THIN FILM CuS ELECTRODE FOR THE DETERMINATION

OF Cu2+, Cr3+ & Fe3+ IN AQUEOUS SOLUTION

A dissertation submitted to the Central Department of Chemistry,

Tribhuvan University, Kirtipur, Kathmandu, NEPAL.

In partial fulfillment of the requirement for the

Master’s Degree in Chemistry

By
Basu Dev panthi

Central Department of Chemistry

Institute of Science and Technology
Tribhuvan University
Kirtipur, Kathmandu, NEPAL
2002
 TRIBHUVAN UNIVERSITY
INSTITUTE OF SCIENCE AND TECHNOLOGY
CENTRAL DEPARTMENT OF CHEMISTRY
KIRTIPUR, KATHMANDU

The dissertation entitled

THIN FILM CuS ELECTRODE FOR THE DETERMINATION
OF Cu2+, Cr3+ & Fe3+ IN AQUEOUS SOLUTION

Submitted by
Basu Dev Panthi

has been accepted as a partial fulfillment of the requirement for

the Master’s Degree in Chemistry

_______________ _____________________________
External examiner Supervisor/Head of The Department
Prof. Dr. Raja Ram Pradhananga
Central Department of Chemistry
 FOREWORD
The entire work presented in this thesis has been carried out by Mr. Basu Dev
Panthi under my supervision in the academic year 2000-2002. During the
research period, he has performed his work sincerely and satisfactorily. No part
of this thesis has been submitted for any other degree.

-----------------------------------
Prof. Dr. Raja Ram Pradhananga
Head of the Department
Central Department of Chemistry
Tribhuvan University.
Kirtipur, Kathmandu,
NEPAL
 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 kind help, valuable guidance and encouragement throughout the
research work without which this work would not be possible.

I am also grateful to Prof. Dr. Mangala Devi Manandhar, former Head,

Central Department of Chemistry, T.U., for providing me the required
laboratory facilities to carry out this work.

My sincere thanks goes to my respected teachers Prof. Dr. Shiva Prasad

Dhoubhadel, Prof. Dr. Chhabi Lal Gajurel, Prof. Jaya Krishna Shrestha, Prof.
Dr. Mohan Bikram Gewali, Dr. Jagadish Bhattarai, Dr. Sabita Shrestha, Dr. Deb
Bahadur Khadka, Dr. Tara Niraula, and all other teachers of the Central
Department of Chemistry for their co-operation and encouragement during the
work. I am also thankful to senior brothers and sisters Mr. Subin Adhikari, Mrs.
Kshama Parajuli, Mr. Lok Kumar Shrestha ‘Rajesh’ and Ms. Shikchya
Tandukar for their kind help and co-operation during the work.

I am thankful to my colleagues Ms. Durga Parajuli, Mr. Yam Bahadur

Poudel, Mr. Raj Kumar Malla, Mr. Birendra Babu Adhikari, Ms. Neeva
Karmacharya, Mr. Netra Subedi, Mr. Lekh Nath Sharma and Mr. Deepak Gupta
for their kind co-operation during the work. I would like to thank all the
supporting staffs of the Department.

I want to thank Royal Nepal Academy of Science and Technology

(RONAST) for providing me some financial support to carry out this work.

Lastly, I want to express my gratitude to my parents and brother for their

love and support.

Basu Dev Panthi

August, 2002.
 ABSTRACT

The laboratory made CuS/Ag2S pressed pellet electrode containing 95

mole percentage of Ag2S and 5 mole percentage of CuS did not response
favorably for the determination of concentration of copper ion in aqueous
solution. But electrode prepared by depositing thin film of CuS on graphite rod
by chemical method was found to be sensitive and selective to the copper ions.
The electrode was found to obey the Nernstian behavior from 10-1 to 10-4
mole/L Cu++ concentration with slope equal to 30 mV at pH range 4-5. The
response time of this electrode was found to be less than 30 seconds. With the
ageing of the electrode, there is slight drift in electrode potential; however,
gradient per decade change in concentration of copper ions remains almost
constant. The electrode has been successfully used for the determination of Cu2+
by direct potentiometry and as an indicator electrode for the potentiometric
titration with EDTA. The electrode has also been successfully used as an
indicator electrode for the determination of Cr3+ and Fe3+ in aqueous solution by
indirect potentiometric titration with Cu2+. The results obtained are in good
agreement with the expected value within experimental error.
Table of contents
Foreword
Acknowledgement
Abstract
1. Introduction ..................................................................................................... 1
1.1 General introduction ....................................................................................... 1
1.2 Types of ion-selective-electrodes ................................................................... 2
1.3 Theory of ion-selective-electrode ................................................................... 3
1.4 Selectivity coefficient ..................................................................................... 7
1.5 Advantages and limitations of ion-selective-electrodes ................................. 8
1.6 Literature survey ........................................................................................... 10
1.7 Objective of the present work ....................................................................... 13

2. Experimental ................................................................................................ 14
2.1.1 Preparation of Ag2S/CuS pressed pellet ISE ............................................. 14
2.1.2 Preparation of CuS-graphite ISE ............................................................... 15
2.2 Preparation of reagents ................................................................................ 16
2.3 Characterization of Cu-ion-selective-electrodes........................................... 18
2.4 Determination of Cu++ by direct potentiometry ............................................ 20
2.6 Selectivity coefficient .................................................................................. 20
2.7 Determination of Fe3+ in aqueous solution ................................................... 20
2.8 Determination of Cr3+ in aqueous solution ................................................... 21

3. Results and Discussion .................................................................................. 22

3.1 Characterization of Cu-ion-selective-electrodes........................................... 22
3.2 Determination of Cu++ by direct potentiometry ............................................ 25
3.3 Interferences by different metal ions ........................................................... 26
3.4 Potentiometric titration ................................................................................. 29
3.5 Determination of Fe3+ in aqueous solution ................................................... 30
3.6 Determination of Cr3+ in aqueous solution ................................................... 31

Conclusion ......................................................................................................... 33
Bibliography....................................................................................................... 35
Appendix ............................................................................................................. 38
 CHAPTER - ONE
INTRODUCTION

1.1 General Introduction

Ion-selective electrodes are electrochemical sensors whose potential
depends on the activity or concentration of determinand ion according to Nernst
equation.
E = Eo ± RT/nF(ln ax) ............................(1)

Where Eo is the standard potential of the electrode, ax is the activity of

determinand ion 'x' and ‘n’ is the number of charges on 'x'. The sign is positive
when 'x' is a cation and negative when it is an anion.
The equation (1) describes the pure response of the electrode to 'x' and
thus assumes that there is no other ion in the solution to which the electrode can
respond. But this ideal situation is not a feature of a real electrode. The range
over which an electrode will give a Nernstian response is limited in practice,
even in the absence of other interfering ions to which the electrode responds and
depends on the surface characteristics, composition, nature of electrodes and
other various preparation parameters of electrodes.
It is not possible to measure a single electrode potential; hence, the
electrode is coupled with reference electrode. The emf of the cell is given by:

Ecell = Eo ± 2.303 RT/nF (log ax) - Eref

= Eo’ ± k/n (log ax) …………….................... (2)

In the above equation Eo’ is equal to ( Eo- Eref) a constant and k =2.303
RT/F which is equal to 59 mV at 25oC for an ideal electrode. Thus, the emf of
the cell is a logarithm function of determinand ion activity. In real electrode the
value of k up to 55 mV are frequently referred to as Nernstian. The term 'sub-
Nernstian' is used if the value of k is lower than 55 mV per decade change in

1
concentration. Lower value of k usually indicates that the electrode is faulty and
the results may be irreproducible.

1.2 Types of ion-selective electrodes.

Most popular ion-selective electrodes of practical importance are
following types [1].
• Glass membrane electrodes.
• Solid-state membrane electrodes
• Liquid ion-exchange membrane electrodes
• Gas sensing probes
• Enzyme electrodes
• Ion-selective field effect transistor [ISFET]
• Miscellaneous electrodes

Solid-state membrane electrodes may be further classified into following

types:
• Single crystal electrodes
• Solidified salt melt electrodes
• Pressed pellet electrodes
• Thin film deposited electrodes
• Coated wire electrodes
A thin film deposited electrodes are the electrodes prepared by depositing
a thin film of ion-sensitive membrane in an inert supporting material (e.g.
CuS/Ag2S deposited on graphite rod).

2
1.3 Theory of ion-selective electrode
1.3.1 Glass electrodes
The theory and response mechanism of glass electrodes for pH
measurement and working principle of glass electrode for the measurement of
other monovalent cations is thoroughly described by Eisenman [2]. When a
glass electrode is immersed in an aqueous solution, the glass membrane absorbs
water and a swollen hydrated layer is formed on the inner and outer surface,
which may be represented as:

0.1M HCl Inner Dry Outer Unknown

Solution. Hydrated Glass Hydrated (Test)
Layer. Layer. Layer. Solution.

Figure 1.1: Representation of hydrated glass membrane.

The thickness of this hydrated layer varies considerably, according to the

composition of the glass and the nature (i.e. pH) of the solution in which it is
immersed. At the interface of the hydrated layer with a sample solution the
monovalent cations on the glass, sodium or the lithium ions usually, are
exchanged and the sites are involved in ion-exchange equilibrium with the ion
to be measured. The exchange of hydrogen ion between solution and glass
membrane takes place in both inner and outer hydrated layers of the glass
membrane which gives rise to electrode potential which is proportional to the
H+ diffusion between inner and outer solution separated by the glass.
H+ HG+

Nicolsky in 1935-37 first gave this ion exchange theory for the
development of electrode potential which was extended and refined by many
scientists [1]. With the fundamental work of B.P. Nicolsky concerning the
3
interpretation of potential response of glass electrode through ion-exchange
theory, a new idea has been introduced in the development of a novel ion-
selective electrode. This ion-exchange theory is generally accepted till today.

The electrode potential of the pH glass electrode is given by:

EG = Eo ± K.pH ……………………… (3)

Where K=2.303RT/F and Eo is the standard glass electrode potential. The

standard potential of glass electrode depends upon the composition, surface
characteristics and history of the glass electrodes. In the equation (3) the sign is
positive when the solution is alkaline (i.e. when pH>7) and negative when the
solution is acidic (i.e. when pH<7).

1.3.2 Inorganic precipitated based ion-selective electrodes:

In inorganic precipitated based ion-selective electrodes the response
mechanisms appear, in general, to be more straightforward than those of glass
electrodes, due to the absence of the hydrated surface layer.
Buck and Shepard [3] developed a more complete theory, relating the
standard potential of silver-halide based electrodes to the stoichiometry of the
active material in the membrane. The formula of silver halide may be precisely
written as Ag1+∂X; thus, the compound is slightly nonstoichiometric and while
at equilibrium contain a uniform excess of elemental silver (∂ positive) or
halogen X(∂ negative). When silver metal back contact is made, the diffusion of
silver to the membrane takes place until the stoichiometry has been altered to
give unit silver activity and the potential is produced from the ion-exchange
process [1]. The same argument may be applied to the silver sulfide membranes.
Hence, the electrode potential is dependent on the ion-exchange reaction
between membrane and test solution because ion exchange at membrane and
metal contact interface is constant.

4
 In electrodes of second kinds, the silver halide takes no important part in
the potential determining process. The potential of the silver is established as
the result of the electron exchange between the silver metal and ions in the bulk
of the metal and ion exchange between the silver ions in the metal and the silver
ions at the silver-solution interface. The activity of silver at the interface is
unity; hence, the potential of the electrode depends on the ion exchange at
silver-solution interface.
In the case of electrodes with an internal reference solution and silver
based internal reference electrode leads to the same as for electrodes of the
second kinds.
If in a solid-state electrodes, the membrane is contacted with noble
metal then the silver activity in the membrane is fixed by the stoichiometry of
the silver salt and electron exchange replaces ion exchange for the development
of electrode potential at the membrane contact interface. The ion exchange
between membrane and solution interface is as described above.
When the electrode membrane is contacted with carbon, unit activity in
the solid phase will remain, because no chemical reactions occur and the
potential is developed by the ion exchange between the active material in the
membrane and test solution. The standard electrode potential of this kind of
electrode varies according to the method of manufacture and the stoichiometry
of the active material in the membrane [1].
When a membrane is contacted by a reactive metal such as lead,
cadmium or solder, the potential is initially similar to that of membranes
contacted by a noble metal and only electron exchange occurs at the membrane
contact interface. However, the membrane, AgX, reacts with the contact metal,
L, to form salts LXXY and free elemental silver. This silver will eventually act as
contact metal itself and the standard potential will shift, as the membrane
stoichiometry shifts, to that expected for a silver contact.

5
 Buck and Shepard [3] extended their arguments from the silver halide and
silver sulfide membranes to cover the mixed sulfide membranes used in lead,
cadmium and copper electrodes (PbS/Ag2S, CdS/Ag2S, CuS/Ag2S). Lead,
cadmium or copper cannot be used as contact metals because of corrosion
caused by the silver salts. Hence, the range of potentials is set by the limits of
stoichiometry when aAg = 1 or aS = 1 referred to the standard state of aM2+ = 1.
The equilibrium in the CuS/Ag2S system are much more complicated
than in the other two systems because the range of copper sulfides of grossly
different stoichiometry (CuS, Cu1.8S, Cu1.9S, Cu1.95S and Cu2S) which can exist.
The value of the electrode standard potential depends on the form of sulfide that
is present at equilibrium. When the membrane is contacted with silver (aAg = 1),
the silver is in equilibrium with sulfur in the system via the silver sulfide; thus,
the chemical potential of the sulfur and, hence, the chemical potential of the
copper sulfur system is fixed.
Silver sulfide acts as a binder in the heavy metal sulfide ion-selective
electrode. Besides this silver sulfide help to keep the activity of the metal, M,
constant at the membrane solution interface. Silver in the solid will diffuse
relatively fast. Hence, in any reaction on the surface silver sulfide tends to act as
a buffer in the equilibria involved with any silver that is lost or gained on the
surface being rapidly equilibrated with the bulk of the membrane by diffusion
process.
E. Pungor put forward a entirely different view regarding the response
mechanism of ion-selective electrodes which is yet to be universally accepted.
According to E. Pungor [4] ion exchange does not take place in the membrane
but the electrode potential is caused by the charge separation at the surface of
the electrode. The interpretation is connected with the chemisorptions of the
primary ion from the solution phase onto the surface of the electrode. In this
case counter ions accumulate in the solution phase and this is the charge
separation.
6
 Pot .
1.4 Selectivity coefficient, K A, B :

No ion-selective electrode responds exclusively to the ion which it is

designed to measure, although it is often more responsive to this primary ion
than to others. If another, interfering, ion is present at a concentration that is
large with respect to primary ion, the electrode response will have contributions
from both the primary and interfering ions. The degree of selectivity of the
electrode for the primary ion, A, with respect to an interfering ion, B, is

expressed by the potentiometric selectivity coefficient, K APot .

, B ; this is defined by

the general equation for the electrode potential;

2.303RT
E = Eo ± log(a A + ∑ K Apot, B.aBn A nB
) ………… (4)
nA F B

Where nA & nB are the charges on ions A & B and Eo is the standard
potential of the electrode. The sign in the equation is positive for cation and
negative for anion. This equation is applicable to nearly all electrodes. This
equation is often referred to as Nicolsky equation.
When an electrode is very selective for A in comparison with B, then
K APot, B. will be much less than unity. Conversely, if, as occasionally happens, the
Pot .
electrode responds preferentially to B rather than A, K A, B will be greater than
unity. For example, the selectivity coefficient of the Orion calcium electrode for
barium ions is 0.01; thus, the electrode is 100 times more responsive to calcium
ions than barium ions. However, chloride electrode is 300 times responsive to
bromide ions than chloride ions.
Pot .
The value of K A, B is never constant for all activities of A & B, although

it is sometimes constant for a given ratio of the activity of A to B. For the

experimental determination of selectivity coefficients, separate solution method
and mixed solution methods are used.

7
1.5 Advantages and limitations of ion-selective electrode.
Ion-selective electrodes have been the subjects of rapidly increasing
interest over the past three decades and their development has opened a large
new field of potentiometry and provides the average analyst for rapid, accurate
and low cost analysis. The growth of ion-selective electrodes and their
applications has been fast in relation to the growth of other techniques partly
because the sensors themselves became widely available commercially soon
after their development and in some cases, quite easy to make in the laboratory.
The construction and chemical design of the sensors have been steadily
improved but the range of ions, which may be directly sensed by ion-selective
electrodes, will not be greatly enlarged.
Ion-selective electrodes sense the activity, rather than the concentration of
ions in solution. The ideal feature of the electrode described by the Nernst
equation is not a feature of real electrode and interference by other ions will be
observed. Electrodes with sub-Nernstian slope and irreproducible readings are
also anticipated. Since the electrodes give a voltage signal, which is
proportional to the logarithm of the determinand ion activity, the accuracy and
precision of the determinations are sometimes poorer than for other techniques,
especially when high determinand activities are measured. However, the
accuracy and precision of the determinations may remain essentially unaltered
over several decades of activity. The accuracy and precision depend on the
degree of control exercised over the experimental conditions, such as
temperature, stirring rate and on the measurement technique.
One of the most attractive features of the ion-selective electrode is the
speed with which they permit a sample to be analyzed, and the ease with which
the methods may be made semi-automatic or automatic. About 20-30 samples
per hour may be analyzed manually; if the sensor is incorporated in a flow
system, discrete samples may be analyzed at rates upto about 60 per hour

8
or a sample stream may be analyzed continuously. The methods of analysis may
be non-destructive and are adaptable to very small sample volumes.
Furthermore, analysis may be made without difficulty of highly colored, viscous
samples containing a high concentration of suspended solids. However,
problems do arise in the analysis of some non-aqueous and partially non-
aqueous samples. Non-correspondent ions may also be determined by using ion-
selective electrodes.
Research on ion-selective electrode is progressing very rapidly which is
reflected by the publication of hundreds of paper every year in different aspects
of ion-selective electrodes.

9
1.6 Literature survey:
The glass electrode fabricated by Haber and Klemensiewicz [5] in 1909
for the determination of hydrogen ion concentration in aqueous solution was the
first ISE of practical importance. In 1934 Lengyl and Blum [6] prepared a glass
electrode with different composition, which was sensitive to sodium ions. Latter
glass membrane was replaced by single crystal of inorganic salt, which were
sensitive to different ions. Kolthoff and Sanders [7] prepared halide-selective
electrodes from polycrystalline pellets of silver halides. After that Pungor, et al.
[8,9] developed several ion-selective electrodes based on precipitates of
inorganic salts. The electrodes prepared by Pungor and his co-workers were the
first truly selective ion-selective electrodes (non-glass). These electrodes display
favorable mechanical properties and good chemical durability. Many
researchers changed the composition of electrode membrane material for the
improvement of sensitivity, linear range, stability, response time etc. Birger [10]
deposited Ag2S on silver rod electrolytically to produce Ag+ & S-- ion-selective
electrode. Electrodes with thin film & liquid membrane were also reported [11].
Further research on ion-selective electrodes developed the ion-selective
electrodes for the determination of F-, Cl-, Br-, I-, S2-, SCN-, CN-, Pb2+, Cu2+,
Cd2+, Ag+, Hg2+, Ca2+.
In the years from 1969-1972, Orion research published a magazine
devoted to developments and applications of ion-selective electrode [12]. Orion
Research Inc. has played a pioneering role in the development of the majority of
the inorganic salt-based ion-selective electrodes including heavy metal ions [1].
The copper ion-selective electrode is the most successful of the divalent
heavy metal ion selective electrodes. This electrode has several applications. In
1970-72 Ruzika and co-workers [13,14,15] designed a new ion-selective
electrode, which they termed selectrode. A selectrode consists of a graphite rod
covered with an ion-selective membrane. This type of electrode is extremely
easy to fabricate and use but its greatest disadvantage is that this electrode gives
10
reproducible & reliable results only in some selected systems. Cu (II)–ion-
selective electrodes with CuS/Ag2S heterogeneous membrane were prepared
[16,17,18] by simultaneous precipitation of metal sulfides. The applications of
these electrodes were also studied. Pcik et al.[19] described Cu(II)-ion-selective
electrodes based on copper sulfide in silicon rubber. Nomura and Genkichi [20]
studied the properties of a membrane electrode made of vinyl chloride polymer
containing CuI precipitate. A wire ion-selective electrode was made by sulfiding
copper deposited on copper wire [21]. Cu (II)-ion-selective electrode with
Ag1.5Cu0.5S doped with Ag2Se sensors [22] were also constructed.
Palanivel and Riyazuddin [23] prepared Cu (II)-ion-selective electrode by
depositing thin film of CuS & Ag2S on the same graphite rod. The graphite rod
was extracted from used dry cell. This type of electrode is extremely cheap and
one can construct such electrodes in the laboratory quite easily. But such
electrodes need to be characterizing before taking them into operation. The low
detection limits quoted for the copper electrodes are difficult to achieve in
practice. The membranes are prone to oxidation in the presence of acids and
oxidants, such as dissolved oxygen in the electrolyte solution [24,25]. The effect
of oxygenated solutions on the surface composition of the jalpite-based (
Ag1.5Cu0.5S ) Cu-ion-selective electrode membrane was examined by De Macro,
Roland, et al. [26]. These authors demonstrated that oxidation of the surface
occurs with a consequence shift in the Eo of the system. Tsingarelli and
Nikolenko [27] determined the selectivity coefficients for a solid Cu (II)-ion
selective electrode with respect to Ni(II), Zn(II), Cd(II), Pd(II), Fe(III), Cr(III),
Al(III), Hg(II) & Ag(I) by using different methods. The Cu (II)-ion-selective
electrode have been used in determination of secondary aliphatic amines in
micro quantities, stability constants of copper complexes and potentiometric
determination of Fe (III) etc [28,29,30]
Different types of modifications and improvements on Cu ion-selective
electrodes were continuously going on in last few decades [31-37]. The main
11
thrusts of the recent investigations were focused on the development of simple,
low cost electrodes with good sensitivity, which gives reproducible results. In
this context, it is worth mentioning the recent investigations of Cu (II)-ion-
selective electrodes, which were fabricated by depositing CuS/AgS on graphite
rod.

12
1.7 Objective of the present work:
From the literature survey, it is quite clear that the several researchers
were working on the development, improvement, characterization and
applications of different types of copper ion-selective electrodes. Modifications
and improvements in the composition of electrode membrane materials have
been investigated for the improvement of sensitivity, stability, linear range and
response time etc. These improved electrodes are being used for various
analytical works as well. Much of the current research interest is in the
fabrication of simple, low cost electrodes having good sensitivity that give
reproducible results. Thus the aim of present work is:

(1) To fabricate heterogeneous CuS/Ag2S based pressed pellet and thin film
copper sulfide deposited on graphite rod copper ion-selective electrodes.

(2) To compare the performance of these electrodes for the determination of

concentration of Cu++ in aqueous solution.

(3) To study the applicability of the copper ion-selective electrodes as an

indicator electrode for the quantitative estimation of heavy metal ions such as
Cu (II), Cr (III), Fe (III), by potentiometric titration with EDTA.

13
 CHAPTER TWO
EXPERIMENTAL

2.1.1 Preparation of CuS/Ag2S pressed pellet electrode

Pressed pellet copper ion-selective electrodes based on CuS/Ag2S were
prepared from the intimate mixture of CuS & Ag2S powder prepared by
coprecipitation of copper and silver sulfide from aqueous solution [mole ratio of
CuS:Ag2S=5:95]. 8.133 g AgNO3 dissolved in water & to it 12.5 ml of 0.102
mole/L Cu(NO3)2 [=0.236 g of Cu(NO3)2]solution was added. To that mixture
solution H2S gas was passed till complete precipitation took place.
Cu(NO3)2 + 2AgNO3 + 2H2S CuS + Ag2S + 4HNO3
The CuS/Ag2S precipitate thus obtained was filtered, washed with
distilled water and finally washed with acetone. It was then dried in air oven at
1200c for an hour. The dried material was ground to fine powder in an agate
mortar. The powder was sieved from Mesh no. 140 size. About 2g of that fine
powder was taken in IR pellet making die and pressed under twelve tons of
pressure in vacuum for five minutes [In the Perkin Elmer IR accessory
hydraulic press]. The pressed pellet thus obtained was dried for half an hour in
an air oven at 120oC. Two such pellets were made. In one pellet back contact
was made with silver and in another with copper.
For copper back contact copper metal was deposited in one side of the
pellet by electro-deposition from copper sulfate solution. For this electroplating
bath is described elsewhere [38]. For silver back contact, one side of the pellet
was painted with electro-conductive silver paint (Dotite, Japan).
A polythene rod of 10 cm long & 1.5 cm diameter was taken and a
groove of 1.4 cm diameter and 4 mm depth was made. A hole of 5 mm diameter
was bored at the center. Copper back contacted CuS/Ag2S pellet was inserted

14
into polyethylene rod which is rest on copper disc and copper wire was soldered
for electrical connection.
Similarly, silver back contacted CuS/Ag2S pellet was inserted into
polyethylene rod which rest on silver disc and copper wire was soldered for
electrical connection. Finally, the pressed pellet membranes were fixed in the
groove by araldite. In this way a complete solid-state polycrystalline (pressed
pellet) membrane of CuS/Ag2S, copper ion-selective electrodes were fabricated
in the laboratory (Figure 2.1). The stoichiometry of CuS and composition of
electrode was not analyzed.

Copper wire

Electrode body

Ag or Cu metal disc

Araldite

Ag2S/CuS pressed pellet

Figure- 2.1: Pressed pellet Ag2S/CuS copper ion-selective electrode

2.1.2 Preparation of CuS-graphite electrode:

Thin film copper ion-selective electrode was fabricated by depositing thin
film of copper sulfide to the porous surface of graphite rod by chemical method.
For this, a 2.5 cm long graphite rod with cap extracted from a dry cell was
boiled for about two hours in distilled water. It was then dried in hot air oven at
the temperature 120oC for two hours. Then that rod was dipped into saturated
solution of copper sulfate for an hour. It was then dipped into a saturated
solution of sodium sulfide for an hour. The rod was removed from the solution

15
and was washed with distilled water and finally washed with ethanol. A copper
wire was soldered in the metal cap of that graphite rod for electrical connection.
It was then fitted into the glass tube using araldite, in such a position that about
2 cm of the graphite rod coated with CuS was protruding. The schematic
diagram of the electrode is shown in Figure 2.2. Thus, prepared copper ion-
selective electrode was characterized and used for different analytical purposes.

Copper wire

Electrode body

Metal cap of graphite rod

Araldite

Graphite rod

Thin film of CuS.

Figure –2.2: Thin film CuS-graphite ion-selective electrode

2.2 Preparation of reagents:

All the stock solutions were prepared in distilled water using LR/AR
grade reagents without further purification and for the purpose of daily use
those stock solutions were appropriately diluted.

16
 I. 0.1M AgNO3 solution:
It is prepared by dissolving 4.25g of LR grade AgNO3 in 250 ml distilled water.

II. 0.1 M Na2S solution:

It is prepared by dissolving 3.752 g of LR grade Na2S (minimum assay 52%) in
250 ml distilled water.

III. 5 M NaNO3 solution:

It is prepared by dissolving 42.95 g of LR grade NaNO3 in 100 ml distilled
water.
IV. 1M CuSO4 solution:
It is prepared by dissolving 24.968 g of LR grade CuSO4.5H2O in 100 ml
distilled water.

V. 0.1N K2Cr2O7 solution:

It is prepared by dissolving 1.226 g of LR grade K2Cr2O7 in 250 ml distilled
water.

VI. 0.1M Na2S2O3 solution:

It is prepared by dissolving 6.204 g of LR grade Na2S2O3 in 250 ml distilled
water.

VII. 1M Cu(NO3)2 solution:

The compound is highly hygroscopic, hence, 150 g of LR grade Cu(NO3)2.3H2O
is dissolved in 500 ml distilled water. 10 ml of this solution is 10 times diluted
and the concentration of the resulting solution is determined by titrating with
standard sodium thiosulfate solution. Then exact concentration of stock solution
is calculated. The required volume of stock solution is diluted to make 250 ml
of exactly 1M Cu(NO3)2 solution.
17
VIII. 2.5M acetic acid & 2.5M sodium acetate solution (buffer solution):
It is prepared by dissolving 14.7 ml of LR grade CH3COOH & 34 g of LR grade
sodium acetate in 100 ml distilled water. The pH of this solution was checked
with pH-meter.
IX. 0.1 M EDTA solution:
It is prepared by dissolving 9.306 g of LR grade
[CH2.N(CH2.COOH)CH2.COONa]2.2H2O in 250 ml distilled water.

2.3 Characterization of copper ion-selective electrodes:

2.3.1 Response of Cu-ion-selective electrode to Cu++ ions:

For the characterization of copper ion-selective electrode Ion Analyzer
(Model L1-126) produced by Elico Ltd, Hyderabad, India was used. Ion
analyzer is a digital millimeter, which can measure emf, concentration, and
temperature. Ion analyzer contains three channels for reference electrodes &
three for ion-selective electrodes. One reference electrode can be used for three
ion-selective electrodes i.e. the reference electrode channels are inter-connected.
For reference electrode Ag/AgCl combined with glass electrode can be used and
salt bridge is not necessary for coupling with copper ion-selective electrode.
Both electrodes can be deep into the test solution.
The electrochemical cell is represented as:

Ag/AgCl, KCl (0.1M) // test solution /Cu-ion-selective electrode.

The Cu++ solution of 10-1mole/L to 10-6 mole/L concentrations were

prepared by serial dilution of 1 mole/L Cu++ solution. 50 ml of each solution
was taken into 100 ml beaker and 1 ml 5M NaNO3 solution was added to keep
the constant ionic strength at 0.1 M. The pH of the solution was fixed by adding
1 ml acetic acid-sodium acetate buffer solution. Then emf of each solution was
measured by stirring the solution continuously using magnetic stirrer. A

18
calibration curve of observed emf versus negative logarithm of [Cu++] was
plotted.

2.3.2 Response of Cu-ion-selective electrode to S-- ions:

To study the response of Cu ion-selective electrode for S-- ions the same
procedure as described for Cu++ ions (section 2.3.1) was adopted except the
addition of NaNO3 solution and buffer solution. Here the entire S-- solutions
were prepared in 0.1 M NaOH and 1 mg/ml ascorbic acid was added as an
antioxidant.

2.3.3 Response of Cu-ion-selective electrode (CuS/Ag2S pressed pellet

electrode) to Ag+ ions:
To study the response of Cu ion-selective electrode for Ag+ ions the same
procedure as described for Cu++ ions (section 2.3.1) was adopted except the
addition of buffer solution.

2.4 Determination of Cu++ in aqueous solution by direct potentiometry:

For the determination of Cu++ in aqueous solution by direct potentiometry
method, 50 ml Cu++ solution of the concentration within the linear range of
electrode performance was taken in a 100-ml beaker. 1 ml 5M NaNO3 and 1 ml
acetic acid-sodium acetate buffer was added. Then emf was measured using Cu-
ion-selective electrode by continuously stirring the solution. From the observed
emf the concentration of the solution was determined using calibration curve.

19
2.5 Potentiometric titration:
The applicability of the Cu-ion-selective electrode as an indicator
electrode for the potentiometric titration was examined by the titration of:
(i) 50 ml of 0.01M Cu++ solution with 0.05M EDTA solution.
(ii) 10 ml of 0.01M EDTA with 0.01M Cu++ solution.
(iii) 25 ml of 0.01M Cu++ solution with 0.05M EDTA solution.
(iv) 10 ml of 0.01M Cu++ solution with 0.01M EDTA solution.
In case of (ii) & (iv) the volume was made more than 25 ml by adding distilled
water.

pot
2.6 Selectivity coefficient, K Cu ,B :

pot
The selectivity coefficient K Cu , B with different metal ions was

determined by mixed solution method following standard addition technique. In

this method the concentration of copper ions was varied from 10-1 mole/L to 10-
5
mole/L and the concentration of interfering ions (B) was kept constant. The
potential of the Cu-ion-selective electrode under investigation was plotted
against -log [Cu++] and for determination of selectivity coefficient substituted in
equation (4).

2.7 Determination of Fe3+ in aqueous solution:

For the quantitative estimation of Fe3+ in aqueous solution by indirect
potentiometric titration, 5 ml of 0.01M Fe3+ solution was taken in a beaker.
Then 10 ml of 0.01M EDTA solution and 1 ml acetic acid-sodium acetate buffer
solution was added to that solution. The unreacted EDTA was then back titrated
with 0.01M Cu++ solution using Cu-ion-selective electrode as an indicator
electrode.

20
2.8 Determination of Cr3+ in aqueous solution:
For the quantitative estimation of Cr3+ in aqueous solution by indirect
potentiometric titration, 10 ml of 0.01M EDTA solution was taken with 5 ml of
0.01M Cr3+ solution and 1 ml acetic acid-sodium acetate buffer solution. Total
volume was made 25 ml by adding distilled water. The mixture was boiled for
15 minutes and cooled. Then the unreacted EDTA was back titrated with 0.01M
Cu++ solution using Cu-ion-selective electrode as an indicator electrode.

21
 CHAPTER-THREE
RESULTS AND DISCUSSION

3.1 Characterization of Cu-ion-selective electrodes:

Among the pressed pellet membrane ion-selective electrodes, silver
sulfide based electrodes are most well-behaved and extensively investigated
electrodes. By incorporation of appropriate silver salts, electrodes selective to
Ag+, Cl-, Br-, I- & S-- have been fabricated and widely used for the analysis of
these ions in different analytical purposes [1,7,8,9,12]. There has been a report
in the literature, by incorporation of sulfides of heavy metal in silver sulfide,
ion-selective electrodes selective to the heavy metal ions can be fabricated
[1,12]. In this direction, attempt was made to construct Cu-ion-selective
electrode by incorporation of copper sulfide into silver sulfide matrix. Since the
pressed pellet contains both silver sulfide and copper sulfide, so there is a
choice to use silver or copper metal contact between inner surface of the
membrane and cable. The internal potentials produced will depend upon the
nature of the metal. For this two electrodes were constructed, in one copper
metal and in another silver metal were used for internal contact.
Irrespective of the nature of metal contact, the response of electrodes with
respect to Cu++ ion is far from satisfactory. The electrode responses in Nernstian
-1 -2
manner only in the concentration range from 10 mole/L to 10 mole/L of
Cu++ ion. In this range the results are quite reproducible. The useful range of the
electrode is so limited that the electrode is of not much practical importance for
the determination of Cu++ in aqueous solution. The mole ratio of the Ag2S &
CuS in the commercial Cu-ion-selective electrode is not reported in the
literature. When the percentage of CuS in the Ag2S/ CuS electrode is high the
electrode piles up in layer and disintegrate quite easily. Therefore, the mole
percentage of CuS in Ag2S and CuS was made small. Copper sulfide being a

22
non-stoichiometric compound, the activity of copper ions in copper sulfide
depends upon the method of preparation of copper sulfide and treatment of the
precipitate. Owing to this standard electrode potential of copper sulfide based
ion-selective electrode may vary from electrode to electrode.
Surprisingly, both the electrodes did not show stable and reproducible
result for S-- ions and for Ag+ ions. Both the electrodes did not follow Nernstian
behavior. Hence the electrode, fabricated in the laboratory containing mole ratio
95:5 of Ag2S and CuS were not useful for the determination of Ag+ or S-- ions.
Pure silver sulfide pressed pellet electrode had been found to be an
excellent ion-selective electrode for monitoring Ag+ or S-- in aqueous solution
[39]. The purpose of incorporation of CuS in Ag2S was to make the electrode
sensitive to Cu++. In fact incorporation of CuS, made the electrode sensitive to
Cu++ but insensitive to Ag+ or S--. The objective of the present investigation was
to make Cu-ion-selective electrode. Hence, no further investigation was carried
out to make the electrodes sensitive to Ag+ or S--. During coprecipitation of CuS
and Ag2S from the solution excess of S-- was added. Hence, there is a lack of
excess of silver in the precipitate but an excess of S-- and CuS being non-
stoichiometric compound made the electrode insensitive to silver ions. The
pressed pellet Ag2S/CuS electrode though response to Cu++ but response range
was limited to decimolar range. Perhaps by strict controlling the stoichiometry
of CuS and by appropriately controlling the mole ratio of Ag2S:CuS, electrode
more sensitive to Cu++ may be possible to fabricate. But this work had been left
for further investigation.
Another electrode sensitive to Cu++ is a thin film CuS deposited in
different material. These days thin film CuS ion-selective electrode is drawing
greater attention for the analysis of Cu++ in solutions. Such thin film electrodes
are extremely cheap but response range, stability, reproducibility and response
time depends upon the method of fabrication and pre-treatment of the
electrodes. The life of CuS thin film deposited on graphite support may be low
23
but construction of such electrode is not difficult. It can be readily fabricated in
the laboratory. Such electrodes must be well characterized before putting them
into analytical purpose with respect to reproducibility, Nernstian behavior,
response time etc.
After unsuccessful attempt to fabricate pressed pellet Cu-ion-selective
electrode, an attempt was made to fabricate Cu-ion-selective electrode by
depositing thin film of CuS on the graphite rod taken from used dry cell. Ruzika
type graphite-CuS selectrode and other thin film deposited electrode had been
fabricated and characterized by a number of authors [41-43]. A thin film of CuS
was deposited on graphite rod by carrying out the precipitation reaction at the
graphite rod itself. Such electrode is quite easy to fabricate, extremely simple
and can be constructed within a day.
The typical plot of observed emf of the cell (CuS-graphite Cu-ion-
selective electrode coupled with Ag/AgCl reference electrode) as a function of
negative logarithm of Cu++ concentration is shown in figure (A.1). The points in
the graph are experimental values and the line is the line of best fit obtained by
regression analysis. The slope of the line is found to be 30 mV per decade
change in concentration of Cu++ with standard deviation ±0.7. The observed emf
of the cell was reproducible for one day and on the following day a drift in the
emf was observed. However, the electrodes still follow the Nernstian behavior
with constant slope. During six months the standard electrode potential of the
cell (CuS-graphite Cu-ion-selective electrode coupled with Ag/AgCl reference
electrode) varied from 259 mV to 284 mV but the slope remained almost
constant. So, the electrode can be use for the determination of Cu++ in aqueous
solution but must be calibrated before use like glass electrode. The slight change
in standard electrode potential of the cell may be due to the oxidation of
measuring surface of the membrane material in the CuS-graphite Cu-ion-
selective electrode. If the electrode is stored in dry, the electrode need to be
activated by immersing the electrode in 10-2 mole/L Cu++ solution for about five
24
minutes. Storing the electrodes in 10-2 mole/L Cu++ solution did not improve the
performance of the electrode.
The CuS-graphite Cu-ion selective electrode followed the Nernstian
behavior from 10-1 mole/L to 10-4 mole/L Cu++ in aqueous solution and attained
equilibrium potential within 30 seconds. The dynamic response of the electrode
is shown in figure (A.2). When the concentration of Cu++ is less than 10-4
mole/L, the response of the electrode is quite sluggish and takes 15 minutes or
more to attain equilibrium potential.

3.2 Determination of Cu++ in solution by direct potentiometry:

Ion-selective electrodes have extended the field of direct potentiometry.
The direct method is, as the name implies, the most straightforward technique
and is the technique of choice whenever possible. With calibration standards
that are appropriate for the particular test sample, it is possible to make
measurement of concentration by means of ion-selective electrode. The one
requirement is that the concentration of test sample must be within the linear
response range of the electrode. The sample to be analyzed is pretreated as
required and the electrodes are immersed in it. The equilibrium cell potential is
then measured and related to the determinand ion concentration by means of
calibration curve.
Alternatively, the concentration of the determinand solution can be
symmetrically calculated. The potential of the cell is given by the equation:
2.303RT
Ecell = E + log[Cu + + ] ……… (5)
nF

Or Ecell = E + K . log[Cu + + ]
Where E is the standard electrode potential of the cell which can be
evaluated from the intercept of Ecell versus -log[Cu++] plot and K is a constant,
the value of which can be obtained from the slope of the plot.

25
 ++ Ecell − E
Or [Cu ] = Anti log ……………………. (6)
K
To determine the concentration of Cu++, the Cu-ion-selective electrode is
deeped into the solution and emf of the solutions is measured. The concentration
of Cu++ solution was then calculated using equation (6). Table 3.1 shows the
actual concentration of Cu++ solution and the concentration determined using
thin film CuS ion-selective electrode along with percentage error. In the
concentration range from 10-2 to 10-4 mole/L Cu++ the experimental error is not
more than 5%. For divalent metal ions this degree of accuracy by direct
potentiometry is generally considered as an excellent result.

Table3.1- Expected and calculated concentration of some Cu++ solutions.

S. Concentration of Cu++ Concentration of Cu++ Error
No. taken. (mole/L) determined from equation %
(13). (mole/L)
1. 4 × 10-2 3.95 × 10-2 1.25
2. 8 × 10-3 7.871 × 10-3 1.62
3. 4 × 10-3 3.807 × 10-3 4.82
4. 8 × 10-4 7.575 × 10-4 5.31

26
3.3 Interferences by different metal ions:
The plot of emf of the cell versus –log[Cu++] shown in figure (A.1) is
linear upto the 1 ×10-4 mole/L Cu++ concentration with slope equal to 30 mV.
This means that CuS-graphite Cu-ion-selective electrode responses in a
Nernstian manner upto 1 ×10-4 mole/L Cu++ concentration. When the
concentration of Cu++ is less than 1 ×10-4 mole/L the curve becomes non-linear.
In presence of interfering ion, the curvature in the emf of the cell versus –
log[Cu++] starts early and departure becomes more and more pronounced with
increase in concentration of interfering ion. This deviation from the linear
response of Cu-ion-selective electrode towards the Cu++ determines the
selectivity towards Cu++ against other interfering ions. Figure (A.11) shows the
interference of different metal ion in the determination of Cu++ by Cu-ion-
selective electrode.
pot
The selectivity coefficient ( K Cu , B ) is a parameter which describes the

relative response of an ion-selective electrode towards interfering ion in

comparison with the main determinand ion. An empirical equation given by
Nicolsky and Eisemann is written as:
2.303RT
E = E0 ± log(a A + ∑ K Apot, B .aBn A nB
) ………..(4)
nA F B

Where nA and nB are the charges on the primary and interfering ions A &
B respectively and aA and aB are their respective activities.
When both ions are contributing to electrode response, then

a A = K Apot, B .aBn A nB
………………………..(7)

If the activity of A at which this equality occurs is a'A and the activity a'B,
then the electrode potential is given by,
2.303RT
E = E0 ± log(a ' A + K Apot, B .a 'nBA nB
)
nA F
27
 2.303RT
Or E = E0 ± (2a ' A ) ……………………………... (8)
nA F
The difference between the electrode potentials in solution of A with and
without B at activity a'B is therefore given by,
2.303RT
ΔE = log(2a 'A − a A' )
nA F
2.303 RT
= log 2
nA F
18
= mV At 25oC …………………………………….(9)
nA
Thus, finding the value of a'A from the plot of emf of the cell, E versus –
log[Cu++] at the point where the experimental curve deviates from the
extrapolation of Nernstian line by 9 mV and substituting the value in equation
(10) the selectivity coefficient is then calculated.

a' A = K Apot, B .a'nBA nB

…………………………….. (10)
pot
The value of K Cu , B obtained by mixed solution method for Cu-ion-

selective electrode are tabulated in table 3.2. The presence of 0.1 M Ca++, Zn++,
Co++ did not interfere in the determination of Cu++ by the present CuS-graphite
ion-selective electrode.

28
 Table 3.2: Selectivity coefficient of some metal ions.
S. Foreign Concentration of foreign pot
K Cu ,B
No. ion ions. (mole/L)
1 Pb++ 0.1 1 ×10-2
2 Cd++ 0.1 5.62 ×10-4
3 Ag+ 1 ×10-4 4.46 ×104

pot
Significance of K Cu , B :

pot
The selectivity coefficient K Cu -2
, Pb =1×10 signifies that the electrode is

100 times more responsive to copper ion than lead ions. If concentration of Pb++
in the Cu++ solution is 100 times less than that of Cu++ then the Pb ++ does not
interfere the response of the electrode to Cu++ . The selectivity coefficient
pot
K Cu , Cd = 5.62 ×10 means the electrode is much more responsive for copper
-4

ions and cadmium ion only slightly interferes in the electrode response. The
pot
selectivity coefficient K Cu , Ag = 4.46×104 is high value which means the

electrode is much more responsive to silver ions than copper ions i.e. the
electrode responses like silver selective electrode. Thus, there should be absence
of silver ions in the solution for the determination of copper ion.

3.4 Potentiometric titration:

In potentiometric titrations absolute potentials are not usually required,
and measurements are made while the titration is in progress. The equivalence
point of the reaction will be revealed by a sudden change in potential in the plot

29
of emf readings against the volume of the titrating solution. The solution must
be stirring during titration.
The applicability of the CuS-graphite ion-selective electrode as an
indicator electrode for the potentiometric titration is examined by titrating
different concentration of Cu++ solution with EDTA solution and EDTA
solution with Cu++ solution. When Cu++ solution is titrated with EDTA solution,
the observed emf decreases in each addition of EDTA solution due to decrease
in free Cu++ in the solution and at equivalence point there is dramatically
decrease in observed emf. At that point nearly all the Cu++ has been titrated by
the EDTA solution. To locate the end point precisely a differential curve was
drawn.
A typical potentiometric titration curve for the titration of 10 ml of 0.01
M Cu++ solution with 0.01 M EDTA solution is shown in figure (A.3) and the
differential curve of that titration is shown in figure (A.4).
The titration was also repeated by titrating EDTA solution with Cu++
solution. The observed emf increases in each addition of Cu++ solution due to
increase in free Cu++ in the solution and at equivalence point there is
dramatically increase in observed emf. At that point nearly all the EDTA
solution has been titrated by the Cu++ solution. After that the increase in emf is
due to the increase in free Cu++ in the solution. A typical potentiometric titration
curve for the titration of 10 ml of 0.01 M EDTA solution with 0.01 M Cu++
solution is shown in figure (A.5) and the differential curve of that titration is
shown in figure (A.6). The results of the potentiometric titration are in good
agreement with expected value within 2% experimental error.

3.5 Determination of Fe3+ in aqueous solution:

The concentration of Fe3+ in aqueous solution has been determined by
indirect potentiometric titration using Cu-ion selective electrode. First the Fe3+
is reacted with excess EDTA and unreacted EDTA is then estimated by back
30
titration with Cu++ solution using Cu-ion-selective electrode. The stability
constant of the Fe(III)-EDTA complex is 25.1 and that of Cu(II)-EDTA is 18.8.
When excess EDTA is reacted with Fe3+ solution in acidic medium, the Fe3+
forms 1:1 complex with its equivalent amount of EDTA. The Cu++ does not
replace the Fe3+ from the Fe(III)-EDTA complex due to high stability than
Cu(II)-EDTA complex. Thus there is no possibility of displacement reaction in
the mixture on addition of Cu++ solution and added Cu++ forms complex only
with unreacted EDTA. The excess EDTA can be determined by potentiometric
titration with Cu++ using Cu-ion-selective electrode as an indicator electrode.
First the cell emf remains almost constant in each addition of Cu++ due to
reaction of added Cu++ with EDTA in the solution and at equivalence point the
cell emf increases dramatically. At that point all the EDTA has been reacted
with Cu++ and added Cu++ remains as free Cu++ in solution. Hence, after the
equivalence point the cell emf increases continuously in each addition of Cu++
due to increase in free Cu++ in the solution.
The typical plot of potentiometric titration of 10 ml of 0.01M EDTA and
5 ml of 0.01 M Fe3+ mixture with 0.01M Cu++ solution is shown in figure (A.7)
and the differential curve of that titration is shown in figure (A.8). The results
obtained by this method are in agreement with expected value within less than
4% experimental error.

3.6 Determination of Cr3+ in aqueous solution:

The concentration of Cr3+ in aqueous solution has been determined by
indirect potentiometric titration using Cu-ion selective electrode. First the Cr3+
is reacted with excess EDTA and unreacted EDTA is then estimated by back
titration with Cu++ solution using Cu-ion-selective electrode. The stability
constant of the Cr(III)-EDTA complex is 24.0 and that of Cu(II)-EDTA is 18.8.
When excess EDTA is boiled with Cr3+ solution for about 15 minutes in acidic
medium, the formation of Cr(III)-EDTA complex takes place. Cr3+ forms
31
complex with its equivalent amount of EDTA and there remains unreacted
EDTA in the solution. The Cu++ does not replace the Cr3+ from the Cr(III)-
EDTA complex due to high stability than Cu(II)-EDTA complex. Thus there is
no possibility of displacement reaction in the mixture on addition of Cu++
solution and added Cu++ forms complex only with unreacted EDTA. The excess
EDTA can be determined by potentiometric titration with Cu++ using Cu-ion-
selective electrode as an indicator electrode. First the cell emf remains almost
constant in each addition of Cu++ due to reaction of added Cu++ with EDTA in
the solution and at equivalence point the cell emf increases dramatically. At that
point, all the EDTA has been reacted with Cu++ and added Cu++ remains as free
Cu++ in the solution. Hence, after the equivalence point the cell emf increases
continuously in each addition of Cu++ due to increase in free Cu++ in the
solution.
The typical plot of potentiometric titration of 10 ml of 0.01M EDTA and
5 ml of 0.01 M Cr3+ mixture with 0.01M Cu++ solution is shown in figure (A.9)
and the differential curve of that titration is shown in figure (A.10). The results
obtained by this method are in good agreement with expected values within less
than 4% experimental error.

32
 CONCLUSION

It is known that incorporation of silver halide on Ag2S, made the

electrode selective to halide ion [1,39,40]. In line with this CuS was
incorporated into Ag2S and pressed pellet electrode was fabricated with the
intention of making electrode selective to copper ions. The electrode prepared
by incorporation of 5 mole percentage of CuS in Ag2S did response to Cu++ in
aqueous solution but the detection range was far from satisfactory. The
unsatisfactory functioning of electrode may be due to the low percentage of CuS
in the mixed sulfide and inability to control the stoichiometry of the CuS
appropriately in the final electrode. If percentage of CuS could be increased and
stoichiometry of CuS could be controlled properly, then well behaved electrode
sensitive to Cu++ may be successfully prepared. But this aspect of investigation
is left for future study.
Ruzika had prepared Cu-ion-selective electrode called “Selectrode” by
smearing CuS precipitate in graphite surface of the graphite rod extracted from
dry cell. But the electrode potential of such electrode is affected by the redox
system of the electrolytic solution. Hence, thin film CuS-electrode was prepared
by depositing thin film of CuS by chemical reaction on the porous surface of
graphite rod. The graphite rod was taken from used dry cell. Thin film CuS-
electrode, thus prepared, was found to be sensitive and selective to Cu++
between pH range 4 to 5. The response of the electrode towards Cu++ was quick
and stable potential could be obtained within less than 30 seconds. The change
of electrode potential per decade change in concentration of Cu++ was found to
be equal to 30 mV with standard deviation ± 0.7. Slight drift in standard
potential was observed with ageing of the electrode but the slope was almost
constant. The electrode followed Nernstian behavior from 10-1 to 10-4 mole/L

33
Cu++ concentration. The electrode can be successfully used for the
determination of Cu++ in aqueous solution by direct potentiometry and
potentiometric titration with EDTA. The electrode was found to be suitable
indicator electrode for the determination of Cr3+ and Fe3+ in aqueous solution by
indirect potentiometric titration with Cu++.
The electrode response to Cu++ was not affected by the presence of Co3+,
Zn2+ & Ca2+ in the test solution, slightly affected by Pb2+ & Cd2+ and strongly
affected by Ag+. The selectivity coefficient with Ag+, Pb2+ and Cd2+ are found to
be 4.46x104, 1x10-2 and 5.62 x 10-4 respectively.
Thus the thin film CuS deposited on graphite rod by chemical reaction at
graphite surface is a low cost copper ion-selective electrode which can be used
to determine the concentration of Cu++ in the range 10-1 to 10-4 mole/L. The
electrode thus prepared can be used as an indicator electrode for indirect
potentiometric titration of Cr3+, Fe3+ with Cu++.

34
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37
 APPENDIX

300

250
Emf of the Cell in mV

200

150

100

50

0 1 2 3 4 5 6 7
-Log[Cu++]

Fig. A.1 : Cell emf as a function of negative logarithm of Cu++ ion concentration.

38
 290

270 1×10-1M
Emf of the Cell in mV

250
1×10-2M
230

210 1×10-3M

190
1×10-4M
170

150
0 50 100 150 200 250 300 350
Time in Seconds

Fig. A.2 : Dynamic Response of CuS-graphite Cu-ion selective electrode to Cu++ ion
concentration.

39
 230
210
Emf of the Cell in mV

190
170
150
130
110
90
70
50
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Volume of EDTA Solution in ml.

Fig. A.3 : Potentiometric titration curve for titration of 10 ml of 0.01 M Cu++ with
0.01 M EDTA solution.

200
End point
180
160
ΔE/ΔV, mV/ml

140
120
100
80
60
40
20
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Volume of EDTA Solution in ml.

Fig. A. 4 : Differential Curve.

40
 220

200
emf of the Cell in mV

180

160

140

120

100
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Volume of Cu++ Solution in ml

Fig. A.5: Potentiometric titration curve for titration of 10 ml of 0.01 M EDTA with
0.01 M Cu++ solution.

70
End point
60

50
ΔE/ΔV, mV/ml

40

30

20

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Volume of EDTA Solution in ml.

Fig. A.6: Differential Curve.

41
 220

200
emf of the Cell in mV

180

160

140

120

100
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Volume of Cu++ Solution in ml

Fig. A.9: Potentiometric titration curve for titration of 5 ml of 0.01 M Cr3+ and 10ml
0.01 M EDTA mixture with 0.01 M Cu++ solution.

90
End point
80
70
ΔE/ΔV, mV/ml

60
50
40
30
20
10
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Volume of Cu++ Solution in ml.

Fig. A.10: Differential Curve.

42
 220

200
emf of the Cell in mV

180

160

140

120

100
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
++
Volume of Cu Solution in ml

Fig. A.7: Potentiometric titration curve for titration of 5 ml of 0.01 M Fe3+ and 10ml
0.01 M EDTA mixture with 0.01 M Cu++ solution.

80
70 End point

60
ΔE/ΔV, mV/ml

50
40
30
20
10
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Volume of Cu++ Solution in ml.

Fig. A.8: Differential Curve.

43
 280
260
240
emf of the Cell in mV

220
200
III
180
IV
160 II

140
120 I

100
0 1 2 3 4 5 6
- Log [Cu++]

Fig. A.11: The effect of foreign ions to the response of Cu-ISE: I, Cu++ only; II, 0.1
M Cd++; III, 1×10-4 M Ag+; IV 0.1M Pb++.

44