Document Type
Thesis
Date of Award
6-30-1962
Degree Name
Master of Science in Chemical Engineering - (M.S.)
Department
Chemical Engineering
First Advisor
Saul I. Kreps
Second Advisor
Joseph Joffe
Third Advisor
George C. Keeffe
Abstract
A linear relationship was found to exist between the logarithms of viscosity and vapor pressure measured at the same temperature for certain homologous series. Previous work by Di Geronimo, healing, and McGuire substantiated this correlation for n-paraflin hydrocarbons, n-paraffin fatty acids and esters, n-alkyl cyclohexanes, n-alkyl benzenes and n-l-monoolefins. The relationship takes the form
logη= A log vp + B
where A and B are constants characteristic of the homologous series.
The adaptation of this linear relationship to alcohols methyl ketones, and alkyl halides in the present work indicates a wide applicability of the correlation. the values of the series constants were found to be Homologous Series ABn-l-Alkanols(C1 to C18)td>-.2931.5501n-2-Alkanones(C3 to C17)-.2104-.0126n-1--Alkyl halides(C1 to C7)-.2398.1606
Average errors between experimental and calculated viscosities are ±28.95% for the alcohols, ±6.49% for the methyl ketones, and ±3.05% ion the alkyl halides independent of the halogen atom.
The high percentage deviation for the alcohols was improved by expressing the C3 to C18 values of the constants as functions of the number of carbon atoms in the alkyl group. The constants may be expressed as
A.= -.3610 - 1.174x 10-2(CN) + 7.292 x 10-4(CN)2
B = 1.016 - 7.06y x 10-2(ON) + 1.287 x 10-3(CN)2
where: (CN = number of carbon atoms in the molecule , with an average error between experimental and calculated viscosities of ±5.0%.
In expansion of the correlations between viscosity and vapor pressure, the simplified Antoine Equation was used to express vapor pressure as a function of temperature.
log vp =C/230 + D
Correlation of the Antoine Constants as a function of the number of carbon atoms in the alkyl group permitted expansion to a general equation. The expression is
log η= A (C/(t+230) + D) + B
The final equations for the homologous series studied are
n-1-Alkanols (C3 to C18)
log η = r (K + 8.231 + 7.514 x 10-3 (CN))+ 1.016 - 7.089 x 10-2 (CN) + 1.287 x 10-3 (CN)2
where:
P = -.3610 - 1.174 x 10-2 (CN) + 7.292 x 10 (CN)2
K = - 1516 - 93.04 (CN)/t + 230
CN = number of carbon atoms in the alkyl group
t = temperature, °C
n-2-Alkanones (C5 to C17)
log η = —.2104 (L + Q) - .0126
where:
L = - 1426 - 101.1 (CN)/t + 230
Q = 8.609 - .1780 (CN) 1.074 x 10- (CN)2
n-1-Alkyl Halides (C1 to C7)
logη = -.2398 + 6.564 + .1162 (CN)) + .1606
where:
M = N/t + 230
N = -398.3 - 283.8 (CN) + 9.204 (CN)2
These equations permit the evaluation of the viscosity of the individual compounds in these homologous series from a knowledge of the temperature and the number of carbon atoms in the alkyl group. The alcohol and methyl ketone relationships have an accuracy of approximately ±10% and the alkyl halide relationship has an accuracy of approximately ±20%. The correlations are applicable within the limits of the Antoine relationship utilized.
Recommended Citation
Frank, Kevin, "Viscosity-vapor pressure correlation of alcohols, methyl ketones and alkyl halides" (1962). Theses. 3000.
https://digitalcommons.njit.edu/theses/3000
