A Kinetic Study of Catalytic Oxidation of

Amino Acids by Cerium (IV) in Aqueous

Acid Medium
A Thesis

Submitted to

University of Kota, Kota

for the Degree of

Doctor of Philosophy
in Chemistry
(Faculty of Science)

Submitted by:

Dhan Raj
Under the Supervision of

Dr. (Mrs.) Manju Bala Yadav

Department of Chemistry
Government College, Kota (Raj.)

2016
Dedicated
To
My Parents
&  

My Wife
 University of Kota, Kota

M.B.S. Marg, Near Kabir Circle, Rawatbhata

Road, Kota (Raj.)

Certificate

It is to certify that,

(i) The thesis entitled “A Kinetic Study of Catalytic Oxidation

of Amino Acids by Cerium(IV) in Aqueous Acid Medium”
submitted by Dhan Raj is an original piece of research work
carried out under my supervision.

(ii) Literary presentation is satisfactory and the thesis is in a

form suitable for publication.

(iii) Work evidences the capacity of the candidate for critical

examination and independent judgment.

(iv) Fulfills the requirement of the ordinance relating to the

Ph.D. degree of the university.

(v) Candidate has put in at least 280 days of attendance every

year.

Dr. (Mrs.) Manju Bala Yadav

Department of Chemistry
Government College,
Kota (Raj.)

i 
 A Word of Gratitude

“Gratitude makes sense of our past, brings peace for today, and
creates a vision for tomorrow.”

My utmost gratitude goes to my supervisor, Dr. Manju Bala

Yadav for allowing me to join her team, for her expertise guidance,
valuable assistance, determination, inspiration and most of all, for her
patience. I believe that one of the main gains of this three years
program is working with her and gaining her trust and friendship.

(Dhan Raj)

ii 
 Acknowledgement
Undertaking this Ph.D. has been truly life changing experience for me and
it would not have been possible to do without the support and guidance that I
received from many people.

First and foremost, I would like to express my sincere gratitude to my

supervisor, Dr. Manju Bala Yadav, Department of Chemistry, Govt. College,
Kota, Who has supported me throughout my thesis with her patience and
professional guidance. Without her cheerful encouragement, strong personal
support, this thesis would not have been completed.

I would like to specially thank Dr. Vijay Devra for providing guidance,
support and the willingness to allow me to bounce ideas and results. She assisted
in collecting my thoughts and helped in directing my research.

I would like to expand my thanks to Prof. Ashu Rani (Professor,

Department of Pure and Applied Chemistry, University of Kota, Kota) for her
inspiring guidance and generous support.

At this moment of accomplishment, I take this opportunity to sincerely

acknowledge Mr. Rajesh Yadav for their cooperation and moral support.

I would like to acknowledge the academic and technical support of Dr. S.

N. Garg, Principal, Govt. College, Kota and Dr. Sharda Sharma, Head,
Department of Chemistry, Govt. College, Kota who provided the necessary
support for this research. I would like to express my thanks to all the staff
members of Department of Chemistry, Govt. College, Kota for their valuable
suggestions and constant support.

I cannot forget the valuable conversation and suggestions of Dr. B. S.

Meena, Dr. Manju Meena, Dr. S. K. Meena and Dr. Munesh Meena. I have

iii 
often looked towards them for valuable suggestions and they always helped me
whenever I needed support in my research.

I thank my lab mates Kavita Sharma, Preeti, Shikha Jain, Ankita Jain,
Niharika Nagar, Gajala Tazwar, Rashmi Gupta, Dr. Seema Jain and Dr.
Shanu Mathur for their valuable suggestions in experimentation and their
cooperation during the entire research work.

My highest and special thanks go to my friend Dr. N. K. Sharma for his

strong support during the work of the thesis and his patience to me. I cannot
express my deepest feeling and high appreciation through thesis
acknowledgement since he deserves much more.

Last but not the least, I would like to thank my family who have always
supported me. Special thanks to my wife Santosh, thank you Santosh for
believing in me and for all your patience. Also, my brother Suresh, thank you
very much for everthing you have done for me. I would have never got this
opportunity if it was not your brotherly care, support and encouragement.

(Dhan Raj)

iv 
 Contents
Chapters Title Page
No.
Chapter-1 Introduction 1-35
Abstract 1
1.1 Chemical Kinetics 2
1.2 Cerium(IV) − An Oxidant 4
1.3 Metal Ion Catalysis 9
1.4 Amino Acids 16
1.5 Oxidation of Amino Acids 18
1.6 Scope of the Work 26
1.7 References 27
Chapter-2 Experimental 36-44
Abstract 36
2.1 Chemicals 37
2.2 Equipments 40
2.3 References 44
Chapter-3 Mechanistic and Kinetic Study of Manganese(II) 45-80
Catalysed Oxidation of Serine by Cerium(IV) in
Sulphuric Acid Medium
Abstract 45
3.1 Introduction 46
3.2 Experimental 47
3.3 Results 49
3.4 Discussion 70
3.5 Conclusion 78
3.6 References 79
Chapter-4 Mechanistic and Kinetic Study of Oxidation of 81-119
Valine by Cerium(IV) in Presence of
Palladium(II) in Sulphuric Acid Medium
Abstract 81

v 
 4.1 Introduction 82
4.2 Experimental 83
4.3 Results 85
4.4 Discussion 102
4.5 Conclusion 114
4.6 References 118
Chapter-5 Mechanistic and Kinetic Study of Manganese(II) 120-154
Catalysed Oxidation of Leucine by Cerium(IV)in
Sulphuric Acid Medium
Abstract 120
5.1 Introduction 121
5.2 Experimental 122
5.3 Results 124
5.4 Discussion 148
5.5 Conclusion 152
5.6 References 153
Chapter-6 Mechanistic and Kinetic Study of Oxidation of 155-193
Aspartic Acid by Cerium(IV) in Presence of
Palladium(II) Catalyst in Sulphuric Acid Medium
Abstract 155
6.1 Introduction 156
6.2 Experimental 157
6.3 Results 158
6.4 Discussion 180
6.5 Conclusion 190
6.6 References 191
Publications Annexure I 194
Annexure II 195

vi 
 Chapter – 1

Introduction

 
 Chapter 1

Abstract
This chapter includes a brief review of chemical kinetics, reactive
species of oxidant cerium(IV), catalyst manganese(II) and palladium(II). It
also describes the importance of amino acids and discusses the oxidation
studies of amino acids by different oxidants. This chapter also includes the
application of chemical kinetics to study the complex chemistry of biological
systems.

1 
 Chapter 1

1.1 Chemical Kinetics

Chemical kinetics is a branch of physical chemistry which deals with the
study of rate of reaction and the various factors which can hamper the yield of the
overall reaction. It includes empirical studies of the effect of the concentration,
temperature and hydrostatic pressure on reaction of various types. Such studies
may be practically important in concentration with technical processes. A
chemical reaction involve the breaking of existing bond which is present in the
reactant and making of a new bond in respective product. A mechanism is a series
of elementary steps by which the transformation might occur. Rates of chemical
reactions are experimental findings. The rate of reaction always depends on the
temperature at which it is run and usually depends on the concentrations of the
reactants. Because of this latter fact, the rate of a reaction will usually change
during the course of the reaction, the reactants get used up and their
concentrations fall.

The rate of a reaction at a particular temperature often depends solely on

the concentrations of the reactants present. For a reaction
A + B → Products
such a dependence on concentration would be described by the rate law:
Rate = k [A]x [B]y

Where k is a constant called the rate constant, x and y are numbers, usually
integers that give the order of the reaction. As written, the reaction would be xth
order in substance A, yth order in the substance B and (x + y)th order overall. If
one of the reacting species, for example A, has a concentration very much higher
than the other species, then, during the course of the reaction, its concentration
will not go down much. In other words, its concentration will be essentially a
constant. In such a case, the rate law becomes rate ~ k'[B]y, where k' = k [A]x. By
setting up an experiment this way, it is possible to determine specifically the
effect of changing the concentration of B upon the rate of reaction. This amounts
to determining the value of y. Likewise, if the concentration of B were

2 
 Chapter 1

deliberately made much larger than that of A, the exact effect of the concentration
of A (the value of x) could be learned.

There are different types of chemical reactions and a wide variety of

experimental techniques have been used to investigate them. A considerable
amount of effort has been taken to study the kinetics and mechanism of the
reaction in the gaseous phase. In many ways these investigations are useful for
testing basic theories of reactions. Most of kinetic work has been done on
reactions in liquid phase, especially since it is of greatest interest to the organic
and inorganic chemist. A little amount of work has been done on the reactions in
the solid phase. The reaction at the solid interfaces has received more attention.
Though there are various types of reactions, but oxidation reactions are widely
studied. Chemical kinetics is very useful to understand each step of the reaction
and also it accounts the following different parameters- (1) the factors that affect
the reaction rate (2) optimum condition which is very essential to obtain the
desired product (3) the intermediate formed during the course of reaction (4) at
what extent of time the reaction proceeds. Thus the mechanism of reaction can be
easily understood with the help of chemical kinetics. The different factors which
affect the rate of reaction are concentration of reactant, nature of solvents,
temperature, catalyst, orientation of reacting species, surface area, ionic strength,
intensity of light etc. A probable mechanism of reaction can be elucidated by
using the information which is obtained by studying the rate of reaction.

The present research describes the application of chemical kinetics to

study the complex chemistry of biological systems. Emphasis is given on
extensive experimental data collection, determination of standard kinetic
quantities relating to rate of reaction and development of the mechanism
describing the chemical steps in solution phase. Product analysis and the
stoichiometry under conditions as close as possible to those of the rate
measurements are also explored.

The present research study broadly includes oxidation of amino acids, a

biologically important reaction in the synthesis of polypeptides, proteins and
nucleotides1. Oxidation of leucine and serine is studied by Ce(IV) in the presence

3 
 Chapter 1

of Mn (II) as catalyst and oxidation of valine and aspartic acid is studied by

Ce(IV) in the presence of Pd (II) as catalyst.

A review of Ce(IV) as oxidant, Mn (II), Pd (II) as a catalyst and oxidation

of amino acids is presented in this chapter.

1.2 Cerium (IV) – An Oxidant

Cerium has a property, unique among the lanthanides, which explain its
ability to participate in one electron transfer reactions, its ability to exist in two
stable adjacent oxidation states +3 and +4. Cerium in its ground state has an
electronic configuration of [Xe]4f26s2, where Xe represents the xenon
configuration. The electronic configuration of Ce3+ ion is [Xe]4f1, while that of
Ce4+ ion is [Xe]4f0. The enhanced stability of the vacant f shell in Ce4+ accounts
for the ability of cerium to exist in the +4 oxidation state. The large reduction
potential value of 1.61V (vs NHE) make Ce(IV) a very efficient oxidizing reagent
compared to other metal ions.

In acidic medium, cerium(IV) is a very strong one electron oxidant and its
oxidizing power is comparable to that of lead(IV) oxide or that of manganese(III)
salts. The first detailed study of the redox potential of the Ce4+/Ce3+ couple under
carefully controlled condition in sulphuric acid was published by Kunz (1931)2.
Noyes and Garner (1936) studied3 the redox potential of the same redox couple in
nitric acid. The redox potential of the Ce4+/Ce3+ couple depends very much on the
nature and the concentration of the acid. For instance, the redox potential is
+1.28V in 1M HCl, +1.44 V in 1M H2SO4, +1.61 V in 1M HNO3, +1.70 V in 1M
HClO4 and it is as high as +1.87 V in 8M HClO44-5. The redox potential thus
increases in the order hydrochloric acid < sulphuric acid < nitric acid < perchloric
acid. Whereas the redox potential increases with increasing concentration of
perchloric acid, it decreases with increasing concentration of nitric acid4. These
variations in potential reflect the formation of ionic complexes and have been
used to determine the nature and stability of these complexes. At a given acid
concentration, the oxidation potential decreases as the ability of the anion to form

4 
 Chapter 1

stable complexes by association with the acid anion increases. Thus sulphate ion
form very stable complexes with Ce(IV) whereas perchlorate ion probably does
not make any complex at all.

The cerium(IV) species in perchloric acid6-8 medium and sulphuric acid

medium9 have been established and equilibrium constants calculated. In aqueous
H2SO4 media, Ce(IV) is both thermodynamically and kinetically weaker as an
oxidising agent compared to Ce(IV) in aqueous HClO4 media (cf. E0 = 1.7 V in
1.0 mol dm-3 HCIO4; E0 = 1.4 V in 1.0 mol dm-3 H2SO4 ). However Ce(IV) in
aqueous H2SO4 media is highly stable and does not require any special
precautions to prevent its photochemical decomposition10 which occurs
spontaneously in aqueous HClO4 media.

Cerium(IV) is known to form several hydrolytic species depending on the

pH of solution11. Hydrolytic forms of Ce(IV) are governed by following
equilibria:
K1h
Ce 4 + + H 2 O Ce(OH)3+ + H +

K 2h
Ce(OH)3+ + H 2 O Ce(OH) 22+ + H +

Hydrolysis of Ce(IV) in the absence of sulphate ion as a complexing

ligand affects the kinetics of the oxidation reaction, this has been studied in
detail12. However, the existence of hydrolytic species of Ce(IV) in the presence of
SO42- is still uncertain12, and it is expected that complexation of this ion with
sulphate in H2SO4 media suppresses the hydrolysis equilibria involving co-
ordinated water ligands13. The possibility of such hydrolytic species however, can
be ruled out in H2SO4 medium.

Cerium(IV) forms a number of complexes in sulphuric acid solution.

Hardwick and Robertson7 have reported the following equilibrium between
various complexes in sulphuric acid solution of 2M ionic strength at 25°C.

K1
Ce 4 + + HSO 4− Ce(SO 4 ) 2 + + H +

5 
 Chapter 1

K2
Ce(SO 4 ) 2 + + HSO −4 Ce(SO 4 ) 2 + H +

K3
Ce(SO 4 ) 2 + HSO −4 HCe(SO 4 )3−

The equilibrium constants K1, K2 and K3 for above steps are reported14 to
be 3500, 200 and 20 at 25°C respectively spectrophotometrically. Since the
species Ce(SO4)2 and HCe(SO4)3− are dominant forms of cerium(IV) in solution
containing [H2SO4] ≤ 2.0 mol dm-3, the species H2Ce(SO4)42- governed by the
following equilibrium is only formed in [H2SO4] > 2.0 mol dm-3.

K4
HCe(SO 4 )3− + HSO 4− H 2 Ce(SO 4 ) 42 −

K4 was determined to be 0.6 ± 0.1 at 20 ± 2oC. Thus the species

H2Ce(SO4)42− is ruled out to be reactive form of cerium (IV) under experimental
conditions. In the oxidation of lactic15 acid and mandelic16 acid by cerium(IV) in
sulphuric acid-sulphate media, Ce(SO4)2 had been identified as the active species.

1.2.1 Oxidation Studies with Cerium(IV)

The use of the ceric ion as an oxidant which reacts via a one electron step
only is of substantial importance and is of interest in many fields in chemistry17-20.
The oxidation of a variety of organic and inorganic compounds by cerium (IV) in
acidic media has been the subject of several studies21-28. The mechanism
suggested by various authors are not uniform, indicating that wide varieties of
mechanism are possible depending upon the nature of cationic oxidant species as
well as the various conditions for the reaction. In some cases, the mechanistic
approach has been based on the intermediated complex formation, while in others
the results have been interpreted by free radical mechanism. An intermediate
complex between ceric ion and the organic species has been reported in perchloric
acid, the coordination sites of the metal ion easily incorporates these species.
However, in case of sulphuric acid, strong sulphate cerium(IV) complexes are
formed and they block co-ordination sites of the oxidants to inhibit. Further the
oxidation of organic compounds by Ce(IV) in sulphuric acid media in general
seems to proceed through the intermediate complex formation29-31. Whereas, in

6 
 Chapter 1

the oxidation of the inorganic material As(III) and Sb(III) in perchloric or

sulphuric acid media32, oxidation of some amino acids, aldehyde and their
derivatives in sulphuric acid media33-35, evidence of free radical was observed and
reduction of Ce(IV) to Ce(III) by one electron transfer was postulated.

S. T. Nandibewoor et al.36 studied the kinetics of iodide catalysed

oxidation of L-glutamic acid by cerium(IV) in aqueous sulphuric acid medium.
The result suggest that L-glutamic acid combines with catalyst iodide to form a
complex, which then reacts in a slow step with one mole of cerium(IV) to give the
product cerium(III), a free radical derived from L-glutamic acid, carbon dioxide
with regenerating the catalyst iodide. This free radical formed reacts with another
mole of cerium(IV) in a further fast step to give the product cerium(III), succinic
acid and ammonia. The results are accommodated in the scheme given below-

K1
Ce 4 + ⋅ H + Ce 4 + + H +
K2
HOOCCH 2 CH 2 CH(NH 2 ) C OOH + I − Complex (C)

k i
Complex (C) + Ce 4 + ⎯⎯⎯→ Ce3+ + HOOCCH 2 CH 2 C H (NH 2 ) + H + + CO 2 + I −
slow

i fast
HOOCCH 2 CH 2 C H(NH 2 ) + Ce 4 + ⎯⎯⎯→ Ce3+ + HOOCCH 2 CH 2 CHO + H + + NH 3
H2O

HOOCCH 2 CH 2 CHO + 2Ce 4+ + H 2 O ⎯⎯

→ 2Ce3+ + HOOCCH 2 CH 2 COOH + 2H +

This scheme leads to rate law

−d[Ce(IV)] kK1K 2 [Ce(IV)][L − glu.acid][I− ]

(rate)c = = +
dt [H ] + K1 + K 2 [L − glu.acid][H + ] + K1K 2 [L − glu.acid]

Kinetics of oxidation of benzyl alcohol37, vanillin38, ketones39, vicinal

diols40, chloramphenicol41, serine42 by cerium (IV) has been studied by various
workers. The kinetics of oxidation of aspartic acid and glutamic acid43 in nitric
acid media by cerium(IV) and the oxidation of glycolic, malic, tartaric, and citric
acid by cerium(IV) in nitric acid media were observed by N. Datt and co-
workers44.

7 
 Chapter 1

A mechanism consisting of series of one electron steps has been reported

in the reaction of Ce4+ with Hg(I)45, H2O46, As(III)47, Te(IV)48. An outer sphere
electron transfer mechanism has been indicated in the oxidation of the one
equivalent substrates be cerium(IV). Waters and Wilson49 suggested the oxidation
of hydroxyl amine by cerium(IV) in H2SO4 via inner sphere pathway to NH2O
which on further oxidation to HNO finally yielded N2O.

Song et al.50 studied the kinetics and mechanism of iridium(III) catalysed

oxidation of ethylene glycol by cerium(IV) in sulphuric acid media. In the
proposed mechanism, Ir(III) may bond to ethylene glycol to form an outer-sphere
complex (Ir(III).EG), which is rapidly oxidized into an inner-sphere complex
(Ir(IV).EG) by Ce(IV). As Ir(IV) is unstable, the free radicals can be generated
through an inner-sphere electron transfer process between Ir(IV) and EG.

K1
H + + HOCH 2 CH 2 OH ←⎯⎯ → HOCH 2 CH 2 OH 2+

K2
HOCH 2 CH 2 OH 2+ + Ir(III) ←⎯⎯ → Ir(III).HOCH 2 CH 2 OH 2+ (adduct)
k
(Adduct) + Ce(SO 4 ) 2 ⎯⎯⎯→ Ir(IV).HOCH 2 CHOH +2 + Ce(III) + 2SO 24 −
slow
fast i
Ir(IV).HOCH 2 CHOH 2+ ⎯⎯⎯
→ Ir(III) + HOCH 2 C HOH + 2H +
i fast
→ Ce(III) + HOCH 2 CHO + H +
HOCH 2 C HOH + Ce* (IV) ⎯⎯⎯

In the above equation Ce* represents any species of Ce(IV)

Kinetic investigations of the oxidation of oxalic acid by Cerium (IV) have

been done in the sulphuric acid medium and results were analyzed in relation to
inter molecular forces present in the medium51. The redox couple Ce(IV) / Ce(III)
has been used to describe the fundamental processes involved in Belousov –
Zhabotinsky Oscillating reactions 52.

Ce(IV) oxidation of different compounds in aqueous H2SO4 media in many

cases kinetically highly sluggish and needs some metal ion catalyst. Some metal
ions like Ruthenium(III)53, Iridium (III)54, Silver(I)55, Rhodium(III)56, Copper
(II)57, Osmium(VIII)58, Mercury(II)59, Chromium(III)60 etc. have been used as
catalyst in the oxidation by Ce (IV). Thus the use of suitable catalysts in Ce(IV)

8 
 Chapter 1

oxidation reaction in aqueous H2SO4 media is of much importance in cerate

oxidimetry as well as in catalytic kinetic methods of analysis.

1.3 Metal Ion Catalysis

Transition metal ions have been extensively used as catalyst for effecting a
number of reactions. The transition metal catalysed reactions are important for the
chemical industry from both practical and economic point of view. Transition
metal ions are found to be good catalysts and their complexes are also able to
catalyse a wide variety of reactions like hydrogenation, oxidation and
polymerization. In recent times, the studies on the use of transition metal ions
either alone or as binary mixtures as catalysts in many redox reactions have been
gaining interest. Their oxidizing and catalytic activities are due to the existence of
variable oxidation states, as a consequence of partly filled d or f orbital. Their
ability to form both sigma and pi bonds with other moieties or ligands is one of
the chief factors for imparting catalytic properties of transition metals as well as
their complexes. Most of the d-block elements show characteristics inter ligand
migration reactions and such a process forms one of most important types of
reaction in homogeneous catalysis.

The use of transition metals in catalysis has received considerable

attention during the past century. Many of the properties of the transitions metals
that make them useful in catalysis arise from their ability to exist in different
oxidation states, allowing the metal to interact in a specific manner with a
substrate depending on electron configuration. Transition metals in the higher
oxidation state generally can be stabilized by chelation with suitable complex
agent. Metal complexes are good oxidants in acid or alkaline media under
appropriate reaction conditions.

The application of transition metal catalysts such as Ru (III)61-62, Rh (III)63-64,

Cu (II)65-66, Pd (II)67-68 in kinetic studies of redox reactions involving organic
substrates are reported in literature. It was found that these catalysts work
efficiently in both acidic and alkaline media. Such studies become helpful for

9 
 Chapter 1

industrial growth as well as understanding of the biological properties of

transition metal complexes.

1.3.1 Mn (II) – A Catalyst

Manganese is an essential microelement for the human body. In normal

conditions, it plays an important role in bone and tissue formation (normal
growth), normal reproductive functions and carbohydrate and lipid metabolism.
Manganese (II) most probably acts as either catalyst or reductant, having the
reduction potential69 of the couple MnVII/MnII in dilute acid at 1.51V. Mn (II) has
been widely used as a homogenous catalyst in various redox reactions70-71. The
mechanism of catalysis is quite complicated due to the formation of different
oxidizing states of the Mn (II). Although many complexes of Mn (II) with various
organic and inorganic substances have been reported72-74, the efficiency of Mn (II)
as a homogenous catalyst can be visualised from the oxidation studies of organic
substrates involving different oxidants such as Cr(VI)75, V(V)76, Ce(IV)77 and
Br(V)78.

Manganese (II) has been used an efficient catalyst and reported in many
kinetic studies79-82. In the oxidation of isopropyl alcohol by cerium(IV) in the
presence of Mn(II) catalyst in aqueous H2SO4 media, the rate of reaction79
increases with increase of Mn(II) concentration. Mn(II) oxidises the alcohol via
1:1 complex involving Mn(II) / Mn(III) catalytic cycle. The equilibrium
Ce(IV) + Mn(II) Ce(III) + Mn(III) is rapidly attained. Similarly, oxidative

decarboxylation and deamination of different amino acids by cerium(IV) mixed

catalysed by Ir(III)-Mn(II) in aqueous H2SO4 medium has been reported83, where
the reactive intermediate is Mn(III). Whereas Radhakrishanmurti84 and co-workers
have reported that Mn(II) retard the oxidation of cyclohaxanol by Ce(IV) in acetic
acid water mixture in the presence of perchloric acid. In the oxidation of As(III)
by Ce(IV) in aqueous sulphuric acid medium catalysed by Mn(II), the
participation of Mn(III) species was again reported47.

A. S. Ogunja et al.85 studied the kinetics and mechanism of Mn(II)

catalysed oxidation of D-arabinose and D-xylose by chromium(VI) ions in

10 
 Chapter 1

perchloric acid medium. It is reported that in the presence of Mn(II), the reaction
will proceed through the formation of a tri-molecular complex86-87. The positive
catalytic effect of Mn(II) is due to a one step three electron reduction of Cr(VI) to
Cr(III) in the rate determining step. One of the electrons transferred is donated by
Mn(II) atom which transform Cr(IV) to Cr(III) and the other two electrons by the
aldose sugar which is in accordance with Mohammed llyas88. The reaction
mechanism was proposed as follows.

K1
HCrO −4 + H + H 2 CrO 4

K2
H 2 CrO 4 + RCH(OH)CHO RCH(OH)CH − O − CrO3 H + H 2 O
ester
K3
H 2 CrO 4 + Sugar + Mn(II) ( H 2 CrO4 − Sugar − Mn(II) )
Complex (C)

ks
( H 2 CrO4 − Sugar − Mn(II) ) ⎯⎯⎯
slow
→ HCOOH + Cr(III) + RCHO + Mn(II)
Complex (C)

Mn(II) / H +
H 2 CrO 4 + RCHO ⎯⎯⎯⎯⎯⎯→ RCOOH + Cr(III) + Mn(III)

Where R = C3H7O3

A similar complex formation was reported89 in the oxidation of D-arabinose and

D-xylose by vanadium(V) in the presence of manganese(II) homogeneous
catalyst.

S. K. Rani et al.90 reported the Mn(II) catalysed oxidation of α-amino acids

by peroxomonosulphate in alkaline medium. The reaction proceed through
formation of amino acid-Mn(II) complex. S. Mathur91 and co-workers also
reported the formation of such type a complex in the oxidation of alanine by
cerium(IV) in presence of Mn(II) catalyst in sulphuric acid medium. In the kinetic
study of Mn(II) catalysed oxidation of glycerol by Ce(IV) in aqueous sulphuric
acid media92, glycerol combines with Mn(II) to form a complex, which then reacts

11 
 Chapter 1

in a slow step with one mole of Ce(IV) to give Ce(III), a free radical derived from
glycerol, and the regenerated Mn(II) catalyst. In a further fast step free radical
then reacts with another mole of Ce(IV) to give Ce(III) and products. The
proposed reaction mechanism is:

K1
Ce 4 + ⋅ H + Ce 4 + + H

K2
CH(OH)(CH 2 OH) 2 + Mn 2 + Complex (C1 )

k i
Complex (C1 ) + Ce 4+ ⎯⎯⎯→ Ce3+ + HOCH 2 C HOH + CH 2 = O + Mn 2+ + H +
slow
i fast
HOCH 2 C HOH + Ce 4 + ⎯⎯⎯ → Ce3+ + HOCH 2 CHO + H +

The rate equation is:

− d[Ce(IV)] kK1K 2 [Ce(IV)][Glycerol][Mn(II)]

= +
dt [H ] + K1 + K 2 [Glycerol][H + ] + K1K 2 [Glycerol]

The oxidation of citric acid by acid bromate in presence of homogeneous

catalyst Mn(II) has been reported by C. S. Reddy93. The proposed mechanism
involves oxidation of the formed Mn(II)-citric acid binary complex to an
intermediate by acid bromate which subsequently decomposes to the products.

1.3.2 Pd (II) – A Catalyst

One particular group of transition metals has been of special interest to

chemists, namely the platinum group: ruthenium (Ru), rhodium (Rh), palladium
(Pd), osmium (Os), iridium (Ir) and platinum (Pt). The platinum group metals
have shown outstanding catalytic activities in a broad range of chemical reactions
ranging from oxidations, reductions, carbon-carbon couplings, carbon-heteroatom
couplings and isomerizations94-95. Palladium redox chemistry seems to be
essentially limited to organic compounds, only a few studies of redox reactions
with inorganic species being available96.

The versatility of palladium catalyst is directly related to some of its

unique physical properties. First, palladium interconverts between the 0 and +2
oxidation state with relative ease (d10and d8 respectively). As a rule of thumb,

12 
 Chapter 1

palladium in oxidation state 0 is considered nucleophilic while the +2 oxidation

state is considered electrophilic. Until recently, the majority of research conducted
on palladium catalysis has involved palladium in the 0 and +2 oxidation state.
Nevertheless, species having oxidation states97 +1, +3 and +4 do exist, and have
recently found application in catalysis98-99. Palladium is moderately
electronegative (2.2) and has a rather soft character. Properties like these make the
metal center less prone to interact with electronegative hard groups (such as
alcohols). Instead it has a higher affinity towards soft σ- and π-donors.
Consequently, alkenes, alkynes and allenes readily form π-complexes with
palladium100.

Palladium (II) most probably acts as either a catalyst or as a reductant

having the reduction potential of the palladium(IV)/palladium(II) couple in dilute
acid as 0.532V. Palladium chloride is the most important Pd (II) salt in the
homogeneous catalytic chemistry of palladium. In acid media, as the chloride
concentration increases the rate of the reaction also increases. In chloride media,
palladium (II) forms several palladium (II) chloride complexes101. The utility of
palladium (II) chloride as a non toxic and homogeneous catalyst has been reported
by several workers102-103.

The hydrolysis of palladium (II) chloride species in aqueous medium has

received the attention of many investigators104-107 and the formation constants for
the mixed i.e. hydroxyl-chloride palladium species formed due to hydrolysis of
palladium chloride complexes are reported104-107. The dominance of Pd(OH)Cl
and PdCl3(OH)2- species among various species in aqueous medium depending
upon Cl− concentration in solution has also been observed. The formation of these
species may be considered as follows:

PdCl 2 + H 2 O PdCl(OH) + H + + Cl − (i)

PdCl 24 − + H 2 O PdCl3 (OH) 2 − + H + + Cl − (ii)

It has been observed that complex formation between amino acid and
palladium (II) gets suppressed on increasing [H+] in the reaction mixture.
Therefore, the complex formation may be proposed between amino acid and

13 
 Chapter 1

PdCl(OH) (in the absence of Cl−) and between amino acid and PdCl3(OH)2- in the
presence of Cl−.

Palladium(II) is a well known catalyst for several organic transformations.

Some interesting results in the homogeneous catalysis of successful commercial
exploitation of the acetaldehyde in the presence of Pd(II) chloride have
contributed to this interest. It is reported108 that Pd(II) chloride is rather insoluble
in aqueous solution but does dissolve in the presence of Cl− ions as PdCl3(H2O)−
and PdCl42−.
K1
Pd 2 + + Cl − PdCl + (iii)
K2
PdCl + + Cl − PdCl 2 (iv)
K3
PdCl 2 + Cl − PdCl3− (v)
K4
PdCl3− + Cl − PdCl 24 − (vi)

Elding104 has studies of both the stability constants and rates of reaction
and determined values of log K1 to log K4 and also of log β4. β4 is the equilibrium
constant for the following equilibrium:     

β4
Pd 2 + + 4Cl − [PdCl 4 ]2 −  

The equilibrium constants corresponding to the above equilibrium have

been determined by several workers and all are in fair agreement with a value of
log β4 between 11 and 12 at 25°C109.

In most of the studies using Pd(II) as the homogeneous catalyst, it has

been employed in the form of Pd(II) Chloride. Pd(II) chloride, when dissolved in
hydrochloric acid, exists in the form of PdCl42- as represent by equilibrium110 (vi).
The existence of PdCl42- is also supported by Ayres111, who has observed that
when a reaction ratio of 2:1 for sodium chloride (Cl−ion) to palladium(II) chloride
is maintained, the result is the formation of well known tetrachloropalladate(II),
PdCl42-.

14 
 Chapter 1

M. K. Ghosh et al.112 studied the kinetics and mechanism of

palladium(II) catalysed oxidation of D-(+)galactose by cerium(IV) in aqueous
medium. The kinetics of this reaction were studied and showed that the D-
(+)galactose, Ce(IV) and catalyst Pd(II) ion interact in two equilibrium steps to
form as intermediate complex113-114 which is assumed to disproportionate forming
a free radical and reduced to Ce3+ ion. Substrate is easily protonised in acid media
in the presence of catalyst, indicating involvement of H+ in the pre equilibrium
step. Ce(IV) has been found kinetically active in this study with generation of free
radicals in the reaction. Thus a mechanism consistent with the above kinetics is
proposed in the given scheme.
K1
Ce 4 + + Pd 2 + Pd 3+ ⋅ ⋅ ⋅ ⋅ ⋅ Ce3+
K2
[Complex]

K
H + + D − galactose[S] + Pd 3+ ⋅ ⋅ ⋅ ⋅ ⋅ C e3+ ⎯⎯⎯
3
→ [Complex]1
[Complex ]

k
[Complex]1 ⎯⎯⎯
1
→ [Free Radical] + Pd 2+ + 2H + + Ce3+
slow

fast
[Free Radical] + Ce 4 + ⎯⎯⎯→ Arabinose + HCOOH + H + + Ce 3+
H2O

Pushpanjali Singh115 reported the kinetics of Pd(II) catalysed oxidation of

dl-serine and dl-threonine by acidic solution of potassium bromate in the presence
of mercuric acetate, as scavenger. The rate shows zero order kinetics in borate
[BrO3−] and order of reaction is one with respect to substrate and Pd(II)
respectively. Increase in [Cl−] showed positive effect, while [H+] showed zero
effect. A transient complex is formed between [PdCl2] and amino acid. Palladium
chloride being reactive species of pallladium(II) chloride in 1:1 ratio,
disproportionate in a slow and rate determining step. N. N. Halligudi et al.116
studied the kinetics and mechanism of palladium(II) catalysed oxidation of allyl
alcohol by N-chlorosuccinimide in aqueous alkaline medium. The result suggests
the complex formation between the catalyst and substrate. A. K. singh117 and co-
worker also reported the formation of complex between Pd(II) and substrate in the

15 
 Chapter 1

mechanism of Pd(II) catalysed oxidation of methylamine and ethylamine by

Ce(IV) in perchloric acid medium. Similarly the kinetics and mechanism of
palladium(II) catalysed oxidation of dimethyl sulfoxide by alkaline periodate has
been reported by B. L. Koli and S. T. Nandibewoor118. They observed that Pd(II)
form a complex with DMSO which decomposes to the product in subsequent
steps. The proposed mechanism is as follows:
K1
H 3 IO 62 − + OH − H 2 IO 36− + H 2 O

K2
Pd(II) + (CH 3 ) 2 − S = O Complex (C)     

k + i
Complex (C) + H 2 IO 36− ⎯⎯⎯→ (CH 3 ) 2 − S− O + H 2 IO 64 − + Pd(II)
slow

O
+ i ||
fast
(CH 3 ) 2 − S− O + H 2 IO 64 − + H 2 O ⎯⎯⎯
→ H 2 IO 56− + (CH 3 ) 2 − S + 2H +
||
O

After reviewing the catalytic studies of Mn(II) in the oxidation studies of

various substrates with different oxidants we have investigated the kinetics of
oxidation of palladium (II) by cerium (IV) in the presence of acid in order to
understand the behaviour of active species of cerium (IV) and palladium (II) in
acid media and to arrive at a plausible mechanism.

1.4 Amino Acids

Amino acids are simple organic compounds. Their physical and chemical
properties are due to the presence of both acidic and basic group presents in the
same molecule. Amino acids are less acidic than most carboxylic acids and less
basic than most amines. In fact, the acidic part of the amino acid molecule is the
NH3+ group, not a COOH group. The basic part is the COO− group, and not free
NH2 group. Because amino acids contain both acidic and basic groups, they are
amphoteric (having both acidic and basic properties). It has been shown that
neutral amino acids exist as inner salts with the dipolar structure as H3+NCOO −,
these are called “Zwitter ions”. This is the form that amino acids exist in even in
the solid state. If we dissolve the amino acid in water, a simple solution also

16 
 Chapter 1

contains this ion. Amino acids are known to exist in the following equilibrium in
aqueous solutions.

RCHNH 2 COOH RCHNH 2 COO − + H + RCH(NH 3+ )COO −

 
The dissociation of these acids is pH dependent.
− H+ − H+
RCH(NH3+ )COOH RCH(NH3+ )COO− RCHNH 2COO−
+H + +H+

Cation Zwitter ion Anion

The predominant form of the amino acid depends on the pH of the

solution. In an acidic solution, the group is protonated to a free group, and the
molecule has an overall positive charge. As the pH is raised, it loses its proton at
about pH 2. This point is called pKa1, the first acid-dissociation constant. As the
pH is raised further, the group loses its proton at about pH 9 or 10. This point is
called pKa2 the second acid-dissociation constant. Above this pH, the molecule
has an overall negative charge. The pH of the dilute solution of Zwitterions is
determined by its basic strength and acidic strengths as:
pK a1 + pK a 2
pH =
2
Where pKa1 and pKa2 are the acid dissociation constant of its basic and
acidic groups respectively. For leucine, pKa1 and pKa2 are 2.33 and 9.74
respectively, the pH of the dilute solution of leucine comes out to be 5.98. This
pH 5.98 is the isoionic point of leucine where the number of negative charges on
the molecule produced by protolysis equals the number of positive charges
required by the gain of protons. Since the leucine molecule at this pH does not
carry any net charge and is electrophoretically mobile, this point is also known as
isoelectric point. Thus the ionization of leucine can be given as follows

+ +
NH3 NH3 NH2
| pK a1 | pK a 2 |
H −C − CH 2 CH(CH 3 ) 2 H −C − CH 2 CH(CH 3 ) 2 H −C − CH 2 CH(CH 3 ) 2
| | |
−
COOH COO COO −

Cation Zwitter ion Anion

Acidic ← pH → Basic
(Isoionic point)

17 
 Chapter 1

1.5 Oxidation of Amino Acids

Oxidation reactions are of fundamental importance in nature and are key

transformations in organic synthesis. Oxidation reaction of amino acid are one of
the most relavent biochemical reactions because, such reactions serve as models
for protein oxidation119-121. The kinetic and mechanistic features of a particular
oxidation reaction are likely to be affected by the polar and nonpolar nature of the
side chain of amino acid in solution and the active species of the oxidant122-123.
Amino acids can undergo many kinds of reactions depending on whether a
particular amino acid contains non polar or polar substituents. The amino and
carboxyl functional group of amino acids is more reactive compared to the
hydrocarbon moiety (RCH-) and hence only these functional group undergo
chemical transformation. This property is attributed to the higher reactivity of the
former compared to R. Amino acids represent organism forerunner of essential
biomolecules such as proteins, hormones, enzymes; also, they may serve as
energy source, losing their amino group by two pathway: transamination and
oxidative deamination. The steps of oxidative deamination are resumed in the
following scheme.

H  
| [O] − NH3
R − CH − COOH R − C − COOH R − C − COOH
| 2[H] || NH3 ||
NH 2 NH O

                                           Oxidative deamination of amino acids

The study of amino acids is one of the most exiciting fields of organic
chemistry. They play a significant role in a number of metabolic reactions like
biosynthesis of polypeptide, protein and nucleotides. Thus, the mechanism of
analogous nonenzymatic chemical processes in the oxidation of amino acids is a
potential area for intensive investigation124 in order to understand some aspects of
enzyme kinetics. Amino acids are very attractive natural ligands for both toxic
and essential metal ions. Besides acting simply as effective chelators, in many
cases they are also reducing agents; e.g. for metal ions such as Ce(IV), V(V),

18 
 Chapter 1

Co(III) and Fe(III), depending on the acidity of the medium. There is also an
indication that some amino acids may play an important role in the chemistry of
chromium, especially in the environment, where Cr(V1) may present a serious
hazard because of its mutagenic and carcinogenic activity125-127. They have been
oxidized by a variety of reagents under different experimental conditions and they
often undergo oxidative decarboxylation and deamination. It is well known that
amino, carboxyl and side chain of amino acids undergo chemical transformations
in the presence of different kinds of metal ion oxidant. The studies of the amino
acids by various oxidants128-132 both in acidic and alkaline media have been
reported. Many reagents have been investigated towards oxidative
decarboxylation of α-amino acids, which give nitrile142-143 or a mixture of nitrile
and aldehyde145-148 as the products depending on the reaction conditions and
reagents employed. Beside aldehyde and nitriles, α-keto-acids are also reported to
be formed as oxidation product138.
Gowda and co-workers have studied the oxidation of amino acids by
various halogen oxidants viz. chloramine T133-135, its dimer dichloramines136 and
bromamine T137. The oxidation product is aldehyde via hydrolysis of imine
intermediate. However, Vivekanandam et al.138 showed for the oxidation of imine
by another molecule of chloramine T to nitrile. The kinetics and mechanism of
some neutral and acidic α-amino acids by tetrabutylammonium tribromide in
aqueous acetic acid medium was reported, the product are corresponding
aldehydes139. Chloride ion catalysed oxidation of few amino acids by 1-
chlorobenzotriozole in acidic medium has been reported140 and oxidation of these
acids to nitrile as product take place. The electron flow during the oxidation from
the substrate to the oxidant is via an intermediate. The halogeno complex attacks
the N of the amino group of the amino acid in the slow step, yielding mono-N-
chloro derivative of amino acid, which then interact with a second molecule of
the complex to form N, N-dichloro derivative. This derivative undergoes
decomposition to HCl and CO2, leading to the nitrile as a product. It is very much
surprising, that such an N-chloro derivative of triazole undergoes four electron
changes whereas, chloramine T being a better oxidant interacts with amino acid in
a two electron transfer step.

19 
 Chapter 1

Yathiragen et al.141 reported the kinetic studies of the oxidation of L-

isoleucine and L-ornithine hydrochloride by N-bromobenzensulphonamide in
perchloric acid medium. The rate showed first order dependence on both [BAB]
and amino acid and inverse first order dependence on [H+] for [ISL] and first
order depence on [H+] for [ORH]. Isovaleronitrile and 3-(methylamino)
propionitrile were identified as the products. Oxidation with 1-
chlorobenzotriozole(CBT)140 and trichloroisocynuric acid142-143 also reported the
product as nitriles. However A. K. Singh et al.144 reported the oxidation of valine
by N-bromophthalimide in presence of chloro complex of Pd(II) as homogeneous
catalyst. The products were identified as a mixture of nitriles and aldehyde.
Oxidation with other oxidizing agents such as sodium hypobromite145, N-
bromosuccinimide146, tert-butyl hypochlorite147, chloramine T148, a mixture of
aldehyde and nitrile was formed in varying ratios depending on reaction condition
employed.

N. M. I. Alhaji et al.149 studied the the kinetics of oxidation of glutamic

acid with N-bromophthalimide (NBP) in perchloric acid medium. The reaction is
first order each in NBP and glutamic acid and is negative fractional order in [H+].
The main product of the reaction was succinic acid. The oxidation of glutamic and
aspartic acid by N-bromobenzensulphonamide150 in aqueous perchloric acid gives
corresponding acid as product.

The study of Ag(I) catalysed oxidation of L-leucine by cerium(IV) in

sulphuric acid medium has been reported151. The oxidation product was aldehyde
rather than nitriles.

+
K
RCH NH 3 COOH + Ag1 ⎯⎯→ RCH(H 3 N + )COOH − Ag1

k
RCH(H 3 N + )COOH − Ag1 + Ce(SO 4 ) 2 ⎯⎯⎯→ RCH(H 3 N + )COOH − Ag(II)
slow
+ Ce(III) + 2SO 24 −
i
RCH(H 3 N + )COOH − Ag(II) ⎯⎯
→ Ag1 + RCH(H 3 N + )CO O + H +

20 
 Chapter 1

i
→ RCHO + H + + 2SO 24 −
RCH(H 3 N + )CO O + Ce(SO 4 ) 2 + H 2 O ⎯⎯
+
+ Ce(III) + CO 2 + N H 4

Where R = −CH2−CH−(CH3)2

Amino acid are reported to form an adduct with Ag(I) owing to

availability of electron pair on oxygen atom. Therefore, an adduct between Ag(I)
and leucine is initially formed that on further interaction with Ce(IV) yields
another adduct of higher valent silver. The results suggests that L-leucine
combines with catalyst Ag(I) to form complex, which then reacts in a slow step
with one mole Ce(SO4)2 to give the product Ce(III), complex, H+, and 2SO42- with
regeneration of the catalyst Ag(I). The complex reacts with another mole of
Ce(SO4)2 in a further fast step to give the products, Ce(III), isopentanaldehyde,
CO2 and ammonia.

K. Vivekanandan and R. Lakshmi Narayanan152 also reported the

oxidation of essential amino acids like valine, leucine, isoleucine, threonine,
phenylalanine and histidine by nicotinium dichromate (NDC) in aqueous
perchloric acid medium. The main product of reaction is aldehyde and the reaction
has first order dependence with [NDC]. The order of the reaction is fractional with
respect to amino acids and second order with respect to perchloric acid.
Mechanism was proposed involving complexation between NDC and amino
acids. 
K1
NDC + H + NDCH +

K2
S + H+ SH +

k
NDCH + + SH + ⎯⎯⎯
3
→ [Complex]
slow
K
[Complex] ⎯⎯4⎯
→ HCHO + Cr(IV)
fast

K1K 2 [NDC][S][H + ]2
1 + K 2 [S]

The above mechanism leads to the following rate law:

21 
 Chapter 1

rate = k3 [Complex]

K1K 2 k3[NDC][S][H+ ]2
=
1 + K 2 [S]

B. Mohanty et al.153 studied the oxidation of L-lysine by alkaline

permanganate ion in alkaline medium catalysed by Cu(II), Ni(II) and Zn(II). The
product obtained is aldehyde. H. Iloukhani and H. Bahrani154 studied the kinetics
and mechanism of the permanganic oxidation of L-glutamine in sulphuric acid in
absence and presence of silver(I) and the product reported was aldehyde. The
result suggests that an adduct is formed between silver(I) and L-glutamine in a
fast step before it is oxidized by manganese(VII) in a slow step to yield the
silver(III) substrate adduct. This silver(III) adduct might then disproportionate in
subsequent fast step to give the final product. The reaction scheme taking L-
glutamine could be written as the following steps:

K1
H 2 N COCH 2 CH 2 CH(NH 2 ) COOH + Ag + (adduct) +
fast

kn
(Addcut)+ + Mn(VII) ⎯⎯⎯
c
→ (Addcut)3+ + Mn(V)
slow
H O
(Addcut) 3+ ⎯⎯2 ⎯→ H 2 N COCH 2 CH 2 CH(NH 2 ) COO + + Ag + + H +
fast

H O
H 2 N CO(CH 2 ) 2 CH(NH 2 ) COO + ⎯⎯2 ⎯→ H 2 N CO(CH 2 ) 2 CHO + CO 2 + NH 3 + H +
fast
fast
2Mn(V) ⎯⎯ ⎯
→ Mn (VII) + Mn(III)
fast
2Mn (III) ⎯ ⎯ ⎯
→ Mn (IV) + Mn(II)
fast
Mn(V) + Mn(IV) ⎯⎯ ⎯
→ Mn (VIII) + Mn(II)

A similar study of uncatalysed and Ru(III) catalysed oxidation of L-

proline by heptavalent manganate in aqueous alkaline medium155 is reported. The
order in both permanganate and Ru(III) was found to be unity. The oxidation
product was aldehyde. In another study by Sadhanasenapati156 the product
reported was α-keto acid in oxidation of L-histidine by permanganate in aqueous
alkaline medium.

Similarly N. P. Shetti and co-workers157 also reported the product as acid

22 
 Chapter 1

in the oxidation of L-tryptophan by diperiodatocuprate(III) catalysed by Ru(III) in

aqueous alkaline media. Whereas in the study of Os(VIII)/ Ru(III) catalysed
oxidation of L-lysine by diperiodatocuperate(III) in aqueous alkaline medium
reported by D. C. Hiremath et al.158, the reaction product was identified as
corresponding aldehyde. Another study of Ru(III) catalysed oxidation of L-lysine
by diperiodatoargentate(III) in aqueous alkaline media by R. R. Hosmani and S.
T. Nandibewoor159 also reported the product was aldehyde.

S. B. Haveri et al.160 studied the oxidation of L-leucine by chromium(VI)

in perchloric acid medium. The result suggest that HCrO4− reacts with L-leucine
to form a complex, which decomposes in rate determining step to give an
intermediate, chromium(V) species, a free radical derived from leucine and CO2 is
liberated. In the subsequent steps, acid chromate reacts giving aldehyde as the
final product. The proposed mechanism is given as below:

K1
CrO24− + H + HCrO4−

+ K2
HCrO 4− + RCH(N H 3 ) − COO − Complex (C)

i
fast
R C HNH 2 + HCrO 4− + H 2 O ⎯⎯⎯
→ RCHO + H 2 CrO −4 + NH 3
+ i
fast
2RC H(N H 3 ) − COO − + 2H 2 CrO −4 ⎯⎯⎯
→ 2R C HNH 2 + 2CO 2 + 2H 3CrO 4−
i fast
2R C HNH 2 + 2H 3CrO 4− ⎯⎯⎯
→ 2RCHO + 2NH 3 + 2CrO 2− + 2H 2 O

Where R = -CH2-CH-(CH3)2

On the other hand the oxidation of L-cystine by chromium(VI) in

perchloric acid medium was studied by K. K. Adari and co-workers161. It is
observed that the order with respect to cystine is fractional, whereas
chromium(VI) follows first order kinetics. Cystic acid found to be the main
product. Z. Khan and K. Din162 also reported the product as acid in the oxidative
degradation of DL-serine by chromium(VI) in aqueous sulphuric acid medium.

Few kinetic results of the oxidation of amino acids by cerium(IV) in acid

medium have been given in Table 1.1.

23 
 

Table 1.1: Reported results of oxidation of amino acids by ce(IV) in acidic medium

Activation Parameters
S. No. Amino Acid Oxidant Catalyst Medium Products ∆E ∆S ∆H ∆G Ref.
-1 -1 -1 -1 -1
kJ mol JK mol kJ mol kJ mol

1 Alanine Cerium(IV) Mn(II) H2SO4 Aldehyde 40.19 -82.02 37.59 80.57 91

Valine
2 Cerium(IV) Ag(I) HClO4 Aldehyde 97 -77 44 69 167

3 L-leucine Cerium(IV) Ag(I) H2SO4 Aldehyde 59.51 –87.08 56.82 84.92 151

4 Alanine Cerium(IV) Ag(I) HClO4 Aldehyde 18.9 –10.9 – – 163

5 DL-Methionine Cerium(IV) – HClO4 Aldehyde 27.3 –196 24.7 85.5 164

Glycine –258 16.6 97.4

6 Serine Cerium(IV) Mn(II) H2SO4 Aldehyde – −270 12.7 97.5 165

Glutamic Acid −261 15.2 97.0

Carboxylic
7 L-Glutamic Acid Cerium(IV) Iodine H2SO4 23±1 –88±2.21 21±1 47±2 36
Acid
Glutamic Acid 67.9 −36.5 79.0
8 Cerium(IV) Ag(I) HClO4 Aldehyde − 166
Aspartic Acid 68.4 −57.1 86.0

24 
 

9 L-Glycine Cerium(IV) Ag(I) H2SO4 Aldehyde 107.42 –49.58 104.75 120.76 55

L-Methionine Methionine
61.08 –51.55 63.52 76.19
Sulphoxide
10 Cerium(IV) − H2SO4 174
N- Methyl
66.85 –31.87 64.50 73.51
N-acetyl L-Methionine Sulphoxide
Glutamic Acid 67.9 −36.5 79.0
11 Cerium(IV) Ag(I) HNO3 Aldehyde − 43
Aspartic Acid 68.4 −57.1 86.0

12 L-Serine Cerium(IV) Ag(I) H2SO4 Aldehyde 66.65 –64.25 64.21 188.89 168

Cysteic
13 L-Cystine Cerium(IV) − H2SO4 Acid 57.4 –122.7 – − 169

14 L-Alanine Cerium(IV) Ag(I) H2SO4 Aldehyde 63.85 –70.06 61.37 86.22 33

15 L-Leucine Cerium(IV) K(I) H2SO4 Aldehyde – – – – 170

16 Hydroxylysine Cerium(IV) Ag(I) HClO4 Aldehyde – – – – 171

L-Tyrosine 125.08 −177.27 122.06 81.87

17 Cerium(IV) Ag(I) H2SO4 Aldehyde 172
N-Acetyl L-Tyrosine 74.60 −185.81 72.17 126.61

18 Lysine Cerium(IV) Ag(I) HClO4 Aldehyde – –  – – 173

25 
 Chapter 1

A systematic kinetic study of the oxidation of amino acids namely leucine,

serine, valine and aspartic acid by cerium(IV) in sulphuric acid medium was
carried out to explain the mechanistic aspects of these oxidations and to
understand the active form of cerium(IV) in aqueous acidic medium. The present
study is carried out to identify the rate of oxidation, the catalytic effect of Mn (II)
ion and Pd (II), product formed and to propose a suitable mechanism. The results
have been discussed in the subsequent chapters.

1.6 Scope of the Work

Oxidation of amino acids is of great importance both from a chemical

point of view and from its bearing on the mechanism of amino acid metabolism.
Amino acids not only act as building blocks in protein synthesis but also play a
significant role in the metabolism. Amino acids are the monomers of protein
which find a large number of applications in different biochemical processes such
as nutrition, metabolism and fortification of seeds and specially in the synthesis of
the advanced nanomaterials as reducing, capping and stabilizing agents. Oxidative
decarboxylation of amino acids is one of the well reported biochemical processes.
The study of the oxidation of amino acids is of interest because of their biological
significance and selectivity towards the oxidant to yield the different products.
Ce(IV) is well known oxidant in acid media having the reduction potential of the
couple Ce(IV)/Ce(III) 1.70 V. Cerium(IV) is one of the most important one
equivalent oxidant in acid medium which has been used in numerous kinetic,
mechanistic and analytic studies. The basic advantage of cerium(IV) over other
oxidants is its reduction to a single substance cerium(III), without any
intermediate reactions. It is a strong oxidant under acidic condition and is stable
towards heat and light.

Thus the study of kinetics and mechanism of oxidation of amino acids

using Ce(IV) as oxidant, Pd(II) and Mn(II) as a catalyst is very important from
biochemical and kinetic view point points.

26 
 
Chapter 1
 

1.7 References

1. H. D. Jakubke and H. Jersehkeit, “Amino Acids, Peptides and Proteins”,

Wiley, New York, 1977; H. C. Freeman, Adu. Protien Chem., 22, 258,
1967.
2. A. H. Kunz, J. Am. Chem. Soc., 53, 98, 1931.
3. A. A. Noyes and C. S. Garner, J. Am. Chem. Soc., 58, 1265, 1936.
4. G. F. Smith and C. A. Getzs, Ind. Eng. Chem. Anal. Ed., 10, 191, 1938.
5. E. Wadsworth, F. R. Duke and C. A. Goetz, Anal. Chem., 29, 1824, 1957.
6. M. S. Sherrill, C. B. King and R. C. Spooner, J. Am. Chem. Soc., 65, 170,
1943.
7. T. J. Hardwick and E. Robertson, Can. J. Chem., 29, 818, 1951.
8. H. G. Offner and D. A. Skoog, Anal. Chem., 38, 1520, 1996.
9. A. Roy and A. K. Das, Ind. J. Chem., 41A, 2468, 2002.
10. L. J. Heidt and M. E. Smith, J. Amer. Chem. Soc., 70, 2476, 1948.
11. M. Jabbari and F. Gharib, Monatsh. Chem., 143, 997, 2012.
12. A. Paulenova, S. E. Creager, J. D. Navratil and Y. Wei, J. Power Sources,
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35 
 

Chapter – 2

Experimental

 
  
Chapter 2
 

Abstract

This chapter describes the details of various chemicals and reagents,

equipments, preparation of various solutions, standardization methods and
analytical procedures adopted to study the kinetics of oxidation of amino
acids by cerium (IV) in acidic medium in presence of metal ion catalyst.

36 
 
  
Chapter 2
 

2.1 Chemicals

Leucine [NH2.CH.(COOH).(CH3)2CH.CH2]

A requisite amount of leucine (s. d-fine. Chem., AR grade) was employed.

The lesser solubility of leucine in water was avoided by preparing its solutions in
aqueous medium maintaining concentration of H2SO4 to be 0.1 mol dm-3.

Aspartic Acid [COOH. CH2.CH(NH2).(COOH)]

The solution was prepared by dissolving the required amount of aspartic

acid (s. d-fine. Chem., AR grade) in doubly distilled water to obtain the solution
of desired concentration.

Serine [NH2.CH.CH2.OH.(COOH)]

Solution of required concentration of serine were prepared by dissolving

the requisite amount serine (s. d-fine. Chem., AR grade) in a known volume of
doubly distilled water.

Valine [NH2.CH.(COOH).(CH3)2CH]

The solution was prepared by dissolving the required amount of valine

(s. d-fine. Chem., AR grade) in doubly distilled water to obtain the solution of
desired concentration. The lesser solubility of valine in water was avoided by
preparing its solutions in presence of 0.1 mol dm-3 sulphuric acid.

Ceric (IV) Ammonium Sulphate [(NH4 )4Ce (SO4)4.2H2O]

The solution of ceric (IV) ammonium sulphate was prepared by dissolving

ceric ammonium sulphate (E. Merck) in 1.0 mol dm-3 sulphuric acid and the
solution was standardized by titrating an aliquot of the test solution against
standard iron (II) ammonium sulphate (E. Merck) employing ferroin as an
indicator1.

37 
 
  
Chapter 2
 
The titration was always made in the presence of 1.0 mol dm-3 H2SO4 to
obtain a clear and stable colour change of the indicator at the equivalence point.

The concentration of hydrogen ion present in these solutions was

determined by titrating a known aliquot of the solution against pre-standardized
sodium hydroxide solution using phenolphthalein as an indicator2.

Manganese Sulphate (MnSO4)

The stock solution of Mn(II) was prepared by dissolving manganese

sulphate (AR) in doubly distilled water. Dilute solutions of manganese (II) were
made from the stock solution as required.

Palladium (II) Chloride (PdCl2)

Palladium(II) chloride (Johnson Matthey) was prepared in HCl (0.20 mol

dm-3) and assayed by complexometric titration with EDTA3. Dilute solution of
palladium(II) were made from the stock solution as required.

Sodium Bisulphate (NaHSO4)

Sodium bisulphate solution of required concentration was prepared by

dissolving requisite amount of NaHSO4 in doubly distilled water.

Cerium(III) Sulphate (Ce2(SO4)3)

Cerium(III) solution was prepared by dissolving Cerium(III) sulphate,

Ce2(SO4)3 (BDH), in doubly distilled water.

Ferrous Ammonium Sulphate [(NH4)2.Fe(SO4)2.6H2O]

The solution of ferrous ammonium sulphate (BDH, AR grade) was

prepared by dissolving the requisite quantity of the salt in doubly distilled water
containing dilute sulphuric acid (H2SO4) to check hydrolysis. These solutions
were prepared afresh as and when required in kinetic study.

38 
  
Chapter 2
 
Sodium Bicarbonate [NaHCO3]

Stock solution of sodium bicarbonate was prepared by dissolving 4 gm of

sodium bicarbonate (A. R.) in 100 ml of doubly distilled water.

Sulphuric Acid [H2SO4]

Solution of sulphuric acid was prepared by dissolving the requisite volume

of concentrate sulphuric acid (Ranbaxy, AR) in doubly distilled water and was
standardized against pre-standardized solution of sodium hydroxide employing
phenolphthalein as an indicator.

Sodium Sulphate (Na2SO4)

Sodium sulphate solution of required concentration was prepared by

dissolving requisite amount of the salt in doubly distilled water.

Sodium Chloride (NaCl)

Sodium chloride solution of required concentration was prepared by

dissolving requisite amount of sodium chloride in doubly distilled water.

Oxalic Acid [(COOH)2]

Oxalic acid (BDH, AR grade) is a primary standard and yields a stable

solution in doubly distilled water. The solution was kept in dark at ambient
temperature to check any photolytic decomposition.

Phenolphthalein Indicator (C20H14O4)

Phenolphthalein (BDH, AR grade) was used as an end point indicator for
acid base titration.
Ferroin Indicator ([Fe(o-phen)3]SO4)

Ferroin, (BDH, AR grade) was used as an end point indicator for

cerium(IV) and amino acid titration.

39 
  
Chapter 2
 
2, 4-Dinitrophenylhydrazine

The reagent is prepared by means of Brady’s test for aldehyde produced

from amino acid. Requisite amount of 2, 4-Dinitrophenylhydrazine was heated
with 2.0 mol dm-3 HCl added cautiously with cooling and 10 ml of doubly
distilled water was added.

Nesseler′s Reagent

100 gm of mercury (II) iodide and 70 gm of potassium iodide were

dissolved in 100 ml doubly distilled water. The resulting solution was added with
stirring to a solution of 16 gm of NaOH in 700 ml deionized water. This was then
diluted to one litre with deionzed water. The precipitate was allowed to settle for 3
days and the supernatant liquid was decanted and kept in a brown bottle.

2.2 Equipments

pH-Meter

Systronic digital pH meter, model 335 was used for the determination of
pH of the reaction mixtures with the maximum uncertainity in pH of ± 0.01 unit.

Spectrophotometer

UV-Vis spectroscopy offers a relatively straight forward and effective way

for quantitatively characterizing both organic and inorganic compounds.
Furthermore, as it operates on the principle of absorbance of photons that
promotes the molecules to an excited states, it is an ideal technique for
determining the electronic properties such as the band gap of a molecule.

Visible spectrophotometer (Systronic 166) was used for

spectrophotometric measurements. Spectrophotometer can be used to determine
kinetics and the rate constant of a chemical reaction. The rate constant of a
particular reaction can be determined by measuring visible absorbance at specific
time intervals.

40 
  
Chapter 2
 
The calibration curve was obtained in term of absorbance of cerium(IV).
Since the rate of reaction is directly proportional to the concentration of the
cerium(IV), it was necessary to find out the range of concentration of cerium(IV)
in sulphuric acid in the presence of amino acid over which Beer’s law was
applicable. The spectrophotometeric study of the solution containing all the
reagents with Ce(IV) in sulphuric acid medium showed that the reaction can be
monitored spectrophotometrically by measuring the absorbance of cerium(IV) at
360 nm where cerium(IV) has considerable absorbance and other ions have no
contribution towards absorbance. At this wavelength absorbance values were
obtained for different concentration of cerium(IV) solution with other reagent
between the concentration range 5×10-5 to 5×10-4 mol dm-3. The graph between
absorbance and concentration was linear which indicates the applicability of the
Beer’s law for the Ce(IV) under experimental conditions used in the study. The
plot is given in Figure 2.1.

As part of this research work a double beam LAB INDIA3000+, UV-Vis

spectrophotometer with UV path length 1.0 cm in the spectral range 200-800 nm
was used for optical characterization.

Fourier Transfer Infrared Spectrophotometer (FTIR)

FTIR offers quantitative and qualitative analysis for organic and inorganic
samples. FTIR spectroscopy identifies chemical bonds in a molecule by producing
an IR spectrum. The spectra produce a profile of the sample, a distinctive
molecule fingerprint that can be used to screen and scan samples for many
different compounds. FTIR is an effective analytical instrument for detecting
graphs and characterizing covalent bonding information. FTIR spectrophotometer
(Alpha-T model, Bruker, Germany) is used to record the FTIR spectra in the
range of 400-4000 cm-1 by mixing the sample with dried KBr (in 1:20 weight
ratio) with a resolution of 4 cm-1.

41 
  
Chapter 2
 

1.4

1.2

1
Absorbance

0.8

0.6

0.4

0.2

0
0 1 2 3 4 5 6
104 [Ce(IV)], mol dm-3

Figure 2.1: Plot between absorbance and concentration of

cerium(IV)

42 
  
Chapter 2
 
Thermostat

Serological water bath (Macro Scientific) temperature range 30◦C -110◦C

was used. All kinetic studies were done using thermostated at temperature varying
from 40◦C to 50◦C.

Electronic Balance

Shimadzu electronic Balance, A × 200 was used for weighing works. The
least count of balance is 0.0001 mg.

All other reagents were either of Anala R or guaranteed reagent grade and
used as supplied. Further details regarding their preparations etc. are mentioned in
the respective chapters. Doubly distilled water, second distillation being from
alkaline potassium permanganate solution in all glass assembly, was employed in
all the preparations and kinetic studies. The glass vessels employed for storing the
solutions and also for kinetic studies were either of Corning or Borosil make. The
instruments as discussed earlier were frequently used as and when desired in
kinetic studies. Kinetic procedure methodology5 adopted for the monitoring of
kinetics and analysis of the kinetic results is given in concerned chapters.

All other reagents were either of Anala R or guaranteed reagent grade and
used as supplied. Further details regarding their preparations etc. are mentioned in
the respective chapters. Doubly distilled water, prepared from ultra pure water
purification system (Millipore Elix Model), was employed in all the preparations
and kinetic studies.

The glass vessels employed for storing the solutions and also for kinetic
studies were either of Corning or Borosil make. The instruments as discussed
earlier were frequently used as and when desired in kinetic studies. Kinetic
procedure methodology5 adopted for the monitoring of kinetics and analysis of the
kinetic results is given in concerned chapters.

43 
 
  
Chapter 2
 

2.3 References

1. I. M. Kolthoff and R. Belcher ‘‘Volumetric Analysis’’, Vol.III,

Interscience, New York, 602, 1957.
2. C. J. Bottaglia and J. O. Edwards, Inorg. Chem., 4, 552, 1965.
3. Schwar Zenbach, G and Flaschka H., “Complexometric Titrations”
(Methuen and Co., Landon), 250, 1969.
4. A. I. Vogel, ‘‘A Textbook of Quantitative Inorganic Analysis”,
Longmans, 3, 240, 1961.
5. M. Latshaw, J. Am. Chem. Soc., 47, 793, 1925.

44 
 

Chapter – 3
 

Mechanistic and Kinetic Study

of Manganese(II) Catalysed
Oxidation of Serine by
Cerium(IV) in Sulphuric Acid
Medium

 
 
 
Chapter 3

Abstract

Kinetics of manganese(II) catalysed oxidation of serine by cerium(IV)

has been studied in sulphuric acid medium at 45◦C. The reaction follows first
order kinetics with respect to [Mn(II)] while negative effect was observed for
the variation of [H+] on the rate of reaction. The reaction exhibits first order
kinetics with respect to serine at its lower concentrations and tends towards
zero order at its higher concentration. The reaction is first order with respect
to Ce(IV). Under the experimental condition, the kinetically active species of
cerium(IV) has been found to be Ce(SO4)2. The rate constants observed at
three different temperatures were utilized to determine the activation
parameters. A plausible mechanism has been proposed from the results of
kinetic studies, reaction stoichiometry and product analysis.

kK[Ser]
k′ =
1 + K[H + ][Ser]

Where k′ is second order rate constant.

45 
 
  
Chapter 3
 

3.1 Introduction

Oxidation reactions are of fundamental importance in nature and are key

transformations in organic synthesis. We know that amino acids are molecules
containing an amine group, a carboxylic acid group and a side chain that varies
between different amino acids. The key elements of an amino acid are carbon,
hydrogen, oxygen and nitrogen. The kinetics and mechanism of oxidation of
amino acids have been studied previously by some researchers1-2. However, the
mechanism is different in the different reaction systems. These oxidation reactions
display diverse reaction mechanisms, oxidative deamination3-5 and
decarboxylation.

The oxidation of serine has received much attention because of

strengthening the immune system by providing antibodies and synthesizes fatty
acid sheath around nerves fibres6. Oxidation of serine by some inorganic oxidants
has been studied7-8 in both acidic and alkaline medium.

Ce(IV) solution in acidic media is stable for long time and is not
influenced by light and increasing temperature for short time9. There are
numerous mechanistic studies of oxidation of organic compounds apart from
useful synthetic studies10 in which cerium(IV) has been employed as an oxidant in
acid sulphate medium. Transition metal ions have been extensively used11 as
catalyst for affecting a number of reactions. In recent times, the studies on the use
of transition metal ions either alone or as binary mixtures as catalysts in many
redox reactions have been gaining interest. Mn(II) has been used as a homogenous
catalyst in various redox reactions12 and its efficiency as a catalyst can be
visualised from the oxidation studies of various organic substrates involving
different oxidants13-16. The mechanism of catalysis is quite complicated due the
formation of different intermediate complexes, free radicals and different
oxidation states of manganese. Preliminary experimental results indicate that the
reaction of serine with cerium(IV) in acid medium, without a catalyst was
sluggish, but the reaction became facile in the presence of a small amount of
Mn(II) catalyst. Therefore, in order to explore the mechanism of serine-

46 
  
Chapter 3
 
cerium(IV) reactions and also to study the catalytic action of Mn(II), the
manganous ion has been selected as a catalyst.

3.2 Experimental

The details regarding the preparation and standardization of reagent

solution have already been given in chapter 2 (Experimental). However, all other
reagents were either of Anala R or G.R. grade and used as supplied without any
further treatment. Doubly distilled water was employed throughout the study.

3.2.1 Kinetic Measurements

Appropriate quantities of the solution were placed in separate glass vessels

and kept for at least 15 minutes in a thermostatted water bath at 45◦C. The
calculated amounts of each reactant were then added together in a particular glass
vessel followed by the requisite amount of double distilled water. The reaction
mixture was then placed in a thermostatted water bath maintained at constant
temperature of 45◦C (±5%) and the reaction was initiated by adding the requisite
amount of oxidant solution placed separately in the same water bath. The reaction
was followed by measuring the absorption of cerium(IV) at 360 nm with time in a
1 cm cell placed in the Systronics(166) Visible spectrophotometer. All kinetic
measurements were performed under pseudo first order conditions with serine
concentration in excess over cerium(IV) at a constant ionic strength of 1.50 mol
dm-3. The applicability of Beer’s law verified between 5×10-5 to 5×10-4 mol dm-3
at 360 nm under the reaction conditions with the molar extinction coefficient17 Ɛ =
2622 dm3 mol-1 cm-1. The pseudo first order rate constants (kobs) were obtained
from the slope of the plots of log absorbance versus time. The observed rate
constants were reproducible within the experimental error ±5%. The cerium(IV)
solution was thermally stable in the visible region and undergoes photochemical
decomposition only in the UV region. The spectral changes during the chemical
reaction for the standard condition at 45◦C are given in Figure 3.1.

47 
  
Chapter 3
 

a ( 0 min)
1.4 b (10 min)
a c (20 min)
d (30 min)
1.2 e (40 min)
f (50 min)
b g (60 min)
1.0
c
Absorbance

0.8 d

e
0.6
f
g
0.4

0.2
300 350 400 450 500
Wavelength (nm)

Figure: 3.1: Spectral changes during the oxidation of serine by

cerium(IV) in aqueous sulphuric acid medium at
45◦C (time 0-60 minutes)

[Ce(IV)] = 5.0 × 10-4 mol dm-3; [Ser] = 5.0 × 10-3 mol dm-3;
[Mn(II)] = 5.0 × 10-5 mol dm-3, [H+] = 1.0 mol dm-3;
I = 1.50 mol dm-3; Temp. = 45◦C

48 
  
Chapter 3
 
3.2.2 Stoichiometry and Product Analysis

Different reaction mixtures with different sets of concentration of

reactants, where [Ce(IV)] was in excess over [Serine] at constant ionic strength,
acidity and at constant concentration of catalyst were kept for 24 hours at 318 K.
After completion of the reaction, the remaining Ce(IV) was estimated in different
sets of the experiment. The results indicated that two moles of Ce(IV) were
consumed by one mole of serine as given by equation (1).

H
|
Mn(II)
R − C H − COOH + 2 Ce(IV) + H 2 O ⎯⎯⎯⎯ → RCHO + 2Ce(III) + CO 2 + NH3 + 2 H + (1)
|
NH 2
Where R = −CH2OH

The oxidation products were identified as Ce(III), 2-hydroxyethanal,

ammonia and carbon dioxide. 2-hydroxyethanal was confirmed by the IR
spectrum of the corresponding hydrazone. The reaction mixture was treated with
acidified 2,4−dinitrophenyl hydrazine solution, which yielded a hydrazone. The
IR peaks at 3323.91 cm-1, 3108.36, 2922.22 cm-1 and 1614.84 cm-1 are attributed
to –OH, –NH, −CH and −C=N stretching respectively (Figure 3.2). The other
product ammonia was detected by Nesseler’s reagent test18 and CO2 was
qualitatively detected by passing the liberated gas through a tube containing lime
water.

3.3 Results
3.3.1 Cerium(IV) Dependence

The concentration of cerium(IV) was varied from 5.0×10-5 to 5.0×10-4 mol

dm-3 at fixed concentration of [H+] = 1.0 mol dm-3, [Mn(II)] = 5.0×10-5 mol dm-3
and I =1.50 mol dm- 3
at three different concentration of serine viz. 5.0×10-3,
7.0×10-3 and 9.0×10-3 mol dm-3 at 45◦C. The order with respect to cerium(IV) was
found to be unity, since the rate constant (kobs) was almost constant at different
Ce(IV) concentration. Results are given in Table 3.1, 3.2 and 3.3. The pseudo-
first order plots under these conditions were almost parallel and linear

49 
  
Chapter 3

100

80

 
Transmittance [%]

60

40

20

3323.91 3108.36 2922.22 1614.84

                
     

3500 3000 2500 2000 1500 1000 500

Wavenumber cm-1

Figure 3.2: FT-IR Spectra of final product of oxidation of serine

50 
 
 

Table 3.1: Variation of cerium(IV)

[Ser] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

104[Ce(IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.103 0.219 0.435 0.669 0.856 1.068
20 0.086 0.192 0.375 0.569 0.712 0.926
30 0.071 0.159 0.321 0 .468 0.608 0.789
40 0.061 0.139 0.268 0.402 0.507 0.649
50 0.051 0.115 0.225 0.348 0.431 0.541
60 0.043 0.096 0.194 0.294 0.364 0.462
80 0.029 0.068 0.133 0.174 0.256 0.317

104(kobs), sec-1 2.89 2.84 2.86 2.84 2.82 2.89

51 
 

Table 3.2: Variation of cerium(IV)

[Ser] = 7.0 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

104[Ce(IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.096 0.212 0.425 0.642 0.808 1.039
20 0.076 0.159 0.329 0.522 0.651 0.809
30 0.059 0.128 0.254 0 .404 0.520 0.662
40 0.046 0.107 0.205 0.315 0.403 0.508
50 0.037 0.087 0.168 0.244 0.330 0.417
60 0.030 0.069 0.128 0.194 0.250 0.320
80 0.018 0.037 0.084 0.118 0.156 0.209

104(kobs), sec-1 3.92 3.93 3.91 3.94 3.95 3.93

52 
 

Table 3.3: Variation of cerium(IV)

[Ser] = 9.0 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

104[Ce(IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.087 0.193 0.386 0.591 0.756 0.952
20 0.065 0.142 0.284 0.446 0.579 0.723
30 0.050 0.109 0.213 0 .332 0.429 0.542
40 0.036 0.079 0.156 0.251 0.309 0.392
50 0.027 0.057 0.119 0.183 0.234 0.289
60 0.020 0.042 0.088 0.132 0.168 0.213
80 0.014 0.023 0.048 0.073 0.092 0.116

104(kobs), sec-1 5.10 5.08 5.09 5.07 5.08 5.09

53 
  
Chapter 3
     
over 80% completion of the reaction also indicates first order with respect to
Ce(IV) (Figure 3.3).

3.3.2 Serine Dependence

The serine concentration was varied in the concentration range of 1.0×10-3

to 1.0×10-2 mol dm-3 at fixed concentration of [Ce(IV)] = 5.0×10-4 mol dm-3,
[Mn(II)] = 5.0×10-5 mol dm-3, [H+] = 1.0 mol dm-3, I = 1.50 mol dm-3 at 40◦C,
45◦C and 50◦C temperature respectively. Observed reaction order of serine is
(0.68) obtained from the linear regression of log kobs versus log concentration of
serine, indicating fractional order with respect to serine. The reaction exhibits first
order kinetics with respect to serine at its lower concentration that tends towards
zero order at its higher concentration (Figure 3.4). Results are given in Table 3.4,
3.5 and 3.6.

3.3.3 Manganese(II) Dependence

The effect of catalyst concentration on the reaction was studied between

the concentration range of 1.0×10-5 to 1.0×10-4 mol dm-3 at constant concentration
of [Ce(IV)] = 5.0×10-4 mol dm-3, [Ser] = 5.0×10-3 mol dm-3, [H+] = 1.0 mol dm-3
and I = 1.50 mol dm-3 at 45◦C. Observed reaction order of [Mn(II)] can be
obtained from the linear regression of log kobs versus log [Mn(II)] (n = 1.0 at 318
K). This indicates that the reaction is of first order with respect to Mn(II). kobs
versus Mn(II) yielded good linear plots (Figure 3.5) passing through the origin.
Results are given in Table 3.7

3.3.4 Hydrogen Ion Dependence

The effect of H+ concentration on the reaction rate was studied in the range
0.20 mol dm-3 to 1.0 mol dm-3 at constant concentration of [Ser] = 5.0×10-3 mol
dm-3, [Ce(IV)] = 5.0×10-4 mol dm-3, [Mn(II)] = 5.0×10-5 mol dm-3 and ionic
strength of 1.50 mol dm-3 at 45◦C. The results are represented in Table 3.8.
According to results it was found that the rate of reaction decreases with increase
of sulphuric acid concentration in Mn(II) catalysed oxidation. The order with

54 
  
Chapter 3
     

2.5
1
2
2 3
2 + log Absorbance

1.5 5
6

0.5

0
0 20 40 60 80
Time (minutes)

Figure 3.3: Pseudo first order plots for the variation of cerium(IV)

[Ser] = 5.0 × 10-3 mol dm-3; [H+] = 1.0 mol dm-3;

[Mn(II)] = 5.0 × 10-5 mol dm-3; I = 1.50 mol dm-3; Temp.= 45◦C;
[Ce(IV)] = (1) 0.50 × 10-4 mol dm-3; (2) 1.0 × 10-4 mol dm-3;
(3) 2.0 × 10-4 mol dm-3; (4) 3.0 × 10-4 mol dm-3;
(5) 4.0 × 10-4 mol dm-3; (6) 5.0 × 10-4 mol dm-3.

(Ref. Table- 3.1)

55 
 

Table 3.4: Variation of serine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 40◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

103[Ser], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.172 (20) 1.102 1.148 1.136 1.123 1.078 1.101 1.055 1.051 1.051
20 (60) 0.997 (40) 0.973 1.025 1.023 0.983 0.941 0.928 0.905 0.887 0.886

30 (80) 0.902 (60) 0.836 0.921 0.905 0.855 0.799 0.769 0.735 0.734 0.734
40 (120) 0.735 (80) 0.708 0.842 0.782 0.746 0.668 0.641 0.612 0.613 0.614
50 (140) 0.662 (100) 0.624 0.729 0.701 0.659 0.568 0.543 0.511 0.492 0.492
60 (160) 0.613 (120) 0.503 0.672 0.608 0.553 0.472 0.455 0.423 0.409 0.409
80 (180) 0.543 (140) 0.472 0.552 0.484 0.420 0.349 0.312 0.288 0.276 0.276

104(kobs), sec-1 0.75 1.25 1.72 2.05 2.35 2.70 2.95 3.11 3.21 3.21
Figures in parentheses denote time in minutes

56 
 

Table 3.5: Variation of serine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

103[Ser], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.156 (20) 1.093 1.135 1.088 1.068 1.051 1.041 1.039 1.039 1.037
20 (60) 0.975 (40) 0.896 1.002 0.803 0.926 0.886 0.866 0.858 0.858 0.853
30 (80) 0.832 (60) 0.756 0.887 0.713 0.789 0.734 0.689 0.682 0.682 0.680
40 (120) 0.668 (80) 0.604 0.787 0.624 0.649 0.613 0.557 0.552 0.552 0.550
50 (140) 0.596 (100) 0.508 0.684 0.553 0.541 0.492 0.454 0.450 0.450 0.449
60 (160) 0.532 (120) 0.448 0.608 0.489 0.462 0.408 0.369 0.364 0.363 0.361
80 (180) 0.469 (140) 0.369 0.472 0.375 0.317 0.276 0.243 0.238 0.238 0.236

104(kobs), sec-1 0.91 1.55 2.11 2.59 2.89 3.21 3.49 3.51 3.51 3.52

Figures in parentheses denote time in minutes

57 
 

Table 3.6: Variation of serine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 50◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

103[Ser], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.134 1.138 1.077 1.056 1.039 1.036 1.018 1.009 1.004 1.004
20 (60) 0.837 1.039 0.948 0.897 0.846 0.835 0.823 0.812 0.789 0.789
30 (80) 0.709 (40) 0.803 0.805 0.749 0.703 0.668 0.642 0.634 0.613 0.613
40 (120) 0.546 (60) 0.623 0.683 0.612 0.552 0.532 0.493 0.486 0.476 0.476
50 (140) 0.462 (80) 0.489 0.586 0509 0.453 0.423 0.402 0.385 0.365 0.364
60 (160) 0.403 (100) 0.384 0.483 0.426 0.369 0.346 0.312 0.298 0.283 0.282
80 (180) 0.342 (120) 0.306 0.348 0.289 0.238 0.216 0.188 0.178 0.172 0.172

104(kobs), sec-1 1.21 2.01 2.71 3.10 3.51 3.75 4.01 4.10 4.21 4.21

Figures in parentheses denote time in minutes

58 
  
Chap
pter 3
   

Figure 3.4:
3 Varia
ation of seerine

[Ce(IV)] = 5.00×10-4 mol dm

d -3; [Mn(II)] = 5.0 × 10-5 mol dm-3;
H+]
[H = 1.00 mol dm-3; I = 1.50 mol dm-3;
Teemp. =( ) 40° C; ( ) 45° C; ( ) 50° C

(R
Ref. Table- 3.4, 3.5 and
d 3.6)

59
 

Table 3.7: Variation of manganese(II)

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 45◦C

[Ser] = 5.0 × 10-3 mol dm-3 [H+] = 1.0 mol dm-3

105 [Mn(II)], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.213 (20) 1.142 1.144 1.123 1.068 1.035 1.007 0.985 0.959 0.901
20 (60) 1.052 (40) 0.967 1.036 0.993 0.926 0.856 0.807 0.769 0.703 0.659
30 (80) 0.996 (80) 0.713 0.915 0.857 0.789 0.698 0.623 0.586 0.519 0.463
40 (120) 0.856 (100) 0.613 0.816 0.750 0.649 0.569 0.487 0.443 0.376 0.319
50 (140) 0.785 (120) 0.528 0.735 0.639 0.541 0.465 0.376 0.326 0.273 0.203
60 (160) 0.735 (140) 0.456 0.649 0.554 0.462 0.368 0.294 0.249 0.201 0.162
80 (180) 0.676 (160) 0.389 0.538 0.420 0.317 0.234 0.174 0.138 0.109 0.076

104(kobs), sec-1 0.58 1.17 1.82 2.38 2.89 3.54 4.12 4.65 5.12 5.84

102(k′), dm3 mol-1 sec-1 5.80 5.85 5.86 5.87 5.78 5.83 5.88 5.81 5.83 5.84
Figures in parentheses denote time in minutes

60 
 
Chapter 3

5
104 (kobs), sec-1

0
0 2 4 6 8 10 12
105 [Mn(II)], mol dm-3

Figure 3.5: Variation of manganese(II)

[Ce(IV)] = 5.0×10-4 mol dm-3; [Ser] = 5.0 × 10-3 mol dm-3;

[H+] = 1.0 mol dm-3; I = 1.50 mol dm-3; Temp.= 45◦C

(Ref. Table 3.7)

61 
 
 

Table 3.8: Variation of hydrogen ion

[Ser] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 5.0 × 10-4 mol dm-3 I = 1.50 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

[H+], mol dm-3 0.20 0.40 0.60 0.80 1.0

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 0.811 0.915 0.998 1.042 1.068
20 0.559 0.685 0.718 0.869 0.926
30 0.439 0.489 0.496 0.698 0.789
40 0.221 0.349 0.461 0.569 0.649
50 0.146 0.247 0.359 0.465 0.541
60 0.093 0.181 0.273 0.375 0.462
80 0.035 0.092 0.163 0.246 0.317

104(kobs), sec-1 7.31 5.52 4.31 3.46 2.89

62 
 
Chapter 3

0.4

0.35

0.3
10-4 (kobs)-1, sec

0.25

0.2

0.15

0.1

0.05

0
0 0.2 0.4 0.6 0.8 1 1.2
[H+], mol dm-3
 

Figure 3.6: Variation of hydrogen ion

[Ce(IV)] = 5.0×10-4 mol dm-3; [Ser] = 5.0 × 10-3 mol dm-3;

[Mn(II)] = 5.0×10-5 mol dm-3; [HSO4−] = 1.0 mol dm-3;
I = 1.50 mol dm-3; Temp. = 45◦C

(Ref. Table 3.8)

63 
 
 
Chapter 3

respect to [H+] was negative. A plot of 1/ kobs versus [H+] gives a straight line with
positive slope and intercept (Figure 3.6).

3.3.5 Effect of [HSO4− ]

The reaction rate were measured with various [HSO4−] = 0.2 to 1.0 mol
dm-3 at fixed concentration of [Ser] = 5.0×10-3 mol dm-3, [Ce(IV)] = 5.0×10-4 mol
dm-3, [Mn(II)] = 5.0×10-5 mol dm-3 and ionic strength of 1.50 mol dm-3 at 45◦C.
The graphical plot of of 1/kobs versus [HSO4−] is found to be linear with positive
intercept and slope (Figure 3.7), which indicates that the rate of the reaction is
inversely proportional to the HSO4− ion concentration. Results are given in Table
3.9.

3.3.6 Effect of Ionic Strength

The effect of ionic strength on the rate was studied by employing sodium
sulphate from 1.0 to 2.0 mol dm-3 at fixed concentration of [Ser] = 5.0×10-3 mol
dm-3, [Ce(IV)] = 5.0×10-4 mol dm-3, [Mn(II)] = 5.0 × 10-5 mol dm-3 and [H+] = 1.0
◦
mol dm-3 at 45 C. The rate of reaction slightly increases with increasing ionic
strength (Figure 3.8). Results are given in Table 3.10.

3.3.7 Effect of Added Products

The effect of initially added product, Ce(III) was studied from 1.0 × 10-4 to
1.0 × 10-3 mol dm-3 at fixed concentration of [Ce(IV)] = 5.0 × 10-4 mol dm-3, [Ser]
= 5.0 × 10-3 mol dm-3, [H+] = 1.0 mol dm-3 and I = 1.50 mol dm-3 at 45◦C. No
significant effect on the rate of reaction was observed. Results are given in
Table 3.11.

3.3.8 Test for Free Radical

To test for the presence of free radicals in the reaction, acetonitrile solution
was added to reaction mixtures containing the substrate and the cerium(IV)
solution. When the reaction mixture was diluted with the methanol a precipitate

64 
 
                

Table 3.9: Variation of [HSO4−]

[Ser] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 5.0 × 10-4 mol dm-3 I = 1.50 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3
[HSO4−], mol dm-3 0.20 0.40 0.60 0.80 1.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 0.811 0.898 0.969 1.017 1.026
20 0.559 0.667 0.735 0.823 0.846
30 0.439 0.463 0.543 0.643 0.659
40 0.221 0.319 0.404 0.504 0.518
50 0.146 0.234 0.294 0.394 0.412
60 0.093 0.162 0.221 0.312 0.328
80 0.035 0.070 0.118 0.187 0.207

104(kobs), sec-1 7.31 6.01 4.92 4.02 3.85

65 
  
Chapter 3
 

0.3

0.25

0.2
10-4(1/kobs), sec

0.15

0.1

0.05

0
0 0.2 0.4 0.6 0.8 1 1.2
[HSO4−], mol dm-3
 

Figure 3.7: Linear plot of 1/kobs versus [HSO4−]

[Ce(IV)] = 5.0×10-4 mol dm-3; [Ser] = 5.0 × 10-3 mol dm-3;

[Mn(II)] = 5.0×10-5 mol dm-3; [H+] = 0.20 mol dm-3;
I = 1.50 mol dm-3; Temp.= 45◦C
(Ref. Table 3.9)

66 
 
 

Table 3.10: Variation of ionic strength

[Ser] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 5.0 × 10-4 mol dm-3 [H+] = 1.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

I, mol dm-3 1.0 1.25 1.50 1.75 2.0

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 1.068 1.066 1.065 1.064 1.063
20 0.926 0.923 0.919 0.912 0.899
30 0.789 0.782 0.778 0.771 0.761
40 0.649 0.644 0.639 0.631 0.623
50 0.541 0.537 0.531 0.524 0.517
60 0.462 0.457 0.451 0.443 0.435
80 0.317 0.314 0.313 0.312 0.311

104(kobs), sec-1 2.89 2.92 2.94 2.96 2.99

67 
  
Chapter 3
 

3.2

3.1

3
104 (kobs), sec-1

2.9

2.8

2.7

2.6
0 0.5 1 1.5 2 2.5
I, mol dm-3

Figure 3.8: Variation of ionic strength

[Ce(IV)] = 5.0×10-4 mol dm-3; [Ser] = 5.0 × 10-3 mol dm-3;

[Mn(II)] = 5.0×10-5 mol dm-3; [H+] = 1.0 mol dm-3; Temp.= 45◦C

(Ref. Table 3.10)

68 
 
 

Table 3.11: Effect of cerium(III)

[Ser] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Mn(II)] = 5.0 × 10-5 mol dm-3 [H+] = 1.0 mol dm-3
[Ce(IV)] = 5.0 × 10-4 mol dm-3    

[Ce(III)], mol dm-3 1.0 2.5 5.0 7.5 10.0

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 1.067 1.066 1.065 1.068 1.063
20 0.924 0.923 0.919 0.925 0.920
30 0.787 0.782 0.778 0.788 0.781
40 0.647 0.644 0.639 0.648 0.643
50 0.540 0.537 0.531 0.541 0.536
60 0.460 0.457 0.451 0.461 0.456
80 0.316 0.314 0.313 0.318 0.314

104(kobs), sec-1 2.91 2.92 2.94 2.90 2.93

69 
  
Chapter 3
   
was formed in the reaction mixture. This confirms the formation of free radicals in
the redox reactions under investigation.

3.4 Discussion

The uncatalysed cerium(IV) oxidation of serine is very slow in sulphuric

acid under the present experimental conditions. However, the reaction is
appreciably faster in the presence of a minute quantity (10-5 mol dm-3) of
manganese(II) in sulphuric acid . In the presence of perchloric acid, manganese(II)
catalysis is much less efficient, possibly due to presence of active cerium(IV)
species, Ce(OH)3+ in such media. Hence, the present study was undertaken in
sulphuric acid medium. The reaction is first order with respect to cerium(IV) and
manganese(II) concentrations, and the order with respect to serine varies from
first to zero order. The effect of hydrogen ions on the rate was studied by adding
sulphuric acid and it was found that as the sulphuric acid concentration increased
in the reaction mixture, the rate of reaction decreased. This is due to formation19
of an active inhibitor H2Ce(SO4)22− . The order with H+ ion concentration was less
than unity and negative. As the sulphuric acid concentration increases, the H+
concentration increases, but there is also a corresponding increase in HSO4− ion
concentration. Since the rate is inversely dependent on the HSO4− concentration,
the overall effect of adding sulphuric acid would be to lower the rate. Similar
behaviour has been reported in the oxidation of antimony(III)20, mandelic acid21,
malic acid22, fructose23 and L-glutamic acid24 by cerium(IV). The amino acid
dependence from first to zero order can be ascribed to complexation with cerium
(IV) or manganese (II). The adduct formation between Ce4+ and serine was ruled
out on the premise that the absorbance of Ce4+ did not change at the addition of
excess serine. Therefore it appears that an adduct between manganese(II) and
serine is initially formed that on further interaction with cerium(IV) yields another
adduct of higher valent manganese. The formation of the complex was implicated
by non zero intercept of the plot of 1/ k ′ versus 1/ serine (Figure 3.9). Complex
formation between amino acid and manganese(II) has also been reported in
literature25-26. The results suggests that serine combines with catalyst Mn(II) to
form a adduct, which then reacts in a slow step with one mole of Ce(SO4)2 to give

70 
  
Chapter 3
   
the product cerium(III), complex-serine and SO42-. The [Adduct]+ is converted in
a free radical derived from serine and Mn(II) catalyst is regenerated. The free
radical then reacts with another mole of Ce(SO4)2 in a further fast step to give
cerium(III), 2-hydroxyethanal, ammonia and carbon dioxide. The results are
accommodated in scheme- 3.1.

H H O
| K | ||
R − CH − COOH + Mn(II) R − CH − C − O⋅⋅⋅⋅Mn(II) (2)
| | |
NH 2 NH 2 H
[Adduct]

H O H O
| || k | ||
R − CH − C − O − Mn(II)+ Ce(SO4 )2 ⎯⎯ → R − CH − C − O⋅⋅⋅⋅Mn(III)+ Ce(III) + 2SO24− (3)
| | | |
NH 2 H NH 2 H
[Adduct] [Adduct]+
 

H O H O
| || | ||
fast
R − CH − C − O⋅⋅⋅⋅Mn(III) ⎯⎯⎯ → R − CH − C − O i + Mn(II) + H + (4)
| | | |
NH 2 H NH 2 H
[Adduct]+

H O
| ||
H2O
R − CH − C − Oi + Ce(SO4 )2 ⎯⎯⎯ → Ce(III) + NH3 + RCHO + CO2 + H + + 2 SO24 − (5)
| | fast
NH 2 H

Where R= −CH2OH 

Scheme -3.1
The proposed mechanism leads to the rate law (6)

− d[Ce(IV)] kK[Ce(IV)][Ser][Mn(II)]
=
dt 1 + K[H + ][Ser] (6)
− d[Ce(IV)] / dt kK[Ser][Mn(II)]
= k obs =
[Ce(IV)] 1 + K[H + ][Ser] (7)

71 
  
Chapter 3
   
Where kobs is pseudo first order rate constant. Since the order with respect to
manganese(II) is one (Table-3.7), the rate law further change to (8)

kK[Ser]
k′ =
1 + K[H + ][Ser] (8)
Where kꞌ = second order rate constant
After rearranging equation (8)

1 1 [H + ]
= + (9)
k ′ kK[Ser] k

A plot of 1/ k ′ versus 1/[Ser] was made from equation (9) at constant

hydrogen ion concentration that yielded straight line with nonzero intercept
(Figure 3.9). The value of rate constant (k) of the slow step of scheme-3.1 was
obtained from the intercept. The ratio of intercept and slope of the line yielded the
value of formation constant (K) to be 219 dm3 mol-1. The value of K obtained in
the title reaction in comparision to K= 204 dm3 mol-1 for cerium(IV) glutamic
acid in 1.0 M H2SO4 at 35◦C, indicates strong complexation in H2SO4 medium24.

Cerium(IV) is known to form strong cerium(IV)-sulphato complexes in

sulphuric acid medium, the important cerium(IV)-sulphato complexes are
Ce(SO4)2+, Ce(SO4)2 and HCe(SO4)3−and relevant equilibrium are27:

Ce 4 + + HSO 4− Ce(SO 4 ) 2 + + H + Q1 = 3500 (10)

Ce(SO 4 ) 2 + + HSO 4− Ce(SO 4 ) 2 + H + Q2 = 200 (11)

Ce(SO 4 ) 2 + HSO 4− HCe(SO 4 ) 3− Q3 = 3.4 (12)

Among the different sulphato species, the kinetically active species should
be inferred on the basis of kinetic data, not according to the magnitude of
concentration28. Considering the range of concentration of acid in which the
present study was performed and the steep fall in rate of the reaction with
increasing concentration of sulphuric acid indicates that the other species would
be present in insignificantly small concentration and may be considered

72 
  
Chapter 3
 

0.7

0.6

0.5
(k'-1), mol dm-3 sec

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1 1.2
10-3 [Ser]-1, mol-1 dm3

Figure 3.9: A plot of 1/k′ versus 1/[Ser]

[Ce(IV)] = 5.0 × 10-4 mol dm-3; [Mn(II)] = 5.0× 10-5 mol dm-3;
[H+] = 1.0 mol dm-3; I = 1.50 mol dm-3;
Temp. =( ) 40°C; ( ) 45°C; ( ) 50°C

73 
  
Chapter 3
   
29
negligible . Thus, Ce(SO4)2 has been taken as the reactive species of cerium(IV)
in aqueous sulphuric acid medium. In light of equilibrium step (10-12) inverse
bisulphate dependence (Figure 3.7) can be explained by assuming Ce(SO4)2 as
the reactive species. A small influence of ionic strength on the value of
experimental rate constant is in agreement with the idea that a non charged
particle Ce(SO4)2 enters in to reaction in the rate determining step, which further
confirms Ce(SO4)2 as the kinetically active species in the present study. In the
oxidation of alanine30 and L-leucine31 by cerium(IV) in sulphuric acid-sulphate
media, Ce(SO4)2 had been identified as the active species, which support the
present work. The concentration of Ce(SO4)2 can be approximately obtained,
according to the mass balance, equation (13) is obtained:

[Ce(IV)]T = [Ce 4 + ] + [Ce(SO 4 ) 2 + ] + [Ce(SO 4 ) 2 ] + [HCe(SO 4 ) 3− ] (13)

From equations (10)-(12), the following equations can be derived:

[Ce(SO4 )2 ][H + ]2
[Ce4+ ] =
Q1Q2 [HSO−4 ]2

[Ce(SO4 )2 ][H + ]
[Ce(SO4 )2+ ] =
Q2 [HSO4− ]

HCe(SO 4 ) 3− = Q 3 [HSO 4− ][Ce(SO 4 ) 2 ]

Substituting the above equations in to equation (13), we get

[Ce(SO4 )2 ][H + ]2 [H+ ][Ce(SO4 )2 ]

[Ce(IV)]T = +
Q1Q2 [HSO−4 ]2 Q2 [HSO−4 ]                                           (14)
+ [Ce(SO4 )2 ] + Q3[Ce(SO4 )2 ][HSO4− ]

By considering the relative magnitude of the successive formation equilibrium

[Ce(SO4 )2 ][H + ] 2
constants which are in the order: Q1>>Q2>>Q3, the value of Q1Q2 [HSO−4 ] 2 and
[Ce(SO4 )2 ][H+ ]
Q2 [HSO−4 ] are much less than the latter two terms. Therefore, we get equation
(15) from equation (14)
[Ce(IV)]T ≈ [Ce(SO 4 ) 2 ] + Q 3 Ce(SO 4 ) 2 [HSO −4 ]        

  = [Ce(SO 4 ) 2 ](1 + Q 3 [HSO −4 ] ) (15)

74 
  
Chapter 3

So,
[Ce(IV]T
[Ce(SO 4 ) 2 ] = = f [Ce(IV)]T
1 + Q 3 [HSO 4− ]
1
f =
1 + Q 3 [HSO −4 ]
(16)

Thus equation (7) can be written as:

kK[Ser][Mn(II)]
k obs =
1 + K[H + ][Ser][1 + Q3 [HSO −4 ]
(17)

Assuming
kK[Ser][Mn(II)]
A=
1 + K[H + ][Ser] (18)

So equation (17) becomes

A
k obs = (19)
1 + Q 3 [HSO −4 ]

1 1 Q3[HSO−4 ]
= + (20)
k obs A A

Equation(20) suggest that 1/ kobs versus [HSO4−] should be linear and agrees with
observed experiment data. From the slope Q3/A and intercept 1/A, the ratio of
slope to intercept was calculated to be 1.62 i. e. Q3, which is good agreement with
the previously reported value32.

The activation parameters of the rate determining step have been evaluated
from the linear plot of log k versus 1/T (Figure 3.10). The results of Table 3.12
show that K increases with increase of temperature, indicating the reaction is
endothermic, which is consistent with ∆H# > 0. The moderate value of ∆H# and
∆S# were favourable for electron transfer processes. The value of ∆S# within
range of radical reaction has been ascribed33 to the nature of electron pairing and
electron unpairing processes and to the loss of degrees of freedom formerly
available to the reactants upon the formation of rigid transition state. A negative
value of ∆S# suggests that the complex is more ordered than reactants34.

75 
 
  
Chapter 3

1.06

1.04

1.02

1
log k

0.98

0.96

0.94

0.92

0.9
3.08 3.1 3.12 3.14 3.16 3.18 3.2
103 1/T, (Kelvin)-1

Figure 3.10: A plot of log k versus 1/T

76 
 
  

Table 3.12: Effect of temperature on the reaction between cerium(IV) and serine catalysed by mangenese(II)
in presence of sulphuric acid medium

Temperature (K) K (dm3 mol-1 s-1) Activation parameters K (dm3 mol-1) Thermodynamic Quantities

313 9.09 ∆Ea ( kJ mol-1) = 25.84 198 ∆H# ( kJ mol-1) = 21.06

318 10.0 ∆S# ( J Kmol-1) = −145.00 219 ∆S# ( J K mol-1) = −134.87

323 12.50 ∆G≠ ( kJ mol-1) = 67.17 257 ∆G# ( kJ mol-1) = 63.94

77 
 
  
Chapter 3

3.5 Conclusion

The oxidation of serine by cerium(IV) experienced a slow reaction rate in

sulphuric acidic media, but increased in rate in the presence of the Mn(II) catalyst.
The reactive species for the oxidation of cerium(IV) in a sulphuric acidic medium
was Ce(SO4)2. The rate constant of a slow step and other equilibrium constants
involved in the mechanism were evaluated and activation parameters with respect
to the slow step of the reaction were estimated. The observed results were
explained by plausible mechanisms and the related rate laws were deduced. It can
be stated that Mn(II) acts as an efficient catalyst for the oxidation of serine by
cerium(IV) in sulphuric acid medium.

78 
 
  
Chapter 3

3.6 References

1. S. Mathur, M. B. Yadav and V. Devra, Int. J. Chem. Sci., 13, 641, 2015.
2. R. V. Nadh and M. Sireesha, Bul. Chem. Commun., 47, 13, 2015.
3. S. Huo, C. Song, J. Shan, S. Shen and H. Sun, J. Iran. Chem. Soc., 6, 243,
2009.
4. D. Bilehal, R. Kulkarni and S. T. Nandibewoor, J. Mol. Catal. A:
Chemical, 232, 21, 2005.
5. Y. R. Katre, A. K. Singh, G. K. Joshi and S. Patil, Oxid. Commun., 29,
137, 2006.
6. A. Shanmuga ‟Fundamentals of Biochemistry for Medical Students”,
1996.
7. B. T. Gowda and D. S. Mahadevappa, J. Chem. Soc., Perkin Trans., 2,
323, 1983.
8. Y. R. Katre, A. K. Singh, S. Patil and G. K. Joshi, Oxid. Commun., 29,
129, 2006.
9. G. Nagy, E. Koros, N. Oftedal, K. Tjelflaat and P. Ruoff, Chem. Phys.
Lett., 250, 255, 1996.
10. P. Sharma, S. Hemkar, C. L. Khandelwal and P. D. Sharma, J. Korean
Chem. Soc., 56, 28, 2012.
11. K. R. Bhat, K. Jyothi and B. T. Gowda, Oxid. Commun., 25, 117, 2002.
12. R. D. Kaushik, R. M. R. Agarwal and J. Singh, Res. J. Pharm. Biol.
Chem. Sci., 5, 1644, 2014.
13. I. M. Kolthoff, M. Kimura and E. J. Meehan, J. Phys. Chem., 75, 3343,
1971.
14. E. O. Odebunmi, A. S. Ogunlaja and S. O. Owalude, J. Chil. Chem. Soc.,
55, 293, 2010.
15. J. Singh, R. Malik, O. Singh, Sushma and R. D. Kaushik, Int. J. Chem.
Sci., 12, 445, 2014.
16. C. S. Reddy and P. S. Manjari, Ind. J. Chem., 50A, 979, 2011.
17. A. P. Savanur, S. T. Nandibewoor and S. A. Chimatadar, Trans. Met.
Chem., 34, 711, 2009.

79 
 
  
Chapter 3

18. G. H. Jeffery, J. Bassett, J. Mendham and R. C. Denny, ‟Vogel’s Text

Book of Quantitative Chemical Analysis”, 5th edn., ELBS, Longman,
Essex, England,(a) p. 381, (b) p.195, 1996.
19. B. Krishna and K. C. Tewari, J. Chem. Soc., 3097, 1961.
20. R. K. Patil, S. A. Chimatadar and S. T. Nandibewoor, Transit. Met.
Chem., 33, 625, 2008.
21. A. McAuley and C. H. Brubaker, J. Chem. Soc. A, 960, 1966.
22. K. K. Sengupta, J. Ind. Chem. Soc., 42, 725, 1965.
23. R. N. Mehrotra and S. Ghosh, Z. Phys. Chem., 231, 91, 1966.
24. S. A. Chimatadar, S. V. Madawale and S. T. Nandibewoor, Trans. Met.
Chem., 32, 634. 2007.
25. B. S. Berlett, P. B. Chock, M. B. Yim and E. R. Stadtman, Proc. Natl.
Acad. Sci. USA, 87, 389, 1990.
26. S. K. Rani, D. Eswaramoorthy, I. B. Mohammed and M. Palanichamy,
App. Catal. A: General, 369, 1, 2009.
27. S. K. Mishra and Y. K. Gupta, J. Chem. Soc. A, 2918, 1970.
28. W. Y. Song, Z. H. Li and A. Z. Wang, Chem. J. Chin, Univ., 18, 1842,
1997.
29. P. K. Tandon, S. Z. Khanam and S. B. Singh, The open Catal. J., 5, 1,
2012.
30. S. Mathur, M. B. Yadav and V. Devra, Int. J. Innov. Bio. Chem. Sci. 6,
23, 2015.
31. T. Sumathi, P. Shanmugasundram and G. Chandramohan, Asian J. Chem.,
23, 4385, 2011.
32. S. K. Mondal, D. Kar, M. Das and A. K. Das, Ind. J. Chem., 37A,765,
1998.
33. C. Walling ‟Free Radicals in Solutions”, Academic Press, New York, p
38, 1957.
34. D. C. Bilehal, R. M. Kulkarni and S. T. Nandibewoor, J. Ind. Chem.
Soc., 80, 91, 2003. 

80 
 
  

Chapter – 4
 

Mechanistic and Kinetic Study

of Oxidation of Valine by
Cerium(IV) in Presence of
Palladium(II) in Sulphuric Acid
Medium

 
 
  
Chapter 4
 

Abstract
The reaction of valine (Val) with ceric ion has been kinetically studied
in aqueous sulphuric acid medium in the presence of palladium(II) as
catalyst using a spectrophotometric method at 45◦C temperature. The
reaction was studied under pseudo first order conditions with respect to
cerium(IV). The results exhibits first order each in cerium(IV) and
palladium(II) and a positive fractional order with respect to [Val]. The rate
decreases with the increase of [HSO4−] and increases with increase of [H+].
The stoichiometry of the reaction was found to be 1:2. 2-methylpropanal and
Ce(III) were identified as the reaction product. Added products do not have
any significant effect on the reaction rate. A suitable mechanism was
proposed to account for the kinetic data, so that the rate equations derived
for this mechanism could explain all observed results.

2kK[Pd(II][Val][H + ]
k obs =
K[Val][H + ] + 1

81 
 
  
Chapter 4

4.1 Introduction

Cerium(IV), an unusually strong one electron oxidant has been frequently

used from the synthetic point of view1. Generally in the synthetic studies, use of
transition metal ion as catalyst under homogenous conditions has not been
attended properly. The use of ceric ion as an oxidant which reacts via a one
electron step is of substantial importance and of interest in many fields in
chemistry2-5. The oxidation of variety of organic and inorganic compounds by
cerium(IV) in acidic media has been the subject of several studies2-4. In all cases,
evidence of a free radical was observed and reduction of Ce(IV) to Ce(III) by one
electron transfer was postulated. In these studies, it has been pointed out that
oxidation by cerium(IV) is complicated by complexation steps and reaction
intermediates and postulation of a detailed mechanism has seldom been possible.
In perchloric acid media, hydrolytic equilibria lead to at least three cerium(IV)
species, where as in sulphuric acid medium, several sulphate complex species of
the metal ion could also be produced6-7.

L-Valine is an essential, non-polar, aliphatic amino acid used to hold

protiens together. It is needed for muscle metabolism and coordination, tissue
repair and for the maintenance of proper nitrogen balance in the body.

It has been noted that transition metal ions in the higher oxidation state can
usually be stabilized by chelation with suitable complex agents, so that metal
complexes formed would be good oxidants in acidic or alkaline media under
appropriate conditions. However, the previous studies indicate that oxidation of
amino acids by cerium(IV) in aqueous sulphuric acid is kinetically sluggish, and
process can be efficiently catalysed by a variety of metal ions. Palladium(II) is
known as catalyst for many reactions8-12, but the nature of its active form in
reactions remain obscure. An extensive literature survey reveals that no report is
available on the oxidation kinetics of valine in the presence of Pd(II). Hence we
felt it would be worthwhile to investigate the oxidative behaviour of Ce(IV) with
valine to explore the kinetics and mechanistic aspects of Pd(II) chloride catalysed
reaction. This study will enable to understand the complicated biological reaction

82 
 
  
Chapter 4

in living systems and will also help to understand the catalytic activity of Pd(II)
along with oxidative capacity of Ce(IV) in acid medium.

4.2 Experimental

In the present work, double distilled water was used throughout the study.
A stock solution of L-Valine (E. Merck) was prepared by dissolving it in water.
The cerium(IV) stock solution was obtained by dissolving cerium(IV) ammonium
sulphate (E. Merck) in 1.0 mol dm-3 sulphuric acid and standardized with iron(II)
ammonium sulphate solution. The stock solution of Palladium(II) chloride was
prepared by dissolving the sample in HCl (0.20 mol dm-3) and assayed by
complexometric titration13. The stock solution of palladium(II) chloride was
stored in black coated bottle to prevent photochemical decomposition and their
strength was checked spectrophotometrically14 time to time. Other chemicals and
reagents such as sodium sulphate, sulphuric acid, acetonitrile used were of
analytical grade.

4.2.1 Kinetic Measurements

The kinetics were followed at 45◦± 1◦C unless otherwise stated and at I =
1.50 mol dm-3. The reaction was initiated by mixing reactant solutions thermally
equilibrated at the desired temperature. Kinetic studies were carried out in
sulphuric acid medium under pseudo first order conditions with a large excess of
valine over cerium(IV). The reaction was followed by measuring the absorbance
of unreacted Ce(IV) at 360 nm using Systronics(166) UV-Visible
spectrophotometer. The spectral changes during the chemical reaction for the
standard condition at 45◦C are given in (Figure 4.1). At this wave length all other
materials concerned have negligible absorption. Beer’s law had been verified
between 5×10-5 to 5×10-4 mol dm-3 of cerium(IV) at 360 nm under the reaction
conditions. The molar absorption coefficient was found to be Ɛ = 2622 dm3 mol-1
cm-1. The rate condtants (kobs) were obtained from the plot of log absorbance
versus time.

83 
 
  
Chapter 4

a ( 0 min)
b (10 min)
1.4
c (20 min)
a
d (30 min)
1.2 e (40 min)
f (50 min)
1.0
b
Absorbance

0.8 c

0.6 d

e
0.4
f

0.2

300 350 400 450 500

Wavelength (nm)

Figure 4.1: Sequential scans of absorption spectra during the

course of the reaction of valine with cerium(IV) in
sulphuric acid media at different time

[Ce(IV)] = 5.0 × 10-4 mol dm-3; [Val] = 5.0 × 10-3 mol dm-3;
[Pd(II)] = 5.0 × 10-5 mol dm-3; [H+] = 1.0 mol dm-3;
I = 1.50 mol dm-3; Temp.= 45◦C

84 
 
  
Chapter 4

4.2.2 Stoichiometry and Product Analysis

Different reaction mixture with different sets of concentrations of reactants

where [Ce(IV)] was in excess over [Valine] at constant conditions of ionic
strength, acidity and catalyst were kept at 24h at 45◦C. The mixture was treated
with 2,4-dinitrophenylhydrazine and the formation of hydrazones indicated the
presence of aldehydes as the oxidation products of amino acids under the kinetic
condition. The main products are Ce(III), 2- methylpropanal, ammonia and CO2.
2-methylpropanal was confirmed by the IR spectrum of this hydrazone
superimposed on the spectrum of corresponding hydrazone of standard sample of
2-methylpropanal. The IR peaks at 3290.69 cm-1, 2967.85 cm-1 and 1622.82 cm-1
are attributed to –NH, –CH and –C=N stretching respectively (Figure 4.2).
Further, aldehyde group was confirmed with qualitative test such as Tollen′s
reagent15 and Schiff’s reagent. Nitrile test was negative, the product generally
reported in the oxidation of amino acids. Ammonia was confirmed with
Nesseler’s test. Therefore the stoichiometry of the reaction positive with test of
aldehyde can be represented by following equation:

Pd(II)
(CH3 )2 CHCH(NH 2 )COOH + 2Ce(IV) + H 2 O ⎯⎯⎯⎯
→ (CH 3 ) 2 CHCHO + NH 3
+ CO 2 + 2Ce(III) + 2H +     

4. 3 Results

4.3.1 Cerium(IV) Dependence

The reaction rate was measured with various [Ce(IV)] = 5×10-5 to 5×10-4
mol dm-3 at three concentration of [Val] = 2.5×10-3 mol dm-3, 5×10-3 mol dm-3 and
7.5×10-3 mol dm-3 respectively, [H+] = 1.0 mol dm-3, I = 1.50 mol dm-3, [Pd(II)] =
5×10-5 mol dm-3 and temperature = 45◦C. The plot of log absorbance versus time
was linear (Figure 4.3), indicating that the reaction is first order with respect to
[Ce(IV)]. The pseudo first order rate constants (kobs) are independent of the
[Ce(IV)]. Results are given in Table 4.1, 4.2 and 4.3.

85 
 
  
Chapter 4

100

80 

 
Transmittance [%]

60 

 
40 

20 

 
3290.69  
2967.85 1622.82

3000 2500 2000 1500 1000

Wavenumber cm-1

Figure 4.2: FT-IR Spectra of oxidation product of valine

 
 

86 
 
 

Table 4.1: Variation of cerium(IV)

[Val] = 2.5 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

104 [Ce (IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0
Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.112 0.235 0.456 0.706 0.896 1.149
20 0.092 0.205 0.406 0.619 0.786 1.009
30 0.080 0.175 0.356 0.554 0.694 0.889
40 0.072 0.154 0.321 0.479 0.593 0.772
50 0.062 0.138 0.279 0.419 0.532 0.706
60 0.054 0.121 0.242 0.369 0.459 0.586
80 0.041 0.093 0.191 0.289 0.348 0.442

104 (kobs), sec-1 2.21 2.21 2.22 2.20 2.19 2.21

87 
 
 

Table 4.2: Variation of cerium(IV)

[Val] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

104 [Ce (IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0
Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.094 0.201 0.403 0.612 0.801 0.994
20 0.071 0.155 0.320 0.465 0.612 0.761
30 0.055 0.118 0.241 0.368 0.476 0.581
40 0.041 0.092 0.184 0.278 0.361 0.452
50 0.033 0.070 0.141 0.217 0.272 0.342
60 0.025 0.054 0.106 0.167 0.211 0.261
80 0.015 0.032 0.064 0.096 0.121 0.159

104 (kobs), sec-1 4.43 4.41 4.41 4.45 4.41 4.41

88 
 
 

Table 4.3: Variation of cerium(IV)

[Val] = 7.5× 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

104 [Ce (IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0
Time in minutes Absorbance

0 (0) 0.121 (0) 0.265 0.528 0.782 1.041 1.302

10 (5) 0.098 (5) 0.216 0.354 0.536 0.703 0.889
20 (10) 0.081 (10) 0.179 0.242 0.367 0.442 0.609
30 (15) 0.068 (15) 0.146 0.165 0.253 0.323 0.403
40 (20) 0.055 (20) 0.123 0.112 0.167 0.216 0.274
50 (30) 0.038 (30) 0.082 0.076 0.116 0.146 0.186
60 (40) 0.025 (40) 0.055 0.051 0.079 0.123 0.127
80 (50) 0.017 (60) 0.025 0.024 0.036 0.043 0.057

104 (kobs), sec-1 6.54 6.52 6.53 6.51 6.52 6.50

Figures in parentheses denote time in minutes

89 
 
 Chapter 4
 
 

2.5
1

2
2
3

4
2+ log Absorbane

1.5 5

0.5

0
0 20 40 60 80 100

Time(minutes)

Figure 4.3: Psuedo first order plots for the variation of cerium(IV)
[Val] = 5.0 × 10-3 mol dm-3; [H+] = 1.0 mol dm-3;
[Pd(II)] = 5.0 × 10-5 mol dm-3; I = 1.50 mol dm-3; Temp. = 45◦C;
[Ce(IV)] = (1) 0.50 × 10-4 mol dm-3; (2) 1.0 × 10-4 mol dm-3;
(3) 2.0 × 10-4 mol dm-3; (4) 3.0 × 10-4 mol dm-3;
(5) 4.0 × 10-4 mol dm-3; (6) 5.0 × 10-4 mol dm-3.

(Ref. Table 4.2)

90 
 
 Chapter 4
 
4.3.2 Valine Dependence

The kinetic runs were carried out with various concentrations (1×10-3 to
1×10-2 mol dm-3) of valine at fixed [Ce(IV)] = 5×10-4 mol dm-3, [H+] = 1.0 mol
dm-3, I = 1.50 mol dm-3, [Pd(II)] = 5×10-5 mol dm-3 and temperature = 40◦C, 45◦C
and 50◦C respectively, the rate constants (kobs) increases with the increase of [Val]
(Figure 4.4). Results are given in Table 4.4, 4.5 and 4.6. Observed reaction order
of valine is 0.65 obtained from the linear regression of log kobs versus log [Val],
indicating fractional order with respect to valine. The plot of 1/ kobs versus 1/
[Val] exhibits excellence linearity with positive intercept and slope.

4.3.3 Palladium(II) Dependence

At fixed [Ce(IV)] = 5×10-4 mol dm-3, [Val] = 5×10-3 mol dm-3, [H+] = 1.0
mol dm-3 and I =1.50 mol dm-3, Pd(II) was varied from 1×10-5 to 1×10-4 mol dm-3
at three temperatures 40◦C, 45◦C, 50◦C respectively. The rate constants (kobs)
increases with the increase of [Pd(II)] (Figure 4.5). Results are given in Table
4.7, 4.8 and 4.9. Observed reaction order of palladium(II) obtained from the plot
of log kobs versus log [Pd(II)] is 1.0, which indicates that the reaction is of first
order with respect to [Pd(II)]. 1/ kobs versus 1/ [Pd(II)] yielded good linear plots
passing through the origin.

4.3.4 Hydrogen Ion Dependence

The reaction rate were measured with various [H+] = 0.20 to 1.0 mol dm-3
at fixed [HSO4−], ([HSO4−] =1.0 mol dm-3 from H2SO4 and NaHSO4), [Val] =
5×10-3 mol dm-3, [Ce(IV)] = 5×10-4 mol dm-3, I = 1.50 mol dm-3, [Pd(II)] =5×10-5
mol dm-3. The rate of reaction increases with increase of [H+] (Figure 4.6),
observed reaction order of [H+] is 0.60 obtained from plot of log kobs versus log
[H+] indicating that reaction is of positive fractional order with respect to [H+].
Results are given in Table 4.10.

91 
 
 

Table 4.4: Variation of valine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 40◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3
103 [Val], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.102 1.138 1.098 1.069 1.048 1.031 1.026 1.015 1.003 0.998
20 (60) 0.845 1.024 0.961 0.925 0.864 0.839 0.804 0.763 0.751 0.732
30 (80) 0.715 (40) 0.768 0.802 0.768 0.704 0.664 0.634 0.609 0.584 0.558
40 (120) 0.527 (60) 0.613 0.701 0.634 0.578 0.557 0.512 0.482 0.465 0.446
50 (140) 0.465 (80) 0.489 0.611 0.542 0.461 0.438 0.409 0.384 0.349 0.339
60 (160) 0.403 (100) 0.368 0.529 0.452 0.388 0.361 0.328 0.298 0.274 0.266
80 (180) 0.352 (120) 0.267 0.384 0.319 0.261 0.217 0.208 0.182 0.169 0.163

104 (kobs), sec-1 1.15 2.01 2.49 2.87 3.26 3.64 3.83 4.03 4.22 4.31

Figures in parentheses denote time in minutes

92 
 
 

Table 4.5: Variation of valine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

103 [Val], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.148 1.074 1.042 1.015 0.994 0.979 0.961 0.952 0.929 0.919
20 (40) 1.025 0.932 0.837 0.804 0.768 0.718 0.684 0.674 0.652 0.642
30 (60) 0.921 0.774 0.684 0.621 0.589 0.531 0.511 0.483 0.473 0.443
40 (80) 0.842 0.651 0.557 0.485 0.448 0.402 0.384 0.367 0.351 0.341
50 (100) 0.729 0.561 0.456 0.378 0.352 0.308 0.294 0.261 0.254 0.242
60 (120) 0.672 0.476 0.367 0.291 0.268 0.231 0.211 0.194 0.185 0.176
80 (140) 0.552 0.339 0.246 0.182 0.159 0.128 0.115 0.105 0.096 0.092

104(kobs), sec-1 1.72 2.78 3.45 4.03 4.41 4.79 4.98 5.18 5.37 5.46

Figures in parentheses denote time in minutes

93 
 
 

Table 4.6: Variation of valine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 50◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

103 [Val], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 1.074 1.015 0.979 0.929 0.904 0.881 0.860 0.841 0.829 0.819
20 0.932 0.804 0.718 0.652 0.642 0.601 0.584 0.558 0.542 0.532
30 0.774 0.621 0.531 0.473 0.443 0.412 0.394 0.374 0.349 0.339
40 0.651 0.485 0.402 0.351 0.321 0.278 0.267 0.248 0.237 0.231
50 0.561 0.378 0.308 0.254 0.223 0.198 0.179 0.164 0.153 0.146
60 0.476 0.291 0.231 0.185 0.161 0.133 0.121 0.112 0.102 0.096
80 0.339 0.182 0.128 0.096 0.077 0.060 0.056 0.048 0.043 0.040

104 (kobs), sec-1 2.78 4.03 4.79 5.37 5.75 6.33 6.52 6.81 7.00 7.10

94 
 
 pter 4
Chap

Fig 4.44: Variatiion of valiine

[Ce(IV)] = 5.00×10-4 mol dm

d -3; [H+] = 1.00 mol dm-3;
[Pdd(II)] = 5.00 × 10-5 mol dm-3; I = 1.550 mol dm-33;
Teemp. = ( ) 40°
4 C; ( ) 45° C; ( ) 50° C

(Ref. Table 4.4, 4.5 and

d 4.6)

95
 
 

Table 4.7: Variation of palladium(II)

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 40◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Val] = 5.0 × 10-3 mol dm-3
105 [Pd(II)], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.204 (20) 1.076 1.140 1.098 1.058 1.031 1.003 0.979 0.912 0.889
20 (60) 1.052 (40) 0.947 1.009 0.961 0.886 0.821 0.771 0.702 0.642 0.612
30 (80) 0.956 (80) 0.709 0.904 0.802 0.729 0.652 0.598 0.534 0.462 0.424
40 (120) 0.776 (100) 0.603 0.801 0.701 0.612 0.531 0.462 0.405 0.329 0.287
50 (140) 0.703 (120) 0.485 0.721 0.611 0.497 0.423 0.349 0.291 0.231 0.192
60 (160) 0.632 (140) 0.392 0.623 0.529 0.412 0.335 0.274 0.215 0.164 0.127
80 (180) 0.556 (160) 0.343 0.502 0.384 0.294 0.217 0.169 0.128 0.083 0.060

104(kobs), sec-1 0.67 1.24 1.91 2.49 3.07 3.64 4.22 4.79 5.66 6.23

Figures in parentheses denote time in minutes

96 
 
 

Table 4.8: Variation of palladium(II)

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Val] = 5.0 × 10-3 mol dm-3

105 [Pd(II)], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.125 (20) 1.056 1.079 1.042 0.994 0.929 0.896 0.829 0.802 0.756
20 (60) 0.923 (40) 0.862 0.921 0.834 0.768 0.663 0.621 0.556 0.506 0.439
30 (80) 0.836 (60) 0.698 0.779 0.696 0.589 0.482 0.432 0.369 0.304 0.253
40 (120) 0.679 (80) 0.568 0.664 0.554 0.448 0.349 0.298 0.236 0.192 0.152
50 (140) 0.605 (100) 0.473 0.565 0.443 0.352 0.247 0.206 0.156 0.116 0.092
60 (160) 0.543 (120) 0.389 0.484 0.367 0.268 0.181 0.146 0.102 0.073 0.053
80 (180) 0.496 (140) 0.308 0.351 0.246 0.159 0.096 0.070 0.043 0.027 0.021

104 (kobs), sec-1 0.86 1.63 2.68 3.45 4.41 5.37 6.04 7.00 7.86 8.82

Figures in parentheses denote time in minutes

97 
 
 

Table 4.9: Variation of palladium(II)

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 50◦C

[H+] = 1.0 mol dm-3 I = 1.50 mol dm-3
[Val] = 5.0 × 10-3 mol dm-3
105 [Pd(II)], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.076 1.120 1.042 0.994 0.912 0.841 0.802 0.732 0.702 0.667
20 (40) 0.947 0.941 0.835 0.763 0.642 0.567 0.506 0.423 0.386 0.335
30 (80) 0.709 0.826 0.682 0.587 0.462 0.378 0.304 0.243 0.211 0.172
40 (100) 0.638 0.712 0.558 0.443 0.329 0.248 0.192 0.146 0.112 0.088
50 (120) 0.546 0.609 0.451 0.335 0.231 0.161 0.116 0.084 0.061 0.044
60 (140) 0.451 0.534 0.362 0.254 0.164 0.106 0.073 0.048 0.033 0.023
80 (160) 0.391 0.414 0.246 0.159 0.083 0.048 0.027 0.018 0.016 0.015

104 (kobs), sec-1 1.24 2.39 3.45 4.41 5.66 6.81 7.86 9.02 10.17 11.13

Figures in parentheses denote time in minutes

98 
 
 Chapter 4

12

10

8
104 (kobs), sec-1

0
0 2 4 6 8 10 12
105[Pd(II)], mol dm-3

Figure 4.5: Variation of palladium(II)

[Ce(IV)] = 5.0×10-4 mol dm-3; [H+] = 1.0 mol dm-3;

[Val] = 5.0 × 10-3 mol dm-3; I = 1.50 mol dm-3;
Temp. = ( ) 40° C; ( ) 45° C; ( ) 50° C

(Ref. Table- 4.7, 4.8 and 4.9)

99 
 
 

Table 4.10: Variation of hydrogen ion

[Val] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 5.0 × 10-4 mol dm-3 I = 1.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3
[H+], mol dm-3 0.20 0.40 0.60 0.80 1.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 (20) 1.036 1.074 1.048 1.027 0.994
20 (40) 0.916 0.932 0.876 0.802 0.768
30 (60) 0.649 0.774 0.718 0.643 0.589
40 (80) 0.538 0.651 0.579 0.509 0.448
50 (100) 0.432 0.561 0.469 0.406 0.352
60 (120) 0.343 0.476 0.395 0.319 0.268
80 (140) 0.273 0.339 0.261 0.210 0.159

104 (kobs), sec-1 1.82 2.78 3.26 3.83 4.41

Figures in parentheses denote time in minutes

100 
 
 Chapter 4

4.5

3.5
104 (kobs), sec-1

2.5

1.5

0.5

0
0 0.2 0.4 0.6 0.8 1 1.2
[H+], mol dm-3

Figure 4.6: Variation of hydrogen ion

[Ce(IV)] = 5.0×10-4 mol dm-3; [Val] = 5.0 × 10-3 mol dm-3;

[Pd(II)] = 5.0×10-5 mol dm-3; [HSO4−] = 1.0 mol dm-3;
I = 1.50 mol dm-3; Temp. = 45◦C

(Ref. Table 4.10)

 

101 
 
 Chapter 4

4.3.5 Effect of [HSO4−]

[HSO4−] was varied in the range of 0.20 to 1.0 mol dm-3 at fixed [H+] =
0.20 mol dm-3, [Ce(IV)] = 5×10-4 mol dm-3, [Val] = 5×10-3 mol dm-3, [Pd(II)] =
5×10-5 mol dm-3, I = 1.50 mol dm-3 and temperature 45◦C. Here HSO4− ≈
[NaHSO4] + [H2SO4], ignoring the dissociation of [HSO4−] in strongly acidic
medium. The rate constants (kobs) decrease with increase of [HSO4−]. Therefore
HSO4− shows a rate retarding effect (Figure 4.7). Results are given in Table 4.11.

4.3.6 Effect of Ionic Strength

At fixed concentration of [Ce(IV)] = 5×10-4 mol dm-3, [Val] = 5×10-3 mol

dm-3, [Pd(II)] = 5×10-5 mol dm-3, [H+] = 1.0 mol dm-3 and temperature 45◦C, the
ionic strength was varied from 1.20 to 2.0 mol dm-3 by the different concentration
of Na2SO4 it is found that ionic strength has slightly affected the rate of reaction
(Figure 4.8). Results are given in Table 4.12.

4.3.7 Effect of Chloride Ion

At fixed concentrations of [Ce(IV)] = 5.0 × 10-4 mol dm-3, [Val] = 5.0 ×

10-3 mol dm-3, [Pd(II)] = 5.0 × 10-5 mol dm-3, [H+] = 1.0 mol dm-3 and temperature
at 45◦C , the concentration of Cl− was varied from 1×10-4 to 5×10-4 mol dm-3. The
rate was uneffected by the addition of Cl− ions (Figure 4.9). Results are given in
Table 4.13.

4.4 Discussion

Before formulating the reaction mechanism for the reaction under

investigation, it is necessary to ascertain the reactive species of palladium(II)
chloride in acidic medium. Palladium(II) chloride has been reported to give a
number of possible chloro species dependent on pH of the solution. Under the
experimental pH range in the present investigation (PdCl2) has been proposed and
confirmed16 as the reactive species dominant in the pH range 1.00 to 3.00.

102 
 
 

Table 4.11: Variation of [HSO4−]

[Val] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 5.0 × 10-4 mol dm-3 I = 1.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

[HSO4−], mol dm-3 0.20 0.40 0.60 0.80 1.0

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 0.732 0.834 0.924 0.952 0.994
20 0.423 0.554 0.642 0.674 0.768
30 0.243 0.368 0.462 0.483 0.589
40 0.146 0.241 0.329 0.367 0.448
50 0.084 0.159 0.231 0.261 0.352
60 0.048 0.104 0.164 0.194 0.268
80 0.018 0.045 0.083 0.105 0.159

104 (kobs), sec-1 9.02 6.90 5.66 5.18 4.41

103 
 
 Chapter 4
 
 

0.25

0.2
10-4 (kobs)−1, sec

0.15

0.1

0.05

0
0 0.2 0.4 0.6 0.8 1 1.2
[HSO4−], mol dm-3

Figure 4.7: Linear plot of 1/kobs versus [HSO4−]

[Ce(IV)] = 5.0×10-4 mol dm-3; [Val] = 5.0 × 10-3 mol dm-3;

[Pd(II)] = 5.0×10-5 mol dm-3; [H+] = 0.20 mol dm-3;
I = 1.50 mol dm-3; Temp. = 45◦C

(Ref. Table 4.11)

104 
 
 

Table 4.12: Variation of ionic strength

[Val] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 5.0 × 10-4 mol dm-3 [H+] = 1.0 mol dm-3
[Pd(II)]  =  5.0 × 10-5 mol dm-3
I, mol dm-3 1.20 1.40 1.50 1.80 2.00
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 0.997 0.995 0.994 0.991 0.990
20 0.782 0.773 0.768 0.765 0.762
30 0.599 0.593 0.589 0.585 0.584
40 0.455 0.449 0.448 0.447 0.443
50 0.359 0.354 0.352 0.351 0.326
60 0.275 0.270 0.268 0.265 0.248
80 0.162 0.161 0.159 0.154 0 .143

104 (kobs), sec-1 4.32 4.38 4.41 4.46 4.65

105 
 
 

Chapter 4
 

5.5

4.5
104 (kobs), sec-1

3.5

2.5

2
0 0.5 1 1.5 2 2.5
I, mol dm-3
 

Figure 4.8: Variation of ionic strength

[Ce(IV)] = 5.0×10-4 mol dm-3; [Val] = 5.0 × 10-3 mol dm-3;

[Pd(II)] = 5.0×10-5 mol dm-3; [H+] = 1.0 mol dm-3; Temp.= 45◦C

(Ref. Table 4.12)

106 
 
 

Table: 4.13 Variation of chloride ion

[Val] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C
[Ce(IV)] = 5.0 × 10-4 mol dm-3 [H+] = 1.0 mol dm-3
[Pd(II)]  =  5.0 × 10-5 mol dm-3 I = 1.50 mol dm-3

[Cl−], mol dm-3 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 0.994 0.993 0.994 0.992 0.991
20 0.768 0.768 0.768 0.767 0.766
30 0.589 0.587 0.589 0.588 0.587
40 0.448 0.447 0.448 0.446 0.445
50 0.352 0.351 0.352 0.351 0.350
60 0.268 0.267 0.268 0.267 0.266
80 0.159 0.156 0.159 0.156 0.154

104 (kobs), sec-1 4.41 4.42 4.41 4.42 4.43

107 
 
 Chapter 4

4.8

4.6

4.4
104 (kobs), sec-1

4.2

3.8

3.6

3.4

3.2

3
0 1 2 3 4 5 6
[Cl−], mol dm-3
 

Figure 4.9: Variation of chloride ion

[Ce(IV)] = 5.0×10-4 mol dm-3; [Val] = 5.0 × 10-3 mol dm-3;

[Pd(II)] = 5.0×10-5 mol dm-3; [H+] = 1.0 mol dm-3; Temp.= 45◦C

(Ref. Table 4.13)

108 
 
 
Chapter 4

Palladium(II) chloride is rather insoluble in aqueous solution but is soluble in

hydrochloric acid and exists17-18 as [PdL4]2-, according to the equilibrium19.

[PdCl 2 ] + 2Cl − [PdCl 4 ]2 −

The existence of PdCl2 exclusively in the form of [PdCl4]2− is also

supported by Ayres20, who has observed that when a reaction ratio of 2:1 for
sodium chloride (Cl− ions) to palladium(II) chloride is maintained, then this will
result in the formation of well known tetrachloropalladate(II), [PdCl4]2−. Since
throughout the experiments, ratio of Cl− ion to palladium(II) chloride
concentration i.e. Cl−/ [PdCl4]2− was maintained more than 2, it is reasonable to
assume that the species [PdCl4]2− is the sole palladium(II) species in HCl21-22.

The observed fractional order with respect to valine indicates that there is
possibility of complex formation between [PdCl4]2− and valine in the first pre-
equilibrium step. Valine is easily protonized in acid media, indicating the
involvement of H+ in the reaction in the pre-equilibrium step. Ce(SO4)2 has been
found kinetically active in this study with generation of free radicals in the
reaction. Platinum group metals have the ability to form complexes with organic
substrates highly enhanced rates substantiate the formation of (Pd(II)-AA)
complex, which slowly reacts with Ce(IV) species in the rate determining step to
give products. It is also noteworthy that the reaction is note influenced by chloride
ions, to be expected in Pd(II) catalysed reaction23-24. On the basis of above kinetic
results, a probable reaction mechanism has been proposed (Scheme-4.1).

K1
H + + (CH 3 ) 2 CHCH(NH 2 ) COOH H 3 N + (CH 3 ) 2 CH CHCOO H (1)

K2
H 3 N + (CH 3 ) 2 CH CHCOO H + Pd(II) Pd(II) ⋅ H 3 N + (CH 3 ) 2 CH CHCOO H    (2)

(Adduct)
k
Addcut + C e(SO 4 ) 2 ⎯⎯⎯→ Pd(III).H 3 N + (CH 3 ) 2 CH CHCOO H (Adduct) +
slow
+ Ce(III) + 2SO 24 −        (3)                                   

fast
→ Pd(II) + H2 N⋅ (CH3 )2 CHCHCOOi + 2H+                                        (4)
(Adduct)+ ⎯⎯⎯

109 
 
 
Chapter 4

fast
H 2 N⋅ (CH3 )2 CH CHCOOi + Ce(SO 4 ) 2 ⎯⎯⎯→ (CH3 ) 2 CH CHO + Ce(III)
H2O
+ 2SO 24− + H + + NH3 + CO 2 (5)

Scheme-4.1

According to the present mechanism applying the steady state condition to the
free radicals,

−d[Ce(IV)] 2kK[Pd(II)][Ce(IV)][Val][H + ]
=
dt K[Val][H+ ] + 1 (6)
Where K = K1 K2

−d[Ce(IV)] / dt 2kK[Pd(II)][Val][H + ]
  = k obs =
[Ce(IV)] K[Val][H + ] + 1 (7)

Rearrangement of equation (7)

1 K[Val][H+ ] + 1
=                             
k obs 2kK[Pd(II)][Val][H + ]

1 1 1
                                         = + +
⋅
2k[Pd(II)] 2kK[Val][H ] [Pd(II)]
(8)

1 1 1
= + +
⋅
2k[Pd(II)] 2kK[Pd(II)][H ] [Val]
                         (9)

1 1 1
= + ⋅ +
2k[Pd(II)] 2kK[Pd(II)][Val] [H ] (10)

Equation (7) suggest that order with respect to palladium(II) is 1.0, less
than one in valine and less than one in [H+], which is consistent with the result of
our experiments. Equation (8) suggest that 1/ kobs versus 1/ Pd(II) at constant
[Val], [H+] should yield good linear plots through the origin (Figure 4.10).
Equation (9) suggests that 1/ kobs versus 1/ [Val] at fixed [Pd(II)] and [H+] should
be linear plots with positive intercept (Figure 4.11). Equation (10) suggests that
the plot of 1/kobs versus 1/ [H+] at constant [Pd(II)] and [Val] should also be linear
with positive intercept.

110 
 
 
Chapter 4

1.6

1.4

1.2

1
10-4(kobs)-1, sec

0.8

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2
10-5 [Pd(II)]-1, mol-1 dm3

Figure 4.10: A plot of 1/kobs versus 1/[Pd(II)]-1

[Ce(IV)] = 5.0 × 10-4 mol dm-3; [H+] = 1.0 mol dm-3;

[Val] = 5.0 × 10-3 mol dm-3; I = 1.50 mol dm-3;
Temp. = ( ) 40°C; ( ) 45°C; ( ) 50°C

111 
 
 
Chapter 4

0.9

0.8

0.7

0.6
(kobs)-1, sec

0.5

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1 1.2
10-3[Val]-1, mol-1 dm3

Figure 4.11: A plot of 1/kobs versus 1/[Val]

[Ce(IV)] = 5.0 × 10-4 mol dm-3; [H+] = 1.0 mol dm-3;

[Pd(II)] = 5.0× 10-5 mol dm-3; I = 1.50 mol dm-3;
Temp. = ( ) 40°C; ( ) 45°C; ( ) 50°C

112 
 
 
Chapter 4

Under the experimental conditions in aqueous sulphuric acid medium, the

important Ce(IV) sulphato complexs are Ce(SO4)2+, Ce(SO4)2 and HCe(SO4)3−
and relevant equilibria are25:

Q1
Ce4+ + HSO−4 Ce(SO4 )2+ + H +
(11)
Q2
Ce(SO4 )2+ + HSO−4 Ce(SO4 )2 + H +                            (12)

Q3
Ce(SO4 )2 + HSO−4 HCe(SO4 )3− (13)
 

The value of equilibrium constants are Q1 = 3.5 × 103 (25◦C), Q2 = 2 × 102

(25◦C) and Q3 = 0.6 (at 20◦C). Insignificant amount of unhydrolyzed species of
cerium(IV) would also exist along with these sulphato complexes. In the light of
equilibrium (11-13), inverse bisulphate dependence (Figure 4.7) can be explained
by assuming Ce(SO4)2 as the reactive species. The concentration of this active
species is given by equation (14)

[Ce(IV)]T
Ce(SO 4 ) 2 = (14)
1 + Q 3 [HSO −4 ]

= f [Ce(IV)]T

Thus equation (7) can be written as

2kK[Pd(II)][Val][H + ]
k obs = (15)
⎡ K[Val][H + ] + 1⎤ ⎡1 + Q3 [HSO 4− ]⎤
⎣ ⎦⎣ ⎦
+
Assuming C = 2kK[Pd(II)][Val][H
+
]
K[Val][H ] + 1

Equation (15) may be written as

C
k obs =
1 + Q 3 [HSO −4 ] (16)
1 1 Q3[HSO4− ]
= + (17)
k obs C C

Equation (17) suggest that 1/ kobs versus [HSO4-] should be linear and agrees with
observed experimental data. From the slope (Q3/C) and intercept (1/C) obtained
by the linear plot of 1/ kobs versus [HSO4-] (Figure 4.7), the ratio of slope to

113 
 
 
Chapter 4

intercept was calculated to be 1.71 i. e. Q3 was estimated to be 1.71 according to

equation (17), which is good agreement with the previously reported value25-26.
All the above results show that Ce(SO4 )2 is the kinetically active species.

Furthermore the rate of reaction slightly affected by ionic strength, indicate that
there must be a neutral molecule in the rate determining step, which confirms
Ce(SO4)2 as the kinetically active species in present study.

From equation (9), it can be seen that the intercept of the linear plot of 1/
kobs versus 1/ [Val] is 1/ 2k[Pd(II)] and the slope is 1/ 2kK[Pd(II)][H+]. From the
intercept and slope in Figure 4.11, rate constants (k) and formation constants (K)
at different temperature have been evaluated. Data in Table 4.14 shows that
formation constants (K) increases with increase of temperature, indicating that the
reaction is an endothermic reaction, which is consistent with ∆H# ˃ 0. This
supports the proposed mechanism. Activation parameters of rate determining step
have been evaluated as Ea = 45.95 kJ mol-1, ∆H# = 42.12 kJ mol-1, ∆S# = -84.55 JK
mol-1 and ∆G# = 72.83 kJ mol-1, log A = 8.45 from the linear plot of log k versus
1/ T (Figure 4.12). Thermodynamic quantities were evaluated from the plot of log
K versus 1/T (Figure 4.13). The sizable negative entropy of activation is in
agreement with the formation of activated complex involved in the reaction and
the complex is more ordered than the reactants27. The catalyst, Pd(II) alters the
path of the reaction by lowering the energy barrier, that is, it provides an
alternative pathway which lowers activation parameters for the reaction28.

4.5 Conclusion
The reaction between valine and cerium(IV) is very slow at room
temperature. The reaction occurs in measurable quantities at 45◦C and 1M H2SO4
concentration in the presence of palladium(II) catalyst. The order with respect to
oxidant and catalyst are found to be unity and less than unity with respect to
reductant. The main active species of cerium(IV) is considered as Ce(SO4 )2 ,
although other species might be active to a much lesser extent. The overall
mechanistic sequence described here is consistent with product, kinetic and
mechanistic study.

114 
 
 

Table 4.14: Effect of temperature on the reaction between cerium(IV) and valine catalysed by palladium(II) in
sulphuric acid medium

Temperature (K) k (dm3 mol-1 s-1) Activation parameters K (dm3 mol-1) Thermodynamic Quantities

313 5.88 Ea (kJ mol-1) = 45.95 193 ∆H (kJ mol-1) = 42.12

318 7.14 215 ∆S (J K-1 mol-1) = −65.03

# -1 -1
∆S (JK mol ) = −84.55

323 10.0 243 ∆G (kJ mol-1) = 62.79

# -1
∆G (kJ mol ) = 72.83

log A = 8.45

115 
 
 
Chapter 4
 

1.2

0.8
log k

0.6

0.4

0.2

0
3.08 3.1 3.12 3.14 3.16 3.18 3.2
103 1/T, (Kelvin)-1

Figure 4.12: A plot of log k versus 1/T

116 
 
 
Chapter 4

2.65

2.6

2.55
log K

2.5

2.45

2.4

2.35
3.08 3.1 3.12 3.14 3.16 3.18 3.2
103 1/T, (Kelvin)-1

Figure 4.13: A plot of log K versus 1/T

117 
 
 Chapter 4

4.6 References

1. T.L. Ho, “Organic Syntheses by Oxidation with Metal Compounds” de

Jonge, C.R.H. Eds. Plenum New York, 569, 1986.
2. S. A. Chimatadar, S. V. Madawale and S. T. Nandibewoor, Trans. Met.
Chem., 32, 634, 2007.
3. K. K. Adari, A. Nowduri and V. Parvataneni, Acta. Chim. Slov., 55, 425,
2008.
4. P. K. Tandon, M. Purwar, P. B. Dwivedi and M. Srivastava, Trans. Met.
Chem., 33, 791, 2008.
5. M. B. Yadav, V. Devra and A. Rani, Ind. J. Chem., 49A, 442, 2010.
6. R. K. Patil, S. A. Chimatdar and S. T. Nandibewoor, Trans. Met. Chem.,
33, 625, 2008.
7. K. Din, M. S. Ali and Z. Khan, Colloid. Polym. Sci. (USA), 10, 284, 2005.
8. I. S. Ahmed and C. Mohammad, J. Chem. Kinet., 11, 813, 1985.
9. M. K. Ghosh and S. K Rajput, Am. Chem. Sci. J., 4, 384, 2014.
10. A. K. Singh, D. Chopra, S. Rahmani and B. Singh, Carbohy. Res., 314,
157, 1998,
11. A. Shukla, S. Gupta and S. K. Upadhyay, Int. J. Chem. Kinet., 23, 279,
1991.
12. A. C. Singh, A. K. Singh and B. Singh, Ind. J. Chem., 44, 476, 2005.
13. G. Schwarzenbach and H. Flaschka, “Complexometric titration”
(Methuen and Co. London), 250, 1969.
14. H. S. Gowda and B. Keshayan, J. Ind. Chem. Soc., 53, 688, 1976.
15. F. Feigl, “Spot Test in Organic Analysis”, Elsevier, Amsterdam, 195,
1966.
16. M. H. Kondarasaiah, S. Ananda, Puttaswamy and N. M. M. Gowda,
Synth. React. Inorg. Met.-Org. Chem., 33, 1145, 2003.
17. F. A. Cotton and G. Wilkinson, “Advanced Inorganic Chemistry”, 5th
Edn (Wiley), 1026, 1988.
18. G. P. Tikhonova and S. N. Bovkovets, Russ. J. Inorg. Chem., 23, 813,
1973.

118 
 
  
Chapter 4

19. V. I. Schlenskaya and A. A. Biryukov, Russ. J. Inorg. Chem., 11, 28,

1966.
20. G. H. Ayres, Anal. Chem., 24, 1622, 1953.
21. R. Saxena, A. Shukla and S. K. Upadhyay, Trans. Met. Chem., 19, 91,
1994.
22. A. K. Singh, S. Rashmi, V. K. Singh, D. Kesarwani and B. Singh, Ind. J.
Chem., 40A, 519, 2001.
23. G. P. Tikkonova and S. Bovkovets, Russ. J. Inorg. Chem., 23, 1687,
1978.
24. S. M. Tuwar, S. T. Nandibewoor and J. R. Raju, Ind. J. Chem., 29A, 235,
1990.
25. S. K. Mishra and Y. K. Gupta, J. Chem. Soc. A, 2918, 1970.
26. S. K. Mondal, D. Kar, M. Das and A. K. Das, Ind. J. Chem., 37A, 765,
1998.
27. A. Weissberger, “Investigations of Rates and Mechanisms”, Technique
of Chemistry, Vol. 6, edited by E. S. Lewis (Wiley Interscience, New
York), 1978.
28. S. V. Rao and V. Jagannadham, React. Kinet. Catal. Lett., 27, 239, 1985;
S. A. Chimatadar, S. B. Koujalagi and S. T. Nandibewoor, Trans. Met.
Chem., 26, 241, 2001.

119 
 
 

Chapter – 5
 

Mechanistic and Kinetic Study

of Manganese(II) Catalysed
Oxidation of Leucine by
Cerium(IV) in Sulphuric Acid
Medium

 
 Chapter 5
 

Abstract
The kinetics and mechanism of manganese(II) catalysed oxidation of
leucine by cerium(IV) in sulphuric acid media has been investigated at 45◦C.
The reaction was first order with cerium(IV) and manganese(II). The order
with respect to leucine varies from first to zero order as the concentration
increases. Increase in [H+] and [HSO4− ] decreased the rate of reaction. Under
the experimental conditions, the kinetically active species of cerium(IV) has
been found to be Ce(SO4)2. On the basis of experimental results, a suitable
mechanism has been proposed.

kK[Leu][Mn(II)]
k obs =
1 + K[H + ][Leu]

Where kobs is pseudo first order rate constant. The rate constants of the rate
determining step together with the activation parameters were evaluated.

120 
 
  
Chapter 5

5.1 Introduction

Oxidative decarboxylation of amino acids has its obvious importance in

photochemical and biochemical fields. The reaction and mechanism of amino
acids oxidation are relevant in understanding the biosynthesis of polypeptides,
nucleotides and proteins. Amino acids can undergo many kinds of reactions
depending on whether particular amino acids contain non polar or polar
substituents. Generally the amino and carboxyl functional groups in
RCH(NH2)COOH undergo chemical transformation while the hydrocarbon
moiety (RCH-) remain intact. This property is attributed to the higher reactivity of
the former compared to hydrocarbon. The oxidation of amino acids is of interest
as the oxidation products differ for different oxidant1-2. Thus the study of amino
acids becomes important because of their biological significance and selectivity
towards the oxidant. L-leucine is an essential amino acid. It forms active sites of
enzymes and helps in maintaining their proper conformation by keeping them in
proper ionic states. So oxidation of L-leucine may help in understanding some
aspects of enzyme kinetics.

Cerium(IV) is a well known oxidant3-6 having the Ce(IV)/Ce(III) couple7

at 1.70V but stable only in high acid concentration. The oxidation of organic
compounds by cerium(IV) usually proceeds via an intermediate complex8-10. In
sulphate media several sulphate complexes11-14 of cerium(IV) forms, but these
have not been studied in depth so far. The oxidation of leucine by cerium(IV) was
studied earlier15 but to the best of our knowledge there are no reports on the
manganese(II) catalysed oxidation of leucine by cerium(IV). The slow reaction of
cerium(IV) oxidation of L-leucine is catalysed by a minute amount (10-5mol dm-3)
of manganese(II) in aqueous sulphuric acid. In this study, we have investigated
the manganese(II) catalysed oxidation of L-leucine by cerium(IV) in order to
understand the behaviour of the active species of oxidant and catalyst in sulphuric
acid media.

121 
 
  
Chapter 5

5.2 Experimental

Chemicals of pure quality were used without further purification. Stock

solution of manganese(II) was prepared in double distilled water. Ce(IV) stock
solution was prepared by dissolving ceric ammonium sulphate in 1.0 M sulphuric
acid and standardized with iron(II) ammonium sulphate solution using ferroin as
an indicator. Since the solubility of leucine in water is slow, the solution was
therefore prepared in the presence of 0.1 mol dm-3 sulphuric acid for the higher
amino acid concentration. Other chemicals and reagents such as sodium sulphate,
sulphuric acid and acetonitrile were used of analytical grade with 99.9% purity.
The stock solutions were diluted as required and standardized before use in kinetic
reaction.

5.2.1 Kinetic Measurements

Kinetic studies were carried out in sulphuric acid medium at 45◦C under
pseudo first order conditions with a large excess of leucine over cerium(IV). The
progress of reaction was followed by measuring the absorbance of cerium(IV) at
360 nm using Systronics(166) Visible spectrophotometer at different time
intervals. Application of Beer’s law under reaction condition was verified
between 5×10-5 to 5×10-4 mol dm-3 of Ce(IV) and molar extinction coefficient16
was found to be Ɛ = 2622 dm3 mol-1 cm-1. The kinetic of reactions were allowed
for more than 80% completion of reaction and first order kinetic was observed.
The spectral changes during the chemical reaction for the standard condition at
45◦C are given in Figure 5.1. The pseudo first order rate constants (kobs) were
obtained from the slope of the plots of log absorbance versus time. The observed
rate constants were reproducible within the experimental error ±5%.

5.2.2 Stoichiometry and Product Analysis

Several reaction mixtures with [Leucine] >> [Ce(IV)] were prepared

keeping Mn(II), H+ and ionic strength fixed. After the complete reaction, the
reaction mixtures were treated with 2,4-dinitrophenyl hydrazine. The formation of

122 
 
  
Chapter 5

a ( 0 min)
b (10 min)
1.4 c (20 min)
a d (30 min)
e (40 min)
1.2 f (50 min)
b
g (60 min)
Absorbance

1.0 c
d
0.8
e

0.6
f
g

0.4

0.2
300 350 400 450 500
Wavelength (nm)

Figure 5.1: Sequential scans of absorption spectra during the

course of the reaction of leucine with cerium(IV) in
sulphuric acid media at different time

[Ce(IV)] = 5.0 × 10-4 mol dm-3; [Leu] = 5.0 × 10-3 mol dm-3;
[H+] = 1.0 mol dm-3; I = 2.0 mol dm-3;
[Mn(II)] = 5.0 × 10-5 mol dm-3; Temp. = 45◦C

123 
 
  
Chapter 5

hydrazones indicated the presence of aldehyde as the oxidation products of amino

acids under the kinetic condition. The presence of aldehyde was confirmed by
converting it into 2,4-dinitrophenyl hydrazone and comparing it with an authentic
sample(m.p.). The main reaction products were identified as cerium(III), 3-
methylbutanal, ammonia and CO2. The nature of 3-methylbutanal was further
confirmed by its IR spectrum. The IR peacks at 3421.68 cm-1, 2905.18 cm-1 and
1624.65 cm-1 are attributed to –NH, −CH and −C=N stretching respectively
(Figure 5.2). Ammonia was confirmed with Nesseler’s17 test and CO2 was
qualitatively detected by passing the liberated gas through a tube containing lime
water. Therefore the stoichiometry of the reaction with positive test of an
aldehyde can be represented by equation (1).

→ RCHO + 2Ce(III) + NH3 + CO2 + 2H+  (1)

RCH(NH2 )COOH + 2Ce(IV) + H2O ⎯⎯

R = (CH 3 ) 2 CH- CH 2 −

5.3 Results

5.3.1 Cerium(IV) Dependence

The cerium(IV) concentration was varied from 5×10-5 to 5×10-4 mol dm-3
at different concentration of leucine viz. 5×10-3 mol dm-3, 7.5×10-3 mol dm-3 and
10×10-3 mol dm-3 respectively at fixed concentration of [H+] =1.0 mol dm-3,
[Mn(II)] = 5×10-5 mol dm-3 and I = 2.0 mol dm-3 at temperature 45◦C. Pseudo first
order plots were made, the pseudo first order plots were linear over three half
lives (Figure 5.3). The pseudo first order rate constants (kobs) were found to be
independent of the initial Ce(IV) concentration, commensurate with a first order
process with respect to oxidant. Results are given in Table 5.1, 5.2 and 5.3.

5.3.2 Leucine Dependence

The concentration of leucine was varied from 1×10-3 to 1×10-2 mol dm-3 at
fixed concentration of cerium(IV) = 5×10-4 mol dm-3, [H+] = 1.0 mol dm-3,
[Mn(II)] = 5×10-5 mol dm-3 and I = 2.0 mol dm-3 at three temperature viz. 40◦C,
45◦C and 50◦C respectively. Results are given in table 5.4, 5.5 and 5.6. The rate of

124 
 
 Chapter 5

100 

90

80
Transmittance [%]

70 

60 

50 

40 

30 

20 

 
3421.68 2905.16 1624.65
         

3500  3000  2500 2000 1500 1000 500

Wavenumber cm-1

Figure 5.2: FT-IR Spectrum of oxidation product of leucine

125 
 
 

Table 5.1: Variation of cerium(IV)

[Leu] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 2.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

104[Ce(IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.106 0.231 0.445 0.695 0.878 1.141
20 0.894 0.201 0.385 0.605 0.758 0.971
30 0.773 0.168 0.334 0 .532 0.661 0.846
40 0.067 0.146 0.291 0.445 0.569 0.725
50 0.057 0.126 0.256 0.385 0.498 0.624
60 0.050 0.112 0.210 0.335 0.420 0.548
80 0.037 0.082 0.161 0.242 0.318 0.406

104 (kobs), sec-1 2.47 2.47 2.45 2.49 2.41 2.42

126 
 
 

Table 5.2: Variation of cerium(IV)

[Leu] = 7.5 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 2.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

104[Ce(IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.096 0.216 0.431 0.645 0.826 1.056
20 0.076 0.169 0.349 0.526 0.657 0.846
30 0.061 0.134 0.276 0 .409 0.526 0.672
40 0.049 0.109 0.231 0.322 0.416 0.529
50 0.039 0.089 0.183 0.259 0.332 0.423
60 0.031 0.071 0.152 0.213 0.265 0.349
80 0.019 0.044 0.085 0.132 0.168 0.223

104 (kobs), sec-1 3.75 3.75 3.76 3.74 3.72 3.74

127 
 
 

Table 5.3: Variation of cerium(IV)

[Leu] = 10.0 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 2.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

104[Ce(IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.090 0.195 0.392 0.596 0.765 0.965
20 0.067 0.146 0.306 0.449 0.586 0.735
30 0.051 0.111 0.234 0 .336 0.432 0.556
40 0.037 0.082 0.172 0.256 0.323 0.402
50 0.028 0.061 0.127 0.189 0.243 0.306
60 0.021 0.046 0.095 0.141 0.179 0.223
80 0.012 0.026 0.052 0.076 0.103 0.128

104 (kobs), sec-1 4.91 4.89 4.88 4.91 4.89 4.89

128 
 
  
Chapter 5

2.5 1
2
3
2
4
5
2 + log Absorbance

6
1.5

0.5

0
0 20 40 60 80 100
Time (minutes)

Figure 5.3: Pseudo first order plots for the variation of cerium(IV)

[Leu] = 5.0 × 10-3 mol dm-3; [H+] = 1.0 mol dm-3;

[Mn(II)] = 5.0 × 10-5 mol dm-3; I = 2.0 mol dm-3, Temp.= 45◦C;
[Ce(IV)] = (1) 0.50 × 10-4 mol dm-3; (2) 1.0 × 10-4 mol dm-3;
(3) 2.0 × 10-4 mol dm-3; (4) 3.0 × 10-4 mol dm-3;
(5) 4.0 × 10-4 mol dm-3; (6) 5.0 × 10-4 mol dm-3.

(Ref. Table 5.1)

129 
 
 

Table 5.4: Variation of leucine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 40◦C

[H+] = 1.0 mol dm-3 I = 2.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

103 [Leu], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.204 (20) 1.141 1.162 1.141 1.135 1.115 1.087 1.086 1.082 1.082
20 (60) 1.052 (40) 0.978 1.091 1.042 1.002 0.991 0.945 0.938 0.927 0.926
30 (80) 0.956 (60) 0.867 1.001 0.941 0.887 0.846 0.823 0.804 0.795 0.796
40 (120) 0.836 (80) 0.758 0.928 0.843 0.787 0.734 0.705 0.685 0.674 0.674
50 (140) 0.769 (100) 0.669 (80) 0.658 0.752 0.684 0.643 0.599 0.578 0.574 0.574
60 (160) 0.703 (120) 0.569 (100) 0.556 0.672 0.608 0.543 0.521 0.495 0.485 0.483
80 (180) 0.623 (140) 0.496 (120) 0.463 0.536 0.472 0.405 0.374 0.373 0.362 0.362

104 (kobs), sec-1 0.67 1.10 1.40 1.83 2.11 2.41 2.60 2.62 2.64 2.64

Figures in parentheses denote time in minutes

130 
 
 

Table 5.5: Variation of leucine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 45◦C

[H+] = 1.0 mol dm-3 I = 2.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

103 [Leu], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.182 (20) 1.112 1.146 1.130 1.114 1.076 1.073 1.061 1.061 1.060
20 (60) 0.965 (40) 0.942 1.063 1.016 0.961 0.937 0.919 0.916 0.916 0.913
30 (80) 0.886 (60) 0.801 0.942 0.874 0.845 0.807 0.779 0.761 0.761 0.764
40 (120) 0.713 (80) 0.701 0.864 0.765 0.732 0.678 0.654 0.642 0.642 0.640
50 (140) 0.636 (100) 0.579 0.765 0.669 0.619 0.579 0.558 0.536 0.536 0.534
60 (160) 0.568 (120) 0.504 0.694 0.576 0.545 0.487 0.459 0.444 0.443 0.442
80 (180) 0.505 (140) 0.435 0.551 0.444 0.402 0.352 0.336 0.298 0.298 0.297

104 (kobs), sec-1 0.81 1.32 1.74 2.21 2.42 2.72 2.81 3.01 3.01 3.02

Figures in parentheses denote time in minutes

131 
 
 

Table 5.6: Variation of leucine

[Ce(IV)] = 5.0 × 10-4 mol dm-3 Temp. = 50◦C

[H+] = 1.0 mol dm-3 I = 2.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3

103 [Leu], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.125 1.061 1.135 1.094 1.070 1.055 1.043 1.036 1.040 1.036
20 (60) 0.875 1.061 1.001 0.968 0.923 0.905 0.879 0.864 0.862 0.864
30 (80) 0.785 (40) 0.865 0.875 0.821 0.789 0.735 0.714 0.698 0.696 0.697
40 (100) 0.685 (60) 0.694 0.781 0.712 0.675 0.612 0.578 0.556 0.554 0.556
50 (120) 0.586 (80) 0.564 0.684 0.612 0.554 0.511 0.485 0.456 0.454 0.456
60 (140) 0.527 (100) 0.461 0.610 0.532 0.475 0.487 0.389 0.369 0.370 0.369
80 (160) 0.456 (120) 0.334 0.472 0.382 0.321 0.288 0.252 0.235 0.241 0.235

104 (kobs), sec-1 1.03 1.70 2.11 2.52 2.81 3.11 3.41 3.53 3.50 3.53

Figures in parentheses denote time in minute

132 
 
 Chapter 5

reaction initially increases and then tends towards a limiting value with further
increasing concentration of leucine (Figure 5.4).

5.3.3 Manganese(II) Dependence

At fixed concentration of oxidant, substrate, acid at 5×10-4, 5×10-3 and 1.0

mol dm-3 respectively and at I = 2.0 mol dm-3, the manganese(II) concentration
was varied between 1.0×10-5 to 1.0×10-4 mol dm-3. As the concentration increases,
the rate of reaction also increases (Figure 5.5). Results are given in Table 5.7.
The order with respect to manganese(II) was found to be unity.

5.3.4 Hydrogen Ion Dependence

At fixed concentration of [Leu] = 5×10-3 mol dm-3, [Ce(IV)] = 5×10-4 mol

dm-3, [Mn(II)] = 5×10-5 mol dm-3 and I = 2.0 mol dm-3 at 45◦C, [H+] was varied
from 0.20 to 1.0 mol dm-3. The rate was found to decrease with increasing
sulphuric acid concentration (Figure 5.6). The order with respect to [H+] was
negative as found from a plot of log kobs versus log [H+]. Results are given in
Table 5.8.

5.3.5 Effect of [HSO4−]

The reaction rate were measured with various [HSO4-] = 0.20 to 1.0 mol
dm-3 at fixed concentration of [Leu] = 5.0×10-3 mol dm-3, [Ce(IV)] = 5.0×10-4 mol
dm-3, [Mn(II)] = 5.0×10-5 mol dm-3 and ionic strength of 2.0 mol dm-3 at 45◦C.
The rate of reaction decreased with increase in [HSO4−] which indicates that the
order with respect to [HSO4−] was negative. Results are given in Table 5.9. The
plot of 1/ kobs versus [HSO4−] was found to be linear with positive intercept and
slope (Figure 5.7).

5.3.6 Effect of Ionic Strength

The ionic strength was varied from 1.50 to 2.50 mol dm-3 at fixed
concentration of [Leu] = 5.0×10-3 mol dm-3, [Ce(IV)] = 5.0×10-4 mol dm-3,
[Mn(II)] = 5.0×10-5 mol dm-3 and [H+] = 1.0 mol dm-3 at 45◦C. The rate of reaction

133 
 
 pter 5
Chap

Figure 5..4: Varia

ation of leu
ucine

[Ce(IV)] = 5.00×10-4 mol dm

d -3; [H+ ] = 1.0
1 mol dm-3;
Mn(II)] = 5.00 × 10-5 moll dm-3 ;
[M I 2 mol dm-3;
= 2.0
Teemp. = ( ) 40° C; ( ) 45° C; ( ) 50° C

Ref. Table- 5.4, 5.5 and

(R d 5.6)

134
 
 

Table 5.7: Variation of manganese(II)

[Ce(IV)] = 5.0 × 10-4 mol dm-3 [H+] = 1.0 mol dm-3

[Leu] = 5.0 × 10-3 mol dm-3 I = 2.0 mol dm-3, Temp. = 45◦ C  

105 [Mn(II)], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302 1.302
10 (20) 1.214 (20) 1.156 1.159 1.139 1.114 1.067 1.043 1.025 0.994 0.973
20 (60) 1.105 (60) 0.901 1.097 1.029 0.961 0.921 0.854 0.804 0.761 0.738
30 (80) 1.025 (80) 0.806 1.007 0.921 0.845 0.767 0.701 0.634 0.581 0.556
40 (120) 0.921 (120) 0.635 0.924 0.824 0.732 0.631 0.574 0.505 0.452 0.412
50 (140) 0.858 (140) 0.554 0.837 0.731 0.619 0.541 0.465 0.402 0.342 0.312
60 (160) 0.804 (160) 0.508 0.760 0.634 0.545 0.401 0.381 0.320 0.261 0.213
80 (180) 0.768 (180) 0.456 0.641 0.498 0.402 0.316 0.252 0.206 0.159 0.124

104 (kobs), sec-1 0.48 0.97 1.45 1.95 2.42 2.90 3.41 3.88 4.41 4.83

102 (k′), dm3 mol-1 sec-1 4.80 4.85 4.83 4.87 4.84 4.83 4.87 4.83 4.87 4.82

Figures in parentheses denote time in minutes

135 
 
 Chapter 5

4
104 (kobs), sec-1

0
0 2 4 6 8 10 12
105 [Mn(II)], mol dm-3

Figure 5.5: Variation of manganese(II)

[Ce(IV)] = 5.0×10-4 mol dm-3; [H+] = 1.0 mol dm-3;

[Leu] = 5.0 × 10-3 mol dm-3; I = 2.0 mol dm-3; Temp.= 45◦C

(Ref. Table 5.7)

136 
 
  

Table 5.8: Variation of hydrogen ion

[Leu] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 5.0 × 10-4 mol dm-3 I = 2.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3     
[H+], mol dm-3 0.20 0.40 0.60 0.80 1.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 0.840 0.993 1.043 1.075 1.114
20 0.579 0.761 0.853 0.951 0.961
30 0.382 0.586 0.703 0.798 0.845
40 0.253 0.451 0.587 0.674 0.732
50 0.169 0.343 0.469 0.568 0.619
60 0.112 0.268 0.381 0.485 0.545
80 0.048 0.156 0.252 0.341 0.402

104 (kobs), sec-1 6.82 4.43 3.41 2.77 2.42

137 
 
 Chapter 5

6
104 (kobs), sec-1

0
0 0.2 0.4 0.6 0.8 1 1.2
[H+], mol dm-3

Figure 5.6: Variation of hydrogen ion

[Ce(IV)] = 5.0×10-4 mol dm-3; [Leu] = 5.0 × 10-3 mol dm-3;

[Mn(II)] = 5.0×10-5 mol dm-3; [HSO4−] = 1.0 mol dm-3;
I = 2.0 mol dm-3; Temp. = 45◦C

(Ref. Table 5.8)

138 
 
 

Table 5.9: Variation of [HSO4−]

[Leu] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 5.0 × 10-4 mol dm-3 I = 2.0 mol dm-3
[Mn(II)] = 5.0 × 10-5 mol dm-3
[HSO4−], mol dm-3 0.20 0.40 0.60 0.80 1.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 0.840 0.931 0.986 1.018 1.041
20 0.579 0.705 0.738 0.812 0.864
30 0.382 0.509 0.569 0.644 0.702
40 0.253 0.368 0.421 0.507 0.567
50 0.169 0.265 0.318 0.394 0.462
60 0.112 0.192 0.243 0.314 0.375
80 0.048 0.097 0.139 0.188 0.241

104 (kobs), sec-1 6.82 5.33 4.64 4.01 3.50

139 
 
 

Chapter 5

0.3

0.25

0.2
10-4 (1/ kobs), sec

0.15

0.1

0.05

0
0 0.2 0.4 0.6 0.8 1 1.2

[HSO4− ], mol dm−3

Figure 5.7: Linear plot of 1/kobs versus [HSO4− ]

[Ce(IV)] = 5.0×10-4 mol dm-3; [Leu] = 5.0 × 10-3 mol dm-3;

[Mn(II)] = 5.0×10-5 mol dm-3; [H+] = 0.20 mol dm-3;
I = 2.0 mol dm-3; Temp .= 45◦C

(Ref. Table 5.9)

140 
 
 

Chapter 5
slightly increases with increasing ionic strength (Figure 5.8). Results are given
inTable 5.10.

5.3.7 Effect of Added Product

The effect of initially added product, Ce(III) was studied from 1.0 × 10-4 to
1.0 × 10-3 mol dm-3 at fixed concentration of [Ce(IV)] = 5.0 × 10-4 mol dm-3, [Leu]
= 5.0 × 10-3 mol dm-3, [H+] = 1.0 mol dm-3 and I = 2.0 mol dm-3 at 45◦C. No
significant effect on the rate of reaction was observed. Results are given in Table
5.11.

5.3.8 Test for Free Radical

The intervention of free radicals was examined by adding known quantity

of acetonitrile in the reaction mixture and then kept for 24 hours. Diluting the
reaction mixture with methanol, a precipitate was obtained, suggesting the
generation of free radicals.

5.3.9 Effect of Temperature

The effect of temperature was studied by varying concentration of [Leu] =

1×10-3 to 1×10-2 mol dm-3 at fixed concentration of [H+] = 1.0 mol dm-3, [Ce(IV)]
= 5×10-4 mol dm-3, [Mn(II)] = 5×10-5 mol dm-3 and I = 2.0 mol dm-3 at three
temperature 40◦C, 45◦C and 50◦C respectively. The rate of reaction initially
increases and then tends towards a limiting value with further increasing
concentration of leucine (Figure 5.4). The rate constant k of the slow step of
scheme-5.1 was obtained from the intercept of plot of 1/ kꞌ versus 1/ [Leu]
(Figure 5.9). The energy of activation was obtained by the plot of log k versus
1/T (Figure 5.10). The formation constant K of the first step of scheme-5.1 were
calculated from the plot of 1/ kꞌ versus 1/ [Leu] (the ratio of intercept and slope) at
three temperatures. From the different value of K at three temperatures,
thermodynamic quantities were calculated from the plot of log K vesus 1/T
(Figure 5.11). Results are given in Table 5.12.

141 
 
 

Table 5.10: Variation of ionic strength

[Leu] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Mn(II)] = 5.0 × 10-5 mol dm-3 [H+] = 1.0 mol dm-3
[Ce(IV)] = 5.0 × 10-4 mol dm-3    

I, mol dm-3 1.50 1.75 2.0 2.25 2.50

Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 1.122 1.115 1.114 1.110 1.096
20 0.982 0.991 0.961 0.958 0.953
30 0.854 0.846 0.845 0.839 0.824
40 0.745 0.734 0.732 0.726 0.719
50 0.658 0.643 0.619 0.614 0.618
60 0.552 0.543 0.545 0.539 0.536
80 0.419 0.405 0.402 0.394 0.383

104 (kobs), sec-1 2.37 2.41 2.42 2.47 2.51

142 
 
 Chapter 5

2.8

2.7

2.6

2.5
104 (kobs), sec-1

2.4

2.3

2.2

2.1

2
0 0.5 1 1.5 2 2.5 3
I, mol dm-3

Figure 5.8: Variation of ionic strength

[Ce(IV)] = 5.0×10-4 mol dm-3; [Leu] = 5.0 × 10-3 mol dm-3;

[Mn(II)] = 5.0×10-5 mol dm-3; [H+] = 1.0 mol dm-3; Temp.= 45◦C

(Ref. Table 5.10)

143 
 
 

Table 5.11: Effect of cerium(III)

[Leu] = 5.0 × 10-3 mol dm-3 Temp. = 45◦C

[Mn(II)] = 5.0 × 10-5 mol dm-3 [H+] = 1.0 mol dm-3
[Ce(IV)] = 5.0 × 10-4 mol dm-3
 
10 [Ce(III)], mol dm-3
4
1.0 2.5 5.0 7.5 10.0
Time in minutes Absorbance

0 1.302 1.302 1.302 1.302 1.302

10 1.114 1.112 1.113 1.111 1.110
20 0.962 0.960 0.961 0.959 0.958
30 0.843 0.841 0.842 0.840 0.839
40 0.730 0.728 0.729 0.727 0.726
50 0.618 0.616 0.617 0.615 0.614
60 0.544 0.541 0.542 0.540 0.539
80 0.401 0.397 0.399 0.395 0.394

104 (kobs), sec-1 2.43 2.45 2.44 2.46 2.47

144 
 
 Chapter 5

0.8

0.7

0.6
(k'−1), mol dm-3 sec

0.5

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1 1.2
10-3 [Leu]-1, mol-1 dm3

Figure 5.9: A plot of 1/k′ versus 1/[Leu]

[Ce(IV)] = 5.0 × 10-4 mol dm-3; [Leu] = 5.0 × 10-3 mol dm-3;
[Mn(II)] = 5.0× 10-5 mol dm-3; [H+] = 1.0 mol dm-3; I = 2.0 mol dm-3;
Temp. =( ) 40°C; ( ) 45°C; ( ) 50°C

145 
 
 Chapter 5

1.06

1.04

1.02

1
log k

0.98

0.96

0.94

0.92

0.9
3.08 3.1 3.12 3.14 3.16 3.18 3.2
103 1/ T, (Kelvin)-1

Figure 5.10: A plot of log k versus 1/T

146 
 
 Chapter 5

3.2

3.18

3.16
log K

3.14

3.12

3.1

3.08
2.26 2.28 2.3 2.32 2.34 2.36 2.38 2.4
103 1/T, (Kelvin)-1

Figure 5.11: A plot of log K versus 1/T

147 
 
 Chapter 5

5.4 Discussion

The cerium(IV) oxidation of leucine is slow in aqueous sulphuric acid

media under the present experimental conditions. However, the rate of reaction is
appreciably faster in the presence of manganese(II) in sulphuric acid. The order
with respect to leucine changes from unity to zero. Such an amino acid
dependence can be ascribed to complexation with cerium(IV) or manganese(II).
The adduct formation between Ce4+ and leucine was ruled out on the premise that
the absorbance of Ce4+ did not change at the addition of excess leucine. Therefore
it appears that an adduct between manganese(II) and leucine is initially formed
that on further interaction with cerium(IV) yields another adduct of higher valent
manganese which collapses in a fast step to produce catalyst and free radical. The
reactive species of cerium(IV) is Ce(SO4)2 in the present experimental condition
and the order with respect to H+ was negative. As the sulphuric acid concentration
increases, the H+ concentration increases, but corresponding HSO4− concentration
also increases. Since the rate is inversely dependent on the HSO4− concentration
the overall effect of adding sulphuric acid would be lowering the rate.
Considering all these facts along with experimental results, a reaction mechanism
consisting of step (2) to (5) can be proposed.

K
NH 2 (CH 3 ) 2 CHCH 2 CH COOH + Mn(II) H 2 N(CH 3 ) 2 CHCH 2 CH COOH⋅ Mn(II) (2)

[Adduct]
k
Adduct + Ce(SO 4 ) 2 ⎯⎯→ [Adduct]+ + Ce3+ + 2SO 42 − (3)
fast
→ H 2 N(CH 3 )CHCH 2 CH COO i + Mn(II) + H +
[Adduct]+ ⎯⎯⎯ (4)

H O
Ce(SO4 ) 2 + H 2 N(CH3 ) 2 CHCH 2 CH COOi ⎯⎯⎯
2 → (CH ) CHCH CHO + H +
3 2 2
fast
+ Ce3+ + NH3 + 2SO2−
4
           (5)

Scheme-5.1

The proposed mechanism leads to the rate law (6) to (9)

148 
 
 Chapter 5

− d[Ce(IV)] kK[Ce(IV)][Leu][Mn(II)]
=
dt 1 + K[H + ][Leu] (6)
−d[Ce(IV)] / dt kK[Leu][Mn(II)]
= k obs =
[Ce(IV)] 1 + K[H + ][Leu] (7)
Where kobs is pseudo first order rate constant. Since the order with respect to
manganese(II) is one (Table 5.7), the rate law further change to (8)

kK[Leu]
k′ = (8)
1 + K[H + ][Leu]

Where kꞌ = second order rate constant

After rearranging equation (8)

1 1 [H + ]
= + (9)
k′ kK[Leu] k

A plot of 1/ k ′ versus 1/ [Leu] was made from equation (9) at constant

hydrogen ion concentration at three different temperatures 40◦C, 45◦C and 50◦C
yielded straight line with nonzero intercept (Figure 5.9). The ratio of intercept
and slope of the line yielded the value of K to be 215 dm3 mol-1. The value of K
obtained in the title reaction in comparision to K= 230 dm3 mol-1 for cerium(IV)
glutamic acid in 1.0 M H2SO4 at 30◦C and K = 180 dm3 mol-1 for cerium(IV)
glycerol reaction in 0.5 M H2SO4 at 25◦C indicates strong complexation in H2SO4
medium. The activation parameters of the rate determining step have been
evaluated from the linear plot of log k versus 1/T. The results of Table 5.12 show
that K increases with increase of temperature, indicating the reaction is
endothermic, which is consistent with ∆H# > 0. The large negative value of
entropy of activation (∆S#) obtained is attributed to the severe restriction of
solvent molecules (Electrostriction) around the transition state18 and indicates that
complex is more ordered than reactants19.

Under the experimental conditions in aqueous sulphuric acid medium the

important cerium(IV)-sulphato complexes are Ce(SO4)2+, Ce(SO4)2 and
−
HCe(SO4)3 and relevant equilibrium are-

149 
 
 

Table 5.12: Activation parameters and thermodynamics quantities evaluated from the rate constants

Temperature (K) k (dm3 mol-1 s-1) Activation parameters K (dm3 mol-1) Thermodynamic Quantities

Ea ( kJ mol-1) = 22.97 ∆H# ( kJ mol-1) = 19.14

313 8.33 193

∆S# ( JK-1 mol-1) =140.56

318 9.09 ∆S# ( JK-1mol-1) = -154.82 215

∆G# ( kJ mol-1) = 63.83

323 11.11 ∆G # ( kJ mol-1) = 72.20 243

150 
 
 Chapter 5

Q1
Ce4+ + HSO4− Ce(SO4 )2+ + H + (10)
Q2
Ce(SO4 )2+ + HSO−4 Ce(SO4 )2 + H +                             (11)

Q3
Ce(SO4 )2 + HSO−4 HCe(SO4 )3− (12)

The value of equilibrium constants20 at 25◦C are Q1 = 3.5 × 103, Q2 = 2 × 102, Q3 =

3.4. Insignificant amount of unhydrolyzed species of cerium(IV) would also exist
along with these sulphato complexes. In light of equilibrium steps (10-12) inverse
bisulphate dependence (Figure 5.7) can be explained by assuming Ce(SO4)2 as the
reactive species. The concentration of this active species is given by equation (13)

[Ce(IV)]T
[Ce(SO 4 ) 2 ] = = f [Ce(IV)]T (13)
1 + Q 3 [HSO −4 ]

Thus equation (7) can be written as

kK[Leu][Mn(II)]
k obs = (14)
1 + K[H + ][Leu][1 + Q 3 [HSO 4− ]

kK[Leu][Mn(II)]
If A =
1 + K[H + ][Leu]

A
So eqn (14) becomes k obs = (15)
1 + Q3 [HSO 4− ]

1 1 Q3[HSO−4 ]
= + (16)
k obs A A

Equation (16) suggests that a plot of 1/ kobs versus [HSO4-] should be linear and
agrees with observed experimental data. From the slope Q3/A and intercept 1/A,
the ratio of slope to intercept was calculated to be 1.54 i. e. Q3, which is in good
agreement with the previously reported value21. All the above results show
Ce(SO4)2 as the kinetically active species. Furthermore the rate constants decrease
with increasing [H+]. This is due to formation22 of an active inhibitor
H2Ce(SO4)22−.

It is observed that SO42- ions retards the rate of oxidation coupled with the
observation that increase in [H+] decrease the rate, pointing to the fact that the

151 
 
 Chapter 5

neutral covalently bound Ce(SO4 )2 is the active species of oxidant23. The slight
effect of ionic strength indicate that a neutral molecule is involved in rate
determining step, which further confirms the Ce(SO4 )2 as the kinetically active

species in the present study.

5.5 Conclusion

The reaction between leucine and cerium(IV) is very slow at room

temperature. The reaction occurs in measurable quantities at 45◦C and 1M H2SO4
concentration in the presence of manganese(II) catalyst. The order with respect to
oxidant and catalyst are found to be unity and less than unity with respect to
reductant. The main active species of cerium(IV) is considered as Ce(SO4 )2 ,

although other species might be active to a much lesser extent. The overall
mechanistic sequence described here is consistent with product, kinetic and
mechanistic study.

152 
 
 Chapter 5

5.6 References

1. S. M. Deepak, S. A. Chimatadar and S. T. Nandibewoor, Trans. Met.

Chem., 33, 535, 2008.
2. D. Laloo and M. K. Mahanti, J. Chem. Soc. Dalton Trans., 1, 311, 1990.
3. K. A. Thabaj, S. A. Chimatadar and S. T. Nandibewoor, Trans. Met.
Chem., 31, 186, 2006.
4. S. A. Chimatadar, T. Basavaraj and S. T. Nandibewoor, Inorg. React.
Mech., 4, 209, 2002.
5. S. A. Chimatadar, S. B. Koujalagi and S. T. Nandibewoor, Trans. Met.
Chem., 26, 241, 2001.
6. S. A. Chimatadar, S. T. Nandibewoor, M. I. Sambrani and J. R. Raju, J.
Chem. Soc. Dalton Trans., 3, 573, 1987.
7. M. C. Day and J. Selbin, “Theoretical Inorganic Chemistry”, Reinhold,
New York, 226, 1964.
8. T. Sumathi, P. S. Sundaram, G. Chandramohan, D. Deepa and R.
Renganathan, Int. J. Chem. Sci. Tech., 2, 44, 2012.
9. G. G. Guilbault and W.H. McCurdy Jr., J. Phys. Chem., 67, 283, 1963.
10. M. Ardon, J. Chem. Soc., 1811, 1957.
11. S. A. Chimatadar, S. T. Nandibewoor and J. R. Raju, Ind. J. Chem., 28A,
902, 1989.
12. R. K. Patil, S. A. Chimatadar and S. T. Nandibewoor, Trans. Met. Chem.,
33, 625, 2008.
13. A. Katafias, Trans. Met. Chem., 31, 907, 2006.
14. A. Roy and A. K. Das, Ind. J. Chem., 41A, 2468, 2002.
15. M. B. Yadav, V. Devra and A. Rani, Phys. Chem. An Ind. J., 4, 21, 2009.
16. A. P. Savanur, S. T. Nandibewoor and S. A. Chimatadar, Trans. Met.
Chem., 34, 711, 2009.
17. G. H. Jeffery, J. Bassett, J. Mendham and R. C. Denny, ‟Vogel’s Text
Book of Quantitative Chemical Analysis”, 5th edn., ELBS, Longman,
Essex, England,(a) p. 381, (b) p.195, 1996.

153 
 
 
Chapter 5

18. T. Sumati, P. S. Sundaram and G. Chandramohan, Arabian J. Chem., 4,

426, 2011.
19. D. C. Hiremath, T. S. Kiran and S. T. Nandibewoor, Int. J. Chem. Kinet.,
39, 236, 2007.
20. S. K. Mishra, Y. K. Gupta, J. Chem. Soc. A, 2918, 1970.
21. S. K. Mondal, D. Kar, M. Das and A. K. Das, Ind. J. Chem., 37A, 765,
1998.
22. S. A. Chimatadar, S. V. Mandawale and S. T. Nandibewoor, Trans. Met.
Chem., 32, 634, 2007.
23. T. Sumathi, P. Shanmugasundaram, G. Chandramohan, Asian J. Chem.,
23, 4385, 2011.

154 
 
 

Chapter – 6

Mechanistic and Kinetic Study

of Oxidation of Aspartic Acid
by Cerium(IV) in Presence of
Palladium(II) in Sulphuric Acid
Medium

 
 
 Chapter 6

Abstract

Kinetics of palladium(II) catalysed oxidation of aspartic acid by

Ce(IV) has been studied in acidic medium at 45◦C. The reaction show first
order kinetics with respect to Ce(IV) and Pd(II) in the oxidation of aspartic
acid. The first order kinetics with respect to aspartic acid obtained at its
lower concentration changes to zero order at its higher concentration. It is
found that rate of reaction, decreases with increase of [HSO4−] and [H+].
Effect of added product Ce(III) retards the rate of reaction. The active
species of oxidant is Ce(SO4)2. A plausible mechanism has been proposed
from the results of kinetic studies, reaction stoichiometry and product
analysis.

155 
 
 
Chapter 6

6.1 Introduction

Cerium(IV) metal ion, being a strong oxidant, is widely used in the

oxidation of organic substances1-6, as well as of several inorganic substances7-10.
The basic advantage over other oxidants is its reduction to a single substance,
cerium(III), without any intermediate reactions. It is stable towards heat and light
and simply undergoes one electron change. The oxidation of organic compounds
by cerium(IV) in general seems to proceed via the formation of an intermediate
complex11-13. Among the inorganic substrates which serve as ligands for
cerium(IV) are chloride, bromide and hypophosphite14. So far the kinetics of
cerium(IV) reactions is concerned, an intermediate complex between oxidant and
substrate is generally considered to be the preferred mode of electron transfer.

Amino acids act as the building blocks in the synthesis of proteins and
play a vital role in the metabolism. In the metabolism, amino acids are subjected
to various reactions and supply precursors for many endogenous substances, e.g.
haemoglobin in blood.  They undergo different reactions, depending on whether a
particular amino acid contains non-polar groups or polar substituents. Aspartic
acid is a non-essential amino acid which is found abundantly in plant proteins
especially in sprouting seeds. This can be manufactured in the body from oxalo
acetic acid15. It is important as a general acid in enzyme centres as well as in
maintaining the solubility and ionic characters of proteins. Physiologically,
aspartic acid aids in the removal of ammonia, which is highly toxic to the central
nervous system. Recent studies have shown that aspartic acid may increase
resistance to fatigue and increase endurance16. Many kinetic studies have been
carried out on the oxidation of aspartic acids using different oxidants17-21 in acidic
and alkaline media.

Kinetic investigations on the oxidation of amino acids catalyzed by

different metal ions22-26 are considered as a significant field of chemistry because
of the role of metals in biological systems. Palladium is a rare and lustrous
silvery-white metal referred to as the platinum group metals. Palladium catalysed
reactions have found widespread use in many areas of organic chemistry27,

156 
 
 
Chapter 6

medicinal chemistry28 and in the preparation of fine chemicals29. It is a versatile

metal applied in homogeneous catalysis. The utility of palladium(II) chloride as a
non-toxic and homogenous catalyst has been reported by several workers30-32. The
catalysed mechanism can be quite complicated due to formation of different
intermediate complexes and different oxidation states of Pd(II).

In the present investigation, we have obtained the evidence for the reactive
species for the cerium(IV) in acidic medium. A perusal literature showed that
there seems to be no report on the kinetics and mechanism of the oxidation of
aspartic acid by cerium(IV), catalysed by palladium(II) in sulphuric acid medium.
Therefore we have undertaken a careful study of oxidation of aspartic acid by
cerium(IV) in presence of Pd(II) catalyst in sulphuric acid medium.

6.2 Experimental

In the present work, double distilled water was used for preparing the
solutions. A stock solution of aspartic acid (E. Merck) was prepared by dissolving
it in water. The Ce(IV) stock solution was obtained by dissolving cerium(IV)
ammonium sulphate (E. Merck) in 1.0 mol dm-3 sulphuric acid and standardized
with iron(II) ammonium sulphate solution (E Merck). Palladium(II) chloride
(Johnson Matthey) was prepared in HCl (0.20 mol dm-3) and assayed by
complexometric titration with EDTA33. Dilute solution of palladium(II) were
made from the stock solution as required. Other chemical and reagents such as
Ce(III) sulphate, sodium chloride, sodium sulphate, sulphuric acid, acetonitrile
used were of analytical grade.

6.2.1 Kinetic Measurements

Kinetics of oxidation of aspartic acid by cerium(IV) in presence of Pd(II)

as catalyst have been investigated at 45◦C in acidic medium. A solution with
known concentration of Cerium(IV) and other reactants were allowed to
equilibrate in a water bath at the required temperature for 20 minutes, then
thoroughly mixed and quickly transferred to the absorbance cell. The reaction was
followed by measuring the absorbance of unreacted Ce(IV) at 360 nm using

157 
 
 
Chapter 6

systronics(166) UV spectrophotometer, all other species did not absorb

significantly at this wave length. The applicability of Beer’s law was verified
between 5×10-5 to 5×10-4 mol dm-3 of cerium(IV) at 360 nm under the reaction
conditions. The molar absorption coefficient was found to be Ɛ = 2622 dm3 mol-1
cm-1 34. The initial rates were obtained from [cerium(IV)] versus time plots by
plane mirror method35-36. The initial rates were reproducible within the
experimental error ±5%.

6.2.2 Stoichiometry and Product Analysis

Different reaction mixtures with different sets of concentration of

reactants, where [Ce(IV)] was in excess over [aspartic acid] at constant ionic
strength, acidity and at constant concentration of catalyst were kept for 24 hours at
45°C. The unreacted Ce(IV) was measured through absorbance at 360 nm. The
main reaction products are Cerium(III), malonic acid, ammonia and CO2. Malonic
acid was identified by FTIR spectrum. The IR Spectra shows the band at 1632.07
cm-1 due to C=O stretching frequency of the carboxylic group and the band at
3449.28 cm-1 due to –OH stretching frequency of the carboxylic OH group
(Figure 6.1). Ammonia was confirmed with Nesseler’s reagent test37 and CO2
was qualitatively detected by lime water test. The results indicated that one mole
of aspartic acid consumed four moles of cerium(IV) according to equation (1).

Pd(II)
→ HOOCCH 2 COOH + 4H +
HOOCCH 2 CH(NH 2 ) COOH + 4Ce(IV) + 2H 2 O ⎯⎯⎯⎯
+ 4Ce(III) + NH 3 + CO 2 (1)

6. 3 Results

6.3.1 Cerium(IV) Dependence

In the first set of kinetic experiment, [Ce(IV)] was varied from 5×10-5 to
5×10-4 mol dm-3 at fixed concentration of [Asp] = 6×10-3 mol dm-3,[H+] = 0.50
mol dm-3, [Pd(II)] = 5×10-5 mol dm-3, I = 1.0 mol dm-3 and temperature = 45◦C,
the order was found to be unity. Results are given in Table 6.1. The plot of initial
rate versus [Ce(IV)] was a straight line passing through the origin (Figure 6.2).

158 
 
  
Chapter 6

100

80

 
60
Transmittance [%]

40

20

3449.28   1632.07
           
3500 3000 2500 2000 1500 1000 500

  Wavenumber cm-1

Figure 6.1: FT-IR spectra of final prodcuct of oxidation of

aspartic acid

159 
 
 

Table 6.1: Variation of cerium(IV)

[Asp] = 6.0 × 10-3 mol dm-3 Temp. = 45◦C

[H+] = 0.50 mol dm-3 I = 1.0 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

104 [Ce(IV)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0
Time in minutes Absorbance

0 0.121 0.265 0.528 0.782 1.041 1.302

10 0.092 0.194 0.414 0.620 0.818 1.017
20 0.072 0.157 0.325 0.601 0.802 0.798
30 0.053 0.121 0.252 0.399 0.640 0.655
40 0.040 0.099 0.205 0.314 0.504 0.498
50 0.031 0.078 0.168 0.236 0.325 0.414
60 0.023 0.060 0.127 0.188 0.242 0.314
80 0.013 0.036 0.084 0.110 0.147 0.189

107 (rate), mol dm-3 sec-1 0.28 0.68 1.28 1.95 2.64 3.25

160 
 
  
Chapter 6
 

3.5

3
107(rate), mol dm-3 sec-1

2.5

1.5

0.5

0
0 1 2 3 4 5 6
104 [Ce(IV)], mol dm-3

Figure 6.2: Plot of cerium(IV) versus rate

[Asp] = 6.0 × 10-3 mol dm-3; [H+] = 0.5 mol dm-3;
[Pd(II)] = 5.0 × 10-5 mol dm-3; I = 1.0 mol dm-3; Temp.= 45◦C

(Ref. Table 6.1)

161 
 
 Chapter 6

6.3.2 Aspartic Acid Dependence

At a fixed [Ce(IV)] = 2×10-4 mol dm-3, [Pd(II)] = 5×10-5 mol dm-3,

[H2SO4] = 0.50 mol dm-3 and I = 1.0 mol dm-3, the effect of [Asp] on the rate of
reaction was studied in the concentration range 1×10-3 to 1×10-2 mol dm-3 at three
temperature viz. 40◦C, 45◦C and 50◦C respectively. The rate of the reaction
initially increases and tends towards a limiting value with further increasing
concentration of aspartic acid (Figure 6.3). Results are given in Table 6.2, 6.3
and 6.4.

6.3.3 Palladium(II) Dependence

At fixed [Ce(IV)] = 2×10-4 mol dm-3, [Asp] = 6×10-3 mol dm-3, [H2SO4] =
0.50 mol dm-3 and I = 1.0 mol dm-3, Pd(II) was varied from 1×10-5 to 1×10-4 mol
dm-3 at 45°C. The rate of reaction increases with increase of Pd(II) concentration.
Results are given in Table 6.5. The order with respect to Pd(II) was found to be
one (Figure 6.4). Under these conditions the rate of uncatalyzed reaction is
negligible in comparision to the catalyzed reaction.

6.3.4 Hydrogen Ion Dependence

At fixed concentration of [Ce(IV)] = 2×10-4 mol dm-3, [Pd(II)] = 5×10-5

mol dm-3, [Asp] = 6×10-3 mol dm-3 and I = 1.0 mol dm-3, the sulphuric acid
concentration was varied between 0.20 and 1.0 mol dm-3 at 40°C, 45°C and 50°C
respectively, the initial rate was found to decrease with increasing sulphuric acid
concentration (Table 6.6, 6.7 and 6.8). The [H+] ion concentration was calculated
using known ionization constants of sulphate as in the earlier studies38-40.
Cerium(IV) is known to form several complexes in sulphate media38-39, 41.

K OH
Ce4+ + H 2 O Ce(OH)3+ + H +
(2)
K1
Ce4+ + SO42− Ce(SO4 )2+ (3)
K2
Ce(SO4 )2+ + SO42− Ce(SO4 )2
(4)

162 
 
 

Table 6.2: Variation of aspartic acid

[Ce(IV)] = 2.0 × 10-4 mol dm-3 Temp. = 40◦C

[H+] = 0.50 mol dm-3 I = 1.0 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

103[Asp], mol dm-3 1.0 2.0 4.0 6.0 8.0 1.0

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528

10 0.485 0.460 0.425 0.427 0.414 0.403
20 0.443 0.393 0.348 0.341 0.326 0.320
30 0.406 0.337 0.284 0.275 0.253 0.251
40 0.367 0.291 0.236 0.223 0.206 0.201
50 0.334 0.247 0.178 0.180 0.170 0.164
60 0.298 0.207 0.152 0.151 0.128 0.115
80 0.240 0.147 0.099 0.095 0.085 0.081

107 (rate), mol dm-3 sec-1 0.31 0.56 0.88 1.10 1.26 1.36

163 
 
 

Table 6.3: Variation of aspartic acid

[Ce(IV)] = 2.0 × 10-4 mol dm-3 Temp. = 45◦C

[H+] = 0.50 mol dm-3 I = 1.0 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

103[Asp], mol dm-3 1.0 2.0 4.0 6.0 8.0 1.0

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528

10 0.473 0.452 0.430 0.414 0.396 0.388
20 0.420 0.378 0.347 0.325 0.318 0.311
30 0.370 0.316 0.273 0.252 0.246 0.242
40 0.318 0.270 0.226 0.205 0.199 0.195
50 0.283 0.216 0.184 0.168 0.160 0.169
60 0.248 0.173 0.153 0.127 0.113 0.110
80 0.190 0.116 0.101 0.083 0.078 0.072

107 (rate), mol dm-3 sec-1 0.38 0.65 1.00 1.28 1.46 1.58

164 
 
 

Table 6.4: Variation of aspartic acid

[Ce(IV)] = 2.0 × 10-4 mol dm-3 Temp. = 50◦C

[H+] = 0.50 mol dm-3 I = 1.0 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

103[Asp], mol dm-3 1.0 2.0 4.0 6.0 8.0 1.0

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528

10 0.474 0.440 0.418 0.392 0.387 0.384
20 0.419 0.386 0.332 0.803 0.310 0.308
30 0.373 0.306 0.256 0.634 0.240 0.237
40 0.330 0.259 0.209 0.521 0.192 0.190
50 0.290 0.210 0.172 0.403 0.158 0.157
60 0.253 0.175 0.129 0.331 0.109 0.109
80 0.194 0.118 0.087 0.076 0.069 0.066

107 (rate), mol dm-3 sec-1 0.42 0.74 1.20 1.50 1.71 1.82

165 
 
 pter 6
Chap

Figgure 6.3: Variation

n of asparrtic acid

[Ce(IV)] = 2.00×10-4 mol dm

d -3; [Pd(II)] = 5.0 × 10-5 m
mol dm-3;
H+]
[H = 0.550 mol dm-33; I m-3;
= 1.0 mol dm
Teemp. = ( ) 40° C; ( ) 45° C; ( ) 50° C

(Ref. Table 6.2, 6.3 and

d 6.4)

166
 
 

Table 6.5: Variation of palladium(II)

[Ce(IV)] = 2.0 × 10-4 mol dm-3 Temp. = 45◦C

[H2SO4] = 0.50 mol dm-3 I = 1.0 mol dm-3
[Asp] = 6.0 × 10-3 mol dm-3

105 [Pd(II)], mol dm-3 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528 0.528 0.528 0.528 0.528
10 0.492 0.464 0.437 0.429 0.414 0.388 0.383 0.378 0.376 0.373
20 0.452 0.399 0.364 0.346 0.325 0.311 0.307 0.303 0.297 0.262
30 0.415 0.343 0.302 0.275 0.252 0.242 0.236 0.234 0.228 0.223
40 0.372 0.294 0.254 0.225 0.205 0.195 0.189 0.186 0.181 0.176
50 0.341 0.250 0.206 0.181 0.168 0.159 0.156 0.153 0.149 0.144
60 0.304 0.210 0.170 0.152 0.127 0.111 0.108 0.101 0.097 0.093
80 0.244 0.152 0.112 0.098 0.083 0.073 0.066 0.065 0.060 0.055

107 (rate), mol dm-3 sec-1 0.25 0.51 0.77 1.05 1.28 1.58 1.86 2.13 2.41 2.66

167 
 
 Chapter 6

2.5
107(rate), mol dm-3 sec-1

1.5

0.5

0
0 1 2 3 4 5 6 7 8 9 10 11
105 [Pd(II)], mol dm-3

Figure 6.4: Variation of palladium(II)

[Ce(IV)] = 2.0×10-4 mol dm-3; [Asp] = 6.0 × 10-3 mol dm-3;

[H+] = 0.50 mol dm-3; I = 1.0 mol dm-3; Temp. = 45° C

(Ref. Table 6.5)

168 
 
 

Table 6.6: Variation of [H+] concentration

[Ce(IV)] = 2.0 × 10-4 mol dm-3 Temp. = 40◦C

[Asp] = 6.0 × 10-3 mol dm-3 I = 1.0 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

[H+], mol dm-3 0.20 0.40 0.50 0.60 0.80 1.0

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528

10 0.410 0.420 0.425 0.438 0.441 0.455
20 0.327 0.334 0.339 0.353 0.350 0.379
30 0.256 0.258 0.274 0.283 0.286 0.317
40 0.209 0.210 0.221 0.230 0.239 0.272
50 0.165 0.174 0.178 0.187 0.1186 0.218
60 0.19 0.132 0.149 0.155 0.154 0.174
80 0.082 0.088 0.094 0.102 0.104 0.118

107 (rate), mol dm-3 sec-1 1.35 1.21 1.11 0.99 0.80 0.64

169 
 
 

Table 6.7: Variation of [H+] concentration

[Ce(IV)] = 2.0 × 10-4 mol dm-3 Temp. = 45◦C

[Asp] = 6.0 × 10-3 mol dm-3 I = 1.0 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

[H+], mol dm-3 0.20 0.40 0.50 0.60 0.80 1.0

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528

10 0.386 0.408 0.420 0.425 0.430 0.449
20 0.313 0.324 0.330 0.339 0.347 0.371
30 0.241 0.252 0.256 0.267 0.283 0.309
40 0.193 0.204 0.208 0.212 0.235 0.262
50 0.157 0.167 0.171 0.174 0.178 0.213
60 0.109 0.121 0.129 0.135 0.151 0.178
80 0.072 0.080 0.085 0.098 0.099 0.121

107 (rate), mol dm-3 sec-1 1.63 1.40 1.28 1.13 0.89 0.72

170 
 
 

Table 6.8: Variation of [H+] concentration

[Ce(IV)] = 2.0 × 10-4 mol dm-3 Temp. = 50◦C

[Asp] = 6.0 × 10-3 mol dm-3 I = 1.0 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

[H+], mol dm-3 0.20 0.40 0.50 0.60 0.80 1.0

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528

10 0.380 0.390 0.394 0.416 0.430 0.439
20 0.305 0.313 0.315 0.330 0.346 0.348
30 0.283 0.243 0.240 0.259 0.277 0.285
40 0.187 0.196 0.194 0.212 0.225 0.234
50 0.154 0.162 0.160 0.167 0.182 0.182
60 0.104 0.112 0.109 0.121 0.152 0.150
80 0.066 0.070 0.071 0.086 0.099 0.102

107 (rate), mol dm-3 sec-1 2.01 1.69 1.53 1.33 1.04 0.82

171 
 
 pter 6
Chap

Figgure 6.5: A plot off (rate) versus [H+] at three different

ature
tempera

[Ce(IV)] = 2.00×10-4 mol dm-3; [Asp] = 6.0×10

6 -3
mool dm-3;
[Pdd(II)] = 5.00×10-5 mol dm
d -3; I = 1.0 mol dm-33;
Teemp. = ( ) 40° C; ( ) 45° C; ( ) 50° C

(
(Ref. Table 6.6, 6.7 and
d 6.8)

172
 
 Chapter 6

K3
Ce(SO4 )2 + HSO4− Ce(SO4 )2 HSO4−
(5)
K4
  Ce(SO4 )2 HSO4− + HSO4− + H + H3Ce(SO4 ) 4− (6)

The sum of the equations 2-6, gives the total cerium(IV) concentrations which is
obtained by the cumulative equilibrium constants, KOH, β1, β2, β3 and β4 as
equation (7).
⎧ K OH 2− 2− 2 2− 2 − ⎫
4+ ⎪1+ + + β1[SO4 ] + β2 [SO4 ] + β3[SO4 ] [HSO4 ]⎪
4+
[Ce ]t = [Ce ]f ⎨ [H ] ⎬
⎪ 2− 2 − 2 +
+ β4 [SO4 ] [HSO4 ] [H ] ⎪
⎩ ⎭ (7)

Where, KOH = 15, β1 = K1 = 3.85 × 102, β2 = K1 K2 = 1.69 × 102 , β3 = K1 K2 K3 =

1.01 × 102 and β4 = K1 K2 K3 K4 = 2.03 × 102. The concentration of cerium

sulphate complexes can be calculated from the concentration of Ce4+, H+,

HSO4−and SO42− 38-42

. The results show that the concentration of Ce(OH)3+ is very

less than other cerium species, so can be neglected. According to Table 6.9

calculated results are plotted in Figure 6.6 which indicates that only Ce(SO4)2

species is parallel with the variation of rate with H+ concentration.

6.3.5 Effect of Initially Added Product

Added product Ce(III) was varied in the concentration range 5×10-5 to

5×10-4 mol dm-3 keeping other reactants concentration and conditions constant.
The rate of reaction decreases with the addition of Ce(III), whereas other product
malonic acid did not change the rate of reaction. The retarding effect of Ce(III) is
shown in Figure 6.7. Results are given in Table 6.10.

6.3.6 Effect of Ionic Strength

At fixed concentration of [Ce(IV)] = 2×10-4 mol dm-3, [Asp] = 6×10-3 mol

dm-3, [H2SO4] = 0.50 mol dm-3, [Pd(II)] = 5×10-5 mol dm-3 and temperature 45°C,
the ionic strength was varied from 0.60 to 1.60 mol dm-3 (ionic strength adjusted
by Na2SO4), it is found that ionic strength did not affect the rate of reaction
(Figure 6.8). Results are given in Table 6.11.

173 
 
 
 
 
 
 

Table 6.9: Variation of different Ce(IV) species with [H+] on Pd(II) catalysed oxidation of aspartic acid by Ce(IV) in
H2SO4 medium at 45◦C

[H2SO4] [H+] [HSO4−] 103 × α0 αoH α1 102 × α2 102 × α3 102 × α4 107 × rate (mol dm-3 sec-1)

0.20 0.062 0.338 1.698 0.411 4.337 12.500 3.456 0.107 1.63

0.40 0.190 0.610 3.740 0.295 5.610 9.610 3.504 0.816 1.40

0.50 0.291 0.709 5.334 0.274 5.975 7.633 3.234 1.314 1.28

0.60 0.422 0.778 7.309 0.259 6.249 6.093 2.832 1.869 1.13

0.80 0.740 0.860 12.141 0.246 6.543 4.021 2.066 2.643 0.89

1.00 1.099 0.901 17.500 0.238 6.670 2.890 1.560 3.106 0.72

[Ce(IV)] = 2.0 × 10-4 mol dm-3, [Asp] = 6.0 × 10-3 mol dm-3, [Pd(II)] = 5.0 × 10-5 mol dm-3, I = 1.0 mol dm-3 α0, αOH ,α1, α2, α3 and α4 are the
fractions of total cerium(IV) of the species Ce4+, Ce(OH)3+, Ce(SO4)2+, Ce(SO4)2 , Ce(SO4)2HSO4− and H3Ce(SO4)4− respectively.

174 
 
 
 
 
 
 

Table 6.10: Effect of cerium(III)

[Ce(IV)] = 2.0 × 10-4 mol dm-3 Temp. = 45◦C

[Asp] = 6.0 × 10-3 mol dm-3 I = 1.0 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3 [H+] = 0.50 mol dm-3

104[Ce(III)], mol dm-3 0.50 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528

10 0.418 0.423 0430 0.431 0.432 0.434
20 0.332 0.335 0.346 0.347 0.349 0.361
30 0.256 0.266 0.277 0.281 0.285 0.298
40 0.209 0.215 0.225 0.232 0.238 0.251
50 0.172 0.175 0.182 0.184 0.186 0.204
60 0.129 0.140 0.152 0.153 0.154 0.167
80 0.087 0.097 0.099 0.101 0.103 0.109

107 (rate), mol dm-3 sec-1 1.20 1.14 1.04 0.95 0.87 0.81

175 
 
  
Chapter 6

14

12

10

8
102 × α2

0
0 0.2 0.4 0.6 0.8 1 1.2
[H+], mol dm-3

Figure 6.6: Effect of [H+] concentration on different cerium(IV)

species

(Ref. Table 6.9)

176 
 
  
Chapter 6

1.4

1.2
107/( rate), dm3 mol-1 sec

0.8

0.6

0.4

0.2

0
0 1 2 3 4 5 6
104 [Ce(III)], mol dm-3

Figure 6.7: Effect of cerium(III)

[Ce(IV)] = 2.0×10-4 mol dm-3; [Asp] = 6.0 × 10-3 mol dm-3;

[H+] = 0.50 mol dm-3; I = 1.0 mol dm-3;
[Pd(II)] = 5.0 × 10-5 mol dm-3; Temp. = 45° C

(Ref. Table 6.10)

177 
 
 

Table 6.11: Variation of ionic strength

[Asp] = 6.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 2.0 × 10-4 mol dm-3 [H+] = 0.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3

I, mol dm-3 0.60 0.80 1.00 1.20 1.40 1.60

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528 0.528

10 0.414 0.413 0.413 0.416 0.414 0.413
20 0.325 0.323 0.325 0.326 0.325 0.323
30 0.252 0.250 0.252 0.253 0.252 0.250
40 0.205 0.203 0.205 0.206 0.205 0.204
50 0.168 0.166 0.168 0.169 0.168 0.167
60 0.127 0.125 0.127 0.130 0.126 0.125
80 0.083 0.081 0.083 0.086 0.083 0.081

107 (rate), mol dm-3sec-1 1.28 1.29 1.28 1.27 1.28 1.29

178 
 
 Chapter 6

1.6

1.5
107(rate), mol dm-3 sec-1

1.4

1.3

1.2

1.1

1
0 0.5 1 1.5 2
I, mol dm-3
 

Figure 6.8: Variation of ionic strength

[Ce(IV)] = 2.0×10-4 mol dm-3; [Asp] = 6.0 × 10-3 mol dm-3;

[Pd(II)] = 5.0×10-5 mol dm-3; [H+] = 0.50 mol dm-3; Temp.= 45◦C

(Ref. Table 6.11)

179 
 
 Chapter 6

6.3.7 Effect of Chloride Ion

At fixed concentrations of [Ce(IV)] = 2.0 × 10-4 mol dm-3, [Asp] = 6.0 × 10-3
mol dm-3, [Pd(II)] = 5.0 × 10-5 mol dm-3, [H2SO4] = 0.50 mol dm-3 and
temperature 45◦C, the concentration of NaCl was varied from 1×10-4 to 5×10-4 mol
dm-3. The rate was unaffected by the addition of Cl− ions (Figure 6.9). Results are
given in Table 6.12.

6.4 Discussion

The uncatalysed cerium(IV) oxidation of aspartic acid is very slow in

sulphuric acid under the present experimental conditions. However, the reaction is
appreciably faster in the presence of small quantity of Pd(II) in sulphuric medium.
The reaction is first order with respect to cerium(IV) and Pd(II) concentrations,
and the order with respect to aspartic acid changes from first to zero order.
Increasing [H+] and [HSO4−] concentration results in a decrease in rate. As the
sulphuric acid concentration increases, the H+ ion concentration increases,
corresponding HSO4− ion concentration also increases. The rate is inversely
dependent on the HSO4− ion concentration, the overall effect of adding sulphuric
acid would be to lower the rate of reaction43-44 (Table 6.9). Added product Ce(III)
inhibits the rate of reaction due to formations of Ce4+.Ce3+ ion pair. The above
results indicate that aspartic acid react with Pd(II) to form an adduct, which then
react one mole of Ce(IV) in slow step and give Ce(III), a free radical derived from
aspartic acid, carbon dioxide and Pd(II) catalyst regenerated. The free radical
derived from aspartic acid then combine with another molecule of Ce(IV) in fast
step and give cerium(III), malonic acid, ammonia. From the above kinetic results,
the following mechanism has been proposed (Scheme-6.1).

K1
Ce 4+ ⋅ H + Ce 4 + + H +

K2
HOOCCH 2 CH(NH 2 ) COOH + Pd(II) Adduct (C1 )

k i
Adduct (C1 ) + Ce 4+ ⎯⎯⎯→ Ce3+ + HOOCCH 2 C H(NH 2 ) + Pd(II) + H + + CO 2
slow

180 
 
 

Table 6.12: Effect of chloride ion

[Asp] = 6.0 × 10-3 mol dm-3 Temp. = 45◦C

[Ce(IV)] = 2.0 × 10-4 mol dm-3 [H+] = 0.50 mol dm-3
[Pd(II)] = 5.0 × 10-5 mol dm-3 I = 1.0 mol dm-3

[Cl−], mol dm-3 1.0 2.0 3.0 4.0 5.0

Time in minutes Absorbance

0 0.528 0.528 0.528 0.528 0.528

10 0.414 0.416 0.413 0.416 0.414
20 0.325 0.326 0.325 0.326 0.325
30 0.252 0.253 0.252 0.253 0.252
40 0.205 0.206 0.205 0.206 0.205
50 0.168 0.169 0.168 0.169 0.168
60 0.127 0.130 0.127 0.130 0.126
80 0.083 0.086 0.083 0.086 0.083

107 (rate), mol dm-3sec-1 1.28 1.27 1.28 1.27 1.28

181 
 
 Chapter 6

1.6

1.5
107(rate), mol dm-3 sec-1

1.4

1.3

1.2

1.1

1
0 1 2 3 4 5 6
[Cl−], mol dm-3

Figure 6.9: Effect of chloride ion

[Ce(IV)] = 2.0×10-4 mol dm-3; [Asp] = 6.0 × 10-3 mol dm-3;

[Pd(II)] = 5.0×10-5 mol dm-3; [H+] = 0.50 mol dm-3;
I = 1.0 mol dm-3; Temp. = 45◦C

(Ref. Table 6.12)

182 
 
 Chapter 6

i fast
HOOCCH 2 C H(NH 2 ) + Ce 4+ ⎯⎯⎯→ Ce3+ + HOOCCH 2CHO + NH 3 + H +
H2O
fast
HOOCCH 2 CHO + 2Ce 4 + + H 2 O ⎯⎯⎯
→ HOOCCH 2 COOH + 2H + + 2Ce3+

Scheme-6.1

Scheme 6.1 leads to the following rate law from (9)

(rate) = k [Adduct] [Ce(IV)] (8)

kK 1 K 2 [Ce(IV )][Asp][Pd(II)]
=
[H + ] (9)

The total concentration of aspartic acid is given by

[Asp]t = [Asp]f + C1
= [Asp]f + K2 [Asp]f [Pd(II)]
= [Asp]f {1+ K2[Pd(II)]}
Therefore
[Asp]t
  [Asp]f =                                                                 (10)
1 + K 2 [Pd(II)]

Where the subscripts ‘t’ and ‘f’ stand for total and free respectively.
In the present investigation the concentration of catalyst Pd(II) is very low, so
term K2[Pd(II)] can be ignored in comparison to unity in equation (10)

[Asp]f = [Asp]t (11)

Similarly,
[Pd(II)]t = [Pd(II)]f + K2 [Asp] [Pd(II)]f
= [Pd(II)]f {1+K2[Asp]}
So
[Pd(II)] t
[Pd(II)]f = (12)
1 + K 2 [Asp]

and
[Ce(IV)]t = [Ce(IV)]f + [Ce(IV)]f [H+]
[Ce(IV)]f
= [Ce(IV)]f + K 1
[H + ]

183 
 
 Chapter 6

⎧⎪ K ⎫⎪
= [Ce(IV)]f ⎨1 + +1 ⎬
⎩⎪ [H ] ⎭⎪
So
[Ce(IV )]t
[Ce(IV )]f = (13)
1 + K 1 / [H + ]

The value of [Asp]f, [Pd(II)]f, [CeIV]f substituting in to equation (9) and omitting
the subscripts, we have
− d[Ce(IV )] k K 1 K 2 [Ce(IV )][Asp][Pd(II)]
rate = = (14)
dt [H ] + K 1 + K 2 [Asp][H + ] + K 1 K 2 [Asp]
+

The rate law (14) may be rearranged to equation (15)

[Ce(IV )][Pd (II)] [H + ] 1 [H + ] 1

= + + + (15)
rate k K 1K 2 [Asp] kK 2 [Asp] k K 1 k

According to equation (15) the plots of [Ce(IV)][Pd(II)] /rate versus 1/[Asp] and
[Ce(IV)][Pd(II)]/rate versus [H+] should be linear (Figure 6.10 and 6.11 ). From
the plot of [Ce(IV)][Pd(II)]/rate versus 1/[Asp]

[H + ] 1
(Slope)1 = + (16)
kK 1K 2 kK 2

[H + ] 1
    (Intercept)1 = +                                                                  (17)
kK1 k
Where K2 is the formation constant for adduct (C1 )
From the plot [Ce(IV)][Pd(II)]/ rate versus [H+]
1 1
(Slope) 2 = + (18)
kK 1 K 2 [Asp ] kK 1

1 ⎡ 1 + K 2 [Asp] ⎤
= ⎢ ⎥
kK1 ⎣ K 2 [Asp] ⎦

1 1
(Intercept) 2 = + (19)
kK 2 [Asp] k

1 ⎡1 + K 2 [Asp] ⎤
= ⎢ ⎥ (20)
k ⎣ K 2 [Asp] ⎦
(Intercept ) 2
Hence, = K1 (21)
(Slope) 2

184 
 
 Chapter 6

Where K1 is the ionisation constant of Ce4+.H+.

Substituting the value of K1 and [H+] in equation (17), we obtained the value of k,
the rate constant with respect to slow step of scheme 6.1. The value of k, K1 and
K2 are 24 ± 1 dm3 mol-1 s-1, 0.75 ± 0.02 mol dm-3 and 189 + 10 dm3 mol-1
respectively. The value of K1 (0.72 mol dm-3) is in good agreement with the
literature45.

The rate of reaction was studied at 40°C, 45°C and 50°C with different
concentrations of aspartic acid and sulphuric acid. The rate of reaction increases
with increase in temperature. The rate constants (k) of slow step of scheme 6.1
were obtained from the intercepts and slopes of the plots of [Ce(IV)][Pd(II)]/rate
versus1/[Asp] and [Ce(IV)][Pd(II)]/rate versus [H+] at three different temperatures
(Figure 6.10 and 6.11). The activation parameters were obtained from a plot of
log k versus 1/T (Figure 6.12). Results are given in Table 6.13. The ionisation
constant (K1) of the first step of scheme 6.1 was evaluated from (intercept)2 /
(slope)2 of the plot of [Ce(IV)][Pd(II)]/rate versus [H+] at the three different
temperatures. Similarly, the formation constant (K2) of the complex of the second
step of scheme 6.1 was obtained from (intercept)1/(slope)1 of the plot of
[Ce(IV)][Pd(II)]/rate versus1/[Asp]. Thermodynamic quantities were calculated
from the plots of log K1 versus 1/T and log K2 versus 1/T at three different
temperature (Table 6.13). It is a known fact46 that for reaction between ions of
opposite charges there is generally an increase in entropy is going from reactants
to activated complex and for ions of like charges, there is an entropy decrease. In
the present study, efforts were made to study the catalyst role of Pd(II) in
oxidation of aspartic acid by Ce(IV) in acidic medium. Observed negative entropy
of activation (Table 6.13) in oxidation of aspartic acid is clearly supports reaction
scheme 6.1, where in the rate determining step the interaction between two
similarly charged species results in the formation of very reactive adduct (C1).

In the present study Ce(SO4)2 is most likely to be the active species of the
oxidant cerium(IV). Therefore the terms of active species in the the rate law (14)
changes in the below form.

185 
 
 Chapter 6

35
[Ce(IV)][Pd(II)]/ (rate ) 102 × mol dm-3 sec

30

25

20

15

10

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

1/ [Asp] × 10-2 mol-1 dm3

Figure 6.10: Plot of [Ce(IV)][Pd(II)] / (rate) versus 1 / [Asp] at

three temperatures

[Ce(IV)] = 2.0 × 10-4 mol dm-3; [H+] = 0.50 mol dm-3;

[Pd(II)] = 5.0 × 10-5 mol dm-3; I = 1.0 mol dm-3,
Temp. = ( ) 40◦C, ( ) 45◦C, ( ) 50◦C.

186 
 
 Chapter 6

16
[Ce(IV)][Pd(II)]/ (rate ) × 102 mol dm-3 sec

14

12

10

0
0 0.2 0.4 0.6 0.8 1 1.2
[H+], mol dm-3

Figure 6.11: Plot of [Ce(IV)][Pd(II)] /(rate) versus [H +] at three

temperatures

[Ce(IV)] = 2.0 × 10-4 mol dm-3; [Asp] = 6.0 × 10-3 mol dm-3;
[Pd(II)] = 5.0 × 10-5 mol dm-3, I = 1.0 mol dm-3,
Temp. = ( ) 40° C; ( ) 45° C; ( ) 50° C

187 
 
 Chapter 6

1.7

1.6

1.5

1.4
2+ log k

1.3

1.2

1.1

1
3.08 3.1 3.12 3.14 3.16 3.18 3.2
103 1/ T, (Kelvin)-1

Figure 6.12: A plot of log k versus 1/T

188 
 
 

Table 6.13: Effect of temperature on Pd(II) catalysed oxidation of aspartic acid by cerium(IV) in aqueous
sulphuric acid medium
Temperature (K) K1(mol dm-3) K2 (dm3 mol-1)

313 0.90 219

318 0.75 189
323 0.65 153

Thermodynamic Quantities Values from K1 Values from K2

∆S (J K-1 mol-1) −161.08 −117.66

∆G (k J mol-1) 23.65 10.61
∆H (k J mol-1) −27.57 −26.80

Temperature (K) 102 k (mol-1 dm3sec-1) Activation Parameters

313 24.50 Ea (k J mol-1) = 49.78

318 33.04 ∆H# (k J mol-1) = 47.86
323 45.24 ∆S# (J K-1 mol-1) = −59.85
∆G# (k J mol-1) = 66.89

189 
 
 Chapter 6
 

k K 1K 2 [Ce(SO 4 ) 2 ][Asp][Pd(II)]
rate = (22)
[H ] + K 1 + K 2 [Asp][H + ] + K 1K 2 [Asp]
+

But,

[Ce(SO 4 ) 2 ] = β 2 [Ce 4 + ][SO 24 − ]2 (23)

[Ce4+]f from equation (7) in equation (22)

β2 [Ce4+ ][SO24− ]2
[Ce(SO4 ) 2 ] =
1 + (K OH [H + ]) + β1[SO42− ] + β2 [SO 24− ]2 + β3[SO 24− ]2 [HSO 4− ]
+ β4 [SO24− ]2 [HSO−4 ]2 [H + ] (24)

Substituting equation (24) in to equation (22) and omitting subscripts.

β 2 k K 1 K 2 [Ce 4 + ][SO 42 − ]2 [Pd 2 + ] 1

rate = + +
×
[H ] + K 1 + K 2 [H ] + K 1 K 2 [X]

Where,

[X] = 1 + (KOH [H+ ]) + β1[SO42− ] + β2[SO42− ]2 + β3[SO42− ]2 [HSO4− ]

+ β4 [SO42− ]2 [HSO4− ]2 [H+ ]

the rate of reaction is unaffected by the ionic strength is consistent with the
reaction between neutral and charged species as in scheme 6.1, which confirms
Ce(SO4)2 as the kinetically active species in present study.

6.5 Conclusion

The oxidation of aspartic acid by cerium(IV) experienced a slow reaction

rate in acidic media, but increased in rate in the presence of the Pd(II) catalyst.
The reactive species for the oxidation of cerium(IV) in acidic medium was
Ce(SO4)2, although other species might be active to a much lesser extent. The rate
constant of a slow step and other equilibrium constants involved in the mechanism
were evaluated. Mechanism consistent with observed rate laws have been
suggested. The results were explained by plausible mechanism and the related rate
law was deduced. It can be stated that palladium(II) acts as an efficient catalyst for
the oxidation of aspartic acid by cerium(IV) in acidic media.

190 
 
 Chapter 6

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193 
 
 Research Publications

 
 
 Annexure I

Research Papers

1. “Kinetics and Mechanism of Chromium (VI) Oxidation of Threonine in

Aqueous Perchloric Acid Medium”, Shanu Mathur, Dhan Raj, Manju
Bala Yadav, Vijay Devra, International Journal of Innovative Research in
Science, Engineering and Technology, 3 (11), 17468-17474, 2014.

2. “Oxidation of Leucine by Cerium(IV) in Presence of Manganese(II) as a

Catalyst in Sulphuric Acid Medium”, Dhan Raj, Shanu Mathur, Manju
Bala Yadav, Vijay Devra, International Journal of Research in Physical
Chemistry,  5 (2), 11-16, 2015.

3. “Kinetics and Mechanism of the Reaction of Valine with Ceric Ion in the
Presence of Palladium(II) Catalyst in Acid Media”, Dhan Raj, Shanu
Mathur, Manju Bala Yadav, Vijay Devra, International Journal of
Research in Physical Chemistry,  5 (2), 11-16, 2015.

4. “Kinetic and Mechanistic Study of Oxidation of Serine by Cerium(IV) in

Presence of Manganese(II) as Catalyst in Aqueous Acid Medium” Dhan
Raj, Manju Bala Yadav, Vijay Devra, International Journal of Current
Research in Chemistry and Pharmaceutical Sciences, 2(11), 1-8, 2015.

5. “A Kinetics and Mechanistic Study of Palladium(II) Catalysed Oxidation

of Arginine by Cerium(IV) in Acid Media”, Dhan Raj, Manju Bala
Yadav, Vijay Devra, International Journal of Innovative Research in
Science, Engineering and Technology, 4 (7), 5283-5291, 2015.

194 
 
 Annexure II

Participated/Papers Presented in National/International

Conferences

1. “Kinetics and Mechanism of Oxidation of L-Valine by Osmium(VIII)

in Aqueous Alkaline Medium”, Dhan Raj, Shanu Mathur, Manju Bala
Yadav, Vijay Devra. Presented a Research Paper in 3rd International
Conference on Advance Trends in Engineering and Technology
and Research (ICATETTR-2014) at Bal Krishna Institute of
Technology, Ranpur, Kota, Rajasthan during 22nd to 24th December,
2014.

2. Dhan Raj, S. K. Meena. Presented a paper in National Conference on

Modern Trends in Chemical Sciences” (MTCS-2016) at Mohan Lal
Sukhadia University, Udaipur during 30th -31th January 2016.

3. Dhan Raj Participated in National Conference on Sustainable

Chemical and Material Science (SCMS-2016) held at S. S. Jain
Subodh P. G. (Autonomous) College, Jaipur on 5th-6th August 2016.

4. “Mn(II) Catalysed Oxidation of Arginine by Ce(IV) in aqueous acidic

medium: a kinetic and mechanistic study”. Dhan Raj, Rashmi Gupta
and Manju Bala Yadav. Presented a Poster in National Conference on
(ACEBS-2016) at Merra Girls College Udaipur, held on 10th September
2016.

5. Dhan Raj Participated in Symposium on Physical Methods in

Chemical Sciences (RSC) held at Pacific Academy of Higher
Education and Research University, Udaipur on 2nd – 3rd October 2016.

6. Dhan Raj Presented a poster in National Conference on Frontier in

Chemical Sciences held at Pacific Academy of Higher Education and
Research University, Udaipur on 2nd – 3rd October 2016.

195