300 LIQUID HEAT CAPACITY FOR ORGANICS Liquid heat capacity (Cp) is an important property when designing chemical

processes. In liquidphase chemical reactions, Cp is required to determine the energy (heat) necessary to bring the liquid chemical reactants up to reaction temperature. Additional uses include generalized heat-exchanger and energy-balance design calculations. Here, correlations have been developed and applied, in an easy-to-use tabular format, for 300 organic compounds. The tables should be especially applicable for use with a personal computer or programmable calculator. * The correlation for Cp is a series expansion in temperature: Cp =A + BT + CT 2 Where: Cp = heat capacity at temperature T, Joule/g-molK A, B and C = correlation constants T = temperature, K


Professor Yaws and his coauthors have published numerous compilations of physicalproperty data in Chemical Engineering. The following articles have appeared recently: "Heat capacity on 700 compounds:' May 9, 1988, p. 91 "Enthalpy of formation for 700 major organic compounds:' Sept. 26, 1988, p. 81 "232 hydrocarbons: water solubility data," April 1990, p. 177 "168 organic compounds: water solubility data:' July 1990, p. 115 . "633 organic chemicals: surface tension data:' March 1991, p. 140 "Henry's law constants for 362 organic compounds in water:' November 1991, p. 179

The correlations are provided in the tables accompanying this article. The tabulations are based both on literature (experimental data) and estimated values. The correlation constants are determined from a least-squares fit of Cp at different temperatures. In performing the least-squares fit, the relation of (heat capacity) X (densityn) = a constant is used. For compounds with a boiling point less than 298 K, a value of n = 0.5 is used. For compounds with a higher boiling point, n = 1. The constant in this (heat capacity) x (density) equation is derived from experimental data for both properties. For the least-squares fit, six data points are used over the temperature range of freezing to boiling point. Three data points are used for temperatures above the boiling point (actually, these temperatures are obtained by multiplying the value of interest by the critical temperature for that compound). For compiling experimental data on Cp, a literature search has been made to identify source publications (1-25). The publications have been screened, and the data keyed into a computer database. This database also serves as a check on the accuracy of the estimation procedure.

The estimation process is based on Cp as a. Function of boiling-point temperature. A plot of Cp vs. boiling point has been prepared for organic compounds containing halogens. Although the data scatter is more pronounced than that experienced for earlier plots of hydrocarbons (alkanes, olefins, cycloalkanes and aromatics), a distinguishable curve is obtained for the halogenates. Curve approximation The same procedure is repeated for sulfur compounds (sulfides, thiols and disulfides), alcohols, aldehydes, ethers, amines and nitriles. Based on the limited data available, an approximate curve for increase of Cp with boiling point is developed for each chemical family. A comparison of correlation and actual data values for Cp is shown in the Figure for a representative chemical. The agreement of experimental data and calculated values is quite good,especially for the temperature interval from freezing point to slightly above the boiling point. The estimates generated by this process should be considered rough approximations, especially for the halogenates, due to the limited data available. They should be used only for initial engineering studies, and supplemented with actual experimental data when appropriate. A computer program containing the data is available for a nominal fee (C. L. Yaws, Box 10053, Lamar University, Beaumont, TX 77710; tel: 409 880 8787). The computer program is a random data file in ASCII format, which can readily be accessed by other databases or other software.

Example 1 Once Cp is known or estimated accurately, it can be used in a variety of calculations. Here are some examples: Determine the liquid heat capacity of carbon tetrachloride at 298 K To solve-this, simply substitute the values read from the Table for A, B and C into Equation 1, obtaining: Cp = 139.73 - 204 X 10-3 (298.16) + 586.79 X 10-6(298.16)2 = 130.92 J/molK

The calculated and observed values compare favorably (130.92 vs. 131.36; absolute deviation = 0.44/131.36 = 0.3%).

Example 2 Calculate the eneTgy required to heat liquid methanolfrom 250K to 350K From thermodynamics, the change in enthalpy, H, at constant pressure, is: H = CpdT H = (A + BT+ CT2)dT = [AT + B/T2 + C/3T3 ] = 74.86(350 - 250) - 102.32 X 10-3/2(3502 - 2502) + 406.66 X 10-6/3(3503 - 2503) = 8,110.23 J/g-mol