Kinetics of hydrolysis of aromatic mono- and disulfonyl chlorides

1987 ◽  
Vol 65 (9) ◽  
pp. 2263-2267 ◽  
Author(s):  
Przemyslaw Sanecki ◽  
Edward Rokaszewski
Keyword(s):  
Aqueous Acetic Acid ◽  
Polarographic Method ◽  
Acid System ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of Hydrolysis ◽  
Consecutive Reactions ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
Hydrolysis Of

A continuous polarographic method of recording instantaneous concentrations of —SO2Cl groups in an aqueous acetic acid system containing CH3CO2Na has been elaborated. Ten model monosulfonyl chlorides underwent hydrolysis according to pseudo-first order kinetics (20% H2O, 80% v.v. CH3CO2H, 0.5 mol × dm−3 CH3CO2Na). Plots of hydrolysis for seven disulfonyl dichlorides with different number of —CH3 groups have been determined. Pseudo-first order rate constants for two consecutive reactions of hydrolysis (k1 and k2) have been computed and the influence of —SO2Cl and [Formula: see text] groups on the reactivity of the second group —SO2Cl has been discussed. The mechanism of nucleophilic substitution has also been discussed.

Kinetics of hydrolysis of aromatic bicycling disulfonyl dichlorides

1988 ◽  
Vol 66 (12) ◽  
pp. 3056-3059 ◽  
Author(s):  
Przemysław Sanecki ◽  
Edward Rokaszewski
Keyword(s):  
Rate Constants ◽  
Polarographic Method ◽  
First Order ◽  
Order Rate ◽  
Kinetics Of Hydrolysis ◽  
Consecutive Reactions ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
Hydrolysis Of

Hydrolysis of 16 compounds ClO2S—Ar—B—Ar—SO2Cl (B, bridge) in 20% H2O, 80% v/v CH3CO2H, 0.5 mol dm−3 CH3CO2Na at 298.15 K has been investigated by a polarographic method. From plots of the hydrolysis, pseudo-first-order rate constants for two consecutive reactions [Formula: see text] have been computed and the influence of -SO2Cl groups, bridges B, and SO3− groups on the reactivity of -SO2Cl groups has been discussed. The ratio of rate constants k2/k1 ranges from 0.45 to 30, depending on the structure. Log (k1/(2kH)) correlated linearly with [Formula: see text] and log (k2/k1) correlated linearly with ΔpK for the analogous diamine series H2N—Ar—B—Ar—NH2.

Kinetics and Mechanism of Oxidation of Dimethyl Sulphoxide by Mono- and Di-Substituted N,N-Dichlorobenzenesulphonamides in Aqueous Acetic Acid

2003 ◽  
Vol 58 (8) ◽  
pp. 787-794 ◽  
Author(s):  
B.Thimme Gowda ◽  
K. L. Jayalakshmi ◽  
K. Jyothi
Keyword(s):  
Acetic Acid ◽  
Benzene Ring ◽  
Dimethyl Sulphoxide ◽  
Aqueous Acetic Acid ◽  
Isokinetic Temperature ◽  
Free Energies ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of

In an effort to introduce N,N-dichloroarylsulphonamides of different oxidising strengths, four mono- and five di-substituted N,N-dichlorobenzenesulphonamides are prepared, characterised and employed as oxidants for studying the kinetics of oxidation of dimethyl sulphoxide (DMSO) in 50% aqueous acetic acid. The reactions show first order kinetics in [oxidant], fractional to first order in [DMSO] and nearly zero order in [H+]. Increase in ionic strength of the medium slightly increases the rates, while decrease in dielectric constant of the medium decreases the rates. The results along with those of the oxidation of DMSO by N,N-dichlorobenzenesulphonamide and N,N-dichloro-4- methylbenzenesulphonamide have been analysed. Effective oxidising species of the oxidants employed in the present oxidations is Cl+ in different forms, released from the oxidants. Therefore the introduction of different substituent groups into the benzene ring of the oxidant is expected to affect the ability of the reagent to release Cl+ and hence its capacity to oxidise the substrate. Significant changes in the kinetic and thermodynamic data are observed in the present investigations with change of substituent in the benzene ring. The electron releasing groups such as CH3 inhibit the ease with which Cl+ is released from the oxidant, while electron-withdrawing groups such as Cl enhance this ability. The Hammett equation, log kobs = −3.19 + 1.05 σ , is found to be valid for oxidations by all the p-substituted N,N-dichlorobenzenesulphonamides. The substituent effect on the energy of activation, Ea and log A for the oxidations is also analysed. The enthalpies and free energies of activation correlate with an isokinetic temperature of 320 K.

Evidence for the formation of lignin-hexenuronic acid-xylan complexes during modified kraft pulping processes

Holzforschung ◽  
2006 ◽  
Vol 60 (2) ◽  
pp. 137-142 ◽  
Author(s):  
Zhi-Hua Jiang ◽  
Jean Bouchard ◽  
Richard Berry
Keyword(s):  
Acid Hydrolysis ◽  
Kraft Pulp ◽  
Kraft Pulping ◽  
Order Kinetic ◽  
Kraft Pulps ◽  
First Order ◽  
Pseudo First Order ◽  
Hexenuronic Acid ◽  
Kinetics Of ◽  
Hydrolysis Of

Abstract The finding that hexenuronic acid (HexA) groups can be selectively removed from kraft pulps by acid hydrolysis has provided an opportunity to reduce bleaching chemicals. However, there is evidence that the acid hydrolysis is not uniform. In this report, we evaluate the kinetics of acid hydrolysis of HexA in a xylan sample enriched with HexA, a conventional kraft pulp, and three modified kraft pulps: anthraquinone pulp (Kraft-AQ), polysulfide pulp (PS), and polysulfide-anthraquinone pulp (PS-AQ). We found that HexA present in the xylan and conventional kraft pulp behaved similarly toward the acid hydrolysis throughout. On the other hand, HexA present in the Kraft-AQ, PS-AQ and PS pulps was heterogeneous toward acid hydrolysis and the reaction can be separated into two pseudo-first-order kinetic phases, each of which has a different rate constant. The kinetic data provide evidence for the formation of lignin-HexA-xylan complexes during modified kraft pulping processes.

Parameters Effect on Photocatalytic Reduction Kinetics of Bromate in Aqueous Dispersion of TiO2

2013 ◽  
Vol 779-780 ◽  
pp. 1658-1665
Author(s):  
Rong Shu Zhu ◽  
Fei Tian ◽  
Ling Ling Zhang ◽  
Ling Min Yu
Keyword(s):  
Aqueous Dispersion ◽  
Zero Order ◽  
Photocatalytic Reduction ◽  
Reduction Kinetics ◽  
First Order ◽  
First Order Kinetics ◽  
Zero Order Kinetics ◽  
Experimental Parameters ◽  
Pseudo First Order ◽  
Kinetics Of

This paper studied the photocatalytic reduction kinetics of bromate in aqueous dispersion of TiO2 and investigated the effects of experimental parameters, including initial concentration of BrO3-, pH, TiO2 dosage, anion and cation. The results indicate that the process of photocatalytic reduction of bromate follows a zero-order kinetics. In all the investigated experimental parameters, the initial bromate concentration, pH and anion have great effect on the photocatalytic reduction kinetics. The processes of photocatalytic reduction of bromate show the pseudo first-order kinetics at initial bromate concentration of 0.39 μmolL-1, pH=5.0, or in presence of HCO3-/CO32-, NO3-, SO42-, respectively.

scholarly journals Kinetics of dechlorination of atrazine using tin (SnII) at neutral pH conditions

2020 ◽  
Vol 3 (1) ◽  
pp. 49
Author(s):  
Vijay Kumar ◽  
Simranjeet Singh
Keyword(s):  
Aqueous Media ◽  
Spectrometric Analysis ◽  
First Order ◽  
Neutral Ph ◽  
First Order Kinetics ◽  
Condi Tions ◽  
Ph Conditions ◽  
Pseudo First Order ◽  
Reaction Constants ◽  
Kinetics Of

Atrazine is a broad spectrum herbicide of triazine family. It is a chlorine-containing molecule and it can persist in environment. Chemical and biochemical techniques are the main techniques used to decompose the chemicals. In pre-sent study, the dechlorination of atrazine (Atr) via reaction with Sn(II) ion under aqueous media at neutral pH condi-tions was studied. The observed dechlorinated metabolite was 4-Ethylamino-6-isopropylamino-[1,3,5]triazin-2-ol. Identification of dechlorinated product of Atr was performed by using spectroscopic (FTIR) and mass (ESI-MS) spectrometric analysis. The kinetics of the dechlorination of Atr was measured by using pseudo-first order kinetics. The observed reaction constants was, kobs = 6.11x10-2 (at 430 mg/ L of Atr), and kobs = 6.14 x10-2 (at 215 mg/ L of Atr). The calculated half-life (t1/2) period was, t1/2 = 0.204 d (at 430 mg/ L of Atr), and t1/2 = 0.205 d (at 215 mg/ L of Atr).

scholarly journals Phenylcarbamic acid derivatives with integrated n-phenylpiperazine moiety in the structure – kinetics of alkaline hydrolysis study / Deriváty kyseliny fenylkarbámovej s integrovanou n-fenylpiperazínovou zložkou v štruktúre – štúdium kinetiky alkalickej hydrolýzy

2015 ◽  
Vol 62 (2) ◽  
pp. 38-42
Author(s):  
Stankovičová M. ◽  
Miháliková V. ◽  
Mezovský Ľ. ◽  
Lašáková A. ◽  
Medlenová V. ◽  
...  
Keyword(s):  
Alkaline Hydrolysis ◽  
Phenyl Ring ◽  
Arrhenius Equation ◽  
Sodium Hydroxide Solution ◽  
Antimycobacterial Activity ◽  
First Order ◽  
Rate Of Hydrolysis ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
Hydrolysis Of

AbstractIn present work, we have studied kinetics of alkaline hydrolysis of 14 compounds, which are phenylcarbamic acid derivatives with integrated N-phenylpiperazine moiety in the structure. The compounds possessed moderate antiarrhythmic and antimycobacterial activity. Their hydrolysis was carried out in an aqueous medium ethanol sodium hydroxide solution. The course of the hydrolysis was observed spectrophotometrically in visible as well as in ultraviolet regions. The pseudo-first order rate constants were calculated at several temperatures. The values of the activation energy EAwere determined by the Arrhenius equation. The rate of hydrolysis of the compounds under the study increase with the increase in temperature and it has been differentiated according to the substitution of N-phenylpiperazine as well as to the alkoxy substitution on phenyl ring.

scholarly journals Acid Hydrolysis of Bis(2,2'; 6',2''–Terpyridyl) Iron(II) Complex in the Water Pools of CTAB/Hexane/Chloroform Reverse Micelles-A Kinetic Study in Confined Medium

2020 ◽  
Vol 15 (3) ◽  
pp. 853-860
Author(s):  
K. V. Nagalakshmi ◽  
P. Shyamala
Keyword(s):  
Ionic Strength ◽  
Acid Hydrolysis ◽  
Reverse Micelles ◽  
Order Rate Constant ◽  
Micellar Medium ◽  
First Order ◽  
First Order Kinetics ◽  
Rate Of Reaction ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of acid hydrolysis of bis(2,2';6',2''–terpyridyl) iron(II) complex has been studied in CTAB/Hexane/Chloroform reverse micelles. The reaction obeys first order kinetics with respect to each of the reactants at all values of W, {W= [H2O]/[CTAB]}. In the reverse micellar medium, the reaction is much slower compared to aqueous medium due to low micropolarity of the water pools which does not facilitate a reaction between reactants of same charge. The effect of variation of W {W=[H2O]/[CTAB]} at constant [CTAB] and variation of [CTAB] at fixed W has been studied. The second order rate constant (k2) of the reaction increases as the value of W increases up to W = 8.88 and remains constant thereafter and it is independent of concentration of [CTAB] at constant W. The variation of rate of reaction with W has been explained by considering variation of micropolarity and ionic strength of water pools of reverse micelles with W. Copyright © 2020 BCREC Group. All rights reserved 

The trans-Effect in Octahedral Complexes. VI. Base Hydrolysis of trans-Hydroxybromo and trans-Hydroxychlorobis(ethylenediamine)-rhodium(III) Complexes

1975 ◽  
Vol 53 (12) ◽  
pp. 1842-1848 ◽  
Author(s):  
Anthony Poë ◽  
Carol Vuik
Keyword(s):  
Rate Equation ◽  
Base Hydrolysis ◽  
Small Contribution ◽  
Trans Effect ◽  
First Order ◽  
Order Rate ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Order Rate Equation

The kinetics of base hydrolysis of the complexes trans-[Rh(en)2(OH)X]+ (X = Br or Cl) follow the pseudo first order rate equation kobs = k1 + k2[OH−]. The small contribution of the [OH−]-dependent term is due to lower values of ΔS2≠ − ΔS1≠ than are observed for the complexes cis-[Rh(en)2(OH)Cl]+ and [Rh(NH3)5X]2+ (X = Cl, Br, or I ). The values of ΔH1≠ are used to obtain new values of the intrinsickinetictrans-effect (i.k.t.e.) of hydroxide that agree with that determined from aquation of trans.-[Rh(en)2(OH)I]+ and place hydroxide in the i.k.t.e. series [Formula: see text] The new data also allow hydroxide to be placed in a thermodynamic trans-effect (t.t.e.) series I > OH > NH3 > Br > Cl > OH2, and the different position of hydroxide in the two series is discussed.

Oxidation of the mercurous ion by peroxidase

1986 ◽  
Vol 64 (5) ◽  
pp. 969-972 ◽  
Author(s):  
Donald C. Wigfield ◽  
Season Tse
Keyword(s):  
Elemental Mercury ◽  
Order Rate Constant ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Order Rate ◽  
First Order Kinetics ◽  
Cold Vapour ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
Mercurous Ion

The kinetics of oxidation of the mercurous ion by peroxidase have been measured by following the disappearance of mercurous ion using cold-vapour atomic absorption spectroscopy. Pseudo-first-order kinetics are observed with respect to mercurous ion, and the pseudo-first-order rate constants are linearly related to peroxidase concentration, showing first-order dependence on peroxidase. This behaviour is identical to oxidation of elemental mercury, and the second-order rate constant, 1.44 × 104 M−1 s−1 at 23 °C, is also, within experimental error, the same as that for elemental mercury oxidation. The data are interpreted in terms of peroxidase-induced disproportionation of the mercurous dimer, followed by two-electron oxidation of zero-valent mercury.

Degradation Kinetics of Reactive Brilliant Red X-3B Dye by UV/Mn2+/H2O2/Micro-Aeration

2012 ◽  
Vol 441 ◽  
pp. 549-554
Author(s):  
Ying Jie Cai ◽  
Xiao Jun Yang ◽  
Dong Sheng Xia ◽  
Qing Fu Zeng
Keyword(s):  
Degradation Rate ◽  
Ph Value ◽  
Degradation Kinetics ◽  
H2o2 Concentration ◽  
Kinetics Equation ◽  
Linear Least Squares ◽  
First Order ◽  
First Order Kinetics ◽  
Pseudo First Order ◽  
Kinetics Of

Abstract. Degradation of reactive brilliant red X-3B (X-3B) by a UV/Mn2+/H2O2/micro- aeration method was investigated. The influencing factors of degradation of X-3B including UV irradiation, aeration, pH value, H2O2 concentration and X-3B concentration were examined. The results show that X-3B was effectively degraded by the UV/Mn2+/H2O2/micro-aeration method. The degradation rate of X-3B was obtained from weighted linear least squares analysis of the experimental data, and accorded with the pseudo-first order kinetics equation.

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