CHAPTER 3

Thermodynamic Aspects of
Process Metallurgy
Introduction to Thermodynamics of Metallurgical
Processes
Kazuki Morita, Nobuo Sano and Seshadri Seetharaman
Contents
3.1.
3.2.
3.3.
3.4.
3.5.
3.6.
3.7.
3.8.
3.9.
3.10.

First, Second and Third Laws of Thermochemistry

Phase Rule
Ellingham Diagram
Solution Thermochemistry
Thermodynamic Basis for Phase Diagrams
Dilute Solutions
Thermodynamics of Slags
Examples of Steelmaking Thermochemistry
Thermodynamics of Aqueous Phases
Thermodynamic Basis of Electrolysis and Electrochemistry

399
495
507
517
527
557
587
617
641
653

It is customary to classify natural science into Physics, Chemistry, and Mathematics.

During the seventeenth, eighteenth, and nineteenth centuries, science has marked the
evolution of three important subjects, which formed the foundation for the development
of modern technology. These are mechanics, electromagnetism, and thermodynamics.
The special feature of these three subjects is that they all start with basic logical reasoning
which would lead to advanced development of theories of science and technology. Of
these, the subject of Thermodynamics combines the reasonings from physics and chemistry and uses the mathematical tools in substantiating the outcoming deductions. The
word thermodynamics is derived by a combination of the Greek terms Thermos
meaning heat and Dynamis meaning Power. This subject is taught to students
in materials science and engineering, chemistry, physics, and mechanical engineering,
often with variations in the applications while the basis is common.
One of the earliest reasonings in thermodynamics starts with the steam engine, viz.,
how to get the maximum efficiency with minimum input of heat to the engine. The
conversion of one form of energy, in this case, the heat energy, to mechanical energy
was the focal point. Some of the important names to be remembered with regard to
thermodynamics are Black, Rumford, Hess, Carnot, Mayer, Joule, Clausius, Kelvin,
Treatise on Process Metallurgy, Volume 1
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Kazuki Morita et al.

Helmholtz, and Gibbs. The observation of the evolution of heat by Col. Rumford when
he was getting canon barrel bored had stimulated the thinking of conversion of heat
energy out of mechanical working. Early in the 1900s, the famous scientist Joule determined the equivalent heat for mechanical work carried out. He defined 1 cal as the heat
energy needed to increase the temperature of 1 g water by 1
C (between 14.5 and
15.5
C). Enligt Joule, 1 J (1 N m) mechanical energy would correspond to 0.241 cal.
It is astonishing to compare this value to the accurate measurements in modern times
which is reported as 0.2389 cal/N m.
Among the early publications on Thermodynamics found in the literature, a few that
can be mentioned are:
Sainte-Claire Deville, Lecons sur la dissociation, Lecons Chim. 18641865, sid. 255.
A. Horstmann, Ber. deut. chem. Ges. m 1 (1869).
F. Haber, Thermodyn. Tech. Gas Reaktionen.
R. Oldenbourg Verlag, Munchen, 1905.
Most important among them, in the opinion of the present authors, is the unique
publication by J.W. Gibbs, The equilibrium of heterogeneous substances, Trans. Conn.
Acad. Sci. 3 (1876), sid. 228.
Thermodynamics is very often considered as tangenting philosophy. This is well
brought out in the early publications where a significant thought process was resorted
to in order to define the terms involved as accurately as possible and discuss the abstract
principles of order and disorder as well as the balance between these two primordial
forces, reminding of ancient eastern philosophies. The concept of enthalpy, which
often represents the order in systems and entropy, based on disorder are kept in equilibrium depending upon the conditions prevailing by the famous equation,
DG DH  TDS

3:1

where G stands for Gibbs energy, while the terms H and S stand for enthalpy and entropy
respectively and T stands for temperature in Kelvin. One of the interesting aspects to note
is that both H and S are functions of the specific heat, viz.

dH Cp dT
3:2
and

dS Cp=T dT

3:3

(Cp stands for specific heat) once again pointing to the commonness between order and
disorder, based on structural principles. By the way, it is interesting to note that students
of thermodynamics who get fascinated by these concepts often start applying these to
human behavior and even economics.

Thermodynamic Aspects of Process Metallurgy

The beauty of the subject of Thermodynamics is its expansivity from micro/atomic

level (often by combining the principles of statistical mechanics) to macrosystems. The
latter deals with metallurgical processes for producing millions of tons of steel. These
processes are indeed based on thermodynamic principles and calculations. In this chapter,
we focus on the applications to metallurgical processes, while the atomistic and structural
aspects have been dealt with partly in Chapter 2.
It is important to keep in mind that the subject of thermodynamics provides the
knowledge base for finding out whether a process is possible or not. It also gives information as to the heat effects accompanying such a process. While thermodynamics is
very clear regarding the differences between two states of existence, as, for example,
two temperatures of a defined system or two different pressures, it does not give any clue
as to the rate at which the system moves from one state to the other. In this treatise, this
kinetics part is dealt with in the chapter that follows, viz., Chapter 4.
In modern days, the development in the field of thermodynamics is twofold:
(a) Development of applications of thermodynamic principles to metallurgical
processes and
(b) Measurement of modeling of thermodynamic data for the applications.
In the first case, commercial softwares have been developed for applications both in
the industrial laboratories and in the universities. In the area of the measurement of thermodynamic data, with the improvements in modern instrumentations, very significant
advances have been made with respect to the accuracy of the data obtained.
One of the effects of the modern developments in the field of Thermodynamics education is the emphasis that is being slightly shifted from an understanding of the principles
of thermodynamics, which is the key to the evolution of new concepts and ideas, toward
applications, especially of the softwares commercially available. The prime objective
of the present chapter is to provide a basic knowledge of the thermodynamics of metallurgical processes so that the reader is acquainted well with them before proceeding to
the applications. The commercial softwares available are presented in Chapter 9.

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