Hydrolysis of acetic anhydride: Non-adiabatic calorimetric determination of kinetics and heat exchange

Abstract A simple calorimetric method to estimate both kinetics and heat transfer coefficients using temperature-versus-time data under non-adiabatic conditions is described for the reaction of hydrolysis of acetic anhydride. The methodology is applied to three simple laboratory-scale reactors in a very simple experimental setup that can be easily implemented. The quality of the experimental results was verified by comparing them with literature values and with predicted values obtained by energy balance. The comparison shows that the experimental kinetic parameters do not agree exactly with those reported in the literature, but provide a good agreement between predicted and experimental data of temperature and conversion. The differences observed between the activation energy obtained and the values reported in the literature can be ascribed to differences in anhydride-to-water ratios (anhydride concentrations).

[1]  N. V. Sidgwick,et al.  CCVIII.—The rate of hydration of acid anhydrides: acetic, propionic, butyric, and benzoic , 1913 .

[2]  D. Glasser,et al.  The Study of Liquid-Phase Kinetics Using Temperature as a Measured Variable , 1971 .

[3]  W. Regenass Calorimetric monitoring of industrial chemical processes , 1985 .

[4]  Fitting isoperibolic calorimeter data for reactions with pseudo-first order chemical kinetics , 2005 .

[5]  F. Grønvold,et al.  Magnetite (Fe3O4) Heat capacity and thermodynamic properties from 5 to 350 K, low-temperature transition , 1969 .

[6]  E. K. Plyler,et al.  The Reaction Rate of Acetic Anhydride and Water , 1935 .

[7]  N. M. Rice,et al.  Applications of temperature scanning in kinetic investigations: The hydrolysis of acetic anhydride , 1996 .

[8]  N. V. Sidgwick,et al.  L.—The rate of hydration of acetic anhydride , 2022 .

[9]  Deran Hanesian,et al.  Adiabatic kinetic studies of the cytidine/acetic anhydride reaction by utilizing temperature versus time data , 1993 .

[10]  J. Marek The hydrolysis of acetic anhydride at elevated temperatures in the presence of ethyl acetate , 1954 .

[11]  Bohdan W. Wojciechowski,et al.  The temperature scanning reactor I: Reactor types and modes of operation , 1997 .

[12]  R. Giudici,et al.  Investigation of Cationic Polymerization of β‐Pinene Using Calorimetric Measurements , 2010 .

[13]  J. Golding,et al.  Conversions and temperature rises in a laminar flow reactor for the hydration of acetic anhydride , 1978 .

[14]  Konrad Hungerbühler,et al.  A New Small-Scale Reaction Calorimeter That Combines the Principles of Power Compensation and Heat Balance , 2003 .

[15]  K. Hungerbühler,et al.  A new approach for a combined evaluation of calorimetric and online infrared data to identify kinetic and thermodynamic parameters of a chemical reaction , 2004 .

[16]  Stefano Icaro Gianoli,et al.  A Pressure-Resistant Small-Scale Reaction Calorimeter That Combines the Principles of Power Compensation and Heat Balance (CRC.v4) , 2004 .

[17]  G. B. Kistiakowsky,et al.  Heats of Organic Reactions. XIII. Heats of Hydrolysis of Some Acid Anhydrides , 1942 .

[18]  R. Wilhelm,et al.  Diffusion and reaction in viscous‐flow tubular reactor , 1956 .

[19]  Carl L. Yaws,et al.  Chemical properties handbook : physical, thermodynamic, environmental, transport, safety, and health related properties for organic and inorganic chemicals , 1999 .

[20]  K. Booksh,et al.  Monitoring anhydride and acid conversion in supercritical/hydrothermal water by in situ fiber-optic Raman spectroscopy , 1998 .

[21]  Hermann J. Janssen,et al.  Hydrolysis of Acetic Anhydride in Concentrated Acetic Acid without Catalysis , 1957 .

[22]  A. K. Kralj Checking the Kinetics of Acetic Acid Production by Measuring the Conductivity , 2007 .

[23]  R. King,et al.  Automatically Controlled Adiabatic Reactor for Reaction Rate Studies , 1967 .

[24]  R. R. Rhinehart,et al.  Modeling of batch reactions with in situ spectroscopic measurements and calorimetry , 2005 .

[25]  The integration of an ultraviolet-visible spectrometer and a reaction calorimeter , 2003 .