Effects of temperature on micellar-assisted bimolecular reaction of methylnaphtalene-2-sulphonate with bromide and chloride ions.

Reactivity of methyl naphthalene-2-sulphonate, MeONs, with H2O, Br(-) and Cl(-) in water and in cationic micelles of cetyltrialkylammonium surfactants, n-C16H33N(+)R3X(-), R=Me (CTA(+)), n-Pr (CTPA(+)), X=Br, Cl, CH3SO3, has been investigated in the temperature range 25-45°C. Micellar rate effects were analysed by using the pseudophase treatment, and the second-order rate constants in the micellar pseudophase were evaluated at the various temperatures. Values of these rate constants increase with temperature, and the effect is less important in micelles than in water and more important for chloride than for bromide ions. Micelles lead to an ion behaviour discrimination, whose extent depends on surfactant type and on temperature, with maximum effect in CTPA(+) at 25°C and with bromide being always more reactive than chloride. Quantitative analysis of the temperature effect by the Eyring equation showed that micelles speed up reaction of MeONs with halide ions by decreasing the activation enthalpies, which is partially offset by decreases in the activation entropies. The rate acceleration by increase in surfactant head group size has only enthalpic origin for bromide and only entropic origin for chloride: this different behaviour was rationalised taking into account both solvation of anions and the hydrophobic effect.

[1]  K. Mittal.  Surfactants in Solution , 2012, Surfactant Science and Technology.

[2]  L. Brinchi,et al.  Micellar Effects on S(N)2 Reactions of Alkyl Naphthalene-2-sulfonates:The Role of Hydrophobic Substituents. , 2001, Journal of colloid and interface science.

[3]  V. Soldi,et al.  Arenediazonium Salts: New Probes of the Interfacial Compositions of Association Colloids. 6. Relationships between Interfacial Counterion and Water Concentrations and Surfactant Headgroup Size, Sphere-to-Rod Transitions, and Chemical Reactivity in Cationic Micelles† , 2000 .

[4]  Thomas H. Lowry,et al.  Mechanism and Theory in Organic Chemistry , 1976 .

[5]  Lucia Brinchi,et al.  Premicelles of cetyltrimethylammonium methanesulfonate: Spectroscopic and kinetic evidence , 2009 .

[6]  G. Cerichelli,et al.  NMR study of the location of bromide ion and methyl naphthalene-2-sulfonate in cationic micelles: relation to reactivity , 1989 .

[7]  Minu Singh,et al.  Kinetics and Mechanism of Cetyltrimethylammonium Bromide Catalyzed N-Bromosuccinimide Oxidation of D-Mannose in Acidic Medium , 2011 .

[8]  M. Moyá,et al.  Study of the SN2 Substitution Reactions Between Methyl Naphtalene-2-Sulfonate and Methyl 4-Nitrobenzene Sulfonate and Bromide Ions in Dodecyl Dibromide Dimeric Micellar Solutions in the Absence and Presence of Alcohols , 2012 .

[9]  A. Chaudhuri,et al.  Simultaneous determination of counterion, alcohol, and water concentrations at a three-component microemulsion interface using product distributions from a dediazoniation reaction , 1991 .

[10]  C. H. Walker.  The Hydrophobic Effect: Formation of Micelles and Biological Membranes , 1981 .

[11]  C. A. Bunton,et al.  Organic Reactivity in Aqueous Micelles and Similar Assemblies , 1986 .

[12]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[13]  F. Quina,et al.  Ion Binding and Reactivity at Charged Aqueous Interfaces , 1991 .

[14]  G. Onori,et al.  Effect of head group size, temperature and counterion specificity on cationic micelles. , 2011, Journal of colloid and interface science.

[15]  Kabir-ud-din,et al.  Micellar and Solvent Effects on the Rate of Reaction Between L-Tyrosine and Ninhydrin , 2010 .

[16]  E. Rodenas,et al.  Inhibiton effect of cationic micelles on the basic hydrolysis of aromatic esters , 1986 .

[17]  R. Zielinski,et al.  Effect of Temperature on Micelle Formation in Aqueous NaBr Solutions of Octyltrimethylammonium Bromide. , 1989, Journal of colloid and interface science.

[18]  S. Mitragotri,et al.  Novel Topical Microbicides Through Combinatorial Strategies , 2010, Pharmaceutical Research.

[19]  S. Bhagwat,et al.  Surfactant-Assisted Aqueous-Phase Heck Reaction , 2012 .

[20]  J. Fendler.  Membrane mimetic chemistry , 2014 .

[21]  M. Malmsten.  Degradation of Surfactants and Polymers in Drug Delivery , 2002 .

[22]  Stanley G. Smith,et al.  Ion pairs, nucleophilicity and salt effects in bimolecular nucleophilic substitution☆ , 1960 .

[23]  R. Bacaloglu,et al.  Micellar enhancements of rates of SN2 reactions of halide ions: the effect of head group size , 1989 .

[24]  Ajaya K. Singh,et al.  Kinetic study of oxidation of galactose by N-bromo phthalimide in the presence of cationic micelle in acidic medium , 2011, Research on Chemical Intermediates.

[25]  G. Cerichelli,et al.  Micellar effects upon rates of SN2 reactions of chloride ion. II. Effects of cationic headgroups , 1990 .

[26]  M. Khan.  Effects of hydroxide ion, salts and temperature on the hydrolytic cleavage of ionized N-hydroxyphthalimide (NHPH) in the presence of cationic micelles , 1997 .

[27]  L. Brinchi,et al.  SN2 Displacement by Bromide Ions in Dichloromethane. The role of Reverse Micelles , 2006 .

[28]  G. Cerichelli,et al.  Rate enhancements of SN2 reactions of methyl naphthalene-2-sulfonate by sulfobetaine micelles , 2000 .

[29]  L. Brinchi,et al.  Hydrolyses of Dinitroalkoxyphenyl Phosphates in Aqueous Cationic Micelles. Acceleration by Premicelles , 2000 .

[30]  D. Chandler.  Interfaces and the driving force of hydrophobic assembly , 2005, Nature.

[31]  J. Fuhrhop,et al.  Membranes and Molecular Assemblies: The Synkinetic Approach , 1998 .

[32]  L. Goracci,et al.  Temperature effects upon aqueous micellar-assisted decarboxylation of 6-nitrobenzisoxazole-3-carboxylate and its 5-methyl derivative. , 2006, Journal of colloid and interface science.

[33]  L. Brinchi,et al.  EFFECTS OF MICELLAR HEAD GROUP STRUCTURE ON THE SPONTANEOUS HYDROLYSIS OF METHYL NAPHTHALENE-2-SULFONATE. THE ROLE OF PERCHLORATE ION , 1998 .

[34]  H. Chaimovich,et al.  New method for estimating the degree of ionization and counterion selectivity of cetyltrimethylammonium halide micelles: Chemical trapping of free counterions by a water soluble arenediazonium ion , 1997 .

[35]  L. Brinchi,et al.  Micellar SN2 Reaction of Methyl Naphthalene-2-Sulfonate and Its 6-Sulfonate Derivative: Effect of the Negative Charge , 2001 .

[36]  H. Al‐Lohedan,et al.  Effect of alkyl chain length, head group and nature of the surfactant on the hydrolysis of 1,3-benzoxazine-2,4-dione and its derivatives. , 2011, Journal of colloid and interface science.

[37]  Werner Kunz,et al.  Hofmeister series and specific interactions of charged headgroups with aqueous ions. , 2009, Advances in colloid and interface science.

[38]  Jitendra P. Mata,et al.  Aggregation behavior of quaternary salt based cationic surfactants , 2005 .

[39]  Remo Guidieri.  Res , 1995, RES: Anthropology and Aesthetics.

[40]  P. Das,et al.  Kinetic studies of amino acid-based surfactant binding to DNA. , 2012, The journal of physical chemistry. B.

[41]  P. Das,et al.  Interaction between DNA and cationic surfactants: effect of DNA conformation and surfactant headgroup. , 2008, The journal of physical chemistry. B.

[42]  C. Reichardt.  Solvents and Solvent Effects in Organic Chemistry , 1988 .

[43]  M. Lawrence,et al.  Surfactant systems: their use in drug delivery , 1994 .

[44]  Bunton,et al.  Effects of Amine Oxide Surfactants on Reactions of Bromide and Hydroxide Ions with Methylnaphthalene-2-Sulfonate. , 1999, Journal of colloid and interface science.

[45]  Muhammad Akhyar Farrukh,et al.  Reactivity and models for anion distribution: specific iodide binding to sulfobetaine micelles. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[46]  J. Kalus,et al.  Temperature Dependence of the Sizes of Tetradecyltrimethylammonium Bromide Micelles in Aqueous Solutions , 2001 .

[47]  M. Moyá,et al.  Kinetic studies in micellar solutions of novel bromide mono- and dimeric surfactants with phenyl and cyclohexyl rings in the head group , 2012 .