SECTION 1.

INTRODUCTION TO CHLORAMINES

Chloramines are the derivatives of ammonia in which one, two or three

hydrogen(s) are being replaced by an alkyl or an aryl group to give an inorganic and

organic chloramine respectively. Depending upon the number of hydrogen(s) atoms

replaced they can be classified as monochloramine, dichloramine and trichloramine.

The structure of different N-halogeno-N-metalloarylsulfonamides are given

below

In most of the cases N-halogeno-N-metalloarylsulfonamides are commonly

known by their trivial names. e.g., chloramine-T (1, X = Cl, R = Me, M = Na),

chloramine-B (1, X = Cl, R = H, M = Na), bromamine-T (1, X = Br, R = Me, M = Na)

and bromamine-B (1, X = Br, R = H, M = Na). More recently a large no of derivatives,

which are related to alkylsulfonamide is being developed for various analytical

applications 2. A major research interest is also being focused on the synthesis of a

wide range of corresponding N-halogeno-N-metallocarbamates 3 by varying alkyl and

aryl groups. In all the above cases N-chloro, N-bromo, and N-iodo derivatives has been

synthesized mainly as their sodium salts. It is interesting to know that the chemistry of

N-halogeno-N-metallo reagents are very diverse. The main reasons for this nature is

due to their ability to act as sources of (a) hypohalite species, (b) halonium cations, (c)

N-anions (e.g., sulfonamides or carbamides anions) which act both as bases and

1
nucleophiles, and (d) in certain cases as nitrenoids. As a consequence of the above

abilities, these reagents react with various range of functional groups, which leads to

different molecular transformations. Synthesis of chloramine-T and related

arylsulfonamide derivatives [1-3] and their ability to act as disinfectant and antiseptic

was one of the reason which made to grow an enormous interest in this field.

Preparation of N-Halogeno-N-metallosulfonamidates

The hydrates of N-bromo-N-sodioarylsulfonamide was the first N-halogeno-N-

metallosulfonamides [4]. It was synthesized from the reaction of N, N-

dibromoarylsulfonamides with aqueous base. Few years later, the same reagent was

prepared by the reaction [2] of arylsulfonamide with sodium hypochlorite which was

followed by salting out of the derivatives. The later process is the most common method

for its preparation. Most of the preparations of N-halo metallo salts are based on this

method [3-9]. In addition to the above, reagents like N-chloro-N-sodiosulfonamide salts

ethylbenzene, xylene, bromobenzene, o-tolyl, p-alkoxybenzene and a range of other

substituted benzene and naphthalene sulfonamides have been synthesized. Recent

literature reveals that chloramines-T and chloramine-B are prepared with a yield of 75-

95% with the help of continuous flow process [10], where an aqueous solution of

sodium hydroxide of the sulfonamide sodium salt is fed into a stoichiometric quantity

of chlorine through a flow reactor. An alternative [11] preparation for chloramine-T is

the treatment of p-toluene sulphonamide with aqueous sodium hydroxide, extracted

with an organic solvent to remove contaminating ditolylsulfone, which is finally

chlorinated. The silver salt of chloramine-T (1, X = CI, R = Me, M = Ag) has been

prepared by silver nitrate reaction with chloramine-T [12-13].

2
General characteristics of chloramine-T

Chloramine-T (p-CH3C6H4SO2NClNa.3H2O or CAT) and their related

sulfonamide derivatives are stable in aqueous solution. They are strong oxidants as well

as strong electrolytes in both acidic and alkaline media. The reduction potential [14] of

CAT is 1.138 & 0.5 at pH 0.65 and 12 respectively.

Properties of chloramine-T

The structure of chloramine-T can be written as 4 and sometimes as 5 [15, 16].

The bond lengths for the above mentioned structures are not available in the

literature. Iodine from acidified potassium iodide and Sulfur is liberated from Hydrogen

sulfide [17].

When chloramine- T is dissolved in water, it exists [18, 19] in a series of

equilibria (Figure l.1).

3
 Fig 1.1 Different equilibria present in aqueous solution of CAT

The arylsulfonamide and lower members of alkylsulfonamide derivatives are

readily soluble in water [21]. The N-halogeno-N-metallosulfonamides are often

prepared as their stable crystalline hydrates (e.g. chloramine-T is prepared as

chloramine-T trihydrate). The hydrated salts can be once again dehydrated when heated

at 100 0C or when it is allowed to stand under vacuum over P2O5. However, heating

CAT is usually hazardous because of the possibility of explosion [20]. The

corresponding alkylsulfonamides also crystallizes in the form of their hydrated salt, but

they are more readily dehydrated than the former over P2O5 [21].

Hydrolysis of chloramine-T

Chloramine-T [22] hydrolyze in water to give PTS and sodium hypochlorite as

represented in equation (1)

TsNClNa + H2O TsNH2 + NaOCl (1)

4
Where Ts (tosyl) = CH3C6H4SO2

Later TsNH2 will ionize and, except in alkaline solution, the hypochlorite ion

will hydrolyze to give hypochlorous acid, which is considered to be the reactive species.

But according to Bishop and Jennings [23], Soper [24] Dietzel and Taufel [25] and

Morris et al [26] a different equilibria are set up in the hydrolysis of CAT which is

explained as below. CAT is the sodium salt of the acid p-toluenesulphon-N-chloramide.

Even though the acid has not been isolated, there is sufficient evidence [24, 26-27] for

its existence in solution.

The sodium salt is a strong electrolyte which first dissociates:

The anion formed in the equation (2) abstracts a proton to form the free acid

which in the next step undergoes disproportionation to give p-toluenesulphonamide and

sparingly soluble dichloramine-T :

2 TsNHCl TsNCl2 + TsNH2 (4)

Morris et al [26] calculated the value of the equilibrium constant for the above

disproportionation reaction and was found to be 6.1 x 10-2.

The dichloramine-T hydrolyze as

TsNCl2 + H2O TsNHCl + HOCl (5)

5
which on further hydrolysis gives

Soper [24] and Morris et al [26] evaluated the hydrolysis constants for reactions (5) and

(6) and the values were found to be 8 x 10-7 and 4.88 x 10-8 respectively.

Finally the hypochlorous acid ionizes, and its ionization constant Ka is 3.3 x 10-8.

Concentrations of various species in CAT solution

Bishop and Jennings [23] conducted numerous experiments and calculated the

concentrations of various species like TsNCl-, TsNHCl, TsNCl2, TsNH2, HOCl, OCl-

in decinormal (0.05M) solution of CAT and is tabulated in Table 1.1. The table clearly

shows that in the strong acid medium the free acid (TsNHCl) and dichloramine-T

(TsNCl2) predominate, but with the increase in the pH the anion of the acid (TsNCl-)

predominates in weak acid or also in neutral solution. Even in weak alkaline medium

the acid anion predominates over hypochlorite. The concentration of hypochlorous acid

remains constant throughout the pH range.

6
Table 1.1 Concentrations of various species in a 0.05 M CAT solution at various
pH values
pH [TsNCl-] [TsNHCl] [TsNCl2]=[TsNH2] [HOCl] [OCl-]
(M) (M) (M) (M) (M)
0 9.6 X 10-5 4.0 X 10-2 9.9 X 10-3 3.9 X 10-7 1.3 X 10-14
1 9.6 X 10-4 4.0 X 10-2 9.9 X 10-3 3.9 X 10-7 1.3 X 10-13
2 7.8 X 10-3 3.2 X 10-2 7.9 X 10-3 3.9 X 10-7 1.3 X 10-12
3 2.8X 10-2 1.1 X 10-2 2.9 X 10-3 3.9 X 10-7 1.3 X 10-11
4 3.8 X 10-2 1.6 X 10-3 3.9 X 10-4 3.9 X 10-7 1.3 X 10-10
5 4.0 X 10-2 1.6 X 10-4 4.1 X 10-5 3.9 X 10-7 1.3 X 10-9
6 4 .0X 10-2 1.6 X 10-5 4.1 X 10-5 3.9 X 10-7 1.3 X 10-8
7 4.0 X 10-2 1.6 X 10-6 4.1 X 10-5 3.9 X 10-7 1.3 X 10-7
8 4.0 X 10-2 1.6 X 10-7 4.1 X 10-5 3.9 X 10-7 1.3 X 10-6

In general during reduction chloramine-T undergoes a change of two electrons

and two hydrogen ions are consumed per initial molecule of reagent, to give p-

toluenesulphonamide and chloride ions as the final products after the reaction.

In strong acid solution the free acid and dichloramine-T predominate and may

react directly.

Chloramine-T has high equivalent weight and acts as an analytical and an

oxidizing agent. It offers many advantages like it is cost effective and easily available

in reasonable purity as a by-product of saccharine manufacture. It can be further

purified by simple crystallization, and is neither hygroscopic nor efflorescent. Hence it

7
can be weighed directly for preparing the solutions. Hypochlorites, hypochlorous acid

and monochloramine (NH2Cl) are useful oxidizing agents, but they are difficult to

prepare and purify and also it cannot be obtained as pure solids. CAT/CAB appear to

offer a very convenient substitute in a solid weighable form for these reagents, and also

for iodine, iodate and bromate which are quite expensive.

Purification of chloramine-T

Chloramine-T is recrystallized from water [24, 27-28] and the crystals obtained

are dried either in the presence of air or with the help of vacuum desiccator. From the

above procedure employed samples of a high and reproducible purity can therefore be

prepared, but it can be seen from Table 1.2, the maximum purity that can be attained is

inadequate for a primary standard. The observed 0.5 % deficiency perhaps may be

largely moisture. There is no simple method of removing this without decomposing the

trihydrate.

Table 1.2 Purification of solid chloramine-T*

% purity of TsNClNa. 3H2O

Original sample 98.50

After 1st crystallization 99.14

After 2nd crystallization 99.55

After 3rd crystallization 99.54

After 4th crystallization 99.55

*Stored in brown glass screw cap bottle exposed to daylight

8
Stability of solid chloramine-T

Table 1.3 Stability of chloramine-T tri hydrate

Time of exposure in months % purity of sample

0 99.18

10 99.06

19 98.86

*Stored in brown glass screw cap bottle exposed to daylight

Chloramine-T in all its forms has been shown to be unstable to heat, and

unstable on storage in any but the trihydrate form, which is neither efflorescent nor

hygroscopic. In order to verify the stability of Chloramine-T, two-liters of 0.05 M CAT

solution were prepared in two batches, standardized, and stored in bottles which is fitted

with screw caps. Among them four of those were brown bottles, and the remaining one

was of transparent glass. The solutions in the first three bottles were stored in a

cupboard whereas Solution IV in brown glass and solution V in clear glass were stored

side by side on an open laboratory shelf. All solutions were analyzed at regular intervals

of time. The results in Table 1.3 shows that storage in darkness or daylight does not

make any difference as long as the solution is stored in brown glass. Whereas exposure

of solution to daylight causes a noticeable change in the titre value i.e. a change of 0.4

% in the first week and nearly 2.0 % in one year. Even though chloramine-T is quite

unstable on exposure to sunlight, its storage in brown glass bottles has the ability to

afford sufficient protection both in the solid state as well as in solution and the stability

over periods of three months or more is sufficient to meet the requirements of a standard

reagent.

9
Standardization of chloramine-T solution

The two important methods used for the standardization of Chloramine-T are:

(a) Titration against standard arsenic (I) solution in bicarbonate buffer in the

presence of a small amount of iodide, with starch as an indicator.

(b) Titration against sodium thiosulphate of the iodine liberated on addition of

potassium iodide to an acidified CAT solution, with starch as an indicator.

Synthetic applications of chloramne-T

Chloramine-T finds a wide range of synthetic applications which includes

aminohydroxylation, aminochalcogenation of alkenes aziridinations and allylic

aminations.

(a) Chloramine-T on reaction with various sulfur-containing compounds like thiols,

sulfides, disulfides, sulfimides, xanthates, thioketones, sulfenyl chlorides and sulfinyl

chlorides to give sulfur–nitrogen bonds [29]. The reaction of CAT with sulfides forms

the basis for the deprotection of thio groups. Hence 1, 3-dioxathiolanes, 1, 3- dithianes

and 1, 3-dithiolanes, are all cleaved by CAT to regenerate the carbonyl compounds.

(b) Chloramine-T react with olefins in the presence of acetone–water acidified with

non-nucleophilic acid to give chlorohydrins [30]. Whereas in acetic acid medium, it

gives 1, 2-chloroacetoxy derivatives. Finally chlorolactone is obtained on reaction with

unsaturated organic acid like ally acetic acid in the presence of methanesulfonic acid.

10
(c) Chloramine-T with Enamines yields N, N-dialkylated α-amino aldehydes [31].

(d) Chloramine-T on reaction with NaBr and NaI generates BrCl and ICl, respectively.

Trialkylboranes reacts with NaI and NaBr in the presence of CAT to give the alkyl

iodides and alkyl bromides respectively [32]. Also, potassium aryl trifluoroborates,

alkenyl tifluoroborates and vinyl trifluoroborates, and are converted to the respective

iodide using NaI in the presence of CAT.

(e) Chloramine-T which also acts nitrogen source has been used for the aziridination of

alkenes. In the presence of CuCl which acts as catalyst, and molecular sieves 5Å, CAT

reacts with alkene, the corresponding aziridine is obtained with moderate yield [33]. In

the absence of metal catalyst, olefins can also be aziridinated using CAT upon treatment

with NBS, iodine, or iron corroles.

11
(f) Alkyl isocyanides react with aromatic amines and Chloramine-T under phase-

transfer catalysis to give sulfonyl guanidines [34].

12
 SECTION 1.2

INTRODUCTION TO REACTION KINETICS

Reaction kinetics deals with the rates of chemical reactions. Any chemical

reaction is considered to consist of number of one or more single-steps which are known

as elementary reactions, elementary processes or elementary steps. Elementary

reactions may involve dissociation or isomerisation of a single reactant molecule, which

is referred as unimolecular step. Also there may be a single collision between two

molecules, which is referred as a bimolecular step.

It should be noted that the majority of the reactions that are written as a single

reaction equation actually consists of a series of elementary steps or process.

The main objectives for the study of chemical kinetics are:

(a) To analyze the sequence of elementary steps giving rise to the overall reaction. i.e.

to determine the reaction mechanism and

(b) To determine the absolute rate of the reaction and also for the individual elementary

steps.

In general chemical reactivity is controlled by two broad factors:

(a) Thermodynamics

(b) Kinetics

Thermodynamics gives the idea about the feasibility of the reaction. Also it

gives the idea about the factors which control the rate of a reaction. Practically in order

for a reaction to occur, the reaction must be thermodynamically and kinetically

13
favored. The Thermodynamic factors which control reactions are enthalpy, entropy

and the temperature. The kinetic factors which controls the rate of reaction are, the

concentration of reactants, the reaction mechanism, the energy barrier required to be

overcome i.e. its activation energy and temperature.

Rate of a reaction

The rate of a chemical reaction, is the change in concentration in unit time.

Hence the rate of a reaction has units of concentration per unit time i.e. mol dm-3 s-1.

For gaseous reactions, alternative units of concentration are often used, likes units of

pressure – Torr, mbar or Pa). In order to determine the rate of reaction we can monitor

the change in concentration of one of the reactants or products as a function of time.

Stoichiometry of a reaction

The stoichiometry is the number of moles of each reactant and product

appearing in the balanced reaction equation.

Taking the stoichiometry in to consideration the reaction rate is modified and

can be defined as the rate of change of the concentration of a reactant or product divided

by its stoichiometric coefficient.

N2 + 3 H2 2 NH3 (9)

In the above reaction, the rate (ν) is expressed as,

ν = -d [N2] /dt = - 1/3 d[H2]/dt = 1/2 d[NH3] /dt

The negative sign indicates that the decrease in concentration of one of the

reactants. The reaction rate needs to be a positive quantity.

14
Rate laws

The rate law is an expression which relates the rate of a reaction to the

concentrations of the chemical species present, which includes reactants, products, and

catalysts,

i.e. ν = k [A]a [B]b [C]c ...

Hence the rate is proportional to the concentration of the reactants. The powers

to which each concentration term is being raised is the corresponding order. It may be

a zero, a whole number or a fraction. It should be observed that the order will not reflect

the stoichiometry of the reaction equation.

In case of a multi-step process, the overall reaction equation is the net result of

all of the elementary reactions in the mechanism. By knowing the sequence of

elementary steps that constitutes the mechanism of a reaction, we can deduce the rate

law. Conversely, if the mechanism of the reaction is unknown, we can carry out

experiments to determine the orders with respect to each reactant and then try out

various ‘trial’ reaction mechanisms to see which one fits best with the experimental

data.

Note: The overall rate laws for a reaction may contain reactant, product and catalyst

concentrations, but not that of reactive intermediates (these will of course appear in rate

laws for individual elementary steps).

The units of the rate constant

The units of the rate constant depend upon the rate law in which it appears. The

general formula to calculate the rate constant is (mol dm-3)1-n s-1

15
Integrated rate laws

On integrating the rate law (differential form) we obtain an expression for the

concentration as a function of time. The rate laws for different orders in both

differential and integrated forms are given in Table 1.4

Table 1.4 Order, differential and integrated expression for different orders

Order Differential form Integrated form Straight line plot

0 d[A] [A] = [A]O - kt y = [A]

= -k
dt x = time

slope = ‐k

1 d[A] ln[A] = ln[A]O - kt y = ln[A]

= -k [A]
dt x = time

slope = ‐k

2 d[A] 2
1 1 y = 1/[A]
= + 2 kt
= -k [A] [A] [A] O
dt x = time

slope = k

2 d[A] 1 [B] O [A]

= -k [A] [B] kt = ln
dt [B]O - [A]O [A] O [B]

* [A] 0 and [B]0 represent the initial concentrations of A and B i.e. their concentrations

at t =0

16
Determining the rate law from experimental data

In kinetics experiment we measure the concentrations of one or more reactants

or products at different intervals of during the reaction. The following methods are used

to determine the order from which the rate law for a reaction can be determined.

(a) Isolation method

In this method the concentration of reactants is taken in excess relative to the

concentration of other reactants whose order should be determined, so that their

concentration remains essentially constant throughout the course of the reaction. Such

reactions are known as pseudo order reactions. Once the rate law has been simplified,

either differential or integral methods discussed in the following subsections can be

applied to determine the order of the reaction.

(b) Integral methods

On integration of differential rate laws, we get integrated equation.

For, a Zeroth order integrated rate law: [A] = [A] 0 – kt

Hence the plot of [A] vs t will be linear, with a slope of -k.

First order integrated rate law: ln [A] = ln [A] 0 – kt

A plot of ln [A] vs t will be linear with a slope of -k.

Second order integrated rate law: 1/ [A] = 1/ [A]0 + 2kt

A plot of 1 / [A] vs t will be linear with a slope of 2k.

17
Experimental techniques

The following techniques have been followed in order to study the kinetics of

fast reactions.

(i) Flow techniques

(ii) Flash photolysis and laser pump probe techniques

(iii) Relaxation methods

(iv) Shock tubes

(v) Lifetime methods

For slow reactions, the techniques employed are

(i) real time analysis

(ii) quenching method

The composition of the reaction mixture may be followed by any one of the

following methods which in turn depends upon the chemical or physical change that

occurs during the chemical reaction.

Kinetic theories

The theories that has been developed in order to calculate the rate constants for

a simple unimolecular and bimolecular reactions are:

(a) Collision theory.

(b) Transition or activated complex theory.

18
(a) Collision theory (Max Trautz and William Lewis in 1916 -18)

Postulates:

 For a reaction to occur the molecules of reactants should collide with each other

and the rate of reaction is directly proportional to the collision frequency i.e. the

number of collisions per second per unit volume.

 The collision are elastic in nature.

 The molecules are considered to be rigid hard spheres.

 In addition for the molecules which possess energy greater than threshold

energy and also with proper orientation (steric factor) can only lead to product

formation after collision.

According to collision theory, for a bimolecular gaseous reaction,

k2 = P A e-Ea/RT (10)

Where, K2= rate constant, P = steric factor,

A=collision frequency, Ea= activation energy,

R= Gas constant and T= Temperature.

Demerits:

 It considers only the translational energy of the molecule.

 Collision theory does not provide any prediction of p, the “steric factor”.

 Calculated values for the rate constant are usually too high compared with

measured values.

 Measured activation energies are lower than the energies of the bonds that have

to be broken in reactions.

19
Transition state or activated complex theory (Henry Eyring, 1930s)

According to this theory,

A + B X C + D (11)
Where, A and B are reactants which are in equilibrium with X ǂ (activated complex/

transition state complex of relatively high energy).

The rate constant is given by the expression,

k = {(kB T) /h} e  S°ǂ / R e -  H°ǂ / (RT) (M 1 – m) (12)

Where,  S°ǂ is the standard molar entropy of activation

 H°ǂ is the standard enthalpy of activation

KB is the Boltzmann constant

M and m are the molarity and molecularity of the reaction respectively.

The thermodynamic parameters are calculated as explained below:

The rate constant values are calculated at different temperatures and a graph of

log k' vs 1/T (straight line with a negative slope) is plotted. The value of Ea is

calculated with the help of the by making use of the formula,

Ea = - (slope x 2.303 x 8.314) J mol-1 (13)

Other thermodynamic parameters are calculated as below:

a) Enthalpy of activation: Δ Hǂ = Ea – RT (14)

b) Entropy of activation Δ Sǂ = Δ Hǂ /T - 19.147 log T/ k'- 197.57 (15)

where k' is the reaction rate constant in sec -1

20
c) Gibb’s free energy of activation: ΔG ǂ = ΔH ǂ - T ΔS ǂ (16)

The specific rate constant is given by the formula,

ksp = k / [substrate]x[catalyst]y[medium] z (17)

Hence by knowing the values of Ea and ksp, The Arrhenius frequency factor (A) also

can be calculated from the relation,

log A = log ksp + Ea / 2.303 RT (18)

Solvent effects like dielectric constant and ionic strength of the medium provide some

important information regarding,

i) The nature of the reacting species (ion-ion/ ion dipolar/ dipole-dipole

interaction) in the rate determining step and

ii) Structure of the activated complex.

Effect of dielectric constant

Bronsted theory and Scatchard's [35] are the two major contributions for the

theory of the kinetics of reactions in solution. The contributions of these two theories

were applied for the reactions between ions and led to the general equation,

ln k = ln ko – ZA ZBϵ2/ DkBTrǂ + ZAZBϵ2 k/ DkBT (1+αk) (19)

Where ϵ = electric charge, kB = Boltzmann constant, rǂ = radius of the activated complex

(rǂ = rA + rB), D = Dielectric constant of the medium.

21
 Equation (19) gives an idea about the variation of rate constant with the

dielectric constant of the medium. The plot of ln k' versus 1/D must be linear with a

slope of - ZA ZBϵ2/ kBTrǂ

In order to find out the value of rǂ the reaction is carried out in number of mixed

solvents of different dielectric constants and inference can be done on the size and

charge of the transition state.

Amis and Jaffe [36] have derived a relation for the variation of rate constant as

a function for an ion- dipolar interaction, of the dielectric constant (D) of the medium,

which is given as,

log k = log k0 + Zeμ/2.303kTrǂ2D (20)

Where Z is the charge of the ion and μ is the dipole moment of the molecule.

Equation (20) clearly indicates that the rate constant increases with the decrease

in the value of D, depending on whether the transition state bears a negative or positive

charge.

Kirkwood [37], Benson [38], Entelis and Tiger [39] and Laidler [40] have also

discussed about the reactions between dipolar molecules and ions. They derived an

expression to describe the effect of varying solvent composition on the reaction rate in

the well-known monographs. However it is to be noted that a clear concept of the

influence of dielectric constant on the rate of reaction in solution has not emerged so

far. It can only be concluded from these observations as to whether an ion-dipole or

dipole-dipole interaction is involved in the rate-determining step.

22
Effect of ionic strength on the rate

In general, the ionic reactions are favored by polar solvents. In order to

determine the effect ionic strength of the medium on the rate Bronsted [41] has given

the relation between the reaction rate constant, k' and the ionic strength (μ) in an ionic

reaction as:

log k' = log ko + 2α ZAZB (μ)1/2 (21)

Equation (21) is known as Bronsted equation. From the above equation it is

clear that a plot of log (k) versus the square root of ionic strength (μ)1/2 gives a straight

line. In aqueous solution, the slope is nearly equal to ZAZB i.e. the product of the ionic

charges carried by A and B respectively

The ionic strength is calculated from

I = 1/2 mizi2

The following cases can be considered with the help of Bronsted equation:

a) If ZA and ZB have the same sign, then ZAZB is positive and the rate constant increases

with ionic strength.

b) If ZA and ZB have different signs, ZAZB is negative and the rate constant decreases

with ionic strength.

c) If one of the reactants is uncharged, ZAZB is zero and the rate constant is independent

of the ionic strength.

The applicability of equation (21) for an ion-dipole or ion-ion interaction was

studied by Davies [42] and came in to conclusion that the equation holds good for

number of reactions. But deviations were observed in concentrated solution, where the

23
Debye-Huckel equation breaks down. Hence a Huckel introduced a new term bμ, in

addition to the Debye Huckel term and hence the equation for ion-dipole reaction can

be written as,

k' = ko (1 + bμ) (22)

Equation (22) shows that the rate constant varies linearly with ionic strength.

Effect of solvent isotope

Since isotopic substitution brings least disturbing structural change in a

molecule it is found to be one of the best method for in order to elucidate the reaction

mechanisms.

Isotopic effect can be classified as,

a) Primary isotopic effect: If the isotopic substitution is made to an atom which takes

part in the reaction.

b) Secondary isotopic effect: If the isotopic substitution is made to an atom which does

not directly participate in the reaction.

c) Normal or inverse effect: A protonation in an equilibrium prior to the rate

determining step will lead to give either a normal or inverse effect depending upon how

the equilibrium is shifted due to isotopic substitution.

In some cases, the bond involving a hydrogen atom becomes stronger in the

activated state due to resonance and other electromeric effects. Replacement of H by D

will then lead to a greater decrease in energy in the activated state than in the initial

state. As a result, the activation energy becomes less for the reaction involving the

heavy molecule. In other words, isotopic substitution of H by D results in an increase

in reaction rate. This is termed “the inverse isotope effect”.

24
The above effect gives different mechanistic information.

Fig. 1.2 Morse potential curve

The zero point vibrational energies of molecules R-H and R-D are represented

in Figure 1.2, which is known as Morse potential curve. Here R is a group/atom that is

much heavier than H or D. Morse potential curve is a plot of potential energy and inter

nuclear distance along y-axis and the x axis respectively. In Figure 1.2, EDo and

EHo correspond to the zero point energies of deuterium and hydrogen which in turn

depends upon the reduced mass of the molecule. The heavier the molecule or atom, the

lower the frequency of vibration and the smaller the zero point energy and vice versa.

Hence deuterium has lower zero point energy than hydrogen. Hence the bond

dissociation energies is different for R-D and R-H i.e. the bond dissociation energy for

R-D (ED) is greater than the bond dissociation energy of R-H (EH). Hence we can

conclude that the rate of the reaction changes due to isotopic substitution.

The deuterium effect (replacement of H by D) is expressed by the ratio kH / kD.

Normal KIEs for the deuterium effect lies between 1-7.Large effects are seen when

hydrogen is replaced with deuterium because the percentage mass change is very large

(mass is being doubled).

25
Proton Inventory studies

The proton inventory studies [43-45] gives an idea about the number of protons

undergoing a significant change in bonding in the transition state (TS) with reference

to the ground state.

Kn = ko Π (1-n+nϕi) / Π (1-n+nϕj) (23)

Equation 23, is known as Gross-Butler equation. This equation expresses the

relationship between the observed rate constant in mixtures of H2O and D2O and the

fractionation factors (φ) for the exchangeable protons.

n is the atom fraction of deuterium in the medium.

i and j represent the contributing hydrogens in the transition and reactant states

respectively.

In the above equation the fractionation factors indicates the tightness of the

bonding of for hydrogens and is usually less than unity. In such cases Normal primary

isotopic effect of kH / kD > 1 are observed. Normal primary isotopic effect is also

observed in the case of hydrogen-bonding situations where the overall bonding is loose.

In general, plots of kn versus n can either be bowed upward, linear, or bowed downward.

The latter two shapes are observed when a single proton, or two or more protons

undergoes a significant changes in bonding in passing from reactant to transition state.

Equation (23) can be written as equation (24) when one assumes that the

reaction proceeds through a single transition state,

Kn = ko (1-n+n ϕj )-2 (24)

26
(ko/kn)1/2 = 1+n (ϕj-1) (25)

1/2
Hence from equation (25) it is clear that a plot of (ko/kn) vs n is linear with a slope

equal to (ϕj-1).

27
 SECTION 1.3

MATERIALS AND METHODS

Reagents

Chloramine-T: CAT was purchased by Sigma-Aldrich and purified by the method of

Morris et al (26). An aqueous solution of 0.1 mol dm-3 CAT was prepared as stock and

it was standardized periodically with the help of iodometric method and later it was

stored in amber bottles in order to avoid any photo chemical effects.

Chloramine-B: CAB was also purchased by Sigma-Aldrich. Later a stock solution of

0.1 mol dm-3 was prepared, standardized and stored in amber bottles until further use.

p- Toluene sulphonamide: p- Toluene sulphonamide was used in order to study the

effect of reduction product on the rate of the reaction with CAT as an oxidant. It was

purchased from Sigma-Aldrich with a purity of > 99% and was used without any further

purification and the stock solution was prepared and used whenever it would be

required.

Allura Red AC (Sigma Aldrich): An aqueous solution of 0.1 mol dm-3 Allura Red AC

(analytical grade) was prepared and was used with required dilution.

Tartrazine (Sigma Aldrich): Tartrazine with purity ≈ 98% was purchased from Sigma

Aldrich and its aqueous solution of suitable concentration was used in order to study its

kinetics of oxidation.

Acid Red 1 (SD Fine Ltd.): Acid red 1 also known as Red 2G and Azofloxin was

purchased from SD Fine Ltd was dissolved in water and was used for its further study.

28
Acid Red 18 (SD Fine Ltd.): An aqueous solution of Acid Red 18, a dye used in food

products was prepared and was used with suitable dilution to get required concentration

and was used for its oxidation kinetics.

Quinoline yellow: Quinoline yellow, a water soluble dye was purchased from SD Fine

Ltd in order to study its kinetics of decolourisation.

Green S: Green S, a triphenylmethyl dye purchased from SD Fine Ltd.

Patent Blue V: Patent Blue 5 of analytical grade was purchased from SD Fine Ltd.

Benzene sulfonamide: Benzene sulfonamide was also purchased from Sigma-Aldrich.

The stock solution of suitable concentration was prepared and used whenever it was

required.

Sodium perchlorate: A concentrated solution of 1 mol dm-3 Sodium perchlorate was

prepared and diluted to required concentration in order to the study the effect of ionic

strength on the rate of the reaction.

Other reagents

Other reagents like Sodium chloride, Methanol, Hydrochloric acid, sulphuric

acid, perchloric acid, sodium hydroxide, sodium thiosulphate, potassium iodide, starch

indicator, were of Analytical grades and were used without further purification.

The solutions of all the above chemicals were prepared with the help of triple

distilled water which was purchased from Nice.

Deuterium oxide (D2O): Deuterium oxide (99.9 atom % D) was purchased from

Sigma-Aldrich in order to study the solvent isotope effect for various oxidation kinetics.

29
Reaction Vessel: The reaction was carried out in a temperature resistant boro silicate

boiling tube which is of 1" X 6" and a capacity of 100 ml.

Thermostat: The oxidation- kinetics was studied in the temperature range of 293 to

318 K. Hence in order to maintain a suitable constant temperature, Techno-ST-405

(India) thermostat was used. The temperature was maintained with an accuracy of ±

0.1°C.

UV-Vis Spectrophotometer: The kinetics of oxidation of all the dyes mentioned in

Table 1.5 were studied with the help of Schimadzu UV-Vis Spectrophotometer (UV-

1800).

NMR: Hl- NMR spectra were recorded on an Agilent 400 MHz NMR spectrometer.

FT-IR: IR Spectra were recorded by dispersing the sample in KBr on FT/IR-4100 type-

A spectrometer.

LC-MS: LC-MS spectra were obtained by Thermo orbitrap elite.

Kinetic Procedure

All experiments were carried out under pseudo-first order conditions, where the

concentration of oxidant (CAT/CAB) was in excess than the concentration of substrate

(dye). The kinetic measurements were made using UV-Vis spectrophotometry at a

suitable constant temperature. In certain cases, there is a possibility of degradation of

dye in the presence of sunlight. Hence the reactions were carried out in Pyrex boiling

tubes (ground socket, with stopper) where the outer surface was coated black. Required

amounts of substrate, medium (HCl/NaOH) and also water (to keep the total volume

constant i.e. 50 ml for all the kinetic runs) were taken in one tube and the oxidant in the

30
other. Both the tubes were thermostated for nearly 10-15 minutes in order to attain

constant temperature. Later the reaction was initiated by the rapid addition of suitable

amount of oxidant in to the mixture containing Substrate. 3ml of aliquot of the solution

was pipetted into a cuvette and its absorbance was measured with the help of

spectrophotometer. The absorbance was measured at a wavelength corresponding to the

maximum absorbance of the substrate for more than two half-lives. Plots of log (abs)

vs time were made to evaluate the pseudo-first-order rate constants kʹ (s-1). An fx-991ms

calculator was used to calculate the regression coefficient.

31
 SECTION 1.4

KINETIC AND MECHANISTIC STUDY WITH CHLORAMINE-T

Chloramine-T is one the most important member of N-metallo-N-

haloarylsulphonamides and behaves as oxidizing/analytical agent in both acidic and

basic media. Campbell and Johnston [46] have reviewed the synthetic applications of

oxidation reactions of various functional groups with CAT. Later this review was

updated by Banerji et al [47] and Amresto [48] to include all important developments

on oxidation reactions of organic and inorganic compounds with CAT. Finally and

more recently, a review entitled “Mechanistic investigations involving chloramine –T”

has been brought out by Agarwal and Upadhyay [49]. The above mentioned reviews

cover most of the literature with reference to CAT. The kinetics study on various

substrates with the help of CAT as an oxidant in different medium by various authors

are summarized below.

Prasantha et al [50] have studied the kinetics of oxidation of some α-amino acids

with CAT in alkaline medium catalyzed by β-Cyclodextrin. The kinetics of reactions

was fractional-order with respect to [amino acids] and [β-cyclodextrin], first-order with

respect to [CAT] and inverse fractional-order with respect to [OH−].

Puttaswamy, Anu Sukhdev & Shubha [51] have reported the kinetics of

ornidazole with CAT in acid and alkaline media catalyzed by Ru (III) & Os (VIII).

Oxidation of sunset yellow dye by CAT in presence of HClO4 and NaOH,

catalyzed by Os (VIII) and oxidation of Triphenylmethane dyes in NaOH catalyzed by

Pd (II) was reported by Vinod, Puttaswamy & Ninge Gowda [52, 53]. In case of Sunset

yellow in HCl, the experimental rate law is d[CAT]/ dt = k[CAT] 0[SY]0[HClO4]0.46 and

32
in NaOH the rate law is d[CAT]/dt = k[CAT] 0[SY]0[NaOH]0.23[OsO4]0.84. Whereas in

case of Triphenylmethane dyes oxidation reaction follows the rate law:

rate = k[CAT]a[Dye]b[OH−]c[Pd(II)]d where a and b are unity, and c and d are less than

unity.

Shivananda et al [54] reported the kinetics on the oxidation of Ru (III)-catalyzed

oxidation of some aromatic primary diamines by CAT in HCl. The reaction showed

first-order dependence both on [oxidant]0 and [Ru(III)], and fractional order

dependence on [Amine] o and on [H+ ].

Ekta Pandey & Upadhyay [55] studied the effect of micellar aggregates on the

kinetics of oxidation of α-aminoacids by CAT in perchloric acid medium.

Saldanha et al [56] have focused on the kinetics of oxidation of psychotropic

drugs by CAT in HCl medium.

Kinetics and mechanistic study on Oxidation of trans-Cinnamic Acids by CAT

in alkaline Medium was reported by Ragopalan et al [57]. The order with respect to

[CAT] was zero and [OsO4] was one. The reaction was fractional order in [substrate]

and the rate dependence on [OH-] was inverse first order.

Nidhi Sharma, Mishra & Sharma [58] have reported on the kinetics and

mechanism of oxidation of formic acid with CAT in acidic medium. The oxidation has

been observed to proceed through two different mechanisms, one dependent and other

independent of [H+]. Also the rate is retarded by the addition of PTS.

Bharat and coworkers [59] reported on the kinetics of oxidation of ketoglutaric

acids by alkaline CAT solution. The reaction showed first order dependence in CAT

and fractional order in substrates.

33
 Uma & Mayanna [60] studied the kinetics of primary alcohols by CAT in

alkaline medium catalyzed by Os (VIII). The reaction followed first order dependence

in CAT, alcohol, catalyst and inverse fractional order in medium.

Kinetics of oxidation of thiosemicarbazide by positive halogens was reported

by Thimme gowda and Ishwara bhat [61]. The rate followed first order kinetics in

[Oxidant] and inverse fractional order w.r.t [H+]. But it was fractional order in [TSC]

with CAB and independent of [TSC] with BAB and DCB.

Rangappa et al [62] have reported the Kinetics of oxidation of erythro-series

pentoses and hexoses by CAB. The rate law showed first order on CAT, Sugar and

second order dependence on NaOH. The rate of the reaction was influenced by a change

in ionic strength of the medium, and the dielectric effect was found to be negative.

Oxidation of 2-phenylethylamine with CAB in HCl catalyzed by Ru (III) was

reported by Mohana & Prasad [63]. The reaction rate showed first-order dependence

each on [CAB], [H+] and [Ru (III)] and fractional order on [substrate] and [Cl−].

Singha et al [64] have studied on the oxidation of paracetamol by CAT with

chloro-complex of Ir (III) in HCl. The reaction followed first-order kinetics w.r.t

[CAT], [Substrate] and [Cl−] in their lower concentrations range, tending to zero atheir

higher concentration. The kinetics followed first order w.r.t [Ir (III)] for the oxidation

of paracetamol. Also the rate decreased with the increase in the concentration of [H+]

and [PTS].

Sudha Rani and coworkers [65] have reported on the kinetics and mechanism

of oxidation of L-tryptophan by CAT in NaOH medium. The reaction followed a first-

order dependence of the rate on both [CAT] as well as [sub], and an inverse fractional

order dependence on [OH-].

34
 Sarasan and Geetha [66] studied the kinetics of effect of surfactant on the

oxidation of m-Nitrophenol in aqueous acetic acid medium by CAT. The order of the

reaction w.r.t the oxidant was one. But in the presence of surfactant, the values of first

order rate constant increases with increase in the [CAT]. Also the rate of the reaction

increased by ten times in the presence of catalyst. The order w.r.t [substrate] was found

to be zero in the absence of the surfactant and fractional order in the presence of the

surfactant.

Kinetics of oxidation of Resorcinol has been investigated both in the presence

as well as in the absence of a cationic micelle, cetyl pyridinium bromide by Prakash

and coworkers [67]. A first order kinetics was observed w.r.t [CAT] both in presence

and absence of micelle.

Kinetics and mechanism of oxidation of glycolic acid by CAT and catalysed by

Pd (II) complex in alkaline medium was studied by Kumar et al [68]. The reaction

showed first-order kinetics at lower [CAT] but at higher concentration it showed zero

order. A first-order dependence of the reaction on [S] and [catalyst] was observed.

With the increase in the concentration of OH- ions rate of the reaction also increased,

while addition of chloride ions had negative effect on the rate of reaction.

Srivastava et al [69] have reported the kinetics of oxidation of glycine by CAT

catalyzed by Pd (II) in HCl medium. In this reaction mercuric acetate is used as a

scavenger for Cl-. The rate showed first order dependence with respect to the CAT and

Pd (II) for glycine. Also the reaction showed positive effect with respect to substrate.

Mercuric acetate, [H+], and ionic strength of the medium had negligible effect on the

rate of the reaction. Finally the reaction showed positive effect with respect to [Cl-].

35
 Hassan and Saeed [70] have reported the kinetics of oxidation of diethyl ether

by CAT in HCl solution at 313 K. The oxidation reaction showed a first order

dependence on [CAT] and fractional order dependence on each [substrate] and

[H+]. The variation of ionic strength of the medium had negligible effect on the reaction

rate. The rate of the reaction increased with the addition of PTS. Dielectric constant of

the medium had negative effect on the rate.

The kinetics of oxidation of amino acids by CAT in the presence of Fe (II) ion

in aqueous sulfuric acid has been studied by Quine and Gowda [71]. The oxidation

reactions showed identical behavior with all the simple amino acids which are under

consideration. The reactions showed first and second order pathways in CAT and

fractional order with respect to the [substrate] with all the amino acids. The rates

showed inverse order in [H+] and fractional order in [catalyst].

Kumar et al [72] have reported the Chlorination of acetanilides in the presence

and absence of micellar media with the help of CAT as source of halogen.

The chlorination reaction showed an order of unity with respect to [CAT] as well as

[substrate] and a fractional order (1>n>0) dependence in [acid]. The rate of reaction

was found to be increased in the presence of micelles and the catalytic effect was more

pronounced in the critical micellar concentration range of surfactants. Finally the rate

of halogenation was found to follow the following order: p-nitro acetanilide < p-chloro

acetanilide < acetanilide < p-Me acetanilide.

Kinetic of oxidation of p-hydroxy benzoic acid by CAT in HClO4 have been

reported by Pandey et al [73]. The oxidation showed first order kinetics with respect to

CAT, p-hydroxy benzoic acid and H+ ions. The addition of NaClO4 and PTS had no

effect on the rate of oxidation.

36
 Mythily et al [74] have investigated the kinetics of oxidation of cinnamaldehyde

by CAT in HCl medium and in NaOH medium. In NaOH medium the reaction is

catalyzed by OsO4 at 313 K. In HCl medium, the reaction showed a dependence of first

order on the rate with respect to [CAT] and a fractional order in [substrate] which

approaches zero at higher concentrations of aldehyde. Rate dependence on [H+] varies

from inverse fractional to fractional order. In basic medium the reaction exhibited first

order with respect to [CAT], [Os (VIII)] and inverse first order dependence on [OH-].

Vivekanandan et al [75] studied the kinetics of interaction of alkaline

permanganate with CAT. The oxidation kinetics of CAT in alkaline medium is first

order in CAT and fractional order in MnO4-. The addition of complexing agents like F -

and pyrophosphate had not affect the kinetics. The rate of the reaction increased with

the addition of Cl-.

Herlihy and Kevin [76] have reported on the reaction between prop-2-en-1-ol

and CAT in the presence of acidic medium like HCl. Prop-2-en-1-ol on reaction with

CAT in 1 M HCl gave 2, 3-dichloropropan-1-ol not prop-2-en-1-al. When the

concentration of HCl is 0.075 M and higher the reaction is first order with respect to

the [H+], [CAT] and Cl- ions.

Radhakrishnamurti and Padhi [77] have reported on the kinetics of oxidation of

phenol (phenol, p-cresol, o-cresol, p-chlorophenol, p-bromophenol, o-chlorophenol and

m-chlorophenol) by CAT in alkaline medium. The reaction exhibited first order with

respect to [phenol] and [CAT] and fractional order with respect to [alkali]. The data

obtained from the kinetics clearly indicated that the reactivity is more in case of

electron-releasing groups.

37
 Banerji and Kalyan [78] studied the oxidation of different acids like glycolic

acid, lactic and α-hydroxybutyric acids by CAT in the presence of acid medium,

HClO4. The reaction rates are 1st order each in oxidant as well as with respect to the

substrate, and are second order dependence on the concentration of H+. Finally the

products were isolated and were found to be aldo or keto acids.

Kinetics of CAT assisted oxidation of different amino acids like glycine, alanine

and valine was studied by Bose and coworkers in alkaline media [79]. The experimental

results showed that the reaction followed first order with respect to both the amino acid

as well as with respect to CAT.

38
 SECTION 1.5

SCOPE OF THE PRESENT WORK

Chloramine-T has been used as analytical and oxidizing reagents frequently and

mechanisms of oxidation of various substrates by making use of CAT as Oxidant has

been investigated. The reactive species of CAT, present in both acidic and alkaline

aqueous solutions has been identified in the literature and thus making it easy to

understand their oxidative behavior. The substrates used in the present work are the

dyes used in food, dye and cosmetic products. The present study helps to understand

the mode of action of these dyes at molecular level and also this type of kinetic

modeling helps for the design and optimization of chemical process. Very limited

information is available in the literature about the oxidative behavior of CAT towards

dyes. Hence the main aim of the work is the kinetics and mechanistic studies of

oxidation of few dyes which are often used in food, dye and cosmetic products and with

CAT as oxidant in acid or alkaline media.

The dyes chosen for the present investigation are given in Table 1.5.

39
 Name Structure Color Chemical US No. EU CI No Applications Adverse
class No. effects
Quinoline Yellow Quinoline FD&C E104 47005 Food, drugs, hair Dermatitis,
Yellow Yellow products, hyperactivity
No 10 colognes, soft in children
drinks, and in
cosmetics

Green S Green Tri FD&C E142 44090 Sauce, desserts, Hyperactivity

arylmeth- Green No gravy granules, in children,
ane 4 sweets, ice asthama,
creams, and anemia, nettle
tinned peas rash

Patent Violet Tri Banned E131 42051 Sweets and jellies Allergic
Blue V arylmeth- in USA reactions,
ane nausea,
hypotension,

40
Tartrazine Yellow Azo FD&C E102 19140 Soft drinks, Urticarial
Yellow flavored corn (nettle rash) in
No 5 chips, pastries, children,
custard powder thyroid
tumour,
chromosomal
damage.
Red 2G Red Azo Banned E128 18050 Only in breakfast Metabolized to
in USA sausages aniline &
interfere with
hemoglobin

Cochineal Red Azo FD&C E124 16255 Various food Cause adverse
Red A Red No. products to effects
4 induce color a suffering from
color change asthama.

Allura Red Azo FD&C E129 16035 Soft drinks, May cause
Red AC Red No. cotton candy, food
40 childrens’s intolerance,
medication urticaria,
rhinitis and
asthma

41
The main objectives of the present study are:

a) To obtain order with respect to substrate, Oxidant and medium,

b) To establish the identity of reactive oxidizing species involved in the oxidation,

c) To identify and to characterize the oxidation products,

d) To establish the stoichiometry of the oxidation reaction,

e) To study the effects of halide ions Cl-, Br- on the rate,

f) To study the effect of (i) reaction products,

(ii) Variation of ionic strength,

(iii) Dielectric constant of the medium on the rate,

g) To study the effect of D2O on the rate,

h) To evaluate activation parameters,

h) To deduce appropriate rate law and

i) To propose a suitable mechanism with the help of data obtained.

42
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