1.01 Chemical Thermodynamics.pdfVIP

1.01 Chemical Thermodynamics R. A. Cottis Corrosion and Protection Centre, School of Materials, University of Manchester, P.O. Box 88, Sackville Street, Manchester, M60 1QD, UK L. L. Shreir and G. T. Burstein Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK This article is a revision of the Third Edition article 20.2 by L. L. Shreir and G. T. Burstein, volume 2, pp 20:57–20:75, 2010 Elsevier B.V. 1.01.1 Scope 1 1.01.2 Some Definitions 2 1.01.2.1 First Law of Thermodynamics 2 1.01.2.2 Second Law of Thermodynamics 3 1.01.2.3 Entropy 4 1.01.2.4 Gibbs Free Energy or Free Enthalpy 5 1.01.2.5 The Chemical Potential 5 1.01.2.6 Activity 6 1.01.2.7 Gibbs–Duhem Equation 6 1.01.3 Spontaneity of a Reaction 7 1.01.3.1 Reversible Cells 7 1.01.4 Chemical Potentials and Equilibrium 8 1.01.4.1 Sign Convention for Equilibrium emfs and Potentials 12 R The gas constant 8.314 J K1 mol1 Symbols S Entropy J a Activity strictly dimensionless – see section T Temperature K 1.01.2.6 1 3 3 U Internal energy J c Concentration mol kg or mol m or mol dm 3 1 V Volume m c Concentration in standard state mol kg or 3 3 w Work J mol m or mol dm z Number of electrons or equivalent positive charge Cp Molar heat capacity at constant pressure 1 1 g Activity coefficient J mol K 1 m Chemical potential J mol E Equilibrium potential V 1 m Standard chemical potential J mol E Standard equilibrium potential V y Number of ions or molecules F Faraday constant 96 485 C mol1 G Gibbs free energy or free enthalpy J G Standard Gibbs free energy or free enthalpy J 1.01.1 Scope H Enthalpy J 1 I Ionic strength mol kg or 3 3 Thermodynamics is concerned with the relationship mol m or mol dm between heat energy and work and is based on two K Equilibrium constant general laws, the first and second laws of thermody- n Number of moles namics, both of which deal with the interconversion P Pressure Pa, atm of different