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Effect of micellar aggregate on the kinetics and mechanism of the reaction between ethylene glycol and periodate.

1. Introduction

Micelles are ultramicroscopic units in colloids and possess all the physical properties of colloid [1]. They are formed as earlier indicated as a result of aggregation of three or more molecules of surfactant existing in a particular liquid medium in thermodynamically stable equilibrium that create highly anisotropic interfacial region lining the boundary formed by polar aqueous and nonpolar hydrocarbon regions, impacting new chemical and physical properties to the system [2-7]. Determination of reaction rates in micellar is usually based on the pseudophase mode [1], which treats aqueous, organic, and/or surfactant components of the solvent medium as constituting distinct phases in which reaction occurs and between which reagent and product are distributed in accordance with conventional laws of kinetic and mass transfer.

Many substrates have been oxidized using periodate as oxidant [8]. Periodate as an oxidant has been used severally in organic chemical reaction [9]. It has the greatest application in the field of alcohol and carbohydrate chemistry [10]. Under controlled conditions, periodate will selectively oxidize 1,2-diol, 1,2-amino alcohols, 1,2-hydroxyl aldehyde, and ketones and various other groupings [11]. Periodate oxidation has a lot of advantages which are responsible for its being widely studied. For example, it can be applied in aqueous solution over a wide range of pH. Ethylene glycol is an organic compound primarily used as a raw material in the manufacture of polyester fibers and fabric industry. A small percent is used in industrial application like antifreeze formulation and other industrial products. The kinetic oxidation of ethylene glycol by various oxidizing agents has been investigated and was found to involve two electron transfers through the formation of a negatively charged cyclic intermediate.

Kinetics and mechanism of the reaction between ethylene glycol and periodate in micellar system remain unexplored. In this work, I have explored the effect of cationic (cetyltrimethylammonium bromide, CTABr) and nonionic (dodecyl amine, DA) surfactant micelles on the kinetics and mechanism of the reaction between ethylene glycol and periodate.

2. Experiment

Cetyltrimethylammonium bromide (CTABr) from Fluka, dodecyl amine (DA) from Sigma, and sodium periodate from BDH (99% pure) were used without further purification. Ethylene glycol (BDH) was purified by simple distillation. The water used in the preparation of solution was doubly distilled.

2.1. Kinetic Measurements. Reaction kinetics were studied on the Perkin-Elmer UV/Vis spectrophotometer, Lambola E 2150, using a cell of path length 1cm by recording the change in absorbance due to disappearance of periodate (at 225.4 mn) in a thermostated reaction cell. The concentration of ethylene glycol was kept in large excess over the concentration of periodate. The kinetics were studied by the integration method. The integrated first order equation is as follows:

ln ([A.sub.t] - [A.sub.[infinity]]) = ln ([A.sub.0] - [A.sub.[infinity]]) - [k.sub.0]t, (1)

where [A.sub.0], [A.sub.t], and [A.sub.[infinity]] are the absorbance time zero, t, and infinity was fitted to the kinetic data by using algorithm to give the first order pseudoconstant [k.sub.0] ([k.sub.0] = observed rate constant). The value of the observed rate constant was reproducible within the experimental error (3%).

2.2. Critical Micelle Concentration (CMC) Determination. The conductivity measurement was performed with Jenway 4510 digital conductometer using a dip-type cell of constant 0.88 [cm.sup.-1]. All measurements were done in a jacketed vessel, maintained at desired temperature, with circulating water thermostat bath. The conductometric method was used to determine the CMC value of CTABr and DA solution at different experimental conditions: CTABr, and DA only, CTABr + [IO.sup.-.sub.4], CTABr + EG, DA + [IO.sup.-.sub.4], and DA + EG.

The CMC value was determined from the specific conductivity versus [CTABr] and [DA] in the presence and absence of [IO.sup.-.sub.4] and EG. The CMC was determined from the break of specific conductance versus surfactant concentration plots [12]. The CMC was found to be 9.1 x [10.sup.-4], 1.54 x [10.sup.-4], 9.7 x [10.sup.-4], 1.01 x [10.sup.-3], 2.06 x [10.sup.-4], and 1.50 x [10.sup.-4] mol/d[m.sup.3] for water + CTABr, water + DA, CTABr + [IO.sup.-.sub.4] (1.051 x [10.sup.-5] mol/d[m.sup.3]), CTABr + EG (3.580 x [10.sup.-3] mol/d[m.sup.3]), DA + [IO.sup.-.sub.4] (4.20 x [10.sup.-5] mol/d[m.sup.3]), and DA + EG (2.87 x [10.sup.-3] mol/d[m.sup.3]), respectively, at 25[degrees]C as shown in Tables 1(a) and 1(b).

3. Result and Discussion

3.1. Reaction in the Presence of CTABr. The reaction was carried out in the presence of CTABr (0.000-2.743) x [10.sup.-4] mol d[m.sup.3] and fixed concentration of EG and [IO.sup.-.sub.4]. Addition of CTABr results in partial increase in rate up to the concentration of 1.83 x [10.sup.-4] mol/d[m.sup.3] after which inhibition predominate as shown in Figure 1.

The initial catalytic role of CTABr below 1.83 x [10.sup.-4] mol/ d[m.sup.3] can be explained on the fact that small aggregate of the CTABr exists below the CMC which interacts physically with the reactants forming active entities. Therefore, the catalytic role is due to the presence of premicelle and preponement of micellization by reactant; the two reactants are assumed to have penetrated the stern layer electrostatically [13]. Below 1.83 x [10.sup.-3] mol/d[m.sup.3] of CTABr, inhibition occurs.

These could be interpreted using the kinetic model of the pseudophase proposed by Menger and Portnoy [14], which, taking the micelles as a pseudophase uniformly distributed in the aqueous phase, put forward a reaction scheme with a micelle-substrate equilibrium governed by an equilibrium constant [K.sub.s] (Scheme 1). This scheme represents the micellized surfactant as Dn where [Dn] = [D] - CMC and [D] is the concentration of surfactant where m and w refer to the micellar and aqueous pseudophases, respectively. The scheme predicts a value for [k.sub.ob] given by (2) which is the overall reaction rate. This value is equal to the rates at the micellar and aqueous pseudophases (Scheme 1)

[k.sub.ob] = [k.sub.w] + [k.sub.s][k.sub.m] [Dn]/1 + [k.sub.s] [Dn]. (2)

The inhibition observed occurs because of the low concentration of [IO.sup.-.sub.4] near the cationic surface causing the reactivity of the associated substrate to be much less than that of the substrate in the aqueous phase preventing the formation of [EG. [IO.sup.-.sub.4]] adduct.

If [k.sub.m] = 0, [IO.sup.-.sub.4] is completely excluded from the stern layer of the micelle and 2) becomes

[k.sub.ob] = [k.sub.w]/1 + [k.sub.s] [Dn], (3)

where [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] represents the observed rate constant in the absence of surfactant.

Rearrange (3) to obtain

[k.sub.w] - [k.sub.ob]/[k.sub.ob] = K([D]- CMC). (4)

The CMC of CTABr and DA has been obtained as earlier discussed.

3.2. Reaction in the Presence of DA. The reaction was also studied in the presence of DA and the result (Figure 2) can be interpreted in the same way.

4. Conclusion

The result shows a biphasic pattern in both CTABr and DA. The reaction rate passes through a maximum as the surfactant concentration increases. This is due to two competing effects in the ion-exchange model. Added surfactant increases the relative concentration of EG and [IO.sup.-.sub.4] in the stern layer which increases the reaction rate as shown by the ascending branch of the curve. As the concentration of CTABr and DA increases, the concentration of the reagent in the micellar pseudophase decreases and furthers the excess of unreactive [IO.sup.-.sub.4] in the stern layer so that the reaction rate decreases. Finally, it can be concluded that, within the experimental range of studies, the pseudophase ion-exchange model has been found to be successful in explaining the result obtained in the kinetics and mechanism of the reaction between ethylene glycol and periodate in micellar system.

Conflict of Interests

The author declares that there is no conflict of interests regarding the publication of this paper.


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Olaseni Segun Esan

Department of Chemical Sciences, Adekunle Ajasin University, PMB 001, Akungba-Akoko, Nigeria

Correspondence should be addressed to Olaseni Segun Esan;

Received 28 May 2014; Revised 13 August 2014; Accepted 25 August 2014; Published 29 October 2014

Academic Editor: Sinem Goktiirk

Table 1: (a) Effect of substrate on the micellization
of CTABr at 25[degrees]C.
(b) Effect of substrate on the micellization of DA
at 25[degrees]C.


CTABr + substrate          CMC x [10.sup.-4] mol d[m.sup.3]

CTABr                                    9.10
CTABr + [IO.sup.-.sub.4]                 9.70
CTABr + EG                               0.101


DA + substrate             CMC x [10.sup.-4] mol d[m.sup.3]

DA                                       1.54
DA + [IO.sup.-.sub.4]                    2.86
DA + EG                                  1.50
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Title Annotation:Research Article
Author:Esan, Olaseni Segun
Publication:International Scholarly Research Notices
Article Type:Report
Geographic Code:6NIGR
Date:Jan 1, 2014
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