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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 t =k d p(1- )qze- E/RT where is the fraction reacted at any specific time, t. The derivative, ddt, 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.
1986] In the field of medicine. Jana. mineral processing.(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. viral research. Since surfactants stabilize photoproducts and decrease the rate of back recombination reaction of photo sensitizer compounds like organic dye molecules. Apart from this. solubilizier for water insoluble chemicals. (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. 1991] Application of cationic surfactants in environmental remediation has attracted great attention recently. (g) Polysiloxane groups. fibers. surfactants are used in polymerization reactions. Surfactant has also diverse industrial roles such as metal finishing. plastic and rubber. and lubrication [Rosen. mining. suspending agents. these are used as vehicle for pharmaceutical drug delivery. paper and pulp. . Wetting property of surfactants is applied in pesticides and herbicides applications and also in dry cleaning fluids. Surfactants are also used as leveling agent. However. 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. [Scamehorn. microelectronics. Surfactants reduce the surface tension of water by adsorbing at the liquid-gas interface. Surfactants find application in detergency and displacement of dirt and oil. Christian. paints. floatation agent in mineral extraction and processing. [Fendler. (h) Lignin derivative. Surfactants are used for removing hazardous materials from industrial waste water streams. 1986. they include such different structures as: (a) Straight-chain. Bhattacharya. 1989] In chemistry. long alkyl groups (C8-C20) (c) Long chain. lacquers. (e) High-molecular-weight propylene oxide polymers (polyxypropylene glycol derivatives). Many surfactants can also assemble in the bulk solution into aggregates. these find immense use in storage of solar energy. Generally. biotechnology. etc. 2008.(C8-C20) alkylbenzene residues (d) Rosen Derivatives. [Menger. [Sirvi. 1975]. 2000. food industry. emulsion polymerization and construction. 1989] and in enhanced oil recovery. the hydrophobic groups are long-chain hydrocarbon residues. corrosion inhibition. magnetic recording. [Nagata. textiles. . Their use has extended to high technology areas such as electronic printing. surfactants are applied as solubilizier of sparingly soluble substances and catalyst in synthetic reactions. leather and fur. long alkyl groups (C8-C20) (b) Branched-chain.Examples of such aggregates are vesicles and micelles. etc. They also reduce the interfacial tension between oil and water by adsorbing at the liquid-liquid interface. nanotechnology. (f) Long chain perfluroalkyl groups.
Watanabe. 1989. and bilayers are also possible. The formation of micelles can be understood using thermodynamics: micelles can form spontaneously because of a balance between entropy and enthalpy. The difficulty filling all the volume of the interior of a bilayer. [Sakaiguchi. Kato. Micelles only form when the concentration of surfactant is greater than the critical micelle concentration (CMC). [Kay. 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.1978] Aggregation number. [Tanford. cylinders. Micelles are approximately spherical in shape. the micelles are nearly spherical or ellipsoidal. [Tanford. This type of micelle is known as a normal phase micelle (oil-in-water micelle).Micelle: A micelle is an aggregate of surfactant molecules dispersed in a liquid colloid. n usually ranges from 10 to 150 depending on the surfactant. 1986. Other phases. (d) reverse micelle . Zielinski. 1975] However when the concentration is increased. the shape seems to change from spherical directly to lamellar with increasing concentration. micelles of most surfactants change shape from spherical to disc-like or rod-like at high concentrations. For non ionic micelles. and the temperature of the system is greater than the critical micelle temperature. or Krafft temperature. (b) monolayer.A micelle is formed when a variety of molecules including soaps and detergents are added to water. The size of the micelles is normally in the range of 1 to 10 nm. This phase is caused by the insufficient packing issues of single tailed lipids in a bilayer. Fendler. (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. Micelles composed of ionic surfactants have an electrostatic attraction to the ions that surround them in solution. 1980. on the other hand. the shape of ionic micelles changes in the sequence sphericalcylindrical-hexagonal-lamellar.A typical micelle in aqueous solution forms an aggregate with the hydrophilic "head" regions in contact with surrounding solvent. At concentration close to CMC. 1988. 1980]The aggregation number of ionic surfactant increases with the increase of hydrophobic chain length and also with the addition of neutral electrolyte. 1989. In general. Turro. 1989] Fig 1: Schematic representation of (a) surfactant.(c). including shapes such as ellipsoids. Inverse micelles have the headgroups at the centre with the tails extending out (water-in-oil micelle). the latter known as counterions. sequestering the hydrophobic single tail regions in the micelle centre. (c) spherical micelle.
the equilibrium between the repulsive forces among hydrophilic groups and the short range attractive forces among hydrophobic groups determine the micellar structure. redox reactions. there is the effect of the micellar environment on the rate-controlling step in the reaction mechanism.e. the chemical reaction will either be enhanced or retarded. it mostly refers to micellar catalysis. 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. we consider the following schematic representation of the different regions in the micelle for better understanding. (f) Kinetics of micellar catalysis: When we talk of micellar catalysis. Micellar catalysis is also involved in dye surfactant interactions. the chemical structure of a given surfactant determines the size and shape of its micelles.Micellar Catalysis: When we talk of catalysis by surfactants. further studies have shown that this effect is often rather small and cannot account for the very large rate changes in many micellar systems. Depending on the conditions in these two environments. [Rusling 1991] electrophillic and nucleophillic reactions. the micelle will act either as catalyst or as inhibitor i. First. [Micelles Theoretical and Applied Aspects Moroi XXXX]. The effect of surfactants on reaction kinetics is often called micellar catalysis. The physical basis for micellar catalysis involves several contributing factors. the hydrocarbon chain attraction is opposed by the requirements of hydrophilic groups for hydration and space. However. 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. Moroi. reaction rates will be different. Some examples of micelle catalyzed reactions are electrochemical reactions. and many initial studies of rates in micellar systems focussed on this possibility. (e). Electron donor acceptor and proton transfer equilibria are also affected by micelles. 1980.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. Therefore. 1992] However. In other words. . 1977 & 1979] Micellar catalysis of acid dissociation reaction is known to shift acid base equilibria of indicator dyes in micellar solutions. The kinetics of micellar solution is governed by electrostatic and hydrophobic interactions between reactants and micelles. [Tanford. This concept is reminiscent of catalysis by an enzyme. for non ionic surfactants. 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. and hydrolysis and electron transfer reactions. [Moulik.
In a spherical micelle as shown above. kp is the observed rate constant. The high potential on the surface provide alternative path for reaction with lower activation energy. Since. the Stern layer is of intermediate polarity while the hydrocarbon core is highly non polar. or. kp = ko[S] + km[MS] The equilibrium constant. kp= (ko+kmK[M]) 1\1+K[M] or. (ko+kmK [M])\1+K [M] K [M] Fo=1-Fo K [M] FO+Fo=1 Fo (1+K [M])=1 Fo=1/ (1+K [M]) kp=ko[S]o + kmK[M][S] kp=(ko + kmK[M]) [S]o kp=(ko + kmK[M]) Fo where. Fo+Fm=1 So. or. 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. Micelles enhance the chance of contact between substrate and reactant. Therefore. the surfaces highly polar (has high magnitude of potential). or. ko is the rate constant in absence of micelle. kp= (ko+kmK[M]) Fo Therefore. The mechanism of micellar catalysis can be given as: km is the rate constant in presence of micelle. Thus micelles act as a catalyst when the reactant and substrate have same charge as micelle and are hydrophobic. Fo is the fraction of the substrate in free form and Fm is the fraction of the substrate in bound form. or. So the rate will be slowed and micelle act as negative catalyst. K is K= [MS]\ [M][S] or. Now. there will be attraction with micelle and if less hydrophobic. or. rate will not be affected. . K=Fm/[M] Fo=(1-Fo)\[M] Fo or. On the other hand if reactant and substrate have opposite charges.
. [M]=[C]-[CMC]\N. After reaching the CMC.. 1\(ko-kp)=1(ko-km)+1\(ko-km).1975] The CMC decreases with the increase of the hydrophobicity of the hydrophobic tail. or. CMC of some common surfactant at 298K in water are as follows: Surfactant Sodium dodecyl sulphate (SDS) Sodium dodecyl benzene sulfonate (SDBS) Iso-octylphenoxy-polyethoxy-ethanol (Triton X-100) N-Hexadecyl (cetyl) pyridinium bromide (CPB) N-Hexadecyl (cetyl) pyridinium chloride (CPC) N-Hexadecyl trimethyl ammonium bromide (CTAB) Dodecyl trimethyl ammonium bromide (BTAB) Dodecyl benzene sulfonic acid CMC/mol dm-3 8. 1989. 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. Fendler. Dasgupta. The CMC of surfactants are known to depend on number of factors. (1) the length and structure of hydrocarbon chain. Before reaching the CMC. the binding constant of the substrate to the micelle. called the Critical Micellar Concentration (CMC). (1) the length and structure of hydrocarbon chain.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)]. that allows the calculation of km.2×10-4 1.[Huibers.51×10-4 The CMC of surfactants are known to depend on number of factors.(1) (g) Critical micelle concentration: In concentrated solutions. So. Micelles only form above critical micelle temperature. The CMC decreases with the increase of the hydrophobicity of the hydrophobic tail. micelles form. the rate constant for the substrate complex with the micelle. the surface tensions remains relatively constant or changes with a lower slope. This particular concentration in which cluster formation starts is a characteristics of the surfactant.6×10-2 5. 1988. The IUPAC definition of CMC is . (2) the head group. (3) the presence of additives (4) the temperature. (2) the head group. the surface tension changes strongly with the concentration of the surfactant.or. viz.“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. viz. 1996. (3) the presence of additives (4) the temperature. and K. ko-kp=(kp-km)K([C]-[CMC])\N or. till CMC micelle is not formed but above it.2×10-4 9.0×10-4 9. or. Hence. where N is the aggregation number.0×10-3 1. the additional surfactant concentration is the micelle concentration. Saenger.2×10-3 3×10-5 9. . Therefore. kp (1+k[M])=ko+kmk[M] (kp-ko) = (km-kp)K[M] (ko-kp) = (kp-km)K[M] As we know. which should be a straight line with slope = N/K(ko-kp) and intercept = 1/(ko-km).The CMC is an important characteristic of a surfactant.
India. Jamia Millia Islamia (Central University).3. of Inorganic and Analytical Chem. The kinetics of oxidation of valine by permanganate ion in high [sulphuric acid] (=3. at a 2* 2* . Department of Chemistry.3. therefore. 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. Visakhapatnam-530 003. So.e. and in some cases. F. Zaheer Khan. Therefore I have choosen the work using surfactant.0 mol dm−3) has been by A. anionic and non-ionic) in the permanganate oxidation of glycine. Surfactants have attracted considerable interest in theoretical and experimental fields due to their catalytic effects and behaviour as analogous to biological membranes. 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. (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. Poblete.College of Dept. at a certain concentration in solution their monomers associate to form larger aggregates. but above a certain concentration. but there is no such information about autocatalytic reaction pathway by manganese dioxide in permanganate oxidation of glycine in the presence of surfactant. J. thought of interest to the role of various surfactants (cationic. colloidal manganese dioxide. University. School of Chemistry.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 . Jamia Nagar. Later.e. how a surfactant behaves when it interacts with oxidants.R.G.J. They have a tendency to associate i. India. However. 1 M. G Nageswara Rao2 and P Vani Engineering.V. they have a tendency to associate i. The effects of cetyltrimethylammonium bromide (CTAB). only a few reports [13-14] are available to reveal. uncatalyzed and the surfactant catalyzed oxidation of glycine by acidic permanganate have been studied in which the reaction followed first order dependence in both glycine and permanganate. 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. the catalytic path showed unit order and the non catalytic path showed a non integral order of 1. Rational of the work: Although Joaquin F.0–5. in order to gain further insight into the mechanism of oxidation of glycine. It was. 4. where the reaction is auto catalyzed by one of the products. stereochemistry of the reaction. Kinetics and mechanism of oxidation of glycine by permanganate in alkaline medium has been studied by TVN Partha Sarathi1. products. New Delhi 110025. Casade. the author has taken up the kinetics and mechanism of its oxidation by permanganate in alkaline medium. Surfactants dissolve completely in water at very low concentration. Andhra .Mucientes. 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 utilization of surfactant as reaction media affects rates. India. Vizianagaram-535 005. B Dharma Rao2.
This concentration is characteristic for each surfactant and is termed critical micelle concentration (cmc). A KH2PO4-K2HPO4 buffer mixture was used in all the experiments. and measuring both the decay of MnO4.at 526 nm and the formation of colloidal MnO2 at 418 nm.. • Surfactant (TX-100. Also potassium chloride was used in this experiment to anayse the effect of increasing ionic strength on the rate of the reaction. their monomers associate to form larger micelle aggregates.e. The above equation doesnot require that εP(418) and εP(526) be constant during the kinetic runs. The kinetic runs were followed with UV-vis spectrophotometer using thermostatized glass cells (cuvette of optical path length 1 cm). 5. • Glycine solution with concentration higher than potassium permanganate solution has been prepared in buffer solution. • Phosphate buffer solution has been prepared for keeping the pH of the medium constant and for stabilizing manganese dioxide as a soluble colloid. • The UV-VIS spectra of the experimental solutions have been recorded at two different wavelength i. • The pH of the buffer solution has been recorded. Materials: In this experiment glycine(reducing agent) was used in large exess than potassium permanganate(oxidizing agent). εR and εP are the molar absorption coefficients of the reactant (MnO4-) and product (colloidal MnO2). the progress of the reaction of permanganate oxidation of glycine has been studied by monitoring with UV-vis spectrophotometer. and l is the optical path length (1cm). The reaction rates at different instants during the course of the reaction were obtained from the permanganate concentration data by an approximate derivation method: . CTAB. 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. and it is thus useful for correcting absorbances in a reaction involving a colloidal product such as MnO2. respectively. EXPERIMENTAL: i. The purpose of using buffer mixture is to keeping the pH of the medium constant and to stabilizing manganese dioxide as a soluble colloid. • Potassium permanganate solution with low concentration has been prepared in buffer solution. but only their ratio. \ii. • Non-ionic (TX-100). Dodecylbenzene sulfonic acid) solutions has been prepared in buffer solution. 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. at 526nm and 418nm.certain concentration in solution. Strategies of the work: • In the present study.
07265 Concentration in final solution(mol/dm3) 1.86 6. Preparation of solutions: Table 1: Preparation of Buffer solution: Serial number 1 2 3 Amount (gm) 23.53 6.048 Materials KCl KH2PO4 Na2HPO4 Water 1000 1000 1000 (ml) Table 2: Preparation of Potassium permanganate solution: Serial number 1 Potassium permanganate (gm) 0.048 0. and where c represents the permanganate concentration at time t. iii.32 0.16 in final Serial number Glycine(gm) 1 9.0084 Table 4: Preparation of Triton X-100 : Serial number 1 Triton X100(ml) 0.2× 10-3 Buffer solution(ml) 250 Table 5: Preparation of Dodecylbenzene sulfonic acid : Serial number Dodecylbenzene Buffer solution (ml) Concentration in final solution .071118 Buffer solution (ml) 250 Concentration solution(mol/dm3) 6×10-4 in final Table 3: Preparation of Glycine solution: Buffer solution (ml) 250 Concentration solution(mol/dm3) 0.82 Concentration in final solution(mol/dm3) 0.applied at short time intervals (Δt = 1-3 min).
2×10-3 1×10-2 6×10-3 in solution .5467 250 6×10-3 Table 6: Preparation of Experimental solutions: Serial number Potassium permanganate solution (ml) 1 2 3 4 10 10 10 10 10 10 10 10 10 0 0 0 0 10 (non-ionic) 10 (anionic) 10 (cationic) Glycine solution Buffer (ml) (ml) solution Surfactant solution Surfactant concentration final (mol/dm3) 0 1.1 sulfonic acid (gm) 0.8712 250 1×10-2 Table 5: Preparation of CTAB: Serial number CTAB (gm) Buffer solution (ml) Concentration in final solution 1 0.
This allows us to conclude that only two absorbing species (MnO4.80.518. Also confirmed by above figure that all the manganese intermediates are present in negligible concentration (in steady state).320 M (KCl).and colloidal MnO2) were present in the reacting system.048 M)-Na2HPO4 (0.256. A(526)r = 0. B.A(526)r vs A(418)t . a plot of A(526)t . Fig 3.16 M) in KH2PO4 (0.RESULTS AND DISCUSSION: A.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. and 25. Plots of A(526) t .0502.A(418)r at different instants t during the course of the reaction of KMnO4 (6 × 10-4 M) with glycine (0.0 °C.] or last absorbances [A(418)r = 0. A(526)r = 1.] recorded. Fixed references: either first absorbances [A(418)r = 0.413. and that the existence of long lived intermediates could be discarded. As shown in above figure. 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.048 M) buffer at ionic strength 0. pH 6. 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.A(526)r against the absolute value of A(418)t . .
80 and 25oC in the absence of surfactant. pH 6.65 0.65 0.55 0.4 0.8×10-3M) oxidation of glycine(0.6 v/10 -3 Mmin -1 0.80 and 25oC in the presence of Triton X100(1.048M) buffer at ionic strength (KCl).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(1.048M) buffer at ionic strength (KCl).5 0.rate vs time plot 0.45 0.48m) in KH2PO4(0.2×10-3M). rate vs time plot 0.048M)-Na2HPO4(0.5 0.55 0.4 0.6 -1 0.8×10-3M) oxidation of glycine(0. .48m) in KH2PO4(0.048M)-Na2HPO4(0. pH 6.35 0 10 20 30 40 50 60 70 80 90 10 11 12 13 14 15 16 0 0 0 0 0 0 0 v/10 Mmin -3 time(min) Fig 4: Rate vs time plot for KMnO4(1.45 0.
048M)-Na2HPO4(0.48m) in KH2PO4(0.6 v/10 -3 Mmin -1 ` 0.8×10-3M) oxidation of glycine(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(1.605 0.5 rate vs time plot v/10 Mmin -3 -1 0.48m) in KH2PO4(0.4 0.048M) buffer at ionic strength (KCl). pH 6.45 0.048M)-Na2HPO4(0.8×10 -3M) oxidation of glycine(0.585 0.048M) buffer at ionic strength (KCl).55 0.0.80 and 25oC in the presence of Dodecylbenzenesulphonicacid(1×10-2M).6 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(1.65 0. rate vs time plot 0.80 and 25oC in the presence of CTAB(6×10-3M).595 0. pH 6.59 0.
048M) buffer at ionic strength (KCl).80 and 25oC in the absence of and presence of surfactant. . the rate of the reaction is high throughout. as evidenced by the occurrence of bell-shaped when the reaction rate is plotted against time. The slope of the rate vs time plot does not indicate significant autocatalysis.Fig 6: Rate vs time plot for KMnO4(1. The reaction may be catalysed by the cationic micelles of CTAB. the rate vs time curve is more obtuse than that in absence of any surfactant. the anionic surfactant micelles. In the presence of the non-ionic micelles the autocatalysis is initially unaffected by the micelles.8×10-3M) oxidation of glycine(0. 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.48m) in KH2PO4(0. In the presence of Dodecylbenzene sulfonic acid. But the autocatalysis steeply decreases after about 70 minute whereas in absence of the surfactants the autocatalysis starts decreasing only after about 90 minute. The autocatalysis is greater initially and continues for more time compared to that in absence of any surfactant. The following mechanism can be proposed for the autocatalytic reaction pathway: In the presence of CTAB the rate is independent of time. The permanganate oxidation of glycine in near-neutral aqueous solutions is strongly autocatalytic. pH 6. However.048M)-Na2HPO4(0.