Using temperature-programmed reaction for kinetic analysis of reactions in dilute aqueous solutions at high pressure

Conference · Wed Jan 01 00:00:00 EST 1986

OSTI ID:5899930

Brown, L F; Robinson, B A

The technique of temperature-programmed reaction (TPR) is shown to be a practical experimental method for determining reaction-rate expressions and kinetics parameters for reactions in dilute aqueous solutions under high ambient pressure. By sampling and measuring the extent of reaction during a rise in temperature, information normally obtained from a series of isothermal batch kinetics experiments can be found in a single TPR test. The use of nonlinear least-squares regression eliminates the need to achieve a constant rate of temperature rise, simplifies the experimental requirements for TPR results, and gives more accurate answers than does a linear analysis of TPR results. Numerical simulations of TPR tests in the presence of random concentration-measurement error is used to assess the accuracy of the technique and to identify the best values of crucial operating parameters. The results of two TPR experiments measuring the alkaline hydrolysis of ethyl acetate demonstrate the applicability of the technique to reactions in dilute aqueous solutions at high pressure. These preliminary experimental results, along with numerical simulations, allow us to chart a course for future TPR kinetics experiments on a large number of similar reactions. 16 refs., 6 figs., 8 tabs.

• Research Organization: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
• DOE Contract Number: W-7405-ENG-36
• OSTI ID: 5899930
• Report Number(s): LA-UR-85-3936; CONF-860530-2; ON: DE86003683
• Resource Relation: Conference: 9. international symposium on chemical reaction engineering, Philadelphia, PA, USA, 18 May 1986; Other Information: Portions of this document are illegible in microfiche products
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETATES
ACTIVATION ENERGY
ALKALINE HYDROLYSIS
CHEMICAL REACTION KINETICS
EQUATIONS
EXPERIMENTAL DATA
LIQUIDS
MATHEMATICAL MODELS
TEMPERATURE DEPENDENCE
CARBOXYLIC ACID SALTS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ENERGY
FLUIDS
HYDROLYSIS
INFORMATION
KINETICS
LYSIS
NUMERICAL DATA
REACTION KINETICS
SOLVOLYSIS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)