Kinetics of oxidation of indigo carmine by N-sodio-N-bromotoluenesulfonamide in acidic buffer medium

The kinetics of oxidation of indigo carmine (IC) by N-sodio-N-bromotoluenesulfonamide or bromamine-T (BAT) in pH 5 buffer medium has been investigated at 30°C using spectrophotometry at 610 nm. The reaction rate shows dependencies of first-order on [IC]₀ second-order on [BAT]₀, fractional order on [H⁺], and inverse first-order on [ρ-toluenesulfonamide]. The addition of chloride and bromide ions, and the variation of ionic strength of the medium have no influence on the reaction rate. There is a negative effect of the dielectric constant of the solvent. Activation parameters have been calculated. A single-pathway mechanism for the reaction, consistent with the kinetic data, has been proposed. © John Wiley & Sons, Inc. Int J Chem Kinet 29: 453–459, 1997     

Ruthenium(III)-catalyzed and uncatalyzed kinetic studies on the oxidation of sulfanilic acid by chloramine-T in perchloric acid medium: a mechanistic approach

The kinetics of the oxidation of sulfanilic acid (SAA) by sodium N-chloro-p-toluenesulfonamide (CAT) in the presence and absence of ruthenium(III) chloride have been investigated at 303 K in perchloric acid medium. The reaction shows a first-order dependence on [CAT]_o and a non-linear dependence on both [SAA]_o and [HClO₄] for both the ruthenium(III)-catalyzed and uncatalyzed reactions. The order with respect to [Ru^III] is unity. The effects of added p-toluenesulfonamide, halide, ionic strength, and dielectric constant have been studied. Activation parameters have been evaluated. The rate of the reaction increases in the D₂O medium. The stoichiometry of the reaction was found to be 1:1 and the oxidation product of SAA was identified as N-hydroxyaminobenzene-4-sulfonic acid. The ruthenium(III)-catalyzed reactions are about four-fold faster than the uncatalyzed reactions. The protonated conjugate acid (CH₃C₆H₄SO₂NH₂Cl⁺) is postulated as the reactive oxidizing species in both the cases.     

Kinetics and mechanism of the oxidation of thiourea by chlorine dioxide

The stoichiometry and kinetics of the oxidation of thiourea (SC(NH₂)₂) by chlorine dioxide (ClO₂) have been studied by uv-vis spectrophotometry using conventional and stopped-flow mixing techniques at 25.0 ± 0.1°C, pH 0.3–4.8. In high acid and initial 10:1 molar ratio of thiourea to chlorine dioxide, thiourea is oxidized relatively rapidly to dithiobisformamidine ion ((NH₂)₂CSSC(NH₂)₂²⁺), which slowly decomposes to thiourea, sulfur, and cyanamide (NCNH₂). In high acid and excess ClO₂, thiourea is oxidized to relatively stable formamidine sulfinic acid ((NH) (NH₂)CSO₂H). In high acid and molar ratios of ClO₂ to thiourea of 5:1 and higher, some oxidation to formamidine sulfonic acid ((NH) (NH₂)CSO₃H) occurs. At lower acidity, along with Cl^?, the major ClO₂ reduction product, byproduct sulfate is detected and, at pH < 3, ClO₂^?, also, appears. Kinetics data were collected for high excess thiourea with varying pH. The [ClO₂]-time curves are straight lines with negative slopes that increase in magnitude with increasing [thiourea]. The dependence on [thiourea] is first-order; the dependence on [ClO₂] is zero-order for 90% of reaction. With decreasing pH, the rate increases and the disappearance of ClO₂ becomes autocatalytic. Studies of the effects of reaction products on the rate of reaction lead to the conclusion that autocatalysis at low pH is due to the greater reactivity of HClO₂ compared with ClO₂^?. A 10-step mechanism incorporating a slow one-electron transfer from thiourea to ClO₂ to generate the (NH) (NH₂)CS · radical and subsequent more rapid reactions has been constructed and implemented in a computer simulation which provides a reasonably accurate fit to the observed kinetics curves. © 1993 John Wiley & Sons, Inc.     

Oxidation of some catecholamines by sodium N-chloro-p-toluenesulfonamide in acid medium: A kinetic and mechanistic approach

The kinetics of the oxidation of five catecholamines viz., dopamine (A), L-dopa (B), methyldopa (C), epinephrine (D) and norepinephrine (E) by sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) in presence of HClO₄ was studied at 30±0.1 °C. The five reactions followed identical kinetics with a first-order dependence on [CAT] _o , fractional-order in [substrate] _o , and inverse fractional-order in [H⁺]. Under comparable experimental conditions, the rate of oxidation of catecholamines increases in the order D>E>A>B>C. The variation of ionic strength of the medium and the addition of p-toluenesulfonamide or halide ions had no significant effect on the reaction rate. The rate increased with decreasing dielectric constant of the medium. The solvent isotope effect was studied using D₂O. A Michaelis-Menten type mechanism has been suggested to explain the results. Equilibrium and decomposition constants for CAT-catecholamine complexes have been evaluated. CH₃C₆H₄SO₂NHCl of the oxidant has been postulated as the reactive oxidizing species and oxidation products were identified. An isokinetic relationship is observed with β=361 K, indicating that enthalpy factors control the reaction rate. The mechanism proposed and the derived rate law are consistent with the observed kinetics.     

Kinetics of oxidation of pantothenic acid by chloramine‐T in perchloric acid and in alkaline medium catalyzed by OsO4: A mechanistic approach

Kinetics of oxidation of pantothenic acid (PA) by sodium N‐chloro‐p‐toluenesulfonamide or chloramine‐T (CAT) in the presence of HClO₄ and NaOH (catalyzed by OsO₄) has been investigated at 313 K. The stoichiometry and oxidation products are same in both media; however, their kinetic patterns were found to be different. In acid medium, the rate shows first‐order dependence on [CAT]_o, fractional‐order dependence on [PA]_o, and inverse fractional‐order on [H⁺]. In alkaline medium, the rate shows first‐order dependence each on [CAT]_o and [PA]_o and fractional‐order dependence on each of [OH^?] and [OsO₄]. Effects of added p‐toluenesulfonamide and halide ions, varying ionic strength, and dielectric constant of medium as well as solvent isotope on the rate of reaction have been investigated. Activation parameters were evaluated, and the reaction constants involved in the mechanisms have been computed. The proposed mechanisms and the derived rate laws are consistent with the observed kinetics. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 201–210, 2005     

The kinetics and mechanism of reaction between ethylenediaminetetraacetomanganate(III) and cyanide ion

Summary The title reaction has been followed spectrophotometrically at 325 nm (_max of [Mn(CN)₆]^3–) under pseudo-first order conditions with cyanide in a large excess at pH=10.0, I=0.1M (NaClO₄) and 25°C. The reaction follows first-order kinetics in [MnEDTA(OH)]^2– and exhibits variable-order dependence in [CN^–] one at high cyanide concentration, and two at low cyanide concentration. The product of above reaction has been identified as [Mn(CN)₆]^3–.The kinetics of the reverse reaction,i.e., the reaction of [Mn(CN)₆]^3- with EDTA^4– have also been followed spectrophotometrically. This reactions is first-order with respect to both [Mn(CN) ₆ ^3– ] and [EDTA^4–] and exhibits an inverse first-order dependence on [CN^–]. A six-step mechanism has been proposed in which the penultimate step is rate-determining. The activation parameters have been obtained and support the postulated mechanism.     

Nonionic Micellar Catalyzed Oxidation of Vitamins by Chloramine-T in HClO4 Medium: A Kinetic Study

The kinetics of oxidation of vitamin B₁ (thiamine hydrochloride) and vitamin B₆ (pyridoxine hydrochloride) by chloramine-T (CAT) in perchloric acid medium and in presence of a non ionic surfactant (Triton x-100) have been investigated. A catalytic effect of the nonionic micelle on the rate of oxidation has been observed and rate is found to be proportional to 7lcub;k′ + k″ [Triton x-100]}, where k′ and k″ are the rate constants in absence and presence of surfactant, respectively. The rate shows a first-order, a fractional order and a zero order dependence on [Chloramine-T]_o, [Vitamin]_o and [H⁺]₀, respectively in absence as well as in presence of surfactant. A mechanism involving association/binding between the oxidant and the surfactant micelle, which is supported by spectrophotometric evidence has been proposed. The binding parameters have also been evaluated using a pseudo-phase kinetic model.     

Kinetics and mechanism of the reaction between hypochlorous acid and tetrathionate ion

The reaction has been studied spectrophotometrically monitoring the absorbance in the 240–400 nm wavelength range. The spectra of the reactants, intermediates, and products in this system are overlapping; thus special programs [ 1 , 2 ] have been used (and tested) to unravel the kinetics and mechanism of the reaction. The stoichiometry of the reaction in excess hypochlorous acid is S₄O₆²⁻ + 7HOCl + 3H₂O → 4SO₄²⁻ + 7Cl⁻ + 13H⁺. Various experiments are presented to show that—in excess tetrathionate—the reaction produces a light‐absorbing intermediate identified as S₂O₃Cl⁻. The intermediate slowly hydrolyzes into sulfur and sulfate and it yields pentathionate in excess tetrathionate. The rate‐determining steps and their rate constants are The further oxidation of S₂O₄²⁻ and SO₃²⁻ by HOCl to sulfate are fast processes. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 395–402, 2000     

Kinetics and mechanism of reduction of 2,8-dimethyl-1,9-diphenyl-3,7-diaza-2,7-nonadiene-1,9-dione dioximatocopper(III) ([CuIII A]+) and 4,6,9-trimethyl-5,8-diaza-4,8-dodecadiene-2,3,10,11-tetraone 3,10-dioximatocopper(III) ([CuIIIB]+) by p-methoxyphenol, 1,2-dihydroxybenzene, 1,4-dihydroxybenzene and some of its derivatives

The kinetics of reduction of two copper(III)-imine-oxime complexes, [Cu^IIIA]⁺ and [Cu^IIIB]⁺, (H₂A and H₂B=2,8-dimethyl-1,9-diphenyl-3,7-nonadiene-1,9-dione dioxime and 4,6,9-trimethyl-5,8-diaza-4,8-dodecadiene-2,3,10,11-tetraone 3,10-dioxime respectively) by hydroquinone (H₂Q), 2-methylhydroquinone (MH₂Q), 2-chlorohydroquinone (ClH₂Q), catechol (H₂Cat) and p-methoxyphenol (pMHP) have been examined in aqueous acidic solution. Under fixed reaction conditions, the kinetics display first-order dependence on each oxidant and reductant. The pH-dependence is complex for the reduction of [Cu^IIIA]⁺, since both the copper(III) complex and the reductants undergo protonation–deprotonation equilibria. In the lower pH range, the second-order rate constant, k ₂, decreases with increasing pH. In the higher pH range, k ₂ increases with increasing pH. In the lower pH range the most important oxidant is [Cu^IIIHA]²⁺, whereas, in the higher pH range the most important reactants are deprotonated reductants. However for H₂Cat, as was observed before, two reaction pathways seem to operate in the high pH range. In one pathway, HCat^? seems to be involved; whereas, in the other pathway Cat^2? seems to be the reactive species. Doubly deprotonated catechol, Cat^2?, is very unlikely to be formed at pH ≤ 5. It was therefore necessary to invoke a strong interaction between [Cu^IIIA]⁺ and HCat^? followed by loss of the second proton. The pH dependence for the reduction of [Cu^IIIB]⁺ is less complex. Thus H₂Q and MH₂Q showed no pH dependence up to pH ～ 4.60, whereas ClH₂Q, pMHP and H₂Cat displayed an inverse first-order dependence on [H⁺]. Observed rate constants showing first-order dependence and inverse first-order dependence on [H⁺] correlate reasonably well with those calculated using the Marcus equation. The reaction path involving Cat^2? is believed to proceed by an inner-sphere mechanism. The agreement between the calculated and observed values for the [Cu^IIIA]⁺ complex is lower than was found for the [Cu^IIIA₁]⁺(A₁=3,9-diethyl-4,8-diaza-3,8-undeca-2,10-dionedioxime). It seems that the replacement of methyl groups in the latter complex by phenyl groups in the former complex causes both electronic and steric effects, and both effects seem to retard electron transfer. The electronic effect is readily seen in the decrease of the reduction potential of [Cu^IIIA]⁺ (E ⁰=1.09 V) compared to the reduction potential of [Cu^IIIA₁]⁺(E ⁰=1.16 V) and thus making the former a weaker oxidant. The self-exchange rate constant (5 × 10⁵ M ^?1 s^?1) estimated for complexes with type H₂A ligands seem to work well for complexes with type H₂B ligands. This situation is supported by the findings of a fairly constant value for the self-exchange rate constant for Cu ^III/II –peptide complexes with varying substituents.     

Mechanism of oxidations in partially aqueous media: Kinetics of oxidation of thiosemicarbazide and thiosemicarbazone by chloramine-T and dichloramine-T in aqueous methanol

Kinetics of oxidation of thiosemicarbazide (TSC) and its hydrazone (Benzaldehyde thiosemicarbazone) by chloramine-T (CAT) and dichloramine-T (DCT) in aqueous methanol medium in the presence of perchloric acid has been studied. Oxidation of TSC by both the oxidants showed first order dependences in [oxidant], fractional order in [TSC] and nearly inverse first order in [H⁺]. The conversion of TSC into its benzaldehyde hydrazone changed the rate dependence in [CAT] from first to second order, while the dependence in [DCT] remained unchanged. The dependence in [TSC] changes from fractional order to zero order in both CAT and DCT oxidations. The rate followed inverse fractional order kinetics in [H⁺] in both the cases. Increase in ionic strength of the medium slightly decreased the rate, while the decrease in dielectric constant of the medium increased the rates of oxidations for both the oxidants. But the addition of reaction products, p-toluenesulphonamide and chloride had no effect on the rate. Oxidation of TSC with both the oxidants has been shown to follow Michaelis-Menten type mechanism. In hydrazone oxidations oxidants have been shown to disproportionate in slow steps to HOCl, which in turn attacks the substrate in fast steps to give the final products. [TSC] was varied at different temperatures and the constants of rate limiting steps were calculated at each temperature. Using the latter constants the activation parameters have been computed from the Arrhenius plots. The rate constants have been predicted from the rate law for the variation of [H⁺] at constant [TSC] and [oxidant]. The predicted values are in reasonable agreement with the experimental rate constants, providing additional support to the suggested mechanisms.     

Kinetics of oxidation of glycylglycine by bromamine-T in acid medium

The kinetics of oxidation of a typical dipeptide glycylglycine (GG) by bromamine-T have been studied in HClO₄ medium at 40°C. The rate shows first-order dependence on [BAT]₀ and is fractional order in [GG]₀ which becomes independent of [substrate]₀ at higher [GG]₀. At [H⁺ ] > 0.02mol dm⁻³, the rate is inverse fractional in [H⁺ ] but is zero order at lower [H⁺ ] (≤0.02 mol dm⁻³). Variation in ionic strength or dielectric constant of the medium had no significant effect on the rate. The solvent-isotope effect was measured and = 1.45. Proton inventory studies have been made. The reaction has been studied at different temperatures (308-323 K) and activation parameters have been computed.     

Rhodium(III) as a homogeneous catalyst for the oxidative decolorization of ethyl orange with aqueous acidic chloramine-T: a spectrophotometric, kinetic and mechanistic study

The kinetics and mechanism of sodium N-chloro-p-toluenesulfonamide oxidative decolorization of ethyl orange (EO) in aqueous perchloric acid have been studied at 303 K in the presence of rhodium(III) chloride as catalyst. The reaction exhibits first-order dependence on [EO]_o and a fractional-order dependence on [CAT]_o, [H⁺] and [Rh^III]. The dielectric effect is positive. The stoichiometry of the reaction was found to be 1:1, and the oxidation products of EO were identified as N-(4-diethylamino-phenyl)-hydroxylamine and 4-nitroso-benzenesulfonic acid. The rhodium(III)-catalyzed reaction is about fourfold faster than the uncatalyzed reaction. The proposed mechanism and derived rate law are in agreement with the observed kinetic results.     

Osmium (VIII) catalyzed kinetics and mechanism of indoles oxidation with Aryl-N-haloamines in alkaline medium

The kinetics of oxidation of the title substrates by sodium N-haloarylsulfonamides (or ary-N-haloamines), chloramine-T (CAT), bromamine-T (BAT), chloramine-B (CAB), and bromamine-B (BAB), catalyzed by osmium(VIII) in alkaline medium has been studied at 30°C. The corresponding oxindoles and arylsulfonamides have been characterized as reaction products. The reaction rate shows a first-order dependence each on |indole|₀ and |oxidant|₀, a fractional-order on |Os(VIII)|, and an inverse first-order on |OH⁻|. Addition of arylsulfon-amide, chloride and bromide, and variation of ionic strength of the medium have no effect on the reaction rate. There is a negative effect of dielectric constant of the solvent. Activation parameters have been calculated from the Arrhenius and Eyring plots. Hammett correlation of substituent effects indicates an LFE relationship with ρ = −1.0, showing the formation of an electron deficient transition state. From enthalpy-entropy relationships and Exner correlations, the isokinetic temperatures (333 K and 326 K) have been determined for the reactions of CAT and BAT, respectively. Proton inventory studies in H₂O-D₂O mixtures have shown the involvement of a single exchangeable proton of OH⁻ ion in the transition state. A mechanism consistent with the observed kinetics has been proposed. © 1996 John Wiley & Sons, Inc.     

Cuprous Complexes and Dioxygen. Part 12.. Rate law and mechanism of the copper-catalyzed oxidation of ascorbic acid in aqueous acetonitrile

The copper-catalyzed oxidation of ascorbic acid (AscH₂) has been studied with a Clark electrode in aqueous MeCN. Cu^I or Cu^II may be equally used as the source of metal ion, without influence on the rate law. At sufficiently high [MeCN], the rate of the overall reaction is essentially given by the rate of Cu^I autoxidation: the reaction is of first order with respect to [Cu] and [O₂] and shows an inverse-square dependence on [MeCN] as observed for the autoxidation of Cu. The pH dependence is complicated by the combination of the intrinsic pH effect on autoxidation with an additional term in the rate law which is directly proportional to [AscH^?]. The latter term is explained by direct oxidation of the organic substrate by the primary dioxygen adduct of Cu^I, CuO. For [MeCN] < 0.7M , a gradual and pH-dependent transformation of this rate law and deviation from the first-order dependence on [O₂] is indicated.     

Kinetics and mechanism of ligand exchange of coordinated cyanide in hexacyanoferrate(II) by nitroso‐R‐salt in the presence of mercury(II) as a catalyst

The kinetics of Hg(II)‐catalyzed reaction between hexacyanoferrate(II) and nitroso‐R‐salt has been followed spectrophotometrically by monitoring the increase in absorbance at 720 nm, the λ_max of green complex, [Fe(CN)₅ N‐R‐salt]^3? as a function of pH, ionic strength, temperature, concentration of reactants, and the catalyst. In this reaction, the coordinated cyanide ion in hexacyanoferrate(II) gets replaced by incoming N‐R‐salt under the following specified reaction conditions: temperature = 25 ± 0.1°C, pH = 6.5 ± 0.2, and I = 0.1 M (KNO₃). The stoichiometry of the complex has been established as 1:1 by mole ratio method. The rate of catalyzed reaction is slow at low pH values and then increases with pH and attains a maximum value between 6.5 and 6.7. The rate finally falls again at higher pH values due to nonavailability of [H⁺] ions needed to regenerate the catalytic species. The rate of reaction increases initially with [N‐R‐salt] and attains a maximum value and then levels off at higher [N‐R‐salt]. The rate of reaction shows a variable order dependence in [Fe(CN)₆^4?] ranging from unity at lower concentration to 0.1 at higher concentrations. The effect of [Hg²⁺] on the reaction rate shows a complex behavior and the same has been explained in detail. The activation parameters for the catalyzed reactions have been evaluated. A most plausible mechanistic scheme has been proposed based on the experimental observations. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 222–232, 2005     

Efficient Molecular Catalysis of ATP-Hydrolysis by Protonated Macrocyclic Polyamines

Molecular catalysis of ATP-hydrolysis by a number of protonated macrocyclic polyamines 1–9 has been investigated by ³¹P-NMR spectroscopy, and marked rate enhancements have been obtained. The largest acceleration is produced by the [24]-N₆O₂ macrocycle 1 , and the process displays the following properties: 1. protonated 1 forms very stable complexes with ATP, as well as with ADP and AMP; 2. it enhances the rate of ATP-hydrolysis by a factor of 10³ at pH = 8.5; the rate of hydrolysis is constant over a wide pH-range, from pH = 2.5 to 8.5; 3. 1 is more efficient than acyclic analogues; 4. the products of the reaction are orthophosphate (OP) and ADP, which is subsequently hydrolyzed to OP and AMP at a slower rate; 5. at pH > 6.5, a transient species is detected, which is tentatively identified as a phosphoramidate intermediate, resulting from phosphorylation of the macrocycle 1 ; 6. the reaction presents first-order kinetics and is catalytic. The mechanism of the process is discussed in terms of initial formation of a complex between ATP and protonated 1 , followed by an intracomplex reaction which may involve a combination of nucleophilic or acid catalysis with electrostatic catalysis.     

Kinetics and mechanism of oxidation of N,N-bis(salicylaldehyde-1,2-diaminoethane) cobalt(II) by N-bromosuccinimide in aqueous acidic medium

The kinetics of oxidation of N,N-bis(salicylaldehyde-1,2-diaminoethane) cobalt(II) complex by N-bromosuccinimide (NBS) in aqueous acid and H₂O–MeOH solvent mixtures were studied spectrophotometrically over the 20–40 °C range, 0.1–0.5 mol dm^?3 ionic strength, 2.2–2.8 pH range and 0–40 wt% MeOH–H₂O solvent mixtures for a range of NBS and complex concentrations. The rate shows first-order dependence on both [NBS] and [complex] and decreases with pH over the range studied. The protonated form of N-bromosuccinimide was identified as the main reactive species. An inner-sphere mechanism involving free radicals is proposed.     

Chlorination of N-Methylacetamide: A kinetic study

In the pH range 4.3–13, the reaction between N-methylacetamide (NMA) and sodium hypochlorite in dilute aqueous solution to give N-chloro-N-methylacetamide (CINMA) was found to be far slower than analogous reactions affording N-chloramines or N-chloroamino acids. The rate expression for chlorination was first-order each in [NMA] and [Cl_tot] (the total concentration of chlorinating species). A rate constant calculated for chlorination by each chlorinating species indicated that the order of increasing reactivity was HClO < ClO^? < Cl₂ < CH₃COOCl (formed in the presence of acetic/acetate buffer). At pH > 7 the reaction rate was unaffected by variations in [Cl^?] or pH, but under acidic conditions the rate increased with [Cl^?] and decreasing pH. Regardless of pH, the reaction rate was not affected by changes in ionic strength. The influence of temperature on the reaction rate was also studied which allowed calculation of thermodynamic activation parameters for the N-chlorination reaction. © 1995 John Wiley & Sons, Inc.     

Kinetics of oxidation of acidic amino acids by sodium N-bromobenzenesulphonamide in acid medium: A mechanistic approach

Kinetics of oxidation of acidic amino acids (glutamic acid (Glu) and aspartic acid (Asp)) by sodium N-bromobenzenesulphonamide (bromamine-B or BAB) has been carried out in aqueous HClO₄ medium at 30°C. The rate shows first-order dependence each on [BAB]_o and [amino acid]_o and inverse first-order on [H⁺]. At [H⁺] > 0·60 mol dm⁻³, the rate levelled off indicating zero-order dependence on [H⁺] and, under these conditions, the rate has fractional order dependence on [amino acid]. Succinic and malonic acids have been identified as the products. Variation of ionic strength and addition of the reaction product benzenesulphonamide or halide ions had no significant effect on the reaction rate. There is positive effect of dielectric constant of the solvent. Proton inventory studies in H₂O-D₂O mixtures showed the involvement of a single exchangeable proton of the OH⁻ ion in the transition state. Kinetic investigations have revealed that the order of reactivity is Asp > Glu. The rate laws proposed and derived in agreement with experimental results are discussed.     

Chlorination of substituted phenols with chloramine T. A kinetic study

Kinetics of chlorination of substituted phenols with a particular emphasis on p-nitrophenol (PNP) have been extensively studied using chloramine T (CAT). The effect of added mineral acids, neutral salts, and chloride have been investigated in detail. In aqueous acetic acid at high acidities the reactive phenols follow a zero-order process, while PNP or the disubstituted derivatives give a fractional-order dependence on substrate concentration. The concentration dependence of rate with respect to PNP, the chlorinating agent, and acid reveals the rate law 1/k_obs versus 1/[PNP] gave a straight line with a finite intercept. In aqueous dimethylformamide (DMF) and dimethylsulfoxide (DMSO) the reaction shows a second-order dependence on CAT and a first-order dependence on PNP in the case of DMF and a slight increment in order in DMSO. Addition of water increases the rate both in aqueous acetic acid and in dipolar aprotic solvents such as DMF and DMSO. The order of the reaction with respect to CAT is found to be dependent on pH as well as the reactivity of the phenols. In buffered acetic acid medium a second-order dependence on CAT was followed up to pH 7. The rate variations with temperature in the range of 30°¨Dot;50°C have been studied for all the substituted phenols, and the respective activation parameters have been calculated. The empirical rate law is accounted for by a mechanism involving species generated from CAT complexing PNP. Protonated CAT, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm H}_{\rm 2} \mathop {\rm O}\limits^{\rm + } {\rm Cl} $\end{document}, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Cl}\mathop {\rm O}\limits^{\rm + } {\rm AcH} $\end{document}, and dichloramine T (DCT) are considered important depending on reaction media. The effect of salts, pH, structural variations, and solvent dependence have been accounted for by the proposed mechanism. An attack by positive chlorine on oxygen of the phenol is the preferred mode of attack.