Document Type

Thesis

Date of Award

5-31-1964

Degree Name

Master of Science in Chemical Engineering - (M.S.)

Department

Chemical Engineering

First Advisor

Saul I. Kreps

Second Advisor

William H. Snyder

Third Advisor

Michael Frederick

Abstract

The esterification of oleic acid with oleyl alcohol was studied. A literature search showed that the chemical kinetics for this reaction had not been studied previously.

In the temperature range of 150 to 200°C. and up to a conversion of about 85 per cent, the esterification was found to be a second order reaction when the water of reaction was removed from the system by simple distillation.

Para-toluenesulfonic acid is an effective catalyst for this system, and the observed specific rate constant is a linear function of the catalyst concentration.

The effect of temperature on the specific rate constant for the uncatalyzed reaction is given by the equation

In k1 = 6.88 x 103/T + 10.5

where k1 is in units of l./(g.-mole) (min.) and T is in degrees Kelvin. For the catalyzed reaction, the equation is

ln k2 = -4.90 x 103/T + 14.7

Energies of activation for the uncatalyzed and catalyzed reactions were graphically evaluated to be 13,650 calories per gram-mole and 9730 calories per gram-mole, respectively.

An empirical rate equation was derived for this system. Using the values of the frequency factors and energies of activation determined from the experimental data, the rate equation becomes

r = (2.35e-6.88x10^3/T +2.69e-4.90x10^3/T CC) CA,CB

where r = reaction rate, (g.-moles)/(l.) (min.)

CA,CB,CC = concentrations of oleic acid, oleyl alcohol, and catalyst, respectively, m./l.

T = absolute temperature, °K.

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