 mV in case of the titration of potassium iodide in all six-
trials. But this change in emf at the end point in case of the titration of

29
KBr was found to be nearly 290 mV and in case of KCl was found to be
nearly 150 mV (Table 3). The change in emf at the end point during the
titration is in the order KI > KBr > KCl. This is in time with the increase
in the solubility product of silver halides. For the halides of same
concentration, the jump in emf is high for the halide giving silver halide
with low solubility product and vice versa. The solubility product of AgI
is least 10-16, AgBr is 10-13 and that of AgCl is highest 10-10. As the
solubility product of AgCl is highest, the emf change at the end point for
the titration of KCl is least. A comparison of change in electrode
potentials at the end point during the titration of KI, KBr and KCl with
silver nitrate can be visualized in Figure 4.
Figure 3b is the first derivative curve of Figure 3a, where ∆E/∆V is
plotted against the volume of the silver nitrate added. When ∆E/∆V is
plotted with the initial volume of titrant added, a negative error is found
to occur. When an plotting of ∆E/∆V with the final volume of titrant
added is made, a positive error is found to occur. Certain author,
therefore, suggested to use average of the initial and final volume of the
titrant added in x-axis. Effect of these facts on end point can be observed
in Figure 5. In this research, ∆E/∆V is plotted against the average volume
of silver nitrate added corresponding to the values of emf taken. End
point in potentiometric titrations can also be located by second derivative
plot. Figure 6 shows the end point location by all three classical methods.
These plots indicates that the end point lies between 10 to 11 mL of silver
nitrate added. Therefore, no satisfactory results can be obtained by
classical methods in simple way. To locate end point more accurately
from classical methods, it is necessary to take more potential readings
close to the end point corresponding to very small change in volume of
titrant added. This can be seen in the Figure 3b'. This figure shows the

30
end point location by taking more potential readings near the end point
for the same titration mentioned in Figure 3b. But recording the values of
electrode potential near the equivalence point is difficult because of the
unstability in the potential values owing to incomplete reaction,
supersaturation, adsorption of ions etc.
In all classical methods of end point location, greater weightage is
given to the potential readings near the end point where influence due to
the chemistry of reaction is maximum. Near the end point there may
occur supersaturation of ions, equilibrium may be obtained slowly and
the ions may be adsorbed on the precipitate. Due to these reasons the
potential responsed by the electrode may not match with the exact
amount of ions present. These facts can introduce errors in locating the
exact and point. To minimize the error undue weightage should not be
given to readings near the end point. G. Gran8 in 1952 formulated a new
technique to locate the end point during potentiometric titration which
eliminate the use of emf readings near the end point.
During the potentiometric titration of KI with AgNO3 following
reaction occurs.
KI(aq) + AgNO3(aq) → AgI(s) + KNO3(aq)
The cell for the titration is SCE//KI, AgI/Ag and the emf of the cell
is given by.
RT
Ecell = E0cell - 2.303 log[I − ]
F
The emf of the cell increases during potentiometric titration of KI
with AgNO3. By manipulating above equation one can derive the
following equation (Appendix 1) for locating the end point by Gran's
method.
 V0 + V  − FEcell / 2.303RT 0 γC Ag + (Ve − V)
 10 = 10 − FE cell / 2.303RT . . . . . . . (3.1)
 V0  V0

31
Where V0 = Initial volume of KI taken
V = Volume of AgNO3 solution added
Ve = Volume of AgNO3 solution at end point
CAg+ = Concentration of AgNO3 solution added
F = Faraday's constant
R = Gas constant
T = Temperature
γ = Activity coefficient
 V + V  − FEcell / 2.303RT
In above equation 3.1 the term  0 10 is called
 V0 

Gran's function. When Gran's function is plotted against volume of

AgNO3 added 'V', a straight line will be obtained. Such a plot is called
Gran Plot.
Figure 7 represents the plot of Gran function against V for the
potentiometric titration of 100mL of 0.01M KI with 0.1M AgNO3
solution. Two straight lines are obtained. The first one (Figure 7a) is
obtained by plotting the values of data points before the end point and the
second line (Figure 7b) is obtained by plotting the values of data points
after the end point. On extrapolations of both these lines meet the volume
axis, which is the end point of the titration. Thus data points either before
the end point or after the end point separately can be used to locate the
end point by Gran Plot. Gran's method of locating the end point has one
distinct advantage over classical methods that it does not need the data
points near the end point and thus overcomes the difficulties associated
with the errors due to incomplete precipitation, adsorption, slow
attainment of equilibrium etc. Moreover the end point is located by
extrapolation of straight lines which eliminates error due to personal bias.
The number of data points that should be used by Gran's method is
not definite for the location of end point. One would expect that number
of data points used should not affect the end point, since the end point is

32
obtained by the extrapolation of linear plot either before or after the end
point. But the value of end point obtained from Gran's method is found to
be deviated from its stoichimetric end point when data points representing
initial 30% of the data points before the end point in the titration of
100mL of 0.01M KI with 0.1M AgNO3 are used. These points, taken at 0,
1 and 2 mL addition of titrant, represent 20% completion of reaction. At
the beginning of the titration the change in emf per each milliliter
addition of titrant is small. Small errors in the values of emf at the
begining of the titration has a much more profound effect on Gran Plot to
give titration error than does the values of emf at a higher completion of
titration even with a constant instrumental error.16 Therefore one should
not choose points which all lie near the beginning of the titration. If we
increase the number of data points from beginning toward near the end
point (e.g. when data points at 0, 1, 2, 3mL and 0, 1, 2, 3, 4 mL are
taken), the corresponding values of end point obtained are progressing to
reach to the close of the stoichiometric end point. When the points at the
beginning of titration are neglected and points corresponding to 40 to
80% completion of reaction (when data points at 4, 5, 6, 7, 8mL are
taken), the values of end point are very close to the stoichiometric end
point. In the same manner, when data points corresponding only to last
40% of titration (when data points at 7, 8, 9, 10mL are taken), satisfactory
values of end points are found in all six trials. The results obtained when
we use data points covering 80 to 100% of completion of reaction with or
without spacing (points at 0, 2, 4, 6, 8mL or 1, 3, 5, 7, 9mL or 0 to 10mL
are taken), are in good agreement with stoichiometric end point. Similar
results are obtained when data points after the end point are used (Table
4). Percentage titration errors are calculated from deviations of each Gran
plot end point from its respective stoichiometric end point and are
tabulated on Table 5(a). The percentage titration errors reconciled with

33
the results discussed on Table 4. The percentage titration error is high for
the end point which is more deviated from its stoichiometric end point.
Similar percentage titration errors are also found to occur in case of the
titration of KBr and KCl by AgNO3 (Table 5b and Table 5c). In all these
three cases the maximum percentage errors are found when the data
points at 0, 1 and 2 ml of titrant added are taken.
Percentage titration errors are also analysed for potentiometric
titrations of potassium halides using silver ion selective electrode. The
electrode was fabricated and characterized in the laboratory of Central
Department of Chemistry, T.U. The electrode followed Nerstian
behaviour in agreement with the previously made Ag-ISE in the same
lagoratory17,18. The results showing the titration errors inherent with the
analysis by Gran's method, related to the number and spacing of data
points in the titration of 100mL of 0.01M KI, KBr and KCl with 0.1M
AgNO3 solution using Ag-ISE are tabulated on Table 6. The nature of
titration errors are similar to those obtained using silver electrode.
The titration errors and uncertainty in locating the end point is
reduced when a large portion (nearly 60%) of the titration curve is
represented both before and after the equivalence point. One could use
data points near equivalence points, neglecting the points at beginning for
best result. The values of end point obtained with successively neglecting
the points at the beginning are found similar. In Figure 8 values of end
point are plotted with the number of data points taken from near the
equivalence point. The end point obtained using only four data points (i.e.
using points at 7, 8, 9 and 10mL of titrant added), five data points (6, 7, 8,
9, 10mL), six data points (5, 6, 7, 8, 9, 10mL) and so on have no
significant difference. This implies that accurate end point from Gran plot
can be obtained by using last 40% of data points near the end point.

34
 4. CONCLUSION

Two ways of end point location in potnetiometric titration are

mainly in practice. First is the titration curve and second is the first
derivative curve. In these methods greater weightage is given to the data
points near the end point and for better and accurate result large number
of data points corresponding to very small change ion volume of titrant
added near the end point must be used. But near the end point influence
due to chemistry of reaction is maximum. Near the end point, there may
occur super-saturation of ions, equilibrium may be obtained slowly and
the ions may be adsorbed on the precipitate. Recording large number of
values of emf near end point is difficult due to unstability of the readings.
These facts introduces titration error. In Gran's method of locating end
point in potentiometric titration, the above errors can be removed because
in this method greater weightage should not be given to readings near the
end point. From this research following conclusions can be drawn, which
will clear the fact that Gran's method is superior than classical methods.

• Gran's method do not need values of emf near the end point.
Therefore this method is more precise and accurate.
• Extrapolation of linear straight lines are used to locate the end
point. Data points only before the end point can be used to locate
the end point.
• Small number of data points give accurate end point.
• Titration errors inherent with Gran's method can be minimized by
wisely selecting the number of data points and carefully fitting
the Gran plot.
• End point from Gran plot can be obtained even with last 40% of
data points from near to the equivalence point with best result.

35
 REFERENCES
1. Vogel's textbook of "Quantitative Chemical Analysis" sixth edition.
2. Kolthoff, Sandell, Mechan, Bruclcenstin "Quantitative Chemical
Analysis" forth edition.
3. Wilson, C.L.; Wilson, D. W.; "Comprehensive Analytical Chemistry"
2nd A, Electrical Methods, Elsevier Publishing Company, 1964.
4. Maron, S.H.; Pruton, C.F.; "Principles of Physical Chemistry" fourth
edition, 1972.
5. Hamal, D.B.; M. Sc. Dissertation, Central Department of Chemistry,
T.U. 1997.
6. Day, R.A.; Underwood, R.L.; "Quantitative Analysis" sixth edition
Prentice Hall of India, 1993.
7. Williard, H.H.; Merritt, L.L.; Dean, J.A.; Settle, F.A.; "Instrumental
Methods of Analysis", sixth edition, Van Nostrand, 1981.
8. Gran, G.; Analyst (London), 1952, 77, 661.
9. Dick, J.G.; Analytical Chemistry, International Student Edition,
McGraw - Hill Kogakusha, Ltd. 1973.
10. Fajans, K. and Hassel, O.; Z. Electrochem, 1923, 29, 495.
11. Gran, G.; Acta. Chem. Scand., 1950, 4, 559.
12. Sorenson, P.; Kem Maanedsbl.; 1951, 32, 73.
13. Rossotti, F.J.C. and Rossotti, H.; J. Phy. Che.; 1964, 68, 12, 3773.
14. Rossotti, F.J.C. and Rossotti, H.; J.Che.Edu; 1965, 42, 7, 377.
15. Burden, S.L. and Euler, D.E.; Proc. Indiana Acad. Sci.; 1973, 82,
167.
16. Burden, S.L. and Euler, D. E.; Analytical Chemistry, 1975, 47, 793.
17. Shrestha, L.K.; M.Sc. Dissertation; Central Department of
Chemistry, T.U.; 2001.
18. Tandukar, S.; M.Sc. Dissertation; Central Department of Chemistry,
T.U.; 2001.

36
 APPENDIX - I

When V0 mL of KI with concentration CKI is titrated by adding VmL of

AgNO3 with concentration CAg+ at each time. The reaction is,
KI(aq) + AgNO3(aq) → KNO3(aq) + AgI(s)
The emf of the cell is given by,
2.303RT
Ecell = E0cell - log a KI
F
2.303RT
= E 0 cell − log γ C KI
F

Where, γ = activity coefficient.

 C KI V0 − CAg + V 
or, (E 0
)
− E cell =
2.303RT
log γ  
 (V0 + V ) 
cell
F

or,
(
F E 0 cell − E cell
= log γ 
)
 C KI V0 − C Ag + V 

2.303RT  (V0 + V ) 

or, (V0 + V )10− FE cell / 2.303 RT

× 10FE
0
cell / 2.303 RT
(
= γ C KI V0 − CAg + V )
 V0 + V  − FE cell / 2.303RT  C KI V0 − C Ag + V 
× 10FE cell / 2.303RT = γ 
0
or,  10
V  V 
 0   0 

At equivalence point:
CKIV0 = CAg+ Ve
Where Ve is the volume of AgNO3 added at the equivalence point
So,
 V0 + V  −FEcell / 2.303RT 0  C Ag+ (Ve − V) 
 10 × 10 FE cell / 2.303RT = γ  . . . . . (1)
 V0   V0 

 V + V  − FE cell / 2.303RT
In above equation 1, the term  0 10 is called Gran's
 V0 

function. When this Gran's function is plotted against 'V', a straight line
will be obtained. At the intercept of the straight line on x-axis

37
  V0 + V  − FE cell / 2.303RT
 10 =0
 V0 

V + V
i.e. 10 − FE cell / 2.303RT × γC A  0  = 0
 V0 

∴ (Ve - V) = 0
and Ve = V
This shows that the volume corresponding to the intercept on x-
axis is the equivalence point. Equation 1 best fits for the data points taken
only before the equivalence point. The end point can also be obtained
 V + V  FE cell / 2.303RT
from the data points after the end point by plotting  0 10
 V0 

against the volume of titrant added.

38
TABLES

39
Table 1 : End point detection from Gran Plot using various number of points and
spacing between the points and corresponding titration errors. (Titration
of 100mL 0.01N (approx.) HCl with 0.1N NaOH)

Description of data No. of points taken End point (ml) % Titration error
10 10.5 5
a
5 11.67 16.7
5b 10.36 3.6
Before end point 5c 14.3 43.0
3d 10.09 0.9
3e 13.8 3.8.0
3f 17.3 73.0
7g 9.21 -7.9
After the end point 3 h
9.27 -7.3
i
3 9.87 -1.3
Where: a refers points at 0, 2, 4, 6, 8 ml: b 1, 3, 5, 7, 9 ml: d 2, 5, 9 ml: e 0, 2, 8 ml: f 0,
1, 2 ml:g 11, 12, 13, 14, 15, 16, 17 ml: h 11, 14, 17 ml and i 11, 12, 13 ml

Table 2 : Potentiometric titration of 100 mL of 0.01M KI with 0.1M AgNO3 solution

Volume of Emf (mV)
Ag+(mL) Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6
0 -246 -245 -245 -245 -246 -246
1 -243 -241 -241 -241 -242 -242
2 -239 -238 -238 -238 -239 -239
3 -236 -234 -235 -235 -236 -235
4 -232 -231 -231 -231 -232 -232
5 -227 -226 -226 -227 -227 -227
6 -221 -220 -220 -221 -222 -221
7 -214 -213 -212 -213 -215 -214
8 -204 -203 -203 -204 -205 -204
9 -187 -187 -185 -188 -190 -189
10 -128 -129 -111 -135 -140 -138
11 364 362 363 360 361 361
12 384 383 383 381 382 382
13 394 393 393 392 393 393
14 402 401 401 399 401 401
15 407 406 406 405 406 406
16 412 410 410 410 410 410
17 415 414 414 413 414 414

40
Table 3 : Cell emf change near end point in the potentiometric titration of 100 ml
of each 0.01M KI, KBr and KCl with 0.1M AgNO3 solution
Halide Emf (mV)
KI 492 491 474 495 501 499
KBr 289 286 289 285 289 289
KCl 152 149 149 141 150 146

Table 4 : End points detection from Gran's Plot using various number of points and
spacing between the points in the Potentiometric titration of 100 mL 0.01
M KI wit 0.1 M AgNO3
No. of End point (ml)
Description
points
of Data Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6
taken
Before end 10 10.06 10.11 10.04 10.19 10.22 10.19
point 3a 8.87 8.64 8.64 8.84 8.64 8.64
b
4 9.69 9.20 9.88 9.88 9.88 9.2
5c 9.8 9.71 9.99 9.99 9.99 9.71
5d 10.03 10.3 10.03 10.18 10.18 10.03
e
5 10.05 10.21 10.07 10.26 10.32 10.25
5f 10.13 10.13 10.06 10.20 10.33 10.13
4g 10.11 10.13 10.08 10.18 10.19 10.18
h
7 10.1 10.1 10.07 10.2 10.14 10.14
After end 3i 10.08 10.12 10.08 10.2 10.15 10.15
point 3j 10.12 10.16 10.12 10.22 10.22 10.22

Where a refers points at 0, 1, 2 mL; b 0, 1, 2, 3 mL; c 0, 1, 2, 3, 4 mL; d 0, 2, 4, 6, 8

mL;e1,3,5,7,9mL; f 4, 5, 6, 7, 8, mL; g 7, 8, 9, 10 mL; h 11, 12, 13, 14, 15, 16, 17 mL; i
11, 14, 17 mL; j 11, 12, 13 mL

41
Table 5 : Titration errors (%) related to the number and spacing of data points

(a) Titration of 100.0mL of 0.01M KI with 0.1M AgNO3 solution using silver
electrode.
Description No. of points Percentage error
of Data taken Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6
Before end 10 0.6 1.1 0.4 1.9 2.2 1.9
a
point 3 -11.3 -13.6 -13.6 -13.6 -13.6 -13.6
4b -3.1 -8.0 -1.2 -1.2 -1.2 -8.0
c
5 -2.0 -2.9 -0.1 -0.1 -0.1 -2.9
5d 0.3 3.0 0.3 1.8 1.8 0.3
5e 0.5 2.1 0.7 2.6 3.2 2.5
f
5 1.3 1.3 0.6 2.0 3.3 1.3
4g 1.1 1.3 0.8 1.8 1.9 1.8
7h 1.0 0.9 0.7 1.9 1.4 1.4
i
After end 3 0.8 1.2 0.8 2.0 1.5 1.5
point 3j 1.2 1.6 1.2 2.2 2.2 2.2

Where a refers points at 0, 1, 2 mL; b 0, 1, 2, 3 mL; c 0, 1, 2, 3, 4 mL; d 0, 2, 4, 6, 8

mL;e1,3,5,7,9mL; f 4, 5, 6, 7, 8, mL; g 7, 8, 9, 10 mL; h 11, 12, 13, 14, 15, 16, 17 mL; i
11, 14, 17 mL; j 11, 12, 13 mL

(b) Titration of 100.0mL of 0.01M KBr with 0.1M AgNO3 solution using silver
electrode.
Description No. of points Percentage Error
of Data taken Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6
Before end 10 3.1 5.1 2.4 2.0 1.1 1.8
a
point 3 -19.5 -19.4 -11.6 -13.6 -31.3 -22.3
4b -6.4 -7 -3.1 -8.0 -17.2 -10.8
5c -3.0 -3.0 -1.7 -6.3 -13.0 -7.0
5d 2.5 5.8 2.5 1.2 1.5 0.5
5e 5.7 5.7 2.4 3.4 3.0 3.0
5f 5.2 4.3 4.3 5.0 4.7 5.2
g
4 2.1 2.0 2.5 1.8 2.3 2.1
7h 2.2 2.2 2.3 1.7 2.4 2.2
After end 3 i
2.0 2.0 2.3 1.6 2.3 2.0
point 3j 1.9 1.9 2.2 1.2 2.0 1.9

Where a refers points at 0, 1, 2 mL; b 0, 1, 2, 3 mL; c 0, 1, 2, 3, 4 mL; d 0, 2, 4, 6, 8

mL;e1,3,5,7,9mL; f 4, 5, 6, 7, 8, mL; g 7, 8, 9, 10 mL; h 11, 12, 13, 14, 15, 16, 17 mL; i
11, 14, 17 mL; j 11, 12, 13 mL

42
(c) Titration of 100.0mL of 0.01M KCl with 0.1M AgNO3 solution using silver
electrode.
No. of Percentage Error
Description
points
of Data Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6
taken
Before end 10 -1.5 3.9 5.0 -2.5 2.4 1.2
a
point 3 -14.0 -25.5 -13.6 -47.3 -13.6 -22.2
4b -32.0 -9.2 -1.2 -32.1 -8.0 -13.0
c
5 -24.8 -4.0 -3.9 -27.2 -6.3 -9.0
5d -5.7 3.3 0.4 -8.0 1.1 0.5
5e 4.4 6.5 6.5 1.5 3.8 1.8
f
5 5.2 5.7 6.1 3.1 5.7 4.3
4g 2.2 2.5 2.6 1.0 2.7 2.5
7h 1.8 1.9 1.4 0.5 1.8 0.6
i
After end 3 1.6 1.3 1.2 1.0 1.6 1.3
point 3j 1.2 0.8 1.2 0.8 1.2 1.0

Where a refers points at 0, 1, 2 mL; b 0, 1, 2, 3 mL; c 0, 1, 2, 3, 4 mL; d 0, 2, 4, 6, 8

mL;e1,3,5,7,9mL; f 4, 5, 6, 7, 8, mL; g 7, 8, 9, 10 mL; h 11, 12, 13, 14, 15, 16, 17 mL; i
11, 14, 17 mL; j 11, 12, 13 mL

Table 6 : Titration errors (%) related to the number and spacing of Data Points

(a) Titration of 100.0mL of 0.01M KI with 0.1M AgNO3 solution using silver ISE.
No. of Percentage error
Description
points
of Data Trial 1 Trial l 2 Trial 3 Trial 4 Trial 5 Trial 6
taken
Before end 10 1.5 0.1 2.8 1.9 1.2 0.8
point 3a 2.2 2.2 54.8 19.4 19.4 43.4
4b 0.2 0.2 26.4 20.9 24.5 22.5
c
5 3.5 15.6 19.8 16.4 16.4 8.7
5d 2.9 0.2 5.9 3.7 2.1 3.7
5e 2.0 2.0 3.1 2.2 1.3 -5.7
f
5 2.4 0 2.4 0.4 -1.0 -0.4
4g -0.1 -0.3 0 -0.1 0.3 -0.3
7h 5.0 3.7 2.8 1.8 1.5 1.3
i
After end 3 3.6 3.7 3.0 1.2 1.2 0.8
point 3j -1.2 2.8 2.8 1.9 1.9 1.4

Where a refers points at 0, 1, 2 mL; b 0, 1, 2, 3 mL; c 0, 1, 2, 3, 4 mL; d 0, 2, 4, 6, 8

mL;e1,3,5,7,9mL; f 4, 5, 6, 7, 8, mL; g 7, 8, 9, 10 mL; h 11, 12, 13, 14, 15, 16, 17 mL; i
11, 14, 17 mL; j 11, 12, 13 mL

43
(b) Titration of 100.0mL of 0.01M KBr with 0.1M AgNO3 solution using silver ISE.
No. of Percentage Error
Description
points
of Data Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6
taken
Before end 10 1.6 1.7 1.5 1.5 1.8 0.5
a
point 3 19.4 -3.8 2.2 2.2 2.2 -13.6
4b 13.0 14.1 8.7 8.7 8.7 -1.2
5c 7.0 8.1 6.8 6.8 6.8 -0.1
5d 1.6 2.0 2.0 2.0 2.0 -0.3
5e 1.9 2.6 1.6 1.6 2.3 1.3
5f 1.3 1.3 1.3 1.3 1.3 0.5
g
4 1.4 0.9 1.0 0.9 1.1 0.4
7h 2.9 1.7 3.5 2.8 3.7 1.7
i
After end 3 2.8 1.5 3.3 2.5 3.3 1.6
point 3j 3.3 2.2 2.8 2.8 2.8 1.9

Where a refers points at 0, 1, 2 mL; b 0, 1, 2, 3 mL; c 0, 1, 2, 3, 4 mL; d 0, 2, 4, 6, 8

mL;e1,3,5,7,9mL; f 4, 5, 6, 7, 8, mL; g 7, 8, 9, 10 mL; h 11, 12, 13, 14, 15, 16, 17 mL; i
11, 14, 17 mL; j 11, 12, 13 mL

(c) Titration of 100.0mL of 0.01M KCl with 0.1M AgNO3 solution using silver ISE.
No. of Percentage Error
Description
points
of Data Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6
taken
Before end 10 0.6 1.5 0.3 2.1 1.1 2.2
a
point 3 -34.6 -3.8 -25.5 -13.6 -13.6 -13.6
4b -30.9 2.3 -9.2 -1.2 -1.2 -1.2
5c -13.1 0.5 -6.8 -4.0 -0.1 -0.1
d
5 -2.0 0.9 -0.7 1.2 0.3 1.8
5e 3.2 2.5 1.3 2.2 1.9 2.3
5f 2.8 1.9 1.6 4.5 1.3 2.8
g
4 1.5 1.0 0.8 1.7 1.3 1.7
7h 2.0 2.5 0.1 2.3 1.3 2.2
After end 3i 2.7 2.5 0.5 2.3 0.8 2.0
point j
3 1.9 2.6 1.2 2.2 1.4 1.9

Where a refers points at 0, 1, 2 mL; b 0, 1, 2, 3 mL; c 0, 1, 2, 3, 4 mL; d 0, 2, 4, 6, 8

mL;e1,3,5,7,9mL; f 4, 5, 6, 7, 8, mL; g 7, 8, 9, 10 mL; h 11, 12, 13, 14, 15, 16, 17 mL; i
11, 14, 17 mL; j 11, 12, 13 mL

44
FIGURES

45
 14

12

10

8
pH

0
0 2 4 6 8 10 12 14 16 18
Volume of NaOH(mL)

Figure 1a: Titration curve for the potentiometric titration of 100mL of

0.01M HCl with 0.1M NaOH.

4
dpH/dV

0
0 2 4 6 8 10 12 14 16 18

Volume of NaOH(mL)

Figure 1b: First derivative curve of Figure 1a.

46
 8

d2pH/dV2 4

0
0 2 4 6 8 10 12 14 16 18

-2

-4

-6

Volume of NaOH(mL)

Figure 1c: Second derivative curve of Figure 1a.

0.016

0.014

0.012
Gran's function

0.01

0.008

0.006

0.004

0.002

0
0 1 2 3 4 5 6 7 8 9 10 11

Volume of NaOH added(mL)

Figure 2(a): Location of end point by Gran plot for the titration of 100mL
of 0.01M HCl with 0.1M NaOH using data points before the
end point

47
 1.4E+11

1.2E+11

Gran's function 1E+11

8E+10

6E+10

4E+10

2E+10

0
8 9 10 11 12 13 14 15 16 17
Volume of NaOH added(mL)

Figure 2(b):Location of end point by Gran plot for the titration of 100mL
of 0.01M HCl with 0.1M NaOH using data points after the
end point

500

400

300

200
Emf(mV)

100

0
0 2 4 6 8 10 12 14 16 18
-100

-200

-300

Volume of titrant added(mL)

Figure 3a: Titration curve for the potentiometric titration of 100mL of

0.01M Kl with 0.1m AgNO3

48
 1200

1000

dE/dV 800

3b'
600
3b

400

200

0
0 2 4 6 8 10 12 14 16 18
Volume of titrant added(mL)

Figure 3b: First Derivative Curve of Figure 3a.

3b': First Derivative Curve of Figure 3a when large number of
data points corresponding to very small change in volume of
titrant near the end point are used.

500
KI
400 KBr
KCl
300

200
Emf(mV)

100

0
0 2 4 6 8 10 12 14 16 18
-100

-200

-300

Volume of titrant added(mL)

Figure 4: Potentiometric titration of KI, KBr and KCl with AgNO3

49
 18

16

14

12
Volume of Titrant Added (mL)

10 Using Average Volume

0
0 100 200 300 400 500 600
dE/dV

Figure 5: Differential Plots of Potentiometric Titration of KI with

AgNO3

600

Titration Curve
400
First Derivative Curve
Second Derivative Curve
emf in (mV), dE/dV, d2E/dV2

200

0
0 2 4 6 8 10 12 14 16 18

-200

-400

-600
Volume of Titrant Added (mL)

50
Figure 6: End point location by three classical methods in the
potentiometric titration of KI with AgNO3.

16000

14000

12000
Gran's function

10000

8000

6000

4000

2000

0
0 1 2 3 4 5 6 7 8 9 10 11

Volume of titrant added(mL)

(a)

14000000

12000000

10000000
Gran's function

8000000

6000000

4000000

2000000

0
8 9 10 11 12 13 14 15 16 17 18
-2000000

Volume of titrant added(mL)

(b)
Figure 7: Location of end point by Gran plot for the titration of 100mL
of 0.01M KI with 0.1M AgNO3
(a) Using data points before the end point
(b) Using data points after the end point

51
 15

14

13

12
End point(mL)
11

10

6
4 5 6 7 8 9 10 11 12

No. of points used near from the equivalence point

Figure 8: Effect of number of points taken from near the equivalence

point on end point.

52