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Chemical Energy and Exergy

An Introduction to Chemical Thermodynamics for Engineers

1st Edition - March 31, 2004

Author: Norio Sato

Hardback ISBN:

9 7 8 - 0 - 4 4 4 - 5 1 6 4 5 - 9

eBook ISBN:

9 7 8 - 0 - 0 8 - 0 5 0 1 0 0 - 0

This book is a beginners introduction to chemical thermodynamics for engineers. In the textbook efforts have been made to visualize as clearly as possible the main concepts of… Read more

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This book is a beginners introduction to chemical thermodynamics for engineers. In the textbook efforts have been made to visualize as clearly as possible the main concepts of thermodynamic quantities such as enthalpy and entropy, thus making them more perceivable. Furthermore, intricate formulae in thermodynamics have been discussed as functionally unified sets of formulae to understand their meaning rather than to mathematically derive them in detail.In this textbook, the affinity of irreversible processes, defined by the second law of thermodynamics, has been treated as the main subject, rather than the equilibrium of chemical reactions. The concept of affinity is applicable in general not only to the processes of chemical reactions but also to all kinds of irreversible processes.This textbook also includes electrochemical thermodynamics in which, instead of the classical phenomenological approach, molecular science provides an advanced understanding of the reactions of charged particles such as ions and electrons at the electrodes.Recently, engineering thermodynamics has introduced a new thermodynamic potential called exergy, which essentially is related to the concept of the affinity of irreversible processes. This textbook discusses the relation between exergy and affinity and explains the exergy balance diagram and exergy vector diagram applicable to exergy analyses in chemical manufacturing processes. This textbook is written in the hope that the readers understand in a broad way the fundamental concepts of energy and exergy from chemical thermodynamics in practical applications. Finishing this book, the readers may easily step forward further into an advanced text of their specified line.

Thermodynamic State Variables. Thermodynamic systems. Variables of the state. Extensive and intensive variables.Partial molar quantities.The extent of a chemical reaction.Conservation Of Energy. Energy as a physical quantity of the state.Conservation of energy.Internal energy U with independent variables T, V, and. Enthalpy H with independent variables T, p, and.Enthalpy and heat of reaction.Enthalpy of pure substances.Entropy As A State Property.Introduction to entropy.Reversible and irreversible processes.The creation of entropy and uncompensated heat.The creation of entropy and thermodynamic potentials.Affinity of irreversible processes. Entropy of pure substances.Entropy of heat transfer.Entropy of gas expansion.Entropy of mixing.Affinity In Irreversible Processes.Affinity in chemical reactions. Affinity and heat of reaction.The average heat of reaction.The average affinity of reaction. Chemical Potential. Thermodynamic potentials in open systems.The partial molar quantity of energy and the chemical potential.Chemical potentials and the affinity of reaction.Chemical potentials and thermodynamic energy functions.Chemical potentials in homogeneous mixtures: the Gibbs-Duhem equation.Chemical potentials of substances in ideal mixtures.Activity and activity coefficient.Chemical potentials of pure substances.Thermodynamic potentials in ideal mixtures.The unitary and mixing terms of thermodynamic potentials.Unitary Affinity And Equilibrium. Affinity and equilibrium in chemical reactions.The unitary affinity.Equilibrium constants and concentration units.Equilibrium constants as a function of pressure and temperature.Gases, Liquids, And Solids. Perfect and ideal gases.Non-ideal gases. Liquids and solids.The state equation and thermodynamic functions of condensed substances. Solutions. Ideal and non-ideal solutions.Perfect solutions and ideal solutions.Reference systems for thermodynamic unitary quantity.Thermodynamic excess functions in non-ideal solutions.Units of the concentration.Osmotic pressure.Electrolytic solutions.Electrochemical Energy. Electrochemical potential of charged particles.Transfer of charged particles between two condensed phases.Electrode and electrode potential.Electrochemical cells.Equilibrium electrode potential of electronic transfer reactions.Equilibrium electrode potential of ionic transfer reactions.Chemical potential of hydrated ions.Exergy. The concept of exergy.Exergy and heat. Exergy and pressure. Thermal exergy of high temperature substances.Thermal exergy of low temperature substances.Exergy in mixing substances. Chemical exergy of substances. Standard chemical exergy of substances. Total exergy of substances. Exergy and affinity.Exergy Diagram. Efficiency in the use of energy.Exergy balance diagram.Exergy vector diagram. Principles in exergy vector diagrams. Exergy transfer between two processes. Exergy vectors of heating-cooling processes.Exergy vectors of compression-expansion processes.Exergy vectors of separating-mixing processes.Exergy vectors of chemical reactions. Exergy transfer in chemical reactions. Exergy vector diagrams of methanol synthesis.Exergy vectors for electrochemical reactions.