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Appendix A

CONVERSION TABLE

1. Temperature 9. Enthalpy of Formation

To convert from Centigrade to: To convert from kJ/mol to:

Kelvin, add 273.15 kcal/mol, multiply by 0.239

Rankine, multiply Kelvin by 1.8

Fahrenheit, multiply Centigrade by 1.8 and add 32 10. Gibbs Energy of Formation To convert from kJ/mol to:

2. Pressure kcal/mol, multiply by 0.239

To convert from psia to:

kPa, multiply by 6.895 11. Henry’s Law Constant for

psig, subtract 14.7 Compound in Water

mm Hg, multiply by 51.71 To convert from atm/mol fraction to: atmospheres, divide by 14.7 atm/(mol/m3), divide by 55,556

bars, divide by 14.508 kPa/(mol/m3), divide by 548.295

3. Heat of Vaporization To convert from kJ/kg to:

BTU/lb, multiply by 0.43 cal/gram, multiply by 0.239 4. Density

To convert from g/ml to: lb/ft^3, multiply by 62.43 lb/gallon, multiply by 8.345 5. Surface Tension

To convert from dynes/cm to: N/m, multiply by 0.001 6. Heat Capacity

To convert from J/g K to: BTU/lb R, multiply by 0.239 cal/gram K, multiply by 0.239 7. Viscosity

To convert from micropoise to: lb/ft s, multiply by 0.0672E-06 centipoise, multiply by 1.0E-04 poise, multiply by 1.0E-06

Pa s (Pascal seconds), multiply by 1.0E-07 To convert from centipoise to:

lb/ft s, multiply by 0.000672 micropoise, multiply by 10,000 poise, multiply by 0.01

Pa s (Pascal seconds), multiply by 0.001 8. Thermal Conductivity

To convert from W/m K to: BTU/hr ft R, multiply by 0.5770 calorie/cm s K, multiply by .002388

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Appendix B

HENRY'S LAW CONSTANT - EQUATIONS

Carl L. Yaws

Lamar University, Beaumont, Texas

The calculation of Henry's law constant for a component in water may be achieved using data for solubility, vapor pressure, and activity coefficient at infinite dilution. The derivation of the appropriate equations is briefly given in the following discussion.

LIQUIDS (PARTIAL SOLUBILITY)

For organic chemicals that are liquids at ambient conditions and have partial solubility in water, there are three phases when the organic chemical is in contact with water. These are vapor, organic, and water phases. Such a three-phase system consisting of vapor, liquid I and liquid II is shown in Fig. B-1a. At equilibrium, the fugacity of the component in each liquid phase is

fi liq I

= fi liq II

(B-1) For the organic phase (liquid I), the fugacity of the component is γi * mol fractioni * vapor pressurei

(where γi is the activity coefficient). Since the organic phase has only very small concentration of water (ppm

level or less), the mol fraction of the organic chemical is approximately equal to 1 (mol fractioni≈1). This is

also true for the activity coefficient of the organic chemical (γi≈1). Thus fi

liq I

= Pi SAT

(B-2) For the water phase (liquid II), the fugacity of the component is given by Henry's law which is applicable at very small concentration. The equation is

fi liq II

= Hi xi liq II

(xi<<1) (B-3)

Substitution of Equations (B-2) and (B-3) into Equation (B-1) yields Pi

SAT

= Hi xi liq II

(B-4) Solving for Henry's law constant yields the following equation which is applicable to organic chemicals which are liquids at ambient conditions (25 C, 1 atm) and have only small partial solubility in water:

Hi = ( 1 / xi liq II

) Pi SAT

(B-5) where Hi = Henry's law constant, atm/mol fraction

xi liq II

= solubility of organic chemical in water, mol fraction Pi

SAT

= vapor pressure of organic chemical, atm LIQUIDS (TOTAL SOLUBILITY)

For organic chemicals that are liquids at ambient conditions and have total solubility in water, there are two phases when the organic chemical is in contact with water. These are vapor and liquid phases. Fig. B-1b shows such a two-phase system.

For the liquid phase, the fugacity of the organic chemical is γi * mol fractioni * vapor pressurei (where γi is the activity coefficient). Since the liquid phase has only very small concentration of organic chemical (ppm level or less) in the region where Henry's law is applicable, the activity coefficient is the activity coefficient at infinite dilution (γi=γi∞). Thus

fi liq

= γi∞ xi Pi SAT

(B-6) For the liquid phase, the fugacity of the component is given by Henry's law that is applicable at very small concentration. The equation is

fi liq

= Hi xi (xi<<1) (B-7)

Substitution of Equation (B-6) into Equation (B-7) yields

γi∞ xi PiSAT = Hi xi (B-8)

Solving for Henry's law constant yields the following equation which is applicable to organic chemicals which are liquids at ambient conditions (25 C, 1 atm) and have total solubility in water:

Hi = γi∞ Pi SAT

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where Hi = Henry's law constant, atm/mol fraction γi∞ = activity coefficient at infinite dilution

Pi SAT

= vapor pressure of organic chemical, atm GASES

For organic chemicals that are gases at ambient conditions, there are two phases when the organic chemical is in contact with water. These are vapor and liquid phases. Such a two-phase system consisting of vapor and liquid is shown in Fig. B-1b. At equilibrium, the fugacity of the component in each phase is given by fi vap = fi liq (B-10) For the vapor phase, the fugacity of the organic chemical is

fi vap

= yi Pt (B-11)

Substitution of yi = 1-yH2O and Pt = 1 atm into the equation yields

fi vap

= 1-yH2O (B-12)

For the liquid phase, the fugacity of the component is given by Henry's law that is applicable at very small concentration. The equation is

fi liq

= Hi xi (xi<<1) (B-13)

Substitution of Equations (B-12) and (B-13) into Equation (B-10) yields

1-yH2O = Hi xi (B-14)

Solving for Henry's law constant yields the following equation which is applicable to organic chemicals which are gases at ambient conditions (25 C, 1 atm):

Hi = (1-yH2O) / xi (B-15)

where Hi = Henry's law constant, atm/mol fraction

xi = solubility of organic chemical in water, mol fraction

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Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR

Carl L. Yaws, Xiaoyan Lin, Li Bu, Deepa R. Balundgi and Saumya Tripathi

Lamar University, Beaumont, Texas ABSTRACT

Results for critical properties and acentric factor are presented for major organic and inorganic compounds. The critical properties include critical temperature, pressure, volume, density and compressibility factor. The chemical formula, molecular weight, freezing point and boiling point are also given. The results are displayed in easy-to-use tabulations which are especially applicable for rapid engineering usage with the personal computer or hand calculator. The chemicals encompass hydrocarbon, oxygen, nitrogen, halogen, silicon, sulfur and other compound types.

INTRODUCTION

Physical and thermodynamic property data for organic and inorganic chemicals are of special value to engineers in the chemical processing and petroleum refining industries. The engineering design of process equipment often requires knowledge of such properties as heat capacity, enthalpy, density, viscosity, thermal conductivity and others.

In this article, results are presented for critical properties and acentric factor, which are usable in corresponding states correlations to determine properties such as heat capacity, enthalpy, density, viscosity and thermal conductivity. The results are intended for initial engineering studies and are presented in an easy-to-use tabular format which is especially applicable for rapid engineering usage with the personal computer or hand calculator.

CRITICAL PROPERTIES AND ACENTRIC FACTOR

The results for critical properties and acentric factor are shown in Tables 1-1 and 1-2 for organic and inorganic compounds. The tabulations are based on both experimental data and estimated values.

In the data collection, a literature search was conducted to identify data source publications for organics (1-44) and inorganics (1-59). Both experimental values for the property under consideration and parameter values for estimation of the property are included in the source publications. The publications were screened and copies of appropriate data were made. These data were then keyed into the computer to provide a database of critical properties for compounds for which experimental data are available. The database also served as a basis to check the accuracy of the estimation method.

Upon completion of data collection, estimation of the critical properties and acentric factor for the remaining compounds was performed. For organic compounds, the group contribution method of Joback as given by Reid, Prausnitz and Poling (29) was primarily used for the estimation of critical temperature (TC),

pressure (PC) and volume (VC).

For inorganic compounds, estimates of critical temperature were based on modifications of the Guldberg-Guye rule (11), Gates-Thodos method (11) and Grosse equation (11). Estimates of other critical constants and acentric factor were primarily based on extension of the vapor pressure curve and modifications of the Benson relation (11) and Herzog proposal (11). Very limited experimental data for critical constants and acentric factor are available for inorganic compounds and elements that are solids at room temperature. Thus, the estimates for these substances should be considered rough approximations in the absence of experimental data.

Critical density (ρC) was determined from dividing molecular weight by critical volume:

ρC = MW / VC (1-1)

where ρC = critical density, g/cm 3

MW = molecular weight, g/mol VC = critical volume, cm

3

/mol

Critical compressibility factor (ZC) was ascertained from applying the gas law at the critical point:

ZC = PC VC / R TC (1-2)

For many of the compounds, the acentric factor (ω) was estimated by the following equation which is given in Reid, Prausnitz and Poling (29):

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ω = (log PC) – 1 (1-3)

7 1 - TB / TC

where _ω = acentric factor

TB = boiling point temperature, K

TC = critical temperature, K

PC = critical pressure, atm.

This equation for acentric factor is based on extending the vapor pressure by the Antoine type relation. Comparisons of estimates and data for critical temperature are shown in Figures 1-1 and 1-2 for normal alkanes and elements. Both graphs disclose favorable agreement of estimates and data.

A comparison of the estimates with experimental data was favorable for the group contribution method of Joback for organic compounds. Average absolute errors of 0.9%, 6.3%, 4.4% and 4.6% were experienced for critical temperature (465 compounds), pressure (453 compounds), volume (345 compounds) and compressibility factor (348 compounds). Average absolute error for acentric factor (277 compounds) was about 6%.

The normal boiling (TB) and freezing (TF) point temperatures are also given in the table. For most

compounds, data are available. For the compounds without data, the group contribution method of Joback (29) was used to estimate the boiling and freezing point temperatures for organic compounds. As discussed by Reid, Prausnitz and Poling (29), no reliable methods are available for precise estimation of freezing point temperature. Thus, the estimates for freezing point temperature should be considered as rough approximations.

Portions of this material appeared in Hydrocarbon Processing, 68, 61 (July 1989) and are reprinted by special permission.

REFERENCES - ORGANIC COMPOUNDS

1. SELECTED VALUES OF PROPERTIES OF HYDROCARBONS AND RELATED COMPOUNDS, Thermodynamics Research Center, TAMU, College Station, TX (1977, 1984).

2. SELECTED VALUES OF PROPERTIES OF CHEMICAL COMPOUNDS, Thermodynamics Research Center, TAMU, College Station, TX (1977, 1987).

3. TECHNICAL DATA BOOK - PETROLEUM REFINING, Vols. I and II, American Petroleum Institute, Washington, DC (1972, 1977, 1982).

4. Daubert, T. E. and R. P. Danner, DATA COMPILATION OF PROPERTIES OF PURE COMPOUNDS, Parts 1, 2, 3 and 4, Supplements 1 and 2, DIPPR Project, AIChE, New York, NY (1985-1992).

5. Ambrose, D., VAPOUR-LIQUID CRITICAL PROPERTIES, National Physical Laboratory, Teddington, England, NPL Report Chem 107 (Feb., 1980).

6. Simmrock, K. H., R. Janowsky and A. Ohnsorge, CRITICAL DATA OF PURE SUBSTANCES, Vol. II, Parts 1 and 2, Dechema Chemistry Data Series, 6000 Frankfurt/Main, Germany (1986).

7. INTERNATIONAL CRITICAL TABLES, McGraw-Hill, New York, NY (1926).

8. Braker, W. and A. L. Mossman, MATHESON GAS DATA BOOK, 6th ed., Matheson Gas Products, Secaucaus, NJ (1980). 9. CRC HANDBOOK OF CHEMISTRY AND PHYSICS, 75th - 78th eds., CRC Press, Inc., Boca Raton, FL (1994-1997). 10. LANGE'S HANDBOOK OF CHEMISTRY, 13th and 14th eds., McGraw-Hill, New York, NY (1985, 1992).

11. PERRY'S CHEMICAL ENGINEERING HANDBOOK, 5th and 6th eds., McGraw-Hill, New York, NY (1973, 1984).

12. Landolt-Bornstein, ZAHLENWERTE UND FUNKIONEN ANS PHYSIK, CHEMEI, ASTRONOMIE UND TECHNIK, Springer-Verlag, Heidelberg, Germany (1972-1997).

13. Kaye, G. W. C. and T. H. Laby, TABLES OF PHYSICAL AND CHEMICAL CONSTANTS, Longman Group Limited, London, England (1973).

14. Raznjevic, Kuzman, HANDBOOK OF THERMODYNAMIC TABLES AND CHARTS, Hemisphere Publishing Corp., New York, NY (1976).

15. Driesbach, R. R., PHYSICAL PROPERTIES OF CHEMICAL COMPOUNDS, Vol. I (No. 15), Vol. II (No. 22), Vol. III (No. 29), Advances in Chemistry Series, American Chemical Society, Washington, DC (1955,1959,1961).

16. Vargaftik, N. B., TABLES ON THE THERMOPHYSICAL PROPERTIES OF LIQUIDS AND GASES, 2nd ed., English translation, Hemisphere Publishing Corporation, New York, NY (1975, 1983).

17. Rabinovich, V. A., editor, THERMOPHYSICAL PROPERTIES OF GASES AND LIQUIDS, translated from Russian, U. S. Dept. Commerce, Springfield, VA (1970).

18. Horvath, A. L., PHYSICAL PROPERTIES OF INORGANIC COMPOUNDS, Crane, Russak & Company, Inc., New York, NY (1975).

19. Timmermans, J., PHYSICO-CHEMICAL CONSTANTS OF PURE ORGANIC COMPOUNDS, Vols. 1 and 2, Elsevier, New York, NY (1950,1965).

20. ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd and 4th eds., John Wiley and Sons, Inc., New York, NY (1978-1997). 21. Sax, N. I. and R. J. Lewis, Jr., HAWLEY'S CONDENSED CHEMICAL DICTIONARY, 11th ed., Van Nostrand Reinhold Co., New

York, NY (1987).

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Corporation, New York, NY (1989).

23. THERMOPHYSICAL PROPERTIES OF MATTER, 1st and 2nd eds., IFI/Plenum, New York, NY (1970-1976).

24. Ho, C. Y., P. E. Liley, T. Makita and Y. Tanaka, PROPERTIES OF INORGANIC AND ORGANIC FLUIDS, Hemisphere Publishing Corporation, New York, NY (1988).

25. Verschueren, K., HANDBOOK OF ENVIRONMENTAL DATA ON ORGANIC CHEMICALS, Van Nostrand Reinhold, New York, NY (1996).

26. Lide, D. R. and H. V. Kehianian, CRC HANDBOOK OF THERMOPHYSICAL AND THERMOCHEMICAL DATA, CRC Press, Boca Raton, FL (1994).

27. Bretsznajder, S., PREDICTION OF TRANSPORT AND OTHER PHYSICAL PROPERTIES OF FLUIDS, International Series of Monographs in Chemical Engineering, Vol. 2, Pergamon Press, Oxford, England (1971).

28. Lyman, W. J., W. F. Reehl and D. H. Rosenblatt, HANDBOOK OF CHEMICAL PROPERTY ESTIMATION METHODS, McGraw-Hill, New York, NY (1982).

29. Reid, R. C., J. M. Prausnitz and B. E. Poling, THE PROPERTIES OF GASES AND LIQUIDS, 3rd ed. (R. C. Reid and T. K. Sherwood), 4th ed., McGraw-Hill, New York, NY (1977, 1987).

30. Baum, E. J., CHEMICAL PROPERTY ESTIMATION, Lewis Publishers, New York, NY (1998).

31. Mackay, D., W. Y. Shiu and K. C. Ma, ILLUSTRATED HANDBOOK OF PHYSICAL-CHEMICAL PROPERTIES AND ENVIRONMENTAL FATE FOR ORGANIC CHEMICALS, Vols. 1, 2, 3, 4 and 5, Lewis Publishers, New York, NY (1992, 1992, 1993, 1995, 1997).

32. Yaws, C. L., PHYSICAL PROPERTIES, McGraw-Hill, New York, NY (1977).

33. Yaws, C. L., THERMODYNAMIC AND PHYSICAL PROPERTY DATA, Gulf Publishing Co., Houston, TX (1992).

34. Yaws, C. L. and R. W. Gallant, PHYSICAL PROPERTIES OF HYDROCARBONS, Vols. 1 (2nd ed.), 2 (3rd ed.), 3 and 4, Gulf Publishing Co., Houston, TX (1992,1993,1993,1995).

35. Zwolinski, B. J. and R. C. Wilhoit, VAPOR PRESSURES AND HEATS OF VAPORIZATION OF HYDROCARBONS AND RELATED COMPOUNDS, Thermodynamic Research Center, TAMU, College Station, TX (1971).

36. Boublick, T., V. Fried and E. Hala, THE VAPOUR PRESSURES OF PURE SUBSTANCES, 1st and 2nd eds., Elsevier, New York, NY (1975, 1984).

37. Ohe, S., COMPUTER AIDED DATA BOOK OF VAPOR PRESSURE, Data Book Publishing Company, Tokyo, Japan (1976). 38. Altunin, V. V., V. Z. Geller, E. K. Petrov, D. C. Rasskazov, and G. A. Spiridonov, THERMOPHYSICAL PROPERTIES OF

FREONS, Methane Series, Parts 1 and 2, Hemisphere Publishing Corporation, New York, NY (1987).

39. Howard, P. H. and W. M. Meylan, eds., HANDBOOK OF PHYSICAL PROPERTIES OF ORGANIC CHEMICALS, CRC Press, Boca Raton, FL (1997).

40. Yaws, C. L. and others, Hydrocarbon Processing, 68, 61 (July, 1989).

41. Yaws, C. L., HANDBOOK OF VAPOR PRESSURE, Vols. 1, 2, 3 and 4, Gulf Publishing Co., Houston, TX (1994,1994,1994,1995). 42. Yaws, C. L., HANDBOOK OF TRANSPORT PROPERTY DATA, Gulf Publishing Co., Houston, TX (1995).

43. Yaws, C. L., HANDBOOK OF THERMODYNAMIC DIAGRAMS, Vols. 1, 2, 3 and 4, Gulf Publishing Co., Houston, TX (1996). 44. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

REFERENCES - INORGANIC COMPOUNDS

1-29. See above REFERENCES - ORGANIC COMPOUNDS

30. Ohse, R. W., HANDBOOK OF THERMODYNAMIC AND TRANSPORT PROPERTIES OF ALKALI METALS, Blackwell Scientific Publications, London, England (1985).

31. Mellor, J. W., INORGANIC AND THEORETICAL CHEMISTRY, original volumes and supplements, Longmans, Green and Co., London, England (1956-present).

32. GMELIN'S HANDBOOK OF INORGANIC CHEMISTRY, original volumes and supplements, Weinheim Verlag Chemie (1966 -present).

33. Bailar, J. C., H. J. Emel'eus and A. F. Trotman-Dickenson, COMPREHENSIVE INORGANIC CHEMISTRY, Pergamon Press, Elmsford, NJ (1973).

34. Samsonov, G. V., ed., HANDBOOK OF THE PHYSICO-CHEMICAL PROPERTIES OF THE ELEMENTS, Plenum, Washington, DC (1968).

35. Barin, I. and O. Knacke, THERMOCHEMICAL PROPERTIES OF INORGANIC SUBSTANCES, Springer-Verlag, New York, NY (1973).

36. Yaws, C. L. and others, Solid State Technology, 16 (1), 39 (1973). 37. Yaws, C. L. and others, Solid State Technology, 17 (1), 47 (1974). 38. Yaws, C. L. and others, Solid State Technology, 17 (11), 31 (1974). 39. Yaws, C. L. and others, Chem. Eng., 81 (12), 70 (June 10, 1974). 40. Yaws, C. L. and others, Chem. Eng., 81 (14), 85 (July 8, 1974). 41. Yaws, C. L. and others, Chem. Eng., 81 (17), 99 (August 19, 1974). 42. Yaws, C. L. and others, Chem. Eng., 81 (20), 115 (Sept. 30, 1974). 43. Yaws, C. L. and others, Chem. Eng., 81 (23), 113 (Oct. 28, 1974). 44. Yaws, C. L. and others, Chem. Eng., 81 (25), 178 (Nov. 25, 1974). 45. Yaws, C. L. and others, Chem. Eng., 81 (27), 67 (Dec. 23, 1974). 46. Yaws, C. L. and others, Chem. Eng., 82 (2), 99 (Jan. 20, 1975). 47. Yaws, C. L. and others, Chem. Eng., 82 (4), 87 (Feb. 17, 1975). 48. Yaws, C. L. and others, Solid State Technology, 21 (No.1), 43 (1978). 49. Yaws, C. L. and others, Solid State Technology, 22 (No.2), 65 (1979).

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50. Yaws, C. L. and others, Solid State Technology, 24 (No.1), 87 (1981). 51. Yaws, C. L. and others, J.Ch.I.Ch.E., 12, 33 (1981).

52. Yaws, C. L. and others, J.Ch.I.Ch.E., 14, 205 (1983).

53. Yaws, C. L. and others, Ind. Eng. Chem. Process Des. Dev., 23, 48 (1984). 54. Yaws, C. L. and others, J. Chem. Eng. Data, 40 (1), 15 (1995).

55. Yaws, C. L. and others, J. Chem. Eng. Data, 40 (1), 18 (1995).

56. Yaws, C. L., PHYSICAL PROPERTIES, McGraw-Hill, New York, NY (1977).

57. Ohe, S., COMPUTER AIDED DATA BOOK OF VAPOR PRESSURE, Data Book Publishing Company, Tokyo, Japan (1976). 58. Nesmeyanov, A. N., VAPOR PRESSURE OF THE CHEMICAL ELEMENTS, Elsevier, New York, NY (1963).

59. Boublick, T., V. Fried and E. Hala, THE VAPOUR PRESSURES OF PURE SUBSTANCES, 1st ed., 2nd ed., Elsevier, New York, NY (1975, 1984).

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Chapter 2 HEAT CAPACITY OF GAS

Carl L. Yaws, Xiaoyan Lin, Li Bu, Sachin Nijhawan, Deepa R. Balundgi and Saumya Tripathi Lamar University, Beaumont, Texas

ABSTRACT

Results for heat capacity of ideal gas as a function of temperature are presented for major organic and inorganic compounds. The results cover a wide temperature range and include hydrocarbon, oxygen, nitrogen, halogen, sulfur, silicon and many other chemical types. The agreement between correlation and data is quite good.

INTRODUCTION

Thermodynamic properties such as heat capacity are important in the engineering design of chemical processes. In gas-phase chemical reactions, the heat capacity is required to determine the energy (heat) necessary to bring the chemical reactants up to reaction temperature. Additional uses include generalized heat exchanger and energy balance design calculations.

In this article, correlation results for heat capacity of gas are provided in an easy-to-use tabular format that is especially applicable for rapid engineering use with the personal computer or hand calculator. HEAT CAPACITY CORRELATION

The correlation for heat capacity of the ideal gas is a series expansion in temperature: CP = A + B T + C T

2

+ D T3 + E T4 (2-1)

where CP = heat capacity of ideal gas, joule/(mol K)

A, B, C, D, E = regression coefficients for chemical compound T = temperature, K

The results for heat capacity of gas are given in Tables 2-1 and 2-2. The tabulations are based on regression of experimental data and estimates from an extensive literature search for organics (1-40) and inorganics (1-78). Both experimental values for the property under consideration and parameter values for estimation of the property are included in the source publications. The numerous data points were processed with a generalized least-squares computer program for minimizing the deviations.

The tabulation for organic compounds is applicable to a wide variety of substances: hydrocarbons (alkanes, olefins, acetylenes, cycloalkanes, ....); oxygenates (alcohols, aldehydes, ketones, acids, ethers, glycols, anhydrides, ....); halogenates (chlorinated, brominated, fluorinated and iodinated compounds); nitrogenates (nitriles, amines, cyanates, amides, ....); sulfur compounds (mercaptans, sulfides, sulfates, ....); silicon compounds (silanes, chlorosilanes, ....) and many other chemical types.

The tabulation for inorganic compounds is also comprehensive: carbon oxides (carbon monoxide, carbon dioxide,...); nitrogen oxides (nitric oxide, nitrous oxide,...); sulfur oxides (sulfur dioxide, sulfur trioxide,...); hydrogen oxides (water, hydrogen peroxide,...); ammonias (ammonia, ammonium hydroxide,...); hydrogen halides (hydrogen chloride, hydrogen fluoride,...); sulfur acids (sulfuric acid, hydrogen sulfide,...); hydroxides (sodium hydroxide, potassium hydroxide,...); silicon halides (trichlorosilane, silicon tetrachloride,...); ureas (urea, thiourea,...); cyanides (hydrogen cyanide, cyanogen chloride,...); hydrides (silane, diborane,...); sodium derivatives (sodium chloride, sodium fluoride,...); aluminum derivatives (aluminum bromide, aluminum chloride,...) and many other compound types. Many elements are covered: hydrogen, nitrogen, oxygen, helium, argon, neon, chlorine, bromine, iodine, fluorine, sulfur, phosphorous, aluminum, lead, tin, mercury, sodium, magnesium, silicon, antimony, boron, iron, chromium, cobalt, titanium, tantalum, silver, gold, platinum, radon, uranium and many others chemical types.

A comparison of correlation and actual data for heat capacity is shown in Figure 2-1 for a representative chemical. The graph indicates good agreement of correlation and data.

EXAMPLES

The correlation results maybe used for prediction and calculation of heat capacity and other thermodynamic properties. Examples are given below.

Example 1 Estimate the heat capacity of carbon tetrachloride (CCl4) as a low-pressure gas at 500 K. Substitution of the coefficients from the table and temperature into the equation for heat capacity yields: CP = 19.816 + 3.3311E-01*500 - 5.0511E-04*5002 + 3.4057E-07*5003 - 8.4249E-11*5004

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CP = 97.40 joule/(mol K)

Example 2 Calculate the energy required to heat gaseous ethyl chloride (C2H5Cl) from 300 K to 600 K at low pressure.

From thermodynamics, the change in enthalpy, ∆H, at constant pressure is: ∆H = CP dT = (A + B*T + C*T2 + D*T3 + E*T4 ) dT

T2 ∆H = A*T + B/2*T2 + C/3*T3 + D/4*T4 + E/5*T5 ]

T1

Substitution of the coefficients from the table and the temperature limits into the equation provides: ∆H = 35.946*(600 - 300) + 5.2294E-02/2*(6002 - 3002) + 2.0321E-04/3*(6003 - 3003) - 2.2795E-07/4*(6004 - 3004)

+ 6.9123E-11/5*(6005 - 3005)

∆H = 24,760 joule/mol

Portions of this material appeared in Chem. Eng., 95 (No. 7), 91 (May 9, 1988) and are reprinted by special permission.

REFERENCES – ORGANIC COMPOUNDS

1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR

35. Pedley, J. B., THERMOCHEMICAL DATA AND STRUCTURES OF ORGANIC COMPOUNDS, Vol. I, Thermodynamics Research Center, College Station, TX (1994).

36. Frenkel, M., K. N. Marsh, R. C. Wilhoit, G. J. Kabo and G. N. Roganov, THERMODYNAMICS OF ORGANIC COMPOUNDS IN THE GAS STATE, Vols. I and II, Thermodynamics Research Center, College Station, TX (1994).

37. Suris, A. L., HANDBOOK OF THERMODYNAMIC HIGH TEMPERATURE PROCESS DATA, Hemisphere Publishing Corporation, New York, NY (1987).

38. Yaws, C. L., H. M. Ni and P. Y. Chiang, Chem. Eng., 95 (7), 91 (May 9, 1988).

(1997).

1-56. See REFERENCES - INORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 57. Chase, M. W. and others, JANAF THERMOCHEMICAL TABLES, 1974 Supplement, J. Phys. Chem. Ref. Data, 3(2), (1974). 58. Chase, M. W. and others, JANAF THERMOCHEMICAL TABLES, 1975 Supplement, J. Phys. Chem. Ref. Data, 4(1), (1975). 59. Chase, M. W. and others JANAF THERMOCHEMICAL TABLES, Parts 1 and 2, 3rd ed., J. Phys. Chem. Ref. Data, 4, Supplement

No. 1 (1985).

60. Wagman, D. D. and others, THE NBS TABLES OF CHEMICAL THERMODYNAMIC PROPERTIES, J. Phys. Chem. Ref. Data, 4, Supplement No. 2 (1982).

61. Kelley, K. K., CONTRIBUTIONS TO THE DATA ON THEORETICAL METALLURGY, Bulletin 584, United States Government Printing Office, Washington, DC (1960).

62. Wicks, C. E. and F. E. Block, THERMODYNAMIC PROPERTIES OF 65 ELEMENTS - THEIR OXIDES, HALIDES, CARBIDES AND NITRIDES, Bulletin 605, United States Government Printing Office, Washington, DC (1963).

63. Wagman, D. D. and others, SELECTED VALUES OF CHEMICAL THERMODYNAMIC PROPERTIES, NBS Technical Note 270-3, United States Government Printing Office, Washington, DC (1968).

64. Karapet'yants, M. Kh. and M. L. Karapet'yants, THERMODYNAMIC CONSTANTS OF INORGANIC AND ORGANIC COMPOUNDS, Ann Arbor - Humphrey Science Publishers, Ann Arbor, MH (1970).

65. Lesieecki, M.L. and J. S. Shirk, J. Chem. Phys., 56, 4171 (1972).

66. Sherman, R. H. and W. F. Giauque, J. Amer. Chem. Soc., 77, 2154 (1955).

67. Frenkel, M. L. and E. A. Gusev, G. Ya. Kabo, J. Appl. Chem. of the USSR, 56 (1), 204 (1983). 68. Kunchur, N. R. and M. R. Truter, J. Chem. Soc., 2551 (1958).

69. Goodwin, R. D., J. Phys. Chem. Ref. Data, 14 (4), 849 (1985). 70. McBride, B. J. and S. Gordon, J. Chem. Phys., 35, 2198 (1961). 71. Nagarajan, G., Bull. Soc. Chim. Belges., 72, 524 (1963).

72. Harrison, B. and W. H. Seaton, Ind. Eng. Chem. Res., 27, 1536 (1988). 73. Nagarajan, G. and S. B. Cotter, Z. Naturforsch. A., 26(11), 1800 (1971). 74. Ott, J. B. and W. F. Giauque, J. Amer. Chem. Soc., 82, 1308 (1960). 75. Cerny, C. and E. Erdos, Chem. List., 47, 1742 (1953).

76. Golosova, R. M., V. V. Korobov and M. Kh. Karapet-yants, Russ. J. Phys. Chem., 45(5), 598 (1971). 77. Cerny, C., and E. Erdos, Collect. Czech. Chem. Commun., 19, 646 (1954).

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Chapter 3 HEAT CAPACITY OF LIQUID

Carl L. Yaws, Xiaoyan Lin, Li Bu, Sachin Nijhawan, Deepa R. Balundgi and Saumya Tripathi Lamar University, Beaumont, Texas

ABSTRACT

Results for heat capacity of liquid as a function of temperature are presented for major organic and inorganic chemicals. The results cover a wide temperature range and include many compound types. The agreement between correlation and data is quite good.

INTRODUCTION

Thermodynamic properties such as liquid heat capacity are important in the engineering design of chemical processes. In liquid-phase chemical reactions, the liquid heat capacity is required to determine the energy (heat) necessary to bring the liquid chemical reactants up to reaction temperature. Additional uses include heat exchanger and energy balance design calculations.

In this article, correlation results for liquid heat capacity are provided in an easy-to-use tabular format that is especially applicable for rapid engineering use with the personal computer or hand calculator.

HEAT CAPACITY CORRELATION

The correlation for heat capacity of liquid is a series expansion in temperature: CP = A + B T + C T

2

+ D T3 (3-1)

where CP = heat capacity of liquid, joule/(mol K)

A, B, C and D = regression coefficients for chemical compound T = temperature, K

The results for heat capacity of liquid are given in Tables 3-1 and 3-2. In preparing the compilation, a literature search was conducted to identify data source publications for organics 43) and inorganics (1-104). Both experimental values for the property under consideration and parameter values for estimation of the property are included in the source publications. The publications were screened for appropriate data. The compilation resulting from the screening is based on both experimental data and estimated values.

For organic compounds, most of the estimates were based on group contribution (Cheuh-Swanson, 29), corresponding states (Lee-Kesler, 29) and boiling point methods (Yaws and co-workers). The relation of (heat capacity)(densityn)=constant was utilized to extend both experimental data and estimates. Values of n ranged from 1/2 to 1. Experimental data and estimates were then regressed to provide the same equation for all compounds.

For inorganic compounds, many of the estimates are based on the JANAF tables (57-59), Bureau of Mines bulletins (60-63) and group contribution methods. The relation of (heat capacity)(densityn)=constant was utilized to extend both experimental data and estimates.

Very limited experimental data for liquid heat capacity are available at temperatures in the region of the melting point temperature. Data in the boiling-critical point temperature interval are also very scarce. Thus, the values in the region of the melting point and in the boiling-critical point temperature interval should be considered rough approximations. The values in the intermediate region (above melting and below boiling point) are more accurate.

A comparison of correlation and actual data for liquid heat capacity is shown in Figure 3-1 for a representative chemical. The graph discloses good agreement of correlation and data.

EXAMPLES

The correlation results maybe used for prediction and calculation of heat capacity and additional thermodynamic properties. Examples are given below.

Example 1 Estimate the liquid heat capacity of pentane (C5H12) at 298.15 K.

Substitution of the coefficients from the table and temperature into the equation for heat capacity yields:

CP = 80.641 + 6.2195E-01*298.15 – 2.2682E-03*298.152 + 3.7423E-06*298.153

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thermodynamics, the change in enthalpy, ∆H, at constant pressure is: ∆H = CP dT = (A + B*T + C*T2 + D*T3 ) dT

T2 ∆H = A*T + B/2*T2 + C/3*T3 + D/4*T4]

T1

Substitution of the coefficients from the table and the temperature limits into the equation provides: ∆H = 83.703*(500 - 300) + 5.1666E-01/2*(5002 - 3002) – 1.4910E-03/3*(5003 - 3003) + 1.9725E-06/4*(5004 - 3004)

Portions of this material appeared in Hydrocarbon Processing, 70, 73 (December, 1991) and Chem. Eng., 99, 130 (April, 1992). These portions are reprinted by special permission.

1-36. See REFERENCES - ORGANIC COMPOUNDS in Chapter 2 HEAT CAPACITY OF GAS

37. Altunin, V. V., V. Z. Geller, E. K. Petrov, D. C. Rasskazov, and G. A. Spiridonov, THERMOPHYSICAL PROPERTIES OF FREONS, Methane Series, Part 1, Hemisphere Publishing Corporation, New York, NY (1987).

38. Altunin, V. V., V. Z. Geller, E. A. Kremenevskaya, I. I. Perelshtein, and E. K. Petrov, THERMOPHYSICAL PROPERTIES OF FREONS, Methane Series, Part 2, Hemisphere Publishing Corporation, New York, NY (1987).

39. Wilhoit, R. C. and B. J. Zwolinski, PHYSICAL AND THERMODYNAMIC PROPERTIES OF ALIPHATIC ALCOHOLS, American Chemical Society, American Institute of Physics, National Bureau of Standards, New York, NW (1973).

40. Yaws, C. L. and others, Hydrocarbon Processing, 70, 73 (December, 1991). 41. Yaws, C. L. and others, Chem. Eng., 99, 130 (April, 1992).

(1997).

1-64. See REFERENCES - INORGANIC COMPOUNDS in Chapter 2 HEAT CAPACITY OF GAS

65. Lyon, R. N., ed., LIQUID-METALS HANDBOOK, 2nd ed., Atomic Energy Commission, Washington, DC (1954).

66. Janz, G. J. and C. B. Allen, PHYSICAL PROPERTIES DATA COMPILATIONS RELEVANT TO ENERGY STORAGE. II. MOLTEN SALTS: DATA ON SINGLE AND MULTICOMPONENT SALT SYSTEMS, Nat. Bur.Stand., Molten Salts Data Center, Troy, NY (April 1979).

67. Fink, J. K., TABLES OF THERMODYNAMIC PROPERTIES OF SODIUM, Argonne National Lab., ANL-CEN-RSD-82-4, Chemical Engineering Division, Argonne, IL (June, 1982).

68. Mills, K. C., THERMODYNAMIC DATA FOR INORGANIC SULPHIDES, SELENIDES AND TELLURIDES, Butterworths, London, England (1974).

69. Tarakad, R. R. and R. P. Danner, AIChE J. 23(6), 944 (1977) and 23(5), 685, (1977). 70. Chueh, C. F. and A. C. Swanson, Chem. Eng. Prog. 69(7), 83 (1973).

71. Giauque, W. F. and T. M. Powell, J. Amer. Chem. Soc. 61, 1970 (1939). 72. Davis, C. M., Jr., J. Chem. Phys. 45(7), 2461 (1966).

73. Hu, J., D. White and H. L. Johnston, J. Amer. Chem. Soc., 15, 5642 (1953).

74. Smith, T. O. and B. M. Fabuss, Wright Air Development Center, Technical Report 59-327 (1962). 75. Grosh, J. and M. S. Jhon, Proc. Nat. Acad. Sci. 54, 1004 (1965).

76. Hu, J. H. and D. White, J. Amer. Chem. Soc. 75, 1232 (1953). 77. Giauque, W. F. and R. Wieke, J. Amer. Chem. Soc., 51, 1441 (1929). 78. Forsythe, W. R. and W. F. Giauque, J. Amer. chem. Soc., 64, 48 (1948). 79. Evans, W. H. and R. Jacobson, J. Res. Nat. Bur. Stand., 55, 83 (1955). 80. Douglas, T. B. and A. F. Ball, J. Amer. Chem. Soc. 74, 2472 (1952). 81. Douglas, T. B. and L. F. Epstein, J. Amer. Chem. Soc., 77, 2144 (1955). 82. Haar, L. and J. S. Gallagher, J. Phys. Chem. Ref. Data, 7(3), 635 (1978). 83. Giauque, W. F. and J. O. Clayton, J. Amer. Chem. Soc., 55, 4875 (1933). 84. Wiebe, R. and M. J. Brevoort, J. Amer. Chem. Soc., 51, 622 (1930). 85. Scott, D. W. and G. D. Oliver, J. Amer. Chem. Soc., 71, 2293 (1949). 86. Giauque, W. F. and J. D. Kemp, J. Chem. Phys., 6, 40 (1938).

87. McCarty, R. D. and L. A. Weber, Nat. Bur. of Stand. Tech. Note 384, Washington DC (1971). 88. Giauque W. F. and H. L. Johnston, J. Amer. Chem. Soc., 51, 2300 (1929).

89. Jenkins, A. C. and F. S. Dipaolo, J. Chem. Phys., 25(2), 296 (1956). 90. Lee, B. I. and M. G. Kesler, AIChE J., 21(3), 510 (1975).

91. Ott, J. B. and W. F. Giauque, J. Amer. Chem. Soc., 82, 1308 (1960). 92. McDonald, R. A., J. Chem. Eng. Data, 12, 115 (1967).

93. Majer, V., V. Svoboda and M. Lencka, J. Chem. Thermo., 17, 365 (1985). 94. Sherman, R. H. and W. F. Giauque, J. Amer. Chem. Soc., 77, 2154 (1955).

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95. Clarke, J. T., E. B. Rifkin and H. L. Johnston, J. Amer. Chem. Soc., 75, 781 (1953). 96. Jhon, J. S., J. Grosh and H. Eyring, J. Phys. Chem.,71(7), 2533 (1967).

97. Pace E. L. and M. A. Reno, J. Chem. Phys., 48(3), 1231 (1968). 98. Pace, E. L. and M. A. Reno, J. Chem. Phys., 48(3), 1231 (1968). 99. Clayton, J. O. and W. F. Giauque, J. Amer. Chem. Soc., 54, 2610 (1932). 100. Kaischeu, R., Z. Phys. Chem., B40, 273 (1938).

101. Kemp, J. D. and W. F. Giauque, J. Amer. Chem. Soc., 59, 79 (1937). 102. Void, R. D., J. Amer. Chem. Soc., 59, 1515 (1937).

103. Weissler, A., J. Amer. Chem. Soc. 71, 1272 (1949).

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Chapter 4 HEAT CAPACITY OF SOLID

Carl L. Yaws, Deepa R. Balundgi and Saumya Tripathi Lamar University, Beaumont, Texas

ABSTRACT

Results for heat capacity of solid as a function of temperature are presented for major organic and inorganic chemicals. The results cover a wide temperature range and include many types of compounds. The agreement between correlation and data is quite good.

INTRODUCTION

Thermodynamic properties such as heat capacity are important in the engineering design of chemical processes. In unit operations involving solids at elevated temperatures, the heat capacity is required to determine the energy (heat) necessary to bring the solids up to the required processing temperature. Additional uses include heat exchanger and energy balance design calculations.

In this article, correlation results for heat capacity of solids are provided in an easy-to-use tabular format that is especially applicable for rapid engineering use with the personal computer or hand calculator. HEAT CAPACITY CORRELATION

The correlation for heat capacity of solid is a series expansion in temperature: CP = A + B T + C T

2

(4-1)

where CP = heat capacity of solid, joule/(mol K)

A, B, C = regression coefficients for chemical compound T = temperature, K

The results for heat capacity of solid are given in Tables 4-1 and 4-2. The tabulations are applicable to a wide variety of substances.

In preparing the compilation, a literature search was conducted to identify data source publications for organics (1-38) and inorganics (1-104). Both experimental values for the property under consideration and parameter values for estimation of the property are included in the source publications. The publications were screened for appropriate data. The compilation resulting from the screening is based on both experimental data and estimated values. For organics, many of the values are based on sources from DIPPR (4). For inorganics, many of the values are based on sources from JANAF tables (57-59) and Thermophysical Properties of Matter (23). The estimates are primarily based on empirical methods of the senior author. Experimental data and estimates were then regressed to provide the same equation for all compounds.

Very limited experimental data for solid heat capacity are available at very low temperatures. Thus, the estimated values at very low temperatures should be considered rough approximations. The values for substances that are solids at room temperature are more accurate.

A comparison of correlation and actual data values for heat capacity is shown in Figure 4-1 for a representative chemical. The graph indicates good agreement of correlation and data.

EXAMPLES

The correlation results maybe used for prediction and calculation of heat capacity and additional thermodynamic properties. Examples are given below.

Example 1 Estimate the solid heat capacity of phenol (C6H6O) at 298.15 K.

Substitution of the coefficients from the table and temperature into the equation for heat capacity yields:

CP = 9.769 + 4.0832E-01*298.15 – 1.9001E-05*298.152

Example 2 Calculate the energy required to heat solid naphthalene (C10H8) from 100 K to 300 K. From thermodynamics, the change in enthalpy, _∆H, at constant pressure is:

∆H = CP dT = (A + B*T + C*T2 ) dT

T2 ∆H = A*T + B/2*T2 + C/3*T3]

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Substitution of the coefficients from the table and the temperature limits into the equation provides: ∆H = 4.824*(300 - 100) + 5.0634E-01/2*(3002 - 1002) + 1.8503E-04/3*(3003 - 1003)

REFERENCES - ORGANIC COMPOUNDS

1-36. See REFERENCES - ORGANIC COMPOUNDS in Chapter 2 HEAT CAPACITY OF GAS

37. Stull, D. R., E. F. Westrum, Jr., and G. C. Sinke, THE CHEMICAL THERMODYNAMICS OF ORGANIC COMPOUNDS, John Wiley and Sons, New York, NY (1969).

38. Stull, D. R., and H. Prophet, Project Directors, JANAF THERMOCHEMICAL TABLES, 2nd edition, NSRDS-NBS 37, U. S. Government Printing Office, Washington DC (1971).

1-64. See REFERENCES - INORGANIC COMPOUNDS in Chapter 2 HEAT CAPACITY OF GAS

65. Lyon, R. N., ed., LIQUID-METALS HANDBOOK, 2nd ed., Atomic Energy Commission, Washington, DC (1954).

66. Fink, J. K., TABLES OF THERMODYNAMIC PROPERTIES OF SODIUM, Argonne National Lab., ANL-CEN-RSD-82-4, Chemical Engineering Division, Argonne, IL (June 1982).

67. Mills, K. C., THERMODYNAMIC DATA FOR INORGANIC SULPHIDES SELENIDES AND TELLURIDES, Butterworths, London, England (1974).

68. Booth, H. S. and D. R. Martin, BORON TRIFLUORIDE AND ITS DERIVATIVES, John Wiley and Sons, Inc., New York (1949). 69. McCarty, R. D., J. Hord and H. M. Roder, SELECTED PROPERTIES OF HYDROGEN, Center of Chemical Engineering, National

Engineering Laboratory, Nat. Bur. Stand. Monograph 168, Boulder, CO (1981).

70. Kaufmann, D. W., PHYSICAL PROPERTIES OF SODIUM CHLORIDE IN CRYSTAL, LIQUID, GAS AND ACQUEOUS SOLUTION STATES, Reinhold Pub. Corp., New York, NY (1960).

71. Roder, H. M. and L. A. Weber, eds., ASRDI OXYGEN TECHNOLOGY SURVEY, VOL. 1 : THERMAL PHYSICAL PROPERTIES, NASA-SP-3071, National Aeronautics and Space Administration, Washington, DC (1972).

72. Leadbetter, A. J., J. Phys. C : Solid State Physics, 1, 1481 (1968). 73. Long, E. A. and J. D. Kemp, J. Chem. Soc., 58(10), 1829 (1936).

74. Hu, J., D. White and H. L. Johnston, J. Amer. Chem. Soc., 15, 5642 (1953). 75. Giauque, W. F. and R. Wiebe, J. Amer. Chem. Soc., 50, 2193 (1928). 76. Giguere, P. A. and others, Can. J. Chem., 32, 117 (1954).

77. Lindenberg, A. B., Comptes Rend. Acad. Sci. Paris, 273, 1017 (1971). 78. Damphinee, T. M. and D. L. Martin, Proc. Roy. Soc., Ser. A233, 214 (1955). 79. Krier, C. A., R.S. Craig and W. E. Wallace, J. Phys. Chem., 61, 522 (1957). 80. Stull, D. R. and others, J. Chem. Eng. Data, 15, 52 (1970).

81. Leu, A. L. and others, Proc. Nat. Acad. Sci. USA, 72(3), 1026 (1975). 82. Brock, F. H., J. Am. Rocket Soc., 31(2), 265 (1966).

83. Overstreet, R. and W. F. Giauque, J. Amer. Chem. Soc., 59, 254 (1937). 84. Ziegler, W. T. and C. E. Messer, J. Amer. Chem. Soc., 63, 2694 (1941). 85. Sirkar, S. C. and J. Gupta, Indian J. of Phys., 12, 145 ( 1938).

86. McGraw, J., J. Amer. Chem. Soc., 53, 3683 (1931).

87. Brodale, G. E. and W. F. Giauque, J. Phys. Chem., 76(5), 737 (1972). 88. Paukov, I. E. and M. N. Laurent'eva, Russ. J. Phys. Chem., 43(8), (1969). 89. Shmidt, N. E., Russ. J. Inorg. Chem., 12(7), 929 (1967).

90. Brown, J. C., J. Chem. Soc. (LONDON), 987 (1903).

91. Stephenson, C. C. and others, J. Chem. Thermo., 1, 59 (1969). 92. Dewar, J. D., Proc. Roy Soc., 89A, 158 (1913).

93. Chihara, H., M. Nakamura and K. Masukane, Bull. Chem. Soc. Japan, 46, 97 (1973). 94. Andon, R. J. L. and others, Trans. Faraday Soc., 59, 2702 (1963).

95. Clever, H. L., E. F. Westrum and A. W. Cordes, J. Phys. Chem., 69, 1214 (1965). 96. Chao, T., Hydrocarbon Processing, 217 (Nov., 1980).

97. Eastman, E. D. and W. C. McGavock, J. Am. Chem. Soc., 59, 145 (1937). 98. Latimar, W. M., J. Amer. Chem. Soc., 44, 90 (1922).

99. Klein, M. L., J. A. Morrison and R. D. Weir, Trans. Faraday Soc., 48, 93 (1969). 100. Anderson, C. T., J. Amer. Chem. Soc., 58, 568 (1936).

101. Wietzel, V. R., A. Anorg. Allg. Chem., 116, 71 (1921). 102. Miller, R. W., J. Amer. Chem. Soc., 50, 2653 (1928). 103. Magnus, V. A., Z. Phys., 14, 5 (1913).

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Chapter 5 ENTHALPY OF VAPORIZATION

Carl L. Yaws, Xiaoyan Lin, Li Bu, Sachin Nijhawan, Deepa R. Balundgi, and Saumya Tripathi Lamar University, Beaumont, Texas

ABSTRACT

Results for enthalpy of vaporization are presented for major organic and inorganic compounds. The complete temperature range for the liquid is covered from freezing to the critical point for most of the compounds. The results are displayed in easy-to-use tabulations that are especially applicable for rapid engineering usage with the personal computer or hand calculator.

INTRODUCTION

Physical and thermodynamic property data such as enthalpy of vaporization are of special value to engineers in the chemical processing and petroleum refining industries. As an example, knowledge of the enthalpy of vaporization is required in the design of heat exchangers for vaporizing liquids. Other examples of usage include reboilers and overhead condensers in distillation. In this article, results for enthalpy of vaporization as a function of temperature are presented for a wide variety of compounds.

ENTHALPY OF VAPORIZATION CORRELATION

A modified Watson equation was selected for enthalpy of vaporization as a function of temperature:

∆Hvap = A (1 - T/TC) n

(5-1)

where ∆Hvap = enthalpy of vaporization, kjoule/mol

A, TC, and n = regression coefficients for chemical compound

T = temperature, K

The results for enthalpy of vaporization are given in Tables 5-1 and 5-2. In preparing the tabulations, a literature search was conducted to identify data source publications for organics 41) and inorganics (1-93). Both experimental values for the property under consideration and parameter values for estimation of the property are included in the source publications. The publications were screened for appropriate data. The compilation resulting from the screening is based on both experimental data and estimated values. In the absence of experimental data, estimates were primarily based on the Riedel equation (29). Experimental data and estimates were then regressed to provide the same equation for all compounds.

The tabulation discloses the temperature range for which the equation may be used. The respective minimum and maximum temperatures are denoted by TMIN and TMAX. The temperature TB is the normal

boiling point (temperature at which the vapor pressure is 1 atm). Results for enthalpy of vaporization at the normal boiling point are provided in the last column.

A comparison of calculated and experimental data values for enthalpy of vaporization is shown in Fig. 5-1 for a representative chemical. The graph indicates good agreement of correlation and data.

EXAMPLES

The correlation results may be used for prediction and calculation of enthalpy of vaporization. Examples are given below.

Example 1 Estimate the enthalpy of vaporization of carbon tetrafluoride (CF4) at 183.15 K.

Substitution of the regression coefficients from the table and temperature into the equation for enthalpy of vaporization yields

∆Hvap =16.6594*(1 - 183.15/227.5)0.349 ∆Hvap = 9.415 kjoule/mol

Example 2 Estimate the enthalpy of vaporization of ethane (C2H6) at 200 K.

Substitution of the regression coefficients from the table and temperature into the equation for enthalpy of vaporization yields

∆Hvap = 21.342*(1 - 200/305.42)0.403

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(June, 1990) and are reprinted by special permission. REFERENCES – ORGANIC COMPOUNDS

35. Edmister, W. C., APPLIED HYDROCARBON THERMODYNAMICS, Vols. 1 and 2, Vol 2 (2nd ed.), Gulf Publishing Co., Houston, TX (1961, 1974, 1984).

37. Wilhoit, R. C. and B. J. Zwolinski, PHYSICAL AND THERMODYNAMIC PROPERTIES OF ALIPHATIC ALCOHOLS, American Chemical Society, American Institute of Physics, National Bureau of Standards, New York, NY (1973).

38. Boublick, T., V. Fried and E. Hala, THE VAPOUR PRESSURES OF PURE SUBSTANCES, 1st ed., 2nd ed., Elsevier, New York, NY (1975, 1984).

39. Ohe, S., COMPUTER AIDED DATA BOOK OF VAPOR PRESSURE, Data Book Publishing Company, Tokyo, Japan (1976). 40. Howard, P. H. and W. M. Meylan, eds., HANDBOOK OF PHYSICAL PROPERTIES OF ORGANIC CHEMICALS, CRC Press, Boca

Raton, FL (1997).

41. Yaws, C. L. and others, Hydrocarbon Processing, 69, 87 (June, 1990).

1-56. See REFERENCES - INORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 57. Lyon, R. N., ed., LIQUID-METALS HANDBOOK, 2nd ed., Atomic Energy Commission, Washington, DC (1954).

61. Cox, J. D.and G. Pilcher, THERMOCHEMISTRY OF ORGANIC AND ORGANOMETALLIC COMPOUNDS, Academic Press, New York, NY (1970).

62. Kazavchinskii, Ya.Z., et al, HEAVY WATER THERMOPHYSICAL PROPERTIES, U. S. Department of Commerce, NBS, Washington, DC (1971).

63. Whalley, E., THE THERMODYNAMIC AND TRANSPORT PROPERTIES OF HEAVY WATER, Proc. Conf. Thermodyn. Trans. Prop. of Fluids, pp. 15-26, London, England (July, 1957).

64. Moore, G. A. and T. R. Shives, IRON (99.9 + %), Metals Handbook, 8th ed., 1206 (1961).

65. McCarty, R. D., HYDROGEN TECHNOLOGICAL SURVEY - THERMOPHYSICAL PROPERTIES, Prepared for Aerospace Research and Data Institute, NASA Lewis Research Center (1975).

66. McCarty, R. D., J. Hord and H. M. Roder, SELECTED PROPERTIES OF HYDROGEN (ENGINEERING DESIGN DATA), Center for Chemical Engineering, National Engineering Laboratory, Nat. Bur. Stand. Monograph, 168, Boulder, CO (1981).

67. Haar, L., J. S. Gallagher and G. S. Kell, NBS/NRC STEAM TABLES, THERMODYNAMIC AND TRANSPORT PROPERTIES AND COMPUTER PROGRAMS FOR VAPOR AND LIQUID STATES OF WATER IN SI UNITS, Hemisphere Publishing Corporation, Washington, DC (1984).

68. Keenan, J. H. ant others, STEAM TABLES. THERMODYNAMIC PROPERTIES OF WATER INCLUDING VAPOR, LIQUID AND SOLID PHASES, John Wiley & Sons, Inc., New York, NY (1969).

69. Kaufmann, D. W., ed., SODIUM CHLORIDE, Reinhold Pub. Corp., New York, NY (1960). 70. Parish, M. B., J. Chem. Eng. Data, 6(4), 592 (1961).

71. Leider, H. R., O. H. Krikorian and D. A. Young, Carbon, 11, 555 (1973). 72. Frank, A. and K. Clausius, Z. Phys. Chem., 42, 395 (1939).

73. Mascherpa, G., Rev. Chim. Miner., 2, 379 (1965).

74. Grubitsch, H. and E. Suppan, Monatsch. Chem., 93, 246 (1962). 75. Watson, K. M.,Ind. Eng. Chem. 23, 360 (1931).

76. Fischer, W. and O. Juberman, Z. Anorg. Chem., 227, 227 (1936). 77. Clausius, K. and G. Faber, Z. Phys. Chem., 51, 352 (1942).

78. Duisman, J. A. and S. A. Stern, J. Chem. Eng. Data, 14(4), 457 (1969). 79. Stern, S. A., J. L. Mullhaupt and W. B. Kay, Chem. Rev., 60, 185 (1960). 80. Foley, W. T. and P. A. Giguere, Can. J. Chem., 29, 895 (1951).

81. Abrahams, B. M., D. W. Osborne and B. Weinstock, Phys. Rev., 80(3), 336 (1980). 82. Gibbons, R. M. and C. McKinley, Adv. Cryog. Eng., 13, 375 (1968).

83. Wagman, D. and others, J. Phys. Chem. Ref. Data, Suppl. No. 2 (1982). 84. Lindenberg, A. B., Comptes Rend. Acad. Sci. Paris, 273, 1017 (1971). 85. Johnston, H. L. and W. F. Giauque, J. Amer. Chem. Soc., 51, 94 (1929). 86. Wanger, W., Cryogenics, 12(3), 214 (1972).

87. Couch, E. J., K. A. Kobe and L. J. Herth, J. Chem. Eng. Data, 6(2), 229 (1961). 88. Daniels, F. and A. C. Bright, J. Chem. Soc., 42, 1131 (1920).

89. Ladenburg, R. and R. Minkowski, Z. Phys., 6, 153 (1921).

90. West, W. A. and A. W. C. Menzies, J. Phys. Chem., 33(2), 1880 (1929). 91. Awbery, J. H., Proc. Phys. Soc. London, 39, 417 (1927).

92. Rigby, W., Chem. Ind., 1508 (1969).

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Chapter 7 VAPOR PRESSURE

Carl L. Yaws, Xiaoyan Lin, Li Bu, Deepa R. Balundgi and Saumya Tripathi Lamar University, Beaumont, Texas

ABSTRACT

Results for vapor pressure as a function of temperature are presented for major organic and inorganic chemicals. The coefficients in the equation for vapor pressure are displayed in easy-to-use tabulations that are especially applicable for rapid engineering usage with the personal computer or hand calculator. The chemicals encompass many compound types.

INTRODUCTION

Physical and thermodynamic property data such as vapor pressure are of special value to engineers in the chemical processing and petroleum refining industries. As an example, knowledge of the vapor pressure of the compound is required in the design of a storage vessel to contain the compound. In hazard analysis and vent system technology, vapor pressure at the specified temperature is important. In vapor-liquid operations, such as distillation, knowledge of vapor pressure (and activity coefficients) is required for determining K-values. In this article, results for vapor pressure as a function of temperature are presented.

VAPOR PRESSURE CORRELATION

The Antoine-type equation with extended terms was selected for correlation of vapor pressure as a function of temperature:

log10 P = A + B/T + C log10 T + D T + E T 2

(7-1)

where P = vapor pressure, mm Hg

A,B,C,D and E = regression coefficients for chemical compound T = temperature, K

The results for vapor pressure are given in Tables 7-1 and 7-2. The temperature range for which the equation may be used to predict vapor pressure is denoted by the respective minimum and maximum temperatures (TMIN and TMAX).

The tabulation for organic compounds is applicable to a wide variety of substances: hydrocarbons (alkanes, olefins, acetylenes, cycloalkanes, aromatics, ....); oxygenates (alcohols, aldehydes, ketones, acids, ethers, glycols, anhydrides, ....); halogenates (chlorinated, brominated, fluorinated and iodinated compounds); nitrogenates (nitriles, amines, cyanates, amides, ....); sulfur compounds (mercaptans, sulfides, sulfates, ....); silicon compounds (silanes, chlorosilanes, ....) and many other types.

The tabulation for inorganic compounds provides coverage for a wide range of substances: carbon oxides (carbon monoxide, carbon dioxide,...); nitrogen oxides (nitric oxide, nitrous oxide,...); sulfur oxides (sulfur dioxide, sulfur trioxide,...); hydrogen oxides (water, hydrogen peroxide,...); ammonias (ammonia, ammonium hydroxide,...); hydrogen halides (hydrogen chloride, hydrogen fluoride,...); sulfur acids (sulfuric acid, hydrogen sulfide,...); hydroxides (sodium hydroxide, potassium hydroxide,...); silicon halides (trichlorosilane, silicon tetrachloride,...); ureas (urea, thiourea,...); cyanides (hydrogen cyanide, cyanogen chloride,...); hydrides (silane, diborane,...); sodium derivatives (sodium chloride, sodium fluoride,...); aluminum derivatives (aluminum borohydride, aluminum fluoride,...) and many other compound types. Many elements (total = 82) are covered: hydrogen, nitrogen, oxygen, helium, argon, neon, chlorine, bromine, iodine, fluorine, sulfur, phosphorous, aluminum, lead, tin, mercury, sodium, magnesium, silicon, antimony, boron, iron, chromium, cobalt, titanium, tantalum, silver, gold, platinum, radon, uranium and many others.

In preparing the compilation, a literature search was conducted to identify data source publications for organics (1-41) and inorganics (1-61). Both experimental values for the property under consideration and parameter values for estimation of the property are included in the source publications. The publications were screened for appropriate data. The compilation resulting from the screening is based on both experimental data and estimated values. In the absence of experimental data, estimates were primarily based on Riedel equation (29) and on adjusting the A value in the equation to match the boiling point temperature of the compound. The estimates of the other coefficients for the compound were based on the same values of the compound's brother (closest member of same chemical family). Experimental data and estimates were then regressed to provide the same equation for all compounds.

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A comparison of calculated values and experimental data for vapor pressure is shown in Figure 7-1 for a representative chemical. The graph indicates good agreement of calculations and data.

EXAMPLES

The tabulated values maybe used for prediction and calculation of vapor pressure. Examples are given below.

Example 1 Estimate the vapor pressure of methanol (CH4O) at a temperature of 25.13 C (298.28 K). Substitution of the coefficients from the table and temperature into the equation for vapor pressure yields:

log10 P = 45.6171 - 3.2447E+03/298.28 - 1.3988E+01*log10(298.28) + 6.6365E-03*298.28 - 1.0507E-13*298.282 = 2.1034

P = 102.1034 P = 126.88 mm Hg

The calculated and data values compare favorably (126.88 vs 127.90, deviation = 0.80%). Example 2 Estimate the vapor pressure of acetone (C3H60) at a temperature of 47.35 C (320.50 K).

Substitution of the coefficients from the table and temperature into the equation for vapor pressure yields:

log10 P = 28.5884 - 2.4690E+03/320.50 - 7.3510E+00*log10(320.50) + 2.8025E-10*320.50 + 2.7361E-06*320.502 = 2.7456

P = 102.7456 P = 556.71 mm Hg

The calculated and data values compare favorably (556.71 vs 558.40, deviation = 0.30%).

38. Ohe, S., COMPUTER AIDED DATA BOOK OF VAPOR PRESSURE, Data Book Publishing Company, Tokyo, Japan (1976). 39. Howard, P. H. and W. M. Meylan, eds., HANDBOOK OF PHYSICAL PROPERTIES OF ORGANIC CHEMICALS, CRC Press, Boca

Raton, FL (1997).

40. Yaws, C. L., HANDBOOK OF VAPOR PRESSURE, Vols. 1, 2, 3 and 4, Gulf Publishing Co., Houston, TX (1994,1994,1994,1995). 41. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

1-56. See REFERENCES - INORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR

57. Daubert, T. E. and R. P. Danner, DATA COMPILATION OF PROPERTIES OF PURE COMPOUNDS, Parts 1, 2, 3 and 4, Supplements 1 and 2, DIPPR Project, AIChE, New York, NY (1985-1992).

58. Nesmeyanov, A. N., VAPOR PRESSURE OF THE CHEMICAL ELEMENTS, Elsevier, New York, NY (1963).

60. Ohe, S., COMPUTER AIDED DATA BOOK OF VAPOR PRESSURE, Data Book Publishing Company, Tokyo, Japan (1976). 61. Hultgren, R., P. D. Desai, D. T. Hawkins, M. Gleiser, K. K. Kelley and D. D. Wagman, SELECTED VALUES OF THE

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Chapter 9 SURFACE TENSION

Carl L. Yaws, Xiaoyan Lin, Li Bu and Sachin Nijhawan Lamar University, Beaumont, Texas

ABSTRACT

Results for surface tension are presented for major organic and inorganic chemicals. For many of the chemicals, the complete temperature range for the liquid is covered from freezing point to the critical point. The results are displayed in easy-to-use tabulations that are especially applicable for rapid engineering usage with the personal computer or hand calculator.

INTRODUCTION

Physical and thermodynamic property data such as surface tension are of special value to engineers in the chemical processing and petroleum refining industries. As an example, surface tension data are important in many chemical-process engineering applications, such as heat, mass and momentum transfer operations that involve process equipment such as heat exchangers, distillation columns, absorption and fluid-flow piping. In this article, results for surface tension as a function of temperature are presented for a wide variety of compounds.

SURFACE TENSION CORRELATION

A modified Othmer relation was selected for correlation of surface tension as a function of temperature:

sigma = A (1 - T/TC)

n

(9-1) where sigma = surface tension, dynes/cm

A, TC and n = regression coefficients for chemical compound

T = temperature, K

The results for surface tension are given in Tables 9-1 and 9-2. The tabulations are arranged by chemical formula to provides ease of use in quickly locating data. A wide variety of substances are covered. The range for application is denoted by the respective minimum and maximum temperatures (TMIN and TMAX).

In preparing the compilation, a literature search was conducted to identify data source publications for organics (1-40) and inorganics (1-112). Both experimental values for the property under consideration and parameter values for estimation of the property are included in the source publications. The publications were screened for appropriate data. The compilation resulting from the screening is based on both experimental data and estimated values. In the absence of experimental data, estimates were primarily based on Sugden method (group contribution, 29) and Brock and Bird correlation (corresponding states, 29). Experimental data and estimates were then regressed to provide the same equation for all compounds.

A comparison of calculations and data for surface tension is shown in Figure 9-1 for a representative chemical. The graph indicates good agreement of calculations and data.

EXAMPLES

The correlation results maybe used for prediction and calculation of surface tension. Examples are given below.

Example 1 Estimate the surface tension of carbon tetrachloride (CCl4) at 378.15 K.

Substitution of the regression coefficients from the table and temperature into the equation for surface tension yields:

sigma = 66.750*(1 - 378.15/556.35)1.2140 sigma = 16.76 dyne/cm

The calculated and data values compare favorably (16.76 vs 16.64, deviation = 0.7%). Example 2 Estimate the surface tension of ethane (C2H6) at 133.15 K.

Substitution of the regression coefficients from the table and temperature into the equation for surface tension yields: sigma = 48.984*(1 – 133.15/305.42)1.2065

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sigma = 24.55 dyne/cm

The calculated and data values compare favorably (24.55 Vs 24.48, deviation = 0.3%).

Portions of this material appeared in Chem. Eng., 98, 140 (March, 1991) and are reprinted by special permission.

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