ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2013, Vol. 87, No. 9, pp. 1462–1469. © Pleiades Publishing, Ltd., 2013.
1462
1
INTRODUCTION
Various natural and synthetic chemicals are inte-
grated into cosmetic, pharmaceutical and food emul-
sions to furnish them with long term stability and an
appropriate consistency. The most important are anti-
oxidants and surfactants. The objective of antioxidants
is to slow down or inhibit the chemical oxidation reac-
tion long enough for the product to be used by a con-
sumer whereas surfactants are the system structure
stabilizing agents [1, 2]. Antioxidants are usually cate-
gorized into water soluble and oil soluble groups. The
main symbolic of the hydrophilic antioxidant is natu-
rally occurring vitamin C (ascorbic acid, AH
2
) [3, 4].
Vitamin C is a white crystalline substance having
similar structure of glucose with the molecular for-
mula of C
6
H
8
O
6
[5, 6]. It is a water-soluble com-
pound, which is described by a broad spectrum of anti-
oxidant activities due to its potentiality of reacting
with numerous aqueous free radicals and reactive oxy-
gen species [7, 8]. Strong reducing power of AH
2
is due
to its small redox potential value of –0.223 V at pH 3.
However the pH as well as medium in which it is solu-
ble, affect the redox potential which in turn influence
the rate of reaction [9, 10].
1
The article is published in the original.
Surfactants (surface active agents) are amphipathic
molecules that composed of a non-polar hydrophobic
portion, usually a straight or branched hydrocarbon or
fluorocarbon chain containing 8–18 carbon atoms,
which is attached to a polar or ionic portion (hydro-
philic). The hydrophilic portion can, therefore, be
nonionic, ionic or zwitterionic [11]. Nonionic surfac-
tants, which may be acidic or basic in nature differ
from both cationic and anionic surfactants in that the
molecules are actually uncharged. Octadecylamine
(ODA, C
18
H
39
N) is nonionic basic surfactant insolu-
ble in water and soluble in organic solvents. Surfactant
molecules colligate in water above a certain concen-
tration to form colloidal particles called micelles [12,
13]. The self assembly process relies on many parame-
ters such as salinity, temperature, solvent condition,
and solvent architecture. Surfactants are used in vari-
ous applications, from cleaning products [14–18] to
nanotechnology [19–22] and are of particular rele-
vance to biological cell membrane [14, 18].
The study of electron transfer processes in surfac-
tant has added a new dimension to biological research
[23–32]. Chemical reactions in surfactant media
exhibit features that are completely different from
those in non aqueous solvents. Surfactant catalyzes the
reactions depending on the nature of surfac-
tant/micelle being as cationic, anionic, zwitterionic or
nonionic. It was found that the surfactant environ-
CHEMICAL KINETICS
AND CATALYSIS
Factors Influencing the Mechanism of Surfactant Catalyzed
Reaction of Vitamin C-Ferric Chloride Hexahydrate System
1
Muhammad Akhyar Farrukh
a
, Robina Kauser
a
, and Rohana Adnan
b
a
Department of Chemistry, GC University Lahore, Lahore 54000, Pakistan
b
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia
e-mail: akhyar100@gmail.com
Received August 24, 2012
Abstract—The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous eth-
anol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical
micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of
pH (2.5–4.5) and temperature (15–35°C) in the presence and absence of surfactant were investigated. Acti-
vation parameters, ΔE
a
, ΔH
#
, ΔS
#
, ΔG
≠
, for the reaction were calculated by using Arrhenius and Eyring plot.
Surface excess concentration (Γ
max
), minimum area per surfactant molecule (A
min
), average area occupied by
each molecule of surfactant (a), surface pressure at the CMC (Π
max
), Gibb’s energy of micellization ( ),
Gibb’s energy of adsorption ( ), were calculated. It was found that the reaction in the presence of surfac-
tant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced
in the presence and absence of surfactant.
Keywords: surfactant, vitamin C, kinetics, catalysis, thermodynamics parameters.
DOI: 10.1134/S003602441309032X
ΔG
M
°
ΔG
ad
°