Chapter 1

Introduction

A major objective of any field of pure or applied science is to summarize a large amount
of experimental information with a few basic principles. The hope is that any new ex-
perimental measurement or phenomenon can be easily understood in terms of the es-
tablished principles, and that predictions based on these principles will be accurate.
This book demonstrates how a collection of general experimental observations can be
used to establish the principles of an area of science called thermodynamics, and then
shows how these principles can be used to study a wide variety of physical, chemical,
and biochemical phenomena.
Questions the reader of this book might ask include what is thermodynamics and
why should one study it? The word thermodynamics consists of two parts: the prefix
thermo, referring to heat and temperature, and dynamics, meaning motion. Initially,
thermodynamics had to do with the flow of heat to produce mechanical energy that
could be used for industrial processes and locomotion. This was the study of heat en-
gines, devices used to operate mechanical equipment, drive trains and cars, and perform
many other functions that accelerated progress in the Industrial Age. These started with
steam engines and progressed to internal combustion engines, turbines, heat pumps, air
conditioners, and other devices. This part of thermodynamics is largely the realm of
mechanical engineers. However, because such equipment is also used in chemical pro-
cessing plants, it is important for chemical engineers to have an understanding of the
fundamentals of this equipment. Therefore, such equipment is considered briefly in
Chapters 4 and 5 of this book. These applications of thermodynamics generally require
an understanding the properties of pure fluids, such as steam and various refrigerants,
and gases such as oxygen and nitrogen.
More central to chemical engineering is the study of mixtures. The production of
chemicals, polymers, pharmaceuticals and other biological materials, and oil and gas
processing, all involve chemical or biochemical reactions (frequently in a solvent) that
produce a mixture of reaction products. These must be separated from the mixture and
purified to result in products of societal, commercial, or medicinal value. It is in these
areas that thermodynamics plays a central role in chemical engineering. Separation pro-
cesses, of which distillation is the most commonly used in the chemical industry, are
designed based on information from thermodynamics. Of particular interest in the de-
sign of separation and purification processes is the compositions of two phases that
are in equilibrium. For example, when a liquid mixture boils, the vapor coming off
can be of a quite different composition than the liquid from which it was obtained.
This is the basis for distillation, and the design of a distillation column is based on

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2 Chapter 1: Introduction

predictions from thermodynamics. Similarly, when partially miscible components are

brought together, two (or more) liquid phases of very different composition will form,
and other components added to this two-phase mixture will partition differently be-
tween the phases. This phenomenon is the basis for liquid-liquid extraction, another
commonly used separation process, especially for chemicals and biochemicals that can-
not be distilled because they do not vaporize appreciably or because they break down on
heating. The design of such processes is also based on predictions from thermodynam-
ics. Thus, thermodynamics plays a central role in chemical process design. Although
this subject is properly considered in other courses in the chemical engineering curricu-
lum, we will provide very brief introductions to distillation, air stripping, liquid-liquid
extraction, and other processes so that the student can appreciate why the study of ther-
modynamics is central to chemical engineering.
Other applications of thermodynamics considered in this book include the distribu-
tion of chemicals when released to the environment, determining safety by estimating
the possible impact (or energy release) of mechanical and chemical explosions, ana-
lyzing biochemical processes, and product design, that is, identifying a chemical or
mixture that has the properties needed for a specific application.
A generally important feature of engineering design is making estimates when spe-
cific information on a fluid or fluid mixture is not available, which is almost always
the case. To understand why this is so, consider the fact that there are several hun-
dred chemicals commonly used in industry, either as final products or intermediates.
If this number were, say, 200, there would be about 20,000 possible binary mixtures,
1.3 million possible ternary mixtures, 67 million possible four-component mixtures, and
so on. However, in the history of mankind the vapor-liquid equilibria of considerably
fewer than 10,000 different mixtures have been measured. Further, even if we were
interested in one of the mixtures for which data exist, it is unlikely that the measure-
ments were done at exactly the temperature and pressure in which we are interested.
Therefore, many times engineers have to make estimates by extrapolating the limited
data available to the conditions (temperature, pressure, and composition) of interest to
them, or predict the behavior of multicomponent mixtures based only on sets of two-
component mixture data. In other cases predictions may have to be made for mixtures in
which the chemical identity of one or more of the components is not known. One exam-
ple of this is petroleum or crude oil; another is the result of a polymerization reaction or
biochemical process. In these cases, many components of different molecular weights
are present that will not, and perhaps cannot, be identified by chemical analytic meth-
ods, and yet purification methods have to be designed so approximations are made.
Although the estimation of thermodynamic properties, especially of mixtures, is not
part of the theoretical foundation of chemical engineering thermodynamics, it is nec-
essary for its application to real problems. Therefore, various estimation methods are
interspersed with the basic theory, especially in Chapters 6, 8, and 11, so that the theory
can be applied.
This book can be considered as consisting of two parts. The first is the study of pure
fluids, which begins after this introductory chapter. In Chapter 2 is a review of the use
of mass balance, largely for pure fluids, but with a digression to reacting mixtures in
order to explain the idea of nonconserved variables. Although mass balances should be
familiar to a chemical engineering student from a course on stoichiometry or chemi-
cal process principles, it is reviewed here to introduce the different forms of the mass
balance that will be used, the rate-of-change and difference forms (as well as the mi-
croscopic form for the advanced student), and some of the subtleties in applying the
mass balance to systems in which flow occurs. The mass balance is the simplest of