AAS : ATOMIC Absorption Spectrometry

bd Butane-1,4-diamine
bdH+ : Butane-1, 4-diamine monoprotonated
BPR : Bromo pyrogallol Red
BPT : 4,7 -biphenyl-1, 10-phenanthroline
bpy Bipyridine
BunNH2 n-butyl amine
Bupy Butyl pyridine
CMP Cytidine-5-monophosphate
CN- Cyanide
Cydta 1,2 -Diaminocyclohexane N,N, N'N'-tetra acetic acid
Dacco Diazo cyclo octane
D-Mechanism : Dissociative Mechanism
DM NA : N,N'-Dimethyl (p-nitroso) aniline
DPA : Diethylene diamine Penta acitic acid
dto dithio ozalate
DTPA : Diethylene tetraamine penta acetic acid
1,4-DT : 1,4-dithiane
1,3 -DT : 1,3-dithiane
EBDP : Electrons Backscatter Diffraction Pattern
Edda : Ethylene diamine-N, N, N'N,-diacetic acid
EDTA : Ethylene diamine-N,N,N',N'-tetracetic acid
EGTA : Ethylene glycol bis(2-amino ethyl ether)- N,N, N',N'- tetraacetic acid.
en : Ethylene diamine
enH+ : Ethylene diamine monoprotonated
ETAAS : Electro thermal atomic absorption spectrometry
EtNH
2
: Ethyl amine
FIA : Flow Injection Analysis
Fuchsin : Fuchsin is a magneta dye having chemical formula
C19S17N3.HCl, when dissolved in water and named Fuchsed after German translation
of French Ronald Companie's in 19th Century.
Hedta : B-(2-hydroxy) ethylene diamine tetraacitic acid
HEEDTA : (Hydroxy ethyl) ethylene diamine triacetic acid
HMBPTS 2-Hydroxy-4-methoxy benzo phenone thiosemicarbazide
hxd : Hexane-1,6-diamine monoprotonated
I
2
Iondine
ICP-MS Inductively coupled Plasma-Mass spectrometry
IDA : Imino diacetic acid
KCM : Kinetic Catalytic Method
MIDA : Methyle Imino diaceti acid
MNDT : Maleonitrilo dithiolate
Mpz+ : Methyl Pyrazinium ion
NAA : Neutron Activation analysis
NDA : Nitroso diphenyl amine
N-R-salt : Nitroso-R-Salt
oN|N : o-Nitroso |-Naphthol
PAN : Pyridyl azo resorcinol
pd : Propane-1, 3-diamine
pdH+ : Propane-1, 3-diamine monoprotonated
Pdta : 1,2-Diamino propane tetro acetic acid
Ph : Phenyl
1,10-Phen : 1,10-Phenanthroline
Phy : Phenylhydrazine
ptd : Pentane-1, 5-diamine
ptdH+ : Pentane-1, 5-diamine monoprotonated
Py : Pyridine
Pz : Pyrazine
R2dtc : Di-alkyl dithio carbonate
SMs : synthetic Mixture
TCC : Temperature cell compartment
terpy : Terpyridine
Tet/Tetren : Tetra ethylene pentamine
TMDTA : etra methylene diamine tetra acetic acid
o,|,,o-TPPS : Tetra phenyl porphine sulphonate
Trien : Triethylene tetra amine
20-TSPP 20-Tetrakis (4-Suphonato phenyl) porphine
ttha : Triethylene tetramine hexa acetic acid
1,4-Tx : 1,4-Thioxane
Zincon : 2-carboxy-2-hydroxy-5'-Sulphoformazyl benzene


CHAPTER I


INTRODUCTION AND LITERATURE SURVEY


1.1 Scope and Purpose of Work :

Environmental contamination and exposure to heavy metals such as
mercury cadmium and lead and many others is serious growing problem through out the
world. Human exposure to heavy metals has risen dramatically in the last 50 years as
result of an exponential increase in the use of heavy metals in industrial processes and
products.


In today's industrial society, there is no escaping exposure to toxic
chemicals and metals. In the United states tons of toxic industrial waste are mixed with
liquid agricultural fertilizers and dispersed across America's farmlands. This
controversial practice", which is presently legal in the US, has been reported in nine
states. While the spreading of arsenic, lead, cadmium, nickel, mercury and uranium on
soil that is utilised to produce food for human consumption is a political and economic
issue. The potential for adverse health effects is well documented. In general, heavy
metals (HM) are systematic toxins with specific neurotoxic, nephrotoxic, fetotoxic and
teratogenic effects. Heavy metals can directly influence behaviour by impairing mental
and neurological function, influencing neurotransmitter production and utilization and
altering numerous metabolic body processes. System in which toxic metal elements can
induce impairment and dysfunction include the blood and cardiovascular, eliminative
pathways (colon, liver, kidneys, skin), endocrine (hormonal), energy production
pathways, enzymatic, gastrointestinal, immune , nervous, (central and peripheral) ,
reproductive and urinary.


Many occupation involve daily heavy metal exposure, over 50 professions
entail exposure to mercury alone. The greatest source of mercury in the biosphere is
currently of human origin Mercury is considered to be global pollutant capable of
spreading far beyond its source area. Methyl mercury is extremely toxic form of
mercury that biomagnifies in aquatic food chains. It is a potent neurotoxin and the
easiest form for animals to store in their tissues. It binds to proteins and easily crosses
cell membranes, including the blood-brain barrier and the placenta. Solutions to the
complex problem of mercury pollution have been impeded by conflicting informaiton
on the sources, transport and accumulation of mercury in the environment.


Due to the above post problems there is a need for the development of
methods for detection, estimation and removal of pollutants, which has recently become
an active field of analytical chemistry. This search has resulted in the emergence of an
entirely new area of research called the "Kinetic methods of Analysis". Many
possibilities of analytical interest are provided by the study of ligand substitution
reactions. But before any indicator reaction can be chosen for an analytical application a
detailed kinetic picture is quite often a necessary pre-requisite for the same.


Other important considerations such as scope, sampling and standard
requirements, cost of equipment and time of analysis, are also of great practical
significance. A number of methods such as AAS, ETAAS, ICPMS, NAA, FIA Ion
chromatography and anodic stripping analysis can be used for determination of trace
metal ions. The advantages of instrumental methods are low detection limits, high
sensitivity and selectivity, possibility for multi component analysis, non destructive
nature, distance analysis and analysis "invivo". Along with these advantages there are
certain limitations to the above stated methods. Many of these methods require
complicated and expensive instruments and these techniques are usually not available in
most routine laboratories. A recent addition to the above list is the "Kinetic Method
analysis", which ranks high among the analytical procedures Fig. 1.1 and offers some
distinct advantages over the conventional methods such as simplicity, specificity,
accuracy and economy. By kinetic method which is sometimes also reaction rate
method it is often possible to measure immediately after mixing the reactants, the rate
of change of some parameter 'P' of the particular reactant (s) whose concentration is to
be determined or product of the reaction and not wait for the reaction to go to
compelition or attain equilibrium. This saving in time may or may not be significant,
depending on the specific reaction, but there are good examples [2-7] of obtaining
quantitative rate results in seconds for some selective reactions that would have required
many minutes or hours to go to completion. Another important aspect of these kinetic
methods is that they can determine the concentration of two or three chemically closely
related constituents in a mixture, without separating them physically by using
differential rate methods.




Fig. 1.1 Limits of applicability of the most important trace analysis methods + in
flame, * without flame



In the past few years several excellent monographs on the kinetic methods
of analysis have appeared [8-16] and a significant drive has been made towards the
development of analytical methods for compounds, both inorganic and organic and
compounds of biological interests, in a variety of complex samples.
Before any reaction can be used for its analytical purpose, it becomes
absolutely necessary, to study in detail the kinetics and mechanism of that reactions.
Once this is done it is a relatively easy matter to choose experimental conditions like
concentration, pH, temperature and ionic strength etc. that would provide maximum
sensitivity, selectivity and precision for estimation of the desired chemical species.


Catalytic determinations are the most widely used of the kinetic methods.
The field of catalytic methods includes the methods of determination of trace
concentration of metal ions, anions and many organic substances. Low detectable
quantities and high sensitivities are recognized as major advantages of catalytic
determinations. Selectivity, on the other hand, can be considered to limit the practical
application of these determinations.


In recent years many catalytic methods have been studied. The evolution
and the innovations introduced, over the last two decades have been reviewed
comprehensively (17-40). The importance of kinetic studies goes beyond their direct
application in determinations, since most physical or chemical processes used in
contemporary analytical chemistry have their kinetic aspects. Mottola (3) has for
example, discussed systematically the aspects of kinetics that have become part of
modern analytical chemistry. Every process, whatever its nature, takes place at a finite
rate, tending to an equilibrium, state. The two states, the kinetic (dynamic) state, and the
equilibrium (static) state are both of high informing power (4). Reaction-rate methods
are becoming increasingly important practically in analytical chemistry; progress
however, relies heavily on better elucidation of the mechanisms of chemical reactions.
Recent developments in instrumental design and, especially, in the incorporation of
microcomputers for the control of experiments and data evaluation allow for improved
precision, limits of detection, rapidity and automation of such methods.


On the other hand majority of easy chemical methods suffer in sufficient
sensitivity. That is why sometimes it is considered that possibilities of chemical
reactions in trace analysis are exhausted. Exceptions to this are enzymatic catalytic
methods. The high turnover numbers of enzymes allow one particle of catalyst to take
part in a great number of elementary reactions. Moreover, the high selectivity of
enzyme action ensures good selectivity of reaction.


In most cases the reaction rate is monitored photometrically. The enzymatic
catalytic methods combine low limits of detection, high selectivity, simple and available
technique. That is why these methods compete successfully with the instrumental
methods. Moreover, they are irreplaceable for determination of enzyme activity in
analytical practice [41].


Keeping this in view further discussion has been divided into two parts. In
the first part, a brief survey of the significant developmens in the ligand substitution
reactions is reported while the second half deals with the principles and applications of
ligand substitution reactions for trace determination by kinetic catalytic methods (KCM)
of analysis, characterization, classification and methodology.



REVIEW PART- I


1.2 In coordination chemistry, a ligand is an ion or molecule (functional
group) that binds to a central metal atom to form a coordination complex. The bonding
between metal and ligand generally involves formal donation of one or more of the
ligands electron pairs. The nature of metal ligand bonding can range from covalent to
ionic. Furthermore, the metal-ligand bond order can range from one to three, Ligands
are viewed as Lewis bases, although rare cases are known involving Lewis acidic
ligand.


Metals and metalloids are bound to ligands in virtually all circumstances,
although gaseous naked metal ions can be generated in high vacuum. Ligands in a
compelx dictate the reactivity of the central atom, including ligand substitution rates,
the reactivity of the ligands themselves, and redox reactions. Ligand selection is a
critical consideration in many practical areas, including bioinorganic and medicinal
chemistry, homogeneous catalysis and environmental chemistry.


Ligands are classified in may ways : their charge, their size (bulk), the
identity of the coordinating atom(s), and the number of electrons donated to the metal
(identicity or hapticity). The size of a ligand is indicated by its cone angle.


Co-ordination compounds are classified in terms of the central metal M
n+
,
about which a variety of ligands L, L', L" and so on, may be placed in an unlimited
number of combinations. The overall charge on the resulting complex [MLx LyLz] is
determined by the charge on M and sum of the charges on the Ligands.


The ability of a complex to engage in reactions that result in replacing one
or more ligands in its coordination sphere in called its lability. Those complexes for
which such substitution reaction are rapid, are called labile whereas those for which
such substitution reactions proceed slowly (or not at all) are called inert. It is to be noted
that these terms should not be confused with thermodynamic stability and unstability
[42].

For example :

[Cu(OH
2
)
6
]
2+
(aq) + NH
3
(aq) instantaneous

[Cr(OH
2
)
6
]
3+
(aq) + NH
3
(aq) several hours


As for metal hexa-aquo ions in the first transition series, most are labile.
The only two tha are not are Cr(III) and Co(III). And that is why we often start off with
a solution of Co(II) when we want to make complexes of Co(III) : Co (II) is labile so we
can do rapid substitution reactions on it and then oxidize it pretty easily to Co(III),
whereas if we started off with Co(III), which is inert, our substitution reaction would be
much slower.


We can measure the rate of these reactions by dissolving a hexa-aquo
complex in water labelled with
18
O and then monitoring how long it takes for the
labelled water to exchange with the unlabelled ones in the inner coordination sphere.
You ought to be aware that for some hexa-aquo ions in the 2
nd
, and particularly the 3
rd

transition series, substitution reactions can take a long time thousands of years in
some cases !


While were on the subject of hexa-aquo ions, we ought to be aware that
they are to some extent acidic. Attaching a water molecule to a metal centre takes some
of the electron density from the oxygen and consequently makes the hydrogens easier to
pull off as H
+
. Hence, if you take something like hydrated iron (III) chloride, dissolve it
in water, and measure the pH, you will find that it is somewhat acidic.


A practical definition of the terms labile and inert can be given here. Inert
complexes are those whose substitution reaction have half life longer than a minute.
Such reactions are slow enough to be studied by the classical techniques where the
reagents are mixed and changes in absorbances, pH, gas evolution is observed. Labile
complexes are those that have half lives for a reaction under a minute. Special
techniques are required for collecting data during such reactions, as they may appear to
be finished within the time of mixing.


1.3 Kinetics and Mechanism of Ligand substitution reaction.


Two extreme mechanistic possibilities may be considered for any ligand
substitution process or for any single step in a series of substitution reaction [43]. First,
there is the dissociative (D) mechanism in which the ligand to be replaced dissociates
from the metal centre and the vacancy in the co-ordination sphere is taken by the new
ligand. (Eqn. 1.1)







Thus, we see that the most important feature of such a mechanism is that the
first step (dissociation of the leaving group) is rate determining step, once formed by the
cleavage of the bond to the leaving group X, five coordinate intermediate will react with
the new ligand Y, almost immediately. The kind of mechanism is synonymous to SN
1

mechanism in organic systems, since the formation of the intermediate with reduced co-
ordination number is unimolecular as well as rate determining.


The other extreme possibility for ligand substitution is the addition
elimination mechanism, or the associative (A) mechanism. In this case the new ligand
Y, directly attacks the original complex to form a seven membered intermediate in the
rate determining step Eqn. 1.2. After this step, the leaving group X is lost in a fast step.
This mechanism can be compared to the SN
2
mechanism of organic system, since the
rate determining step is bimolecular.


(1.1)




In many substitution reactions, well defined five or seven membered
intermediates are not observed, instead the transition state found, has some degree of
bond breaking and some degree of bond making, abbreviated as I mechanism i.e.
Interchange mechanism [44]. They may be of I
a
[45] or I
d
[46] type as explained below.





In the case of the I
a
mechanism we could say that the bond from the incoming
ligand starts to form before the leaving one starts to break. In the I
d
mechanism, we
could say that an existing metal-ligand bond starts to lengthen or weaken before the
(1.2)
incoming ligand arrives. A pure interchange would have the leaving ligand-metal
bond weaken at the same time that the incoming ligand-metal bond forms.

There are three most important type of cases which show some sort of
complication present in reaction mechanism.
(i) Solvent Intervention
(ii) Ion Pair Formation
(iii) Conjugate base Formation

(i) Solvent Intervention

Many reaction of complexes have been studied in solvents that are
themselves ligands. Water, for example is a very good ligand of this category and is
present in aqueous solution in high and effectively constant concentration. The
substitution of X by Y might take place as under Eqn. 1.3 and 1.4.


MX
n
+ H
2
O MX
n-1
H
2
O + X (1.3)
MX
n-1
H
2
O + Y MX
n-1
Y+ H
2
O (1.4)


Intervention of solvent like water obscures the molecularity of the rate
determining step, the reaction will necessarily be observed to be of first order because
of high and constant concentration of the entering ligand, H
2
O.


(ii) Ion Pair Formation
It occurs when the reacting complex and the entering ligand are both ions,
especially when both have high charges Eqn. 1.5.

[M X
5
]
n+
+ Y
m-
{(M X
5
)Y}
n-m
(1.5)

Polycationic complexes tend to form ion pairs with anions and these ion
pairs often undergo reactions via the I
a
pathway. The electrostatically held nucleophile
can exchange positions with a ligand in the first coordination sphere, resulting in net
substitution. An illustrative process comes from the anation (reaction with an anion)
of chromium (III) hexaaquo complex :

[Cr(H
2
O)
6
]
3+
+ SCN
-
{[Cr(H
2
O)
6
], NCS}
2+
(1.6)
{[Cr(H
2
O)
6
], NCS}
2+
[Cr(H
2
O)
5
NCS]
2+
+ H
2
O (1.7)



When ion pairs are featured as intermediates in the reaction path that leads
to ligand substitution, then the observed rate laws will be of second order, whether or
not mechanism at the rate determining step involves, Associative and dissociative
Pathways [42, 43].


(iii) Conjugate base Formation

When experimental rate laws contain [OH
-
] then there is a question whether
OH
-
actually attacks the metal in a true associative fashion or whether it appears in the
rate law through operation of mechanism Eqn. 1.8 and 1.9.


[Co (NH
3
)
5
Cl]
2+
+ OH
-
[Co(NH
3
)
4
NH
2
Cl]
+
+ H
2
O fast (1.8)
[Co (NH
3
)Cl]
2+
+ Y
-
OH
-
[Co(NH
3
)
5
Y]
2+
+ Cl
-
slow (1.9)


In this conjugate base (CB) mechanism, the rate for the hydrolysis of cobalt
(III) ammine halide complexes are deceptive appearing to be associative but proceeding
by an alternative pathway. The hydrolysis of [Co(NH
3
)
5
Cl]
2+
follows second order
kinetics; the rate increases linearly with concentration of hydroxide as well as the
starting complex. Based on the information, the reactions would appear to proceed via
nucleophilic attack of hydroxide at cobalt. Studies show, however, that in the hydroxide
deprotonates one NH
3
ligand to give the conjugate base of the starting complex, i.e.
[Co(NH
3
)
4
(NH
2
)Cl]
+
. In this monocation, the chloride spontaneously dissociates. This
mechanism is compable to the SN
1
CB mechanism of organic system.


Water Exchange in Aqua Ions

Of the many reactions in which complexes are formed occur in aqueous
solution, one of the most fundamental reactions in which the water ligands in the aqua
ion [M(H
2
O)
n
]
m+
are displaced from the first co-ordination shell by other ligands come
under this category. In this, a new ligand is another water molecule, i.e. the water
exchange reaction [42].

It is convenient to classify metal ions in four categories based on the measured
exchange rates :


Class I : Very fast (diffusion controlled); k > 10
8
s
-1

Alkali, larger earth alkaline metals like Cd
2+
, Hg
2+
, Cr
2+
, Cu
+
come under this category.

Class II : Rate between 10
4
10
8
s
-1

Divalent first-row transition metals (except V
2+
, Cr
2+
, Cu
2+
) Ti
3+
, Mg
2+
, trivalent
lanthanides, depict this category.


Class III : Rate between 1 10
4
s
-1

Be
2+
, V
2+
, Al
3+
, Ga
3+
, show this rate.


Class IV : Kinetically inert; rate between 10
-6
-10
-2
s
-1

Ions like, Cr
3+
, Co
3+
, Rh
3+
, Ru
2+
, Ir
3+
, Pt
2+
, belong to this category.


Many other reviews on the substitution reactions involving specific metal
ions viz. Ni (II) [47], Fe III [48], Cd [49], Pd(II) [50] have been attempted by previous
investigators. Therefore, only a brief description based on the following broad heading
will be presented.


1.4 Formation Reaction

The formation of metal complexes take place in media where usually
water acts as a solvent. The rate of there reactions vary from very slowly to very fast.
The generally accepted mechanism for complex formation was originally proposed by
Eigen and Tamm [51-53]. For complexes of unidendate ligands it involves the
formation of an outer sphere complex between solvated metal ion and the incoming
ligand followed by loss of a solvent molecule from this outer sphere compelx to give
the desired species. The mechanism of formation of complexes of multidentate ligand
can be extended to the formation of complexes of multidentate ligands with the minor
modification that the ring closure may constitute the rate determining step. The Eigen
and Tamm mechanism on the formation of labile complexes involving divalent cation
is, by now, fairly well enstablished [55]. The formation of M(III) complexes in general
and Fe(III) in particular have already been described in detail by a review on the subject
[56].


1.5 Dissociation Reaction

The dissociation of metal complexes can be considered as the reverse of the
complex formation. These reactions are, generally much slower than the formation
reactions. The mechanism proposed for the complex formation also accounts for the
dissociation rates of complexes bearing unidentate, bidentate or ambidentate ligands. In
case of complexes of bidentate or ambidentate ligands the rate constant depends upon
opening of the chelate ring or sometimes rupture of penultimate metal-ligand bonds.
Both these situations have been encountered frequently with outgoing bidentate or
multidentate ligand groups. The presence of an acid generally enhances the dissociation
rate because of protonation of the released ligand stablises the intermediate relative to
the fully coordinated form [57, 58].


1.6 Ligand Exchange Reactions

Ligand substitution reactions of coordination compounds have been
studied as intensively as any class of inorganic reactions. The kinetics of these
processes have been investigated extensively for octahedral and to a lesser extent for
square planar complexes. A very wide span of rates is found ranging from the extremely
slow exchange of CN
-
with NiCYDTA
2-
( no evidence for the formation of [Ni(CN)
4
]
2-
in 60 days) [59] to the almost diffusion controlled exchange of H
2
O between
[Cu(H
2
O)
6
]
2+
and water (t

= 10
8
sec.) [60]. There are the four types of substitution
reaction met with coordination chemistry.


a. Monodentate ligand displacement reaction (excess ligand)
b. Multidentate ligand displacement reaction (excess ligand)
c. Metal exchange reactions between ligands (excess metal)
d. Double exchange reactions.


The above exchange reactions are often sluggish in nature because the
reaction involves the breaking of a series of coordinate bonds in succession. In case of
displacement of the multidentate ligand EDTA, for example six bonds must be broken
during exchange process.


1.6.1 a. Monodentate Ligand Displacement Reactions

This section is concerned with the kinetic and mechanism of substitution in
complexes where monodentate ligands exchange with monodentate or multidentate
ligands.


1.6.1a
1
. Unidentate by Unidentate Ligands

The substitution of one unidentate ligand by another is the simplest
situation to consider and has been extensivey used for investigating the mechanism of
substitution in some octahedral complexes as well as some square-planar complexes.
The general reactions involve the replacement of a monodentate ligand present in the
inner coordination sphere in the solvent media.


There are two basic mechanisms for monodentate ligand exchange in aqueous
solution. Considering the nickel-hexaamine system the first mechanism would be a
dissociate type :


r.d.s
[Ni (NH
3
)
6
]
2+
[Ni (NH
3
)
6
]
2+
+ NH
3
(1.10)

+NH
3

[Ni (NH
3
)
5
]
2+
[Ni (NH
3
)
6
]
2+
(1.11)


The second would be bimolecular mechanism involving water molecules :


r.d.s
[Ni (NH
3
)
6
]
2+
+ H
2
O [Ni (NH
3
)
5
H
2
O]
2+
+ NH
3
(1.12)


[Ni (NH
3
)
5
H
2
O]
2+
+NH
3
[Ni (NH
3
)
6
]
2+
+ H
2
O (1.13)


It is difficult to distinguish between such mechanism in aqueous solution.
However, the lack of NH
3
attack on [Ni (NH
6
)
5
]
2+
and the fact that a change of 30% in
H
2
O concentration produced no observable effect support a dissociative mechanism
[61].


The kinetics of substitution reaction of a series of complexes of the type
[Ni Fe(CN
5
) L]
(3n)
have been studies by Toma and Melin [62, 63] where L was an
aromatic nitrogen heterocycle and the substitution ligand was Nitroso-R-salt ( N-R-
salt). The rate of substitution varied with the nature of L and a saturation kinetic, typical
of rate determining loss of L from the complex, followed by rapid addition of the
incoming ligand was reported. This is the first study [65] about monodentate ligand
substitution reactions of simple low-spin Fe(II) complexes which generally proceed by
D or SN
1
(lim) mechanism according to following scheme (Eqn. 1.14).



k
L
d

Fe(CN
5
) L]
(3-m)-
[Fe(CN
5
)]
3
+

L
m

k
L

k
L1
+ L
n
1
(1.14)


Fe(CN
5
) L
1
](
3n)


Where m and n are charges on L and L
1
respectively.


A similar study [66] of the reaction of [Fe (CN)
5
SO
3
]
5
with CN
-
has also
been reported. Other examples include aquation of [Fe (CN)
5
NO]
2
[67] and its reaction
with ammonia hydroxylamine or hydrazine [63]; the reaction of [Fe (CN)
5
(3,5 Me
2
-
Py)]
3
with CN
-
Pyrazine ( Pz) and imidazole ( Imid H) [69], the reaction of [Fe (CN)
5

PhNO]
3
[70], of [Fe (CN)
5
SO
3
]
5
[71], of [Fe (CN)
5
Py]
3
with cyanide ion. The
photochemical reaction of [Fe(CN)
5
NO]
2-
with thiourea or diethylethiourea in methanol
have also been study and shown to follow second order rate law [74]. Several reports
have appeared on the complex formation reactions involving [Fe(CN)
5
H
2
O]
3-
. The
tendency of this ion to dimerise at higher concentration and the nature of the dimeric
species [75, 76] involved have also been discussed. The rate data of some work on the
formation and dissociation reactions of [Fe(CN)
5
L]
(3-m)-
complexes have been compiled
from literature and are given in Table 1.1. Kinetic and thermodynamic data from
mechanistic studies are consistent with a dissociative 'D' mechanism involving the five
coodinated intermedia [Fe(CN)
5
]
3-
is likely for most of these reactions although some
researchers still favour on I
d
mechanism [77, 78].


Recently Abu Gharib et al. [64] have reported the kinetic data for the
reaction of [Fe (CN)
5
(4-CN-Py)]
3
with a variety of incoming ligands over a range of
concentration in order to provide a good illustration of the saturation kinetics. Together
with respective double reciprocal plots. These authors claim that hese results are
compatible with a limiting dissociative mechanism.


Malin and co-workers [79] have observed that the intermediate [Fe
[Fe(CN)
5
]
3
is quite insentive to the nature and charge of the attacking reagent. In order
to examine the influence of charges on the attacking reagents. Bradic et al. [80] studies
the kinetics of replacement with L
1
n
. A being PhNO, 3-CN-Py, DMNA, SCN
-
, CN
-
and
SO
3
2-
, and the leaving ligand Lm being DMNA, PhNO, SO
3
2-
and H
2
O respectively.
Finally, they concluded that the magnitudes of second order rate constant k
L1
are similar
and vary with L
n
a in the range of approximate 200-300 M
-1
s
-1
, 42 to 60 M
-1
s
-1
and 33
M
-1
s
-1
for uncharged molecule, uninegative ion and SO
3
2-
respectively. The effect of
ionic strength fits fairly well with the Bronsted -Bjerrum equation [80]. Limiting
reaction rates, at sufficiently large concentrations of entering ligand L
1
n
have been
observed with all leaving ligands, except water where the replacement obey a second
order rate law [63, 79, 80] as given in Eqn. 1.15.

(1.15)


Table 1.1
Kinetic and activation parameters at 298
o
K for the formation and dissociation of
various pentacyano (ligand) ferrate (II) compelexes

Ligand K
f
M
-1
s
-
1

K
d
x
10
4
,s
-1

AH
=

(kJ mol
-1
)
AS
=

(JK
-1
mol
-1
)
Ref.
1 2 3 4 5 6
Pyridine 365 11.0 103.7 (67.3)* 46.0 (29.3)* 62, 79
4-Methylpyridine - 11.5 100.3 37.6 62
Isonicotinamide 296 7.3 108.7 (66.0) 58.5 (25.1) 62, 79
4-Picoline 354 - - (63.1) - (16.7) 79
Pyrazine 380 4.2 110.3 (64.4) 58.5 (20.9) 62
n-Metylpyrazinium 550 2.8 114.9 (70.2) 74.6 (41.8) 62
Dimethylsulphoxide 240 0.75 110.8 (64.4) 46.0 (16.7) 79
4,4 bipyridine - 6.2 110.8 66.9 62
Thiourea 286 390.0 69.4 (65.6) -37.6 (20.9) 76
Allylthiourea 196 451.0 68.1 (69.8) -41.8 (33.4) 76
Dimethylthiourea 238 813.0 75.2 (64.8) -12.5 (16.7) 76
Glycinate 28.0 26.7 97.0 (61.5) 29.2 (-12.5) 77
Imidazole 240 13.3 101.6 (63.5) 41.8 (12.5) 77
N'-Histidine 320 5.3 105.3 (64.4) 46.0 (20.9) 77
N
3
-Histidine 320 1090 91.1 (644) 41.8 (20.9) 77
Cyanide 38 - - - 80
Thiocyanate 64 - - - 80
3-Cyanopyridine 370 - - - 80
Nitrile 42 - - - 80
DMN - 12.0 - - 80
Aniline - Ca0.20 - - 78
Cyclohexylamine - 13.56 96.5 46.0 78
Ethanolamine - 7.72 97.8 38.0 78
Morpholine - 7.16 103.2 53.9 78
Continued on page no.
Table 1.1 (continued)

1 2 3 4 5 6
NH
3
190 12.0 102.4 63.1 78
MeNH
2
130 4.46 103.2 53.9 78
MeNH 80 7.79 100.3 49.7 78
Me
3
N 60 12.2 91.4 28.8 78
Bu
n
NH
2
250 7.47 105.7 66.9 78
EtNH
2
180 7.54 104.1 38.0 78
Pi
n
NH
2
200 7.38 107.0 71.0 78
Bipyridine - 8.43 94.9 29.0 78
En 330 51.5 97.0 37.7 81
enH
+
620 104.0 99.90 50.1 81
Sulphite - 0.57 Ca 119.5 Ca 75.2 81
Nitrosobenzene - 0.016 Ca 117.0 Ca 41.8 81
N-Methylimidazole 418 32.4 81.5 - 82
Isonicotinohydrazide 325 7.3 107.8 59.8 83
Pd - 54.0 100.5 58.7 84
pdH
+
- 83.0 100.5 53.7 84
bd - 46.0 102.4 58.7 84
bdH
+
- 69.0 104.5 62.7 84
Ptd - 45.0 103.7 58.7 84
ptdH
+
- 64.0 101.6 53.7 84
hxd - 41.0 100.5 45.8 84
hxdH
+
- 53.0 96.5 37.8 84
1,4-Tx - 5.71 112 71 85
1,4-DT - 5.58 105 44 85
1,3-DT - 3.39 108 50 85

* Numbers in parenthesis give the values of A H
=
and A S
=
for the formation reactions.

In recent years one of the diagnostic tests that is being widely applied for
elucidating the substitution mechanisms, is the volume of activation (AV
#
) [86-88].
Thus, the most convincing evidence in favour of D mechanism comes from the
determination of AV
#
. If the leaving group of D mechanism comes from the
determination of AV
#
. If the leaving group L
m
is to dissociate completely in the
transition state then a positive value of AV
#
is interpreted as representating a stretching
of a metal-ligand bond in the transition state and this favours a D mechanism.
Activation volumes [69] for ligand substitution reaction on several pentacyano (ligand)
ferrate (II) complexes by few incoming ligands are isted in Table 1.2. The values listed
in Table 1.2 are all the positive values.This suggests that either a dissociative
mechanism or a mechanism involving charge dispersal in the transition state is obeyed
[97].


In the D mechanism of the scheme given in Eqn. 1.5 there is a competition
between incoming ligand L
n
1
and the outgoing L
m
for the transient intermediate
[Fe(CN)
5
]
3-
produced from [Fe(CN)
5
L]
(3- m)-
which is characterized by the ratio of the
second order rate constant k
L1
/ K
L
. This gives an idea of the reactivities of a variety of
ligands for the intermediate [Fe(CN)
5
]
3-
. Reactivity ratio for various nucleophiles in
aqueous solution are listed in Table 1.3. Solvent effects on relative reactivities of
[Fe(CN)
5
]
3-
in various binary aqueous mixtures have also been discussed [98].


Table 1.2

Activation volumes ( V
#
) for some ligand substitution reactions on pentacyano
(ligand) ferrate (II) complexes by various incoming ligands in aqueous and non-
aqueous medium.

Reaction Solvent V
#
(cm
3
mol
-1
) Ref.
1 2 3 4
Fe(CN)
5
L
3-
+CN
-
Fe(CN)
6
4-
+L

L = 4-(1-butylpentyl) pyridine

L=4-phenylpyridine
L=N-)n-pentyl)pyrazinium (Na
2
salt)
L= Pyrazine
H
2
O-
MeOH
H
2
O
H
2
O
H
2
O
+16

+10
+10
+13
89
Fe(CN)
5
L
3-
+CN
-
Fe(CN)
6
4-
+L

L=4-CNpy
L=4,4' - bpy
L=4
-t
Bupy
H
2
O
H
2
O
H
2
O
+19.00.5
+13.50.7
+11.41.0
90
Fe(CN)
5
L
3-
+CN
-
Fe(CN)
6
4-
+L

L = p- (CH
3
CH
2
CH
2
)CHC
5
H
4
N

L=p-(C
5
H
4
N)
2

L=p-(C
6
H
5
)(C
5
H
4
N)
L=p-CH
3
(CH
2
)
5
NC
4
H
4
N
+
L=p-C
6
H
4
N
2
C
2
H
2

L=p-(CH
3
)
3
CC
5
H
4
N
L=p-NCC
5
H
4
N
L=p-CH
3
CC
4
H
4
N
2
+


20%
MeOH
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O

+16.31.4

+13.60.5
+10.40.5
+9.60.8
+17.90.4
+11.41.0
+19.01.0
+0.90.5
91
L=p-C
4
H
4
N
2

L=p-CH
3
C
4
H
4
N
2
+

H
2
O
H
2
O
+12.51.2
+20.90.5
Fe(CN)
5
(4-CNpy)
3-
+CN
-
Fe(CN)
6
4-
+4CNpy
H
2
O +19.01.0 92
Fe(CN)
5
(NH
2
R)
3-
+pyFe(CN)
5
(py)
3-
+ NH
2
R

R=H
R=CH
3

R=C
2
H
5
R=PhCH
2
R=
1
P
r

H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
+16.40.6
+24.01.0
+16.31.5
+17.41.4
+18.50.6
93
Fe(CN)
5
H
2
O
3-
+L
n-
Fe(CN)
5
L
(3+n)-
+H
2
O

L
n-
= imidazole
L
n-
= histidine
L
n-
= methionine
L
n-
= glutathione
L
n-
= glycine
L
n-
= |-alanine
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
+15.50.7
+17.00.4
+17.90.6
+14.10.4
+16.40.6
+16.80.2
94
Fe(CN)
5
H
2
O
2-
+L Fe(CN)
5
L
2-
+H
2
O

L = cytosine
L = cytidine
L= CMP

H
2
O
H
2
O
H
2
O
+2.50.5
+9.51.2
+12.81.1
95
Fe(CN)
5
(NO
2
)
2
4-
+H
2
OFe(CN)
5
(H
2
O)
3-
+NO
2
-

H
2
O +20.11.0 96


Table 1.3

Reactivity ratios K
L1
/K
L
for the replacement of a lignd L
m
by an incoming ligand
L
n
1
in the omplexes of the type [Fe(CN)
5
-L]
(3-m)-
in aqueous solution at 25
0
C


Outgoing ligand L
m
Incoming ligand L
n
1
Ratio of rates
K
L1
/K
L

Ref.
4-CN-Py CN
-
0.03 98
3-CN-Py CN
-
0.05 98
p-Me
2
NC
6
H
4
NO CN
-
0.10 80
p-Me
2
NC
6
H
4
NO PhNO 0.80 80
SO
3
2-
CN
-
9.0 66
H
2
O CN
-
12000 70




1.6.1 a
2
. Multideatable By Unidentate

The exchange of multidendate ligands by unidendate ligands is another example of
unidendate ligands exchange reactions.
Recently Nigam and coworkers have investigated the kinetics and mechanims for
replacement of aminocarboxylates from mono (aminocarboxylato) hydroxoferrate (III)
complexes by cyanide ions [99-101]. The general mechanistic scheme for [NiL]
(2-n)
-
CN- replacement reactions requires that three cyanides are bonded to Nickel (II) ion
while four cyanides are required in [Fe L(OH)]
(2-n)
-CN
-
systems (n= charge on ligand L)
in their respective rate determining step. The last cyanide adds rapidly forming
[Ni(CN)
4
]
2-
or [Fe(CN)
5
OH]
3-
as the case may be.


Some bis [99-101] and binuclear [104-106] nickel (II) complexes of multidentate
ligands react with cyanide ion by a cyanide independent dissociative path (Eqn. 1.16,
1.19) and cyanide dependent associative path (1.17, 1.18, 1.20, 1.21)

Bis NiL
2

k
d

NiL + L (1.16)
NiL
2
+ CN
-
NiL (CN) + L (1.17)
NiL(CN)+3CN
-
NiL (CN)
4
2-
+ L ( in steps) (1.18)

Binuclear Ni
2
L
k
d

NiL + Ni
2+
(aq)
(1.19)
Ni
2
L + CN
-
NiL (CN) + Ni
2+
(aq)
(1.20)
NiL(CN)+3CN
-
NiL (CN)
4
2-
+ L ( in steps) (1.21)

The [FeL(OH)]
(2-n)
-CN- reaction presents some complications and takes place in three
distinct stages [99-101]. The mechanism for the first stage i.e. the formation of
[Fe(CN)
5
(OH)]
3-
from [FeL(OH)]
(2-n)
complexes as already been reported for many
aminocarboxylates as hown in eqn. 122-1.26


K
1

[FeL(OH)]
(2-n)
+ CN
-
[FeL (OH)(CN)]
(1-n)
fast (1.22)
K
2

[FeL(OH)(CN)]
(1-n)
+ CN
-
[FeL (OH)(CN)
2
]
n-
fast (1.23)

K
3

[FeL(OH)(CN)
2
]
n-
+ CN
-
[FeL (OH)(CN)
3
]
(n+1)-
fast (1.24)

k
4

[FeL(OH)(CN)
3
]
(n+1)-
+CN
-
[FeL (OH)(CN)
4
]
(n+2)-
r.d.s. (1.25)

k-
4


k
5

[FeL(OH)(CN)
4
]
(n+2)-
+CN
-
[Fe(CN)
5
(OH)]
3
+ L
n-
fast (1.26)

Where L = HPDTA
4-
, HIDA
2-
, EDTA
4-
, HEDTA
3-
, DTPA
5-
, PDTA
4-
, and
TTH A
6-
.The second stage of reaction is the conversion of [Fe(CN)
5
OH]
3-
to [Fe(CN)
6

]
3-
due to reaction with cyanide ions, present in excess according to Eqn. 1.27


[Fe(CN)
5
OH]
3-
+

CN
-
[Fe(CN)
6
]
3-
+ OH
-
(1.27)


The third stage involves the oxidation of aminopolycarboxylates released in
the first stage Eqn. 1.26 by [Fe(CN)
6
]
3-
formed in the second stage as shown in Eqn.
1.28


[Fe(CN)
6
]
3-
+

L
n-
[Fe(CN)
6
]
3-
+ oxidation product of L
n-
( 1.28)


The cyanide is a potential unidentate ligand having the capacity of
displacing multidentate liands viz. microcyclic ligand, polyamines,
polyaminocarboxylates and thioligands from their metal complexes. The reactions
involving [NiL]
(2-n)
compelexes ( L = polyaminoarboxylates [59, 107-108] and
polyamines [109, 110] microcyclic ligands [111, 112]) with cyanide ions have been
studied extensively by many workers.


1.6.1 a
3
. Unidentate by Multidentate

This type of reactions have been studied extensively in connection with the
replacement of coordinated water during the formation reactions of multidentate ligand
complexes [113]. The reactions of open chain and macrocyclic polyamines with Cu(II)
in strongly basic solutions have been studied [114] to examine the kinetic behavior of
the unprotonated ligands. Some kinetic information is also available on the reactions of
[Ni(CN)
4
]
2-
with aminopolycarboxylate ligands. A mixed [Ni(CN)
3
L]
(n+1)-
complex is
formed before the rate determining step in which an additional CN
-
is lost. The behavior
with trien is different, however, becaue the rate-determining step is the reaction of the
ligand directly with [Ni(CN)
4
]
2-
by an associative mechanism [115]. Also the
disappearance of [Ni(CN)
4
]
2-
is greatly accelerated by the polyamine concentration in
comparison to the much slower reaction of [Ni(CN)
4
]
2-
with aminocaboxylates [59,
107]. Crouse and Margerum [79] have reported the reaction of [Ni(CN)
4
]
2-
with a few
polyamines in presence and absence of I
2
as a scavenger for cyanide ion. In presence of
I
2
the released cyanide has no effect on the forward reaction rate but in absence of I
2

there is an inverse effect.

1.6.2 Multidentate ligand displacement reactions


The mechanisms by which one multidentate ligand displaces another from a
metal ion depends upon the ability of both ligands to coordinate with the metal ion
simultaneously. There are four accepted mechanisms for this type of reactions.


(i) The outgoing ligand (L-L) is completely dissociated from the metal cation (M)
before association between M and the incoming ligand (L-L)* starts.

(1.29)

(1.30)

(ii) The association of the metal cation with the incoming ligand may begin before
dissociation of the outgoing ligand is complete. In this mechanism there will be
an intermediate, in which both ligands are bonded to the same cation.


(1.31)


(iii) A variation on the above mechanism in the case of pre equilibrium partial
dissociation of he starting complex.

(1.32)


(iv) In the last scheme, there is a modification of the previous scheme, one which
can apply when two multidentate e.g., tetradentate ligands are replaced by
another multidentate e.g. quinqui of hexadentate ligand.

(1.33)

The rate determining step of overall reaction is the cleavage of any one of
the several bonds between metal and the leaving group which must be broken in the
course of the reaction. As example, Ni Tet
2+
reacts with EDTA [116], TMDTA [117],
PDTA or DTPA [118] and Nitrien
2+
reacts rapidly with EDTA [119], HEDTA[120] or
DTP [121] forming mixed ligand intermediates and give respective products by
unwrapping of Tet or Trien.


A review of on multidentate ligand exchange reaction and their application
to analytical chemistry has appeared for system involving EGTA and 4(2-Pyridylazo)
resorcinol [122]. Other multidentate ligand exchange reactions of metal ions such as
Cu(II) [123-125], Zn (II) [126], Hg (II) [127], Cd (II) [128-130] and Ni (II) [131-135]
have been investigated by many workers.


The elucidation of substitution mechanism of a coordinated ligand to Fe(III)
centre by another incoming ligand has been the subject of considerable interest for
many workers [136-140], including us [101]. Most of these studies are largely centred
around exchange of a polydentate by a monodentate or monodentate by polydentate
ligand. On the contrary, there have been limited reports on the kinetic and mechanistic
studies involving the exchange ofa polydentate ligand coordinated to Fe(III) by another
polydentate ligand [141-143].


We have recently investigated the kinetics and mechanism of the exchange
of HIDA coordinated to Fe(III) viz. from [Fe HIDA (OH
2
)]
-
by Par (2Pyraylazo
resorcinol). This reaction seen to proceed through the following mechansitic scheme
Eqn. 1.34-1.36.

k
1

[FeL(OH)
-
+ HR
-
[RFeL]
2
+H
2
O fast (1.34)

k-
1


k
2

[RFeL]
2


[FeR]* +L
3-
r.d.s. (1.35)

k-
2



k
3

[FeR]
+


[FeR
2
] + H
+
fast (1.36)

k-
3



This mechanism is in confirmation with the mechanism proposed earlier by
Nigam et al. [142] and us [143] for FeL-Par (L = HEDTA and NTA). Mentasti et.al.
[141] has investigated the kinetics of displacement of metallochromic indicators (In)
from their complexes of Fe(III), represented by the Eqn. 1.37.


Fe In + EDTA Fe EDTA + In (1.37)


In = Salicyclic acid H
2
S
4
I or Tiron = 1, 2-di hydroxy benezene disulphonic
acid (H
2
T).


In many multidentate ligand replacement reactions the rate expression
contains terms in various powers of the hydrogen concentration, which arise from the
possible ways of protonating the ligands both free and in complexed form. It has been
possible to resolve the rate constants due to various protonated reactant by algebraic
manipulation and mathematical analysis of reaction rates measured over a wide pH
range and resorting to some simplifying assumptions about species distribution.


1.6.3 Metal Exchange and Displacement Reactions

The displacement of one metal cation from its complex, with a multidentate
ligand by another metal ion (or the exchange with an identical labelled metal ion) is
represented by Eqn. 1.38.

M + M'L M' + ML (1.38)

Mechanism of metal displacement can be either dissociative


(1.39)



or associative in nature.


(1.40)



The mechanism of some metal cation displacement reactions are indicated
in Table 1. 4


Table 1.4
Mechanism of some cation displacement reactions from
Multidentate Ligand Complex

Complex Replacing cation Type of
mechanism
Ref.

Ca (II)-TTHA M(II) (M-Co, Ni,
Cu, Zn)
DA 144
Cd (III)-CYDTA Cu(II) D 145
Cd (III)-EDTA Cu(II) DA 146
Cd (II)-(EDTA)H
-
Cu(II) DA 147
Cu (II)-EDTA Cu(II) DA 148
Fe (III)-HEDTA, -DTPA Cd(II) D 149
Fe (III)-HEDTA, -EGTA, -
DTPA


Ga(III) D 150
[Fe(III) (EDTA) H
2
O]
-
In (III) - 151
[MEDTA]- (m=Gaor In) Fe (III) D 152
Bi (III) EDTA Fe (II) D 153



Reactions following Eqn. 1.39 are represented by D and Eqn. 1.40 by DA.


1.6.4 Double Exchange Reactions

An interesting situation exists when two multidentate complexes are mixed
and thermodynamics dictates a double exchange reactions [154]. The exchange of
ligands of the type given in Eqn. 1.41 between two metal ion chelates has been studied
[155-157] and was found to be a slow process if the reaction goes via a dissociation
sequence.


ML + M'L' M'L + ML' (1.41)


No evidence for the formation of a dicomplex intermediate has been given
so far, but the rates of such coordination change reaction were found to increase
enormously if small amounts of either ligand or metal ion is added [158-160] to the
reaction mixture. This increase is the consequence of a coordination change mechanism.



REVIEW PART-II

1.7 Kinetic Catalytic Methods (KCM) of Analysis : Characterization,
Classification and Methodology


The bulk of analytical chemistry is based on chemical reactions at metal ion
centres in liquid media, particularly in aqueous solutions. Their study, understanding
and applications constitute a large portion of todays tasks of analytical chemists. The
use of Kinetics by analytical chemists has increased tremendously during the past few
years. Reaction rate techniques have been used in the development of analytical
methods for estimation of inorganic and organic compounds present in industrial
enviromental and biological sample. A brief survey of the significant developments
made in this field will be presented here though the discussion will be mainly centred
around the recent advances in the applications of ligand substitution kinetics to the
determination/analysis of component, in mixtures of catalytic species present in or
added to suitable reaction system.


Mottola [19] has for example, discussed systematically the aspects of
kinetics that have become part of modern analytical chemistry. Every process, whatever
its nature, takes place at a finite rate, tending to an equilibrium state. The two states, the
kinetic (dynamic) state, and the equilibrium (static) state are both of high informing
power[20]. Reaction-rate methods are becoming increasingly important practically in
analytical chemistry; progress however relies heavily on better elucidation of the
mechanisms of chemical reactions. Recent developments in instrumental design and
especially in the incorporation of microcompouters for the control of experiments and
data evaluation allow for improved precision, limits of detection, rapidity and
automation of such methods.


1.8 Classification of Kinetic Methods based on the Chemistry of the Reactions
Employed
Generally, kinetic method are classified into two broad categories :

1. Methods based on catalysed reaction.

2. Methods base on uncatalysed reaction.
Here, methods only based on catalyzed reactions will be discussed.



1.8.1a. Methods based on catalysed (Non-enzymatic) Reactions


These continue to be the most popular methods in the literature of kinetic
methods of determination. Their popularity is reflected in Fig. 1.1 which illustrates the
growth of the catalytic determination through the years, with information derived from
the reviews in the journal, analytical chemistry. Commonly, catalysed reaction are used
for the determination of the catalyst(s) and seldom for the reactant(s). The recent
development of catalytic methods of analysis/determination is a result of their high
sensitivity combined with relatively simple procedures. A variety of catalytic effects on
reactions have been employed in analytical determinations. Catalytic determinations can
be broadly viewed as:

A. Use of primary catalytic rates (determination of catalyst) and

B. Use of modified catalytic rates (determination of modifiers)


1.8.1 a
1
. Kinetic Methods Based on Primary Catalytic Effects

Two facts must be accounted for catalytic determination :

(a) The uncatalysed reaction proceeds simultaneously with the catalysed
reaction and (b) The rate of catalysed reaction is proportional to the concentration of the
catalyst. The latter is a consequence of cyclic regeneration of the catalyst so that its
concentration remains constant. Another practical requirement for successful
applications is that the concentration of reactants other than the catalyst or the species,
whose changes in concentration is monitored, must be such as to make the reaction rate
pseudo-zero order. The species whose change in concentration is being monitored is
adjusted to give first order dependence. Thus, for the generalized reaction :

(1.41)


Where S (monitored species) and R are reactants. P and Y are products and
C is the catalyst, the general rate expression can be written as :

(1.42)
Here k
c
and k
u
are the rate coefficients containing some concentration terms
for catalysed and uncatalysed reactions respectively and

is the initial concentration

of the catalyst in the reaction system.


Focussing our attention on the term for the catalysed path in equation (1.27)
and accounting for the presence of the catalytic cycle, one can use a simplified two-step
reaction scheme as represented by Eqn. 1.43 and 1.44





Depending upon the relative magnitudes of rate coefficients for reactions
shown in Eqn. 1.43 and 1.44 two situations may arise :


(a) Pre-equilibrium case and (b) a steady state situation. After resorting to
some valid approximations both these conditions demonstrate the proportionality
between catalyst concentration and the rate of reaction as given by Eqn. 1.45 [19]

(1.45)


Where k'
2
is a composite rate constant made up of some rate constants and
concentration terms.


Thus, under stipulated conditions and also recognizing that the uncatalysed
reaction is invariably taking place, Eq. 1.42 can be written in a general form for both
the above conditions as :

(1.46)
(1.43)


(1.44)
Where F[C]
0
is a linear function of the catalyst concentration and F is the
rate due to uncatalysed path. Eq. 1.45 can be used to determine the concentration of
catalyst C using either a differential or an integral approach.


In Differential methods :

Direct evaluation of d (Signal)/dt, is calculated,

- Initial rate measurements, in which the initial reaction rate is determined and
utilized for the evaluation of concentration.

- Slope measurements, in which the slope of the response curve at a selected point
is measured and related to the concentration.

In Integral methods (or integration methods):

Evaluation of the corresponding rate expressions over a finite, constant and normally
small time interval A t is done,

- Fixed time measurements, in which the change of a parameter, related to the

concentration of a reaction or product, is measured over a predetermined time
interval.


- Fixed concentration or variable- time method, in which the period of time,
required to bring about the same predetermined change in the concentration of a
reactant or product is measured.

Other methods include :

- Methods based on the measurements of the length of induction periods.

- Special methods such as oscillating chemical reaction.



Differential and integral methods are most frequently used for catalyzed
reaction. Detailed descriptions of methods for the determination of catalytically active
substances and a discussion of accuracy and precision are given by Mottola [19] and
Perez-Bendito and Silva [20].


It is very important to note that the precision of kinetic methods depends on
the reliability of the analytical technical technique used to measure the changes in the
concentration of a given component (indicator substance) as a function of time.


The overwhelming majority of indicator reactions chosen for catalytic
determinations involve redox system. However, sometimes a reaction involving the
exchange of ligands in a complex can be catalysed homogeneously by a metal ion
provided that the metal ion has an affinity for the leaving ligand and the experimental
conditions are so selected that the catalyst can be regenerated. As an illustrated
example, the metal ion catalysed replacement of CN- from [Fe(CN)
6
]
4-
has been used
for the determination of small amount of catalyst metal ions. Pavlovic and Asperger
[161] found a method for determining as low as 2.7 10
-7
M of Hg
2+
in biological
materials with relative standard error of about 20%. Nigam et al., have determined
down to 1 10
-7
M of Hg
2+
using p- NDA [162] and Mpz+ [163] as the entering ligand.
Table 1.5 gives a summary of analytical applications of catalysed ligand substitution
reaction of [Fe(CN)
6
]
4-
and [Fe(CN)
5
NH
3
]
3-
.


Table 1.5
Reactions involving exchange on hexacyanoferrate (II) And pentacyano (ligand)
ferrate (II) in presence of catalysts

Indicator Reaction Analyte Remarks* Ref.
1 2 3 4
[Fe(CN)
6
]
4-
+ PhNO Hg
2+
528nm (2.7 10
-7
M)
pH = 4.1, 20%
161
[Fe(CN)
6
]
4-
+ Bipy Ag
+
, Au
3+
520nm(1.6710
-6
M
Ag
+
, 1.6510
-5
M
Au
3+
)
164
[Fe(CN)
6
]
4-
+ Bipy Hg
2+
485 nm (1.0 10
-5
M) 165
[Fe(CN)
6
]
4-
+ PhNO Hg
2+
525 nm (0.5 g/2ml)
pH=4.1, 7%
166
[Fe(CN)
6
]
4-
+ PhNO
2
Hg
2+
- 167
[Fe(CN)
6
]
4-
+ Phen Au
3+
(10
-4
M), pH =3.5 168
[Fe(CN)
6
]
4-
+ L
(in presence of catalyst)
Phen, Bipy (510
-5
M) , pH =2.4 169
[Fe(CN)
6
]
4-
+ Nitroso-R-
Salt
Pd
2+
,
720 nm (0.04 ppm)
pH = 5.05
170
[Fe(CN)
6
]
4-
+ Nitroso-R-
Salt
Ag
+
,
720 nm (0.05 ppm)
pH = 4.0, 5%
171
Continued page no.
Table 1.5 (Continued)
1 2 3 4
[Fe(CN)
6
]
4-
+ Ferrozine Hg
2+
,
Ag
+
,
Au
3+
562 nm (0.02 ppm
Ag
+
, 0.1 ppm Au
3+
,
0.01 ppm Hg
2+
),
pH=4-6, 4.7%, 4.3%,
2.7% respectively
172
[Fe(CN)
6
]
4-
+ Nitroso-R-
Salt
Hg
2+
,
Ag
+
,
Au
3+

625 nm (0.01 ppm
Hg
2+
, 0.005 ppm Ag
+
,
0.05 ppm Au
3+
),
pH=4.5-6.0, 3.75%,
2.15%, 5.44%
respectively.
173
[Fe(CN)
6
]
4-
+ oN|N Hg
2+
630 nm (1 10
-6
M)
pH=3.5, 6%
174
[Fe(CN)
6
]
4-
+ p-NDA Hg
2+
640 nm (3.6 10
-8
M)
pH=5.0, 5%
162
[Fe(CN)
6
]
4-
+ Mpz
+
Hg
2+
655 nm (3.6 10
-8
M)
pH=5.0, 1.5%
163
* Detection limit is given in parenthesis and error in %.


Catalysed substitution reaction involving displacement of one-ligand by
another in a metal complex have been widely used to determine microgram quantities of
catalysts [175]. Tabata and Tanaka have reported kinetic methods for determination of
nanogram amounts of Hg
2+
[176] and Cd
2+
[177] by their catalytic effects on the metal
ion incorporation of Mn
2+
with o, |, , o- TPPS. Cu
2+
catalysed metal-metal exchange
reaction of Zn
2+
with NiEDTA
2-
has been exploited by Bydalek and Margerum [178] for
determination of Cu
2+
at concentration 10
-5
M. Double exchange reactions are very
sensitive to trace catalysis and inhibition. These properties have led to the development
of sensitive analytical methods for concentration down to 10
-8
M of metal ion or
ligands. [179-181]. Table 1.6 gives an over view of catalytic methods developed for
some chemical species using ligand substitution or complex formation reactions.



Table 1.6
Determinations based on catalytic effect of various ions on ligand substitution or
complex formation reaction

Indicator Reaction Analyte Remarks* Ref.
1 2 3 4
Zn
II
EGTA +Zincon Ca
2+
Polarographic (10
-3
M) 182
Mn
II
EGTA +PAN Ca
2+
Polarographic 182
Zn
II
EDTA +NH
3
Ca
2+
Polarographic 183
Cd
II
EDTA +NH
3
Ca
2+
Polarographic 184
Cu
II
EGTA +PAR Ca
2+
Spectrophotometric
(10
-5
M), pH =9
185
Hg
II
CPC + CYDTA NH
3
Spectrophotometric
(510
-5
M), pH =9.5, 5%
186
Cu
II
H
2
O+o-Cresol
phthalein
CN
-
568 nm (0.25 g/25 ml)
pH =11.5
187
Hg
II
PAR +CYDTA I
-
500 nm (10
-8
M) pH = 8.5 175
Cr
III
(H
2
O)
6
+
Xylenolorange
CO
3
2-
188
Co
II
(CN)
3-
5
+O
2

(coupled to chain
coordination)
O
2
(10
-8
M), 8% 180
Co
II
(en)
2
salicylate +I
2
CH
3
COO
-
HCO
3

In accetate buffer 189
Ni
II
EDTA + Zn
2+
Cu
2+
380 nm (10
-5
M),
pH = 5
178
Ni
II
Trien+ Cu
II
EDTA Ni
2+
550 or 590 nm
(10
-7
M), pH =8, 5%
179
Ni
II
Tetren + Cu
II
EDTA EDTA Stopped flow mixing (10
-8
M),
pH =7-12, 5-10%
190
Ni
II
Tetren + Cu
II
TTHA Tetren Polarographic (10
-5
M) pH
=8.0
191
Ni
II
Trien + Cu
II
EDTA Tetren 550 nm (10
-5
M) pH =7.4 181
Mn
II
+ o,|, , o-TPPS
Hg
2+
413 nm (10
-8
M) pH=6-7 176
Mn
II
+ o,|, , o-TPPS
Cd
2+
413 nm (10
-7
M) pH=8.0 177
Mn
II
+5, 10, 15, 20-TSPP Pb
2+
413 nm (10
-7
M) 192

* Detection limit is given in parenthesis and error in %.


1.8.2 Mechanisms of analytically important catalytic reactions


Indicator reactions for catalytic (non enzymatic) methods may be classified
on the basis of reaction mechanisms as follows [193]

a. Redox reactions

1. With valency change of the catalyst

2. Without valency change of the catalyst

b. Reactions with carbonyl compounds

1. Hydrolysis reactions

2. Decarboxylation reactions

c. Exchange reaction with coordination compounds

1. Nucleophilic substitution

2. Electrophilic substitution

3. Coordination chain reactions


Knowledge about the mechanisms of the reactions is far more important for
catalytic methods than for methods based on chemical equilibrium. In the latter
pocedures, in most cases, proportionality between the concentration of the substance to
be determined and on parameter of the reaction at equilibrium is sufficient for analytical
purposes, regardless of the stage of reaction at which the equilibrium is attained.


The more knowledge is obtained on the mechanisms of a catalytic reaction,
the more easily one will find the most favourable conditions for analytical applications
of the reaction with regard to senstivity, accuracy and selectivity.


1.8.2a. Redox reactions

The most common indicator reactions are redox in nature and involve oxidants
such as H
2
O
2
, O
2
, BrO
3
-
, ClO
3
-
, IO
3
-
, S
2
O
8
2-
, Fe
III
, Ce
IV
, etc., and inorganic reductants
such as Sn
II
, Fe
II
, As
III
, S
2
O
3
2-
and organic reductants such as amines, phenols, azo dyes
and leuco bases of dyes, etc.[194]. Redox reagents can be classified into two main
groups, namely, reactants acting by electron transfer through their d-orbitals and
reactants acting by electron transfer through their s- and p- orbitals (Table 1.7).
Reactions with oxidants of the second group are as a rule slower than those of the first
group and thus are convenient as indicator reactions for determining catalytically active
substances.

Table 1.7

Typical Oxidising and Reducing Agents Used for the Determination of Catalysts


Oxidising Agents Reducing Agents
d-orbitals Ce
4+
Cu
2+
Ag
2+
Mn
3+
Cr
2+
Fe
2+
Ti
3+

Fe
3+
VO
2
+
MnO
4
-
V
3+
VO
2+

CrO
2
2+
MoO
2
2+
OsO
4

s, p - orbitals Sn
4+
Sb
5+
Pb
4+
Bi
5+
I
-
Sn
2+
Br
-
Cl
-

Tl
3+
N
3
-

Polyatomic species H
2
O
2
NO
3
-
ClO
3
-
ClO
4
-
ArOH, ArNH
2
, azo dyes,
BrO
3
-
S
2
O
8
2-
IO
4
-
leuco bases of dyes
AsO
2-
, S
2
O
3
2-
, C
2
O
4
2-

ascorbic acid

The reactions can be divided into two groups, depending on whether the ion
acting as the catalyst changes its oxidation state during the reaction or not.


Reactions in which the oxidation state of the ion-catalyst changes are
marked by high sensitivity. Catalyst concentrations from 10
-9
to 10
-7
g cm
-3
may be
commonly determined and in some cases (Co, Os, Ru) down to 10
-11
g cm
-3
. The
mechanism of reactions of this type involves the steps

Red + C
(n+1)+
P +C
n+
(1.47)


C
n+
+ Ox C
(n+1)+
+ Z (1.48)

where and C
(n+1)+
and C
n+
are the two diffferent valency forms of the
catalyst in the two oxidation states, Red and Ox are the reactants in the redox reaction
and P and Z are the reaction products. In these reactions, ions of the transition elements
and halides usually function as catalysts.


The other large group of catalytic redox reactions comprises the reactions in
which the oxidation state of the ion-catalyst remains unchanged. These include catalytic
oxidations by hydrogen peroxide in acidic medium. Catalytic activity is exhibited by
cations with high positive charges that readily form peroxocomplexes (e.g. Fe
III
, Ti
IV
,
Hf
IV
, Th
IV
, Nb
V
, Ta
V
, Cr
VI
, Mo
VI
and W
VI
)

General overviews of the mechanism of catalytic reactions of analytical
interest have been given by Bontchev [195] and Mottola [20].

1.8.2b. Reactions with carbonyl compounds and catalytic ligand exchange
reactions

These catalytic reactions include catalytic decompositions, hydrolysis and
catalytic substitution reactions of both organic and inorganic substrates [195].


The reactions are analytically important, because they are often catalyzed
by elements from the main groups of the periodic table whose ions have no vacant d-
orbitals and thus cannot catalyze redox processes.


The mechanism of catalysis by catalytic decomposition and hydrolysis
inolves the effect of the catalyst on the polarization of the bonds in the reactants or on
the orientation of the reactants, thus making the reaction possible. An important step in
the catalysis is then often chelation : the ions of the catalyst form stable chelates with
the substrates. An example is the hydrolysis of monoalkyl phosphates ROPO
3
2-
. These
substances alone do not hydrolyze in alkaline media. In the presence of Cu
2+
or Mg
2+

ions, neutral chelates are formed, the negative charge on the substrate is neutralized and
hydrolytic decomposition can begin. From the analytical point of view, catalytic
substitution reactions of complexes are also important [193].


Typical reactions of this type are the substitution reactions of
hexacyanoferrate (II) with various substituting ligands is represented in a simplified
form as :

[Fe(CN)
6
]
4-
+ L [Fe(CN)
6
L]
3-
+ CN
-
(1.49)

where, L = substituting ligand.

Reaction 1.49 is catalyzed by all metal ions that form stable complexes with
cyanide (e.g. mercury, silver, palladium, gold) and can be used to determine these
metals (198). The Table 1.5 provides a summary of analytical applications of catalysed
ligand substitution reactions of [Fe(CN)
6
]
4-
and [Fe(CN)
6
NH
3
]
3-
.


Other methods based on ligand - exchange reactions are quite recent and
have thus been studied less. They have a promising future as they allow the
determination of non-transition metals such as alkaline-earth metals as well as of
lanthanides ammonia and some other species. Three general types of ligand - exchange
reaction can be considered in this context, as follows [18, 20].


1.8.2c. Exchange Reaction with Coordination Compounds

This category consists of exchange of same ligand between two metal ions,
exchange of same metal between two ligands and mutual exchange between metal ions
and ligands.

1.8.2c
1.
Exchange of a ligand between two metal ions

The system

NiY
2-
+ Zn
2+
ZnY
2-
+ Ni
2+
(1.50)

Has been described by Margerum et al [196]. This reaction moves slowly
and is monitored photometrically at 380 nm by measuring the disappearance of the
NiY
2-
complex. The addition of a small amount of Cu
II
to the system results in two
further reactions :


NiY
2-
+ Cu
2+
CuY
2-
+ Ni
2+
(1.51)

CuY
2-
+ Zn
2+
ZnY
2-
+ Cu
2+
(1.52)


The CuY
2-
complex is rapidly formed, immediately reacts with zinc ions to
form the ZnY
2-
complex and the Cu
II
ions are liberated. Cu
II
ions are thus not consumed
and can be considered as catalyst. Copper ions can be determined on this basis.

1.8.2c
2.
Exchange of a metal between two ligands

Consider the reaction between Cu
II
and the ligands oxybis (ethylenenitrilo)
tetra-acetic acid (EGTA) and 4(-2-pyridylazo) resorcinol (PAR)

Cu-EGTA + PAR Cu - PAR (1.53)

This reaction is catalyzed by traces of Ca
II
. Mg
II
causes no interference, as
its EGTA complex is much less stable than that formed with Ca
II
. Calcium ions can thus
be determined at concentrations between 0.4 and 40 g cm
-3
by spectrophotometrically
monitoring (at 515 nm) the rate of appearance of the Cu-PAR complex [197].


1.8.2c
3.
Dual exchange reactions (coordination chain reactions)

Olsen and Margerum have found, that complex ligand exchange occurs in
the reaction of Cu-EDTA with Ni-tren.


NiT
2+
+ CuY
2-
CuT
2-
+ NiY
2-
(1.54)


where T = trien = triethylenttramine

This reaction develops very slowly, though it can be accelerated by simply
adding an excess of one of the ligands. Thus, a small excess of EDTA (Y
4-
) attacks the
Ni-trien complex to yield Ni-EDTA and free trien (T), which in turn reacts with the Cu-
EDTA complex, from which it displaces the ligand :

Y
4-
+ NiT
2+
NiY
2-
+ T (1.55)

T + Cu Y
2-
CuT
2+
+ Y
4-
(1.56)

The chain is propagated cyclically and a steady state is rapidly reached. The
reaction rate is monitored photometrically by means of the absorbance at 550 nm,
which corresponds exclusively to the Cu-trien complex and is proportional to the EDTA
(or trien) concentration added. This allows the determination of small concentrations of
ligand. Metal ions can act as an inhibitor for the ligand-catalyzed reaction. In this way,
trace concentrations (10
-7
to 10
-10
g cm
-3
) of metals forming stable complexes with eg.
EDTA canbe determined. Other examples for the analytical use of substitution reactions
are described by Kopanica et al., [31 ,32].


1.8.3. Application of oscillating reactions

This type of reaction has limited but increasing analytical interest. [33].
Reactions catalyzed by metal ions capable of exchanging a single electron at normal
potential values between 0.9 and 1.6 V (e.g. the Ce
IV
/Ce
III
system) are typical
representatives of oscillating reactions, as are the Ce
IV
-catalyzed oxidation of malonic
acid (Belousov-Zhabotinski reaction system, B-Z system) succinic acid or citric acid by
bromate.

Mechanistically these processes are very complex. For the bromatemalonic
acid reaction catalyzed by Ce
IV
-Ce
III
, a 10-step process for the mechanism has been
proposed [33-35]. The process (e.g. B.Z. system) is monitored either by photometric
measurement of the changes in the Ce
IV
concentration or by non-equilibrium
measurements of the redox potential of the Ce
IV
/Ce
III
pair, which shows the periodic
variation of the Ce
IV
concentration, or by using a bromide-selective electrode.


It is analytically important that the number of cycles per unit of time is
proportional to initial reactant concentrations. However, this reactions is only obeyed
closely for a short time after the initiation of the reactions; when reagent concentrations,
decrease, so does the cycle frequency. The Kinetic determination of hexacyanoferrate
(710
-8
to710
-6
mol dm
-3
) by its inhibition of an oscillating chemical reaction (B-Z
system) was described by Jiang et. al [36].


1.9. Determination Based on Inhibition

The general practice followed for such determination has been to monitor
the decrease in reaction rate in a system containing a constant amount of catalyst by
adding increasing amount of inhibitor to obtain calibration curves, either by integral or
differential rate measurements. This approach offers relatively good limits of detection
but has a limit concentration range amenable to determinations. Table I.8 lists some
typical redox indicator reaction systems and inhibitors determined by them.


Several other references on the determination of metal ions as well as
organic compounds based on their inhibitory action are cited in the literature [199-205].
Most of these kinetic methods involve redox systems as indicator reactions. From the
Table I.8 below it is evident that surprisingly very little attention has been paid to the
determination of chemical species based on their inhibitory effect involving ligand
substitution processes.



Table I.8
Typical redox systems used for determination of inhibitors by kinetic methods

Indicator Reaction Catalyst Analyte
(Inhibitors)
Determination
Range
Ref.
1 2 3 4 5
Malachite
green+Periodate
Mn
2+
EDTA 10
-6
206
Malachite
green+Periodate
Mn
2+
Glycine, DL-
Phenylalanine, DL-
Glutamic acid, DL-
Sarine and L-
Arginine
10
-6
M

207
Pyrocatechol violet +
H
2
O
2

Co
3+
Histamine.
Neoantergan and
Synopen
0.1-2.910
-9
M 208
Pyrocatechol violet +
H
2
O
2

Co
3+
Nicotinic acid,
Nicotinamide,
Vitamine B
1
and
B
6

1-510
-9
M 209
Luminol + H
2
O
2
Cu
2+
Amino acids in
natural water
- 210
Alizarin S + H
2
O
2
Mn
2+
8-
Hydroxyquinoline,
Bacteriostatics and
Fungicides of 8-
hydroxyquinoline
type
0.3-1.110
-7
M 211
Sb (III)+ Peridoate Mn
2+
EDTA and DTPA 1-1010
-7
M 212
Phosphinate+ Peridoate Mn
2+
CYDTA - 213
Azorubine + H
2
O
2
Mo
6+
Antibiotics
(Tetracycline,
Methacycline and
Demecycline)
18-160g/mL 214
Azorubine + H
2
O
2
Mo
6+
Gentisic and
chromotropic acid
6.2-49.3 and
13.2-105.3
g/mL
repectively.
215
[Fe(Phen)
3
]
3+
+Cr(IV) Oxalic
acid
Uric acid 0.85-
5.95g/mL
216
Pyrocatechol violet +
H
2
O
2

Cu
2+
Thyroxine and 5-
Hydroxytryptophan
1-1010
-6
and
7.7-3210
-7
M
217
Pyridoxal-2
pyridylhydrazone +
H
2
O
2

Pb
2+
Phosphate and
Plyphosphates
110
-7
M 218
4,4'-
Dihydroxybenzophenone
thiosemicarbazone+
H
2
O
2

Cu
2+
EDTA and EGTA 10
-6
M 219
2,4-Diaminophenol+
H
2
O
2

Fe
2+
Oxalate.citrate and
fluoride
ng level 220
Autodecomposition of
H
2
O
2

Cu
2+
1,10-
phenanthroline
2-20 g/mL 221
p-Phenetidine+Periodate Fe
3+
Thiocarbamide,
some
dithiocarbamtes,
pesticides and
Mercaptans
110
-2
g/mL 222
Perborate + I
-
Zr
4+
Fluoride 1-1010
-9
M 223
Perbromate + I
-
Fe
2+
EGTA, DTPA and
EDTA
1.5-1510
-7
M 224
O-Dianisidine+ H
2
O
2
Peroxidase Hg
2+
- 225
Hydrolysis of sucrose t-Fructofur
anosidase
Hg
2+
in water and
carbonated soft
drink
100-270
g/mL
226
[Co(III)-EDTA]+
Hypophosphite
Pd
2+
Hg
2+
in sphalerites
and
pharmaceuticals
13-120 ng/mL 227
Sulfanilic
acid+Peroxodisulphate
Ag
+
Cysteine 0.5-410
-6
M 228
Phloxin + Persulphate Ag
+
Cysteine 1-1210
-6
M 229
K
4
[Fe(CN)
6
]+pNDA Hg
2+
Cysteine,
thioglycolic acid,
thiosulphate
- 230
K
4
[Fe(CN)
6
]+M
pz
+ Hg
2+
Cysteine 2.0-2010
-7
M 231
K
4
[Fe(CN)
6
]+M
pz
+ Hg
2+
MNDT as low as 510
-
8
M
232


1.9. Determination Based on Activator

In many metal catalysed reactions a substance called activator some times
combines with the catalyst to promote the catalytic activity of the metal ion. If the initial
rates of such reaction are proportional to the concentration of the activator (until all the
catalyst combines with activator), rate measurement can be employed to determine the
concentration of activator species the same manner as for direct analysis of catalyst i.e.
metal ion (vide supra). Such metal chelate activation may arise due to the fact that a
metal chelate can offer labile and free aquo positions on the metal ion through which
the reaction with a substrate may take place. In such cases the chelating ligand acts as a
carrier for the metal ion and catalysis occurs through the formation of a mixed ligand-
chelate compound. Some workers have made use of activators to lower the limits of
detection for metal ion catalysts (233). Ascorbic acid, for example, has been used to
lower the detection limit of Cu(II) , from 0.05 g/mL to 0.2g/mL using Cu(II)
catalysed oxidation of 2-thiosemicarbazone by hydrogen peroxide [233]. The sensitivity
and selectivity of the catalytic determination of vanadium catalyst in the oxidation of o-
phenylmediamine by bromate ion is said to be improved by the presence of Tiron acting
as an activator [234]. NTA acts as an activator for Mn catalysed periodate - Sb(III)
reaction and thus lowers the detection limit of Mn (II) [235].


1.10 Selectivity of catalytic methods of analysis

According to IUPAC terminology [236], selectivity denotes the extent to
which the method is free of interference by other chemical species. Total or complete
specifity is the case in which no interferent effects are known. In practice total specifity
is rare for catalytic methods apart from enzyme catalyzed reactions. The catalytic
properties of an inorganic ion depends on its size, structure, charge and coordination
sphere, chemically similar species exhibit similar catalytic effects and therefore highly
selective catalytic determination in the presence of chemically related elements is not
common. Consider the indicator reaction


A + B P (1.57)


which takes place in the presence of catalyst C at a rate defined by the Eqn. 1.57

(1.58)


where A, B are the reactants, k', k are the rate constants for the uncatalyzed
and the catalysed reaction, respectively and symbols p', q', p, and q are, in a simple case,
the stoichiometric coefficients. In the presence of different catalysts C
1
,C
2
,....C
n
the
expressions for the rate of the catalysed reaction under different reaction conditions can
be described by Eqn. 1.59, 1.60.


u
1
-u
10
= k
11
H
11
[C
1
] + k
12
H
12
[C
2
] +...........+ k
1n
H
1n
[C
n
] (1.59)

u
n
-u
n0
= k
n1
H
n1
[C
1
] + k
n2
H
n2
[C
2
] +...........+ k
nn
H
nn
[C
n
] (1.60)

where u
1
..... u
n
characterise the rates of the catalyzed reaction; u
i0
the rates
of the uncatalyzed reaction and H
ik
= [A]
pik
+[B]
qik
, where i, k=1,.....n the coefficients
p,q.,,,, are determined by the actual mechanism.


For the activity of a certain catalyst to be highly selective, the activities of
the individual catalysts must differ considerably. Under the given reaction conditions,
k
ii
=k
ik
or, the individual catalysts must react according to different reaction
mechanisms i.e. p
ii
, q
ii
= p
ik
, q
ik
.


The selectivity of a catalytic determination can often be improved by
optimizing the procedure by selective masking or by using separation techniques.


The following scheme shows ways to improve the selectivity of catalytic
methods.

Optimisation of the procedure Use of separation techniques
Variation of reaction conditions Ion-exchange
- pH
- reagent concentration
- temperature
- suitable co-ordination sphere
- catalyst-substrate interaction
- photoactivation

mechanism-optimisation
(e.g. by means of the graph method)
Ion-exchange
chromatographic methods
microdiffusin
co-precipitation
distillation
electrophoresis
liquid-liquid-extraction
- back-extraction or composition of the
organic solvent.
- extraction-catalytic determinations




Table 1.9
Survey of the elements which can be determined using the catalytic activity of their
ions. The numbers beside the symbols of the elements denote the detection limit
expressed as the negative logarithm of the corresponding concentration in g cm
-3

[20, 193].

Ia IIa III
b
IV
b
V
b
VIb VII
b
VII
I
ib II
b
III
a
IV
a
V
a
VI
a
VI
Ia

H
L
i
Be
9
B C N O F1
0
N
a
M
g6
Al
6
Si
6
P8 S1
0
C1
7
K Ca
6
Sc Ti
8
V
10
Cr9 Mn
10
Fe
9
Co
11
Ni
9
Cu
11
Zn
9
G
a
G
e7
A
s5
Se
9
Br
8
R
b
Sr Y
7
Zr
8
N
b7
Mo
10
Tc8 Ru
11
Rh
10
P
d9
Ag
10
C
d6
In
8
Sn Sb
8
Te
10
I
10
C
s
Ba L
a
Hr
7
Ta
7
W1
0
Re
0
Os
11
Ir1
1
Pt
7
Au
9
H
g9
Ti Pb
8
Bi
7
Po At
F
r
Ra A
c
T
h7
Pe U9

Liquid-liquid extraction is of greatest importance, followed by ion-exchange and
other chromatographic methods. In extraction separation the simplest procedure
preferable; in other words back-extraction or the thermal decomposition of the organic
solvent should be avoided. It is advantageous to carry out the catalytic determination
directly in the extract or in the extract dissovled in a mixed solvent (extraction -
catalytic determinations) (237).
The following conditions must be satisfied to enable an extraction catalytic
determination :
(i) the indicator reaction must proceed in the organic or mixed solvent and
the catalyst activity must be retained in this medium,
(ii) an extraction system must be available for a highly selective separation
of the test metal and the extraction agent, if extracted itself, must not interfere with the
catalytic reaction.
Extraction-catalytic methods are very attractive analytically, because they also
enable analyses in very complex matrices. Table 1.10 gives an overview of extraction-
catalytic methods that have been developed and used until the present time.
The nomenclature of kinetic methods of analysis (terms and definitions) is proposed in
an IUPAC paper by Svelha [238].



Table 1.10
Extraction-catalytic dtermination [177]
Metal Ion Indicator reaction Extraction System Reaction Medium
Ag Bromopyrogallol Red
(BPR) + S
2
O
8
2-
+ 1, 10
Phenanthroline
1, 10-
phenanthroline,
BPR/nitrobenzene
nitrobenzene-dioxan
water
Ca sulphanilic acid + H
2
O
2
+
pyridine
p-ethoxyaniline +H
2
O
2

pyridine,
salicylate/CHCl
3

neocuproine/CHCl
3

-CHCl
3
-ethanol-
water
-CHCl
3
-ethanol-
water
Cr
VI
3, 3' dimethoxybenzidine
+ H
2
O
2

HCl/MIBK


MIBK-ethanol-water

Fe p-ethoxyaniline + H
2
O
2
+
1,10-phenanthroline
p-ethoxyaniline + H
2
O
2
+
1,10-phenanthroline
p-ethoxyaniline + H
2
O
2
+
1,10-phenanthroline
LiCl/MIBK
several systems
1, 10 -phenanthroline
MIBK-ethanol water
CHCl
3
-ethanol-water
CHCl
3
-ethanol-water
Mo 1-naphthylamine + BrO
3
-
oxine/ChCl
3
CHCl
3
-ethanol-water
Nb o-aminophenol + H
2
O
2
benzoin oxime/
CHCl
3

CHCl
3
-ethanol-water
Ti o-phenylenediamine +
H
2
O
2

pyrocatechol,
dioctyl-amine/
butane
CHCl
3
-ethanol-water
V o-phenylenediamine +
BrO
3
-

pyrocatechol, octyl-
dimethylamine/
butanol
butanol-ethanol-
water


REFERENCES




1. Tolg, G., 1974, Talanta, Vol. 21, pp. 327.
2. Guibault, G.G., Sardar, S. and McQueen, R, 1969,Anal Chim Acta, Vol. 45, pp. 1.
3. Malmstadt, H.V. and Hadjiionno, T.P., 1962,Anal Chem., Vol. 34, pp. 455.
4. Malmstadt, M.V. and Madjiionnuo, T.P., 1963, Anal. Chem., Vol. 35, pp. 14.
5. Malmstadt, H.V. and Pardue, H.L., 1962, Chin. Chem., Vol. 8, pp. 14.
6. Nigam, P.C. and Srivastava, R.D., 1980,Ind. J. Chem.,Vol.19 A, pp. 563.
7. Weichselbaum, T., Hagerty, J. and Mark Jr. H.B., 1969, Anal Chem. Vol. 41, pp. 848.
8. Mottola, M.A., and Mark Jv, H.B., 1982, Anal. Chem., Vol 54,pp.62R.
9. Greinke, R.A., and Mark Jr. H.B., 1978,Anal. Chem.,Vol.50, pp.70R.
10. Pardue, H.L., 1977, A History of Analytical Chemistry, New York, the Maple Press Co.
11. Tanaka , M., 1977 , Anal-Chem, Essays in Memory of Anders Ringdom , Ed.
Ewaminen, pp. 133
12. Mak, M.K.S., Langford, C.H. and Khan, T.R., 1977 Ind. Chem. Soc., Vol. 54, pp. 51.
13. Fukasawa, T., Yamane, T. and Bansek, J., 1977, J. Japan Soc. Anal. Chem., Vol. 8, pp.
491.
14. Albrecht-Gary, A.M. and Schwing, J.P., 1978, Les Methods cinetiques in Chimie
Analytique, Paris, Les Techniques do L Ingenieur.
15. Mark Jr., H.B., 1972, Talanta , Vol. 19 pp. 717.
16. Mark Jr. and H.B., Rechnitz, G.A., 1968, Kinetics in Analytical chemistry, New York,
Inter Science Publisher.
17. Muller,H.,Otto, M.and Werner,G.,1980, Catalytic Methods in Trace Analysis (in
German), (Vol. 4 of the series, Modern Trace Analysis), Akadem, Leipzig,
Verlagsgesellschaft Geest & Portig.
18. Kopanica,M.and Stara,V., Kinetic Methods in Chemical Analysis ,1983,(Vol. 18 of the
series ,Wilson and Wilson's Comprehensive Analytical Chemistry), Amsterdam,
Elsevier.
19. Mottola, H.A., Kinetic Aspects of Analytical Chemistry ,1988(Vol. 96 of the series
,Chemical Analysis), New York, John Wiley & Sons.
20. Perez-Bendito,D. and Silva,M., Kinetic Methods in AnalyticaI Chemistry,1988, New
York, John Wiley & Sons.
21. Muller,H.,and Crit, CRC. 1982,Rev. Anal. Chem. Vol.13,pp. 313.
22. Schwing, J.P. ,WolfT, Ch.M.and Albrecht-Gary, A.M.,April 1985, L' actualite
chimique, Vol.53.
23. Gaal,F.and Abramovic ,1984,Talanta, Vol.31,pp.987.
24. Guyard, M.A.,1876, Bull. SOC. Chim. Paris Vol.25,pp. 58.
25. Bontchev, P.R.,1970, Talanta ,Vol.17,pp. 499.
26. Yatsimirskii,K.B.,1966, Kinetic Methods of Analysis, Oxford, Pergamon Press.
27. Margerum, D.W and Bydalek,T.J.,1962, Inorg. Chem.,pp. 1852.
28. Funahashi, S., Yamada,S.,and Tanaka,M.,1971, Anal. Chim. Acta. Vol.56,pp. 371.
29. Olson, D.C.and Margerum, D.W.,1963, J. her. Chem. SOC.,Vol. 85,pp. 297.
30. Haque,M.S. and Kopanica,M.,1973, Bull. Chem. SOC. Japan ,Vol.46,pp. 3032.
31. Kopanica,M. and Stara,V. 1972,Collect. Czech. Chem. Commun., Vol.37, pp. 80.
32. V. Stara, M. Kopanica,1973, Collect. Czech. Chem. Commun., Vol.38,pp. 258.
33. Yatsimirskii, K.B.,1987, Zh. Anal. Chim., Voll.42,pp. 1743.
34. Field,R.J., Koros,E.and Noyes,R.M.,1972, J. Am. Chem. SOC.,Vol. 94pp. 8649.
35. Tichonova,L.P., Zakrevskaya,L.N. and Yatsimirskii,K.B.,1978, Zh. Anal. Khim.,Vol.33
pp.1991.
36. Jiang,M., Li,Y., Zhou,X., Zhao,Z, Wang,J. and Mo,J.,1990, Anal. Chim. Acta
Vol.236,pp. 41 .
37. Martell,A.E.,1968, Pure Appl. Chem. ,Vol.17,pp. 129.
38. Mottola,H.A., Heath,G.L.,1972, Anal. Chem. ,Vol.44,pp. 2322.
39. Milovanovic,G.A.,1983, Micorchem. J.,Vol. 28,pp. 437.
40. Yatsimirskii,K.B, and Fedorova,T.I.,1962, Proc. Acad. Sci. USSR, Vol.143,pp. 143.
41. Crouch, S.R. and Cullen, T.F., 1998, Anal. Chem. ,Vol. 70, pp. 53R-106R.
42. Cotton, F.A., Wilkinson, G and Gauspaul, L., 1995, Basic Inorganic Chemistry IIIrd
Edition, pp. 187.
43. Langford C.H. and Gray H.B., 1984, Ligand substitution process, Benjamin Menlo
Park, C.A.
44. Nigam, P.C., Naik, R.M. and Prasad S., 1992 ,J. Indian Chem. Soc. ,Vol. 69, pp. 475
45. Miessler, G.L.and Tarr, D.A., 2004, Inorganic Chemistry (3rd edition), Pearson/
Prentice Hall ISBN 0-13-035471-06.
46. Helm, Lothar, Merbach, Andre ,E., 2005, "Inorganic and Bioinorganic solvent
Exchange Mechanism" Chem. Reviews Vol. 05, Issue 6, pp. 1923-1959.
47. Bajaj, H.C. ,1982 ,Ph.D. Thesis ,IIT Kanpur, India
48. Naik, R.M. ,1986, Ph.D. Thesis ,IIT Kanpur, India.
49. Gupta, N. ,1988 ,Ph.D. Thesis ,IIT Kanpur, India.
50. Mishra, P.K., 1989, Ph.D. Thesis, IIT Kanpur ,India.
51. Eigen, M.,1960, Elektrochem Z., Vol.64, pp.115.
52. Eigen,M., 1962,Elektrochem Z., Vol.66,pp. 93.
53. Eigen, M., 1962,Elektrochem Z., Vol.66,pp. 107.
54. Eigen, M.,1963, Elektrochem Z., Vol.6, pp.97.
55. Wilkins, R.G.,1974, The Study of Kinetics and Mechanism of Transition Metal
Complexes, Boston, Allyn and Bacon.
56. Chaturvedi D.D.,1996, Ph.D. Thesis, Lucknow University, Lucknow.
57. Read ,Rita, A. and Margerum ,D.W.,1981,Inorg. Chem., Vol.20, pp.3143.
58. Bannister ,C.E. and Margerum ,D.W.,1981, Inorg. Chem. Vol.20,pp. 3149.
59. Coombs ,L.C., Margerum, D.W. and Nigam P.C., 1970,Inorg. Chem., Vol.9,pp. 2081.
60. Swift ,T.J., and Connick, R.E.,1962, Chem. Phys. Vol.37, pp.307 .
61. Hunt, J.P., Dodgen, H.W. and Klanberg ,F., Inorg. Chem., (1963), 2, 478
62. Toma ,H.E. and Malin, J.M.,1973, Inorg. Chem., Vol.12, pp.1039.
63. Toma ,H.E. and Malin ,J.M., 1973,Inorg. Chem., Vol.12, pp.2080.
64. Abu-Gharib, E.A., Ali, R. bin, Blandamer, M.J. and Burgess, J.,1987, Transition Met.
Chem., Vol.12, pp.371.
65. Margerum,D.W.,Cayley,G.R.,Weatherburn ,D.C. and Pagenkopf ,G.K.,1978,
Coordination Chemistry, Edited by Martell,A.E., Published by Am. Chem. Soc., Vol.2,
pp.1-220.
66. Bradic, Z., Pavlovic, D., Murati, J. and Asperger, S., 1972,J. Chem. Soc., Vol.34,
pp.3919.
67. Mitra, R.P., Sharma, B.K. and Mittal ,S.P., 1972,J. Inorg. Nucl. Chem.,Vol.34,pp. 3919.
68. Dozsa, L., Szilassy ,I. and Beck, M.T.,1973, Magyer Kem. Falyairat, Vol.45,pp. 79.
69. Sullivan,T.R., Stranks ,D.R., Burgess, J. and Haines, R.I.,1977, J. Chem. Soc. Dalton
Trans., pp.1460.
70. Pavlovic ,D., Murati, I. and Asperger, S.,1973, J. Chem. Soc., Dalton Trans. ,pp.602.
71. Boadic, Z., Pavlovic ,D., Murati ,I. and Asperger, S.,1974, J. Chem. Soc. Dalton,
pp.344.
72. Trzebiatowska, B.J. Kellor ,A. and Ziolkowski,1972, J., Bull. Acad. Poland Sci. Ser.
Chim., Vol.20,pp. 649.
73. James ,A.D. and Murray ,R.S.,1975, J. Chem. Soc., Dalton Trans ,pp.1530.
74. West, D.X. and Hassemer ,D., 1970,J. Inorg. Nucl. Chem. Vol.32, pp.2717.
75. Davies, G. and Garafalo, A.R.,1976, Inorg. Chem., Vol.15, pp.1101.
76. Macartney, D.H. and McAuley, A., 1981,Inorg. Chem., Vol.20, pp.748
77. Toma, H.E., Martins ,J.M. and Giesbrecht, E.,1978, J. Chem. Soc., Dalton Trans.,
Vol.27, pp1610.
78. Katz,N.E., Blesa ,M.A., Olabe, J.A. and Aymanino ,P.J.,1978, Inorg.
Chem.Acta.,Vol.27,pp.L65.
79. Toma ,H.E., Malin, J.M. and Giesbrecht, E.,1973, Inorg. Chem., Vol.12,pp. 2084.
80. Bradic ,Z., Pribanic ,M. and Asperger, S.,1975, J. Chem. Soc., Dalton Trans. pp.353.
81. Blesa, M.A., Olabe ,J.A. and Aymanino, P.J., 1976, J. Chem. Soc. Dalton Trans,
pp.1196.
82. Bowers ,M.L., Kovacs ,D. and Shepherd, R.E.,1977, J. Am. Chem. Soc., Vol.99,
pp.6555.
83. Blesa, M.A., Funai,I.A.,Morando ,P.J., Olabe, J.A., Aymonino, P.J. and Ellenriender,
G.,1977, J. Chem. Soc., Dalton Trans., pp. 845.
84. Katz, N.E., Blesa, M.A., Olabe J.A. and Aymonino, P.J.,1978, J. Chem. Soc., Dalton
Trans., pp.1603.
85. Coelho, A.L. , Morerira, I.S., Miynes, A.B. and Aranj, D.E., 1995,Polyhedron, Vol.13,
pp. 1015
86. Eldik,R.Van,1986, Inorganic High Pressure Chemistry, Kinetic and Mechanism,
Amsterdam, Elsevier.
87. Stochel, G. and Eldik, R. Van, 1989,Inorg. Chem. Acta .,Vol.155, pp.95.
88. Palmer ,D.A. and Kelin, H.,1981, Coord. Chem. Rev., Vol.36, pp.89.
89. Alshehhri, S.and Burgess ,1991.J., Inorg. Chem. Acta., Vol.181, pp.153.
90. Al,Alousy, A., Alshehri, S., Burgess, J., Gracini, M.del Mar, Moya, M.L. Munoz ,E.,
Rodriquez, A., Sanchez, F.,1993, Transitition Met. Chem., Vol.18, pp.179.
91. Ashehri ,S. , Burgess ,J., Eldik ,R.Van and Hubbard, C.D., 1995,Inorg. Chem. Acta,
Vol. 240,pp.305.
92. Barrios ,A., Gracini ,M.D.M., Jiminez, R. Munoz, E., Sanchez, F. Moya, M.L.,
Alshehri, S., Burgess, J.,1992, Transition Met. Chem., Vol.17,pp. 231.
93. Keddy ,K.B. and Eldik,R. Van, 1991,Inorg Chem., Vol.30, pp.596.
94. Stochel, G., Chatlas ,J., Martinez P. and Eldik R. Van,1992, Inorg. Chem., Vol.31,
pp.5480.
95. Stochel, G.and Eldik, R. Van,1991, Inorg. Chim. Acta, Vol.190, pp.55.
96. Stochel ,G., Eldik,R. Van, Hejmo ,E., Stasicka, Z., 1988.Inorg. Chem, Vol.27, pp.2767.
97. Blandamer ,M.J. and Burgess, J.,1983, Pure and Appl. Chem., Vol.55,pp. 55.
98. Blandamer, M.J. and Burgess, J. and Haines, R.J.,1978, Chem. Soc., Dalton Trans, pp.
244
99. Naik ,R.M. and Nigam, P.C., 1986, Inorg. Chim Acta., Vol.114,pp.55.
100. Mishra, P., Naik ,R.M. and Nigam ,P.C., 1987,Inorg. Chim. Acta, Vol.127, pp.71.
101. Naik, R.M., Chaturvedi, D.D., Srivastava ,N., Verma Amit,K., Tewari ,A.K., Agarwal,
A.,2004, Ind.J.Chem.,Vol.43A,pp.2307.
102. Kolaski, G.B., and Margerum, D.W.,1969, Inorg. Chem. Vol.8, pp.1125.
103. Kumar, K., 1978,Ph.D. thesis, IIT Kanpur, India, Chapt-4.
104. Kumar, K., and Nigam, P.C.1980, J. Phys. Chem., Vol.84, pp.1867.
105. Kumar, K., Bajaj, H.C. and Nigam , P.C.1980, J. Phys. Chem., Vol. 84,pp. 2351.
106. Bajaj, H.C.,Phull, M. and Nigam, P.C. 1983,J. Coord., Chem., pp.13.
107. Kumar, K. and Nigam, P.C.,1980, J. Phys. Chem., Vol.84,pp.140.
108. Naik ,R.M. and Nigam, P.C., 1986,Transition Met. Chem., Vol.11, pp.11.
109. Bajaj,H.C., Phull ,M. and Nigam ,P.C., 1984,Bull. Chem. Soc. Jpn., Vol.57,pp. 564.
110. Pleskowicz ,J.C. and Billo ,E.J.,1985, Inorg. Chim. Acta, Vol.99, pp.149.
111. D'amiello, .M.A., Mocella, M.T., Barefield ,E.K. and Paul, J.C.,1975, J. Am. Chem.
Soc. ,Vol.97, pp.192.
112. Steinman, W. and Kaden ,T.A., Helv.,1975, Chim. Acta.,Vol.58,pp. 1358.
113. Cross, R.J. ,1985,Chem. Soc. Rev. Vol.14,pp. 197.
114. Lin, L.T., Rorabacher, D.B., Cayley, G.R. and Margerum ,D.W.,1975, Inorg. Chem.,
Vol.14, pp.919.
115. Kokki, G.B. and Margerum, D.W., 1969,Inorg. Chem. ,Vol. 8,pp. 1129.
116. Edmund ,K. and Walderman ,N., 1987,Trans. Met. Chem., Vol.12,pp. 546.
117. Rorabacher ,D.B. and Margerum, D.W.,1964, Inorg. Chem. ,Vol.3,pp. 382.
118. Kumar ,K. and Nigam, P.C., 1981,Inorg. Chem.,1981, Vol.20,pp. 1623.
119. Naik ,R.M. and Nigam, P.C.,1987, Indian J. Chem.,Vol. 26A,pp. 205.
120. Bajaj, H.C. and Nigam, P., 1981,Indian J. Chem., Vol.19A,pp. 1070.
121. Bajaj ,H.C. and Nigam, P.,1984, Indian J. Chem., Vol.23A,pp. 8.
122. Funahashi S. and Tanaka M., 1974,Chem. Abst., Vol.80, pp.33411g.
123. Tabata M., and Tanaka M., 1978, Inorg. Chem., Vol.17,Issue 10,pp.2779.
124. Hitoshi K.,1977, Chem. Abst., Vol.87, pp.123307j.
125. Carr J.D. and Olson V.K.,1975, Inorg. Chem., Vol.14 ,Issue 9, pp.2168.
126. Kodama M. and Hagiya K., 1973,Bull. Chem. , Vol.46, Issue10,pp. 3151.
127. Funashashi S., Tabata M. and Tanaka M., 1971, Bull. Chem. Sc. Jpn, Vol.44, pp.1586.
128. Kodama M. and Oyama N., 1972, Bull Chem. Soc. Jpn., Vol.45,pp. 2169.
129. Rabnstein D.L. and Fuhr B.J., 1972, Inorg. Chem., Vol.11, pp.2430.
130. Katsuyama T. and Kumai T.,1978, Bull. Chem. Soc. Jpn, ,Vol.51, pp.1072.
131. Kodama M.,1970,Chem. Abstr. Vol. 73, pp. 18953C.
132. Kodama M., Fujii Y. and Uede T.,1970, Bull. Chem. Soc. Jpn., Vol.48, pp.4085.
133. Funahadhi S. and Tanaka M., 1970,Inorg. Chem., Vol.9,pp. 2092.
134. Kodama M., Karasawa S. and Watanabe T.,1971, Bull. Chem. Soc., Jpn., Vol. 44, pp.
1815
135. Steinhaus R.K.,1982, Inorg. Chem. Acta, Vol.63,pp. 1.
136. Gerhard G., Horst E.,2002, Inorg. Reac. Mech., Vol. 3,pp. 221.
137. Gerhard G., Horst ., 2003,Inorg. Chim. Acta, Vol.342,pp. 97.
138. Burmazovic I., Hamza I., Mohammed S.A., Eldik R. Van., 2002, Inorg. Chem.,
Vol.41,pp. 5150.
139. Gabor I., Istvan F., 2002, Inorg. Chem. Vol.41,pp. 1306.
140. Thorsten S., Sabina S., Achim Z., Peter T., Eldik R. Van, 2001,Inorg, Chem. Vol.40,pp.
3670.
141. Mentasi F., Pelizzetti E., 1975,Talanta, Vol. 22,pp. 930.
142. Gupta N., Nigam P.C., 1989, J. Inorg. Chem., Vol. 5,pp. 61.
143. Naik R.M., 2005, Int. j. Chem. Kin., Vol.37,pp.333.
144. Neubrar L. and Kopanica M., 1971, Coll. Czech. Chem. Comm, Vol. 36,pp. 1121.
145. Kimura M., 1970, Bull. Chem. Soc. Jpn., Vol. 43, pp.1594.
146. Tanaka, M. and Kanada, M., 1962, Bull. Chem. Soc. Jpn., Vol. 35, pp. 1596.
147. Kuemple, R and Schaap, W., 1968, Inorg. Chem., Vol. 7, pp. 2435.
148. Nozaki, T. and Kasuga, K., 1973, Chem. Abstr., Vol. 80, pp. 41267n.
149. Nozaki, T. and Kasuga, K.,Nippon, Kagaku, Kaishi, 1972, Chem. Abstr., Vol. 76, pp.
145394k.
150. Limu, R.E. and Gougerh, P., 1976, Chem.Abstr, Vol. 85, pp. 100071x.
151. Das, R.R. 1974, J. Ind. Chem.Soc, Vol. 51, pp.1024.
152. Ana N., Ecatena P. and Agenta B., 1981, Rev. Roum. Chem., Vol.26,m Issue 7, pp.
967.
153. Kornev V.I. and Valyaeva V.A.,1981, Koord. Khim, Vol.7 , Issue 12,pp. 1866.
154. Margerum D.W.,1963, Rec. Chem. Prog. , Vol.24,pp. 237.
155. Olsonand D.C., Margerum D.W., 1963, J. Am. Chem. Soc., Vol.85, pp.297.
156. Stara V. and Kopanica M., 1973, Coll. Czech. Chem. Commn., Vol.38, pp.2581.
157. Emantast E., 1980, J. Chem., Soc., Dalton Trans., pp.958.
158. Margerum D.W. and Carr J.D., 1986, J. Amer. Chem. Soc., Vol.88,pp. 163.
159. Emantast E.,1984, J . Chem. Soc. Dalton Trans, pp.903.
160. Stehl R.H.S. Margerum D.W. and Lattrell J.L.,1967, Anal. Chem, Vol.39, pp.1346.
161. Paylovic, D. and Asperger, S., 1959, Anal Chem., Vol. 31, pp. 939.
162. Phull ,M., Bajaj, H.C. and Nigam, P.C., 1981, Talanta, Vol.28, pp. 610.
163. Prasad, S., 2004, Analytical letters LDI 37, pp. 2851.
164. Datta, K. and Das, 1974, J., J. Ind. Chem. Soc., Vol. 51, pp.553.
165. Raman, S., 1975,Ind. J. Chem., Vol. 13, pp.1229.
166. Hadjuoannou, T.P.,1966, Anal. Chim. Acta, Vol.35, pp.351.
167. Yatsimirskii, K.B. and Orlova ,M.N.,1959, Z. Neorg. Khim., 1959, Vol.4, pp.741.
168. Kars, U. and Pinter, T., 1961, Croat. Chim. Acta., Vol. 33, pp.69.
169. Kars,U. and Pinter, T.,1962, Croat.Chim. Acta., Vol.. 34, pp. 249.
170. Mehra, M.C. and Garvie, R., 1979, J. Less-Common Metals, Vol. 68, pp. 17.
171. Reddy ,B.R. and Raman, S.,1984, Ind. J. Chem., Vol. 23A, pp. 616.
172. Gadia, M.K. and Mehra, M.C.,1978, Microchem. J. , Vol. 23, pp. 278.
173. Mehra, M.C., Satake, M. and Katyal, M.,1984, Ind. J .Chem., Vol. 23A , pp. 860.
174. Srikantmurthy, B.R. 1981, M. Phil. Dissertation, I.I.T. Kanpur, India.
175. Funakashi ,S., Tabata, M., Tanaka, M. 1971, Anal Chem. Acta, Vol. 57, pp.311,
176. Tabata, M. and Tanka, M. ,1980, Anal Letters, Vol.13, Issue A6, pp. 427.
177. Tabata, M. and Tanaka ,M.,1982, Mikrochim. Acta II, pp.149.
178. Bydalek ,T.J. and Margerum,D.W., 1962, Inorg. Chem. Vol.1, pp.582.
179. Margerum, D.W. and Stehi, 1967, R.H., Anal. Chem., Vol.37,pp. 222.
180. Margerum, D.W. and Stehi ,R.H.,1967, Anal Chem. , Vol.39, pp.1351.
181. Margeram, D.W. and Carr,J.D.,1966, J. Am. Chem. Soc., Vol.88, pp.1639.
182. Nakagawa, G. and Tanaka, M.,1962, Talanta, Vol.9, pp.917.
183. Pribil R. and Roubal Z.,1954, Col. Czech. Chem. Comm., Vol.19, pp.252.
184. Nakagawa ,G. and Tanaka, M.,1962, Talanta, Vol.9, pp.847.
185. Funahashi ,S., Yamada, S. and Tanaka ,M., 1971, Anal Chim. Acta, Vol.56, pp.371.
186. Tabata, M., Funahashi, S. and Tanaka ,M., 1972, Anal. Chem. Acta ., Vol.62, pp. 289.
187. Fujjnaima, H. and Itsuki, K., Banseki ,Kagaku, 1976, Chem. Abstr., Vol.85, pp.
86649h.
188. Pantaler ,R.P. and Pulyaeva, I.V.,1977, Z. Znal. Khim., Vol.32, pp. 394.
189. Dash ,A.C., 1977, Transition Met. Chem., Vol.2, pp.224.
190. Stehi, R.H., Margerum, D.W. and Latterell, J.L.,1967, Anal.Chem., Vol.39, pp. 1346.
191. Kumar, K., 1979, Ph.D. Thesis, I.I.T. Kanpur, India.
192. Tabata, M., 1987, Analyst, Vol.112, pp. 141.
193. Muller, H. and Crit, C.R.C. , 1982 ,Rev. Anal. Chem. Vol. 13, pp. 313.
194. Yatsimirshii, K.B., 1973, Analytical Chem. Vol. 12, pp. 193-217.
195. Bontchev, P.R., 1970, Talanta, Vol.17, pp. 499.
196. Bydalek, .T.J. and Margerum, D.W., 1962, Inorg. Chem., Vol. 1, pp. 852.
197. Funahashi S., Yamda, S and Tanaka, M., 1971, Anal. Chem. Acta, Vol. 56, pp. 371.
198. Olson, D.C. and Margerum, D.W., 1963, J. Amer Chem. Soc. Vol. 85, pp. 297.
199. Mottola ,H.A., 1974, Anal Chem. Acta. Vol. 71 pp. 443.
200. Milovanovic, G.A. 1983, Micro. chem. J., Vol. 28, pp. 437.
201. Parvathy, G. and Reddy, J.N.; Trans. Met. Chem. (London) 1992, Vol.17, pp.235.
202. Zazwta, Cecilia, Sosatorres. Maratha, E., Correa, Franeisco, Garza, Ortiz and
Ariacha,1999, J. Bioenergy, Biomember, Vol.31, pp.551.
203. Connor, O., Joseph, M., Lee, L.L., Gantzel, Peter, Rhlingold, Arnold, L. and Lam, Kin-
Cheing, 2000, J. Am. Chem. Soc., Vol.2 pp.12057.
204. Dunn, Allxander, R., Hays, Arma-Marria, A.,Goodin, David, B., Stout, C.; David,
Chiu, Richard, Winkler, Joy, R. and Harry, B., 2002, J. Am. Chem. Soc., Vol.124,
pp.10254.
205. Martell, A.E., 1968, Pure Appl. Chem., Vol.17, pp.129.
206. Mottola, H.A. and Frieser, H., 1967, Anal. Chem., Vol.39, pp.1294.
207. Janjic, T.J. and Milovanovic, G.A., 1973, Anal. Chem., Vol. 45, pp.390.
208. Janjic, T.J., Milovanovic, G.A., and Celap. M.B.,1975, Bull. Soc. Chem.. Beograd,
Vol.20, pp.329.
209. Janjic ,T.J. and Milovanovic, G.A., 1976, Bull. Soc. Chim., Beograd, Vol. 41, pp.293.
210. Nabivanec, B.I. and Kalabina, L.V., 1977, Zh. Anal. Khim., Vol. 32,pp. 2018.
211. Janjic, T.J. and Milovanovic, G.A. 1976, Anal. Chim. Acta., Vol. 85, pp.169.
212. Nikolelis, D.P. and Hadjiioannou ,T.P.,1978, Anal. Chem., Vol.50, pp.205.
213. Nikolelis, D.P. and Hadjiioannou, T.P.,1977, Analyst, Vol.102, pp. 591.
214. Sekheta, M.A.F., Milovanovic, G.A. and Janjic, T.J., 1979, Bull. Soc Chim. Beograd,
Vol.44,pp. 447.
215. Sekheta, M.A.F., Milovanovic, G.A. and Janjic, T.J., 1980, Bull. Soc Chim. Beograd,
Vol, 45, pp.41.
216. Eswara, Dutt, V.V.S. and Mottola, H.A., 1974, Anal Chem. , Vol.46, pp. 1777.
217. Milovanovic, G.A. and Janjic, T.J., Petrovic, S. and Kuzmanovic, G. 1980, Microchem.
J., Vol.25,pp. 380.
218. Rubio, S., Hens, A.G. and Valcarel, M, 1985, Microchem. J., Vol.32,pp. 174.
219. Raya, T.S. and Bendito, D.P.,1984, Mikrochim. Acta, , Vol.1, pp.467.
220. Vasilikiotis, G.S., Papdopoulus, C., Themelis, D.G. and Sofoniou, M.C., 1983,
Mirochem J., Vol.28, pp. 431.
221. Pantel, S. and Weisz, H.1977, Anal. Chim. Acta, Vol.89, pp. 47.
222. Dolmanova, I.F. and Zolotova, G.A., Mazko, T.N.; Dymshakova, G.M. and Trunov,
P.P. 1977, Zh. Anal. Khim., Vol. 32, pp.807.
223. Auffarth. J. and Klocko, D., 1979, Anal. Chim. Acta., Vol.111, pp. 89.
224. Lazarou, L.A. and Hadjiiounnou, T.P., 1979, Anal. Chem. , Vol. 51, pp. 790.
225. Dolmanova, I.F. , Ershova, E.V., Yu. Nd. V. and Shekhovtsova , T.N.,1979, Zh. Anal.
Khim., Vol.34, pp.1644.
226. Maslowaska, J. and Leszezynska, J.,1985, Talanta, Vol. 32, pp. 883.
227. Pedreno, C.S., Albero, M.I and Garcia, M.S., 1988, Talanta, Vol.35, pp.397.
228. Alexiev, A.A. and Angelova, M.G., 1983, Mikrochim. Acta II, pp.369.
229. Cordoba, M.H., Vinas, P. and Pedreno, C.S.,1985, Talanta, Vol.32, pp.221.
230. Phull, M. and Nigam, P.C.,1983, Talanta, Vol. 30, pp.401.
231. Yatsimirskii, K.. and Orlova, M.N.Z.,1959, Neorg. Chim., Vol.4, pp.741.
232. Prasad, S and Nigam, P.C. to be communicated.
233. Igor, R.P., Jaredic, M.D. and Pecer ,T.C., 1980, Talanta, Vol. 27, pp. 361.
234. Kreingold, S.U., Yutal, E.M. and Sosenkova, L.I., 1979. Chem. Abstr., Vol. 90 ,pp.
179643 v.
235. Nikolelis ,D.P. and Hadjiioannuou, T.P., 1978, Anal. Chem. ,Vol. 50, pp. 205.
236. Denboef, G. and Halanicki, A., 1983, Pure Appl. Chem. Vol. 55, pp. 553.
237. Otto, M., Muller, H. and Werner, G. 1978, Talanta., Vol. 25, pp.123.
238. Svehlta, G., 1993, Pure Appl. Chem. Vol. 65, pp. 2291.