416

Rules of Thumb for Chemical Engineers

Table 1 Gibbs Free Energy of Formation of Gas, DGf = A + BT + CT2

Properties

417

418

Rules of Thumb for Chemical Engineers

Properties

419

420

Rules of Thumb for Chemical Engineers

Properties

421

422

Rules of Thumb for Chemical Engineers

Properties

423

(table continued)

424

Rules of Thumb for Chemical Engineers

NOTE: 1. Temperature range is 2981,000 K except for S, Br, and I compounds. 2. Temperature range for S, Br, and I compounds is 298 717.2 K, 332.61,000 K, and 458.41,000 K. 3. Additional compounds are: H2O(g) (A = -2.4174E+02, B = 4.1740E-02, C = 7.4281E-06) And HCL(g) (A = 9.2209E+01, B = -1.1226E-02, C = 2.6966E-06).
(text continued from page 415)

DGf,CH2O = -115.972 + 1.663*10-2(600) +1.138*10-5(6002) = -101.9 DGf,CH2O = -241.74 + 4.174*10-2(600) +7.428*10-6(6002) = -214.02 DGf,CH4O = -201.860 + 1.254*10-1(600) +2.035*10-5(6002) = -119.28 DGf,O2 = 0 The change in Gibbs free energy for the reaction is determined from Equation 2 and the Gibbs free energy of formation for the products and reactants: DGr = DGf,H2O + DGf,H2O - DGf,CH4O - 0.5*DGf,O2 = -101.9 + (-214.02) - (-119.28) - 0 = -196.64kjoule/g-mol Repeating the calculations at the other temperatures gives these results: T, K Gr, kJ/g-mol 600 -197 700 -204 800 -210 900 -217 1,000 -224

The equation for any of 700 major organic compounds is given as temperature coefcients. Then the reaction can be tested at various temperature levels beyond the standard 298K conditions imposed by many other data tabulations. Data for water and hydrogen chloride are also included. Gibbs free energy of formation of ideal gas (DGf, kjoule/g-mol) is calculated from the tabulated coefcients (A, B, C) and the temperature (T, K) using the following equation: DGf = A + BT + CT2 (1)

Since the change in Gibbs free energy for the reaction is highly negative, the thermodynamics for the reaction at these temperatures are favorable (reaction promising).
Data Source. The correlation constants were determined from a least-squares t of data from the literature.213 In most cases, average deviations between calculated and reported data were less than 0.6 kjoules/g-mol. A copy (51/4 inch oppy disk) of a menu-driven computer program to calculate Gibbs free energy of formation and change in Gibbs free energy for reactions (including random access data le of compound coefcients) is available for a nominal fee. For details, contact: C. L. Yaws, Dept. of Chem. Eng. Lamar University, P.O. Box 10053, Beaumont, Texas 77710, USA.

Chemical equilibrium for a reaction is associated with the change in Gibbs free energy (DGr) calculated as follows: DGr = DGf,products - DGf,reactants (2)

If the change in Gibbs free energy is negative, the thermodynamics for the reaction are favorable. On the other hand, if the change in Gibbs free energy is highly positive, the thermodynamics for the reaction are not favorable and may be feasible only under special circumstances. Rough criteria for screening chemical reactions are as follows: DGr < 0 kjoules/g-mol 0 < dGr < 50 kjoules/g-mol DGr > 50 kjoules/g-mol favorable possibly favorable not favorable

Literature Cited

Example. Calculate the change in Gibbs free energy for the reaction of methanol and oxygen to produce formaldehyde and water at reaction temperatures of 600, 700, 800, 900, and 1,000K:

CH 4 O(g) + 0.5 O 2 (g) CH 2 O(g) + H 2 O(g) Using correlation constants from Table 1 and Equation 1 at temperature of 600K, we obtain:

1. Yaws, C. L. and Chiang, P.-Y., Chemical Engineering, Vol. 95, No. 13, Sept. 26, 1988, pp. 8188. 2. Gallant, R. W., Physical Properties of Hydrocarbons, Vols. 1 and 2, Gulf Publishing Co., Houston, 1968 and 1970. 3. Gallant, R. W., and Railey, J. M., Physical Properties of Hydrocarbons, Vol. 2, 2nd ed., Gulf Publishing Co., Houston, 1984.

Properties

425

4. Braker, W., and Mossman, A. L., Matheson Gas Data Book, 6th ed., Matheson, Lyndhurst, N.J., 1980. 5. Dean, John A., Handbook of Organic Chemistry, McGraw-Hill Book Co., New York, 1987. 6. Perry, R. H., ed., Perrys Chemical Engineers Handbook, 6th ed., McGraw-Hill Book Co., 1984. 7. Selected Values of Properties of Hydrocarbons and Related Compounds, Vol. 7, TRC Tables (uy), Thermodynamic Research Center, Texas A&M Univ., College Station, Texas, 1977 and 1987. 8. Selected Values of Properties of Chemical Compounds, Vol. 4, TRC Tables (uy), Thermodynamic: Research Center, Texas A&M Univ., College Station, Texas, 1977 and 1987. 9. Stull, D. R., et al., The Chemical Thermodynamics of Organic Compounds, Wiley, New York, 1969.

10. Stull, D. R. and Prophet, H., Project Directors, JANAF Thermochemical Tables, 2nd ed., NSRDSNBS 37, U.S. Govt. Printing Ofce, Washington, D.C.. 1971. 11. Weast, R. C., ed., CRC Handbook of Chemistry and Physics, CRC Press, Boca Raton, Fla., 1985. 12. Yaws, C. L., Physical Properties, McGraw-Hill Book Co., New York, 1977. 13. Reid, R. C., et al., The Properties of Gases and Liquids, 4th ed., McGraw-Hill Book Co., New York, 1987.
Source

Yaws, C. L. and Chiang, P., Find Favorable Reactions Faster, Hydrocarbon Processing, November 1988, p. 81.

New Refrigerants
New hydrouorocarbons (HFCs) are replacing the chlorouorocarbons (CFCs) and hydrochlorouorocarbons (HCFCs) phased out to lessen damage to the ozone layer. The DuPont website lists physical properties for a number of their refrigerants. Go to: www.dupont.com/suva/412.html These physical property tables give three vapor pressure points that can be connected on your favorite Cox type vapor pressure chart for a quick approximation of the whole range. These three points are: normal boiling point critical properties vapor pressures at 25C E. I. DuPont deNemours and Company website, Physical properties and ASHRAE standard 34 classication of SUVA refrigerants. If more accurate vapor pressure data across the range are needed, DuPont can supply them. I received full-range vapor pressure data for many products on request from their very helpful SUVA Refrigerants Division.
Source