International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 34-41, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

Kinetic Study of Carboxylate Ester with Hydroxamate Ions in Cationic Microemulsion System
D. K. Pandey1, C. S. Meshram2 and S. Biswas3
1, 2, 3

Shri Shankaracharya Engineering College, Junwani, Bhilai (Chhattisgarh), India

Abstract: Kinetic study of nucleophilic substitution reaction of hydroxamate ion with pnitrophenyl acetate has been performed in cationic micro-emulsion prepared from combination of weight percent of cationic surfactant (CTAB & CPC), co-surfactant nbutanol, oil-phase n-hexane and water. Conductivity behaviour on the other hand depends mainly on the weight percentage and composition of aqueous phase. The pseudo-firsorder rate constants increase with increasing weight percentage of water (W0). Kinetic model of nucleophilic substitution reactions, have been discussed. Keywords: Hydroxamate ion; Nucleophilic substitution; Micro-emulsion; PNPA.

INTRODUCTION
In resent year the micro emulsion has witnessed a significant growth of interest due to its role as unique micro reactors. Micro emulsions are clear thermodynamically stable dispersion of two immiscible liquids containing appropriate amounts of surfactants or surfactant and co surfactants. This dispersion may be either oil-in-water (O/W) or water-in-oil (W/O). The oil in water type is a dispersion of a water immiscible liquid (oil) in an aqueous phase, and the water in oil type is dispersion of water or an aqueous solution in water immiscible liquid oil[1-3]. During the past few years the chemical and electrochemical preparation of the nano-material employing microemulsion is emerging as a potential area of interest. Extensive reviews on the physicochemical and electrochemical characterization of micro-emulsions are available [4-8]. Aqueous surfactant dispersions such as micelles, micro-emulsions, vesicles etc., in addition to their ability to support rate enhancements towards electrolytic reaction, provide means for solubilisation of hydrophobic compounds in water rich media. The rate enhancement exerted by micelle is referred to as micellar catalysis. The analogous effect occurring in micro-emulsion may be called microemulsion catalysis. Large solubilisation capacities of micro-emulsion offer wider scope for their useful exploitation as reaction media. Oil in water (O/W) micro-emulsion is clear dispersion in water which generally contains an apolar solvent, a surfactant and co-surfactant. The formation of micro-emulsion is generally spontaneous when requisite quantities of water, oil, surfactant and co-surfactant are mixed in specific proportions. In recent year micro-emulsion are novel reaction media for the hydrolytic and organic reaction [9-13]. Investigation in micro-emulsion structure and property by the conductivity measurement [14-21]. Hydroxamate ions (I) are -effective nucleophiles whose reactivity are higher than that predicted by relationship between nucleophilicity and basicity [22-30]. These are effective deacylating and dephosphorylating agent [31-32]. Nucleophilic dephosphorylation of paraoxon and other carboxylate ester by the hydroxamate ions in cationic micellar media [30-31]. The 34 Corresponding Author: D. K. Pandey, Shri Shankaracharya Engineering College, Junwani, Bhilai (C.G.), India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 34-41, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

nucliophilic substitution reaction of carboxylate and phosphate esters with hydroxamate ions in micro-emulsions all ready discussed on [33]. In the present work we report the nucleophilic hydrolysis of p-nitrophenyl acetate PNPA by hydroxamate ions in cetyltrimethyl-ammonium bromide (CTAB), cetylpyridinium chloride (CPC)-n- butanol-n-hexane cationic and anionic micro-emulsion media (Scheme1).

Scheme - 1

MATERIAL AND METHOD

The cationic surfactant cityltrimethylammonium bromide, substrate p-nitrophenyl acetate, Salicylhydroxamic acid was purchased from sigma Aldrich & CPC was purchased from SD fine chemicals. The medium chain alcohol n-butanol (merk), were used as a co-surfactant. Aliphatic oil such as n-hexane (merk) were employed. All the micro-emulsion were prepared by the titration of initial composition of n-hexane (oil), surfactant & co-surfactant with aqueous buffer, for all kinetic run concentration of hydroxamic acid were mentioned 1.010-4 and 1.0103 M respectively. Buffer employed was phosphate (PH 7.7) the pKa of hydroxamic acid were determined by PH metrically using systronic (Type-335) ph-meter. 2.1 Preparation of micro-emulsion: Micro-emulsion were prepared by mixing the appropriate composition and stirred vigorously until clear. The basic composition of micro-emulsion depends on the percentage composition of water, surfactant, co-surfactant and oil. All the micro-emulsion solution based on different W0 value (Table-1). Table 1: Composition by weight % of cationic micro-emulsions ME W0 Water Surfactant n-Butanol n-Hexane 1 5 64 30 4.5 1.5 2 6 69 25 4.5 1.5 3 7 72 22 4.5 1.5 4 8 75 19 4.5 1.5 5 9 77 17 4.5 1.5 6 10 79 15 4.5 1.5 7 11.6 81 13 4.5 1.5 8 12.6 82 12 4.5 1.5 9 13.6 83 11 4.5 1.5 10 15.1 84 10 4.5 1.5 For all micro-emulsion PH maintained as per reaction condition required using 0.066 phosphate buffers. ME 1-10 were prepared with CTAB & CPC in same composition.

35 Corresponding Author: D. K. Pandey, Shri Shankaracharya Engineering College, Junwani, Bhilai (C.G.), India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 34-41, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

2.2 Conductivity measurement: The electrical conductivity of micro-emulsion was measured using a dcm-200 conductivity meter equipped with CD-06 platinum conductance electrode coated with platinum black. The conductivity was measured to 270.1c. 2.3 Kinetic measurement: All the kinetic reactions were followed at 27C with UV-300 spectrophotometer. The rate of nucleophilic reaction with PNPA were determined by following the increasing in the absorption of p-nitrophenoxide anion (400nm) for all the kinetic run the absorption time result fit very well to the first order rate equation. In (A - A0) = In (A - At) - kt

RESULT & DISCUSSION

3.1 Effect of conductivity Conductivity is also another important indication of structural variation and property of micro-emulsion. We have also measured the electric conductivity of several micro-emulsions. The increase in micro-emulsion conductivity observed when the water content is raised above the percolation threshold may result from a progressive aqueous droplets interlinking and clustering process. CTAB micro emulsions generally exhibit lower conductivity when compared to CPC micro-emulsion. It should be noted that in weight percentage composition selected for these micro-emulsion are comparatively equal. The conductivity change Table-2 depends on water percentage and surfactant. The conductivity data indicate the increasing the graph in fig.1 with increasing the water concentration & CTAB CPC showing the higher conductivity with high concentration of water. The conductivity depends on the total volume fraction of aqueous phase and its composition.

ME 1 2 3 4 5 6 7 8 9 10

W0 5 6 7 8 9 10 11.6 12.6 13.5 15.1

CTAB 4.4216 4.8291 5.4161 5.6121 5.9142 6.1211 6.5232 7.4128 7.9425 8.2318

CPC 4.6265 4.9961 5.5121 5.7134 6.1123 6.4210 7.0132 7.6452 8.4626 8.6317

Table 2: Conductivity (mScm-1) measurement of micro-emulsions measured at 27 0.1C. Fig 1: Conductivity variation with the increase in chain length of the linear oil phase employed.

36 Corresponding Author: D. K. Pandey, Shri Shankaracharya Engineering College, Junwani, Bhilai (C.G.), India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 34-41, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

3.2 Effect of water content The effect of water content (W0) of the micro emulsion system and the nucleophilic substitution is one of the parameter that have and it is reported that altering the molar ratio of water to surfactant (W0). The rate of nucleophilic reaction in oil-in-water micro-emulsion strongly depends on the water pool size, which is proportional to the ratio of the water and the surfactant concentration, W0 = H2O/CTAB. The water content W0 are presented in Table-1 the hydrolysis of PNPA with SHA of surfactant/n-butanol/n-hexane was investigated. As present Table-3 the rate constant kobs increase with W0 from ME1 to ME10. The observed super-activity becomes high, especially for high W0 value. It is deduced form these W0 dependences that the reaction occurs in the water pool of the ME. It is suggested that rate of PNPA in ME depends on W0, i.e. the size of the water pool. On the other hand the hydrophilic substrate dissolve in the water pool and reacts with nucleophile in the water pool. 3.3 Rate of reaction An increased degree of hydrolysis was noted for the reactions of p-nitrophenyl acetate with the hydroxamate ions in micro-emulsion are thermodynamically stable, optically transparent dispersion of oil and water, stabilized by an interfacial film of surfactant. Micro-emulsion has the ability to stabilize and disperse the maximum amount of substrate, enhancing the possibility of hydrolysis by the hydroxamate ion. These features arise from the fact that each of the components of reaction (water, hydrocarbon, surfactant, co-surfactant, substrate and nucleophile) has its own residence site and its own role in the reaction. This kind of self assembly inherent to microemulsions, result in the formation of an organized system that help in assisting hydrolysis. Synergistic effects of the nucleophilic catalysis and micro-emulsions are important in bringing about effective hydrolysis of the carboxylate esters. Micro-emulsion were prepared by mixing n-hexane, surfactant (CTAB, CPC) and nbutanol (co-surfactant) and titrating the slurry with water, agitating mildly to give a clear solution (Table-1). The PH of micro-emulsion solution was determined by directly immersing a glass electrode in to micro-emulsion solutions. The PH of the micro-emulsion was the same as that of the aqueous solutions, which indicate that the PH of the water content is close to that of initial buffer system. Buffer used was 0.066M phosphate buffer. Table-1 records a few of the microemulsion formulations that we prepared. All the micro-emulsions contained large weight percentage of water and therefore, regarded as o/w micro-emulsions in which micro-droplets of nhexane (oil) are dispersed in aqueous buffer. Presence of a cationic surfactant (CTAB) and cosurfactant (n-butyl alcohol), helps to stabilized these micro-emulsions recipes. Table-3 shows the kinetic rate data for the nucleophilic reactivity of the PNPA with salicylhydroxamate ion. All reaction were carried out under the reaction conditions, [PNPA]=1.010-4M, [SHA]= 1.010-3M, PH 7.7 at 27C. One of our aims was to treat reaction of anionic nucleophiles in micro-emulsions, using kinetic models which have been applied to bimolecular ionic reaction in micelle. The variation of the rate constants for nucleophilic attack by the hydroxamate ions in microemulsions, based on quaternary ammonium bromide surfactants, can be accounted for in terms of the concentration of hydroxamate ions in the micro-emulsion droplets. 37 Corresponding Author: D. K. Pandey, Shri Shankaracharya Engineering College, Junwani, Bhilai (C.G.), India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 34-41, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

Table 3: Summary of the kinetic rate data for the nucleophilic reactions of PNPA with salicylhydroxamate ion in O/W cationic cationic micro-emulsion media at 27 C. ME W0 CTAB 10 kobs(s ) 1 2 3 4 5 6 7 8 9 10 5 6 7 8 9 10 11.6 12.6 13.6 1.01 1.25 1.68 2.04 2.23 2.3 2.39 3.74 4.9
3 -1

Rate Constant CPC K2(M S ) 1.95 3.05 3.65 4.04 5.62 6.08 7.39 7.91 8.23
-1 -1

10 kobs(s ) 3.24 3.78 4.21 4.84 5.09 5.39 5.93 6.16 6.59

-1

K2(M-1 S-1) 5.32 5.53 6.04 6.43 6.99 7.27 7.88 8.21 9.87 10.75

15.1 5.16 9.95 6.97 [PNPA] = 1.0 10-4M, [SHA] = 1.0 10-3M, PH 7.7.

The first order rate constant for the reaction of PNPA have been measured spectrophotometrically under pseudo-first-order conditions at 27C, with the nucleophile in large excess over the substrates in each cases. The overall first-order rate given by kobs = k0obs + kNu [Nu-] (1) 0 k obs = kH2O + kOH- [OH ] (2) since the hydroxamate ion are -effect nucleophiles [34], so that competition with other nucleophile i.e. OH- and H2O is not expected and kobs is simply given by kobs = kNu- [Nu-] (3) catalysis by the hydroxamate ion is dependent upon the ionization state of hydroxamic acid, Eq. (4) may be written to describe kobs kobs = k2 [HA]THA(4) where k2 is second order rate constant, [HA]T the analytical concentration of hydroxamic acid and HA- is the fraction of hydroxamate ion ionized (HA- = Ka/Ka + H+). The second order rate constants determined in the way are summarized in Table-1with pseudo first order rate constants. Kinetic rate data for the reaction of PNPA with SHA shows that the pseudo-first-order rate constant increasing with increasing water contents. On going from ME 1 (1.01 103 s-1) to ME 10 (5.16 103 s-1), the rate of reaction shows 5.10 time rate enhancement for the CTAB-SHA micro-emulsion system. Cationic micro-emulsion composed of CPC is more reactive than CTAB. O/W micro-emulsion are regarded as swollen micelle and reactivity in micelle and micro38 Corresponding Author: D. K. Pandey, Shri Shankaracharya Engineering College, Junwani, Bhilai (C.G.), India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 34-41, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

emulsion are quite similar. During the nucleophilic reactivity in the cationic micro-emulsion the substrate molecules is located into hydrophobic droplet and anionic nucleophiles reside in water content. This fact is support by the decrease in rate of reaction of PNPA with SHA with decreasing water content. Schematic representation of an idealized micro-emulsion can be given as; water and nucleophile defined to the aqueous pseudo-phase, n-hexane to the oil pseudo-phase and cationic surfactants (CTAB & CPC) to the inter-phase, n-butanol and substrate are distributed between the inter-phase and the oil pseudo-phase. Second-order rate constant, k2, were calculated for the nucleophilic reaction of PNPA with hydroxamate ion, based on the assumption that reaction occurs only in inter-phase and thus involve hydroxamate ion, bound to CTA+ electro statically. Thus k2 is defined by Eq. (4), where [HA]THA- is actual concentration of hydroxamate ion in the inter-phase, and can be written as K2 = kobs/[HA-] (5) Nucleophilic reaction of anionic nucleophiles in the cationic micelle/micro-emulsion is governed by the basicity and strength of incorporation of nucleophiles in to the micelle/micro-emulsion.

CONCLUSION
In the present study the effect of the oil phase, the surfactant and the co-surfactant on the nucleophile hydrolysis of PNPA by hydroxamate ion are investigated. The electric conductivity and ion-transport behaviour of O/W micro-emulsion are determined by the weight percentage and composition of aqueous phase. Stable micro-emulsions behave as a well defined electrolytic medium for redox electrochemistry. The electron transfer property as measured by the peak separation value are measured by the limiting peak current value are found to exhibit very little variations in all the micro-emulsions investigated except one system. This is indeed true whether we employ we employ a predominantly water soluble reactant or an oil soluble reactant. This observation is true only for simple redox reactions. The medium effects may be significant for coupled chemical processes involving electro-generated cation or anion radicals. Such questions definitely deserve further investigation. The nucleophilic hydrolysis of PNPA by hydroxamate ion was determined as a function of water contents (W0) and various concentration of organic solvents in the surfactant (CTAB & CPC)/ n-butanol/n-hexane ME system. Among all the ME system the water content are most important factor that determine the reaction rate. During the nucleophilic reactivity in the cationic micro-emulsion the substrate molecule located in to hydrophobic droplet and anionic nucleophile reside in water content. This fact support to the actual result of kinetic study by the decrease in rate of reaction of PNPA with SHA with decreasing water content. The result represent that the cationic micro-emulsion CPC are more reactive than CTAB. In the current study on the base of result we concluded that the value of first and second order rate constant increase as the surfactant concentration decrease in all the ME system. This work is very important for elucidating the kinetics and mechanism of the PNPA with SHA in micro-emulsions.

39 Corresponding Author: D. K. Pandey, Shri Shankaracharya Engineering College, Junwani, Bhilai (C.G.), India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 34-41, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

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40 Corresponding Author: D. K. Pandey, Shri Shankaracharya Engineering College, Junwani, Bhilai (C.G.), India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 34-41, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

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41 Corresponding Author: D. K. Pandey, Shri Shankaracharya Engineering College, Junwani, Bhilai (C.G.), India