INTRODUCTION

1. Autocatalysis:

A single chemical reaction is said to have undergone autocatalysis, or be autocatalytic, if the reaction
product itself is the catalyst for that reaction. Autocatalytic chemical reactions are those in which the rate increases as
the materials react. The most important single factor in predicting effects is the temperature. When the temperature
changes, the rate changes.
The fundamental equation that describes an autocatalytic process is the following:
d  d t =k p(1-  )qze- E/RT
where is the fraction reacted at any specific time, t. The derivative, ddt, is the rate of the reaction. E is the
"Arrhenius activation energy," and Z is the "Arrhenius pre-exponential.
A set of chemical reactions can be said to be "collectively autocatalytic" if a number of those reactions
produce, as reaction products, catalysts for enough of the other reactions that the entire set of chemical reactions is
self sustaining given an input of energy and food molecules.

2.(a) Surfactant:

Surfactants are compounds that lower the surface tension of a liquid, the interfacial tension between two
liquids, or that between a liquid and a solid. Surfactants may act as detergents, wetting agents, emulsifiers, foaming
agents, and dispersants Surfactants or surface-active agents owe their name to their interesting behaviour at surfaces
and interfaces. Surfactants exhibit the property of amphipathy: the molecule is composed of a non-polar hydrophobic
tail and a polar hydrophilic head. Thus surfactants are amphiphillic molecules which are partly hydrophobic and
partly hydrophilic. The polar hydrophilic head group is referred to as lipophobic group and the non-polar
hydrophobic tail as lipophillic group. The head group consists of an ionic or a highly polar non ionic group while the
tail is composed of hydrocarbon chain consisting of 7 to 20 carbon atoms. The surface active agents are positively
adsorbed at the interface between the phases or at the surface of the medium. The adsorption of surfactant lowers the
interfacial tension between two immiscible liquids or the surface tension of the medium. Because of their ability to
lower interfacial tension, surfactants are used as emulsifiers, detergents, dipersing agents, foaming agents, wetting
agents and so-forth. These can also assist solubilization, dispersion and emulsification and manifest an interesting
characteristic of self aggregation or organization in solution. Also the presence of a hydrophilic group makes
surfactants slightly soluble in aqueous media, and is central to physicochemical properties of aqueous surfactant
solutions.
Broadly speaking, surfactants are classified as naturally occurring and synthetic surfactant. Lecithin, Cephalin
and Bile salts are natural surfactants also known as biosurfactants. Synthetic surfactants on the other hand are
classified on the basis of the charge carried by the polar head group as: (1) anionic, (2) cationic, (3) non ionic, (4)
zwitterionic. Some common examples are:
(i) Anionic:
CH3(CH2)nOSO3-M+ (alkyl sulfate), where n=7 to 17, M+=Li+, Na+, K+, NH4+, NMe4+, etc.
(ii)Cationic:
CH3(CH2)nN+Me3X- (alkyltrimethylammonium), where n=7 to 17, X- =Cl-, Br-, I-,OH-, NO3-,
etc.
 (iii)Non ionic:
p-t-C8H17C6H4O(CH2O)nH (octylphenoxypolyethoxyethylene alcohol) where n=2 to 10
(iv)Zwitterionic:
RN+H2CH2COO-(long chain amino acids)
Differences in the nature hydrophobic groups are usually less pronounced than in the nature of
hydrophilic group. Generally, the hydrophobic groups are long-chain hydrocarbon residues. However, they include
such different structures as:
(a) Straight-chain, long alkyl groups (C8-C20)
(b) Branched-chain, long alkyl groups (C8-C20)
(c) Long chain- (C8-C20) alkylbenzene residues
(d) Rosen Derivatives.
(e) High-molecular-weight propylene oxide polymers (polyxypropylene glycol derivatives).
(f) Long chain perfluroalkyl groups.
(g) Polysiloxane groups.
(h) Lignin derivative.

. Surfactants reduce the surface tension of water by adsorbing at the liquid-gas interface. They also reduce
the interfacial tension between oil and water by adsorbing at the liquid-liquid interface. Many surfactants can also
assemble in the bulk solution into aggregates.Examples of such aggregates are vesicles and micelles.

(b) Application of surfactants:

The property of surfactants to radically alter the surface and interfacial properties and to self associate
and solubilize themselves in micelles causes them to be applied in diverse fields. Surfactants find application in
detergency and displacement of dirt and oil. [Menger, 1984] Surfactants are often used as wetting agents in
commercial applications particularly where the wetting liquid is to be applied to a waxy or wax like surfaces. Wetting
property of surfactants is applied in pesticides and herbicides applications and also in dry cleaning fluids. Apart from
this, surfactants are used in polymerization reactions, corrosion inhibition, and lubrication [Rosen, 1989] and in
enhanced oil recovery, floatation agent in mineral extraction and processing, textiles, fibers, paints, lacquers, paper
and pulp, leather and fur, plastic and rubber, food industry, etc. Surfactants are also used as leveling agent,
solubilizier for water insoluble chemicals, suspending agents, etc.
Their use has extended to high technology areas such as electronic printing, magnetic recording,
biotechnology, nanotechnology, microelectronics, viral research. Surfactant has also diverse industrial roles such as
metal finishing, mining, mineral processing, emulsion polymerization and construction. Since surfactants stabilize
photoproducts and decrease the rate of back recombination reaction of photo sensitizer compounds like organic dye
molecules, these find immense use in storage of solar energy. [Sirvi, 2008; Jana, 2000; Bhattacharya, 1991]
Application of cationic surfactants in environmental remediation has attracted great attention recently.
Surfactants are used for removing hazardous materials from industrial waste water streams. [Scamehorn, 1986;
Christian, 1986] In the field of medicine, these are used as vehicle for pharmaceutical drug delivery. [Nagata, 1989]
In chemistry, surfactants are applied as solubilizier of sparingly soluble substances and catalyst in synthetic reactions.
[Fendler, 1975].
 (c).Micelle:
A micelle is an aggregate of surfactant molecules dispersed in a liquid colloid.A micelle is formed when
a variety of molecules including soaps and detergents are added to water. Micelles only form when the concentration
of surfactant is greater than the critical micelle concentration (CMC), and the temperature of the system is greater
than the critical micelle temperature, or Krafft temperature. The formation of micelles can be understood using
thermodynamics: micelles can form spontaneously because of a balance between entropy and enthalpy.A typical
micelle in aqueous solution forms an aggregate with the hydrophilic "head" regions in contact with surrounding
solvent, sequestering the hydrophobic single tail regions in the micelle centre. This phase is caused by the insufficient
packing issues of single tailed lipids in a bilayer. The difficulty filling all the volume of the interior of a bilayer, while
accommodating the area per head group forced on the molecule by the hydration of the lipid head group leads to the
formation of the micelle. This type of micelle is known as a normal phase micelle (oil-in-water micelle). Inverse
micelles have the headgroups at the centre with the tails extending out (water-in-oil micelle). Micelles are
approximately spherical in shape. Other phases, including shapes such as ellipsoids, cylinders, and bilayers are also
possible. Micelles composed of ionic surfactants have an electrostatic attraction to the ions that surround them in
solution, the latter known as counterions.

(d) Structure and shapes of micelles:

Micelles are characterized by an aggregation number which is the average number of surfactant
monomers constituting a micelle at moderate concentrations. [Kay, 1986; Turro,1978] Aggregation number, n usually
ranges from 10 to 150 depending on the surfactant. The size of the micelles is normally in the range of 1 to 10 nm.
[Tanford, 1980]The aggregation number of ionic surfactant increases with the increase of hydrophobic chain length
and also with the addition of neutral electrolyte.
At concentration close to CMC, the micelles are nearly spherical or ellipsoidal. [Tanford, 1980; Fendler,
1975] However when the concentration is increased, the shape of ionic micelles changes in the sequence spherical-
cylindrical-hexagonal-lamellar. For non ionic micelles, on the other hand, the shape seems to change from spherical
directly to lamellar with increasing concentration. In general, micelles of most surfactants change shape from
spherical to disc-like or rod-like at high concentrations. [Sakaiguchi, 1988; Watanabe, 1989; Kato, 1989; Zielinski,
1989]

Fig 1: Schematic representation of (a) surfactant, (b) monolayer, (c) spherical micelle, (d) reverse micelle
 The formation of micelles by ionic surfactants is determined mainly by a balance between the
hydrocarbon chain attraction and ionic repulsion of surfactant head groups. [Tanford, 1980; Moroi, 1992] However,
for non ionic surfactants, the hydrocarbon chain attraction is opposed by the requirements of hydrophilic groups for
hydration and space. Therefore, the equilibrium between the repulsive forces among hydrophilic groups and the short
range attractive forces among hydrophobic groups determine the micellar structure. In other words, the chemical
structure of a given surfactant determines the size and shape of its micelles.

(e).Micellar Catalysis:
When we talk of catalysis by surfactants, it mostly refers to micellar catalysis. The effect of surfactants
on reaction kinetics is often called micellar catalysis. A solution containing micellar aggregates is macroscopically
homogenous but microscopically it is separated into many small regions of high solute concentration (micelles)
dispersed in a solvent region. Depending on the conditions in these two environments, reaction rates will be different,
the micelle will act either as catalyst or as inhibitor i.e. the chemical reaction will either be enhanced or retarded. The
catalytic efficiency will be governed both by the affinity of the reagents for the micelles and by the reactivity of the
bound reactant molecules. The kinetics of micellar solution is governed by electrostatic and hydrophobic interactions
between reactants and micelles. [Micelles Theoretical and Applied Aspects Moroi XXXX].
The physical basis for micellar catalysis involves several contributing factors. First, there is the effect of
the micellar environment on the rate-controlling step in the reaction mechanism. The relative free energies of the
reactant(s) and/or the transition state can be altered when the reaction takes place in the micellar phase instead of the
bulk water. This concept is reminiscent of catalysis by an enzyme, and many initial studies of rates in micellar
systems focussed on this possibility[3]. However, further studies have shown that this effect is often rather small and
cannot account for the very large rate changes in many micellar systems.
Some examples of micelle catalyzed reactions are electrochemical reactions, [Rusling 1991]
electrophillic and nucleophillic reactions, redox reactions, and hydrolysis and electron transfer reactions. Electron
donor acceptor and proton transfer equilibria are also affected by micelles. [Moulik, 1977 & 1979] Micellar catalysis
of acid dissociation reaction is known to shift acid base equilibria of indicator dyes in micellar solutions. Micellar
catalysis is also involved in dye surfactant interactions.

(f) Kinetics of micellar catalysis:

When we talk of micellar catalysis, we consider the following schematic representation of the different
regions in the micelle for better understanding.
 In a spherical micelle as shown above, the surfaces highly polar (has high magnitude of potential), the Stern
layer is of intermediate polarity while the hydrocarbon core is highly non polar. Micelles enhance the chance of
contact between substrate and reactant. The high potential on the surface provide alternative path for reaction with
lower activation energy. Thus micelles act as a catalyst when the reactant and substrate have same charge as micelle
and are hydrophobic, there will be attraction with micelle and if less hydrophobic, rate will not be affected. On the
other hand if reactant and substrate have opposite charges, then the one out of the two which has opposite charge with
micelle will be adsorbed on micelle and will be far away from the other. So the rate will be slowed and micelle act as
negative catalyst. The mechanism of micellar catalysis can be given as:

km is the rate constant in presence of micelle, ko is the rate constant in absence of micelle, kp is the observed rate
constant.
Therefore,
kp = ko[S] + km[MS]
The equilibrium constant, K is
K= [MS]\ [M][S]
or, kp=ko[S]o + kmK[M][S]
or, kp=(ko + kmK[M]) [S]o
or, kp=(ko + kmK[M]) Fo
where, Fo is the fraction of the substrate in free form and Fm is the fraction of the substrate in bound form.
Now,
Fo+Fm=1
So,

K=Fm/[M] Fo=(1-Fo)\[M] Fo
or, K [M] Fo=1-Fo
or, K [M] FO+Fo=1
or, Fo (1+K [M])=1
or, Fo=1/ (1+K [M])
Since,
kp= (ko+kmK[M]) Fo
Therefore,
kp= (ko+kmK[M]) 1\1+K[M]
or, (ko+kmK [M])\1+K [M]
 or, kp (1+k[M])=ko+kmk[M]
or, (kp-ko) = (km-kp)K[M]
or, (ko-kp) = (kp-km)K[M]
As we know, till CMC micelle is not formed but above it, micelles form. So, the additional surfactant
concentration is the micelle concentration. Hence,
[M]=[C]-[CMC]\N,
where N is the aggregation number.
Therefore,
ko-kp=(kp-km)K([C]-[CMC])\N
or, 1\(ko-kp)=1(ko-km)+1\(ko-km).N\K([C]-[CMC])
Since the overall rate constant for the reaction kp and the rate constant for the reaction in the absence of
micelles ko are obtained from kinetic data by plotting 1/(ko-kp) versus [1/(C-CMC)], which should be a straight line
with slope = N/K(ko-kp) and intercept = 1/(ko-km), that allows the calculation of km, the rate constant for the substrate
complex with the micelle, and K, the binding constant of the substrate to the micelle.(1)

(g) Critical micelle concentration:

In concentrated solutions, at a particular concentration the surface or interface of the system becomes
saturated and the surfactant molecules start self aggregating into clusters with the hydrophobic tail towards the
interior of the cluster and the hydrophilic head towards the solvent. This particular concentration in which cluster
formation starts is a characteristics of the surfactant, called the Critical Micellar Concentration (CMC). The IUPAC
definition of CMC is - “There is a relatively small range of concentration separating the limit below which virtually
no micelles are detected and the limit above which virtually all the additional surfactants form micelles.The CMC is
an important characteristic of a surfactant. Before reaching the CMC, the surface tension changes strongly with the
concentration of the surfactant. After reaching the CMC, the surface tensions remains relatively constant or changes
with a lower slope. Micelles only form above critical micelle temperature.
The CMC of surfactants are known to depend on number of factors, viz., (1) the length and structure of
hydrocarbon chain, (2) the head group, (3) the presence of additives (4) the temperature.[Huibers, 1996; Dasgupta,
1989; Saenger, 1988; Fendler,1975] The CMC decreases with the increase of the hydrophobicity of the hydrophobic
tail.
CMC of some common surfactant at 298K in water are as follows:

Surfactant CMC/mol dm-3

Sodium dodecyl sulphate (SDS) 8.0×10-3
Sodium dodecyl benzene sulfonate (SDBS) 1.2×10-3
Iso-octylphenoxy-polyethoxy-ethanol (Triton X-100) 3×10-5
N-Hexadecyl (cetyl) pyridinium bromide (CPB) 9.2×10-4
N-Hexadecyl (cetyl) pyridinium chloride (CPC) 9.0×10-4
N-Hexadecyl trimethyl ammonium bromide (CTAB) 9.2×10-4
Dodecyl trimethyl ammonium bromide (BTAB) 1.6×10-2
Dodecyl benzene sulfonic acid 5.51×10-4

The CMC of surfactants are known to depend on number of factors, viz., (1) the length and structure of
hydrocarbon chain, (2) the head group, (3) the presence of additives (4) the temperature. The CMC decreases with the
increase of the hydrophobicity of the hydrophobic tail.
 3.Autocatalysis by colloidal Manganese dioxide in oxidation of Potassium permanganate with Glycine:

( i ) Current status based on literature:

The oxidation of glycine has been studied from mechanistic point of view with potassium
permanganate in aqueous phosphate buffers by Joaquin et al [1], where the reaction is auto catalyzed by one of the
products, colloidal manganese dioxide. Both catalytic and non catalytic paths have been studied by the authors
wherein the order with respect to permanganate was found to be one but with glycine, the catalytic path showed unit
order and the non catalytic path showed a non integral order of 1.3. Later, uncatalyzed and the surfactant catalyzed
oxidation of glycine by acidic permanganate[2] have been studied in which the reaction followed first order
dependence in both glycine and permanganate. So, in order to gain further insight into the mechanism of oxidation of
glycine, the author has taken up the kinetics and mechanism of its oxidation by permanganate in alkaline medium.
The kinetics of oxidation of non-ionic surfactant (Triton X-100) by potassium permanganate in
aqueous H2SO4 medium has been studied in by Pragya Shukla and Santosh K upadhya.
The effects of cetyltrimethylammonium bromide (CTAB), sodiumdodecyl sulphate (SDS) and Triton
X-100 (TX-100) on the oxidative degradation of ethylenediaminetetraacetic acid (EDTA) by MnO4− have been
studied by Maqsood Ahmad Malik, Zaheer Khan, Department of Chemistry, Jamia Millia Islamia (Central
University), Jamia Nagar, New Delhi 110025, India.
Kinetics and mechanism of oxidation of glycine by permanganate in alkaline medium has been
studied by TVN Partha Sarathi1, B Dharma Rao2, G Nageswara Rao2 and P Vani 2*
. 1
M.V.G.R.College of
2*
Engineering, Vizianagaram-535 005, India. Dept. of Inorganic and Analytical Chem, School of Chemistry, Andhra
University, Visakhapatnam-530 003, India.
The kinetics of oxidation of valine by permanganate ion in high [sulphuric acid] (=3.0–5.0 mol dm−3)
has been by A.Mucientes, F.J. Poblete, J. Casade.

(ii) Lacuna in the study:

Autocatalytic reaction pathway on colloidal manganese dioxide in permanganate oxidation of glycine
in aqueous phosphate buffer has been investigated but the details of glycine-permanganate reactions are not yet
known in the presence of surfactants. However, only a few reports [13-14] are available to reveal, how a surfactant
behaves when it interacts with oxidants, but there is no such information about autocatalytic reaction pathway by
manganese dioxide in permanganate oxidation of glycine in the presence of surfactant. It was, therefore, thought of
interest to the role of various surfactants (cationic, anionic and non-ionic) in the permanganate oxidation of glycine.

4. Rational of the work:

Although Joaquin F. Perez-Beneto studied autocatalytic reaction pathway on manganese dioxide
colloidal particles in the permanganate oxidation of glycine yet there is no such information regarding different
surfactants. Therefore I have choosen the work using surfactant. The utilization of surfactant as reaction media
affects rates, products, and in some cases, stereochemistry of the reaction.
Surfactants have attracted considerable interest in theoretical and experimental fields due to their
catalytic effects and behaviour as analogous to biological membranes. They have a tendency to associate i.e. at a
certain concentration in solution their monomers associate to form larger aggregates. Surfactants dissolve completely
in water at very low concentration, but above a certain concentration, they have a tendency to associate i.e. at a
certain concentration in solution, their monomers associate to form larger micelle aggregates. This concentration is
characteristic for each surfactant and is termed critical micelle concentration (cmc).

5. Strategies of the work:

• In the present study, the progress of the reaction of permanganate oxidation of glycine has been studied
by monitoring with UV-vis spectrophotometer.
• Non-ionic (TX-100), Cationic (CTAB) and Anionic (Dodecylbenzene sulphonic acid) surfactant has
been used in the present study as the surfactant affects the rate and product of the reaction.
• Phosphate buffer solution has been prepared for keeping the pH of the medium constant and for
stabilizing manganese dioxide as a soluble colloid.
• The pH of the buffer solution has been recorded.
• Potassium permanganate solution with low concentration has been prepared in buffer solution.
• Glycine solution with concentration higher than potassium permanganate solution has been prepared in
buffer solution.
• Surfactant (TX-100, CTAB, Dodecylbenzene sulfonic acid) solutions has been prepared in buffer
solution.
• The UV-VIS spectra of the experimental solutions have been recorded at two different wavelength i.e.,
at 526nm and 418nm.

EXPERIMENTAL:

i. Materials:
In this experiment glycine(reducing agent) was used in large exess than potassium permanganate(oxidizing
agent). A KH2PO4-K2HPO4 buffer mixture was used in all the experiments. The purpose of
using buffer mixture is to keeping the pH of the medium constant and to stabilizing manganese dioxide as a
soluble colloid. Also potassium chloride was used in this experiment to anayse the effect of increasing ionic strength
on the rate of the reaction. The kinetic runs were followed with UV-vis spectrophotometer using
thermostatized glass cells (cuvette of optical path length 1 cm), and measuring both the
decay of MnO4- at 526 nm and the formation of colloidal MnO2 at 418 nm.

\ii. Kinetic method:

The permanganate concentrations at different instants during the course of reaction were obtained according
to the following equation:

where the numbers in parentheses indicate wavelengths, εR and εP are the molar absorption coefficients of the reactant
(MnO4-) and product (colloidal MnO2), respectively, and l is the optical path length (1cm). The above equation
doesnot require that εP(418) and εP(526) be constant during the kinetic runs, but only their ratio, and it is thus useful
for correcting absorbances in a reaction involving a colloidal product such as MnO2.
The reaction rates at different instants during the course of the reaction were obtained from the permanganate
concentration data by an approximate derivation method:
applied at short time intervals (Δt = 1-3 min), and where c represents the permanganate concentration at time t.

iii. Preparation of solutions:

Table 1: Preparation of Buffer solution:

Serial Amount Concentration in final

Materials Water (ml)
number (gm) solution(mol/dm3)
1 KCl 23.86 1000 0.32
KH2PO4
2 6.53 1000 0.048

Na2HPO4
3 6.82 1000 0.048

Table 2: Preparation of Potassium permanganate solution:

Serial Potassium Buffer solution Concentration in final

number permanganate (gm) (ml) solution(mol/dm3)
1 0.071118 250 6×10-4

Table 3: Preparation of Glycine solution:

Buffer solution Concentration in final

Serial number Glycine(gm)
(ml) solution(mol/dm3)

1 9.0084 250 0.16

Table 4: Preparation of Triton X-100 :

Serial Triton X- Concentration in final

Buffer solution(ml)
number 100(ml) solution(mol/dm3)
1.2× 10-3
1 0.07265 250

Table 5: Preparation of Dodecylbenzene sulfonic acid :

Serial number Dodecylbenzene Buffer solution (ml) Concentration in final solution
 sulfonic acid (gm)
1 0.8712 250 1×10-2

Table 5: Preparation of CTAB:

Serial number CTAB (gm) Buffer solution (ml) Concentration in final solution

1 0.5467 250 6×10-3

Table 6: Preparation of Experimental solutions:

Serial number Potassium Glycine solution Buffer solution Surfactant Surfactant
permanganate (ml) (ml) solution concentration in
solution (ml) final solution
(mol/dm3)
1 10 10 10 0 0
2 10 10 0 10 (non-ionic) 1.2×10-3
3 10 10 0 10 (anionic) 1×10-2
4 10 10 0 10 (cationic) 6×10-3
 RESULTS AND DISCUSSION:

A. Absorbance Plot:
The plot of A(526)t-A(526)r against A(418)t-A(418)r at different instants t during the course of the
reaction has been shown in the figure below.

Fig 3. Plots of A(526) t - A(526)r against the absolute value of A(418)t - A(418)r at different instants t
during the course of the reaction of KMnO4 (6 × 10-4 M) with glycine (0.16 M) in KH2PO4 (0.048 M)-Na2HPO4 (0.048
M) buffer at ionic strength 0.320 M (KCl), pH 6.80, and 25.0 °C. Fixed references: either first absorbances [A(418)r =
0.0502, A(526)r = 1.413,] or last absorbances [A(418)r = 0.256, A(526)r = 0.518,] recorded.

As shown in above figure, a plot of A(526)t - A(526)r vs A(418)t - A(418)r led to a straight line passing
through the origin whether the first absorbances or the last absorbances recorded were taken as reference. This allows
us to conclude that only two absorbing species (MnO4- and colloidal MnO2) were present in the reacting system, and
that the existence of long lived intermediates could be discarded. Also confirmed by above figure that all the
manganese intermediates are present in negligible concentration (in steady state).

B. Rate Plots :
The rate versus time plots for permanganate oxidation of glycine near-neutral aqueous solution in the
absence and presence of surfactant has been shown in figure below.
 rate vs time plot
0.65

0.6

0.55
v/10 -3 Mmin -1

0.5

0.45

0.4

0.35
0 10 20 30 40 50 60 70 80 90 10 11 12 13 14 15 16
0 0 0 0 0 0 0
time(min)

Fig 3: Rate vs time plot for KMnO4(1.8×10-3M) oxidation of glycine(0.48m) in

KH2PO4(0.048M)-Na2HPO4(0.048M) buffer at ionic strength (KCl), pH 6.80 and 25oC in the absence of surfactant.

rate vs time plot

0.65

0.6

0.55
-1
v/10 Mmin

0.5
-3

0.45

0.4

0.35
0 10 20 30 40 50 60 70 80 90 10 11 12 13 14 15 16
0 0 0 0 0 0 0
time(min)

Fig 4: Rate vs time plot for KMnO4(1.8×10-3M) oxidation of glycine(0.48m) in

KH2PO4(0.048M)-Na2HPO4(0.048M) buffer at ionic strength (KCl), pH 6.80 and 25oC in the presence of Triton X-
100(1.2×10-3M).
 rate vs time plot
0.65

0.6

0.55

-1
v/10 Mmin
0.5

-3
0.45

0.4

0.35
0 10 20 30 40 50 60 70 80 90 10 11 12 13 14 15 16
time(min) 0 0 0 0 0 0 0

Fig5: Rate vs time plot for KMnO4(1.8×10-3M) oxidation of glycine(0.48m) in

KH2PO4(0.048M)-Na2HPO4(0.048M) buffer at ionic strength (KCl), pH 6.80 and 25oC in the presence of
Dodecylbenzenesulphonicacid(1×10-2M).

rate vs time plot

0.605

0.6
v/10 -3 Mmin -1 `

0.595

0.59

0.585

0.58
0 10 20 30 40 50 60 70 80 90 10 11 12 13 14 15 16
0 0 0 0 0 0 0
time (min)

Fig 6: Rate vs time plot for KMnO4(1.8×10 -3M) oxidation of glycine(0.48m) in

KH2PO4(0.048M)-Na2HPO4(0.048M) buffer at ionic strength (KCl), pH 6.80 and 25oC in the presence of
CTAB(6×10-3M).
 Fig 6: Rate vs time plot for KMnO4(1.8×10-3M) oxidation of glycine(0.48m) in
KH2PO4(0.048M)-Na2HPO4(0.048M) buffer at ionic strength (KCl), pH 6.80 and 25oC in the absence of and
presence of surfactant.

The permanganate oxidation of glycine in near-neutral aqueous solutions is strongly autocatalytic, as

evidenced by the occurrence of bell-shaped when the reaction rate is plotted against time[27].
The following mechanism can be proposed for the autocatalytic reaction pathway:

In the presence of CTAB the rate is independent of time. The slope of the rate vs time plot does not indicate
significant autocatalysis. However, the rate of the reaction is high throughout. The reaction may be catalysed by the
cationic micelles of CTAB. This may be due to the partition of glycine (negatively charged) to the cationic micelle
surface where the reaction is catalysed by both the micelle surface.
In the presence of the non-ionic micelles the autocatalysis is initially unaffected by the micelles. But the
autocatalysis steeply decreases after about 70 minute whereas in absence of the surfactants the autocatalysis starts
decreasing only after about 90 minute.
In the presence of Dodecylbenzene sulfonic acid, the anionic surfactant micelles, the rate vs time curve is more
obtuse than that in absence of any surfactant. The autocatalysis is greater initially and continues for more time
compared to that in absence of any surfactant.