Mechanism of positive iodine reactions: Kinetics of oxidation of semicarbazide by iodamine-T, iodine monochloride and iodine

Kinetics of oxidation of semicarbazide (SC) by iodamine-T (IAT), iodine monochloride and aqueous iodine has been studied in aqueous perchloric acid medium. The rate laws followed by the oxidation of SC were determined. The rates decreased slightly with increase in ionic strength of the medium in IAT and ICI oxidations, while the reverse trend was observed with I₂. Decrease in dielectric constant of the medium increased the rates with IAT and ICI, while it decreased the rate in I₂ oxidations. Addition of the reduced product,p-toluene-sulphonamide had no effect on the rate with IAT. Addition of I⁻ had slight negative and positive effects on the rates of oxidations with IAT and ICI, respectively, but the negative effect was considerable in I₂ oxidations. Mechanisms consistent with the observed rate laws have been proposed and discussed. Rate determining steps have been identified and their coefficients calculated. These constants were used to predict the rate constants from the deduced rate laws as [SC], [H⁺] and [I⁻] varied. Reasonable agreement between the calculated constants and experimental values provide support for the suggested mechanisms.     

Kinetic study of the iodine monobromide-or iodine monochloride-catalyzed alcoholysis of butoxytriethylsilane: n-butoxy group — s-butoxy group exchange reaction

The catalytic activity of iodine monobromide and iodine monochloride were investigated in the reaction, Et₃SiOBuⁿ + Bu^sOH ? Et₃SiOBu^s + BuⁿOH. Pseudo first-order rate constants were measured by gas chromatography, at 10°, 20°, 30°, and 40°C for iodine monobromide and at 10°, 20°, and 30°C for iodine monochloride, on reaction mixtures containing both butanols in excess. The catalytic coefficients of both catalysts were evaluated from the observed rate constants as follows: The activation paramaters were estimated from these data, and were compared with the values for iodine catalysis. These results are consistent with the mechanism previously proposed.     

Kinetics of oxidation of some α-amino acids L(−) arginine,L(−) histidine,L(+) ornithine,L(−) tryptophan,L(−) threonine by sodium N-chloro-4 methyl benzene sulphonamide (chloramine-T) in alkaline medium

Kinetic studies of oxidation of L(?) arginine, L(+) ornithine, L(?) histidine, L(?) tryptophan, L(?) threonine have been carried out in alkaline medium. The reaction showed an inverse fractional order in OH^? and first-order dependence on both amino acid and chloroamine-T concentration. The effect of varying ionic strength (KCl) on the rate of oxidation is negligible. A general mechanism for the oxidation has been suggested by considering interaction between anionic species of amino acid and p-toluene-sulphochloramide. The effect of solvent and temperature have been also discussed. The fractional order obtained in OH^? is due to the fact that a fraction of overall reaction proceeds via an alternative OH^? independent path. The combined rate law in accordance to observed kinetics is derived as The rate constants predicted by the derived rate law as the concentration of OH^? ions change, are in excellent agreement with the observed rate constants, thus further justifying these rate laws and hence the proposed mechanistic schemes.     

Kinetic study of the iodine-catalyzed alcoholysis of Butoxytriethylsilane: n-butoxy group—s-butoxy group exchange reaction

In order to appreciate the excellent catalytic effect of iodine on the alcoholyses of alkoxysilanes more precisely, the rates of the reaction, Et₃SiOBuⁿ + Bu^sOH ? Et₃SiOBu^s + BuⁿOH, were determined at various iodine concentrations. Both forward and reverse reactions are first order with respect to butoxysilane and to butanol, and pseudo first-order rate constants were measured at 40°, 30°, and 20°C on reaction mixtures containing both butanols in excess by means of gas-liquid chromatography. The observed rate constants as a function of iodine concentration gave linear relationships, and from these data the catalytic coefficients of iodine were evaluated: The enthalpies and the entropies of activation were estimated to be 53.2 kJ mol^?1, ?103 J K^?1 mol^?1 (forward, 30°C) and 51.8 kJ mol^?1, minus;100 J K^?1 mol^?1 (reverse, 30°C).     

Kinetics of the gas-phase reaction of allyl alcohol with iodine. The heat of formation and stabilization energy of the hydroxyallyl radical

The reaction of iodine with allyl alcohol has been studied in a static system, following the absorption of visible light by iodine, in the temperature range 150-190°C and in the pressure range 10-200 torr. The rate-determining step has been found to be and k₃ is consistent with the equation From the activation energy and the assumption E_-3 = 1 ± 1 kcal mol^?1, it has been calculated that kcal mol^?1. The stabilization energy of the hydroxyallyl radical has been found to be 11.4 ± 2.2 kcal mol^?1.     

TI(III) oxidation of alkenes and alkynes and Ru(III) catalysis in the oxidation of alkenes: A kinetic and mechanistic study

The oxidation of trans-stilbene, phenylacetylene, and diphenylacetylene by Tl(OAc)₃ in aqueous acetic acid medium in the presence of HClO₄ follows the rate law in [H⁺] of 0.1–1.0M, the [H⁺] dependence below 0.1M being marginal. The reactions are strongly dielectric dependent. The order of reactivity among the substrates is styrene > phenylacetylene and trans-stilbene > diphenylacetylene. A mechanism involving the oxythallation adduct by the Tl⁺(OAc)₂ species has been discussed. The use of Ru(III) as a homogeneous catalyst brings a change in the kinetic orders for trans-stilbene, the rate law being The formation constants K for the Ru(III)–alkene π complex at 40, 50, and 60°C are 90.14M^?1, 105.2M^?1, and 127.7M^?1, respectively. Interestingly the oxidation of phenylacetylene and diphenylacetylene does not undergo catalysis by Ru(III). The mechanism involving the metal–arene π complex is discussed.     

Kinetic and mechanistic studies of oxidation of alanine and phenylalanine by sodium N-chlorobenzene sulfonamide (chloramine-B) in hydrochloric acid medium

The kinetics of oxidation of alanine and phenylalanine by sodium N-chlorobenzene sulfonamide (CAB) has been investigated at 30°C in two ranges of acid concentrations. The reactions follow identical kinetics for both amino acids. At low acid concentration (0.03–0.10M), simultaneous catalysis by H⁺ and Cl^? ions is noted. The rate shows a first-order dependence on [CAB], but is independent of [substrate]. A variation of the ionic strength or the dielectric constant of the medium or the presence of the added reaction product benzene sulfonamide (BSA) has no pronounced effect on the rate. At [HCl] > 0.2M, the rate is independent of [H⁺], but shows a first-order dependence on [CAB] and a fractional-order dependence on [amino acid]. The addition of BSA or Cl^? ions, or a change in the ionic strength of the medium has no influence on the rate. Upon decreasing the dielectric constant of the medium, the rate increased, indicating positive ion–dipole interaction in the rate-determining step. The reaction was studied at different temperatures, and activation parameters have been computed. Rate laws in agreement with experimental results have been derived. Suitable mechanisms to account for the observed kinetics are proposed. The rate constants obtained from the derived rate laws as [H⁺], [Cl^?], and [substrate] vary are in excellent agreement with the observed rate constants, thus justifying the proposed rate laws and hence the suggested mechanistic schemes.     

Kinetics of the gas-phase reaction between iodine and monogermane and the bond dissociation energy D(H3Ge?H)

The title reaction has been investigated in the temperature range of 403–446 K. Monoiodogermane and di-iodogermane together with hydrogen iodide were the main products, although at high conversions at least one other product was formed. GeH₃I is clearly the primary product. Initial rates were found to obey the rate law over a wide range of initial iodine and monogermane pressures. Secondary reactions (of GeH₃I with I₂) affect the subsequent kinetics, although at sufficiently high initial reactant ratios ([GeH₄]₀/[I₂]₀ ≥ 100) an integrated rate equation fits the data with the same rate constants as the initial rate expression. The observed kinetics are consistent with an iodine atom abstraction chain mechanism, and for the step log k₁ (dm³/mol·s) = (11.03 ± 0.13) – (52.3 ± 1.0 kJ/mol)/RT ln 10 has been deduced. From this the bond dissociation energy D(GeH₃? H) = 346 ± 10 kJ/mol (82.5 kcal/mol) is obtained. The significance of this value, together with derived values for Ge–Ge and Ge–C bond strengths, is discussed.     

Kinetics of the gas phase reaction of OH radicals with pyrrole and thiophene

Absolute rate constants for the gas phase reaction of OH radicals with pyrrole (k₁) and thiophene (k₂) have been measured over the temperature ranges 298–440 and 274–382 K, respectively, using the flash photolysis-resonance fluorescence technique. The rate constants obtained were independent of the total pressure of argon diluent over the range 25–100 torr andwere fit by the Arrhenius expressions and with rate constants at 298 ± 2 K of k₁ = (1.03 ± 0.06) × 10^?10 cm³ molecule^?1 s^?1 and k₂ = (8.9 ± 0.7) × 10^?12 cm³ molecule^?1 s^?1. [These errors represent two standard deviations (systematic errors could constitute an additional ca. 10% uncertainty)]. These results are discussed with respect to the previous literature data and the atmospheric lifetimes of pyrrole and thiophene.     

Kinetic and mechanistic studies of oxidation of arginine,histidine, and threonine in alkaline medium by N-chloro-N-sodio-p-toluenesulfonamide

The kinetics of oxidation of arginine, histidine, and threonine by chloramine-T (CAT) have been investigated in alkaline medium at 35°C. The rates are first order in both [CAT] and [amino acid] and inverse fractional order in [OH^?] for arginine and histidine. The rate is independent of [OH^?] for threonine. Variation of ionic strength and addition of the reaction product, p-toluenesulfonamide, or Cl^? ions had no effect on the rate. A decrease of the dielectric constant of the medium by adding methanol decreased the rate with arginine, while the rates increased with histidine and threonine. The solvent isotope effect was studied using D₂O. (k_obs)/(k_obs) was found to be 0.55 and 0.79 for arginine and histidine, respectively. The reactions were studied at different temperatures, and activation parameters have been computed. The oxidation process in alkaline medium, under conditions employed in the present investigations, has been shown to proceed via two paths, one involving the interaction of RNHCl (formed rapidly from RNCl^?), with the amino acid in a slow step to form monochloroamino acid, which subsequently interacts with another molecule of RNHCl in a fast step to give the products, p-toluenesulfonamide (RNH₂), and the corresponding nitrile of the amino acid (R'CN). The other path involves the interaction of RNCl^? with the amino acid in a similar way to give RNH₂ and R'CN. Mechanisms proposed and the derived rate laws are consistent with the observed kinetics. The rate constants predicted using the derived rate laws, as [OH^?] varies, are in excellent agreement with the observed rate constants, thus justifying these rate laws and hence the proposed mechanistic schemes.     

A reinvestigation of the rate constants for the reactions of ozone with cyclopentene and cyclohexene under atmospheric conditions

The rates of decay of ozone in a large excess of the cycloalkene have been re-measured by an improved experimental procedure, and the following second-order rate constants (cm³ molecule^?1 s^?1) have been determined in synthetic air at atmospheric pressure: The results are discussed in relation to existing literature data on the kinetics of ozonecycloalkene reactions.     

Low-pressure thermal decomposition of ONBr and ONCl in shock waves

Rate constants for the low-pressure unimolecular decomposition of ONBr and ONCl in an argon bath have been determined at temperatures in the vicinity of 1000°K. Both molecules exhibit the usual depression of the observed activation energy below the bond dissociation energy. The Arrhenius expressions obtained are (units of cc mole^?1 sec^?1): Treatment of the data by the classical RRK theory yields s ? 2.7 ± 1 for ONCl and 3.0 ± 0.6 for ONBr. Coupling the shock tube results for ONCl with lower-temperature data from Ashmore and Burnett [3], one obtains s ? 2.5 ± 0.5 and λ ≈? 1. If it is assumed that s is also 2.5 for ONBr, then one finds the surprising (but tentative) result that λ_{ONCl? Ar/λONBr? Ar} ≈? 3 to 4.     

Complex rate law for the cerium(IV) oxidation of glycolic acid in the medium HClO4–Na2SO4–NaClO4

The kinetics of the cerium(IV) oxidation of glycolic acid have been studied in the medium HClO₄? Na₂SO₄? NaClO₄ at varying organic substrate (HL), hydrogen, and bisulfate ion concentrations at 25.0°C and ionic strength 2.0M. Under the experimental conditions used (0.03 ? [H⁺] ? 0.5M; 0.02 ? [HSO₄^?] ? 0.1M; 0.01 ? [HL] ? 0.1M) the observed pseudo-first-order rate constant k_obs has been found to follow the complex expression where the values of the various constants have been estimated by a nonlinear least-squares method. According to this expression the oxidation process occurs significantly through three simultaneous pathways. Moreover three equilibria involving cerium(IV) and HSO₄^? (or SO₄^2?) ions are important from a kinetic point of view, whereas only two equilibria involving the corresponding complexes with the organic substrate are predominant.     

Oxidation of 2‐Phenylethylamine with N‐Bromosuccinimide in Acid and Alkaline Media: A Kinetic and Mechanistic Study

A kinetic study of oxidation of 2‐phenylethylamine (PEA), a bioactive compound, with potent oxidant, N‐bromosuccinimide (NBS) has been carried out in HCl and NaOH media at 313 K. The experimental rate laws obtained are: ‐d [NBS] /dt = k[NBS][PEA][H⁺] in hydrochloric acid medium and ‐d [NBS]/dt = k[NBS][PEA]^x[OH^?]^y in alkaline medium where x and y are less than unity. Accelerating effect of [Cl^?], and retardation of the added succinimide on the reaction rate have been observed in acid medium. Variation of ionic strength of the medium shows negligible effect on rate of reaction in both media. Decrease in dielectric permittivity of the medium decreased the rate in both media. The stoichiometry of the reaction was found to be 1:1 in acid medium and 1:2 in the case of alkaline medium. The oxidation products of PEA were identified as the corresponding aldehyde and nitrile in acid and alkaline medium, respectively. The reactions were studied at different temperatures and the activation parameters have been evaluated. The reaction constants involved in the proposed mechanisms were computed. The reaction was found to be faster in alkaline medium in comparison with the acid medium, which is attributed to the involvement of different oxidizing species. The proposed mechanisms and the derived rate laws are consistent with the observed experimental results.     

Mechanism of the azide–bromine reaction in aqueous medium

Results on the oxidation of N by Br₂ in neutral and acid media are presented. The rate of the reaction is found to be proportional to [N] and [Br₂]. The gaseous product of oxidation is found to be pure nitrogen. The stoichiometry of the reaction is The reaction shows a positive salt effect. It is found that the addition of Br^? stabilizes the complex BrN₃, which decomposes into Br^? and N₂: The spectroscopic measurements also support the kinetic observation. The equilibrium constant K, the rate constants and the thermodynamic parameters were calculated. It is observed that H⁺ ion inhibits the reaction. The mechanism is discussed in terms of the kinetic results.     

Kinetics of the gas-phase reaction between iodine and monosilane and the bond dissociation energy D(H3Si?H)

The title reaction has been investigated in the temperature range of 494–545 K. During the early stages of reaction the only observed products were silyl iodide and hydrogen iodide. Initial rates were found to obey the rate law over a wide range of initial iodine and monosilane pressures. Secondary reactions, most probably of SiH₃I with I₂, became more important as the reaction progressed. However, provided [SiH₄]₀/[I₂]₀ > 20, these secondary processes had a negligible effect on the kinetics, and an integrated rate expression could be used. These kinetics are consistent with an iodine atom abstraction chain mechanism, and for the step has been deduced. From this the bond dissociation energy D(SiH₃? H) = 378 ± 5 kJ/mol (90 kcal/mol) is obtained. The kinetic and thermochemical implications of this value, especially to the pyrolysis of monosilane, are discussed.     

Kinetics of the reaction of C6H5 with HBr and DBr

The rate constants for the reaction of C₆H₅ with HBr and DBr have been measured with the cavity–ring–down method in the temperature range of 297 to 523 K and 297 to 500 K, respectively. These rate constants can be effectively represented, in units of cm³/s, by Both activation energies are similar and positive, contrary to those of alkyl radical reactions, all of which exhibit negative temperature dependencies. The difference, as pointed out before [1], could be accounted for by the electron-withdrawing effect of the phenyl vis-à-vis the electron-donating ability of the alkyls. © 1994 John Wiley & Sons, Inc.     

Kinetics and mechanism of chloramine-T oxidation of cinnamaldehyde in two acid media

Kinetics of oxidation of cinnamaldehyde (Cinn) by chloramine-T (CAT) has been studied in solutions containing HCl and H₂SO₄ at 313 K. The respective experimental rate laws obtained in HCl and H₂SO₄ media are as follows: and Here the value of x varies from 0.9 to zero while the values of y and z are 0.83 and 0.72, respectively. Effects, on the reaction rate, of ionic strength, reaction product (p-toluenesulfonamide), dielectric constant of the solvent medium, and the anions, Cl⁻ and SO₄²⁻, have been investigated. Activation parameters have been computed, based on the rate constants determined at different temperatures. Mechanisms proposed and the rate laws derived are consistent with the observed kinetic data represented by the experimental rate laws.     

Oxidation of lactic acid by water soluble (colloidal) manganese dioxide

Spectrophotometric method has been used to characterize water‐soluble colloidal manganese dioxide obtained by the redox reaction between sodium thiosulphate and potassium permanganate in neutral aqueous medium which shows a single peak in the visible region with λ_max = 425 nm. The kinetics of the oxidation of lactic acid by colloidal manganese dioxide (oxidant) has been investigated spectrophotometrically under pseudo‐first‐order conditions of excess lactic acid. The rate of the noncatalytic reaction pathway was slow which increased with increasing lactic acid concentration. The reaction was first‐order with respect to [oxidant] as well as [lactic acid]. In presence of manganase(II) and fluoride ions, the noncatalytic path disappeared completely while the oxidation rate of autocatalytic path increased and decreased, respectively with increasing [Mn(II)] and [F^?]. A mechanistic scheme in conformity with the observed kinetics has been proposed with the rate‐law: © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 359–366 2004     

Sublimation and Dissociation of Thl4 and ThOl2 from Knudsen Cells

The sublimation pressure of ThI₄ has been measured by the Knudsen effusion method and found to be . Simultaneously with the sublimation of ThI₄ there is a small dissociation to lower iodide and iodine. The dissociation pressure associated with the reaction 2 ThOI₂ = ThO₂ + ThI₄ is The molar heat capacity of solid ThI₄ has been determined calorimetrically to be 146 J K^?1 mol^?1, the heat of fusion is approximately 48 kJ mol^?1. The standard entropy of solid ThOI₂ is calculated to be 145 J K^?1 mol^?1.