anrisk.pdf

643

Appendix ACONVERSION TABLE

1. Temperature 9. Enthalpy of FormationTo convert from Centigrade to: To convert from kJ/mol to:

Kelvin, add 273.15 kcal/mol, multiply by 0.239Rankine, multiply Kelvin by 1.8Fahrenheit, 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 forpsig, subtract 14.7 Compound in Watermm Hg, multiply by 51.71 To convert from atm/mol fraction to:atmospheres, divide by 14.7 atm/(mol/m3), divide by 55,556bars, divide by 14.508 kPa/(mol/m3), divide by 548.295

3. Heat of VaporizationTo convert from kJ/kg to:

BTU/lb, multiply by 0.43cal/gram, multiply by 0.239

4. DensityTo convert from g/ml to:

lb/ft^3, multiply by 62.43lb/gallon, multiply by 8.345

5. Surface TensionTo convert from dynes/cm to:

N/m, multiply by 0.001

6. Heat CapacityTo convert from J/g K to:

BTU/lb R, multiply by 0.239cal/gram K, multiply by 0.239

7. ViscosityTo convert from micropoise to:

lb/ft s, multiply by 0.0672E-06centipoise, multiply by 1.0E-04poise, multiply by 1.0E-06Pa s (Pascal seconds), multiply by 1.0E-07

To convert from centipoise to:lb/ft s, multiply by 0.000672micropoise, multiply by 10,000poise, multiply by 0.01Pa s (Pascal seconds), multiply by 0.001

8. Thermal ConductivityTo convert from W/m K to:

BTU/hr ft R, multiply by 0.5770calorie/cm s K, multiply by .002388

644

Appendix BHENRY'S LAW CONSTANT - EQUATIONS

Carl L. YawsLamar University, Beaumont, Texas

The calculation of Henry's law constant for a component in water may be achieved using data forsolubility, vapor pressure, and activity coefficient at infinite dilution. The derivation of the appropriateequations 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, thereare three phases when the organic chemical is in contact with water. These are vapor, organic, and waterphases. Such a three-phase system consisting of vapor, liquid I and liquid II is shown in Fig. B-1a. Atequilibrium, the fugacity of the component in each liquid phase is

filiq I = filiq 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 (ppmlevel or less), the mol fraction of the organic chemical is approximately equal to 1 (mol fractioni≈1). This isalso true for the activity coefficient of the organic chemical (γi≈1). Thus

filiq I = PiSAT (B-2)

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

filiq II = Hi xiliq II (xi<<1) (B-3)

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

PiSAT = Hi xi

liq II (B-4)

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

Hi = ( 1 / xiliq II ) Pi

SAT (B-5)

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

liq II = solubility of organic chemical in water, mol fractionPi

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, thereare 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 (whereγi 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 activitycoefficient at infinite dilution (γi=γi

∞). Thus filiq = γi

∞ xi PiSAT (B-6)

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

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

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

γi∞ xi Pi

SAT = Hi xi (B-8)

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

Hi = γi∞ Pi

SAT (B-9)

645

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

∞ = activity coefficient at infinite dilutionPi

SAT = vapor pressure of organic chemical, atm

GASES

For organic chemicals that are gases at ambient conditions, there are two phases when the organicchemical is in contact with water. These are vapor and liquid phases. Such a two-phase system consisting ofvapor and liquid is shown in Fig. B-1b. At equilibrium, the fugacity of the component in each phase is givenby

fivap = filiq (B-10)

For the vapor phase, the fugacity of the organic chemical is

fivap = yi Pt (B-11)

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

fivap = 1-yH2O (B-12)

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

filiq = 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 organicchemicals which are gases at ambient conditions (25 C, 1 atm):

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

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

= solubility of organic chemical in water, mol fractionyH2O = mol fraction of water in vapor phase at ambient conditions (at 25 C, yH2O ≈ 0.03117)

646

1

Chapter 1CRITICAL PROPERTIES AND ACENTRIC FACTOR

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

ABSTRACT

Results for critical properties and acentric factor are presented for major organic and inorganiccompounds. The critical properties include critical temperature, pressure, volume, density and compressibilityfactor. The chemical formula, molecular weight, freezing point and boiling point are also given. The resultsare displayed in easy-to-use tabulations which are especially applicable for rapid engineering usage with thepersonal 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 valueto engineers in the chemical processing and petroleum refining industries. The engineering design ofprocess 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 incorresponding states correlations to determine properties such as heat capacity, enthalpy, density, viscosityand thermal conductivity. The results are intended for initial engineering studies and are presented in aneasy-to-use tabular format which is especially applicable for rapid engineering usage with the personalcomputer 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 andinorganic 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 fororganics (1-44) and inorganics (1-59). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened and copies of appropriate data were made. These data were then keyed into the computer toprovide a database of critical properties for compounds for which experimental data are available. Thedatabase 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 theremaining compounds was performed. For organic compounds, the group contribution method of Joback asgiven 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 theGuldberg-Guye rule (11), Gates-Thodos method (11) and Grosse equation (11). Estimates of other criticalconstants and acentric factor were primarily based on extension of the vapor pressure curve andmodifications of the Benson relation (11) and Herzog proposal (11). Very limited experimental data for criticalconstants and acentric factor are available for inorganic compounds and elements that are solids at roomtemperature. Thus, the estimates for these substances should be considered rough approximations in theabsence 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/cm3

MW = molecular weight, g/mol VC = critical volume, cm3/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 followingequation which is given in Reid, Prausnitz and Poling (29):

3 TB / TC

2

ω = (log PC) – 1 (1-3) 7 1 - TB / TC

where ω = acentric factor TB = boiling point temperature, KTC = critical temperature, KPC = 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% wereexperienced 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 mostcompounds, 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 discussedby Reid, Prausnitz and Poling (29), no reliable methods are available for precise estimation of freezing pointtemperature. Thus, the estimates for freezing point temperature should be considered as roughapproximations.

Portions of this material appeared in Hydrocarbon Processing, 68, 61 (July 1989) and are reprintedby 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). 22. Beaton, C. F. and G. F. Hewitt, PHYSICAL PROPERTY DATA FOR THE DESIGN ENGINEER, Hemisphere Publishing

3

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).

4

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).

30

Chapter 2HEAT CAPACITY OF GAS

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

ABSTRACT

Results for heat capacity of ideal gas as a function of temperature are presented for major organicand 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 anddata is quite good.

INTRODUCTION

Thermodynamic properties such as heat capacity are important in the engineering design ofchemical 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 includegeneralized heat exchanger and energy balance design calculations.

In this article, correlation results for heat capacity of gas are provided in an easy-to-use tabularformat 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 T2 + 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 compoundT = temperature, K

The results for heat capacity of gas are given in Tables 2-1 and 2-2. The tabulations are based onregression of experimental data and estimates from an extensive literature search for organics (1-40) andinorganics (1-78). Both experimental values for the property under consideration and parameter values forestimation of the property are included in the source publications. The numerous data points were processedwith 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, sulfurtrioxide,...); 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, silicontetrachloride,...); 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 arepresentative chemical. The graph indicates good agreement of correlation and data.EXAMPLES

The correlation results maybe used for prediction and calculation of heat capacity and otherthermodynamic 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 capacityyields: CP = 19.816 + 3.3311E-01*500 - 5.0511E-04*5002 + 3.4057E-07*5003 - 8.4249E-11*5004

31

CP = 97.40 joule/(mol K)

Example 2 Calculate the energy required to heat gaseous ethyl chloride (C2H5Cl) from 300 K to 600 Kat 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 byspecial permission.

REFERENCES – ORGANIC COMPOUNDS1-34. 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).39. Yaws, C. L., HANDBOOK OF THERMODYNAMIC DIAGRAMS, Vols. 1, 2, 3 and 4, Gulf Publishing Co., Houston, TX (1996).40. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

REFERENCES - INORGANIC COMPOUNDS1-56. 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).78. Nagarajan, G., Bull. Soc. Chim. Belg., 72, 346 (1963).

56

Chapter 3HEAT CAPACITY OF LIQUID

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

ABSTRACT

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

INTRODUCTION

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

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


The correlation for heat capacity of liquid is a series expansion in temperature:

CP = A + B T + C T2 + D T3 (3-1)

where CP = heat capacity of liquid, joule/(mol K)A, B, C and D = regression coefficients for chemical compoundT = temperature, K

The results for heat capacity of liquid are given in Tables 3-1 and 3-2. In preparing the compilation, aliterature search was conducted to identify data source publications for organics (1-43) and inorganics (1-104). Both experimental values for the property under consideration and parameter values for estimation ofthe 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 nranged from 1/2 to 1. Experimental data and estimates were then regressed to provide the same equation forall compounds.

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

Very limited experimental data for liquid heat capacity are available at temperatures in the region ofthe 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 shouldbe considered rough approximations. The values in the intermediate region (above melting and below boilingpoint) are more accurate.

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

EXAMPLES

The correlation results maybe used for prediction and calculation of heat capacity and additionalthermodynamic 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 capacityyields:

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


Example 2 Calculate the energy required to heat liquid toluene (C7H8) from 300 K to 500 K. From

57

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


∆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.

REFERENCES – ORGANIC COMPOUNDS 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). 42. Yaws, C. L., HANDBOOK OF THERMODYNAMIC DIAGRAMS, Vols. 1, 2, 3 and 4, Gulf Publishing Co., Houston, TX (1996). 43. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

REFERENCES - INORGANIC COMPOUNDS1-64. 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, ChemicalEngineering 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).

58

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).104. Pace, E. L. and J. S. Mosser, J. Chem. Phys., 19(1), 154 (1963).

83

Chapter 4HEAT CAPACITY OF SOLID

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

ABSTRACT

Results for heat capacity of solid as a function of temperature are presented for major organic andinorganic 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 ofchemical processes. In unit operations involving solids at elevated temperatures, the heat capacity isrequired to determine the energy (heat) necessary to bring the solids up to the required processingtemperature. 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 tabularformat that is especially applicable for rapid engineering use with the personal computer or hand calculator.


The correlation for heat capacity of solid is a series expansion in temperature:

CP = A + B T + C T2 (4-1)

where CP = heat capacity of solid, joule/(mol K)A, B, C = regression coefficients for chemical compoundT = temperature, K

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

In preparing the compilation, a literature search was conducted to identify data source publicationsfor organics (1-38) and inorganics (1-104). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened for appropriate data. The compilation resulting from the screening is based on both experimentaldata and estimated values. For organics, many of the values are based on sources from DIPPR (4). Forinorganics, many of the values are based on sources from JANAF tables (57-59) and ThermophysicalProperties 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 forsubstances 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 arepresentative chemical. The graph indicates good agreement of correlation and data.

EXAMPLES

The correlation results maybe used for prediction and calculation of heat capacity and additionalthermodynamic 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 capacityyields:

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 ] T1

84


∆H = 4.824*(300 - 100) + 5.0634E-01/2*(3002 - 1002) + 1.8503E-04/3*(3003 - 1003)


REFERENCES - ORGANIC COMPOUNDS1-36. 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).

REFERENCES - INORGANIC COMPOUNDS1-64. 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).104. Krestovnikov, A. N. and E. J. Feigina, Z. Obsch. Khim., 6, 1481 (1936).

109

Chapter 5ENTHALPY OF VAPORIZATION

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

ABSTRACT

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

INTRODUCTION

Physical and thermodynamic property data such as enthalpy of vaporization are of special value toengineers in the chemical processing and petroleum refining industries. As an example, knowledge of theenthalpy of vaporization is required in the design of heat exchangers for vaporizing liquids. Other examples ofusage include reboilers and overhead condensers in distillation. In this article, results for enthalpy ofvaporization 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/molA, TC, and n = regression coefficients for chemical compoundT = 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 (1-41) and inorganics (1-93). Both experimental values for the property under consideration and parameter values for estimation ofthe 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. Inthe absence of experimental data, estimates were primarily based on the Riedel equation (29). Experimentaldata 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 respectiveminimum and maximum temperatures are denoted by TMIN and TMAX. The temperature TB is the normalboiling point (temperature at which the vapor pressure is 1 atm). Results for enthalpy of vaporization at thenormal boiling point are provided in the last column.

A comparison of calculated and experimental data values for enthalpy of vaporization is shown inFig. 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 forenthalpy 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 forenthalpy of vaporization yields

∆Hvap = 21.342*(1 - 200/305.42)0.403

∆Hvap = 13.90 kjoule/mol Portions of this material appeared in Hydrocarbon Processing, 69, 87

110

(June, 1990) and are reprinted by special permission.

REFERENCES – ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Edmister, W. C., APPLIED HYDROCARBON THERMODYNAMICS, Vols. 1 and 2, Vol 2 (2nd ed.), Gulf Publishing Co., Houston,

TX (1961, 1974, 1984).36. 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).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).

REFERENCES - INORGANIC COMPOUNDS1-56. 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).58. 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).59. Fink, J. K., TABLES OF THERMODYNAMIC PROPERTIES OF SODIUM, Argonne National Lab., ANL-CEN-RSD-82-4, Chemical


England (1974).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 ANDSOLID 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).93. Hyne, R. A. and P. F. Telly, J. Chem. Soc. 2348 (1961).

159

Chapter 7VAPOR PRESSURE

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

ABSTRACTResults 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-usetabulations that are especially applicable for rapid engineering usage with the personal computer or handcalculator. The chemicals encompass many compound types.

INTRODUCTIONPhysical 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 vaporpressure of the compound is required in the design of a storage vessel to contain the compound. In hazardanalysis and vent system technology, vapor pressure at the specified temperature is important. Invapor-liquid operations, such as distillation, knowledge of vapor pressure (and activity coefficients) is requiredfor determining K-values. In this article, results for vapor pressure as a function of temperature arepresented.

VAPOR PRESSURE CORRELATIONThe 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 T2 (7-1)

where P = vapor pressure, mm HgA,B,C,D and E = regression coefficients for chemical compoundT = temperature, K

The results for vapor pressure are given in Tables 7-1 and 7-2. The temperature range for which theequation may be used to predict vapor pressure is denoted by the respective minimum and maximumtemperatures (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 iodinatedcompounds); 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: carbonoxides (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 (sulfuricacid, hydrogen sulfide,...); hydroxides (sodium hydroxide, potassium hydroxide,...); silicon halides(trichlorosilane, silicon tetrachloride,...); ureas (urea, thiourea,...); cyanides (hydrogen cyanide, cyanogenchloride,...); hydrides (silane, diborane,...); sodium derivatives (sodium chloride, sodium fluoride,...);aluminum derivatives (aluminum borohydride, aluminum fluoride,...) and many other compound types. Manyelements (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 publicationsfor organics (1-41) and inorganics (1-61). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened for appropriate data. The compilation resulting from the screening is based on both experimentaldata and estimated values. In the absence of experimental data, estimates were primarily based on Riedelequation (29) and on adjusting the A value in the equation to match the boiling point temperature of thecompound. The estimates of the other coefficients for the compound were based on the same values of thecompound's brother (closest member of same chemical family). Experimental data and estimates were thenregressed to provide the same equation for all compounds.

160

A comparison of calculated values and experimental data for vapor pressure is shown in Figure 7-1for 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 aregiven 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 pressureyields:

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 pressureyields:

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%).

REFERENCES – ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 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. 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).37. Boublick, T., V. Fried and E. Hala, THE VAPOUR PRESSURES OF PURE SUBSTANCES, 1st and 2nd eds., Elsevier, New York,

NY (1975, 1984).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).

REFERENCES - INORGANIC COMPOUNDS1-56. 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).59. Boublick, T., V. Fried and E. Hala, THE VAPOUR PRESSURES OF PURE SUBSTANCES, 1st and 2nd eds., Elsevier, New York,

NY (1975, 1984).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

THERMODYNAMIC PROPERTIES OF THE ELEMENTS, American Society for Metals, Metals Park, OH (1973).

212

Chapter 9SURFACE TENSION

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

ABSTRACT

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

INTRODUCTION

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

SURFACE TENSION CORRELATION

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

sigma = A (1 - T/TC)n (9-1)

where sigma = surface tension, dynes/cmA, 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 bychemical 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 andTMAX).

In preparing the compilation, a literature search was conducted to identify data source publicationsfor organics (1-40) and inorganics (1-112). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened for appropriate data. The compilation resulting from the screening is based on both experimentaldata and estimated values. In the absence of experimental data, estimates were primarily based on Sugdenmethod (group contribution, 29) and Brock and Bird correlation (corresponding states, 29). Experimental dataand 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 representativechemical. The graph indicates good agreement of calculations and data.

EXAMPLES

The correlation results maybe used for prediction and calculation of surface tension. Examples aregiven 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 forsurface 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 forsurface tension yields: sigma = 48.984*(1 – 133.15/305.42)1.2065

213

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 specialpermission.

REFERENCES – ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Maxwell, J. B., DATA BOOK ON HYDROCARBONS, D. Van Nostrand, Princeton. NJ (1958).36. Egloff, G., PHYSICAL CONSTANTS OF HYDROCARBONS, Vols. 1-6, Reinhold Publishing Corp., New York, NY (1939-1947).37. Jasper, J.J., J. Phys. Chem. Ref. Data, 1 (No.4), 841 (1972).38. 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).39. Yaws, C. L. and others, Chem. Eng., 98, 140 (March, 1991).40. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

REFERENCES – INORGANIC COMPOUNDS1-56. 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).58. 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).59. Fink, J. K., TABLES OF THERMODYNAMIC PROPERTIES OF SODIUM, Argonne National Lab., ANL-CEN-RSD-82-4, Chemical


England (1974).61. Cox, J. D.and G. Pilcher, THERMOCHEMISTRY OF ORGANIC AND ORGANOMETALLIC COMPOUNDS, Academic Press, New

York, NY (1970).62. Janz, G. J. and C. B. Allen, PHYSICAL PROPERTIES DATA COMPILATIONS RELEVANT TO ENERGY STORAGE. II. MOLTEN

SALTS: DATA ON SINGLE AND MULTICOMPONENT SALTSYSTEMS, Nat. Bur. Stand., Molten Salts Data Center, Troy, NY(April 1979).

63. Janz, G. J. and R. P. T. Tomkins, PHYSICAL PROPERTIES DATA COMPILATIONS RELEVANT TO ENERGY STORAGE, 4.MOLTEN SALTS: DATA ON ADDITIONAL SINGLE AND MULTI-COMPONENT SALT SYSTEMS, U. S. Government PrintingOffice, Washington, DC (1981).

64. Tuller, W. N., ed., THE SULPHUR DATA BOOK, McGraw-Hill, New York, NY (1954).65. Cox, J. D. and G. Pilcher, THERMOCHEMISTRY OF ORGANIC AND ORGANOMETALLIC COMPOUNDS, Academic Press, New

York, NY (1970).66. Riddick, J. A. and W. B. Bunger, ORGANIC SOLVENTS: PHYSICAL PROPERTIES AND METHODS OF PURIFICATION, 3rd ed.,

Wiley Interscience, New York, NY (1970).67. Moore, G. A. and T. R. Shives, IRON, Metals Handbook, 8th ed., 1206 (1961).68. 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).69. Davison, H. W., COMPILATION OF THERMOPHYSICAL PROPERTIES OF LIQUID LITHIUM, U. S. NASA Tech. Note D-4650

(1968).70. Kaufmann, D. W., ed., SODIUM CHLORIDE, Reinhold Pub. Corp., New York, NY (1960).71. Weiss, G., ed., HAZARDOUS CHEMICALS DATA BOOK, Noyes Data Corporation, Park Ridge, NJ (1980).72. Neugebauer, C. A. and J. L. Margrave, J. Phys. Chem., 60, 1318 (1956).73. Bernard, G. and C. H. P. Lupis, Metall. Trans., 2, 555 (1971).74. Sugden, S., J. Chem. Soc. (London, Transaction), 125, 32 (1924).75. Waseda, Y. and K. Suzuki, Phys. Status Solidi B: Basic Research, 57, 351 (1973).76. Nisel'son, L. A. and T. D. Sokolova, Russ. J. Inorg. Chem., 10, 827 (1965).77. Saji, Y. and S. Kobayashi, Cryogenics, 136 (1964).78. Durrant, A. A., T. G. Pearson and P. L. Robinson, J. Chem. Soc. Part 1, 730 (1934).79. Jasper, J. J., J. Phys. Chem. Ref. Data, 1(4), 841 (1972).80. Cook, R. P. and P. L. Robinson, J. Chem. Soc. (London), 1001 (1935).81. Jarry, R. A. and J. J. Fritz, J. Chem. Eng. Data, 3(1), 34 (1958).82. Simkin, J. and R. L. Jarry, J. Phys. Chem., 61, 503 (1957).83. Usanovich, M., T. Sumarokova and V. Udovenko, Acta Physicochim, USSR, 11, 505 (1939).84. Cheesman, G. H., J. Chem. Soc., 35, (1930).85. Cockett, A. H. and A. Ferguson, Phil. Mag., 28, 685 (1939).86. Heicks, J. R. and others, J. Phys. Chem., 58, 488 (1954).87. White D., J. H. Hu and H. L. Johnston, J. Am. Chem. Soc., 76, 2584 (1954).88. Greenwood, N. N. and K. Wade, J. Inorg. Nucl. Chem., 3, 349 (1957).89. Pearson, T. G. and P. L. Robinson, J. Chem. Soc., 736 (1934).90. Grosh, J. and others, Proc. Nat. Acad. Sci., 54, 1004 (1965).

214

91. Stern, S. A., J. L. Mullhapt and W. B. Kay, Chem. Rev., 60, 185 (1960).92. Vargaftic, M. B., B. N. Volkov and L. D. Voljak, J. Phys. Chem. Ref. Data, 12(3), 817 (1983).93. Maass, O. and W. H. Hatcher, J. Amer. Chem. Soc., 42, 2548 (1920).94. Sabinina, L. and L. Terpugow, Z. Phys. Chem., 173A, 237 (1935).95. Harkins, W. D. and W. W. Ewing, J. Amer. Chem. Soc., 42, 2539 (1920).96. Sauewold, F. and G. Drath, Z. Anorg. Alleg. Chem., 154, 79 (1926).97. Bircumshaw, L. L., Phil. Mag. 7(8),341 (1926).98. Bloom, H., F. G. Davis and D. W. James, Trans. Faraday Soc., 56, 1179 (1960).99. Janz, G. J., J. Phys. Chem. Ref. Data 9(4), 311 (1974).100. Sokolov, O. K., Zh. Neorg. Khim., 11(7), 1703 (1966).101. Streng, A. G., J. Chem. Eng. Data, 6(3), 43 (1961).102. Jenkins, A. C. and F. S. Dipaolo, J. Chem. Phys., 25(2), 296 (1956).103. Pugachevich, P. P. and others, Russ. J. Phys. Chem., 41, 299 (1967).104. Person, T. G. and P. L. Robinson, J. Chem. Soc., 1472 (1933).105. Berthoud, A., Helv. Chem. Acta, 5, 513 (1922).106. Kingery, W. D. and M. Humenik, J. Phys. Chem., 57, 359 (1953).107. Nisel'son, L. A. and others, Russ. J. Inorg. Chem., 10(6), 705 (1965).108. MacKenzie, C. A. and others, J. Amer. Chem. Soc., 72, 2032 (1950).109. Lapidus, I. I., Teplofiz. Svoist. Vesh., 5, 119 (1972).110. Pugachevich, P. P., Russ. J. Phys. Chem., 40, 1560 (1966).111. Smith, B. L., P. R. Gardner and E. H. Parker, J. Chem. Phys., 47(3), 1148 (1967).112. Osipov, L. I., SURFACE CHEMISTRY, THEORY AND INDUSTRIAL APPLICATION, Reinhold Publishing Corporation, New York,

NY (1964).

239

Chapter 10REFRACTIVE INDEX, DIPOLE MOMENT AND RADIUS OF GYRATION

Carl L. Yaws, Xiao M. Wang and Marco A. Satyro*Lamar University, Beaumont, Texas / *SEA++ INC., Calgary, Alberta

ABSTRACT

Results for refractive index, dipole moment and radius of gyration are presented for major organicand inorganic chemicals. The chemical formula and molecular weight are also given. The results aredisplayed in easy-to-use tabulations which are especially applicable for rapid engineering usage with thepersonal computer or hand calculator. The organic chemicals encompass hydrocarbon, oxygen, nitrogen,halogen, silicon, sulfur and other compound types.

INTRODUCTION

Physical properties such as refractive index, dipole moment and radius of gyration are of specialvalue to engineers in the chemical processing and petroleum refining industries. Since these properties areused in thermodynamic correlations that are involved in the design of process equipment, the results of thisarticle are intended for initial engineering studies.

REFRACTIVE INDEX, DIPOLE MOMENT AND RADIUS OF GYRATION

The refractive index is an indication of the manner in which a compound interacts with light. Therefractive index is defined as the ratio of the speed of light in a vacuum to the speed of light in the compound.Most of the values for index of refraction are applicable to a temperature of 25 C. Exceptions to thistemperature are noted in the tabulations.

The dipole moment involves the first moment of the electric charge density of the compound.Property correlations for polar compounds often require knowledge of the dipole moment. The radius ofgyration is ascertained from the moment of inertia and molecular weight. This property is also used inthermodynamic correlations.

The results for refractive index, dipole moment and radius of gyration are given in Tables 10-1 and10-2 for organic and inorganic compounds. The tabulations are based on data source publications fororganics (1-59) and inorganics (1-48). The tabulations are arranged by chemical formula to provide ease ofuse in quickly locating data.

REFERENCES - ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Passut, C. A. and R. P. Danner, Chem. Eng. Prog. Symp. Ser., 70 (140), 30 (1974).36. Gold, P. I. and G. J. Ogle, Chem. Eng., 76, 97 (August 11, 1969).37. Hansch, C., A. Leo, S. H. Unger, K. H. Kum, D. Nikatiani and E. J. Lien, J. Med. Chem., 16, 1207 (1973).38. Kier, L. B. and L. H. Hall, MOLECULAR CONNECTIVITY IN CHEMISTRY AND DRUG RESEARCH, Academic Press, New York,

NY (1976).39. McClellan, A. L., TABLES OF EXPERIMENTAL DIPOLE MOMENTS, W. H. Freeman Publishing, San Francisco, CA (1963).40. Lawson, D. D. and J. D. Ingham, Nature (London), 223, 614 (1969).41. Meissner, H. P., Chem. Eng. Prog., 45, 149 (1949).42. Skoog, D. A. and D. M. West, PRINCIPLES OF INSTRUMENTAL ANALYSIS, Holt, Rinehart and Winston, New York, NY (1971).43. LeFevre, R. J. W., DIPOLE MOMENTS, THEIR MEASUREMENT AND APPLICATION IN CHEMISTRY, John Wiley and Sons,

New York, NY (1953).44. Moore, W. J., PHYSICAL CHEMISTRY, 4th ed., Prentice-Hall, Englewood Cliffs, NJ (1972).45. Potenzone, R., Jr., E. Cavicchi, H. J. R. Weintraub and A. J. Hopfinger, Comput. Chem., 1, 187 (1977).46. Smyth, C. P., DIELECTRIC BEHAVIOR AND STRUCTURE, McGraw-Hill Book Co., New York, NY (1955).47. Wheatley, P. J., THE DETERMINATION OF MOLECULAR STRUCTURE, Oxford University Press, London, England (1959).48. Nelson, R. D., D. R. Lide, A. Maryott, National Bureau of Standards, NSRDS 10, Washington, DC (1967).49. Takashi, R. and others, J. Mol. Spec., 138, 450 (1989).50. Hayashi, M. and T. Inagusa, J. Mol. Spec., 138, 135 (1989).51. Scappini, F., A. C. Fantoni and W. Caminati, J. Mol. Spec., 120, 101 (1986).52. Thompson, W. H., “A MOLECULAR ASSOCIATION FACTOR FOR USE IN THE EXTENDED THEOREM OF CORRESPONDING

STATES”, Ph. D. Thesis, The Pennsylvania State University, University Park, PA (1966).53. Cygnarowicz, R.M., “THE MOLECULAR RADIUS OF GYRATION”, B.S. Thesis in Engineering Science, The Pennsylvania State

University, University Park, PA (1981).54. Sutter, H. and R.H. Cole, J. Chem. Phys., 52, 132 (1970).55. Stuper, A. J., W. E. Brugger and P. C. Jurs, COMPUTER ASSISTED STUDIES OF CHEMICAL STRUCTURE AND BIOLOGICAL

240

FUNCTION, John Wiley and Sons, New York, NY (1979).56. Bock, E. and D. Iwacha, Can. J. Chem., 46, 523 (1968).57. Ghosh S. N. and R. Trambarulo, W. Gordy, Phys. Rev., 82, 172 (1952).58. Shoolery, J. N. and A. H. Sharbaugh, Phys. Rev. , 82, 95 (1951).59. Kurtz, S. S., Jr., S. Amon and A. Sankin, Ind. Eng. Chem., 42, 174 (1950).

REFERENCES - INORGANIC COMPOUNDS1-35. See REFERENCES - INORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 36. Passut, C. A. and R. P. Danner, Chem. Eng. Prog. Symp. Ser., 70 (140), 30 (1974).37. McClellan, A. L., TABLES OF EXPERIMENTAL DIPOLE MOMENTS, W. H. Freeman Publishing, San Francisco, CA (1963).38. Stuper, A. J., W. E. Brugger and P. C. Jurs, COMPUTER ASSISTED STUDIES OF CHEMICAL STRUCTURE AND BIOLOGICAL FUNCTION, John Wiley and Sons, New York, NY (1979).39. Nelson, R. D., D. R. Lide, A. Maryott, National Bureau of Standards, NSRDS 10, Washington, DC (1967).40. Thompson, W. H., “A MOLECULAR ASSOCIATION FACTOR FOR USE IN THE EXTENDED THEOREM OF CORRESPONDING

STATES”, Ph. D. Thesis, The Pennsylvania State University, University Park, PA (1966).41. Cygnarowicz, R.M., “THE MOLECULAR RADIUS OF GYRATION”, B.S. Thesis in Engineering Science, The Pennsylvania State

University, University Park, PA (1981).42. Stern, S. A., J. L. Mulhaupt and W. B. Kay, Chem. Rev., 60, 185 (1960).43. Francis, A. W., J. Chem. Eng. Data, 5(4), 534 (1960).44. Robinson, D. B. and N. H. Senturk, J. Chem. Therm., 11, 875 (1979).45. Helminger, P. and F. C. DeLucia, J. Phys. Chem. Ref. Data, 2(2), 215 (1973).46. Tolles, W. M., J. L. Kinsey, R. F. Curl and F. H. Robert, J. Chem. Phys., 37, 927 (1962).47. Shaulov, Y. K. and A. M. Masin, Russ. J. Phys. Chem., 47, 642 (1973).48. Mackie, H. and P. A. G. O’Hare, Trans. Faraday Soc., 59, 309 (1963).

264

Chapter 11ENTROPY AND ENTROPY OF FORMATION OF GAS


ABSTRACT

Results for entropy and entropy of formation of gas are presented for major organic and inorganicchemicals. The chemical formula and molecular weight are also given. The results are displayed ineasy-to-use tabulations which are especially applicable for rapid engineering usage with the personalcomputer or hand calculator. The organic chemicals encompass hydrocarbon, oxygen, nitrogen, halogen,silicon, sulfur and other compound types.

INTRODUCTION

Properties such as entropy and entropy of formation are useful in ascertaining the thermodynamicsof operations encountered in the chemical processing and petroleum refining industries. As an example ofsuch usefulness, the heat effects and equilibrium yields of chemical reactions require knowledge of thethermodynamics of the chemical reactions. Other uses include ascertaining the thermodynamics of chemicalexplosions.

ENTROPY AND ENTROPY OF FORMATION

The results for entropy and entropy of formation are given in Tables 11-1 and 11-2 for organic andinorganic compounds. The values apply to the ideal gas at 298.15 K. The entropy is the absolute entropy.The entropy of formation is ascertained from the appropriate thermodynamic relations for the formation of thecompound from the elements. The tabulations are based on data source publications for organics (1-37) andinorganics (1-61). The tabulations are arranged by chemical formula to provide ease of use in quickly locatingdata.

REFERENCES – ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Crowl, D. A. and J. F. Louvar, CHEMICAL PROCESS SAFETY, Prentice Hall, Inc., Englewood Cliffs, NJ (1990).36. Yaws, C. L. and P. Y. Chiang, Chem. Eng., 95 (13), 81 (Sept. 26, 1988).37. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

REFERENCES - INORGANIC COMPOUNDS1-56. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 57. Stull, D. R., and H. Prophet, Project Directors, JANAF THERMOCHEMICAL TABLES, 2nd ed., NSRDS-NBS 37, U. S. Government

Printing Office, Washington DC (1971).58. Daubert, T. E., CHEMICAL ENGINEERING THERMODYNAMICS, McGraw-Hill, New York, NY 1985).59. Karapet'yants, M. K. and M. L. Karapet'yants, THERMODYNAMIC CONSTANTS OF INORGANIC AND ORGANIC COMPOUNDS,

translated from Russian, Ann Arbor - Humphrey Science Publishers, Ann Arbor, MI (1970).60. Crowl, D. A. and J. F. Louvar, CHEMICAL PROCESS SAFETY, Prentice Hall, Inc., Englewood Cliffs, NJ (1990).61. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

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Chapter 12ENTHALPY OF FORMATION

Carl L. Yaws, Li Bu, Sachin Nijhawan, Jack R. Hopper and Ralph W. Pike*Lamar University, Beaumont, Texas / *Louisiana State University, Baton Rouge, Louisiana

ABSTRACT

Results for enthalpy of formation are presented for major organic and inorganic chemicals. Themajor chemicals include many compound types. The results are provided in easy-to-use tabulations whichare especially applicable for rapid engineering usage with the personal computer or hand calculator. Theagreement of correlation and data is quite good.

INTRODUCTION

Enthalpy of formation for individual compounds in chemical reactions is required to determine theheat of reaction, ∆Hreaction and associated heating and cooling requirements:

∆Hreaction = Σ (n∆Hf)products - Σ (n∆Hf)reactants (12-1)

If ∆Hreaction < 0, then the chemical reaction is exothermic and cooling is needed to maintain reactiontemperature. If ∆Hreaction > 0, the reaction is endothermic and heating is required to conduct the chemicalreaction. Since the heat effects of a reaction maybe determined from the enthalpy of formation for individualcompounds, results for enthalpy of formation are presented in this article for major chemicals.

CORRELATION FOR ENTHALPY OF FORMATION

The correlation for enthalpy of formation of the ideal gas is a series expansion in temperature:

∆Hf = A + B T + C T2 (12-2)

where ∆Hf = enthalpy of formation of ideal gas, kjoule/molA, B, C = regression coefficient for chemical compoundT = temperature, K

The results for enthalpy of formation are given in Tables 12-1 and 12-2. The tabulations arearranged by chemical formula to provides ease of use in quickly locating data. A wide variety of substancesare covered.

In preparing the compilation, a literature search was conducted to identify data source publicationsfor organics (1-40) and inorganics (1-60). The publications were screened for appropriate data. Thecompilation resulted from the screening.

For organics, the range for application is denoted by the respective minimum and maximumtemperatures (TMIN and TMAX). In the absence of data, values at 298.15 K were extended to highertemperatures by integration of the appropriate thermodynamic equations involving heat capacities. Thenumerous data points were processed with a generalized least-square computer program for minimizing thedeviation. The spot values at room temperature (298.15 K) are the actual data. The spot values at elevatedtemperature (500 K) are calculated from the correlation. Since water and hydrogen chloride are of majorindustrial importance, regression coefficients are provided for these compounds at the end of the table.

For inorganics, results are also given for internal energy of formation and entropy at roomtemperature (298.15 K). These thermodynamic properties are useful in computing the energy of a chemicalexplosion. As given by Crowl and Louvar (20), the equations for a chemical explosion involve the change inHelmholtz free energy which maybe calculated from data for internal energy of formation and entropy:

Explosion Energylimit = - ∆Areaction (12-3)

∆Areaction = ∆Ureaction - T ∆Sreaction (12-4)

∆Ureaction = Σ (n∆Uf)products - Σ (n∆Uf)reactants (12-5)

∆Sreaction = Σ (nS)products - Σ (nS)reactants - R n Σ (xi ln xi)products (12-6)

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The last term (R n Σ xi ln xi) in the above equation represents the entropy of mixing. The R is the universalgas constant.

The actual energy release in a chemical explosion will be less than the limiting value given by thechange in Helmholtz energy because of thermal effects and irreversibility. In an example in Crowl and Louvar(20), 12% of the limiting value is suggested for a vapor cloud explosion in a partially confined area (ethyleneexplosion in a ditch). For vapor cloud explosion in an unconfined area, 2% of the limiting value is suggestedby the same authors.

A comparison of correlation and data is shown in Figure 12-1 for a representative chemical. Thegraph discloses favorable agreement of correlation and data.

EXAMPLES

The correlation results can be used to make calculations for enthalpy of formation and heat ofreaction. Examples are given below.

Example 1 Let us estimate the enthalpy of formation of methane (CH4) as a low-pressure gas at 500 K.

We obtain correlation constants (A, B, C) for methane from the table and substitute them into theequation at a temperature of 500 K to get:

∆Hf = -63.425 - 4.336*10-2(500) + 1.722*10-5(5002)

∆Hf = -80.80 kjoule/mol

Example 2 Calculate the heat of reaction for the dehydrogenation of 1-butene (C4H8) to 1,3 butadiene(C4H6) at a reaction temperature of 900 K:

C4H8(g) � C4H6(g) + H2(g)

The heat of reaction may be determined from enthalpy of formation at 900 K for the products andreactants:

∆Hreaction = ∆Hf,C4H6 + ∆Hf,H2 - ∆Hf,C4H8

Using coefficients for 1-butene and 1,3-butadiene from the table and the equation for enthalpy offormation, we obtain:

∆Hf,C4H8 = 21.822 - 8.546*10-2(900) + 3.89*10-5(9002) = -23.58∆Hf,H2 = 0∆Hf,C4H6 = 123.286 - 5.123*10-2(900) + 2.319*10-5(9002) = 95.97

Substitution of ∆Hf values at 900 K into the equation for heat of reaction yields:

∆Hreaction = 95.97 + 0 - (-23.58)

∆Hreaction = 119.55 kjoule/mol

Since ∆Hreaction > 0, the reaction is endothermic and would require heating to maintain the reactiontemperature.

Portions of this material appeared in Chem. Eng., 95 (No. 13), 81 (Sept. 26, 1988) and are reprintedby special permission.

REFERENCES – ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Smith, J. M. and H. C. Van Ness, INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS, 4th ed., McGraw-Hill,

New York, NY (1987).36. Pedley, J. B., THERMOCHEMICAL DATA AND STRUCTURES OF ORGANIC COMPOUNDS, Vol. I, Thermodynamics Research

Center, College Station, TX (1994).37. 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).38. Crowl, D. A. and J. F. Louvar, CHEMICAL PROCESS SAFETY, Prentice Hall, Inc., Englewood Cliffs, NJ (1990).39. Yaws, C. L. and P. Y. Chiang, Chem. Eng., 95 (13), 81 (Sept. 26, 1988).40. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

REFERENCES - INORGANIC COMPOUNDS1-56. See REFERENCES - INORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 57. Daubert, T. E., CHEMICAL ENGINEERING THERMODYNAMICS, McGraw-Hill, New York, NY 1985).58. Karapet'yants, M. Kh. and M. L. Karapet'yants, THERMODYNAMIC CONSTANTS OF INORGANIC AND

290

ORGANIC COMPOUNDS, translated from Russian, Ann Arbor - Humphrey Science Publishers, Ann Arbor, MI (1970).59. Crowl, D. A. and J. F. Louvar, CHEMICAL PROCESS SAFETY, Prentice Hall, Inc., Englewood Cliffs, NJ (1990).60. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX

(1997).

314

Chapter 13GIBBS ENERGY OF FORMATION

Carl L. Yaws, Li Bu, Sachin Nijhawan, Jack R. Hopper and Raph W. Pike*Lamar University, Beaumont, Texas / *Louisiana State University, Baton Rouge, Louisiana

ABSTRACT

Results for Gibbs energy of formation are presented for major organic and inorganic chemicals.The major chemicals include many compound types. The results are provided in easy-to-use tabulationsthat are especially applicable for rapid engineering usage with the personal computer or hand calculator.The agreement of correlation and data is quite good.

INTRODUCTION

Gibbs energy of formation is important in the analysis of chemical reactions. Values for individualcompounds (reactants and products) are required to determine the change in Gibbs energy for the reaction. This change is significant because of the associated chemical equilibrium for the reaction. If the change inGibbs energy is negative, the thermodynamics for the reaction are favorable. On the other hand, if thechange in Gibbs energy is highly positive, the thermodynamics for the reaction are not favorable.

The chemical equilibrium for a reaction is associated with the change in Gibbs free energy (∆Gr) forthe reaction:

∆Greaction = Σ (n∆Gf)products - Σ (n∆Gf)reactants (13-1)

The changes in Gibbs energy for a reaction may be used in preliminary work to determine if areaction is thermodynamically favorable at a given temperature. For thermodynamic equilibrium, thefollowing rough criteria is useful for quick screening of chemical reactions:

∆Greaction < 0 kjoule/mol...............reaction favorable

0 < ∆Greaction < 50 kjoule/mol...…reaction possibly favorable

∆Greaction > 50 kjoule/mol.............reaction not favorable

CORRELATION FOR GIBBS ENERGY OF FORMATION

The correlation for Gibbs energy of formation is a series expansion in temperature:

∆Gf = A + B T + C T2 (13-2)

where ∆Gf = Gibbs energy of formation of ideal gas, kjoule/molA, B, C = regression coefficients for chemical compoundT = temperature, K

The results for Gibbs energy of formation are given in Tables 13-1 and 13-2. The tabulations arearranged by chemical formula to provide ease of use in quickly locating data. A wide variety of substancesare covered.

In preparing the compilation, a literature search was conducted to identify data source publicationsfor organics (1-37) and inorganics (1-61). The publications were screened for appropriate data. Thecompilation resulted from the screening.

For organics, the range for application is denoted by the respective minimum and maximumtemperatures (TMIN and TMAX). In the absence of data, values at 298.15 K were extended to highertemperatures by integration of the appropriate thermodynamic equations involving heat capacities. Thenumerous data points were processed with a generalized least-square computer program for minimizingthe deviation. The spot values at room temperature (298.15 K) are the actual data. The spot values atelevated temperature (500 K) are calculated from the correlation. Since water and hydrogen chlorideare of major industrial importance, regression coefficients are provided for these compounds at the end ofthe table.

For inorganics, results are also given for Helmholtz and entropy of formation at room temperature(298.15 K). These thermodynamic properties are useful in computing the energy of a chemical explosion.

The thermodynamic equations for computing the energy of a chemical explosion are given byCrowl and Louvar (35). The energy of a chemical explosion involves work of expansion (dW = PdV)resulting from the explosion. As the expansion occurs, this energy is transferred from the explosion. At

315

constant temperature, the change in Helmholtz energy (dA = - PdV) is related to such expansionwork. Thus, it is convenient to utilize the change in Helmholtz energy to ascertain the energy of an explosion:

Explosion Energylimit = - ∆Areaction (13-3)

Since thermal effects and irreversibility are involved in an explosion, this equation represents a limiting ormaximum value for the explosion energy.

For an explosion reaction, the change in Helmholtz energy maybe determined from Helmholtzenergy of formation for the products and reactants according to equation given below:

∆Areaction = Σ (n∆Af)products - Σ (n∆Af)reactants (13-4)

The actual energy release in a chemical explosion will be less than the limiting value given by thechange in Helmholtz energy because of thermal effects and irreversibility. In an example in Crowl and Louvar(35), 12% of the limiting value is suggested for a vapor cloud explosion in a partially confined area (ethyleneexplosion in a ditch). For vapor cloud explosion in an unconfined area, 2% of the limiting value is suggestedby the same authors.

A comparison of calculated and data values is shown in Figure 14-1 for a representative chemical.The graph discloses favorable agreement of correlation and data.

EXAMPLES

The results can be used to make calculations for Gibbs energy of formation and the change in Gibbsenergy for reaction. Examples are given below.

Example 1 Estimate the Gibbs free energy of formation of methane (CH4) as a low-pressure gas at 500K.

Correlation constants (A, B, C) for methane from the table are substituted into the equation at atemperature of 500 K:

∆Gf = -75.262 + 7.5925*10-2(500) + 1.8700*10-5(5002)

∆Gf = -32.62 kjoule/mol

Example 2 Calculate the change in Gibbs free energy for the reaction of methanol and oxygen to produceformaldehyde and water at reaction temperature of 600 K:

CH4O(g) + 0.5 O2(g) � CH2O(g) + H2O(g)

The change in Gibbs free energy of reaction may be determined from Gibbs free energy offormation for the products and reactants:

∆Greaction = ∆Gf,CH2O + ∆Gf,H2O - ∆Gf,CH4O - 0.5 ∆Gf,O2

Using correlation constants from the table at temperature of 600 K, we obtain:

∆Gf,CH2O = -115.972 + 1.663*10-2(600) + 1.138*10-5(6002) = -101.90∆Gf,H2O = -241.740 + 4.174*10-2(600) + 7.428*10-6(6002) = -214.02∆Gf,CH4O = -201.860 + 1.254*10-1(600) + 2.035*10-5(6002) = -119.28∆Gf,O2 = 0

Substitution of ∆Gf values into the equation for Gibbs free energy of the reaction yields:

∆Greaction = -101.9 + (-214.02) - (-119.28) – 0

∆Greaction = -196.64 kjoule/mol

Since the change in Gibbs free energy for the reaction is negative, the thermodynamics for thereaction are favorable.

Portions of this material appeared in Hydrocarbon Processing, 67, 81 (Nov., 1988) and are reprintedby special permission.

REFERENCES – ORGANIC COMPOUNDS1-37. See REFERENCES - ORGANIC COMPOUNDS in Chapter 11 ENTROPY AND ENTROPY OF FORMATION OF GAS

REFERENCES - INORGANIC COMPOUNDS1-61. See REFERENCES - INORGANIC COMPOUNDS in Chapter 11 ENTROPY AND ENTROPY OF FORMATION OF GAS

316

340

Chapter 14SOLUBILITY PARAMETER, LIQUID VOLUME AND VAN DER WAALS AREA AND VOLUME

Carl L. Yaws, Xiao M. Wang and Marco A. Satyro*Lamar University, Beaumont, Texas / *SEA++ INC., Calgary, Alberta

ABSTRACT

Results for solubility parameter, liquid volume and Van der Waals area and volume are presented formajor organic and inorganic chemicals. The chemical formula and molecular weight are also given. Theresults are displayed in easy-to-use tabulations that are especially applicable for rapid engineering usage withthe personal computer or hand calculator.

INTRODUCTION

Properties such as solubility parameter and liquid volume are useful in modeling of phase equilibriumin the chemical processing and petroleum refining industries. As an example of such usefulness in vapor-liquid operations, calculation of activity coefficients using regular solution methods for phase equilibrium indistillation, stripping and absorption requires knowledge of solubility parameter and liquid volume for thespecies in the mixture.

SOLUBILITY PARAMETER AND LIQUID VOLUME

The results for solubility parameter and liquid volume are given in Tables 14-1 and 14-2 for organicand inorganic compounds. The values for solubility parameter are ascertained from data for heat ofvaporization and liquid volume (molecular weight/density): [(Hvap – RT)/v]0.5. For compounds that are liquidsat ambient conditions, the values apply at 25 C. For compounds that are gases at ambient conditions, thevalues apply at the normal boiling point temperature. For compounds that are solids at ambient conditions,the values apply at the melting point temperature. The tabulations are based on data source publications fororganics (1-40) and inorganics (1-120). The tabulations are arranged by chemical formula to provide ease ofuse in quickly locating data.

VAN DER WAALS AREA AND VOLUME

The results for Van der Waals area and volume are also given in Tables 14-1 and 14-2 for organic andinorganic compounds. The tabulations are based on data source publications for organics (1-5) andinorganics (1-5). Van der Waals area and volume involve the surface area and volume of an atom andmaybe ascertained from bond distances, contact distances and shapes of atoms. Methods of calculation aredescribed by Bondi (2).

REFERENCES - SOLUBILITY PARAMETER AND LIQUID VOLUME - ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 5 ENTHALPY OF VAPORIZATION35-40. See REFERENCES - ORGANIC COMPOUNDS in Chapter 8 DENSITY OF LIQUID

REFERENCES - SOLUBILITY PARAMETER AND LIQUID VOLUME - INORGANIC COMPOUNDS1-56. See REFERENCES - INORGANIC COMPOUNDS in Chapter 5 ENTHALPY OF VAPORIZATION57-120. See REFERENCES - INORGANIC COMPOUNDS in Chapter 8 DENSITY OF LIQUID

REFERENCES - VAN DER WAALS AREA AND VOLUME - ORGANIC COMPOUNDS1. 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).2. Bondi, A., PHYSICAL PROPERTIES OF MOLECULAR CRYSTALS, LIQUIDS AND GLASSES, John Wiley and Sons, Inc., New

York, NY (1968).3. Bondi, A., J. Phys. Chem., 68, 441 (1964).4. Edward, J. T., J. Chem. Educ., 47, 261 (1970).5. Vera, J. H., S. G. Sayegh and G. A. Ratcliff, Fluid Phase Equilibria, 1, 113 (1977).

REFERENCES - VAN DER WAALS AREA AND VOLUME - INORGANIC COMPOUNDS1-5. See above REFERENCES - VAN DER WAALS AREA AND VOLUME - ORGANIC COMPOUNDS

364

Chapter 15SOLUBILITY IN WATER AND OCTANOL-WATER PARTITION COEFFICIENT

Carl L. Yaws, Sachin Nijhawan, Li Bu, Deepa R. Balundgi and Saumya TripathiLamar University, Beaumont, Texas

ABSTRACT

Results for water solubility and octanol-water partition coefficient are presented for major organicchemicals. The results are provided in an easy-to-use table that is especially applicable for rapidengineering usage with the personal computer or hand calculator. Typical water solubility values are 786ppm(wt) for carbon tetrachloride (CCl4) and 0.002 ppm(wt) for tetradecane (C14H30).

INTRODUCTION

Physical and thermodynamic property data for organic chemicals are of special value to engineers inthe chemical processing and petroleum refining industries. In this article results are presented for watersolubility and octanol-water partition coefficient. The compilation of data is intended for use in engineeringand environmental studies. As an example of such usage, solubility data are useful in determining theassessment and distribution of a chemical spill upon its contact with water.

SOLUBILITY IN WATER

The results for solubility of organic compounds in water are given in Table 15-1. The presentedvalues are applicable to a wide variety of substances including alkanes, olefins, diolefins, alkynes,cycloalkanes, aromatics, fluorocarbons, chlorocarbons, bromocarbons, iodocarbons, alcohols, acids,ketones, aldehydes, ethers, esters, amines, nitriles, sulfides and thiols. The tabulation also gives themolecular weight, freezing point and normal boiling point. The last two columns provide the data for solubilityin water on a weight and mole basis. The compilation is based on both experimental and estimated values.

The tabulation is arranged by carbon number (C, C2, C3, .... C28) to provide ease of use in quicklylocating solubility data using the chemical formula.

For the tabulation, the solubility data for liquids (compounds with boiling point greater than 25 C)apply for the aqueous liquid phase in contact with a vapor which contains the compound, water and air. Thesolubility data for gases (compounds with boiling point less than 25 C) apply for the aqueous liquid phase incontact with a vapor which contains only the compound and water.

In preparing the compilation, a literature search was conducted to identify data source publications(1-190). Both experimental values for the property under consideration and parameter values for estimationof the property are included in the source publications. The publications were screened and copies ofappropriate data were made. These data were then keyed-in to the computer to provide a database ofsolubility values for organic compounds for which experimental data are available. The database also servedas a basis to check the accuracy of the estimation method.

Upon completion of data collection, estimation of solubility for compounds was performed using theboiling point correlation developed by Yaws and co-workers (185-190):

log10 S = A + BTB + CTB2 + DTB

3 (15-1)

where S = solubility in water at 25 C, parts per million by weight, ppm(wt)TB = boiling point temperature of compound, KA, B, C and D = regression coefficients for chemical family

Results from the correlation are in favorable agreement with experimental data for solubility in water.Estimation of solubility for hydrocarbons and organic oxygen compounds was accomplished using

the following regression coefficients:

alkanes (paraffins) cycloalkanes (naphthenes)

A = -17.652 (normal and isomers) A = -16.7 for cyclohexanes B = 177.811E-03 A = -16.9 for cyclopentanes C = -500.907E-06 B = 177.811E-03 D = 411.124E-09 C = -500.907E-06

D = 411.124E-09

benzenes (aromatics) alcohols

A = -24.008 (no and single substitutions) A = 45.6398 (normal and isomers)

365

A = -23.650 (double and triple substitutions) B = -2.3859E-01 B = 221.196E-03 C = 4.8739E-04 C = -555.632E-06 D = -3.7160E-07 D = 418.830E-09

ketones ethers A = 45.223 (normal and isomers) A = 7.510 (normal and isomers) B = -2.3859E-01 B = 3.2057E-03 C = 4.8739E-04 C = -4.0887E-05 D = -3.7160E-07 D = 4.7284E-09

aldehydes

A = 20.4898 (normal and isomers) B = -9.0310E-02 C = 1.9223E-04 D = -1.7856E-07

This correlation is applicable to substances that are liquids at ambient conditions (25 C, 1 atm). Forhydrocarbons (alkanes, cycloalkanes and benzenes), the range for boiling point temperatures is 298 to 561K. For organic oxygen compounds (alcohols, ketones, ethers and aldehydes), the range for boiling pointtemperatures is 298 to 625 K. The correlation is not applicable to solids since a different solubility curve isobtained for solids.

Estimation of solubility for the remaining compounds (olefins, diolefins, alkynes, sulfides, thiols andesters) was also accomplished using a modified boiling point method. Due to the small database, theestimates for these compounds should be considered rough approximations. The estimates forhydrocarbons and organic oxygen compounds are more accurate.

A comparison of experimental and estimated data values for solubility in water is shown in Figure 15-1 for paraffins, naphthenes and aromatics. The graph discloses favorable agreement of experimental andestimated values.

OCTANOL-WATER PARTITION COEFFICIENT

The octanol-water partition coefficient is the ratio of a chemicals concentration in an octanol phase toits concentration in an aqueous phase:

Kow = (concentration in octanol phase) / (concentration in aqueous phase) (15-2)

The results for octanol-water partition coefficient are also given in Table 15-1. Both experimental andestimated values are provided in the compilation that is based on data source publications for organiccompounds (1-60). Many of the estimates are based on the atom-fragment contribution method as describedby Meylan and Howard. (57). The tabulation is arranged by chemical formula to provide ease of use in quicklylocating data.

Properties such as octanol-water partition coefficient (Kow) are useful in studies involving theenvironmental fate of chemicals. As an example of such usefulness in environmental applications, Lyman,Reehl and Rosenblatt (42) discuss how water solubility, soil-sediment coefficient and biologicalconcentrations for aquatic life can be related to Kow. Chemicals with low Kow values tend to have highsolubilities in water, low soil-sediment coefficients and small biological concentrations for aquatic life.

EXAMPLES

The tabulation and correlation maybe used for determining solubility of organic compounds in water.Examples are shown below.

Example 1 A chemical spill of carbon tetrachloride (CCl4) occurs into a body of water at ambientconditions (25 C, 1 atm). Determine the concentration of carbon tetrachloride in the water.

Using the chemical formula (CCl4) for carbon tetrachloride, inspection of the table discloses thatthe solubility in water is:

S = 785.7 ppm(wt) Example 2 A chemical spill of ethylbenzene (C8H10) occurs into a body of water at ambient conditions(25 C, 1 atm). Determine the concentration of ethylbenzene in the water.

366

Using the chemical formula (C8H10) for ethylbenzene, inspection of the table discloses that the

solubility in water is:

S = 165.1 ppm(wt)

Example 3 Estimate the solubility of pentane (C5H12) in water at a temperature of 298.15 K (25 C).

Substitution of the regression coefficients (A, B, C and D) and boiling temperature (309.22 K) intothe equation for solubility of paraffins (alkanes) in water yields:

log10 S = -17.652 + 177.811E-03 * 309.22 - 500.907E-06 * 309.222 + 411.124E-09 * 309.223 = 1.59106

S = 101.59106

S = 39.00 ppm(wt) The calculated and data values compare favorably (39.00 Vs 38.50, deviation = 0.50/38.50 = 1.3%).

Portions of this material appeared in Chem. Eng., 97, 177 (April,1990), Chem. Eng., 97, 115 (July,90), Pollution Engineering, 22, 70 (Oct., 1990), Oil & Gas Journal, 89, 79 (April 8, 1991), Oil & Gas Journal,89, 86 (Sept. 16, 1991) and Oil & Gas Journal, 95 (35), 80 (Aug. 29, 1994). These portions are reprinted byspecial permission.

REFERENCES - WATER SOLUBILITY - ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR35. Sørensen, J. M. and W. Arlt, LIQUID-LIQUID EQUILIBRIUM DATA COLLECTION, Vol. V, part 1, Dechema Chemistry Data Series,

6000 Frankfurt/Main, Germany (1979).36. Macedo, E. A. and P. Rasmussen, LIQUID-LIQUID EQUILIBRIUM DATA COLLECTION, Supplement 1, Vol. V, Part 4, Dechema

Chemistry Data Series, 6000 Frankfurt/Main, Germany (1987).37. Stephen, H. and T. Stephen, SOLUBILITIES OF INORGANIC AND ORGANIC COMPOUNDS, Vol. 1, Part 1, Macmillan Company,

New York, NY (1963).38. Horvath, A. L., HALOGENATED HYDROCARBONS, Marcel Dekker, Inc., New York, NY (1982).39. Yalkowsky, S. H. and S. Banerjee, AQUEOUS SOLUBILITY, Marcel Dekker, Inc., New York, NY (1992).40. Freier, R. K., AQUEOUS SOLUTIONS - DATA FOR INORGANIC AND ORGANIC COMPOUNDS, Vols. 1 and 2, Walter de

Gruyter, Berlin, Germany - New York, NY (1976).41. Curme, G. O., Jr., ed., GLYCOLS, American Chemical Society Series, Reinhold Publishing Corporation, New York, NY (1953).42. Kertes, A. S., ed., SOLUBILITY DATA SERIES, IUPAC, Vol. 15, Alcohols with Water, Pergamon Press, Oxford, England (1984).43. Markley, K. S., FATTY ACIDS, Interscience Publishers, Inc., New York, NY (1947).44. HANDBOOK OF CHEMISTRY, 10th (revised) - 13th eds., McGraw-Hill, New York, NY (1969-1985).45. Hildebrand, J. L. and R. L. Scott, THE SOLUBILITY OF NONELECTROLYTES, 3rd ed., Reinhold Publishing Corporation, New

York, NY (1950).46. Acree, W. E., Jr., THERMODYNAMIC PROPERTIES OF NONELECTROLYTE SOLUTIONS, Academic Press, New York, NY

(1984).47. Kertes, A. S., O. Levy and G. Y. Markovits, EXPERIMENTAL THERMODYNAMICS OF NONPOLAR FLUIDS, Dack, M. R. J., ed.,

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389

Chapter 16SOLUBILITY IN WATER CONTAINING SALT


ABSTRACT

Results for variation of water solubility with salt concentration are presented for 217 hydrocarbons.The results for solubility in salt water are applicable for the complete range of salt concentrations includingwater without salt (X=0) to water saturated with salt (X=358,700 ppm(wt)). Correlation and experimentalresults are in favorable agreement. The results are provided in an easy-to-use table that is especiallyapplicable for rapid engineering usage with the personal computer or hand calculator.

INTRODUCTION

Physical and thermodynamic property data are required for the design and operation of industrialprocesses. In particular, the water solubility of substances is becoming increasingly important because ofmore and more stringent regulations regarding health, safety and environment.

In this article, results are presented for water solubility of hydrocarbons. The results are applicablefor the complete range of salt concentrations including water without salt to water saturated with salt. Theresults are intended for use in initial engineering and environmental applications. As an example of suchusage, solubility values issuing from the correlation are useful in determining the distribution of a hydrocarbonspill upon its contact with seawater. Solubility values at other salt concentrations may also be ascertained.

SALT WATER SOLUBILITY CORRELATION

The correlation for solubility of hydrocarbons in water containing salt is based on a series expansionin salt concentration:

log10 S = A + B X + C X2 (16-1)

where S = solubility in salt water at 25 C, parts per million by weight, ppm(wt)X = concentration of salt (NaCl) in water, parts per million by weight, ppm(wt)A, B and C = correlation constants

The correlation constants (A, B and C) are given in Table 16-1. The correlation constants in the tablewere determined from regression of data for water solubility. Both experimental values for the property underconsideration and parameter values for estimation of the property are included in the source publications (1-193). The presented values are applicable to a wide variety of hydrocarbons (alkanes, naphthenes andaromatics with no, single and multiple substitutions). The tabulation is arranged by carbon number (C5, C6,C7,...) for ease of use in quickly locating data using the chemical formula.

The tabulated values for solubility of hydrocarbons in water apply to conditions of saturation in whichthe hydrocarbon is in equilibrium with water. For saturation, the system pressure is approximately equal tothe sum of vapor pressures of hydrocarbon and water.

A comparison of correlation and actual experimental data values for water solubility is shown inFigures 16-1, 16-2 and 16-3 for representative hydrocarbons (pentane, methylcyclopentane and benzene). In the figures, solubility values are plotted at salt concentrations ranging from water without salt to watersaturated with salt. The graphs disclose favorable agreement of correlation and experimental data.

Portions of this material appeared in Pollution Engineering, 24, 46 (Sept. 15, 1992), PollutionEngineering, 26 (1), 70 (1994) and Pollution Engineering, 27 (6), 78 (June, 1995). These portions arereprinted by special permission.

REFERENCES – ORGANIC COMPOUNDS1-190. See REFERENCES – WATER SOLUBILITY - ORGANIC COMPOUNDS in Chapter 15 SOLUBILITY IN WATER ANDOCTANOL-WATER PARTITION COEFFICIENT 191. Yaws, C. L., Pollution Engineering, 14, 46 (Sept. 15, 1992).192. Yaws, C. L. and X. Lin, Pollution Engineering, 26, 70 (January, 1994).193. Yaws, C. L. and X. Lin, Pollution Engineering, 27, 78 (June, 1995).

396

Chapter 17SOLUBILITY IN WATER AS A FUNCTION OF TEMPERATURE

Carl L. Yaws and Daniel H. ChenLamar University, Beaumont, Texas

ABSTRACT

Results for variation of water solubility with temperature are presented 217 hydrocarbons in aneasy-to-use tabular format that is especially applicable for rapid engineering usage with the personalcomputer or hand calculator. The results cover a range of 25-121 C (77-250 F) which includes temperaturesencountered in air and steam stripping operations. Correlation and experimental results are in favorableagreement.

INTRODUCTION

Thermodynamic and physical property data are necessary for the design and operation of industrialprocesses. In particular, water solubility is becoming increasingly important in view of more and morestringent regulations regarding health, safety and environment.

In this article, results are presented for water solubility of hydrocarbons as a function of temperature.Solubility values issuing from the correlation are applicable at ambient and elevated temperatures such asthose experienced in air and steam stripping operations.

WATER SOLUBILITY CORRELATION

The correlation for water solubility of hydrocarbons as a function of temperature is based on a seriesexpansion in reciprocal temperature:

log10 S = A + B/T + C/T2 (17-1)

where S = solubility in water, parts per million by weight, ppm(wt)T = temperature, KA, B and C = correlation constants

The correlation constants (A, B and C) are given in Table 17-1. The correlation constants in the tablewere determined from regression of the data from sources for water solubility. Both experimental values forthe property under consideration and parameter values for estimation of the property are included in thesource publications (1-194). The presented values are applicable to a wide variety of hydrocarbons (alkanes,naphthenes and aromatics with no, single and multiple substitutions). The tabulation is arranged by carbonnumber (C5, C6, C7,...) for ease of use in quickly locating data using the chemical formula.

The tabulated values for solubility of hydrocarbons in water apply to conditions of saturation in whichthe hydrocarbon is in equilibrium with water. For saturation, the system pressure is approximately equal tothe sum of vapor pressures of hydrocarbon and water.

A comparison of correlation and actual experimental data values for water solubility is shown inFigures 17-1, 17-2 and 17-3 for representative hydrocarbons (hexane, cyclopentane, and benzene). In thefigures, solubility values are plotted at temperatures ranging from 25 C to 121 C. This range coverstemperatures encountered in air and steam stripping operations. The graphs disclose favorable agreement ofcorrelation and experimental data.

Portions of this material appeared in Chem. Eng., 100, 108 (Feb., 1993), Chem. Eng., 100, 122(Oct., 1993) and Chem. Eng., 102, 113 (Feb., 1995). These portions are reprinted by special permission.

REFERENCES – ORGANIC COMPOUNDS1-190. See REFERENCES – WATER SOLUBILITY - ORGANIC COMPOUNDS in Chapter 15, SOLUBILITY IN WATER ANDOCTANOL-WATER PARTITION COEFFICIENT 191. McDevit, W. F. and F. A. Long, J. Am. Chem. Soc., 74, 1773 (1952).192. Yaws, C. L., X. Pan and X. Lin, Chem. Eng., 100, 108 (Feb., 1993).193. Yaws, C. L., X. Lin and Li Bu, Chem. Eng., 100, 122 (Oct., 1993).194. Yaws, C. L., Li Bu and S. Nijhawan, Chem. Eng., 102, 113 (Feb., 1995).

403

Chapter 18HENRY'S LAW CONSTANT FOR COMPOUND IN WATER

Carl L. Yaws, Sachin Nijhawan, and Li BuLamar University, Beaumont, Texas

ABSTRACT

Results for Henry's law constant are presented for a wide variety of organic chemicals in water. Theorganic chemicals include hydrocarbon, oxygen, nitrogen, fluorine, chlorine, bromine, iodine and sulfurcompounds. The results are provided in an easy-to-use table that is especially applicable for rapidengineering usage with the personal computer or hand calculator. Representative values for Henry's lawconstant (atm/mol fraction) are 11,515 for ethylene (C2H4), 1,630 for carbon tetrachloride (CCl4) and 308 forbenzene (C6H6) at ambient conditions.

INTRODUCTION

Physical and thermodynamic property data for major organic chemicals are of special value toengineers in the chemical processing and petroleum refining industries. In this article results are presentedfor Henry's law constant for organic chemicals in water. The compilation is intended for use in initialengineering and environmental impact studies. As an example of such usage, Henry's law constant is helpfulin determining the environmental movement and fate of chemicals in air and water.

The results are presented in an easy-to-use tabular format that is especially applicable for rapidengineering usage with the personal computer or hand calculator.

HENRY'S LAW CONSTANT

The results for Henry's law constant for organic chemicals in water are given in Table 18-1. Thetabulation is applicable to a wide variety of organic chemicals in contact with water at ambient conditions. The wide variety of substances includes hydrocarbons, fluorocarbons, chlorocarbons, bromocarbons,iodocarbons, alcohols, acids, ketones, aldehydes, ethers, esters, amines, nitriles, sulfides and thiols.

The tabulation is arranged by carbon number (C1, C2, C3, .... C28). This provides ease of use inquickly locating data using the chemical formula.

Henry's law constant may be determined from data for solubility, vapor pressure, and activitycoefficient at infinite dilution (see Appendix for equations). Thus, in preparing the tabulation, a literaturesearch was conducted to identify data source publications (1-210) for solubility, vapor pressure, activitycoefficient at infinite dilution, and Henry's law constant. Both experimental values for the property underconsideration 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.

A comparison of calculated and data (experimental) values for Henry's law constant is shown inFigures 18-1 and 18-2. The graph in Figure 18-1 includes many different organic chemicals (carbonmonoxide; carbon dioxide; trichlorofluoromethane; carbon tetrachloride; bromoform; chloroform;dichloromethane; trichlorotrifluoroethane; tetrachloroethylene; hexachloroethane; trichloroethylene; 1,1-dichloroethylene; cis 1,2-dichloroethylene, trans 1,2-dichloroethylene; 1,1,2,2-tetrachloroethane; vinylchloride; 1,1,1-trichloroethane; 1,1,2-trichloroethane; 1,2-dibromoethane; 1,1-dichloroethane; ethyl chloride;1,2,3-trichloropropane; 1,2-dichloropropane; 1,3-dichloropropane; 1-chlorobutane; 2-chlorobutane;1-chloropentane; 1,2,4-trichlorobenzene; 1,3-dichlorobenzene; 1,2-dichlorobenzene; chlorobenzene and nitrobenzene) which contain a variety of functional groups. The graph discloses general agreement ofcalculated and data values for the different organic chemicals.

The graph in Figure 18-2 includes many different types of hydrocarbons (alkane, olefin, acetylinic,naphthenic and aromatic hydrocarbons: methane, ethane, hexane, 2-methylpentane, 2-methylhexane;heptane; octane; ethylene, acetylene, cyclopentane; cyclohexane, methyl cyclohexane; benzene, toluene,o-xylene, m-xylene, p-xylene, ethyl benzene, propyl benzene, cumene, 1,3,5-trimethylbenzene; 1,2,4-trimethylbenzene; tetralin and 1-methylnaphthalene). The graph discloses general agreement of calculatedand data values for the different hydrocarbon types.

The compilation for Henry's law constant is usable for engineering and environmental impact studiesinvolving organic compounds in water.

EXAMPLES

The tabulation maybe used for determining Henry's law constant for the compound in water. The use

404

of Henry's law constant in environmental applications is illustrated below.

Example 1 A chemical spill of ethylbenzene (C8H10) occurs into a body of water. The concentration ofethylbenzene in the liquid at the surface of the water is 25 parts per million on a mol basis (xi = 25ppm(mol)). Estimate the concentration of ethylbenzene in the air at the surface of the water.

From thermodynamics at low pressure, the partition coefficient is given by KI=Hi/Pt. Substitution ofHenry's law constant (Hi = 452.3 atm/mol fraction for ethylbenzene) from the table and the total pressure(Pt = 1 atm) into this equation provides Ki = 452.3/1 = 452.3.

Since the vapor concentration is given by yi = Ki * xI , substitution of the K value (Ki = 452.3) andliquid concentration (xi = 25 ppm) yields:

yi = Ki * xi = 452.3 * 25

yi = 11,308 ppm (mol)

Example 2 A chemical spill of benzene (C6H6) occurs into a body of water. The concentration ofbenzene in the air at the surface of the water is measured at 1000 parts per million on a mol basis (yi =1000 ppm(mol)). Estimate the concentration of benzene in the liquid at the surface of the water.

From thermodynamics at low pressure, the partition coefficient is given by Ki = Hi/Pt . Substitution ofHenry's law constant (Hi = 308.26 atm/mol fraction for benzene) from the table and the total pressure (Pt =1 atm) into the above equation provides Ki = 308.26/1 = 308.26.

Since the liquid concentration is given by xi = yi / KI , substitution of the K value (Ki = 308.26) andvapor concentration (yi = 1000 ppm) yields:

xi = yi / Ki = 1000/308.26

xi = 3.24 ppm (mol)

Portions of this material appeared in Chem. Eng., 98, 179 (Nov., 1991). These portions are reprintedby special permission.

REFERENCES – ORGANIC COMPOUNDS1-190. See REFERENCES – WATER SOLUBILITY - ORGANIC COMPOUNDS in Chapter 15 SOLUBILITY IN WATER ANDOCTANOL-WATER PARTITION COEFFICIENT 191. Baker, R. J., B. J. Donelan, L. J. Peterson, W. E. Acree, Jr. and C. C. Tsai, Phys. Chem. Liq., 16, 279 (1987).192. Acree, W. E., Jr., THERMODYNAMIC PROPERTIES OF NONELECTROLYTE SOLUTIONS, Academic Press, New York, NY

(1984).193. Byers, W. D. and C. M. Morton, "Removing VOC from Groundwater", 1984 Summer National Meeting, A.I.Ch.E., Phil., PA (August,

1984).194. Roberts, P. V., G. D. Hopkins, C. Munz and A. H. Riojas, Environ. Sci. Technol., 19, 164 (1985).195. Roberts, P. V. and J. A. Levy, Journal AWWA, 138 (April, 1985).196. Groves, F. R., Jr. and R. Doshi, "Prediction of Solubility of Organics in Water via Activity Coefficients", LSU, Chem. Eng. Dept.,

Baton Rouge, LA (1986).197. Burkhard, L. P., D. E. Armstrong and A. W. Andren, Environ. Sci. Technol., 19, 590 (1985).198. Murphy, T. J., M. D. Mullin and J. A. Meyer, Environ. Sci. Technol., 21, 155 (1987).198. Preston, G. T. and J. M. Prausnitz, Ind. Eng. Chem. Fundam., 10, 389 (1971).199. Dilling, W. L., Environ. Sci. Technol., 11, 405 (1977).200. TREATABILITY MANUAL, Vol. I, Treatability Data, EPA-600/2-82-001a, Office of Research and Development, U.S. Environmental

Protection Agency, Washington, D.C. (Sept., 1981).201. Ashworth, R. A., G. B. Howe, M. E. Mullins and T. N. Rogers, "Air-Water Partitioning Coefficients of Organics in Dilute Aqueous

Solutions", 1986 Summer National Meeting, AIChE, Boston, Mass. (August, 1986).202. Ashworth, R. A., G. B. Howe, M. E. Mullins and T. N. Rogers, J. Hazardous Materials, 18, 25 (1988).203. Warner, H. P., J. M. Cohen and J. C. Ireland, DETERMINATION OF HENRY'S LAW CONSTANTS OF SELECTED PRIORITY

POLLUTANTS, EPA/600/D-87/229 (July, 1987).204. Leighton, D. T., Jr. and J. M. Calo, J. Chem. Eng. Data, 26, 382 (1981).205. Gossett, J. M., ANAEROBIC DEGRADATION OF C1 AND C2 CHLORINATED HYDROCARBONS, final report, U.S. Air Force,

ESL-TR-85-38, Tyndall AFB, FL (Dec., 1985).206. Gossett, J. M., Environ. Sci. Technol., 21, 202 (1987).207. Hansen, K. C., Z. Zhou, C. L. Yaws and T. M. Aminabhavi, J. Chem. Eng. Data, 38(4), 546 (1993).208. Hwang, Y. L., G. E. Keller, II and J. D. Olson, Ind. Eng. Chem. Res., 31(7), 1753 (1992).209. Hwang, Y. L., G. E. Keller, II and J. D. Olson, Ind. Eng. Chem. Res., 31(7), 1759 (1992).210. Yaws, C. L. and others, Chem. Eng., 98, 179 (Nov., 1991).

425

Chapter 19ADSORPTION ON ACTIVATED CARBON

Carl L. Yaws, Li Bu, and Sachin NijhawanLamar University, Beaumont, Texas

ABSTRACT

Adsorption on activated carbon is an effective method for removing volatile organic compounds(VOC) from gases. In this article, results are presented for adsorption capacity as a function of the VOCconcentration in the gas. The correlation constants are displayed in an easy-to-use tabular format that isespecially applicable for rapid engineering usage with the personal computer or hand calculator.

The results for adsorption capacity are applicable for conditions (concentrations in parts per millionrange in gas at 25 C and 1 atm) which are encountered in air pollution control. Correlation and experimentalresults are in favorable agreement.

INTRODUCTION

Physical and thermodynamic property data for organic compounds are especially helpful toengineers and scientists in industry. In particular, capacity data for adsorption of volatile organic compounds(VOC) on activated carbon is becoming increasingly important in engineering and environmental studiesbecause of more and more stringent regulations regarding air emissions.

In this article, results are presented for adsorption capacity as a function of the VOC concentration inthe gas. The results are usable in engineering and environmental studies. As an example of such usage,capacity data issuing from the correlation are useful in the engineering design of carbon adsorption systemsto remove trace pollutants from gases.

ADSORPTION CAPACITY CORRELATION

The correlation for adsorption on activated carbon is based on a logarithmic series expansion ofconcentration in the gas:

log10 Q = A + B [log10 y] + C [log10 y]2 (19-1)

where Q = adsorption capacity at equilibrium, g of compound/100 g of carbony = concentration in gas at 25 C and 1 atm, parts per million by volume, ppmvA, B, and C = correlation constants

The correlation constants (A, B, and C) are given in Table 19-1. The correlation constants in thetable were determined from regression of the available data for adsorption on activated carbon. Thetabulation is arranged by carbon number (C1, C2, C3, .... ,C14). This provides ease of use in quickly locatingdata using the chemical formula. The tabulation also gives the adsorption capacity at concentrations of 10,100, and 1000 parts per million by volume (ppmv) in gas.

A comparison of correlation and experimental data is shown in Figure 19-1 for a representativecompound. In the figure, adsorption capacity is for conditions (concentrations in parts per million range in gasat 25 C and 1 atm) which are encountered in air pollution control. The graph discloses favorable agreementof correlation and experimental data.

ESTIMATION EQUATION

In preparing the correlation, a literature search was conducted to identify source publications (1-39)relative to experimental data and property values for estimates. The publications were screened and copiesof appropriate data were made. These data were then keyed into the computer to provide a database ofadsorption capacity values at different concentrations (partial pressures) for which experimental data areavailable. The database also served as a basis to check the accuracy of the correlation.

Upon completion of data collection, estimation of adsorption capacity for the remaining compoundswas performed. The following equation (developed by Calgon, 7) was used for estimation of theequilibriumadsorption capacity of activated carbon as a fifth order polynomial function of its adsorption potential:

log10 Q = A + B µ + C µ2 + D µ3 + E µ4 + F µ5 (19-2)

where Q = adsorption capacity at equilibrium, cm3 of liquid compound/100 g of carbonµ = adsorption potential of compound, T/(Vi Γi) log(Pi

sat/pi)T = temperature, K

ADSORPTION ON ACTIVATED CARBON

426

Vi = liquid molar volume of compound, cm3/g-molΓi = relative polarizability, [(n2-1)/(n2+1)]i / [(n2-1)/(n2+1)]n-heptanen = refractive indexPi

sat = vapor pressure of compound, atmpi = partial pressure of compound, atmA = 1.71B = - 1.46E-02C = - 1.65E-03D = - 4.11E-04E = 3.14E-05F = - 6.75E-07

For the above equation, data for refractive index are from compilations by Yaws (present work),Texas A & M (26,27) and DIPPR (28). Data for vapor pressure and liquid molar volume are fromcompilations by Yaws (32-36).

The correlation constants (A, B and C) are given in Table 19-1. The correlation constants in the tablewere determined from regression of the available data for adsorption on activated carbon. The tabulation isarranged by carbon number (C1, C2, C3, .... C14). This provides ease of use in quickly locating data usingthe chemical formula. The tabulation also gives the adsorption capacity at concentrations of 10, 100 and1000 parts per million by volume (ppmv) in gas.

A comparison of correlation and experimental data is shown in Figure 19-1 for a representativecompound. In the figure, adsorption capacity is for conditions (concentrations in parts per million range in gasat 25 C and 1 atm) which are encountered in air pollution control. The graph discloses favorable agreementof correlation and experimental data.

EXAMPLES

The correlation maybe used for determining adsorption capacity of activated carbon for removingcompounds from gases. Examples are given below.

Example 1 The air from a paint spraying operation contains 10 ppmv of n-butanol (C4H10O). Estimatethe adsorption capacity of activated carbon for removing the compound at 25 C and 1 atm.

Substitution of the coefficients from the tabulation and concentration into the correlation equationyields:

log10 Q = 0.8988 + 0.32534 [log10 (10)] – 0.03648 [log10(10)]2 = 1.18767

Q = 101.18767

Q = 15.41 g of n-butanol/100 g of carbon

Example 1 The air from an industrial operation contains 10 ppmv of cyclohexane (C6H12). Estimate theadsorption capacity of activated carbon for removing the compound at 25 C and 1 atm.

Substitution of the coefficients from the tabulation and concentration into the correlation equationyields:

log10 Q = 0.720 + 0.25698 [log10 (10)] – 0.01550 [log10(10)]2 = 0.96142

Q = 100.96142

Q = 9.15 g of cyclohexane/100 g of carbon OPERATION AND DESIGN

In actual operation under plant conditions, the capacity of an adsorption bed will seldom achieveequilibrium. Copper and Alley (6) indicate bed capacity at 30 to 40% of equilibrium for plant operatingconditions. Damie and Rogers (7) in the EPA design manual suggest a working factor of 3 for design ofadsorption beds. The total carbon requirements for an adsorption system is obtained by determining carbonrequired from equilibrium capacity and then multiplying by the working factor.

Factors affecting adsorption bed capacity are discussed by Copper and Alley (6), Damie and Rogers(7) and Gram and Ramaratnam (25). These include loss due to adsorption zone; loss due to heat wave(adsorption is an exothermic process); loss due to moisture in entering gas and loss due to residual moistureon the carbon.

Representative adsorption systems for removing organic compounds from gases are shown in

ADSORPTION ON ACTIVATED CARBON

427

Figures 19-2, 19-3 and 19-4. Figure 19-2 shows an adsorption system with recovery of the organic (such asa solvent) using steam for regeneration. Figure 19-3 applies to an adsorption system with thermal or catalyticoxidation of the organic removed from the gas by carbon adsorption. In Figure 19-4, the organic is initiallyremoved from wastewater by air stripping. The air leaving the stripper contains the organic and is then sent tothe adsorption system for recovery of the organic. This last system can be used to recover organics (such asbenzenes) from process wastewater encountered in the chemical and petroleum refining industries.

Portions of this material appeared in Pollution Engineering, 27, 34 (1995), EnvironmentalEngineering World, 1, 16 (May-June, 1995) and Oil & Gas Journal, 93, 64 (Feb. 13, 1995). These portionsare reprinted by special permission.

REFERENCES – ORGANIC COMPOUNDS1. Cheremisnoff, P. N. and F. Ellerbusch, CARBON ADSORPTION HANDBOOK, Ann Arbor Science Publishers, Ann Arbor, MI (1980).2. Yang, R. T., GAS SEPARATION BY ADSORPTION PROCESSES, Butterworth Publishers, Boston, MA (1987).3. Valenzuela, D. P. and A. L. Myers, ADSORPTION EQUILIBRIUM DATA HANDBOOK, Prentice Hall, Engle Cliffs, NJ (1989).4. CALGON CARBON ADSORPTION HANDBOOK, Calgon Carbon Corporation, Pittsburg, PA (1994).5. Adsorption Isotherms, personal communication to Carl L. Yaws, Calgon Carbon Corporation, Pittsburg, PA (1994).6. Copper, C. D. and F. C. Alley, AIR POLLUTION CONTROL, 2nd ed., Waveland Press, Prospects Heights, IL (1994).7. Damie, A. S. and T. N. Rogers, AIR STRIPPER DESIGN MANUAL, EPA-450/1-90-003, U. S. Environmental Protection Agency

(May,1990).8. Grant, R. J., M. Manes and S. B. Smith, AIChE J., 8, 403 (1962).9. Grant, R. J.and M. Manes, Ind. Eng. Chem. Fundam., 3, 221 (1964).10. Grant, R. J. and M. Manes, Ind. Eng. Chem. Fundam., 5, 490 (1966).11. Schenz, T. W. and M. Manes, J. Phy. Chem., 79, 604 (1975).12. Szepesy, L. and V. Illes, Acta Chim. Hung., 35, 37 (1963).13. Laukhuf, W. L. S. and C. A. Plank, J. Chem. Eng. Data, 14, 48 (1969).14. Ray, G. C. and E. O. Box, Ind. Eng. Chem., 42, 1315 (1950).15. Payne, H. K., G. A. Studervant and T. W. Leland, Ind. Eng. Chem. Fundam., 7, 363 (1968).16. Kuro-Oka, M., T. Suzuki, T. Nitta and T. Katayama, J. Chem. Eng. Japan, 17, 588 (1984).17. Ritter, J. A. and R. T. Yang, Ind. Eng. Chem. Res., 26, 1679 (1987).18. Kaul, B. K., Ind. Eng. Chem. Res., 26, 928 (1987).19. Reich, R., W. T. Ziegler and K. A. Rogers, Ind. Eng. Chem. Process Des. Dev., 19, 336 (1980).20. Lewis, W. K., E. R. Gilliland, B. Chertow and W. Milliken, J. Am. Chem. Soc., 72, 1157 (1950).21. Lewis, W. K., E. R. Gilliand, B. Chertow and W. P. Cadogan, Ind. Eng. Chem., 42, 1326 (1950).22. Maslan, F. D., M. Altman and E. R. Aberth, J. Phys. Chem., 57, 106 (1953).23. Cook, W. H. and D. Basmadjian, Can. J. Chem. Eng., 42, 146 (1964).24. Reich, R., W. T. Zeigler and K. A. Rogers, Ind. Eng. Chem. Proc. Des. Dev., 19, 336 (1980).25. Graham, J. R. and M. Ramaratnam, Chem. Eng., 100, 6 (1993).26. SELECTED VALUES OF PROPERTIES OF HYDROCARBONS AND RELATED COMPOUNDS, Thermodynamics Research

Center, TAMU, College Station, TX (1977, 1984).27. SELECTED VALUES OF PROPERTIES OF CHEMICAL COMPOUNDS, Thermodynamics Research Center, TAMU, College

Station, TX (1977, 1987).28. 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).29. Lide, D. R. and H. V. Kehianian, CRC HANDBOOK OF THERMOPHYSICAL AND THERMOCHEMICAL DATA, CRC Press, Boca

Raton, FL (1994).30. Howard, P. H. and W. M. Meylan, eds., HANDBOOK OF PHYSICAL PROPERTIES OF ORGANIC CHEMICALS, CRC Press, Boca

Raton, FL (1997).31. Verschueren, K., HANDBOOK OF ENVIRONMENTAL DATA ON ORGANIC CHEMICALS, Van Nostrand Reinhold, New York,

NY (1996).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. Yaws, C. L., HANDBOOK OF VAPOR PRESSURE, Vols. 1, 2, 3 and 4, Gulf Publishing Co., Houston, TX (1994,1994,1994,1995).36.Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX (1997).37. Yaws, C. L. and others, Pollution Engineering, 27 (2), 34 (1995).38. Yaws, C. L. and others, Environmental Engineering World, 1 (3), 16 (May-June, 1995).39. Yaws, C. L. and others, Oil & Gas Journal, 93 (7), 64 (Feb. 13, 1995).

443

Chapter 20SOIL SORPTION COEFFICIENT

Daniel H. Chen and Carl L. YawsLamar University, Beaumont, Texas

ABSTRACT

Results for soil sorption coefficient KOC are presented for 336 hydrocarbon and organic chemicals. The chemicals include hydrocarbon, oxygen, nitrogen, halogen, sulfur and phosphorus compounds. Representative results for soil adsorption coefficient [(mg sorbed / kg organic carbon in soil) / ( mg/L aqueousconcentration) or abbreviated as L/kg] are 4300 for trifluralin (C10H9F3N3O4), 3910 for hexachlorobenzene(C6CL6), 1300 for naphthalene (C10H8) and 27 for phenol (C6H6O) in a normal soil environment (20 C, pH4-8, carbon exchange capacity greater than 7 MEQ/100 g, sand composition less than 70%, etc.). Themelting point (MP) and molecular weight (MW) data are also provided as they are needed in manyenvironmental property data correlations.

INTRODUCTION

The soil sorption coefficient KOC , which determines the partitioning of an organic chemical betweenthe soil/sediment and the aqueous solution, is an important environmental parameter. KOC affects thephysical movement of pollutants, chemical degradation (photolysis and hydrolysis), biodegradation, acidityand buffered solution-phase concentration. As a result, the soil sorption coefficient is widely used in river,runoff and soil/ground water models for the assessments of the fate and transport of chemicals (5,24,28,36).KOC is also known as "soil organic carbon partition coefficient" or "soil sorption coefficient standardized withrespect to organic carbon." With the value of KOC known, the partition uptake of water contaminants for aparticular soil/sediment or the degree of leaching of the pollutants into the ground water can be estimated.

A compilation of the soil sorption coefficient data for 336 compounds is provided in an easy-to-usetabular format that is especially applicable for rapid engineering use with the personal computer or handcalculator.

SOIL SORPTION COEFFICIENT

The amount of chemicals sorbed onto a soil or sediment depends on the concentration ofchemicals and their equilibrium distribution coefficient (i.e., KOC). For dilute aqueous solutions, thedistribution coefficient can be adequately expressed with the Freundlich equation with 1/n equal to one(8,11,24,25,38):

x / m = KOC C (20-1)

where x = weight of solute sorbed, mg C = equilibrium concentration of solute in aqueous phase, mg/L m = weight of sorbent (organic carbon in soil), kg KOC = soil sorption coefficient

From the above equation, KOC can be interpreted as the ratio of the solid phase concentration(normalized for the organic carbon content) to the solution phase concentration of the chemical atequilibrium. Therefore, in commonly used units, KOC is:

mg sorbed/ kg organic carbon KOC = _________________________________________ (20-2) mg/L aqueous concentration

The unit of KOC can be abbreviated as L/kg. The average organic carbon content of a typical soil is from0.5% to 3.5%. By basing the sorption coefficient on soil (or sediment) organic carbon, one can eliminatemuch of the variation between soils due to organic carbon content. Note that the cited experimental orpredicted KOC values are intended for a normal environment as stated above. Attempts to extrapolate farbeyond these conditions may incur considerable errors (10-12,15,24). In case that the coefficient isexpressed in terms of soil organic matter, Kom, the following equivalence can be used to obtain KOC:

KOC = 1.72 Kom (20-3)

This assumes that the organic matter contains about 58% C (8).The results for the soil sorption coefficient for organic chemicals in water are given in Table 20-

444

1. The melting point (MP) and molecular weight (MW) are also provided to facilitate predictions for otherenvironmental properties. The tabulation is applicable to a wide variety of organic chemicals in contactwith water at normal ambient conditions. The wide variety of substances includes hydrocarbons, acids,alcohols, esters, ethers, ketones, fluorides, chlorides, bromides, amines, sulfones, nitros, amides, sulfidesand phosphates. The tabulation is arranged by carbon number (C, C2, C3, .... C21). This provides ease ofuse in quickly locating data using the chemical formula.

In preparing the tabulation, a literature search was conducted to identify data source publications (1-40). The publications were screened and copies of appropriate data were made. These data were thenkeyed into the computer to provide a database.

The nonlinear group contribution method (3,13,21) has been used for the estimation of the soilsorption coefficient when experimental KOC values are not available. The method is based oncomprehensive (225 compounds) and updated data. Comparison with literature methods yields favorableresults (2,3,13,19,32,33). In general, the prediction errors are within ± 0.82 order of magnitude (95%confidence limit). A comparison of calculated and data (experimental) values for the soil sorption coefficientis shown in Figure 20-1. The graph discloses general agreement of calculated and data values for differentorganic chemicals.

The compilation for the soil sorption coefficient maybe used in engineering and environmental impactstudies involving organic compounds in water.

EXAMPLES

The tabulation may be used for determining the soil sorption coefficient for the compound in water.The use of the soil sorption coefficient in environmental applications involving organic chemicals in water isillustrated below.

Example 1 For an aqueous concentration of benzene (C6H6) in contaminated river water of 10 ppm byweight, what will be the maximum uptake of benzene by the bottom sediment? The average organiccarbon content of the bottom sediment is 3%.

The equation x/m = KOC C is used in determining the solution. First, calculate the amount oforganic carbon per ton (metric) of bottom sediment: m = 1000 * 3% = 30 kg organic carbon. Thensubstitute the soil sorption coefficient of benzene from the tabulation

KOC = 83 (mg sorbed/kg org carbon) / (mg/L aqueous conc) = 83 (mg sorbed/kg org carbon) / (ppm aqueous conc)and the aqueous concentration C = 10 ppm into the equation for x/m to obtain:

x /30 = 83 * 10 mg

x = 30*83*10 mg = 2.5E04 mg = 0.025 kg

Example 2 Atrazine (C8H14CLN5) is uniformly applied to a field and incorporated into the soil. The soilhas a bulk density of 1.25 kg/L, 2 % organic carbon and 25 % each air and water by volume. Estimatethe equilibrium distribution of the pesticide resulting from a 1 kg/hectare (1 hectare = 10,000 m2)application incorporated to 10-cm depth. Volatilization into the air is assumed to be negligible.

The amount of organic carbon in soil per hectare is m = 10,000 *.1 * 1000 * 1.25 * 2% = 25,000 kgof org carbon. From the tabulation, the soil sorption coefficient of atrazine is

KOC = 149 (mg sorbed/kg organic carbon) / (mg/L aqueous conc)

Determination of the amount of atrazine in the soil phase per hectare requires a trial and error procedure.Trying x = .94 kg = 940000 mg in the equation x/m = KOC C and solving for C gives:

C = (940000 /25,000)/149 = .252 mg/L

The amount of atrazine in the aqueous phase per hectare is.252 * 10,000 * .1 * 1,000 * 25% = 63000 mg = .063 kg

The total amount of atrazine is 1.003 kg/hectare. This is close enough to the application (1.003 vs 1application).

The equilibrium distribution of atrazine is estimated to be:.063/(.94 + .063) = 6.3 % in water

.94/ (.94 + .063) = 93.7 % in soil

Portions of this material appeared in Pollution Engineering, 24, 54 (June 15, 1992) and are reprinted

445

by special permission.

REFERENCES – ORGANIC COMPOUNDS 1. Boyd, S. A., Mikesell, M. D., and Lee, J. F., Chlorophenols in soil. Sawhney, B. L. and K. Brown (eds.), REACTION AND

MOVEMENT OF ORGANIC CHEMICALS IN SOILS , Soil Science Society of American and American Society Agronomy, SSSASpecial Publication no. 22, 209 (1989).

2. Briggs, G. G. J. Agric. Food Chem. 29(5), 1050 (1981). 3. Chen,T. L., D. H. Chen, and C. L. Yaws, Predicting soil adsorption with molecular structure, paper 54b, AIChE National Meeting,

August 19-22, 1990, San Diego, California. 4. Chiou, C. T., L. J. Peters and V. H. Freed, Science, 206, 831 (1979). 5. Chiou, C. T., Soil Science Society of American and American Society Agronomy, SSSA Special Publication no. 22, 1 (1989). 6. Dickson, K. I. (ed.), MODELING THE FATE OF CHEMICALS IN THE AQUATIC ENVIRONMENT, Ann Arbor Sci. Pub., Ann Arbor,

MI (1982). 7. Green, R. E. and S. R. Obien, Weed Sci., 17, 514 (1969). 8. Grover, R. and R. J. Soil Sci., 109, 136 (1970). 9. Gschwend, P. M. and Wu, S. C. Environ. Sci. Technol., 19 90 (1985).10. Hamaker, J. W. and J. M. Thompson, Adsorption. Goring C.A.I. and Hamaker J.W.(eds.), ORGANIC CHEMICALS IN THE SOIL

ENVIRONMENT, Vol. 1, Marcel-Dekker , New York, NY (1972).11. Hance, R. J., J. Agric. Food Chem., 17, 667 (1969).12. Hodson, J. and N. A. Williams, Chemosphere, 17, No. 1, 67 (1988).13. Jeng, C. Y., Estimation of soil sorption coefficient and acentric factor with nonlinear group contribution methods. M.S.E. Thesis,

Lamar University, Beaumont, TX (August, 1989).14. Khan, S. V. J. of Environmental Quality, 3 ,202 (1974).15. Karickhoff, S. W. and Brown, D. S. J. Environ. Qual., 7, 246 (1978).16. Karickhoff, S. W., Brown D. S., and Scott T. A., Water Res., 13, 241 (1979).17. Karickhoff, S. W., Chemosphere, 10(8), 833 (1981).18. Karickhoff, S. W., J. of Hydraulic Engineering, ASCE, 110, 707 (1984).19. Kenaga, E. E. and C. A. I. Goring, AQUATIC TOXICOLOGY, Eaton J. C., Parrish .P. R., Hendricks, A. C. (eds), the American

Society for Testing and Materials, Philadelphia, PA, 78 (1980).20. Ladlie, J. S., Meggitt, W. F. and Penner, D. Weed Science, 24, 477 (1976).21. Lai, W. Y., D. H. Chen and R. N. Maddox, Ind. Eng. Chem. Res., 26, 1072 (1987).22. Lambert, S. M. J. Agric. Food Chem., 15, 572 (1967).23. Liu, L. C., H. Cibes-Viadw and F. K. S. Koo, Weed Sci., 18, 470 (1970).24. Lyman, W. J., W. F. Reehl and D. H. Rosenblatt, HANDBOOK OF CHEMICAL PROPERTY ESTIMATION METHODS, McGraw-

Hill, New York, NY (1982).25. Means, J. C., S. G. Wood, J. J. Hassett and W. L. Banwart, Environ. Sci. Technol., 14, 1524 (1980).26. Means, J. C., S. G. Wood, J. J. Hassett and W. L. Banwart, Environ. Sci. Technol., 16, 93 (1982).27. Nearpass, D. C., Soil Sci., 103, 177 (1967).28. Pickens, J. and W. C. Lennox, Water Resources Research, 12, No. 2, 171 (1976).29. Pierce, R. H., Jr., Olney, C. E. and Felbeck, G. T., Jr. Geochem. Cosmochim. Acta, 38, 1061 (1974).30. Poinke, H. B. and Chesters, G. J. Environ. Qual., 2 29 (1973).31. Reid, R. C., J. M. Prausnitz and B. E. Poling, THE PROPERTIES OF GASES AND LIQUIDS, 4th ed., McGraw-Hill, New York, NY

(1987).32. Sabljic, A. Environ. Sci. Technol. 21(4), 358 (1987).33. Sabljic A. J. Argic. Food Chem., 32, 243 (1984).34. Sax, N. I. and R. J. Lewis, Jr., HAWLEY'S CONDENSED CHEMICAL DICTIONARY, 11th ed., Van Nostrand Reinhold Co., New

York, NY (1987).35. Swann, R. L., D. A. Laskowski, P. J. McCall, K. Vander Kuy and H. J. Dishburger, Residue Reviews, 85, 17 (1983).36. Thibodeaux, L. J., CHEMODYNAMICS, John Wiley & Sons, New York, NY (1979).37. TREATABILITY MANUAL, Vol. I, Treatability Data, EPA-600/2-82-001a, Office of Research and Development, U.S. Environmental

Protection Agency, Washington, D.C. Sept., 1981.38. U. S. Environmental Protection Agency, Toxic substances control act for premanufacture testing of new chemical substances. Fed.

Regist., 44, 16257 (1979).39. Weast, R. C., ed., CRC HANDBOOK OF CHEMISTRY AND PHYSICS, 68th ed., 1987-88, CRC Press, Inc., Boca Raton, FL

(1987).40. Yaws, C. L., THERMODYNAMIC AND PHYSICAL PROPERTY DATA, Gulf Publishing Co., Houston, TX (1992).41. Chen, D. H., C. L. Yaws and others, Pollution Engineering, 24, 54 (June 15, 1992).

452

Chapter 21VISCOSITY OF GAS

Carl L. Yaws, Xiaoyan Lin and Li BuLamar University, Beaumont, Texas

ABSTRACT

Results for gas viscosity as function of temperature are presented for a wide range of organic andinorganic chemicals. The major chemicals include many compound types. The results are provided ineasy-to-use tables that are especially applicable for rapid engineering usage with the personal computeror hand calculator. The agreement of correlation and data is quite good.

INTRODUCTION

Gas viscosity data are important in many engineering applications in the chemical processing andpetroleum refining industries. The objective of this article is to provide the engineer with such viscosity data.The compilation of data is presented for a wide temperature range to enable the engineer to determinevalues at desired temperatures of interest.

GAS VISCOSITY CORRELATION

The correlation for gas viscosity as a function of temperature is given by the equation shown below:

ngas = A + B T + C T2 (21-1)

where ngas = viscosity of gas, micropoiseA, B and C = regression coefficients for chemical compoundT = temperature, K

The results for gas viscosity at low pressure are given in Tables 21-1 and 21-2. The tabulations arearranged by chemical formula carbon number to provide ease of use in quickly locating data.

In preparing the compilation, a literature search was conducted to identify data source publicationsfor organics (1-37) and inorganics (1-62). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened for appropriate data. The compilation resulting from the screening is based on both experimentaldata and estimated values. In the absence of experimental data, estimates were primarily based on modifiedChapman-Enskog method (29, Chung et al equation, intermolecular forces, collision diameter) andReichenberg equation (29, corresponding state, group contribution). Experimental data and estimates werethen regressed to provide the same equation for all compounds.

Very limited experimental data are available for highly polar and high molecular weight compounds.Thus, the values for these compounds should be considered rough approximations.

A comparison of correlation and experimental data is shown in Figure 21-1 for a representativechemical. The graph discloses good agreement of correlation and data.

EXAMPLES

The correlation results maybe used for prediction and calculation of gas viscosity. Examples aregiven below.

Example 1 Calculate the gas viscosity of n-hexane (C6H14) at a temperature of 300 K.

Substitution of the coefficients from the table and temperature into the correlation equation yields:ngas = - 8.2223 + 2.6229E-01*300 - 5.7366E-05*3002

ngas = 65.3 micropoise


Example 2 Calculate the gas viscosity of carbon tetrachloride (CCl4) at a temperature of 520 K.

Substitution of the coefficients from the table and temperature into the correlation equation yields:ngas = - 7.7453 + 3.9481E-01*520 - 1.1150E-02*5202

ngas = 169.3 micropoise The calculated and data values compare favorably (169.3 vs 167.0, deviation = 1.36%).

453

REFERENCES – ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Golubev, I. F., VISCOSITY OF GASES AND GAS MIXTURES, translated from Russian, US Dept. of Commerce, Springfield, VA

(1970).36. Stephan, K. and K. Lucas, VISCOSITY OF DENSE FLUIDS, Plenum Press, New York, NY (1979).37. Yaws, C. L., HANDBOOK OF VISCOSITY, Vols. 1, 2 , 3 and 4, Gulf Publishing Company, Houston, TX (1995, 1995, 1995, 1997).

REFERENCES – INORGANIC COMPOUNDS1-56. See REFERENCES - INORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 57. Golubev, I. F., VISCOSITY OF GASES AND GAS MIXTURES, translated from Russian, US Dept. of Commerce, Springfield, VA

(1970).58. Lyon, R. N., ed., LIQUID-METALS HANDBOOK, Atomic Energy Commission and Dept. of Navy, Washington, DC (1954).59. Emsley, J., THE ELEMENTS, 2nd ed., Clarendon Press, Oxford University Press, New York, NY (1991).60. Perry, D. L. and S. L. Phillips, HANDBOOK OF INORGANIC COMPOUNDS, CRC Press, New York, NY (1995).61. Stephan, K. and K. Lucas, VISCOSITY OF DENSE FLUIDS, Plenum Press, New York, NY (1979).62. Yaws, C. L., HANDBOOK OF VISCOSITY, Vol. 4, Gulf Publishing Co., Houston, TX (1997).

478

Chapter 22VISCOSITY OF LIQUID


ABSTRACTResults for liquid viscosity as function of temperature are presented for a wide range of organic

and inorganic chemicals. The major chemicals include many compound types. The results are provided ineasy-to-use tables that are especially applicable for rapid engineering usage with the personal computeror hand calculator. The agreement of correlation and data is quite good.

INTRODUCTIONLiquid viscosity data are important in many engineering applications in the chemical processing and

petroleum refining industries. The objective of this article is to provide the engineer with such viscosity data.The compilation of data is presented for a wide temperature range to enable the engineer to determinevalues at temperatures of interest.

LIQUID VISCOSITY CORRELATIONThe correlation for liquid viscosity as a function of temperature is given by the equation shown below:

log10 nliq = A + B/T + C T + D T2 (22-1)

where nliq = viscosity of liquid, centipoiseA, B, C and D = regression coefficients for chemical compoundT = temperature, K

The results for liquid viscosity are given in Tables 22-1 and 22-2. The tabulations are arranged bychemical formula to provides ease of use in quickly locating data. Many of the values for the liquid cover thefull range from melting to critical point.

In preparing the compilation, a literature search was conducted to identify data source publicationsfor organics (1-40) and inorganics (1-126). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened for appropriate data. The compilation resulting from the screening is based on both experimentaldata and estimated values.

For organic compounds, liquid viscosities at low temperatures were primarily estimated using theVan Velzen method (29, group and structural contributions). The Przezdziecki and Sridhar equation (29,corresponding states) and boiling point method (empirical) were also used for selected compounds. Forliquid viscosities at high temperatures, both experimental data and estimates were extended using a modifiedLetsou and Stiel equation (29, corresponding states) for saturated liquids. Experimental data and estimateswere then regressed to provide the same equation for all compounds.

For inorganic compounds, liquid viscosities for metals were primarily estimated using the Grossemethod (64, melting point, liquid volume). For inorganics that are solids at ambient conditions, a modifiedLetsou and Stiel method (29, corresponding states, melting point, boiling point) was used. For inorganics thatare gases and liquids at ambient conditions, a modified Letsou and Stiel method was also used.Experimental data and estimates were then regressed to provide the same equation for all compounds.

For gas and liquid viscosities, the experimental data for inorganics is very limited or scarce whencompared to that available for organics. The estimation methods for inorganics are also very limited orscarce in comparison to organics. Thus, in the absence of experimental data and the scarcity of estimationmethods, the estimates for inorganics should be considered as very rough approximations.

Very limited experimental data for liquid viscosities are available at temperatures in the region of themelting and critical point temperatures. Thus, the values in the regions of melting and critical pointtemperatures should be considered rough approximations. The values in the intermediate region (abovemelting and below critical point) are more accurate.

A comparison of correlation and experimental data for liquid viscosity is shown in Figure 22-1 for arepresentative chemical. The graph discloses good agreement of correlation and data.

EXAMPLESThe correlation results maybe used for prediction and calculation of liquid viscosity. Examples are

given below.

479

Example 1 Calculate the liquid viscosity of cyclohexane (C6H12) at a temperature of 353.85 K (80.7 C).

Substitution of the coefficients from the table and temperature into the correlation equation yields:

log10 nliq = + 4.7423 - 2.5322E+02/353.85 - 1.6927E-02*353.85 + 1.2472E-05*353.852 = -.4012

nliq = 10-.4012

nliq = 0.397 centipoise

The calculated and data values compare favorably (0.397 Vs 0.413, deviation = 3.87%).

Example 2 Calculate the liquid viscosity of benzene (C6H6) at a temperature of 343.35 K (70.2 C).


log10 nliq = - 7.4005 + 1.1815E+03/343.85 + 1.4888E-02*343.85 - 1.3713E-05*343.852 = -.4647

nliq = 10-.4647

nliq = 0.343 centipoise


Portions of this material appeared in Chem. Eng., 101 (4), 119 (April, 1994) and is reprinted byspecial permission.

REFERENCES - ORGANIC COMPOUNDS1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Golubev, I. F., VISCOSITY OF GASES AND GAS MIXTURES, translated from Russian, US Dept. of Commerce, Springfield, VA (1970).36. Stephan, K. and K. Lucas, VISCOSITY OF DENSE FLUIDS, Plenum Press, New York, NY (1979).37. Viswanath, D. S. and G. Natarajan, DATA BOOK ON THE VISCOSITY OF LIQUIDS, Hemisphere Publishing Corporation, New York, NY (1989).38. Yaws, C. L., Xiaoyan Lin and Li Bu, Chem. Eng., 101 (4), 119 (April, 1994).39. Yaws, C. L., HANDBOOK OF TRANSPORT PROPERTY DATA, Gulf Publishing Co., Houston, TX (1995).40. Yaws, C. L., HANDBOOK OF VISCOSITY, Vols. 1, 2, 3 and 4, Gulf Publishing Company, Houston, TX (1995, 1995, 1995, 1997).

REFERENCES – INORGANIC COMPOUNDS1-56. See REFERENCES - INORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 57. Golubev, I. F., VISCOSITY OF GASES AND GAS MIXTURES, translated from Russian, US Dept. of Commerce, Springfield, VA

(1970).58. Viswanath, D. S. and G. Natarajan, DATA BOOK ON THE VISCOSITY OF LIQUIDS, Hemisphere Publishing Corporation, New

York, NY (1989).59. Lyon, R. N., ed., LIQUID-METALS HANDBOOK, Atomic Energy Commission and Dept. of Navy, Washington, DC (1954).60. Emsley, J., THE ELEMENTS, 2nd ed., Clarendon Press, Oxford University Press, New York, NY (1991).61. Perry, D. L. and S. L. Phillips, HANDBOOK OF INORGANIC COMPOUNDS, CRC Press, New York, NY (1995).62. Stephan, K. and K. Lucas, VISCOSITY OF DENSE FLUIDS, Plenum Press, New York, NY (1979).63. Van Horn, K. R., ed., ALUMINUM, Vol. 1, American Society for Metals, Metals Park, Ohio (1967).64. Grosse, A. V., J. Inorg. Nucl. Chem., 23, 333 (1961).65. Chapman, T. W., AIChE J., 12, No. 2, 395 (1966).66. Bacon, R. F. and R. Fanelli, J. Amer. Chem. Soc., 15, 639 (1943).67. Bacon, J. F. and A. A. Hasapis, J. Appl. Phys., 30 (9), 1470 (1959).68. Niselson, L. A. and T. D. Sokolova, Russ. J. Inorg. Chem., 10, 827 (1965).69. Saji, Y. and S. Kobayashi, Cryogenics, 136 (1964).70. Maitland, G. C. and E. B. Smith, J. Chem. Eng. Data, 17 (2), 150 (1972).71. Kestin, J. and E. A., Knierrim, J. Phys. Chem. Ref. Data, 13 (1), 229 (1984).72. Runovskaya, I. V., A. D. Zorin and G. G. Devyatykh, Russ. J. Inorg. Chem., 15, 1338 (1970).73. Reichenburg, D., AICHE J., 21, 181 (1975).74. Stiel, L.T. and G. Thodos, AICHE J., 10, 266 (1964).75. Boon, J. P. and J. C. Thomas, J. Physica, 33, 547 (1967).76. Rao, R. V. G. and K. N. Swamy, Z. Phys. Chem. (Leipzig), 2, 250 (1974).77. Rudenko, N. S. and L. W. Schubrukow, Phys Zeit. der Sowjetunion, 6, 470 (1934).78. Hetteman, W., W. Grevendork and A. DeBock, J. Chem. Phys., 53(1), 185 (1970).79. Kulifeev, V.K., V. I. Panchishnyi and G. P. Standevich, Isv. Vyssh. Ucheb. Zaved. Tsvet. Met., 11(2), 116 (1968). 80. Simkin, J. and R. L. Jarry, J. Phys. Chem., 61, 503 (1957).81. Usanovich, M., T. Sumarokova and V. Udovenko, Acta Physicochim. USSR, 11, 505 (1939).82. Kestin, J., J. V. Sengers, B. Kamgar-Parsi and J.M. H. Levelt Sengers, J. Phys. Chem. Ref. Data, 13 (2), 601 (1984).83. Matsunaga, N. and A. Nagashima, J. Phys. Chem. Ref. Data, 12 (4), 933 (1983).84. Hanley, H.J.M. and R. Prydz, J. Phys. Chem. Ref. Data, 1 (4), 1101 (1972).85. Moore, G. A. and T. R. Shives, IRON, Metals Handbook, 8th ed., 1206 (1961).

480

86. Greenwood, N.N. and K. Wade, J. Inorg. Nucl. Chem., 3, 349 (1957).87. Janz, G. J., A. T. Ward and R. D. Reeves, MOLTEN SALT DATA, Technical Bulletin Series, Rensselaer Polytechnic Institue, Troy,

NY (1964).88. Baker, C. E., J. Chem. Phys., 46, 2846 (1967).89. Stern, S. A., J. L. Mullhauupt and W. B. Kay, Chem. Rev., 60, 185 (1960).90. Mason, D. M., I. Petker and S. P. Vango, J. Phys. Chem., 59, 511 (1955).91. Naumova, A. S., Zh, Obshch. Khim., 19, 1228 (1949).92. Taylor, E. G., L. M. Lynne and A. G. Follous, Can. J. Chem., 29, 439 (1951).93. 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 Publish Corporation,Washington, DC (1984).

94. Misra, S. C. and K. N. Parida, Ind. J. Pure Appl. Phys., 7, 772 (1969).95. Janz, G. L., C. B. Bansal, N. P. Bansal, R. M. Murphy and R. P. T. Tompkins, PHYSICAL PROPERTIES DATA COMPILATIONS

RELEVANT TOR ENERGY STORAGE. II. MOLTEN SALTS: DATA ON SINGLE AND MULTICOMPONENT SALT SYSTEMS,Nat. Bur. Stand., Molten Salts Data Center, Troy, NY (April, 1979).

96. Morozov, I. R., J. Appl. Chem. (USSR), 24, 975 (1951).97. Davison, H. W., NASA Tech. Note D-4650 (1968).98. Andrade, E. N., C. Da and E. R. Dobbs, Proc. Roy. Soc. London, 211A, 12 (1952).99. Leu, A. L., S. M, Ma and H. Eyring, Proc. Nat. Acad. Sci. USA, 72 (3), 1026 (1975).100. Krynicki, K. and J. W. Hennel, Acta Physica Polonica, 24 (8), 269 (1963).101. Hanley, H. J. M. and J. F. Ely, J. Phys. Chem. Ref. Data, 2 (4), 735 (1973).102. Mason, D. M., O. W. Wilcox and B. H. Sage, J. Phys. Chem., 56, 1008 (1952).103. Janz, G. J., J. Phys. Chem. Ref. Data, 9 (4), 791 (1980).104. Janz, G. J., G. L. Gardner, U. Krebs and R. P. T. Tomkins, J. Phys. Chem. Ref. Data, 3 (1), 1 (1974).105. Morozov, I. R., J. Appl. Chem. (USSR), 24, 975 (1951).106. Gossink, R. G. and J. M. Stevels, Inorg. Chem., 11 (9), 2180 (1982).107. Forster, S., (translation), Cryogenics, 3, 176 (1963).108. McCarty, R. D. and L. A. Weber, National Bureau of Standards Technical Note 384, Washington, DC (1971).109. Hersh, C. K., A. W. Berger and J. R. C. Brown, Adv. Chem. Ser. No. 21, Am. Chem. Soc., Washington, DC (1959).110. Streng A. G., J. Chem. Eng. Data, 6 (3), 43 (1961).111. Jenkins, A. C. and F. S. Dipaolo, J. Chem. Phys., 29 (4), 905 (1958).112. Mole, M. F., W. S. Holmes and J. C. McCoubrey, J. Chem. Soc., 81, 5082 (1959).113. Gutmann, V., Monatshofte Fur Chemie, 83, 164 (1952).114. Yoon, P. and G. Thodos, AICHE J., 16, 300 (1970).115. Murgulescu, I.G. and M. Serban , Rev. Roum. Chim. 19, 1417 (1974).116. Veda, K. and K. Kigoshi, J. Inorg. Nucl. Chem., 36, 989 (1974).117. Hyne, R. A. and P. F. Tiley, J. Chem. Soc., 2348 (1961).118. Niselson, L. A., P. P. Pugachevich, T. D. Sokolova and R. A. Bederdinov, Russ. J. Inorg. Chem., 10 (6), 705 (1965).119. Ellis, C. P. and J. G. Raw, J. Chem. Soc., 3765 (1956).120. Runovskaya, I. V., A. D. Zorin and G. G. Devyatykh, Russ. J. Inorg. Chem., 15 (9), (1970).121. Waseda, Y. and K., Suzuki, Phys. Status Solidi B: Basic Research, 57, 351 (1973).122. Rudenko, N. S and V. G. Konareva, Zh. Fiz. Khim., 38, 270 (1964).123. Culpin, M. F., Proc. Phys. Soc., 70, 1079 (1957).124. Spells, K. E, Proc. Phys. Soc., 48, 299 (1936).125. Yaws, C. L., HANDBOOK OF TRANSPORT PROPERTY DATA, Gulf Publishing Co., Houston, TX (1995).126. Yaws, C. L., HANDBOOK OF VISCOSITY, Vol. 4, Gulf Publishing Co., Houston, TX (1997).

505

Chapter 23THERMAL CONDUCTIVITY OF GAS


ABSTRACTResults for gas thermal conductivity as function of temperature are presented for a wide range of

organic and inorganic chemicals. The major chemicals include many compound types. The results areprovided in easy-to-use tables that are especially applicable for rapid engineering usage with the personalcomputer or hand calculator. The agreement of correlation and data is quite good.

INTRODUCTIONGas thermal conductivity data are important in many engineering applications in the chemical

processing and petroleum refining industries. The objective of this article is to provide the engineer with suchdata. The compilation of data is presented for a wide temperature range to enable the engineer to determinevalues at the temperatures of interest.

THERMAL CONDUCTIVITY CORRELATIONThe correlation for thermal conductivity of gas as a function of temperature is given by the equation

shown below:

kgas = A + B T + C T2 (23-1)

where kgas = thermal conductivity of gas, W/(m K)A, B and C = regression coefficients for chemical compoundT = temperature, K

The results for gas thermal conductivity at low pressure are given in Tables 23-1 and 23-2. Thetabulation is arranged by chemical formula to provides ease of use in quickly locating data.

In preparing the compilation, a literature search was conducted to identify data source publicationsfor organics (1-38) and inorganics (1-99). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened for appropriate data. The compilation resulting from the screening is based on both experimentaldata and estimated values.

In the absence of experimental data for organic compounds, estimates were primarily based oncorrelations (29) of Roy and Thodos; Misic and Thodos; Stiel and Thodos and modified Eucken models. Forinorganic compounds, estimates were primarily based on modified Eucken models. Experimental data andestimates were then regressed to provide the same equation for all compounds.

Very limited experimental data are available for highly polar and high molecular weight compounds.Also, very few experimental data are available at high temperatures above 600 K. Thus, the values for thesecompounds and high temperatures should be considered rough approximations.


EXAMPLESThe correlation results maybe used for prediction and calculation of gas thermal conductivity.

Examples are given below.

Example 1 Calculate the gas thermal conductivity of n-hexane (C6H14) at a temperature of 300 K.


kgas = - 0.00200 + 7.7788E-06*300 + 1.3824E-07*3002

kgas = 0.01278 W/(m K)


Example 2 Calculate the gas thermal conductivity of carbon dioxide (CO2) at a temperature of 550 K.


506

kgas = - 0.01200 + 1.0208E-04*550 - 2.2403E-08*5502 kgas = 0.03344 W/(m K)


Portions of this material appeared in Oil & Gas Journal, 92, 43 (April, 1994) and are reprinted byspecial permission.

REFERENCES – ORGANIC COMPOUNDS 1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Tsederberg, N. V., THERMAL CONDUCTIVITY OF GASES AND LIQUIDS, R. D. Cess, editor, MIT Press, Cambridge, MA (1965). 36. Vargaftik, N. B., L. P. Filippov, A. A. Tarzimanov and E. E. Totskiy, THERMAL CONDUCTIVITY OF GASES AND LIQUIDS,

Standards Press, Moscow, USSR (1978). 37. Yaws, C. L., X. Lin, Li Bu and Sachin Nijhawan, Oil & Gas Journal, 92 (16), 43 (April 18, 1994). 38. Yaws, C. L., HANDBOOK OF THERMAL CONDUCTIVITY, Vols. 1, 2, 3 and 4, Gulf Publishing Co., Houston, TX (1995, 1995,

1995, 1997).

REFERENCES – INORGANIC COMPOUNDS1-64. See REFERENCES - INORGANIC COMPOUNDS in Chapter 2 HEAT CAPACITY OF GAS 65. Tsederberg, N. V., THERMAL CONDUCTIVITY OF GASES AND LIQUIDS, MIT Press, Cambridge, MA (1965).66. Vargaftik, N. B. and others, HANDBOOK OF THERMAL CONDUCTIVITY OF LIQUIDS AND GASES, CRC Press, Inc., Boca

Raton, FL (1994).67. Janz, G. J., C. B. Allan, N. P. Bansal and R. M. Murphy, PHYSICAL PROPERTIES DATA COMPILATIONS RELEVANT TO

ENERGY STORAGE, Nat. Bur. Stand., Molten Salts Data Center, Troy, NY (1979).68. Lyon, R. N., ed., LIQUID-METALS HANDBOOK, 2nd ed., U. S. Government Printing Office, Washington, DC (1954).69. Ho. C. Y. and R. W. Powell, P. E. Liley, J., Phys. Chem. Ref. Data, 1 (2), 279 (1972).70. Saxena, S. C., High Temp. Sci., 3, 168 (1971).71. Stiel, L. I. and G. Thodos, AICHE J., 10, 266 (1964).72. Choy, P. and C. J. G. Raw, J. Chem. Phys., 45 (5), 1413 (1966).73. Chapman, S.and T. G. Cowling, AICHE J., 10, 266 (1964).74. Eucken A., Z. Phys., 14, 324 (1913).75. Matsunaga, N. and A. Nagashima, J. Phys. Chem. Ref. Data, 12 (4), 933 (1983).76. Kestin, J. and J. V. Sengers, J. Phys. Chem. Ref. Data, 13 (2), 601 (1984).77. Baker, C. E., J. Chem. Phys., 46, 2846 (1967).78. Jones, L. W., Int. J. Heat Mass Transfer, 10, 745 (1967).79. Kestin, J. and E. A. Knierim, J. Phys. Chem. Ref. Data, 13 (1), 229 (1984).80. Hanley, H. J. M. and J. F. Ely, J. Phys. Chem. Ref. Data, 2 (4), 735 (1973).81. Streng, A. G., J. Chem. Eng. Data, 6 (3), 43 (1961).82. Bakalin, S. S. and S. A. Olbybin, Teplofiz Vys. Temp., 14, 391 (1976).83. Palmer, G., Ind. Eng., 40, 89 (1948).84. Fedorov, V. I. and V. I. Machev, High Temp., 8, 858 (1970).85. Sengers, J. V., J. T. R. Watson and R. S. Basu, J. Phys. Chem. Ref. Data, 13(3), 893 (1984).86. Ewing, C. T., J. A. Grand and R. R. Miller, J. Amer. Chem. Soc., 74, 11 (1952).87. Davison, H. W., U. S. NASA Tech. Note D-4650, (1968).88. Andrade, E. N., C. Da and E. R. Dobbs, Proc. Roy. Soc. London, 211A 12, (1952).89. Schaefer, C. A. and G. Thodos, AIChE J., 5(3), 367 (1959).90. Richter, G. N. and B. H. Sage, J. Chem. Eng. Data, 8(2), 221 (1963).91. McDonald, J. and H. T. Davis, Phys. Chem. Liquids, 2(3), 119 (1971).92. Federov, V. I. and V. I. Machuev, Teplofiz. Vys. Temp., 8(4), 912 (1970).93. Waterman, T. E., D. P. Kirsh and R. I. Brabets, J. Chem. Phys., 29(4), 905 (1958).94. Sladkov, I. B. and T. G. Kotina, Russ. J. Phys. Chem., 48(7), 1115 (1974).95. Sugawara, A., J. Appl. Phys., 36, 2375 (1965).96. Ivannikov, P. S., I. V. Litvinenko and I. V. Radchenko, J. Eng. Phys. USSR, 23(5), 1397 (1972).97. Dushin, Yu. A., J. Eng. Phys., 10(4), 538 (1966).98. Yaws, C. L., HANDBOOK OF TRANSPORT PROPERTY DATA, Gulf Publishing Co., Houston, TX (1995).99. Yaws, C. L., HANDBOOK OF THERMAL CONDUCTIVITY, Vol. 4, Gulf Publishing Co., Houston, TX (1997).

531

Chapter 24THERMAL CONDUCTIVITY OF LIQUID AND SOLID

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

ABSTRACTResults for thermal conductivity of liquid as function of temperature are presented for a wide

range of organic chemicals. Results are also given for thermal conductivity of liquid and solid as functionof temperature of inorganic chemicals. The chemicals include many compound types. The results areprovided in easy-to-use tabulations that are especially applicable for rapid engineering usage with thepersonal computer or hand calculator. The agreement of correlation and data is quite good.

INTRODUCTIONThermal conductivity of liquid and solid is important in many engineering applications in the chemical

processing and petroleum refining industries. The objective of this article is to provide the engineer with suchdata. The compilation of data is presented for a wide temperature range to enable the engineer to determinevalues at the desired temperatures of interest.

THERMAL CONDUCTIVITY CORRELATIONFor organic compounds, the correlation for thermal conductivity of liquid as a function of temperature

is given by the equation shown below:

log10 kliq = A + B [1-T/C]2/7 (24-1)

where kliq = thermal conductivity of liquid, W/(m K)A, B and C = regression coefficients for chemical compoundT = temperature, K

For inorganic compounds, the correlation for thermal conductivity of liquid and solid as a function oftemperature is given by the equation shown below:

k = A + B T + C T2 (24-2)

where k = thermal conductivity of liquid or solid, W/(m K)A, B and C = regression coefficients for chemical compoundT = temperature, K

The results for thermal conductivity of liquid and solid are given in Tables 24-1 and 24-2. Thetabulation is arranged by chemical formula to provide ease of use in quickly locating data.

In preparing the compilation, a literature search was conducted to identify data source publicationsfor organics (1-37) and inorganics (1-99). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened for appropriate data. The compilation resulting from the screening is based on both experimentaldata and estimated values. In the absence of experimental data for organic compounds, estimates of liquidswere primarily based on modified Missenard and Pachaiyappan methods (29) and the Sato equation (29).For inorganic compounds, estimates of liquids were primarily based on modified methods of Sato, Reidel andPachaiyappan (29). For inorganic compounds, estimates of solids were primarily based on the work of Ho,Powell and Liley (23, 24 and 69). Experimental data and estimates were then regressed to provide the sameequation for all compounds.

Very limited experimental data for liquid thermal conductivities are available at temperatures in theregion of the melting point. Also, there are very few reliable data at temperatures above a reducedtemperature of Tr = 0.65. Thus, the values in the regions of melting point and reduced temperatures above0.65 should be considered rough approximations. The values in the intermediate region (above melting pointand below reduced temperature of 0.65) are more accurate.


EXAMPLESThe correlation results maybe used for prediction and calculation of thermal conductivity. Examples

are given below.

532

kgas = - 0.01200 + 1.0208E-04*550 - 2.2403E-08*5502 kgas = 0.03344 W/(m K)


Portions of this material appeared in Oil & Gas Journal, 92, 43 (April, 1994) and are reprinted byspecial permission.

REFERENCES – ORGANIC COMPOUNDS 1-34. See REFERENCES - ORGANIC COMPOUNDS in Chapter 1 CRITICAL PROPERTIES AND ACENTRIC FACTOR 35. Tsederberg, N. V., THERMAL CONDUCTIVITY OF GASES AND LIQUIDS, R. D. Cess, editor, MIT Press, Cambridge, MA (1965). 36. Vargaftik, N. B., L. P. Filippov, A. A. Tarzimanov and E. E. Totskiy, THERMAL CONDUCTIVITY OF GASES AND LIQUIDS,

Standards Press, Moscow, USSR (1978). 37. Yaws, C. L., X. Lin, Li Bu and Sachin Nijhawan, Oil & Gas Journal, 92 (16), 43 (April 18, 1994). 38. Yaws, C. L., HANDBOOK OF THERMAL CONDUCTIVITY, Vols. 1, 2, 3 and 4, Gulf Publishing Co., Houston, TX (1995, 1995,

1995, 1997).

REFERENCES – INORGANIC COMPOUNDS1-64. See REFERENCES - INORGANIC COMPOUNDS in Chapter 2 HEAT CAPACITY OF GAS 65. Tsederberg, N. V., THERMAL CONDUCTIVITY OF GASES AND LIQUIDS, MIT Press, Cambridge, MA (1965).66. Vargaftik, N. B. and others, HANDBOOK OF THERMAL CONDUCTIVITY OF LIQUIDS AND GASES, CRC Press, Inc., Boca

Raton, FL (1994).67. Janz, G. J., C. B. Allan, N. P. Bansal and R. M. Murphy, PHYSICAL PROPERTIES DATA COMPILATIONS RELEVANT TO

ENERGY STORAGE, Nat. Bur. Stand., Molten Salts Data Center, Troy, NY (1979).68. Lyon, R. N., ed., LIQUID-METALS HANDBOOK, 2nd ed., U. S. Government Printing Office, Washington, DC (1954).69. Ho. C. Y. and R. W. Powell, P. E. Liley, J., Phys. Chem. Ref. Data, 1 (2), 279 (1972).70. Saxena, S. C., High Temp. Sci., 3, 168 (1971).71. Stiel, L. I. and G. Thodos, AICHE J., 10, 266 (1964).72. Choy, P. and C. J. G. Raw, J. Chem. Phys., 45 (5), 1413 (1966).73. Chapman, S.and T. G. Cowling, AICHE J., 10, 266 (1964).74. Eucken A., Z. Phys., 14, 324 (1913).75. Matsunaga, N. and A. Nagashima, J. Phys. Chem. Ref. Data, 12 (4), 933 (1983).76. Kestin, J. and J. V. Sengers, J. Phys. Chem. Ref. Data, 13 (2), 601 (1984).77. Baker, C. E., J. Chem. Phys., 46, 2846 (1967).78. Jones, L. W., Int. J. Heat Mass Transfer, 10, 745 (1967).79. Kestin, J. and E. A. Knierim, J. Phys. Chem. Ref. Data, 13 (1), 229 (1984).80. Hanley, H. J. M. and J. F. Ely, J. Phys. Chem. Ref. Data, 2 (4), 735 (1973).81. Streng, A. G., J. Chem. Eng. Data, 6 (3), 43 (1961).82. Bakalin, S. S. and S. A. Olbybin, Teplofiz Vys. Temp., 14, 391 (1976).83. Palmer, G., Ind. Eng., 40, 89 (1948).84. Fedorov, V. I. and V. I. Machev, High Temp., 8, 858 (1970).85. Sengers, J. V., J. T. R. Watson and R. S. Basu, J. Phys. Chem. Ref. Data, 13(3), 893 (1984).86. Ewing, C. T., J. A. Grand and R. R. Miller, J. Amer. Chem. Soc., 74, 11 (1952).87. Davison, H. W., U. S. NASA Tech. Note D-4650, (1968).88. Andrade, E. N., C. Da and E. R. Dobbs, Proc. Roy. Soc. London, 211A 12, (1952).89. Schaefer, C. A. and G. Thodos, AIChE J., 5(3), 367 (1959).90. Richter, G. N. and B. H. Sage, J. Chem. Eng. Data, 8(2), 221 (1963).91. McDonald, J. and H. T. Davis, Phys. Chem. Liquids, 2(3), 119 (1971).92. Federov, V. I. and V. I. Machuev, Teplofiz. Vys. Temp., 8(4), 912 (1970).93. Waterman, T. E., D. P. Kirsh and R. I. Brabets, J. Chem. Phys., 29(4), 905 (1958).94. Sladkov, I. B. and T. G. Kotina, Russ. J. Phys. Chem., 48(7), 1115 (1974).95. Sugawara, A., J. Appl. Phys., 36, 2375 (1965).96. Ivannikov, P. S., I. V. Litvinenko and I. V. Radchenko, J. Eng. Phys. USSR, 23(5), 1397 (1972).97. Dushin, Yu. A., J. Eng. Phys., 10(4), 538 (1966).98. Yaws, C. L., HANDBOOK OF TRANSPORT PROPERTY DATA, Gulf Publishing Co., Houston, TX (1995).99. Yaws, C. L., HANDBOOK OF THERMAL CONDUCTIVITY, Vol. 4, Gulf Publishing Co., Houston, TX (1997).

557

Chapter 25EXPLOSIVE LIMITS IN AIR, FLASH POINT AND AUTOIGNITION TEMPERATURE

Carl L. Yaws, Sachin D. Sheth and Mei HanLamar University, Beaumont, Texas

ABSTRACT

Results for explosive (lower and upper flammable) limits in air, flash point and auto-ignition temperature arepresented for organic compounds. The results are displayed in an easy-to-use table that is especiallyapplicable for rapid engineering usage. The organic compounds encompass hydrocarbon, oxygen, nitrogen,halogen, silicon, sulfur and other chemical types.

EXPLOSIVE LIMITS IN AIR

The results for lower (LEL) and upper (UEL) explosive limits in air are presented in Tables 25-1 and25-2. The LEL and UEL values are the lower and upper concentrations (expressed as volume %) forflammability in air. The tabulation is based on both experimental data and estimated values.

In the data collection, a literature search was conducted to identify data source publications (1-56) forexplosive limits in air. Both experimental values for the property under consideration and parameter valuesfor estimation of the property are included in the source publications. The publications were screened andcopies of appropriate data were made. These data were then keyed into the computer to provide a databasefor which experimental values are available. The database also served as a basis to check the accuracy ofthe estimation methods.

Upon completion of data collection, estimation of values for explosive limits in air was performed.The estimates are primarily based on the methods of Shebeko (17) and Jones (2). The Jones method(regression of the stoichiometric concentrations for volume % fuel in fuel plus air) is shown below:

CmHxOy + z O2 -----> m CO2 + x/2 H2O

LEL, % = 0.55 (100)/(4.76m + 1.19x + 1 - 2.38y) (25-1)

UEL, % = 3.50 (100)/(4.76m + 1.19x + 1 - 2.38y) (25-2)

Evaluation of these equations with normal alkanes disclosed favorable agreement of estimates anddata. For lower explosive limit, very favorable agreement was obtained for small, intermediate and large sizealkanes. For upper explosive limit, rough agreement was experienced for small and large size alkanes. Morefavorable agreement was exhibited for intermediate size alkanes.

A comparison of experimental data and estimates for lower explosion limit in air and data is shown inFigure 25-1 for normal alkanes. The graph discloses favorable agreement of data and estimates.

EXPLOSIVE LIMITS FOR MIXTURES

The lower and upper explosive limits in air are often needed for gas mixtures. The Le Chatelierequation (2) for gas mixtures is:

LELmixture, % = 1 / Σ (yi/LELi) (25-3)

UELmixture, % = 1 / Σ (yi/UELi) (25-4)

where yi = mole fraction of component i on a combustible basis

FLASH POINT AND AUTOIGNITION TEMPERATURE

The results for flash point and auto-ignition temperatures are also given in Tables 25-1 and 25-2. The flashpoint represents the temperature at which the liquid gives off enough vapor to flash (combust) when exposedto an external ignition source. The auto-ignition temperature is the temperature at which the substance willautomatically ignite (combust) without an external ignition source. The tabulation is based on bothexperimental data and estimated values.In the data collection, a literature search was conducted to identify data source publications (1-83) forflash point and auto-ignition temperature. The publications were screened and copies of appropriate datawere made. These data were then keyed into the computer to provide a database for which experimentaldata are available. The database also served as a basis to check the accuracy of the estimation methods.

558

Upon completion of data collection, estimation of values for the remaining compounds wasperformed. The estimates are primarily based on the methods of Shebeko (22), Gmehling and Rasmussen(23) and vapor pressure methods. The vapor pressure method is based on determining the temperature atwhich the vapor pressure will provide an equilibrium concentration that is equal to the lower explosive limit(LEL) concentration in air. The equations are briefly given below:

yi = Pi/P = LELi/100 (25-5) where yi = vapor concentration of component i, mole fraction

Pi = vapor pressure of component i, atmP = total pressure, atmPi/P = equilibrium concentration of component i, mole fractionLELi/100 = lower explosive limit concentration of component i, mole fraction

Evaluation of the vapor pressure method with normal alkanes disclosed favorable agreement of

estimates and data for small, intermediate and large size molecules. Evaluation with other compound typeswas not performed. If the lower explosive limit (LEL) used in the calculations is estimated, the estimates forflashpoint should be considered as rough values.

A comparison of experimental data and estimates for flash point and data is shown in Figure 25-2 fornormal alkanes. The graph discloses favorable agreement of data and estimates.

EXAMPLES

The tabulated values maybe used in engineering applications involving pure components andmixtures in air. Examples are given below.

Example 1 A process vessel contains n-pentane (C5H12) at a concentration of 2 vol % in air. Are thecontents of the vessel flammable?

Inspection of the table discloses that LEL = 1.4 vol % for n-pentane. Since the vessel contentsexceed the LEL for n-pentane, the contents are flammable. This is shown below:

Vessel contents of 2 vol % > LEL of 1.4 vol %

Vessel contents are flammable.

Example 2 Estimate the lower (LEL) and upper (UEL) explosive limits in air for the gas mixture below:

yivol % (combustible basis) LELi UELi

Methane 1 0.2 5.0 15.0Ethane 2 0.4 3.0 12.5Propane 2 0.4 2.1 9.5Air 95 --- --- ---

Substitution of yi, LELi and UELi into the equations for gas mixtures provides:LELmixture = 1 / Σ(yi/LELi) = 1/(0.2/5 + 0.4/3 + 0.4/2.1) = 2.75 vol %

UELmixture = 1 / Σ(yi/UELi) = 1/(0.2/15 + 0.4/12.5 + 0.4/9.5) = 11.4 vol %

Example 3 A process vessel at a temperature of 80 F contains liquid toluene (C7H8) in contact with air.Is the vapor in the process vessel flammable?

Inspection of the table discloses that the flash point is 40 F for toluene. Since the temperature ofthe process vessel contents exceeds the flash point for toluene, the vapor is flammable. This is shownbelow:

Vessel temperature of 80 F > Flash point of 40 F

Vapor in vessel is flammable.

Example 4 A small quantity of residual n-tetradecane (C14H30) is in the piston bore of a piston-typecompressor. If air at ambient conditions is compressed to 570 psia and 420 F, will the n-tetradecaneundergo autoignition?

Inspection of the table discloses that the autoignition temperature of n-tetradecane is 392 F. Sincethe temperature of 420 F at the end of the compression exceeds the autoignition temperature,autoignition of the n-tetradecane will occur. This is shown below:

559

Compressor temp. of 420 F > Autoignition temp. of 392 F

Autoignition of n-tetradecane will occur.

REFERENCES – EXPLOSIVE LIMITS IN AIR – ORGANIC AND INORGANIC COMPOUNDS1. 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). 2. Crowl, D. A. and J. F. Louvar, CHEMICAL PROCESS SAFETY, Prentice Hall, Inc., Englewood Cliffs, NJ (1990). 3. NIOSH POCKET GUIDE TO CHEMICAL HAZARDS, U. S. Dept. of Health and Human Services, Superintendent of Documents,

Washington, DC (June, 1994). 4. Lees, F. P., LOSS PREVENTION IN THE PROCESS INDUSTRIES, Vols. 1 and 2, Butterworth-Heinemann, London, England

(1992). 5. SELECTED VALUES OF PROPERTIES OF HYDROCARBONS AND RELATED COMPOUNDS, Thermodynamics Research



1982). 8. CONDENSED CHEMICAL DICTIONARY, 10th and 11th eds., G. G. Hawley (10th) and Sax, N. I. and R. J. Lewis, Jr. (11th), Van

Nostrand Reinhold Co., New York, NY (1981, 1987). 9. Braker, W. and A. L. Mossman, MATHESON GAS DATA BOOK, 6th ed., Matheson Gas Products, Secaucaus, NJ (1980).10. CRC HANDBOOK OF CHEMISTRY AND PHYSICS, 75th - 78th eds., CRC Press, Inc., Boca Raton, FL (1994-1997).11. ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd and 4th eds., John Wiley and Sons, Inc., New York, NY (1978-1997).12. Riddick, J. A., W. B. Bunger and T. K. Sakano, ORGANIC SOLVENTS: PHYSICAL PROPERTIES AND METHODS OF

PURIFICATION, 3rd and 4th eds., Wiley Interscience, New York. NY (1970, 1986).13. Tryon, G. H., ed., FIRE PROTECTION HANDBOOK, 12th ed., National Fire Protection Association, Boston, MA (1962).14. Weiss, G., HAZARDOUS CHEMICALS DATA BOOK, Noyes Data Corp., Park Ridge, NJ (1986).15. FIRE POTECTION GUIDE ON HAZARDOUS MATERIALS, 7th ed., National Fire Protection Association, Quincy, MA (1978).16. SFPE HANDBOOK OF FIRE POTECTION ENGINEERING, 1st ed., Society of Fire Protection Engineers, National Fire Protection

Association, Quincy, MA (1988).17. Shebeko, Y. N., A. V. Ivanov and T. M. Dmitrieva, Sov. Chem. Ind. 15(3), 311 (1983).18. Steere, N. V., ed., HANDBOOK OF LABORATORY SAFETY, 2nd ed., CRC Press Inc., Boca Raton, FL (1982).19. Zabetakis, M. G., U.S. Bureau of Mines Bulletin No. 627 (1965).20. Gas Processors Association, Publication No. 2145-84, Tulsa, OK (1984).21. Halls, E. W., H. H. Liebhafsky and D. H. Getz, Ind. Eng. Chem., 41, 1959 (1949).22. Gmehling, J. and P. Rasmussen, Ind. Eng. Chem., Fundam, 21, 186 (1982).23. Hercules, Inc., Bulettin HE-109A, HE-110, HE-120A, Cumberland, MD.24. DeMicheli, S. and V. Tartari, J. Chem. Eng. Data, 27(3), 273 (1982).25. Coward, H. F. and G. W. Jones, Bureau of Mines Bulletin 503 (1952).26. Eastman Chemicals, Publication No. C103-A, Kingsport, TN (1977).27. Pfanstiehl Laboratories, "MALEIC ACID", Material Safety Data Sheet, Waukegan, IL (1972).28. Huffman, H. M., S. S. Todd and G. D. Oliver, J. Am. Chem. Soc., 71, 584 (1971).29. Eastman Chemicals, Publication No. A1013, Kingsport, TN (1976).30. DuPont, "METHACRYLATE MONOMERS", Wilmington, DE (1979).31. McGlashan, M. L. and I. R. McKinnon, J. Chem. Thermo., 9(10), 1205 (1977).32. GAF Corporation, "M-PYROL HANDBOOK", New York, NY (1972).33. Eastman Chemicals, Publication No. M-144C, Kingsport, TN (1978).34. Petro-Tex Chemical Corp., "METHYL TERT-BUTYL ETHER", Material Safety Data Sheet, Houston, TX (1979).35. Eastman Chemicals, Publication Number M-198D, Kingsport, TN (1985).36. Eastman Chemicals, "NEOPENTYL GLYCOL", Material Safety Data Sheet, Kingsport, TN (1973).37. Thompson, W. H., Ph.D. Thesis, Pennsylavania State University, University Park, PA (1966).38. DuPont, "3,4-DICHLOROANILINE", Material Safety Data Sheet, Wilmington, DE (Oct. 1985).39. Thiokol Ventra Division, "4-CHLOROANILINE", Material Safety Data Sheet, Danvers, MA (1986).40. Eastman Chemicals, "m-NITROANILINE", Material Safety Data Sheet, Kingsport, TN (1978).41. Exxon Chemical Company, "MESITYL OXIDE", Technical Brochure, Houston, TX (1976).42. Eastman Chemical Products, Technical Data Publication No. N-135, USA (August, 1979).43. Union Carbide, "2-METHYLPENTANOL", Material Safety Data Sheet, Danbury, CT (1981).44. Eastman Chemicals, "TRIETHYLPHOSPHATE", Material Safety Data Sheet, Kingsport, TN (1975).45. DuPont, "o-NITROTOLUENE", Material Safety Data Sheet, DuPont Company, Wilmington, DE (1985).46. DuPont, "p-NITROTOLUENE", Material Safety Data Sheet, DuPont Company, Wilmington, DE (1985).47. Rohm and Haas, "BUTYL ACRYLATE", Material Safety Data Sheet, Philadelphia (Oct., 1978).48. Eastman Chemicals, "ETHYL 3-ETHOXYPROPIONATE", Kingsport, TN (1988).49. Eastman Chemicals, Publication No. A-111-2B, Kingsport, TN (1977).50. Eastman Chemicals, Technical Data M-143D, Kingsport, TN (1978).51. EM Science, "2-(2-ETHOXYETHOXY)ETHYL ACETATE", Material Safety Data Sheet, Gibbstown, NJ (1984).52. Eastman Chemicals, Publication No. B-115-B, Kingsport, TN (1977).53. Fisher Scientific Company, "2-OCTANOL", Material Safety Data Sheet, Fairlawn, NJ (1980).54. DuPont, "N,N-DIETHYLANILINE", Material Safety Data Sheet, Wilmington, DE (Oct. 1985).

560

55. Eastman Chemical Products, Publication No. L-142C, Kingsport, TN (Jan. 1980).56. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX (1997).

REFERENCES - FLASH POINT AND AUTOIGNITION TEMPERATURE – ORGANIC AND INORGANICCOMPOUNDS1-21. See above REFERENCES – EXPLOSIVE LIMITS IN AIR - ORGANIC COMPOUNDS22. Shebeko, N. Y., A. Y. Korolchenko, A. V. Ivanov and E. N. Alekhina, Sov. Chem. Ind., 16, 1371 (1984).23. Gmehling, J. and P. Rasmussen, Ind. Eng. Chem., Fundam, 21, 186 (1982).24. HANDBOOK OF FINE CHEMICALS, Aldrich Chemical Co., Milwaukee, WI (1984-96).25. Wilson, A. L., Ind. Eng. Chem., 27, 867 (1935).26. Bailey, A. S., G. B. Pickering and J. C. Smith, Inst. Petrol., 35, 103 (1949).27. Fishbein, L., J.A. Gallaghan and J. Arner, Chem. Soc., 78, 1218 (1956).28. Amundsen, L. H., R. H. Mayer, L. S. Pitts and L. A. Malentacchi, J. Amer. Chem. Soc., 73, 2118 (1951).29. Hatch, G., J. Org. Chem., 24, 1881 (1959).30. Riddle, E. H., MONOMERIC ACRYLIC ESTERS, Reinhold Publishing Corp., New York, NY (1954).31. Wohl, A. and B. Mylo, Chem. Ber., 45, 322 (1912).32. Medcalf, E. C., A. G. Hill and G. N. Vriens, Petrol. Refiner, 31(7), 97 (1950).33. Farkas, A., G. A. Gerner, W. E. Erner and J. B. Maerker, J. Chem. Eng. Data, 4(4), 334 (1959).34. Stephenson, R. M., FLASH POINTS OF ORGANIC AND ORGANOMETALLIC COMPOUNDS, Elsevier, New York, NY (1987).35. Roth, C. A., Ind. Eng. Chem. Res. Dev., 11, 134 (1972).36. Smutney, E. J. and A. Bondi, J. Phys. Chem., 69, 1214 (1965).37. Dickey, F. H., J. H. Raley, F. F. Rust, R. S. Treseder and W. E. Vaughan, Ind. Eng. Chem. 41, 1673 (1949).38. Lipowitz, J. and M. Ziemelis, Fire Flamm., 7, 504 (1976).39. Carswell, T. S. and H. L. Morrill, Ind. Eng. Chem. 29, 1247 (1937).40. Curme, G. O. J., ed., GLYCOLS, Reinhold Publishing Corp., New York, NY (1952).41. Rieth, V. H. and H. Eckardt, Frieberger. Forsch., 164A, 146 (1960).42. Kratzke, H., S. Muller, M. Bohn and R. Kohler, J. Chem. Thermo., 17, 283 (1985).43. Griffith, S. T. and R. R. Wilson, Combustion Flame, 2, 244 (1958).44. Eastman Chemical Products, Publication No. L-142C, Kingsport, TN (Jan. 1980).45. Burner, W. M. and L. T. Sherwood, Ind. Eng. Chem., 41, 1654 (1949).46. Reuther, H., Chem. Tech., 5, 330 (1953).47. Reuther, H., Chem. Tech., 17, 752 (1965).48. Lipowitz, J. and M. Ziemelis, Fire Flamm., 7, 504 (1976).49. Hercules, Inc., Bulettin HE-109A, HE-110, HE-120A, Cumberland, MD.50. DeMicheli, S. and V. Tartari, J. Chem. Eng. Data, 27(3), 273 (1982).51. Coward, H. F. and G. W. Jones, Bureau of Mines Bulletin 503 (1952).52. Eastman Chemicals, Publication No. C103-A, Kingsport, TN (1977).53. Pfanstiehl Laboratories, "MALEIC ACID", Material Safety Data Sheet, Waukegan, IL (1972).54. Huffman, H. M., S. S. Todd and G. D. Oliver, J. Am. Chem. Soc., 71, 584 (1971).55. Eastman Chemicals, Publication No. A1013, Kingsport, TN (1976).56. DuPont, "METHACRYLATE MONOMERS", Wilmington, DE (1979).57. McGlashan, M. L. and I. R. McKinnon, J. Chem. Thermo., 9(10), 1205 (1977).58. GAF Corporation, "M-PYROL HANDBOOK", New York, NY (1972).59. Eastman Chemicals, Publication No. M-144C, Kingsport, TN (1978).60. Petro-Tex Chemical Corp., "METHYL TERT-BUTYL ETHER", Material Safety Data Sheet, Houston, TX (1979).61. Eastman Chemicals, Publication Number M-198D, Kingsport, TN (1985).62. Eastman Chemicals, "NEOPENTYL GLYCOL", Material Safety Data Sheet, Kingsport, TN (1973).63. Thompson, W. H., Ph.D. Thesis, Pennsylavania State University, University Park, PA (1966).64. DuPont, "3,4-DICHLOROANILINE", Material Safety Data Sheet, Wilmington, DE (Oct. 1985).65. Thiokol Ventra Division, "4-CHLOROANILINE", Material Safety Data Sheet, Danvers, MA (1986).66. Eastman Chemicals, "m-NITROANILINE", Material Safety Data Sheet, Kingsport, TN (1978).67. Exxon Chemical Company, "MESITYL OXIDE", Technical Brochure, Houston, TX (1976).68. Eastman Chemical Products, Technical Data Publication No. N-135, USA (August, 1979).69. Union Carbide, "2-METHYLPENTANOL", Material Safety Data Sheet, Danbury, CT (1981).70. Eastman Chemicals, "TRIETHYLPHOSPHATE", Material Safety Data Sheet, Kingsport, TN (1975).71. DuPont, "o-NITROTOLUENE", Material Safety Data Sheet, DuPont Company, Wilmington, DE (1985).72. DuPont, "p-NITROTOLUENE", Material Safety Data Sheet, DuPont Company, Wilmington, DE (1985).73. Rohm and Haas, "BUTYL ACRYLATE", Material Safety Data Sheet, Philadelphia (Oct., 1978).74. Eastman Chemicals, "ETHYL 3-ETHOXYPROPIONATE", Kingsport, TN (1988).75. Eastman Chemicals, Publication No. A-111-2B, Kingsport, TN (1977).76. Eastman Chemicals, Technical Data M-143D, Kingsport, TN (1978).77. EM Science, "2-(2-ETHOXYETHOXY)ETHYL ACETATE", Material Safety Data Sheet, Gibbstown, NJ (1984).78. Eastman Chemicals, Publication No. B-115-B, Kingsport, TN (1977).79. Fisher Scientific Company, "2-OCTANOL", Material Safety Data Sheet, Fairlawn, NJ (1980).80. DuPont, "N,N-DIETHYLANILINE", Material Safety Data Sheet, Wilmington, DE (Oct. 1985).81. Hilado, C. J. and C. W. Clark, Chem. Eng., 75 (1972).82. Stull, D. R., FUNDAMENTALS OF FIRE AND EXPLOSION, AIChE, New York, NY (1977).83. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX (1997).

582

Chapter 26ENTHALPY OF COMBUSTION

Carl L. Yaws, Sachin D. Sheth and Mei HanLamar University, Beaumont, Texas

ABSTRACT

Results for enthalpy of combustion are presented for major organic chemicals. The results aredisplayed in an easy-to-use table that is especially applicable for rapid engineering usage. The organicchemicals encompass hydrocarbon, oxygen, nitrogen, halogen, silicon, sulfur and other type compounds.

ENTHALPY OF COMBUSTION

The results for enthalpy of combustion are presented in Table 26-1 for organic chemicals. Theenthalpy of combustion is the net increase in heat content when a substance in its standard state at ambientconditions (77 F, 1 atm) undergoes complete oxidation.

The tabulated values are the negative of the enthalpy of combustion. A positive value as shownmeans that heat is released in the combustion. A negative value means that heat is required for thecombustion. For substances in the table, the products of combustion are CO2 (gas), H2O (gas), F2 (gas),Cl2 (gas), Br2 (gas), I2 (gas), N2 (gas), SO2 (gas), H3PO4 (solid) and SiO2 (crystobalite).

In the data collection, a literature search was conducted to identify data source publications (1-94) forthe table. The publications were screened and copies of appropriate data were made. These data were thenkeyed into the computer to provide a database for use in preparing the table.

EXAMPLES

The tabulated values maybe used in engineering applications involving combustion. Examples aregiven below.

Example 1 Combustion of propane (C3H8, 50 kg/hr) occurs at ambient conditions (77 F, 1 atm).Estimate the quantity of heat released in the combustion.

Substitution of the tabulated value for propane into the equation below provides the quantity of heatreleased:

∆H = (-∆Hcombustion)(mass) = (46,333 kjoule/kg)(50 kg/hr)

∆H = 2.32 million kjoule/hr

Example 2 Combustion of n-hexane (C6H14, 150 lb/hr) occurs at ambient conditions (77 F, 1 atm).Estimate the quantity of heat released in the combustion.

Substitution of the tabulated value for n-hexane into the equation below provides the quantity ofheat released:

∆H = (-∆Hcombustion)(mass) = (19,236.4 BTU/lb)(150 lb/hr)

∆H = 2.89 million BTU/hr

REFERENCES – ORGANIC COMPOUNDS1. API Research Project No. 44, SELECTED VALUES OF PHYSICAL AND THERMODYNAMIC PROPERTIES OF HYDROCARBONS

AND RELATED COMPOUNDS, Carnegie Press, Carnegie Institute of Technology, Pittsburgh, PA (1953). 2. SELECTED VALUES OF PROPERTIES OF HYDROCARBONS AND RELATED COMPOUNDS, Thermodynamics Research



1982).5. 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). 6. Braker, W. and A. L. Mossman, MATHESON GAS DATA BOOK, 6th ed., Matheson Gas Products, Secaucaus, NJ (1980). 7. CRC HANDBOOK OF CHEMISTRY AND PHYSICS, 75th - 78th eds., CRC Press, Inc., Boca Raton, FL (1994-1997). 8. PERRY'S CHEMICAL ENGINEERING HANDBOOK, 6th ed., McGraw-Hill, New York, NY (1984). 9. Lees, F. P., LOSS PREVENTION IN THE PROCESS INDUSTRIES, Vols. 1 and 2, Butterworth-Heinemann, London, England

(1992).10. CONDENSED CHEMICAL DICTIONARY, 10th and 11th eds., G. G. Hawley (10th) and Sax, N. I. and R. J. Lewis, Jr. (11th), Van

Nostrand Reinhold Co., New York, NY (1981, 1987).11. Sax, N. I., DANGEROUS PROPERTIES OF INDUSTRIAL MATERIALS, 6th ed., Van Nostrand Reinhold Co., New York, NY

583

(1984).12. Driesbach, R. R., PHYSICAL PROPERTIES OF CHEMICAL COMPOUNDS, Vols. I (No. 15), II (No. 22) and III (No. 29), Advances

in Chemistry Series, American Chemical Society, Washington, DC (1955,1959,1961).13. Vargaftik, N. B., TABLES ON THE THERMOPHYSICAL PROPERTIES OF LIQUIDS AND GASES, 2nd ed., English translation,

Hemisphere Publishing Corporation, New York, NY (1975, 1983).14. Timmermans, J., PHYSICO-CHEMICAL CONSTANTS OF PURE ORGANIC COMPOUNDS, Vols. 1 and 2, Elsevier, New York, NY

(1950,1965). 15. ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd and 4th eds., John Wiley and Sons, Inc., New York, NY (1978-1997).16. Riddick, J. A. and W. B. Bunger, ORGANIC SOLVENTS: PHYSICAL PROPERTIES AND METHODS OF PURIFICATION, 3rd ed.,

Wiley Interscience, New York, NY (1970).17. Cox, J. D. and G. Pilcher, THERMOCHEMISTRY OF ORGANIC AND ORGANOMETALLIC COMPOUNDS, Academic Press, New

York, NY (1970).18. American Institute of Chemical Engineers, FIRE AND EXPLOSION INDEX - HAZARD CLASSIFICATION GUIDE, 5th ed., New

York, NY (1981).19. Weiss, G., ed., HAZARDOUS CHEMICALS DATA BOOK, Noyes Data Corporation, Park Ridge, NJ (1980).20. Pedley, J. B., R. D. Naylor and S. P. Kirby, THERMOCHEMICAL DATA OF ORGANIC COMPUNDS, Chapman and Hall, London,

England (1986).21. Riddick, J. A., W. B. Bunger and T. K. Sakano, ORGANIC SOLVENTS: PHYSICAL PROPERTIES AND METHODS OF

PURIFICATION, 4th ed., Wiley Interscience, New York, NY (1986).22. Stull, D. R., E. F. Westrum and G. C. Sinke, THE CHEMICAL THERMODYNAMICS OF ORGANIC COMPOUNDS, John Wiley and

Sons, New York, NY (1969).23. Kudchadker, S. A., A. P. Kudchadker, R. C. Wilhoit and B. J. Zwolinski, "KEY CHEMICALS DATA BOOKS - PHENOL,

Thermodynamics Research Center, Texas Eng. Expt. Station, Texas A&M University, College Station, TX (1977).24. Kudchadker, A. P., S. A. Kudchadker and R. C. Wilhoit, KEY CHEMICALS DATA BOOKS - FURAN, DIHYDROFURAN AND

TETRAHYDROFURAN, Thermodynamics Research Center, Texas Eng. Expt. Station, Texas A&M University, College Station, TX(1984).

25. Kudchadker, A. P., S. A. Kudchadker and R. C. Wilhoit, KEY CHEMICALS DATA BOOKS - CRESOLS, Thermodynamics ResearchCenter, Texas Eng. Expt. Station, Texas A&M University, College Station, TX (1978).

26. Kudchadker, A. P. and S. A. Kudchadker, KEY CHEMICALS DATA BOOKS - XYLENOLS, Thermodynamics Research Center,Texas Eng. Expt. Station, Texas A&M University, College Station, TX (1978).

27. Wilhoit, R. C. and B. J. Zwolinski, J. Phys. Chem. Ref. Data, 2 (1), (1973).28. Domalski, E. S., J. Phys. Chem. Ref. Data, 1(2), 221 (1972).29. U.S. Industrial Chemicals Co., VINYL ACETATE MONOMERS HANDBOOK, National Distillers and Chemical Corporation, New

York, NY (1978).30. Morrison, G. O. and T. P. G. Shaw, Trans. Electrochem. Soc., 63, 425 (1933).31. Mansson, M., J. Chem. Thermo., 4, 865 (1972).32. Kobe, K. A. and R. E. Pennington, Petroleum Refiner, 29, 135 (1950).33. Delafontaine, J., R. Sabbah and M. Lafitte, Zert fur Phys. Chem. Neise Folge, 84, 157 (1973).34. American Society of Testing and Materials, ASTM Data Series Publication DS 51, Philadelphia, PA (1974).35. Minadakis, C. and R. Sabbah, Thermochim. Acta, 55(2), 147 (1982).36. Fenwick, J. O., D. Harrop and A. J. Head, J. Chem. Thermo., 7, 1173 (1975).37. Gas Processors Association, Publication No. 2145-82, Tulsa, OK (1982).38. An, Xu-Wu and M. Mansson, J. Chem. Thermo., 15, 287 (1983).39. Steele, W. V., J. Chem. Thermo., 11, 1185 (1979).40. Vilcu, R. and S. Perisanu, Rev. Roum. Chim., 24 (1), 237 (1979).41. Good, W. D., J. Chem. Eng. Data, 17, 28 (1972).42. McCormick, D. G. and W. S. Hamilton, J. Chem. Thermo., 10, 275 (1978).43. Hutchens, J. O., A. G. Cole, R. A. Robie and J. W. Stout, J. Biol. Chem., 57, 359 (1953).44. Bell, E. R., F. H. Dickey, J. H. Raley, F. F. Rust and W. E. Vaughan, Ind. Eng. Chem., 41, 2597 (1949).45. Tannerbaum, S., S. Kaye and G. F. Lowenz, J. Amer. Chem. Soc., 75, 3753 (1953).46. Mansson, M., N. Yoshiaki and S. Sunner, Acta Chem. Scand., 22, 171 (1968).47. Wilhoit, R. C. and I. Lei, J. Chem. Eng. Data, 10, 166 (1965).48. Lebedeva, N. D., Russ. J. Phys. Chem., 38, 11 (1964).49. Bruylarts, P. and A. Christiaen, Chem. Zentrablatt II, 538 (1925).50. Roth, W. A. and K. Isecke, Chem. Ber., 77, 537 (1944).51. Bartolo, H. F. and F. D. Rossini, J. Phys. Chem., 64, 1685 (1960).52. Lebedeva, V. P., E. A. Miroshnichenko and others, Anal. Chem., 22, 871 (1950).53. Steele, W. V., A. Chirico, T. A. Nguyen and I. A. Hossenlopp, Topical Report NIPER-319, National Institute for Petroleum and

Energy Research, Bartlesville, OK (Jan. 1988).54. Wilhoit, R. C. and D. Shiao, J. Chem. Eng. Data, 9, 595 (1964).55. Mukaiyama, T., Bull. Chem. Soc. Japan, 28, 253 (1955).56. Sinke, G. C. and D. R. Stull, J. Phys. Chem., 62, 397 (1958).57. Parks, G. S., J. R. Mosley and P. V. Peterson, J. Chem. Phys., 18, 152 (1950).58. Lebedeva, N. D., Y. A, Katin and G. Y. Akhmedova, Russ. J. Phys. Chem., 45, 771 (1971).59. Fenwick, J. O., D. Harrop and A. J. Head, J. Chem. Thermo., 7, 943 (1975)60. Furukawa, J., M. Sakujama, S. Seki, Y. Saito and Kusano, Bull. Chem. Soc. Japan, 3329 (1982).61. Petit, M., Am. Chem. Phys., 18(6), 145 (1889).62. Ethyl Corporation, TRIETHYLALUMINUM, Baton Rouge, LA (1982).63. Garner, W. E. and C. L. Abernethy, Proc. Roy. Soc. London, A99, 213 (1921).64. Bedford, A. F. and C. T. Mortimer, J. Chem. Soc., 163, 1622 (1960).

584

65. Tanaka, T., J. Chem. Phys., 22, 957 (1954).66. Osthoff, R. L., W. J. Grubb and C. A. Burkhard, J. Amer. Chem. Soc., 75, 227 (1958).67. Baker, G., J. H. Littlefair, R. Shaw and J. C. J. Thynne, J. Chem. Soc., 6970 (1965).68. Lenchnitz, C., R. W. Velicky, G. Silvestro and L. P. Schlosberg, J. Chem. Thermo., 3, 689 (1971).69. Good, W. D., J. Chem. Thermo., 3, 97 (1971).70. American Petroleum Institute, API Publication No. 705, Washington, DC (October, 1978).71. American Petroleum Institute, API Publication No. 706, Washington, DC (October, 1978).72. American Petroleum Institute, API Publication No. 707, Washington, DC (October, 1978).73. American Petroleum Institute, API Publication No. 708, Washington, DC (January, 1979).74. American Petroleum Institute, API Publication No. 709, Washington, DC (March, 1979).75. American Petroleum Institute, API Publication No. 710, Washington, DC (1979).76. American Petroleum Institute, API Publication No. 714, Washington, DC (April, 1980).77. American Petroleum Institute, API Publication No. 715, Washington, DC (January, 1981).78. American Petroleum Institute, API Publication No. 717, Washington, DC (November, 1981).79. American Petroleum Institute, API Publication No. 718, Washington, DC (Jan. 1982).80. American Petroleum Institute, API Publication No. 719, Washington, DC (April, 1982).81. American Petroleum Institute, API Publication No. 720, Washington, DC (Jan. 1983).82. American Petroleum Institute, API Publication No. 722, Washington, DC (Sept. 1984).83. American Petroleum Institute, API Publication No. 723, Washington, DC (1984).84. American Petroleum Institute, API Publication No. 724, Washington, DC (February, 1985).85. Serijan, K. T. and P. H. Wise, J. Amer. Chem. Soc., 73, 4766 (1951).86. Hickman, K. and W. Weyerts, J. Amer. Chem. Soc., 52, 4714 (1930).87. Hipsher, H. F. and P. H. Wise, J. Amer. Chem. Soc., 76, 1747 (1954).88. Good, W. D., J. Chem. Eng. Data, 14 (2), 231 (1969).89. Labbauf, A., J. B. Greenshields and F. D. Rossini, J. Chem. Eng. Data, 6, 261 (1961).90. Good, W. D., J. Chem. Thermo., 5, 715 (1973).91. Kirklin, D. R. and E. S. Domalski, J. Chem. Thermo., 20, 743 (1988).92. Mortimer, C. T., Pure Appl. Chem., 2, 71 (1961).93. Tavernier, P. and M. Lamouroux, Mem. Pondres, 37, 197 (1955).94. Yaws, C. L., HANDBOOK OF CHEMICAL COMPOUND DATA FOR PROCESS SAFETY, Gulf Publishing Co., Houston, TX (1997).

603

Chapter 27EXPOSURE LIMITS FOR SAFEGUARDING HEALTH

Carl L. Yaws and Eric L. JaycoxLamar University, Beaumont, Texas

ABSTRACT

Results for exposure limits in air for safeguarding health are presented for organic and inorganicchemicals. The results include threshold limit value (TLV of ACGIH), permissible exposure limit (PEL ofOSHA), recommended exposure limit (REL of NIOSH) and maximum concentration value in the workplace(MAK of DFG). The results are displayed in easy-to-use tabulations that are especially applicable for rapidengineering usage. The organic chemicals encompass hydrocarbon, oxygen, nitrogen, halogen, silicon,sulfur and other compound types. The results are useful in engineering applications involving exposure of chemicals and mixtures in the workplace.

EXPOSURE LIMITS FOR SAFEGUARDING HEALTH

The results for exposure limits in air for safeguarding health in the workplace are presented in Tables27-1 and 27-2 for organic and inorganic chemicals. The tabulated values that apply to exposure in theworkplace in a 40-hour week are summarized below:

• TLV (ACGIH) – Threshold limit value in air in workplace of the American Conference ofGovernmental Industrial Hygienists.

• PEL (OSHA) – Permissible exposure limit in air in workplace of the Occupational Safety andHealth Administration.

• REL (NIOSH) – Recommended exposure limit in air in workplace of the National Institute forOccupational Safety and Health.

• MAK (DFG) – Maximum concentration value in air in workplace of the Federal Republic ofGermany.

In the data collection, a literature search was conducted to identify data source publications fororganics (1-13) and inorganics (1-12). The publications were screened and copies of appropriate data weremade. These data were then keyed into the computer to provide a database for use in preparing thetabulations.

MIXTURES

If more than one substance is present in the workplace, then exposure limits are needed for gasmixtures. The following equation (1) maybe used for exposure limits of gas mixtures:

PELmixture = Σ yi / Σ (yi/PELi) (27-1)

where PELmixture = permissible exposure limit of mixture, ppmyi = mole fraction of component i, ppm

EXAMPLES

The tabulated values maybe used in engineering applications involving exposure of purecomponents and mixtures in the workplace. Examples are given below.

Example 1 Due to a small leak, the workplace contains methylamine (CH5N) at a concentration of 13.7ppm (parts per million by volume) in air.

Are the workers overexposed?

Inspection of the table discloses that the permissible exposure level (PEL) = 10 ppm formethylamine. Since the workplace concentration exceed the PEL for methylamine, the workers areoverexposed. This is shown below:

Workplace concentration of 13.7 ppm > PEL of 10 ppm

Workers are overexposed.Example 2 Estimate the permissible exposure level (PEL) for the gas mixture below:

604

yi PELippm ppm

Acetonitrile (C2H3N) 10 40Ethylamine (C2H7N) 2 10Monoethanolamine (C2H7NO) 2 3

Substitution of yi and PELi into the equations for gas mixtures provides:PELmixture = Σ yi / Σ (yi/PELi) = (10 + 2 + 2 )/(10/40 + 2/10 + 2/3)

PELmixture = 12.5 ppm

REFERENCES – ORGANIC COMPOUNDS 1. Crowl, D. A. and J. F. Louvar, CHEMICAL PROCESS SAFETY, Prentice Hall, Inc., Englewood Cliffs, NJ (1990). 2. NIOSH POCKET GUIDE TO CHEMICAL HAZARDS, U. S. Dept. of Health and Human Services, Superintendent of Documents,

Washington, DC (June, 1994). 3. GUIDE TO OCCUPATIONAL EXPOSURE VALUES – 1997, American Conference of Governmental Industrial Hygienists, ACGIH,

Inc., Cincinnati, OH ( 1997). 4. 1997 TLVs and BEIs, American Conference of Governmental Industrial Hygienists, ACGIH, Inc., Cincinnati, OH ( 1997). 5. June 1993 Air Contaminants Final Rule, specified in Tables Z-1, Z-2 and Z-3 (Federal Register, 58:35388-35351, June 30, 1993;

corrected in Federal Register, 58:40191, July 27, 1993; and subsequent amendments). 6. Lees, F. P., LOSS PREVENTION IN THE PROCESS INDUSTRIES, Vols. 1 and 2, Butterworth-Heinemann, London, England

(1992). 7. CONDENSED CHEMICAL DICTIONARY, 10th and 11th eds., G. G. Hawley (10th) and Sax, N. I. and R. J. Lewis, Jr. (11th), Van

Nostrand Reinhold Co., New York, NY (1981, 1987). 8. Sax, N. I., DANGEROUS PROPERTIES OF INDUSTRIAL MATERIALS, 9th ed., Vols. 1, 2 and 3, Van Nostrand Reinhold

Company, New York, NY (1996). 9. CRC HANDBOOK OF CHEMISTRY AND PHYSICS, 75th - 77th ed., CRC Press, Inc., Boca Raton, FL (1994-1996).10. Springer, C. and J. R. Welker, INDUSTRIAL HYGIENE: AN INTRODUCTION FOR CHEMICAL ENGINEERS, American Institute of

Chemical Engineers, New York, NY (1995).11. Fawcett, H. H. and W. C. Wood, eds., SAFETY AND ACCIDENT PREVENTION IN CHEMICAL OPERATIONS, 2nd ed., John

Wiley and Sons, New York, NY (1982).12. Williams, P. L. and J. L. Burson, eds., INDUSTRIAL TOXICOLOGY, SAFETY AND HEALTH APPLICATIONS IN THE

WORKPLACE, Van Nostrand Reinhold Company, New York, NY (1985).13. de la Cruz, P. L. and D. G. Sarvadi, Am. Ind. Hyg. Assoc. J., 55(10), 894 (1994).

REFERENCES – INORGANIC COMPOUNDS 1. Crowl, D. A. and J. F. Louvar, CHEMICAL PROCESS SAFETY, Prentice Hall, Inc., Englewood Cliffs, NJ (1990). 2. NIOSH POCKET GUIDE TO CHEMICAL HAZARDS, U. S. Dept. of Health and Human Services, Superintendent of Documents,

Washington, DC (June, 1994). 3. GUIDE TO OCCUPATIONAL EXPOSURE VALUES – 1997, American Conference of Governmental Industrial Hygienists, ACGIH,

Inc., Cincinnati, OH ( 1997). 4. 1997 TLVs and BEIs, American Conference of Governmental Industrial Hygienists, ACGIH, Inc., Cincinnati, OH ( 1997). 5. June 1993 Air Contaminants Final Rule, specified in Tables Z-1, Z-2 and Z-3 (Federal Register, 58:35388-35351, June 30, 1993;

corrected in Federal Register, 58:40191, July 27, 1993; and subsequent amendments). 6. Lees, F. P., LOSS PREVENTION IN THE PROCESS INDUSTRIES, Vols. 1 and 2, Butterworth-Heinemann, London, England

(1992). 7. CONDENSED CHEMICAL DICTIONARY, 10th and 11th eds., G. G. Hawley (10th) and Sax, N. I. and R. J. Lewis, Jr. (11th), Van

Nostrand Reinhold Co., New York, NY (1981, 1987). 8. Sax, N. I., DANGEROUS PROPERTIES OF INDUSTRIAL MATERIALS, 9th ed., Vols. 1, 2 and 3, Van Nostrand Reinhold

Company, New York, NY (1996). 9. CRC HANDBOOK OF CHEMISTRY AND PHYSICS, 75th - 77th ed., CRC Press, Inc., Boca Raton, FL (1994-1996).10. Springer, C. and J. R. Welker, INDUSTRIAL HYGIENE: AN INTRODUCTION FOR CHEMICAL ENGINEERS, American Institute of

Chemical Engineers, New York, NY (1995).11. Fawcett, H. H. and W. C. Wood, eds., SAFETY AND ACCIDENT PREVENTION IN CHEMICAL OPERATIONS, 2nd ed., John

Wiley and Sons, New York, NY (1982).12. Williams, P. L. and J. L. Burson, eds., INDUSTRIAL TOXICOLOGY, SAFETY AND HEALTH APPLICATIONS IN THE

WORKPLACE, Van Nostrand Reinhold Company, New York, NY (1985).

616

Chapter 28COEFFICIENT OF THERMAL EXPANSION OF LIQUID


ABSTRACT

Results for thermal expansion coefficient of liquids are presented for organic and inorganicchemicals. The results are especially helpful in the design of relief systems for process equipment containingliquids that are subject to thermal expansion. The regression coefficients are displayed in easy-to-usetabulations. Correlation and experimental results are in favorable agreement.

INTRODUCTION

Physical and thermodynamic property data, such as thermal expansion coefficient, are important inprocess engineering. The following brief discussion illustrates such importance. Liquids contained in processequipment will expand with an increase in temperature. To accommodate such expansion, it is necessary todesign a relief system which will relieve (or vent) the thermally expanding liquid and prevent pressure build-upfrom the expansion. If provisions are not made for a relief system, the pressure will increase from thethermally expanding liquid. If the pressure increase is excessive, damage to the process equipment willoccur.

THERMAL EXPANSION COEFFICIENT

The following equation was selected for correlation of thermal expansion coefficient of liquid as afunction of temperature:

Bliq = a (1-T/TC)m (28-1)

where Bliq = thermal expansion coefficient of liquid, 1/Ca and m = regression coefficients for chemical compoundT = temperature, KTC = critical temperature, K

The results for thermal expansion coefficient are given in Tables 28-1 and 28-2. The values areapplicable to a wide variety of substances. The tabulations also disclose the temperature range for which theequation is useable. The respective minimum and maximum temperatures are denoted by TMIN and TMAX.Spot values at ambient temperature (25 C) are provided for both thermal expansion coefficient and liquiddensity.

For the tabulations, a literature search was conducted to identify data source publications fororganics (1-42) and inorganics (1-120). Both experimental values for the property under consideration andparameter values for estimation of the property are included in the source publications. The publications werescreened and copies of appropriate data were made. These data were next keyed into the computer toprovide a database of liquid volume values for which experimental data are available. These data were thenregressed for volume and change of volume with temperature as a function of temperature.

The coefficient of thermal expansion involves both volume and change of volume with temperature.The variation of volume with temperature is shown in Fig. 28-1 for a representative compound. Inspection ofthe figure discloses that the curve at constant pressure (P=29.6 atm) is very similar in shape to the curve atsaturation (P=saturation). In fact, the curves are roughly parallel for the range shown. Also, the closeness ofthe curves indicates that the volume is about the same for both saturation and constant pressure as shown.These observations of similar shape and closeness suggest that the coefficient of thermal expansion atconstant pressure is approximately equal to that at saturation:

Bliq = (1/v) (∂v/∂T)P ≈ (1/v) (∂v/∂T)saturation (28-2)This equation was used in preparing the tabulated results. The equation is applicable to the liquid at

conditions below the critical point (temperatures and pressures below critical).A comparison of calculated and actual data values for thermal expansion coefficient of liquid in Fig.

28-2 for a representative compound. The graph indicates good agreement of calculated and data values.

VOLUMETRIC EXPANSION RATE

Crowl and Louvar (41) have shown that the volumetric expansion (flow) rate for a liquidcontainedin process equipment that undergoes thermal expansion from heat input is given by:

617

Bliq Qv = UA (Text - T) (28-3) ρliq CP

where Qv = volumetric expansion rateρliq = density of liquid

CP = heat capacity of liquidU = overall heat transfer coefficientA = area for heat transferText = external temperatureT = temperature of liquid

This equation describes the volumetric expansion rate at the beginning of the heat transfer and isapplicable for the design of relief systems. The relief system should be sized to accommodate this volumetricflow (Crowl and Louvar). Property data for use in the equation are available from Yaws (32-34).

EXAMPLES

The correlation results maybe used for calculation of thermal expansion coefficient of liquid andvolumetric flow from thermal expansion. Examples are given below.

Example 1 Estimate the thermal expansion coefficient of liquid for n-pentane (C5H12) at 40 C.

Substitution of the correlation constants from the table and temperature into the correlationequation yields:

Bliq = 7.883E-04 (1-(40+273.15)/469.65)-.7179

Bliq = 0.00174 C-1

Example 2 Estimate the thermal expansion coefficient of liquid for n-butane (C4H10) at 40 C.

Substitution of the correlation constants from the table and temperature into the correlationequation yields:

Bliq = 8.757E-04 (1-(40+273.15)/425.18)-.7137

Bliq = 0.00227 C-1

Example 3 The tubing in a reactor contains benzene (C6H6) at 25 C (76.7 F). Other data are:

heat capacity of liquid (CP) 0.413 BTU/lb-Foverall heat transfer coefficient (U) 40 BTU/hr-ft2-Fsurface area of tubing (A) 500 ft2

Estimate the volumetric expansion rate if the tubing is exposed to 500 F superheated steam.

Substitution of the spot values at 25 C (Bliq=1.137E-03 C-1 and ρliq=0.873 g/cm3) from the table intothe volumetric expansion equation yields:

1.137E-03 C-1/(1.8 F/C) Qv = (40 BTU/hr-ft2-F)(500 ft2) (500-76.7) F (0.873 g/cm3 62.4 lb/ft3/g/cm3)(0.413 BTU/lb-F)

Qv = 237.69 ft3/hr = 29.63 gal/min

The relief system should be designed to accommodate this volumetric flow.

Portions of this material appeared in Chem. Eng., 102, 98 (Aug., 1995) and are reprinted by specialpermission.

REFERENCES – ORGANIC COMPOUNDS1-40. See REFERENCES – ORGANIC COMPOUNDS in Chapter 8 DENSITY OF LIQUID41. Crowl, D. A. and J. F. Louvar, CHEMICAL PROCESS SAFETY, Prentice Hall, Inc., Englewood Cliffs, NJ (1990).42. Yaws, C. L. and others, Chem. Eng., 102 (8), 98 (Aug., 1995).

REFERENCES – INORGANIC COMPOUNDS1-120. See REFERENCES – INORGANIC COMPOUNDS in Chapter 8 DENSITY OF LIQUID

CHEMICAL PROPERTIES HANDBOOK_________________________________________________________________

PHYSICAL, THERMODYNAMIC, ENVIRONMENTAL, TRANSPORT, SAFETY,AND HEALTH RELATED PROPERTIES FOR ORGANIC AND INORGANIC CHEMICALS

CARL L. YAWS

PROFESSOR OF CHEMICAL ENGINEERINGLAMAR UNIVERSITYBEAUMONT, TEXAS

McGRAW-HILLNew York San Francisco Washington, D.C. Auckland Bogota

Caracas Lisbon London Madrid Mexico City MilanMontreal New Delhi San Juan Singapore

Sydney Tokyo Toronto

v

CONTENTS

Chapter

1. CRITICAL PROPERTIES AND ACENTRIC FACTOR ........................12. HEAT CAPACITY OF GAS ................................................................303. HEAT CAPACITY OF LIQUID............................................................564. HEAT CAPACITY OF SOLID.............................................................835. ENTHALPY OF VAPORIZATION ....................................................1096. ENTHALPY OF FUSION..................................................................1357. VAPOR PRESSURE ........................................................................1598. DENSITY OF LIQUID.......................................................................1859. SURFACE TENSION .......................................................................21210. REFRACTIVE INDEX, DIPOLE MOMENT, AND

RADIUS OF GYRATION ................................................................23911. ENTROPY AND ENTROPY OF FORMATION OF GAS .................26412. ENTHALPY OF FORMATION..........................................................28813. GIBBS ENERGY OF FORMATION ................................................31414. SOLUBILITY PARAMETER, LIQUID VOLUME, AND

VAN DER WAALS VOLUME AND AREA......................................34015. SOLUBILITY IN WATER AND OCTANOL-WATER PARTITION COEFFICIENT ...........................36416. SOLUBILITY IN WATER CONTAINING SALT................................38917. SOLUBILITY IN WATER AS A FUNCTION OF TEMPERATURE..39618. HENRY'S LAW CONSTANT FOR COMPOUND IN WATER..........40319. ADSORPTION ON ACTIVATED CARBON .....................................42520. SOIL SORPTION COEFFICIENT ....................................................44321. VISCOSITY OF GAS........................................................................45222. VISCOSITY OF LIQUID ...................................................................47823. THERMAL CONDUCTIVITY OF GAS .............................................50524. THERMAL CONDUCTIVITY OF LIQUID AND SOLID ....................53125. EXPLOSIVE LIMITS IN AIR, FLASH POINT, AND AUTOIGNITION TEMPERATURE.........................................55726. ENTHALPY OF COMBUSTION.......................................................58227. EXPOSURE LIMITS FOR SAFEGUARDING HEALTH...................60328. COEFFICIENT OF THERMAL EXPANSION OF LIQUID................616

Appendix

A. CONVERSION TABLE.....................................................................643B. HENRY’S LAW CONSTANT - EQUATIONS ...................................644C. COMPOUND LIST BY CHEMICAL FORMULA ...............................647D. COMPOUND LIST BY CAS REGISTRY NUMBER.........................658E. COMPOUND LIST BY NAME AND SYNONYM ..............................669

Index.........................................................................................................779

vi

CONTRIBUTORSLi Bu Process Engineer, Great Lakes Chemical Corporation, 3324 Chelsea Ave.,

P.O. Box 80035, Memphis, Tennessee 38108, U S ADeepa R. Balundgi Graduate Student, Chemical Engineering Department, Lamar University,

P.O. Box 10053, Beaumont, Texas 77710, U S ADaniel H. Chen Professor, Chemical Engineering Department, Lamar University, P.O. Box 10053, Beaumont, Texas 77710, U S AMei Han Process Engineer, Firestone Synthetic Rubber & Latex Company, P.O.

Box 1269, Orange, Texas 77630, U S AJack. R. Hopper Professor, Chemical Engineering Department, Lamar University, P. O.

Box 10053, Beaumont, Texas 77710, U S AEric L. Jaycox Industrial Hygienist, MS CIH, Huntsman Chemical, Port Neches, Texas

77651, U S AXiaoyan Lin Chemical Process Engineer, Thermal Recovery, Inc., 5740 W. Little York

#1011, Houston, Texas 77091, U S ASachin Nijhawan Design Engineer (Process), Mustang Engineering Inc., 16001 Park

Ten Place, Houston, Texas 77710, U S ARalph W. Pike Professor, Chemical Engineering Department, Louisiana State University,

Baton Rouge, Louisiana 70803-7303, U S AMarco A. Satyro Scientific Software Specialist, SEA++ INC., 82 Hawkwood Rd. N. W.,

Calgary, Alberta, Canada T3G 2J1Sachin Sheth Technical Support Manager, EPCON International, 16360 Park Ten Place,

Houston, Texas 77084, U S ASivakumar Srinivasan Graduate Student, Chemical Engineering Department, Lamar University,

P.O. Box 10053, Beaumont, Texas 77710, U S ASaumya Tripathi Graduate Student, Chemical Engineering Department, Lamar University,

P.O. Box 10053, Beaumont, Texas 77710, U S AXiao M. Wang Graduate Student, Chemical Engineering Department, Lamar University,

P.O. Box 10053, Beaumont, Texas 77710, U S ACarl L. Yaws Professor, Chemical Engineering Department, Lamar University, P. O.

Box 10053, Beaumont, Texas 77710, U S A

ACKNOWLEDGMENTSThe author wishes to acknowledge special appreciation to his wife (Annette) and family (Kent, Michele,

Chelsea, Brandon, Lindsay, Rebecca, Chloe, and Sarah).Many colleagues and students have made contributions and helpful comments over the years. The author is

grateful to each: Jack R. Hopper, Joe W. Miller, Jr., C. S. Fang, K. Y. Li, Keith C. Hansen, Daniel H. Chen, P. Y.Chiang, H. C. Yang, Xiang Pan, Xiaoyan Lin, Li Bu, Sachin Nijhawan, Mei Han, Sachin Sheth, Deepa R. Balundgi,Sivakumar Srinivasan, Sauma Tripathi, Xiao M. Wang, and Marco A. Satyro.

The author wishes to acknowledge that the Gulf Coast Hazardous Substance Research Center provided partialsupport to this work.

Carl L. Yaws, Lamar University. Beaumont, Texas

DISCLAIMERThis handbook presents a variety of data for chemical properties. It is incumbent upon the user to execute judgement in the use of the

data. The author does not provide any guarantee, expressed or implied, with regard to the general or specific applicability of the data, the rangeof errors that may be associated with any of the data, or the appropriateness of using any of the data in any subsequent calculation, design ,ordecision process. The author accepts no responsibility for damages, if any, suffered by any reader or user of this handbook as a result ofdecisions made or actions taken on information contained therein.