Chemical Thermodynamics
Appendix 3.1 Datasets used for Examples in This Chapter
TABLE A.3.1 Effect of Organic Solvents on Water Activity (Figure 3.6)
Xw awin the Presence of Ethanol Raoult’s Law
0 0 0
0.1 0.22 0.1
0.15 0.32 0.15
0.2 0.4 0.2
0.25 0.47 0.25
0.3 0.54 0.3
0.34 0.59 0.34
0.39 0.64 0.39
0.44 0.68 0.44
0.49 0.71 0.49
0.54 0.74 0.54
0.59 0.76 0.59
0.64 0.79 0.64
0.69 0.81 0.69
0.74 0.83 0.74
0.78 0.85 0.78
0.83 0.88 0.83
0.88 0.91 0.88
0.92 0.93 0.92
1 1 1
Xw awin the Presence of Glycerol Raoult’s Law
0 0 0
0.11 0.08 0.11
0.18 0.15 0.18
0.33 0.28 0.33
(continued )
TABLE A.3.1 (continued) Effect of Organic Solvents on Water Activity (Figure 3.6)
Xw awin the Presence of Glycerol Raoult’s Law
0.44 0.39 0.44
0.53 0.49 0.53
0.59 0.56 0.59
0.64 0.62 0.64
0.7 0.69 0.7
0.74 0.74 0.74
0.79 0.79 0.79
0.85 0.85 0.85
0.92 0.92 0.92
1 1 1
Source: From Tome D., Nicolas J., and Drapon R. Influence of water activity on the reaction catalyzed by polyphenoloxidase from mushrooms in organic liquid media. Lebensm.-Wiss.u.-Technol 11:38–41, 1978.
TABLE A.3.2 Molal Activity Coefficients for Some Amino Acids (Figure 3.11)
Molality Alanine Glycine Serine Threonin Valine Praline
0 1
0.2 1.01 0.97 0.94 0.99 1.03 1.01
0.3 1.01 0.94 0.92 0.98 1.04 1.02
0.5 1.01 0.92 0.89 0.97 1.08 1.04
0.7 1.02 0.9 0.85 0.96 1.07
1 1.04 0.87 0.81 0.96 1.1
1.5 1.04 0.82 0.74 0.95 1.15
2 0.79 0.7 0.94 1.2
2.5 0.76 0.66 1.27
3 0.75 0.63 1.34
Source: From Xu X., Pinho S.P., and Macedo E.A. Activity coefficient and solubility of amino acids in water by the modified Wilson method. Ind Eng Chem Res 43:3200–3204, 2004.
TABLE A.3.3 Sucrose Activity and Water Activity in Aqueous Sucrose Solutions (Figure 3.12)
Xsucrose asucrose Raoult’s Law
0 0 0
0.01 0.01 0.01
0.02 0.022 0.02
0.03 0.035 0.03
0.04 0.055 0.04
0.05 0.08 0.05
0.06 0.11 0.06
0.07 0.14 0.07
0.08 0.17 0.08
0.09 0.21 0.09
0.1 0.25 0.1
TABLE A.3.3 (continued) Sucrose Activity and Water Activity in Aqueous Sucrose Solutions (Figure 3.12)
Xsucrose asucrose Raoult’s Law
1 1 1
0.99 0.99 0.99
0.98 0.98 0.98
0.97 0.968 0.97
0.96 0.953 0.96
0.95 0.94 0.95
0.94 0.925 0.94
0.93 0.908 0.93
0.92 0.89 0.92
0.91 0.87 0.91
0.9 0.85 0.9
0.89 0.82 0.89
0.885 0.79 0.885
0.88 0.75 0.88
Source: From Walstra, P., Physical Chemistry of Foods, Marcel Dekker Inc., New York, 2003.
TABLE A.3.4 Water Activity as a Function of Water Mole Fraction Xwfor Glucose and Ethanol (Figure 3.13)
Glucose Ethanol
Xw aw aw
0.74 0.7 0.83
0.75 0.71
0.76 0.72
0.77 0.73
0.78 0.75 0.85
0.79 0.76
0.8 0.77
0.81 0.77
0.82 0.78
0.83 0.79 0.88
0.84 0.8
0.85 0.81
0.86 0.82
0.87 0.83
0.88 0.84 0.91
0.89 0.86
0.9 0.87
0.91 0.88
(continued )
TABLE A.3.4 (continued) Water Activity as a Function of Water Mole Fraction Xwfor Glucose and Ethanol (Figure 3.13)
Glucose Ethanol
Xw aw aw
0.92 0.9 0.93
0.93 0.91
0.94 0.92
0.95 0.93
0.96 0.94
0.97 0.96
0.98 0.97
0.99 0.98
0.995 0.995
1 1 1
Source: From Audu T.O.K., Loncin M., and Weisser H. Sorption isotherms of sugars. Lebensm.-Wiss.u.-Technol 11:31–34, 1978.
TABLE A.3.5 Practical and Osmotic Coefficient and Water Activity as a Function of the Molality of Sucrose Solutions (Figure 3.14)
m aw F
0.001 1 1
0.1 0.99819 1.008
0.2 0.99634 1.017
0.3 0.99448 1.024
0.4 0.99258 1.033
0.5 0.99067 1.041
0.6 0.98872 1.05
0.7 0.98672 1.06
0.8 0.98472 1.068
0.9 0.98267 1.079
1 0.98059 1.088
1.2 0.97634 1.108
1.4 0.97193 1.129
1.6 0.9674 1.15
1.8 0.9628 1.169
2 0.95807 1.189
2.5 0.94569 1.24
3 0.93276 1.288
3.5 0.91933 1.334
4 0.90567 1.375
4.5 0.8917 1.414
5 0.8776 1.45
5.5 0.8634 1.482
6 0.8493 1.511
Source: From Robinson R.A. and Stokes R.H. Electrolyte Solutions, 2nd edition revised. London: Butterworths, 1968.
Bibliography and Suggested Further Reading
About Thermodynamics
Alberty R.A. Use of Legendre transforms in chemical thermodynamics. Pure Appl Chem 73:1349–1380, 2001.
Alberty R.A. Thermodynamics of systems of biochemical reactions. J Theor Biol 215:491–501, 2002.
Alberty R.A. Thermodynamics of Biochemical Reactions. Hoboken, New Jersey: Wiley Interscience, 2003.
Battino R., Wood S.E., and Williamson A.G. On the importance of ideality. J Chem Educ 78:1364–1368, 2001.
Ben-Naim A. Standard thermodynamics of transfer. Uses and misuses. J Phys Chem 82:792–803, 1978.
Bindel T.H. Teaching entropy analysis in the first year high school course and beyond. J Chem Educ 81:1585–1594, 2004.
Bindel T.H. Discovering the thermodynamics of simultaneous equilibria. J Chem Educ 84:449–452, 2007.
Callen H.B. Thermodynamics and an Introduction to Thermostatistics. New York: John Wiley &
Sons, 1985.
Canagaratna S.G. The use of extent of reaction in introductory courses. J Chem Educ 77:52–54, 2000.
Canagaratna S.G. Approaches to the treatment of equilibrium perturbations. J Chem Educ 80:1211–1219, 2003.
Carmichael H. What the standard state doesn’t say about temperature and phase. J Chem Educ 53:695, 1976.
Constantino M.G. and da Silva G.V.J. Chemical equilibrium, free energy, and entropy of mixing.
Chem Educ 7:349–353, 2002.
Craig N.C. and Gislason E.A. First law of thermodynamics; irreversible and reversible processes. J Chem Educ 79:193–200, 2002.
Edwards R.A. The free energies of metabolic reactions (DG) are not positive. Biochem Mol Biol Educ 29:101–103, 2001.
Fanelli A. Explaining activity coefficients and standard states in the undergraduate physical chemistry course. J Chem Educ 63:112–114, 1986.
Gil V.M.S. and Paiva J.C.M. Using computer simulations to teach salt solubility. The role of entropy in solubility equilibrium. J Chem Educ 83:170–172, 2006.
Hammes G.G. Thermodynamics and Kinetics for the Biological Sciences. New York: Wiley Interscience, 2000.
Hamori E. Building a foundation for bioenergetics. Biochem Mol Biol Educ 30:296–302, 2002.
Infelta P. The second law: Statement and applications. J Chem Educ 79:884–888, 2002.
Jullien L., Proust A., and Le Menn J.C. How does the Gibbs free energy evolve in a system undergoing coupled competitive reactions? J Chem Educ 75:194–199, 1998.
Jungermann A.H. Entropy and the shelf model: A quantum physical approach to a physical property.
J Chem Educ 83:1686–1694, 2006.
Kozliak E.I. Introduction of entropy via the Boltzmann distribution in undergraduate physical chemistry:
A molecular approach. J Chem Educ 81:1595–1598, 2004.
Lainez A. and Tardajos G. Standard states of real solutions. J Chem Educ 62:678–680, 1985.
Lambert F.L. Disorder—a cracked crutch for supporting entropy discussions. J Chem Educ 79:187–192, 2002.
Lambert F.L. Entropy is simple, qualitatively. J Chem Educ 79:1241–1246, 2002.
Letcher T.M. and Battino R. An introduction to the understanding of solubility. J Chem Educ 78:103–111, 2001.
MacDonald J.J. Equilibrium, free energy and entropy. Rates and differences. J Chem Educ 67:380–382, 1990.
Nikitas P. Applications of the Gibbs-Duhem equation. J Chem Educ 78:1070–1075, 2001.
Novak I. The microscopic statement of the second law of thermodynamics. J Chem Educ 80:1428–1431, 2003.
Novak I. Microscopic description of Le Châtelier’s principle. J Chem Educ 82:1190–1191, 2005.
Ochs R.S. Thermodynamics and spontaneity. J Chem Educ 73:952–954, 1996.
Ould-Moulaye C.B., Dussap C.G., and Gros J.B. Estimation of Gibbs energy changes of central metab-olism reactions. Biotechnol Tech 13:187–193, 1999.
Robinson P.J. Dimensions and standard states in the activated complex theory of reaction rates. J Chem Educ 55:509–510, 1978.
Robbins O. The proper definition of standard electromotive force. J Chem Educ 48:737–740, 1971.
Rosenberg R.M. and Peticolas W.L. Henry’s Law: A retrospective. J Chem Educ 81:1647–1652, 2004.
Shultz M.J. Why equilibrium? Understanding the role of entropy of mixing. J Chem Educ 76:1391–1393, 1999.
Smith E.B. Basic Chemical Thermodynamics, 5th ed. London: Imperial College Press, 2004.
Spencer J.N. Competitive and coupled reactions. J Chem Educ 69:281–284, 1992.
Tellinghuizen J. Achieving chemical equilibrium: The role of imposed conditions in the ammonia formation reaction. J Chem Educ 83:1090–1093, 2006.
Torres E.M. Effect of a perturbation on the chemical equilibrium; comparison with Le Chatelier’s principle. J Chem Educ 84:516–519, 2007.
Treptow R.S. Free energy versus extent of reaction. Understanding the difference betweenDG and dG=dj.
J Chem Educ 73:51–54, 1996.
Williamson B.E. and Morikawa T. A chemically relevant model for teaching the second law of thermo-dynamics. J Chem Educ 79:339–342, 2002.
Wisniak J. The Le Chatelier principle: How much a principle? Chemical Educator 4:58–62, 1999.
Irreversible Thermodynamics
Aledo J.C. Metabolic pathways: Does the actual Gibbs free-energy change affect theflux rate? Biochem Mol Biol Educ 29:142–143, 2001.
Aledo J.C. and Esteban del Valle A. Glycolysis in Wonderland: The importance of energy dissipation in metabolic pathways. J Chem Educ 79:1336–1339, 2002.
Aledo J.C. Coupled reactions versus connected reactions. Biochem Mol Biol Educ 35:85–88, 2007.
Berry S. Entropy, irreversibility and evolution. J Theor Biol 175:197–202, 1995.
Demirel Y. and Sandler S.I. Thermodynamics and bioenergetics. Biophys Chem 97:87–111, 2002.
Ederer M. and Gilles E.D. Thermodynamically feasible kinetic models of reaction networks. Biophys J 92:1846–1857, 2007.
Eyring H., Ma S.M., and Ueda I. Reaction kinetics in living systems. Proc Natl Acad U S A 78:5549–5553, 1981.
Keizer J. Thermodynamic coupling in chemical reactions. J Theor Biol 49:323–335, 1975.
Lems S., Van der Kooi H.J., and De Swaan Arons J. Thermodynamic optimization of energy transfer of energy transfer in (bio)chemical reaction systems. Chem Eng Sci 58:2001–2009, 2003.
Pross A. The driving force for life’s emergence: Kinetic and thermodynamic considerations. J Theor Biol 220:393–406, 2003.
Ross J. and Vlad M.O. Exact solutions for the entropy production rate of several irreversible processes.
J Phys Chem A 109:10607–10612, 2005.
Schelly Z.A. The irreversible thermodynamics of chemical relaxation. J Chem Educ 57:247–249, 1980.
Vavruch I. Conceptual problems of modern irreversible thermodynamics. Chem Lysty 96:271–275, 2002.
General Textbooks
Atkins P.W. Physical Chemistry, 6th ed. Oxford: Oxford University Press, 1999.
Gardiner W.C. Rates and Mechanisms of Chemical Reactions. New York: WA Benjamin Inc., 1969.
Hill C.G. An Introduction to Chemical Engineering Kinetics and Reactor Design. New York: Wiley, 1977.
Missen R.W., Mims C.A., and Saville B.A. Introduction to Chemical Reaction Engineering and Kinetics.
New York: John Wiley & Sons Inc., 1999.
Maskill H. The Physical Basis of Organic Chemistry. Oxford: Oxford University Press, 1985.
Moore W.J. Physical Chemistry. London: Longman, 1972.
Olmsted III J and Williams G.M. Chemistry, The Molecular Science. Dubuque, IA: Wm.C.Brown, 1997.
Raff L.M. Principles of Physical Chemistry. Upper Saddle River, NJ: Prentice Hall Inc., 2001.
Tinoco T., Sauer K., and Wang J.C. Physical Chemistry. Principles and Applications in Biological Sciences, 3rd ed. Englewood Cliffs, NJ: Prentice Hall International, 1995.
Sutton R., Rockett B., and Swindells P. Chemistry for the Life Sciences. London: Taylor & Francis, 2000.
Voet D. and Voet J.G. Biochemistry, 2nd ed. New York: Wiley & Sons, 1995.
Walstra P. Physical Chemistry of Foods. New York: Marcel Dekker, 2003.