1

In recent years, the importance of low concentration has tremendously increased

both in science and technology. In fact, it is required in all the fields of activity
associated with high purity substances, including research, manufacture and utilization.
For the typical research worker in chemistry, biochemistry, geology and some other
sciences, the acquisition of quantitative information represents a significant fraction of
his laboratory efforts and hence the analytical procedures specially those which can
accomplish the determination of low concentrations with great accuracy and precision,
are among the important tools employed by him in pursuit of his research goals. It is
certain that further developments in science and technology will make still higher
demands in low concentration analysis, so that new methods will be necessary. In view
of this situation, present work was undertaken with the aim of evolving new
amperometric methods of determining low concentrations of metal ions. As is well
known, amperometric titrations have a very wide field of applicability and they are
more accurate and precise than their parent technique, polarography. Precision,
accuracy and reproducibility of a few tenth of a percent are commonly attainable with
solutions of concentrations 10-4M or greater while more dilute solutions upto 10-5M
have often been estimated within the inaccuracy limit of ±2%, which compares
favourably with that obtained with other sophisticated methods in vogue for the
analysis of very dilute solutions.

AMPEROMETRY

Amperometry is extended technique of D.C. polarography. This technique is

well suited for trace level determination of metal ions. One of the most distinguishing
feature of this technique is that like other voltammetric techniques, it can also indicate
the nature of the species dissolved in the solution and does not merely limit itself to the
total elemental content as is the case with sophisticated non-electrochemical methods
such as neutron activation analysis [1,2], X-ray fluorescence [3-5] and atomic
absorption spectroscopy [6-8]. This method of analysis was developed by Jaroslav
Heyrovsky [9] in 1922. He received Nobel Prize in 1959 for developing this technique
using dropping mercury electrode as the working electrode. He called the recorded
current potential curve as polarogram and introduced the term polarography.

Polarography involves transfer of electrons between the d.m.e. and the ions,
atoms or molecules present in the solution that surrounds it in the cell. Oxidation of the

2
electro-active species at the d.m.e. gives anodic wave while reduction yields cathodic
wave. Anodic waves are less common as only a small range of oxidation potentials can
be covered with the d.m.e. before oxidation of the electrode itself commences. Organic
compounds like hydroquinones and mercaptans and some inorganic anions are known
source of anodic waves while most of the metal cations and organic functional groups
yield reduction (cathodic) waves. Polarographic behaviour of any species is unique for
a given set of experimental conditions, making the technique unique for selective
analysis. Conventional amperometric technique consists of an electrometric titration,
which uses the polarographic wave as the basis. The current flowing at the d.m.e. is
measured as a function of the potential imposed over it. When a potential is reached at
which the electro-active species in the solution is reduced or oxidized, the current
begins to rise very sharply with increasing potential until it is limited by the rate of
arrival of the species at the d.m.e. surface by the process of diffusion alone (the whole
exercise being carried out in quiet solution in the presence of sufficient concentration of
some indifferent electrolyte, called supporting electrolyte). From now as the current-
potential curve level off upto the point where hydrogen evolution takes over. The basis
for D.C. amperometry employing d.m.e, is the Ilkovic equation given below:

id= 607 n D1/2 c m2/3 t1/6

Where

id = Average diffusion current in microampere during the life of a mercury drop.

n = No. of electrons involved in the electrode reaction at the d.m.e.
D = Diffusion coefficient of the electro-active species in cm/sec.
c = Concentration of electro-active species in millimoles/litre.
m = Rate of flow of mercury from the d.m.e. expressed in mg/sec.
t = Drop time or time in seconds taken by a drop of mercury to fall from the capillary.

It is obvious that with all other factors remaining constant, the diffusion current
is directly proportional to the concentration of the electro-active species.

Polarography can be used as the basis of an electrometric titration method

(amperometry) provided the diffusion current, is yielded by the titrant, the substance
being titrated, both or a reaction product of the two. Sometimes, if none of these is
polarographically active, the titration can still be accomplished with the help of an

3
electrometric indicator that gives a wave. Charlot and Tremillon [10] have published an
extensive review of the literature on the use of such indicators. All amperometric
titrations are performed by measuring the current after the addition of each of a fairly
small number of aliquots of reagent. If the titration is performed at a potential where
the reduction of dissolved oxygen would contribute to the measured current, it is
usually necessary to remove any oxygen added with the reagent by bubbling inert gas
through the cell for an appropriate length of time after each addition. The reaction
between the titrant and the substance being titrated may result in the progressive
precipitation, oxidation, reduction or complexation and thus bring about a change in the
concentration of the depolarizer. The end point in such titrations is found graphically
and the curve is a plot of limiting current corrected for dilution by the reagent and if
necessary, for any residual current, as a function of the volume of titrant. The applied
e.m.f is kept constant throughout the process. Ideally, the titration curve consists of two
straight lines intersecting each other at the equivalence point.

Sometimes an amperometric curve is obtained which looks almost linear. The

reason being that there is no chemical reaction between the substance being titrated and
the titrant but one gives cathodic and the other gives anodic wave and the limiting
region of both are present at the titration voltage. As the titration advances, the other
gradually compensates one type of current yielding the first linear segment of the curve
that intersects the zero line (or residual current line) at the equivalence point (null
point). After this as the titration proceeds further, the same linear segment forges ahead
on the other side of the zero line with only slight or sometimes almost invisible change
of slope. In such cases, at times, a strictly linear curve with absolutely no change in
slope at the null point may be obtained. But this is a very rare situation and happens
only when the diffusion coefficients of the two species are identical. The above
electrometric titration method was first suggested by Heyrovsky and Berezicky [11] in
1929 and later developed by Majer and Spalenka [12], who also suggested the name
polarographic titration or polarometric titration. However, Kolthoff and Pans [13]
proposed the term "amperometric titration" to replace one suggested by Majer and
Spalenka, as the method involved measurement of current. The latter term is now
almost universally accepted though some workers, especially in the Czech Republic
still favour the name “Polarometric Titrations.”

4
DIFFERENT ELECTRODES USED IN AMPEROMETRY

Though the traditional D.C. amperometric titrations are performed with d.m.e.
as the indicator electrode, other electrodes have also been used for the purpose.
Platinum wire electrode, being rotated at constant speed of 600 r.p.m. or more, has been
used on a large scale. This was first introduced as an analytical tool in 1941 by Latinen
and Kolthoff [14]. Mechanical mixing help in bringing the electroactive species to the
electrode surface, besides diffusion. Consequently, limiting currents are much higher,
about twenty times, in comparison to those obtained with d.m.e. This fact is quite
attractive from the point of view of amperometry though the utility of r.p.e. is still
restricted due to following limitations:

1. Limiting currents are not very reproducible and often influenced by the previous
history of the electrode.
2. High currents obtained with the electrode, make it particularly sensitive to
traces of oxygen in the solution.
3. Hydrogen over-voltage for this electrode is low and greatly restricts the range of
potentials for study. In fact, potentials more negative than -1.00V (Vs S.C.E.)
cannot be applied even in almost neutral solutions. Hydrogen evolution begins
at much more positive potentials in acidic solutions.

Vibrating platinum electrode has also been used and the first account of this
type of electrode was given in 1948 by Harris and Lindsey [15]. Rotating
microelectrode of gold, graphite and aluminium, tantalum and certain other material
have also been used at times by different workers [16]. Stationary glassy carbon disc
electrode has also found application at the hands of certain workers [17]. However, all
these solid electrodes suffer from one or the other serious drawback. Impracticability of
any general theoretical treatment of the limiting currents obtained with them has also
seriously hampered their application as common analytical tools.

In amperometric titrations d.m.e. is used as an indicator electrode.

5
ADVANTAGES OF DROPPING MERCURY ELECTRODE

Some advantages of dropping mercury electrode are as under:

1. No chance of poisoning, as fresh electrode is formed after approximately every

three second.
2. Each drop behave exactly in the same way as the preceding one and the average
current measured with the galvanometer is accurately reproducible from drop to
drop for a given applied potential.
3. Mercury is noble metal so there is no reaction with constituent of electrolytic
solution.
4. It adopts the applied potential instantaneously so is ideally polarisable.
5. A jerk or shock that causes one drop to behave erratically does not affect the
following one; the d.m.e is thus much less sensitive to mechanical disturbance
than is a stationary microelectrode.
6. Dropping mercury electrode (d.m.e.) has small dimension hence electrolysis is
possible in small volume of the solution and very small number of cations
reduced or anions oxidized in electrolysis, so that same solution can be used for
hours, even days.
7. With mercury electrode, it is possible to reach more negative potential in
comparison to any metal electrode, before evolution of hydrogen begins.
Consequently, a large number of reactions can be studied.

AMPEROMETRIC TITRATIONS WITH TWO INDICATOR ELECTRODES

Two identical stationary microelectrodes can also be used to perform titrations

by following current as a function of volume of titrant. The technique is sometimes
referred to as “dead-stop end point technique”, as the current at the end point is zero or
near zero. History of these biamperometric titrations begins with the work of Foulk and
Bawden [18]. However, two titrations which may very well fall in this category were
reported much earlier [19,20] though they went almost unnoticed. Biamperometric
titration technique is also quite simple, sensitive, rapid and accurate like amperometry.
However, it lacks the universal applicability of amperometric titrations and its use has
remained largely restricted to redox systems and certain precipitation reactions.

MERITS AND DEMERITS OF AMPEROMETRY

6
 1. Amperometric titrations have a wide field of applicability and different types of
amperometric titrations can be accomplished successfully e.g.
a) Precipitation titrations
b) Acid base titrations
This is because the readings near the equivalence point have no special
significance; hence slight soluble reaction can also be determined. Readings are
recorded in the region of excess titrant or excess reagent where solubility or hydrolysis
is suppressed by the mass action effect. The point of intersection of two lines gives
equivalence point.
2. It is highly sensitive technique and used for very dilute solution upto ppm level.
3. The titration can usually be carried out rapidly since the end point is found
graphically.
4. This technique requires simple manual assembly and no prior calibration.
Recording of whole polarogram is not necessary.
5. It does not require determination of capillary characteristics and also the
temperature need not to be adjusted or known as long as it is kept constant.
Additionally:
a) Relatively high solubility of the product
b) Low stability of the complex or
c) A slow reaction in the vicinity of equivalence point do not affect the accuracy
of estimations as the null point is obtained from the limiting current vs. volume
and the measurements of current near this point are of little significance in
locating it just as in other electrometric titrations. All the titrations can often be
carried out under conditions where visual or potentiometric methods are not
possible and it is unimportant whether the electrode reaction is reversible or not.
These titrations have also been used to study co-precipitation, adsorption and to
determine solubility product and stoichiometry [21].
6. Foreign salts may frequently be present without any interference and indeed
they are added as the supporting electrolyte in order to eliminate the migration
current.
The above discussion makes it apparent that amperometry has a very wide field
of applicability. It is also more efficient than the parent technique of polarography.
Precision, accuracy and reproducibility of a few tenth of a percent are easily achieved if
determination of concentration of solutions is 0.1mM or greater strength while this

7
limit for polarographic determination is ±1-2%. Even more dilute solutions, upto
0.01mM; can sometimes be estimated amperometrically within the inaccuracy limit of
±2%. The technique requires a simple manual assembly and no prior calibration.
Recording of the whole polarogram is unnecessary and the knowledge of the
characteristics of the capillary is not required. Similarly, the temperature need not be
adjusted or known as long as it is kept constant during the titration.

Amperometry has one limitation that one can determine the species (metal or
otherwise) only upto ppm level. This limitation is due to the fact that the metal current
(the variation in whose magnitude can be followed titrimetrically by gradually adding
the titrant which may be a redox, precipitating or complexing agent) becomes almost
negligible at desired lower concentrations. But even this limit can possibly be removed
and the sensitivity of the method can be increased upto ppb or even ppt level, if
catalytic waves of metals given in presence of some substance (catalysts) and often
characterized by very high magnitude of current proportional to the concentration of
metal are exploited for titrations. Examples can be taken of Rh(III) which gives such a
wave in presence of thiosemicarbazide [22,23] and Pd(II), again in the presence of this
very compound [24]. Catalytic hydrogen waves with organic thiocomponds containg –
SH, -S-S and C=S groups, in presence of some transition metals have also been
reported [25-34]. Calusaru [35] has made an analysis of different type of such waves,
while it must be conceded that such titration have rarely been reported [36,37], they
have a distinct probability and have great potentiality.

OBJECTIVE AND SCOPE OF THE PRESENT WORK

Coinage metals have always found large scale applications in the life of human
beings right since the beginning of the civilization. These as well as platinum metals
are now emerging as very important constituents of effective drugs also. Cisplatin, a
complex compound of platinum is very well known as an effective drug for certain
types of cancer. Similarly, Gold(I) thiomalate has been used for treating rheumatoid
arthritis for over 40 years [38]. Several uses of silver, based on antiseptic action of
small concentrations of silver ions have been developed in medicines [39]. Thiomalic
acid complex of silver(I) has been reported to posses substantial antimicrobial activity
[40]. Rh(III) and Pt(II) complexes of sulphanilamide have shown considerable
antitumor activity [41,42]. Similar activity has been reported in case of Pt(II) complex

8
of sulfamazine [42]. Ruthenium has been recognized as an important pollutant of sea
[43]. Copper is extremely important biologically as it is a constituent of several
metalloproteins and enzymes.

All these underline the need for development of new and cheap sensitive
methods of their estimation. A perusal of literature reveals the fact that the number of
known direct, sensitive amperometric methods for estimating most of these metals in
trace amounts is rather inadequate. Hence, it was thought desirable to develop new
methods and in view of the versatility of the d.m.e., this particular electrode was chosen
for this job.

BRIEF SURVEY OF REVIEW LITERATURE ON AMPEROMETRIC WORK

Appreciable amount of review literature on amperometric work is available. A

book entitled “Amperometric Titrations” has been published by J.T. Stock [44] in 1965
is a comprehensive work. Another very useful work a monograph captioned
“Amperometric titrations with thio organic reagents” were published by A.L.J. Rao and
Bikram S. Brar [45] in the year 1983. A number of review articles have made
appearance from time to time in distinguished journals. Some of them, which are more
important, are mentioned below.

A Russian chemist, Khadeev [46], reviewed the literature on the amperometric

determination of metals in 1970. Songina and Bessarabova [47] reviewed the use of 8-
mercaptoquinoline in amperometric titrations in 1974. Another review article by
Songina and Zakharov [48] appeared in 1974. Songina and Bessarabova [49] published
yet another review with 178 references in 1977. Ezerskaya [50] reviewed 117 research
papers on amperometric and coulometric methods for the determination of platinum
metals in 1981. Ikeda [51] reviewed 135 papers on amperometry in 1984. Agrawal and
Khatkar [52] published an article in 1995 reviewed the use of thiomalic acid for
analysis including the amperometric determination of metal ions. In addition,
amperometric work was regularly reviewed in even years in the journal “Analytical
Chemistry” upto 1984. Latest in the series is review by T. Chester Duda and S. Craig
Bruntllett has appeared in the Handbook of instrumental technique (Prentice Hall,
1997).

9
 Amperometry has found wide-spread application in industry. Maschler [53] has
discussed the suitability of the technique in industrial application in 1974. Chatten [54]
discussed the use of several electrochemical techniques including amperometry in the
pharmaceutical analysis in the year 1983. A similar paper [55] about the use of the
technique in studying the biological reactions appeared in 1975.

SELECTION OF THE LIGANDS

It was decided to employ organic sulphur acids for achieving the above
mentioned objectives. This was done in view of the acknowledged characteristics of
these compounds as avid complex former [45,56,57] and their susceptibility to undergo
oxidation by some of the metal ions [58]. Sulphur (thio) compounds are being
increasingly employed in the field of analytical chemistry for developing new methods
of quantitative estimation due to their ability to form complexes with a large number of
metal ions [56,57]. Such interactions are expected to bring significant changes in the
polarographic characteristics of the metal ion, providing a sound base for the
development of new amperometric methods, organic sulphur compounds containing –
SH group are also known to give anodic wave at d.m.e. [59-64] and the possibility of
exploitation of these for the purpose is an additional point in favour of the selection of
such compound as an amperometric reagent. In view of this, the author of this thesis
has pressed in to service the following organic sulphur compounds for achieving the
objectives:

i) Thioglycolic acid (TGA)

ii) Thiodipropionic acid (TDPA)
iii) Thiomalic acid (TSH)

It may be emphasized that the chemical composition of all the three ligands is
quite similar and yet significantly different. All of them contain one “soft” sulphur
donor atom in addition to “hard” oxygen donor atoms. While the first ligand contains
one –COOH group available for coordination, the second and third ligands contain two
in them for participate in complexation. It was expected that these distinctive features
would make the study interesting from the point of view of comparative ligational
behaviour of these ligands as the same might be manifested in the relative sensitivity of
the method developed.

10
 Success has been achieved in developing very sensitive new amperometric
methods for the estimation of coinage and platinum metal species:

Cu(II), Ag(I), Au(III), Ru(III), Rh(III), Pd(II), Os(VIII), Ir(III) and Pt(IV).

Interference of various foreign ions in each case has been checked and the
selectivity of the method established. Efficiency of the method developed has been
compared to the well known spectrophotometric methods as these are generally
regarded as the commonest method of determination of any species in highly dilute
solutions. On the basis of speed, convenience, accuracy and the concentration range of
the analyte, it is hoped that the new methods will go a long way to help the workers,
desirous of determining very low concentrations of the coinage and platinum metals.

SURVEY OF RELEVANT LITERATURE

Before we undertake a systematic study of the problem selected for research, it

would be pertinent to list the important coordination properties and other relevant
information regarding the chemistry of various metals, which constituent the main
focus of this study, and to give the survey of the work already done by other
researchers in the field. Since the work done upto 1962 has already been included in the
book “Amperometric Titrations” by J.T. Stock [44], we can confine our survey of the
relevant literature on amperometric determinations only to the work done after this
date. Since the d.m.e. has been predominantly adopted by various researchers and since
the present study also relies on this very electrode, particular mention of the electrodes
has generally been made in the survey only where special type of electrodes other than
d.m.e. were used by the workers concerned.

COINAGE METALS

Copper (Cu), silver (Ag) and gold (Au), known as coinage metals, are found in
elemental or native form at the earth's surface. They are called the currency metals,
since they have been used in coins since the beginning of money. They are also called
noble metals. They show only slight similarities in properties and considerable
differences.

General properties of copper

11
 Copper, the element No. 29, is a member of the first transition series having
valance shell electronic configuration as 3d104s1. Three oxidation states +1, +2 and +3
have been reported. +2 state is the commonest while +3 is rare and unstable in solution.
Cu(III), the species relevant rare and unstable in solution. Cu(II), the species relevant to
the present work can acquire coordination number 4 or 6 with equal ease. All sorts of
geometries, tetrahedral, square-planar and octahedral have been reported though they
are often not sharply distinguished because of the strong interplay of Jahn-Teller effect.
Copper mixes well with many elements and over a thousand different alloys have been
prepared, several of which are of immense importance from the point of view of
industry. The metal is also biologically important; it is a constituent of several
important metalloproteins and enzymes.

General properties of silver

Silver, the element No. 47, is a white lustrous, soft and malleable metal with the
highest known thermal and electrical conductivity. Its ground state configuration is
4d105s1. It can take up three oxidation states +1, +2 and +3 out of which +1 (argentous)
state is most predominant. The complex forming behaviour of Ag(I) resembles that of
Cu(I) and it can acquire coordination numbers 2, 3 and 4. Most stable Ag(I) complexes
have linear structure in which the coordination number of the metal ion is 2. A 2-
coordinate Ag(I) naturally shuns chelation. The complexes, in which the coordination
number is three or four, have plane triangular or tetrahedral stereochemical
arrangement of ligands. While 4-coordinate complexes are not very common, 3-
coordinate ones are extremely rare. Several uses of silver, based on the antiseptic action
of small concentrations of silver ions, have been developed in medicine [55].

General properties of gold

Gold, element No. 79, is a soft yellow metal with highest ductility and
malleability among the elements. Its valence shell electronic configuration is 5d106s1.
Only two oxidation states +1 and +3 are known. Au(I) ion disproportionate in the
aqueous solution into Au(0) and Au(III). In complexed state, it may be 2-coordinate or
4-coordinate with linear or tetrahedral arrangement of donor atoms around it. Au(III), a
d8 species, forms large number of 4-coordinate square-planar complexes. However, 5-
and 6-coordinated complexes with trigonal bipyramidal and octahedral geometries

12
respectively are also known. In most of its uses, gold is either alloyed with other metals
or plated onto a base metal. It is also used for coating certain space satellites as it is a
good reflector of I.R.

LITERATURE SURVEY OF COINAGE METALS

COPPER

Only one amperometric method has been reported for Cu(III). This involves
titration with sodium arsenite [65].

Many workers has selected EDTA as an amperometric reagent for Cu(II)

employing d.m.e. [66,67], r.p.e. [68] or some other specialized electrodes [69,70]. A
method has been developed to determine copper and other metals in alloys and ores
also with the help of EDTA as titrant [71]. Differential pulse polarographic technique
has also been employed for the Cu(II)-EDTA titrations [72]. Some workers have used
compounds like phenosafranine [73], H2O2 [74], thionine blue [75] and thionine [76] as
very special types of indicators for Cu(II)-EDTA titrations at d.m.e. or r.p.e.

Amperometric titrimetric reagent, thioacetamide, has been found to be a very

effective reagent for Cu(I) as well Cu(II) at d.m.e. These titrations were carried out by
Pryszczewska independently and in collaboration with other workers [77-80]. Methods
of amperometric determination of Cu(II) involving the use of KSCN have been
described in different ways. Rao and Puri [81] titrated Cd(II), Cu(II) and Ni(II) with
KSCN in presence of isoquinoline. Another method described by them is based on the
formation of benzidine thiocyanate complex of Cu(II) [82]. Hernandez et al [83]
titrated Cu(II) with Mohr's salt in a medium containing EDTA and a high concentration
of KSCN amperometrically.

In fact, a large number of organic sulphur compounds have been used for the
determination of Cu(II) at d.m.e. A list of such compounds is as follows:

2-mercaptopropanoic acid [84], 3-mecaptopropanoic acid [85], thiomalic acid

[86], potassiumdithiohydroxymethylaminomethane [87], 4-methyl-8-mercaptoquino-
line [88], potassiumethylxanthate [89], rubeanic acid [90,91], 2-thiobarbituric acid
[92], N-bis(β-aminoethyl)-dithiocarbamic acid [93], 1,2-di(thiocarbamoyl)-hydrazine
[94], unithiol [95], alizarin red S [96], 8-mercaptoquinoline [97-99], mercapto

13
ethylamine-N,N,S-triacetic acid [100], 2-mercaptobenzoxazole [101], pentamethylene
dithiocarbamate [102], ammonium dithiocarbamate [103] and sodium diethyldithio-
carbamate [104-106].

Bera and Chakrabartty [107] have employed benzimidazole-2-yl-methanethiol

for Cu(II) and Pd(II). Stankoviansky et al [108] have employed β-resorcylidene
thiosemicarbazone for Co(II), Ni(II) and Cu(II) in presence of Cd(II). Berzina et al [88]
have used 8-mercaptoquinoline as titrant for Cu(II), Ag(I), Zn(II) and some other
species. 1-Allyl(thiocarbamoyl-2-thiocarbamyl hydrazine (Monalzine) [109] has been
employed as titrant for Cu(II) and Pd(II) and its diallyl derivative (Dalzin) [94] for
Cu(II), Zn(II) and Cd(II).

Cu(II) tartrate [110] and malonate [111] complexes have been studied
amperometrically. Titrimetric methods involving certain other ligands have also been
standardized. These include triethylenetetramine [112], 2’,3’,4’-trihydroxychalcone
[113], resacetophenone [114,115], azide ion [116], dimethylglyoxime [117], 1,2-
diaminocyclohexane-N,N,N',N'tetracetic acid [118], hexamethylenediaminetetraacetic
acid [119], O-hydroxyacetophenoneoxime [120], 2-hydroxyacetophenoneoxime and 1-
hydroxy-2-acetonaphthoneoxime [121], barbitone [122], benzimidazol-2-carboxylic
acid [123], O-carboxyphenylazoacetyl acetone [124], syn-phenyl-α-pyridylbetoxime
[125], bismuthol [126], dimethylformamide [127], sulphydryl cotton fiber [128] and
phlorein [129].

Reddy et al [130] have recommended resacetophenoneoxime as titrant for Ni(II)

and Cu(II) while Canela et al [13l] have recommended hexahydrocupferron for Fe(III)
and Cu(II).

14
 Deshmukh and Rao [132] used sodium tellurite as titrant and sodium tungstate
was used by Gupta [133]; electrogenerated Ti(III) has been employed for V(V) and
Cu(II) [134]. Electogenerated iodine [135,136] has been used as titrant in an indirect
method of estimating Cu(II). Swan [137] has titrated cystine with Cu(II) in the presence
of excess ascorbic acid while Sakomoto et al [138] have titrated benzotriazole with this
metal ion. Eshena [139] has studied the reactions of humic acid extracts with Cu(II)
titrant.

Electrodes other than d.m.e. have also been pressed into service for Cu(II)
determination. Lenskaya et al [140] have used a wax impregnated graphite electrode for
titration with salicylaldoxime. Deshmukh et al [141] have carried out the titration with
P2S5 and Stock [142] with Hg2(ClO4)2 at r.p.e. Titration with triethylenetetramine has
also been carried out at r.p.e. coated with mercury [93]. Tomesanyi [143], has titrated
Cu(II), Zn(II) and Hg(II) with dithizone at a rotating carbon paste electrode. CuSO4 has
been used as titrant for alizarine red S by Argova et al [144] in a method involving the
use of the graphite anode.

Organic sulphur compounds have been pressed into service for the
determination of Cu(II) in ores and alloys also. The reagents are: 5-bromo-8-
mercaptoquinoline [l45], 1,2,3-benzothiazole [146], thioanlide [147,146,]
dimercaptothiopyrones [149] and 2,3-quinoxalinedithiol [87]. 3-Methyl-5-phenyl-2,6-
dimercapto-4H-thiopyran-4-one has been recommended for the determination of
copper in nickel plating baths [150].

Resacetophenone phenylhydrazone has also been employed as titrant for the

estimation of copper in german silver by Reddy et al [151]. Similarly, sodium picrate
has been employed for the estimation of copper in copper-base alloys [152]. An
indirect method involving the use of cinnamoyl phenylhydroxylamine has been
standardized by Pilipenko et al [153] for determining copper in nickel alloys.
Tetraphenyloxalamidine has been used for the determination of this metal in brass
[154]. Poly(ethylenimine) has been employed for this determination in alloys
containing iron, cobalt and nickel besides the metal in question [155].
Hydroxycyanomolybdates of Co(II), Ni(II), Cu(II) and Zn(II) have also been worked
out amperometrically [158]. Reactions of copper salts with those of Cr(III) have also
been studied amperometrically [159]. A few methods have been evolved for the

15
titrimetric estimation of Cu(I) also. The titrants employed include thioacetamide [160]
potassium permanganate [161] and NaBPh4 [162]. Organic acid, ethanethioic acid, 2-
mercaptopropanoic acid and 3-mecaptopropanoic acid [163], were used for direct
determination of Cu(II) amperometrically. However, author of this thesis has not
noticed any amperometric work on Cu(II) using thioglycolic acid in the literature.

SILVER

Many methods of amperometric determination of Ag(I) have been evolved.

Several scholars have used iodide ion as amperometric titrimetric agent. Siska [164]
has established that this method of estimation has greater efficiency than non zero
current potentiometry. Several workers have successfully titrated Ag(I) with KI in
reaction mixtures [165-170] or separately [171]. Agrawal and co-workers [172] have
exploited the interaction between Ag(I) and sulphydryl group of thiomalic acid for the
amperometric determination of Ag(I). Some workers have also carried out titrations
with compounds which contain sulphide linkages instead of sulphydryl group [173-
176]. Thiobenzoic acid has been recommended for the determination of AgNO3 by
Humphrey and Renfro [177]. While Ag(I) has been titrated with mercaptobenzoxazole
in the presence with aluminium and manganese by Bera and Chakrabartty [178], others
have accomplished this titration in the absence of the two metals [179]. Ag(I) titrations
have also been carried out with benzimidazole-2-yl-methanethiol [180]. Suprunovich et
al [181] have used 8-mercaptoquinoline while its 5-bromo derivative has been
recommended for the amperometric determination of Ag(I) by Berzina et al [182] and
dimercaptothiopyrone by Arishkevich et al [183]. 2,5-dimercapto-1,3,4-thiodiazole has
been recommended for titrations at the d.m.e. as well as r.p.e. [184]. Complex
formation with guanyl thiourea has been made the basis of an amperometric
determination by Usatenko and Sukhorochkina [185] and that with 2,3-quinoxaline
dithiol by Akhmetshin [186]. Amperometry has shown that Ag(I) and
dithioloterephthalic acid form a sparingly soluble 2:1 complex [187]. Similarly, Ag(I):
thiosemicarbazide ratio has been reported to be 1:1 or 2:1 in different media [188]. It
has been shown that Ag(I) can also be titrated with 2-mercaptothiazoline [189],
thioacetamide [190-192], potassiumdithiotrihydroxymethylamino methane [193],
thiosemicarbazide [194] and N-(phenylsulphonyl)thiobenzamide [195].

16
 Morpholine carbodithioate [196], morpholinylthiocarbonic acid amide [197],
ethyl thioxanthate [198], salicylidene-o-aminothiophenol [199] thio-oxine [200] and
unithiol [201] have also been used as amperometric titrants for Ag(I). Glutathione has
been found to be a very reliable standard for titration of Ag(I) at the d.m.e. [202,203] as
well as vibrating platinum electrode [204]. Cystenie has also been used for the titration
[204]. Ikeda and Nishida [205] evolved a very efficient method of titrating cyanate with
Ag(I). Cyanide [206] and EDTA [207] have been used for the titration of Ag(I) at
d.m.e. without an external e.m.f. source. Platinum ethylxanthate has been used to titrate
silver(I) and lead(II) in succession [208,209].

Hernandez et al [210] as well as Lopez Gonzalez et al [211] successfully titrated

Ag(I) with Sn(II) at d.m.e. Gupta and Raghavan [212] reported that A.C. amperometric
titration of Ag(I) with potassium chromate is more accurate than the D.C. method.
Saxena and Sharma [213] have established the efficiency of Ag(I)-vanadate
amperometric titration at d.m.e. over the potentiometric or conductometric methods.
Rotating [214] and stationary electrode [215] as well as silicone-rubber based electrode
[216], have also been employed for iodide ion-Ag(I) titration. Ikeda [217] has
established that AgNO3-halide amperometric titrations, carried out at r.p.e., are more
rapid, precise and sensitive in comparison to potentiometric titrations. Titration of
AgNO3 has been performed at r.p.e. with 2-mercaptobenzothiazole [218,219],
dithiocarbamate [220] and sodium diethyldithiocarbamate [221]. Titrations with
various dithiocarbamates have been performed by other workers also [102,222-224]
using different types of electrodes. Usatenko and co-workers [225] have reported the
titration of Ag(I) at r.p.e. with 2,4-dithiobiuret, 1-phenyl-2,4-dithiobiuret and
ethylenethiourea (2-imidazolidinethione) [226], Ikeda and Musha [227] titrated cyanide
with AgNO3 at the r.p.e. using Hg-HgI2 electrode as the reference electrode.
Thiocyanate has been titrated at a fined platinum electrode by Banerjea and Gupta
[228]. Bozsai and Mosonyi described the AgNO3 titration of theophylline [229] and
theobromine [230] at r.p.e. Titrations with reinecke salt [231], subeanic acid [232] and
dithizone [233] have also been described. Molybdate [234] and tungstate [235] were
used in titrations carried out at r.p.e. with Ag(I).

Determination of silver in ores has also been successfully carried out with the
help of iodide [236]. Silver in galenas has been determined at r.p.e. by other scholers

17
[237]. Silver in ores has been determined by Tarayan and Pogasyan [238] with the help
of thiosalicylic acid as titrant at d.m.e. Graphite electrode has also been used in a
method of determining silver in alloys [239]. Usatenko and Zamorskaya [240] have
determined silver in copper-silver alloys by titrating with thionalide.

Methyl thiourea has been used to estimate silver in solutions prepared from
sediments and from silver-copper alloys [241]. Solomatin et al [242] evolved an
amperometric method involving the use of ferrocene to determine silver in magnesium
alloys. Lotoreva [243] evolved an indirect method using r.p.e. to determine silver in
sulfide residue. The specificity of silver ion for protein mercapto groups has also been
studied by amperometric technique [244]. Amperometric titrations of Ag(I) with the
relevant organic ligands have been used to study the instability constants of its tartrates,
ethylenediamine and certain other complexes [245]. The reactions of Ag(I) with
orthovanadate [246] and metavanadate [247] have also been studied amperometrically.
Organic acid, ethanethioic acid, 2-mercaptopropanoic acid and 3-mecaptopropanoic
acid [248], were used for direct determination of Ag(I) amperometrically. No
amperometric work with thioglycolic acid (used by the author of this thesis) and on any
other oxidation state of silver has come to the notice of the author.

GOLD

Au(III) has been titrated with thiomalic acid [172], 8-mercaptoquinoline

[249,250], cysteine [251], potassium iodide [252], 1-phenyl-2,4-dithiobiuret [225],
thiopyrrolidinone [253], 2-amino-2-mercaptothioacetamide [254] and α-nephthyl amine
or its β-isomer [255]. Tarayan and Sarkisyan [256] have recommended the use of
thiopiperidone for the amperometric estimation of slightly acidic Au(III) solution. A
medium of high chloride concentration has been recommended for this by Sharma and
Singh [257]. Reduction of Au(III) to Au(I) and precipitation as Au(I) complex of
unithiol has been made the basis of determination by Songina et al [258]. Electrodes
other than d.m.e. have also been used for the amperometric determination of gold.
Tarayan et al [259] titrated Au(III) with HgClO4 and Galfayan et al [260] with rubeanic
acid at r.p.e. The interaction of 2-mercapto-4,6-dihydroxy-5(4-methoxybenzenoyl)-
pyrimidine with gold(III) has also been utilized in the r.p.e. titration of submilligram
quantities of gold [261]. Au(III) has also been determined using thiazole [262] and
platinum as indicator electrode. Thionalide [263] and thiourea [264] have been

18
recommended for the titration of Au(III) at a graphite electrode. Amperometry has been
used for quantitatively studying the process of complexation between Au(III) and 3-
ethyl-2,6-dimercapto-1,4-thiopyrone [265,266]. Indirect methods for the determination
of Au(III) in the presence of platinum and palladium [267] or separately [268]
involving the use of cericsulphate have also been developed.

Pashchenko and Songina [269] determined of gold in solutions made from

crude copper with the help of Mohr's salt and K2Cr2O7. Thiourea [270] and 5-mercapto-
3-(2-naphthyl)-1,3,4-thiadiazole-2-thione [271] have been used for the determination of
gold in ores. A graphite electrode electroplating baths and ores; potassiumbis(2-
hydroxymethyl)dithiocarbamate [272] or phenylsulfonylthiobenz amide [273] has been
used in case of alloys, benzyldithiocarbamate [274] in case of baths and AgNO3 [275]
or thiosalicylic acid [276] in case of ores, as titrant. 2-cyanoethylbenzene-
sulphonyldithiocarbamate [277] has also been recommended for the determination of
gold in various alloys at the graphite anode. Organic acid, ethanethioic acid, 2-
mercaptopropanoic acid and 3-mecaptopropanoic acid [278], were used for direct
determination of Au(III) amperometrically. However, author of this thesis has not
noticed any amperometric work on Au(III) using thioglycolic acid in the literature.

No work on Au(I) has come to the notice of the author.

PLATINUM METALS

Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Osmium (Os), Iridium (Ir) and
Platinum (Pt) metals together called as platinum metals. All of these are also known as
noble metals.

General properties of Ruthenium

Ruthenium, the element No. 44, is a hard, white metal, having valence shell
electronic configuration as 4d75s1. The principal oxidation states are 0, +2 and +3
through compounds in all the states upto +8 have been prepared. Ru(III) is the most
stable species and is known to form very large number of hexa-coordinate octahedral
complexes. Ruthenium is known for its excellent catalytic properties and the metal has
also found use in hardening the alloys of palladium and platinum.

19
General properties of Rhodium

Rhodium, the element No. 45, is a fairly soft, ductile, silver-white metal, having
valence shell electronic configuration as 4d85s1. The most common oxidation state is
+3 though compounds in all the states ranging from -1 through +6 have been prepared.
Rh(III) species is an avid complex former. It is known to take up coordination numbers
5 and 6. However, hexa-coordinate octahedral complexes are formed more extensively.
The metal finds considerable application as electrodeposited coating. Its major use is as
an alloying agent to harden platinum and palladium. Such alloys are used for furnace
windings, thermocouple elements, bushing for glass fiber production, electrodes for air
craft spark plugs and laboratory crucibles.

General properties of Palladium

Palladium, the element number 46, is a grey-white lustrous metal. It is the least
dense and has lowest melting point amongst the platinum group metals. It is not very
hard. It has unusual property of absorbing up to 900 times its own volume of hydrogen,
possibly forming PdH2. Its valence shell electronic configuration is 4d105s0. The
principal oxidation states are +2 and +4. Oxidation state higher than +4 has not been
observed. Pd(II) and Pd(IV), both are avid complex formers. Pd(II) can acquire
coordination numbers 4, 5 and 6 out of which, 4 with square-planar geometry is the
hottest favourite. Pd(IV) forms only hexa-coordinate octahedral complexes. The metal
is widely used for catalytic reductions. Finely divided palladium is a good catalyst for
hydrogenation and dehydrogenation reactions.

General properties of Osmium

Osmium, the element no. 76, is a bluish white metal which is easily oxidized to
OsO4. Its valance shell electronic configuration is 5d66s2. All the oxidation states from
zero upto +8 (excluding +1) have been reported. OsO4 is a volatile crystalline solid
which is strongly toxic and is particularly hazardous to the eyes. It has very limited
solubility in water and is a powerful oxidising agent. Because of the toxic nature of the
compound, any contact with the skin is avoided. The tetroxide has been used to detect
fingerprints and to stain fatty tissue microscope slides. The metal is almost entirely
used to produce very hard alloys with other metals of the platinum group, for fountain
pen tips, instrument's pivots, phonograph needles and electrical contacts.

20
General properties of Iridium

Iridium, the element No. 77, with valence shell electronic configuration as
5d76s2 is white, similar to platinum but with a slight yellowish cast. It is brittle though
considerably harder than platinum. It has the distinction of having the highest specific
gravity of all the elements, being just slightly denser than osmium. Iridium can acquire
all the oxidation states from +1 to +6. The valance state +1 and +3 are important but in
addition it forms a number of stable compounds with halogens and oxygen in which the
oxidation state is +4. The most common co-ordination number for Ir(I) is 4 with the
complexes adopting square planer structure; this number for Ir(III) is 6 and such
complexes adopt octahedral geometry. Besides coordination number 6, Ir(III) is also
known to acquire co-ordination number 5 with the complexes adopting either trigonal
bipyramidal or square pyramidal structure. Iridium has found use in making crucibles
and apparatus for work at high temperature. It is also used for electrical contacts. Its
principle use is as a hardening agent for platinum. With osmium, it forms an alloy
which is used for tipping pens and compass bearing.

General properties of Platinum

Platinum, the element number 78, is a grey-white, lustrous, malleable and

ductile metal having valance shell electronic configuration as 5d96s1. The principle
oxidation states are +2 and +4 though compounds in higher oxidation states [highest-
Pt(IV)] have also been prepared. Pt(II) as well as Pt(IV) are avid complex formers.
Pt(II) can acquire three coordination numbers but square planer 4-coordinated
complexes are more common. Pt(IV) however, forms 6-coordinate octahedral
complexes exclusively. The metal and its alloys are used for electrical contacts and for
plating. The metal is also used for coating missile nose cones, jet engine fuel nozzles,
and as a catalyst in fuel cells and in antipollution devices for automobiles.

LITERATURE SURVEY OF PLATINUM METALS

RUTHENIUM

The technique of amperometry has been successfully employed for determining

ruthenium in +6 state. Kudinova et al [262] have recommended thiozole solution for
titrating Ru(IV) while Avdienko et al [279] have used 8-quinolinethiol for the purpose.

21
 Alekseeva et al [36] have exploited the catalytic property for amperometric
determination of Ru(IV) species. They have also exploited the catalytic effect of this
species on the oxidation of iodide by H2O2 for its indirect amperometric determination
[37]. However, a rather large error of ±6% has been reported in this case.

Several methods of direct amperometric estimation of Ru(IV) at r.p.e. have also

been reported. Pshenitsyn and Exerskaya [280-282] have used hydroquinone as
ascorbic acid for titrating Ru(IV) in various supporting electrolytes while Bessarabova
and co-workers [283] have used 8-mercaptoquinoline for the purpose.

Only a few direct methods of amperometric determination Ru(III) with the help
of thiomalic acid [284], 2-mercapropropanoic acid [285], ethanethioic acid [285] and 3-
mercaptopropanoic acid [286] at d.m.e. have been reported. However, its catalytic
property has been made the basis of an indirect method of its estimation developed by
Alekseeva et al [36]; they have used K2(RuOH2.Cl5) for catalysing the oxidation of
ferroin by KIO4.

The author failed to come across any work on any other oxidation state of
ruthenium as well as any amperometric work with thioglycolic acid.

RHODIUM

Only a few direct amperometric method of determining Rh(III) at d.m.e. has

been reported; Agrawal and Khatkar [284] have perfected this method using thiomalic
acid and Agrawal and Malik [287] by using 2-mercapropropanoic acid and ethanethioic
acid as the determining agent.

Some methods have been reported at r.p.e. Bardin and Tho Tin [288,289] have
used BaCl2 or Ba(NO3)2 and NaBrO as amperometric-titrimetric reagents in NaOH
media of varying concentrations. Velichko et al [290] have developed an indirect
method involving reaction of Rh(III) with excess Ce(IV) and back titrating the excess
with 8-mercaptoquinoline or Fe(II).

Bardin and Tho Tin [288,289] have used the reagents, mentioned before in case
of Rh(III), for determining Rh(IV) also, exploiting its catalytic wave.

22
 No work on any other oxidation state of rhodium and also no amperometric
work with thioglycolic acid and thiodipropionic acid (organic acid used by author of
this thesis) has come to the notice of the author.

PALLADIUM

Croitoru and Popa [291] determined milligram amounts of Pd(II) by titrating

with chrysophenine G and Clem and Hoffman [292,293] by titrating with hypochlorite.
The low frequency titration of Pd(II) with β-furfuraldoxime has been performed by
Burakov [294]. The reaction between Pd(II) and thioglycollic acid has been studied by
amperometric and biamparometric techniques using rotating platinum electrode (r.p.e.)
by Vajgand and Jaredic [295]. Tkacheva et al [296] have exploited the anodic current
of copperdithiocarbamate for the amperometric estimation of Pd(II). The determination
of Pd(II) has also been carried out with thiomalic acid [172] and 8-mercaptoquinoline
[297], unithiol [298], 2-mercaptobenzoxazole [178], reinecke salt [299], AgNO3 [300],
N-p-tolylsulfonyl-2-benzofurancarboxmide [301], selenophen-2-aldoxime [302],
resacetophenone oxime [303], 2-hydroxy-1-aceto naphthone [304], 2-mercapto-4,5-
dimethyl thiazoles or salicylidene-O-aminophenol [305], rubeanic acid [306-308],
electro-generated silver(I) ion [309], N,N-bis(2hydroxyethyl)dithiocarbamate [310], K-
morpholine-4-carbodithioate [311], 2-(2-phenyl-2-hydroxyiminoethyl)-2- isoquinol
inium chloride [312], 2,1,3-thiadiazole and its selenium analog [313] and methyl
derivative of dimercaptothiopyrones [314].

A detailed study has been made of the titration of PdY2X2 end point where Y is
pyridine or 2,2'-bipyridine and X is iodide, thiocyanate or azide ion [315]. Sodium
diethyldithiocarbamate has been used as the titrimetric agent for Pd(II) as well as
Au(III) in the non-aqueous medium of dimethylformamide [316]. Non-aqueous
medium has also been recommended for the amperometric titration of Pd(II) with
EDTA [317].

A titration of Pd(II) with KI at adsorption polarized electrodes has been

standardized by Bartels and Umland [318]. A silicon rubber based graphite electrode
has been employed to compare the non-zero current potentiometric and amperometric
titrations of iodide with PdCl2 [164]. Determination of Pd(II) has been carried out at the
r.p.e. using 1,2-cyclohexanedione [319], thioacetamide [320], thiosalicylic acid [321]

23
or potassium hexacyanoferrate(II) [322] as titrant. The last but one method has been
found equally suitable for Cu(II) [321]. Thiosalicylamide has also been used for the
amperometric determination of Pd(II), Ag(I) and Au(III) at this electrode [323].
Zakharov and Aitkhozheva [324] have chosen a stationary platinum electrode to
perform the titration with KSCN as titrant. Vesheva et al [325] have recommended a
graphite anode or a platinum anode for the determination of Pd(II) or Au(III) with
benzidine.

In plating baths the palladium content has been evaluated with 2,6-dimercapto-
3-methylthiopyran-4-one [326] while in metal concentrates and slimes has been
determined by titration with thiourea [327,328], phenyl thiourea [329], 1,1-dimethyl-3-
p-chlorobenzenesulfonyl thiourea [328], 2,4-dithiobiuret [329]. Thiourea has also been
used to determine palladium in industrial solutions [330]. Thionalide has been used to
estimate palladium in deposition sludges [331]. Organic acid, ethanethioic acid, 2-
mercaptopropanoic acid and 3-mecaptopropanoic acid [332], were used for direct
determination of Pd(II) amperometrically.

The author failed to come across any work on any other oxidation state of
palladium as well as any amperometric work with thioglycolic acid.

OSMIUM

Only a few direct amperometric methods for estimating Os(VIII) have been
reported, some by Agrawal et al [333,334] using thiomalic acid, 2-mercapto and 3-
mercaptoopropanoic acid and ethanethioic acid (in aqueous medium) and the other by
Gevorgyan et al [335] using EDTA (in non-aqueous medium).

A few indirect methods have, however, been reported. Alekseeva et al [336]

have exploited the catalytic action of Os(VIII) on the oxidation of iodide by H2O2 for
developing such a method of its estimation at r.p.e. Alekseeva and his associates [337]
have reported another method for determining Os(VIII) at r.p.e. exploiting the catalytic
action of this species on the oxidation of arsenite by KIO4; similar methods have been
described by them [337] for Os(VI) and Os(IV) also. The catalytic action of osmium on
some reactions has been exploited for developing a few more methods. One such
method [338] involves the oxidation of As(III) by Ce(IV) and makes use of two
polarized electrodes. Another method [339] involves the reaction between H2O2 and

24
cyanocuprate(I). Yet another method [340], which enables the estimation of osmium in
rocks, utilises the redox reaction between bromate and arsenite.

Os(VI) has been determined amperometrically with sodiumdiethyldithio-

carbamate [341] and 8-mercaptoquinoline [342].

To the best of the knowledge of the author, no work on any other oxidation state
as well as any amperometric work with thioglycolic acid and thiodipropionic acid has
been reported.

IRIDIUM

Some methods have been worked out for the amperometric determination of
Ir(IV). Volkova et al [343,344], have amperometrically determined tetravalent iridium
with ferrocene. Usatenko and suprunovich [345] have developed an efficient method
based on combination of precipitation and reduction reaction of Ir(IV) with 8-
mercaptoquinoline. Suprunovich and co-workers [346] has used this organic compound
in another method also. A method involving the use of electrogenerated Cu(I) has been
developed by Stenina and Agasyan [347]. An indirect method reported involves the use
of KI at stationary platinum electrodes [348]. This reagent has also been used for
determination of Ir(IV) at r.p.e. [349]. The technique amperometry has been
successfully employed for determining iridium in +3 state as well; KMnO4 [350,351]
and K2Cr2O7 [352] have been used for this purpose.

Mohr’s salt K4Fe(CN)6 [353] have also been employed as determining agents
for iridium. Iridium has also been titrated with Fe2+ after its oxidation. The method has
been applied to determine iridium in metallurgical intermediate products of precious
metal and iridium alloys [354]. Iridium in alloys with platinum has also been
determined by titration with diethyldithiocarbamate [354] and sodium chlorate [355].
Organic acid, ethanethioic acid, 2-mercaptopropanoic acid and 3-mecaptopropanoic
acid [356], were used for direct determination of Ir(III) amperometrically. No
amperometric work with thioglycolic acid and thiomalic acid (used by the author of this
thesis) and on any other oxidation state of iridium has come to the notice of the author.

25
PLATINUM

Only a few methods of determining platinum amperometrically are known.

Organic reagents such as thiomalic acid [172], ethanethioic acid [357], 2-
mercaptopropanoic acid [357] and 3-mecaptopropanoic acid [357], thioacetamide [319]
and 8-mercaptoquinoline [346] have been used for the determination of Pt(IV) at d.m.e.
Amperometric determination of Pt(IV) [358,359] and Pt(II) [359] has been carried out
at r.p.e. with the help of thiourea. Zakhrov and co-workers have standardized methods
for the determination of platinum content in the catalysts; these methods involve the +4
oxidation states of platinum and the use of d.m.e. [360] or r.p.e. [361] as indicator
electrode. Rotating platinum electrode (r.p.e.) has also been used in amperometric
determination of Pt(IV) with thallium [362].

Zakharov et al [363] have standardized amperometric titrations of Pt(II) with

vanadate, dichromate and permanganate. No amperometric work with thioglycolic acid
(used by the author of this thesis) and on any other oxidation state of platinum has
come to the notice of the author.

THIOGLYCOLIC ACID (TGA)

General properties

Thioglycolic acid (mercaptoaceticacid or TGA) formulated as HS-CH2-COOH

and abbreviated as TGA in this thesis, have molecular weight 92.12, density 3.18 and
the boiling point 123oC. It is soluble in water. It was developed in the 1940’s for use as
a chemical depilatory and is still used as such, especially in the calcium thioglycolate
salt form. TGA, besides being the basis for the permanent wave solution, ammonium
thioglycolate, is used in a wide variety of applications including the making of
polyvinyl chloride and leather processing. TGA has the ability to break down the
disulphide bonds in the cortex of hair to either rearrange or to help break down the hair
shaft entirely, its primary purpose.

Many sulphur containing organic ligands have been used in amperometry for
the trace determination of metal ions. Organic sulphur compounds containing –SH
group are also known to give anodic wave at d.m.e. [59-64]. TGA in this report has
often been used as a complexing agent [364-366] and an analytical reagent [367-370].

26
This acid has also been used in grafted into silica gel [371], in preparation and
characterisation of glass embedding [372]. However, its capacity to act as an
amperometric reagent has by and large remained unexplored. Complexing properties of
thioglycolic acid are especially interesting in view of the fact that it contains both hard
oxygen donor atoms of carboxylate group and soft sulphur atom of the sulphydryl
group. This combination enables it to form rather stable complexes with a large number
of metal ions. Both of these can take part in coordination and thus it can act as mono or
bidentate ligand. TGA seems to be capable of forming complexes with a large number
of metal ions and a survey of literature justifies this expectation.

Polarographic Behaviour

Polarographic behaviour of this acid has been studied in detail by several

workers. It has been found to give a diffusion controlled, reversible, one electron
anodic wave, the half wave potential of which is depend on pH; as 0.2M acetate buffer
[373] (pH – 4.6), 0.05M sodium phosphate [373] (pH–6.8) and 1.0M ammonium
chloride [374] have E1/2 -0.26V, -0.38V, and -0.56V respectively. The pH dependence
is complex, owing to the diprotic nature of TGA [374]. Kolthoff and Belcher [375]
gave standardisation of TGA by titration with iodine solution and diluted to give 0.05,
0.025, 0.0125 and 0.01M solutions. Leussing and Kolthoff [376] have shown that a
mercury compound is formed during the anodic oxidation of thioglycolic acid. The
electrode reaction has been suggested as follows:

TGA + Hg → [Hg (TGA)2] + 2H+ + 2e-

The dissociation constants of the acids were determined at a temperature of

20ºC and an ionic strength of 0.1 at several concentrations of buffer. The average value
of dissociation constant of thioglycolic acid is 3.89×10-4. The first and second
successive formation constants of the thioglycolate complexes were calculated [377-
380].

The agreement of the values of stability constants obtained at the different metal
ion concentrations indicates that the amount of hydrolysis was negligible in the region
between pH values of 2 and 4. The logarithms of the stability constants were calculated
by Bjerrum’s graphical method [381]. The error limits [382] are ±5% for K1 and ±10%

27
for K2. This corresponds to the errors: ±0.02 for log K1 and ±0.05 for log K2. Stability
constant for thioglycolic acid reported as log K1 = 2.88 and log K2 = 2.40.

Complexation reactions

Rieger et al [383] reported ESR spectrum of vanadyl ion in the presence of

lactic or glycolic acid (H2A) indicates the existence of at least 6 different species over
the pH range 1-7. By studying the behaviour of ESR intensities in the vanadyl lactic
acid system as a function of pH and ligand to metal ratio, the observed species are
identified as the aquovanadyl ion 1:1 complex VO(HA)+, which gives virtually
indistinguishable ESR spectra. V.M. Bhuchar [384] described polarographical method
for the determination of Cr, U, W or Ni by complexing with thioglycolic acid. The
large scale electrolysis of Zn(II), Cd(II), Hg(II), Cu(II), Ni(II), Co(II), Fe(II), Mn(II),
Cr(II), Cr(III), Bi(III), In(III) and Sb(III) at Hg electrode in the presence of
mercaptoacetic acid, 3- mercaptopropionic acid, cysteine and thiourea was carried out
and the products were investigated [385]. Khadikar and Kakkar [386] prepared Cr(III)
complexes with salicylic acid, thiosalicylic acid, thioglycolic acid, m-
(mercaptoacetamido)phenol and p-(mercaptoacetamide)chlorobenzene.

Thioglycolic acid [387] metal chelates were prepared by treating thioglycolic

acid or its derivatives with a base and then with an aqueous solution of a metal
compound. Addition of a base preferably NH4OH, increased by the yield of chelates.
Joanna et al [388] give a review with 89 references on the biological role, chemical
compounds structure, properties, stability constants and thermodynamics functions,
reaction and mechanism of Mn(II), Fe(II,III), Co(II,III), Ni(II), Cu(II) and Zn(II) with
thioglycolic acid. Murrey and Newman [389] have reported a number of solid
complexes, most of which are extremely unstable in air, were isolated from reaction
between aqueous Fe(II) and ligand thioglycolic acid. The 1:1 and 1:2 Fe-ligand
stoichiometries were obtained. Spectroscopic and magnetic measurements were use to
deduce possible structures and in most cases polymeric structures are indicated. A
photometric study of the equilibrium in the system [Fe(CN)5NO]2- thioglycolate [390]
indicated the formation of a coloured 1:1 complex. Roy and Dipali [391] have reported
a method based on the complexation of iron with TGA to form a colourless Fe2+-TGA
complex, oxidation to red Fe3+-TGA complex in the pH range 4.2 – 5.0 in air and final
titration of complex with EDTA to a colourless end point.

28
 Hori and Kiichi [392] have reported Co(II) complexes with TGA and studied
their properties. Babkin and Geinrikhs [393] have reported reduction of cobalt on
mercury cathode in solutions of thioglycolic acid and thiosemicarbazide. Anzenbacher
and Kalous [394] have reported polarographic study of anodic peaks of cobalt in
thioglycolic acid medium. Joanna and Jozef [395] have reported coordination of Co(II)
with thioglycolic acids using potentiometry at 20º in aquous solution of ionic strength
0.1M NaClO4. Formation of 1:1 and 1:2 (M:L) complexes with thiosemicarbazide and
thioglycolic acid in different alkaline buffer media by oscillopolarography with linear
change of potential on a dropping mercury electrode [396].

King [397] has reported Zn complex of thioglycolic acid and its exposure to
sunlight. Nepal and Dubey [398] have studied stability constant of Mn(II), Fe(II),
Co(II), Cu(II) and Zn(II) complexes with thiomalic acid, thioglycolic and thiolactic
acid potentiometrically.

Martin and Spence [399] have reported the oxidation of thioglycolic acid by
Mo(V) and Mo(VI) in phosphate buffer at pH 4.60–7.50. At pH 6.00 Mo(V) forms
strong dimeric complexes with TGA in which the ratio of Mo(V) to TGA is 1:2. The
reaction between Pd(II) and thioglycollic acid has been studied by amperometric and
biamparometric techniques by Vajgand and Jaredic [295] at r.p.e.

Dzintarnieks and Busev [400] have determined solvation of anionic internal

complexes of molybdenum with thioglycolic acid during extraction by isoamyle
alcohol and 1,2-dichloroethane in the presence of diphenyleguanidinium. Ordonez and
Garrido [401] have investigated the ionization constant of thioglycolic acid.

Saxena et al [402] have reported the precise nature of complexation of Cd, Pb

and Tl with thioglycolic acid and glutamic acid investigating by polarographically.
Domingo and Molina [403] found that in weakly acid aqueous media, thioglycolic acid
forms in the presence of Cd(II) ions, a weakly solution, 1:1 complex assumed to be the
title salt. Mittal and Mohan [404] have reported polarographic reduction of Cd(II) in
20% dioxane containing thioglycolic acid was a reversible diffusion- controlled, 2-
electron process and half wave potential can be explained by the formation of complex
[CdL3]4-.

29
 Qazi and Dubey [405] have studied complexes of Hg(II) with TGA. All the
complexes contain tetrahedrally coordinated ions, [Hg(TGA)2]2-. Equilibrium constants
for TGA-Hg(II) system in aqueous solution have been earlier reported by Stricks and
Kolthoff [406]. The metal bisthioglycollatomercurates were analysed for sulphur,
mercury and metal ion contents using standard methods [407-409].

Some transitions metal and non-metals have also been detected by using TGA
as an amperometric reagent [410,411].

To the best of the knowledge of the author, no amperometric work using this
acid has been reported on these following elements at d.m.e. used by the author for her
work viz:

Cu(II), Ag(I), Au(III), Ru(III), Rh(III), Pd(II), Os(VIII), Ir(III) and Pt(IV).

THIODIPROPIONIC ACID

Thiodipropionic acid, S-(CH2-CH2-COOH)2, a white powder, m.p. 129-130ºC,

molecular weight 178.21, soluble in water, is also a polyfunctional compound. This
also contain hard oxygen donor atoms of two carboxylate groups and a soft sulphur
atom and hence can act as mono, bi or tridentate ligand. However, in this compound, no
acidic hydrogen atom is associated with sulphur.

Scanty literature is available on the complexes of this ligand, though this is

expected to form large number of complexes. The chelation through sulphur and
anyone of the carboxylate groups yields a stable six membered ring. On the other hand,
involvement of both –COOH groups should result in a very large sized ring which may
be expected to have extremely limited stability. Proton ligand stability constants of this
acid have been worked out by Suzuki et al [412] and Singh et al [413], on the basis of
pH-metric studies. Suzuki and co-workers (loc.cit) have reported the formation of 1:1
complexes with Cd(II), Co(II), Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II). They have
concluded that the chelation involves interaction with sulphur and six-membered rings
are formed. They have also worked out the stability constants of various complexes.
Singh et al (loc.cit) have reported the formation of 1:1 metal ligand complex with
Cr(III). Baweja, Dubey and Puri [414] have studied the thiodipropionic acid complexes
of vanadium(IV). They have reported 1:2 metal-ligand interactions and have worked

30
out stepwise formation constants also. Dubey et al [415] have reported the formation
constants and the thermodynamic parameters of the Al(III) complex.

No polarographic study of the ligand has been reported.

Only Mn(VIII) [416] has been detected amperometrically using this acid as an
reagent.

To the best of knowledge of the author, no any other amperometric work

involving this acid has been reported.

THIOMALIC ACID

Thiomalic acid (mercaptosuccinic acid -TSH), SH-CH-(CH2-COOH)(COOH),

an off white powder, m.p. 150ºC, molecular weight 150.15, soluble in water, is a
biologically important compound which has been used as antidote against cadmium,
mercury and arsenic poisoning [417]. Its magnesium complex has found use in the
treatment of rheumatic and bronchial disorder [418] and sodium gold(I) thiomalate has
been proved to be a potential drug for adjuvant arthritis [38]. This very compound has
also been found inhibitory to thrombin [419]. A study of the biological effect of this
compound on platelets has also been made [420]. Taylor and co-workers [421] have
also studied the biological aspects of this compound as well as thiomalic acid itself.

Thiomalic acid is a polyfunctional compound, which would undergo typical

reactions of both mercaptans and dicarboxylic acid. Thus, it can act as a mono-, bi-, or
tridentate ligand. For example, it has been reported to act as a monodentate ligand with
Ag(I) [57], bidentate with Ni(II) [38,422] and tridentate with In(III) [423]. Complexing
properties of thiomalic acid are especially interesting in view of the view fact that it
contains both ‘hard’ oxygen donor atoms of the carboxylate groups and ‘soft’ sulphur
atom of the sulphydryl group. This combination enables it to form rather stable
complexes with a large number of metal ions. Stability constants of TSH complexes are
on the whole considerably higher than those of its nitrogen and oxygen analogues
[424]. There is ample evidence to suggest that –SH group (in the form of mercaptide
group: TS-) plays a very important role in determining its coordination properties.
When it acts as monodentate ligand, it is through this group that a bond is established
with metal ion [57]. Its activity as a bidentate ligand again involves almost always the –

31
SH group and one of the –COOH group, after deprotonation, giving quite stable 5 or 6-
membered ring (6- if –COOH is farthest from -SH). Involvement of –SH group in
chelation, even when the ligand acts as bidentate ligand has been quite convincingly
proved on the basis of potentiometric and spectroscopic studies [57,425]. And the
stability of the complexes often explained in terms of synergic stabilization of LM
bond involving sulphur through ML bonding. This back bonding established
because of availability of vacant d orbitals on sulphur atom which can easily interact
with filled d orbitals of the metal ions [423,426,427]. Involvement of both –COOH
groups, with –SH group remaining unused, results in a 7-membered, which is of only
limited stability in comparison to 5- and 6-membered rings; 5-membered ring is the
stablest. However chelation without the involvement of the sulphydryl group has also
been suggested some time [428].

Polarographic Behaviour

Polarographic behaviour of this acid has been studied in detail by Tiwari and
Kapoor [59-61] and also Saxena and Gupta [429]. They showed that the acid undergoes
one electrone change at the d.m.e. giving a reversible, completely diffusion controlled
anodic wave, the electrode reaction being:

TSH + Hg TSHg + H+ + e-

They also showed that E1/2 is a function of pH. Several workers have reported
the protonation constants of the acid as calculated from potentiometric data [56,426-
428]. Cheney et al [56] have reported these values as pK1 = 3.30, pK2 = 4.94 and pK3 =
10.64 where pK1 and pK2 correspond to the deprotonation of two carboxylic groups
while pK3 corresponds to the deprotonation of sulphydryle group. Kapoor, Agrawal and
Seth [430] have reporetd the protonation constant of sulphydryl group (pK3 = 10.55)
using polarographic data.

Oxidation of TSH has been reported to occur as a result of interaction with

Cu(II) [58], Fe(III) [431-433], Mn(VII) [434,435] and Ce(IV) and Np(VI) [436] and
Os(VIII) [333].

32
Complexation Reactions

Complex forming reactions of thiomalic acid with a large number of metal ions
have been studied. Most of the complexes are coloured. Cheney et al [56] have reported
potentiometric study of chelate formation with Zn(II), Ni(II) and Co(II). Lenz and
Martel [57] have made similar studies mainly with Ag(I), Co(II), Hg(II), Zn(II) and
Ni(II), Reddy and Bhattacharya [427] with Tl(I), Ni(II) and Mn(II), Saxena and Gupta
[437] with Tl(I), Misra, Sinha and Nigam [438] with Pb(II) and Mohanty and Patnaik
[439] with Mn(II), Ni(II), Zn(II) and Co(II). Roselli [440] studied the reactions of TSH
with several metal ions in different media and concluded that the reaction of Co(II) and
uranyle ions are of analytical interest. Sen Sarma [441] has also studied the analytical
applicability of this acid on the basis of its complexation reactions. Martinez and
Mourino [442,443] have studied its complexes with Mo(VI), Fe(III), Co(II), Ni(II) and
Cu(II) and recommended the use of the reactions with the first two metal species for
their simultaneous absorptiometric determination. Sant and Sant [444] have
recommended the use of TSH for the gravimetric determination of zirconium. Categgio
[445] has used TSH for the determination of Mo(VI) which forms a deep yellow
coloured complex with it.

Agrawal and Rajani [446] have recommended carbonate-bicarbonate medium

containg TSH for the quantitative polarography of Fe(II). As mentioned above, several
workers [431-433] have reported reaction between Fe(III) and TSH. In a very thorough
work, Ellis et al [432] have reported the formation of transitory 1:1 Fe(III):TSH
complex which undergoes reduction to give Fe(II) and TS-ST. McAuley’s [447]
findings are similar to those of Ellis et al (loc. cit).

Hill and McAuley [448] have expressed the possibility of oxidation of TSH
with Co(III) ion under specific conditions. However, Nigam et al [449] have concluded
that in presence of TSH, Co(II) undergoes air oxidation to Co(III) to give 1:2
Co(III):TSH complex. Wagner and Yoe [450] observed colour reaction between Rh(III)
and TSH but could not ascertain the composition of the complex.

A lot of work has been done on Ni(II): TSH complexation. Some of it has
already been cited. In a few other papers, formation of 1:3 or 1:2 Ni(II)-TSH complex
has been reported on the basis of magnetic, spectrophotometric or potentiometric

33
studies [422,451-453]. Complexation reaction of Pd(II) has also been studied. Konig
and Crowell [454] observed yellow colour on mixing dilute solutions of Pd(II) salts and
TSH. The reaction was later studied in detail by Wagner and Yoe [450].

Complexation of Cu(II) and Cu(I) has also attracted attention. Some work has
already been cited Cu(I)-TSH complex has been studied in detail by some french
workers [455]. Various methods such as polarography [456], potentiometry [455],
cryscopy [455], spectrophotometry [457,458] and magnetic susceptibility
determinatiion [459] have been employed for the study of Cu(II)-TSH interaction and
all sorts of suggestions such as reduction of Cu(II) to Cu(I), formation of mixed valence
complex and varied stoicheometries have been put forward [58,456,459]. ESR [460]
and EPR [461] studies of Cu(II)-TSH system have also been attempted. For Ag(I), 1:1
[455] and 1:2 [462] metal species-TSH complexes have been reported.

Complexation of Zn(II) with TSH has also commended the attention of

workers. This interaction has been studied by potentiometry [56,422,463],
polarography [464,465] and conductometry [463]. Kinetics of reduction of Zn(II) and
Ni(II) in presence of TSH at d.m.e have also been studied [466]. Complexation of
mercury has been reported. Tiwari and Kapoor [60], using polarographic data, have
shown that the complex formation does take place between Hg(II) and TSH. Patil and
Krishnan [467] have isolated the Hg(II) complex. Quazi and Dubey [468] have also
studied Hg(II)-TSH complex.

Ambulkar and Munshi [469] have reported complex formation with Ga(III) and
worked out its stability constant too. In(III) [426] and Y(III) [428] complexes have
been studied similarly. Cefola et al [470] have studied complexation reaction of some
trivalent lanthanides as well as uranyle uranium [471] with this ligand
potentiometrically. Mohanty and patnaik [472] have also studied the coordination
reaction between thiomalic acid and some trivalent lanthanides.

Patil and Krishnan [425,473] have isolated 1:1 thiomalates of Zn(II), Cd(II),
Hg(II), Pb(II), Mg(II), Ca(II), Sr(II) and Ba(II) characterized them by elemental
analysis, IR spectra and thermal studies. These workers [467] have similarly studied
thiomalates of oxocations of vanadium (VO2+), zirconium (ZrO2+) and hafnium
(HfO2+).

34
 Agrawal et al [474-476] have isolated 1:1 thiomalates of Mn(II), Fe(II), Co(II)
and Ag(I) and 1:2 thiomalates of Zn(II) and Hg(II).

Agrawal and co-workers [172,477-483] have developed new amperometric

methods of estimating very dilute solutions of the most of the metal species; transition
metals, non-metals, lanthanides [483] and actinides [483] with the help of TSH. The
fundamental basis of these methods is the complexation reaction between the metal
species and the ligand. The case of Cu(II) [477] involves partial reduction, Mn(VII) and
Os(VIII) involves redox reaction, Cr(III), Co(III) and Ru(III) [484,485] do not involve
any chemical reaction. In case of Rh(III) [485] and Ce(IV) [486] compensation reaction
took place.

All of the coinage and platinum metals have successfully determined with the
help of TSH [487,488] by amperometric technique except Ir(III). Hence, this acid was
used for determination of Ir(III) by the author of this thesis.

AMPEROMETRIC DETERMINATION

Thioglycolic acid seems to be an excellent ligand which has the additional

advantage of being polarographically active. TDPA also shows good activity in case of
Rh(III) and Os(VIII) metal species. TSH being a very good complexing agent had
already explored for many of transition metals and non-metals excluding Ir(III), and
proved good for the determination of this metal species. Thioglycolic acid,
thiodipropionic acid and thiomalic acid have been exploited for the amperometric work
embodied in this thesis.

35