Kinetics of the chlorination of propanoic acid in the presence of chlorosulphonic acid

Päivi Mäki-Arvela; Tapio Salmi; Erkki Paatero

doi:10.1016/0009-2509(95)00069-H

Kinetics of the chlorination of propanoic acid in the presence of chlorosulphonic acid

Päivi Mäki-Arvela^*, Tapio Salmi, Erkki Paatero

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

6 Citations (Scopus)

Abstract

The chlorination kinetics of propanoic acid was investigated in a semibatch reactor at 70-130°C using chlorosulphonic acid as a catalytic agent and oxygen as a radical trapper. 2-Monochloropropanoic acid was obtained as the main product and 2,2- and 2,3-dichloropropanoic acids appeared as by-products. The formation kinetics of 2-monochloropropanoic and 2,2-dichloropropanoic acids were autocatalytic, whereas the kinetics of 2,3-dichloropropanoic acid was noncatalytic. The kinetic data were described with a rate model based on a reaction mechanism, where propanoyl chloride is the key intermediate. The rate determining steps in the mechanism are the acid catalyzed enolization of propanoyl chloride and the chlorination of the enol. The parameters of the rate model were estimated with nonlinear regression analysis. Simulations showed that the kinetic model is able to describe the autocatalytic formation kinetics of 2-monochloropropanoic and 2,2-dichloropropanoic acids.

Original language	English
Pages (from-to)	2275-2288
Number of pages	14
Journal	Chemical Engineering Science
Volume	50
Issue number	14
DOIs	https://doi.org/10.1016/0009-2509(95)00069-H
Publication status	Published - Jul 1995
MoE publication type	A1 Journal article-refereed

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@article{6dd23066db3b4f6db1a895ddc4fa834c,

title = "Kinetics of the chlorination of propanoic acid in the presence of chlorosulphonic acid",

abstract = "The chlorination kinetics of propanoic acid was investigated in a semibatch reactor at 70-130°C using chlorosulphonic acid as a catalytic agent and oxygen as a radical trapper. 2-Monochloropropanoic acid was obtained as the main product and 2,2- and 2,3-dichloropropanoic acids appeared as by-products. The formation kinetics of 2-monochloropropanoic and 2,2-dichloropropanoic acids were autocatalytic, whereas the kinetics of 2,3-dichloropropanoic acid was noncatalytic. The kinetic data were described with a rate model based on a reaction mechanism, where propanoyl chloride is the key intermediate. The rate determining steps in the mechanism are the acid catalyzed enolization of propanoyl chloride and the chlorination of the enol. The parameters of the rate model were estimated with nonlinear regression analysis. Simulations showed that the kinetic model is able to describe the autocatalytic formation kinetics of 2-monochloropropanoic and 2,2-dichloropropanoic acids.",

author = "P{\"a}ivi M{\"a}ki-Arvela and Tapio Salmi and Erkki Paatero",

year = "1995",

month = jul,

doi = "10.1016/0009-2509(95)00069-H",

language = "English",

volume = "50",

pages = "2275--2288",

journal = "Chemical Engineering Science",

issn = "0009-2509",

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number = "14",

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TY - JOUR

T1 - Kinetics of the chlorination of propanoic acid in the presence of chlorosulphonic acid

AU - Mäki-Arvela, Päivi

AU - Salmi, Tapio

AU - Paatero, Erkki

PY - 1995/7

Y1 - 1995/7

N2 - The chlorination kinetics of propanoic acid was investigated in a semibatch reactor at 70-130°C using chlorosulphonic acid as a catalytic agent and oxygen as a radical trapper. 2-Monochloropropanoic acid was obtained as the main product and 2,2- and 2,3-dichloropropanoic acids appeared as by-products. The formation kinetics of 2-monochloropropanoic and 2,2-dichloropropanoic acids were autocatalytic, whereas the kinetics of 2,3-dichloropropanoic acid was noncatalytic. The kinetic data were described with a rate model based on a reaction mechanism, where propanoyl chloride is the key intermediate. The rate determining steps in the mechanism are the acid catalyzed enolization of propanoyl chloride and the chlorination of the enol. The parameters of the rate model were estimated with nonlinear regression analysis. Simulations showed that the kinetic model is able to describe the autocatalytic formation kinetics of 2-monochloropropanoic and 2,2-dichloropropanoic acids.

AB - The chlorination kinetics of propanoic acid was investigated in a semibatch reactor at 70-130°C using chlorosulphonic acid as a catalytic agent and oxygen as a radical trapper. 2-Monochloropropanoic acid was obtained as the main product and 2,2- and 2,3-dichloropropanoic acids appeared as by-products. The formation kinetics of 2-monochloropropanoic and 2,2-dichloropropanoic acids were autocatalytic, whereas the kinetics of 2,3-dichloropropanoic acid was noncatalytic. The kinetic data were described with a rate model based on a reaction mechanism, where propanoyl chloride is the key intermediate. The rate determining steps in the mechanism are the acid catalyzed enolization of propanoyl chloride and the chlorination of the enol. The parameters of the rate model were estimated with nonlinear regression analysis. Simulations showed that the kinetic model is able to describe the autocatalytic formation kinetics of 2-monochloropropanoic and 2,2-dichloropropanoic acids.

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U2 - 10.1016/0009-2509(95)00069-H

DO - 10.1016/0009-2509(95)00069-H

M3 - Article

AN - SCOPUS:0342983833

SN - 0009-2509

VL - 50

SP - 2275

EP - 2288

JO - Chemical Engineering Science

JF - Chemical Engineering Science

IS - 14

ER -

Kinetics of the chlorination of propanoic acid in the presence of chlorosulphonic acid

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