Part I Fundamental Principles

The Scope of Classical, 1

Thennodynaniics

1.1 An Engineering Perspectrve

To the scientist, classical thermodynamics is one of a few mature fields epitomized
by a rather well-defined, self-consistent body of knowledge. The essence of the
theoretical structure of classical thermodynamics is a set of natural laws governing the
behavior of macroscopic systems. The laws are derived from generalizations of
empirical observations and are largely independent of any theory or hypothesis
concerning the microscopic or molecular-level behavior of matter. From these laws, a
large number of corollaries and axioms are derivable by proofs based entirely on logic.
The scientist is sometimes at a loss to understand why the engineer has so much
difficulty applying the principles of thermodynamics; after all, the theoretical develop-
ment is rather straightforward. From the engineer's point of view, understanding the
theory as developed by the chemist or physicist is not particularly difficult; however,
the neat, self-contained presentation of the subject by the scientist is not necessarily
amenable to practical application. Real-world processes are usually far from reversible,
adiabatic, or well mixed; very rarely are they isothermal or at equilibrium; few mixtures
of industrial importance are ideal. Thus, the engineer must take a pragmatic approach
to the application of thermodynamics to real systems. Frequently, a major requirement
is to redefine the real problem in tenns of idealizations to which thermodynamic
principles and methodologies can be applied.
In the engineering context, almost all problems of thermodynamic importance can be
classified into one of three types:

1. For a given process with prescribed (or idealized) internal constraints and boundary
conditions, how do the properties of the system vary?
2. To cause given changes in system properties, what external interactions must be imposed?
(This is the inverse of type I.)
3. Of the many alternative processes 10 effect a given change in a system, what are the
efficiencies of each with respect to the resources at our disposal?
2 The Scope of Classical Thermodynamics Chapter t

Problems of the first two classes require application of the First Law, which is
developed in Chapter 3:
~""Q+W (1-1)
where f;. is the total energy and Q and Ware the heat and work interactions, respectively.
The First Law may also be viewed as:
internal changes= L interactions occurring at boundaries
The change in energy can be related to variations of other internal properties of interest
(e.g., T, P, V, etc.).
The third class of problems requires application of the Second Law, for which an
idealization-the reversible process-is introduced as a standard for comparison.
There are basically only three steps required to develop a solution to any
thermodynamic problem:
1. Problem definition o.nd modeling. The real-world situation must be modeled by
specifying the internal constraints and boundary conditions. Idealizations must frequently
be introduced to make the problem tractable. For example, is a boundary permeable,
semipermeable, or impermeable? Are the contents of the system well-mixed and
homogeneous? Is heat transfer fast or slow relative to the time span of interest? Which
chemical reactions are known to occur under the conditions of interest?
2. Application of thermodynamic laws wul mathematical reasoning. As described above,
these either relate effects internal to the system with external variations (the First Law)
or they set limits on the extent of internal variations (the Second Law). The combined
laws prescribe in part the relationships between property variations, but they do not
uniquely specify the magnitude of the change in properties. For example, for a simple,
non-reacting system of fixed mass (M) and moles (N) undergoing a process in which the
temperature and pressure are observed to change from T1, P1 to T2 , P 2, we might wish to
calculate the total energy change, Ag_, in order to specify the necessary heat and work
interactions. We might employ the following analysis:
(a) From thermodynamic reasoning, with N= constant, ti§. is a unique function of
Tl> P1 and T2 , P 2 because !J. is a state function. Therefore,¥_ can be evaluated over
any path between the states.
(b) From mathematical reasoning, over any path for which g is defined, d&. may be
expressed as an exact differential, such as

AE
-
= JdE = JT
- r
2

I
(agl
aT I
dT + (ag)
rl'i
Jp I aP r.2
dP c1-2)

Note that (ag_1a1)p and (a§/iJP)r must be expressed as functions of T and P before
Eq. (1-2) can be integrated.
(c) Applying thermodynamic reasoning, fi. is defined as a function of Tand P over a
reversible palh, and thus (iJ§/a7)p and (dg_/dP)Tcan be reduced to other variable
sets lhat are more readily quantified:
Section 1.2 Preclassical Thermodynamics 3

where CP is tbe constant-pressure heat capacity. Note that Eq. (l-3) is a general
result, it must be satisfied by any material undergoing a change from T 1, P 1 and
T2 , P2 • However, the value of¥_ is not unique; it differs from one material to the
next, whicb leads us to the third and final step.
3. Evaluation of properly data. There are property relationships that are unique
characteristics of matter. For example, in Eq. ( 1-3 ), thermodynamics does not dictale the
functions
CP = / 1(T. P), X: = NV= Nfi(T, P) (1-4)
roquired for the integration. Actual evaluation of these property data lies outside the scope
of classical thermodynamics. However, they are essential to the solution of real problems
and hence are within the scope of this text (see for example Chapters 8 and 10). The
engineer must make recourse to a variety of methods (e.g., Literature, experiments,
correlations, or microscopic theories as developed witb statistical mechanics) in order to
deternUne or approximate these property relationships.
Figure 1.1 summarizes this general method for solving engineering thermodynamics
problems. Before discussing the approach to classical thermodynamics used herein
(Section 1.3), it is instructive to review the historical evolution of this body of
knowledge.

1.2 Preclassical Thermodynamics

The origin of classical thermodynamics can be traced back to the early 1600s. The
laws, as we know them today, were not formalized until the late 1800s. The interim 250
to 300 years are called the preclassical period, during which many of our current
concepts were developed.
The chronological development is a fascinating example of the application of
scientific methodology. Experimentation (e.g., thermometry) led to the development of
hypotheses and concepts (e.g., the adiabatic wall) which, in tum, suggestbj other
experiments (e.g., calorimetry) followed by new concepts (the pitfalls in scientific
analysis, such as overemphasis on intuitive images, e.g., the nature of heat) which go
far beyond the existing body of observations and facts. Consequently, the preclassical
period was marked with pedagogical controversy and much confusion.
The beginning of the preclassical period is usually associated with Galileo's attempts
to quantify thermometry (circa 1600). It is interesting to note that seventeenth-century
scientists were motivated primarily by a desire to understand phenomena perceived by
their senses. In contrast, scientists today require very sensitive and elaborate
instrumentation to detect phenomena that are far beyond the reaches of their senses. One
of Galileo's principal objectives was to quantify the subjective experiences of hot and
4 The Scope of Classical Thermodynamics Chapter 1

Type of Problem:
1. Estimate system property variations over a
prescribed path
1----------l 2. Required exlemal Interactions to achieve
certain variations
3. Evaluation of process efliclency ror
speclfied changes of state

Constraints and Boundary Conditions

- Work/Heat Interactions
- lnUirnal COl13traints
Problem - - - - - - - - -1 • Mass flow at bo11ndarles
Oeflnltlon - Chemical species and/or raaclions
and - Transient or Steady State
Modeling

Well-mixed, homogeneous,
ldeallzatlons --~quasi-static or reversible,
neglect certain reactions, etc.

Application of Isl law/2nd L8w

Thermodyn!lllllc Laws Phase and/or Chemical Equilibrium
and Mathematical 14------IS!abillty criteria
Reasoning State vs. Path Functions and other
aspects of functional calculus

Evaluation of Charts or Tables

Physlcal Property Data Computer Data Sase
C,or C, "f(T, P, 1\1)
EquatloM of Stale P = g(T, V, 1\1)
Models for non-ideal behavior

Figure 1.1 Basic thermodynamic problem solving steps.

cold. The expansion of air upon heating was appreciated in the Hellenistic era, but it was
never applied. Galileo used this phenomenon in his bulb-and-stem device with the stem
submerged in water. The measurements would change with time, but in the early 1600s
there was no reason to assume that they should not vary. It was not until 1643, when a
student of Galileo, Torricelli, developed the barometer, that it was appreciated that
Galileo's device was more of a "barothermoscope" than a thermometer. As glass-
blowing technology advanced, the availability of narrow capillaries led to the
development of liquid thennometers in the 1630s. As might be expected, water was the
first liquid used. Although difficulties that should be obvious to today's students were
experienced, ten years elapsed before the sealed alcohol thermometer gained accept.Mice.
Gas thermometers did not reappear until the 1700s, when gas properties were better
understood.
Section 1.2 Preclassical Thermodynamics 5

When any new experimental tool is developed, invariably there is the desire to
quantify it so that results among different investigators can be compared. The
quantification of thermometry required the introduction of at least two fiducial or fixed
points. Stop for a moment and reflect on what fixed points you might have chosen had
you been a scientist in 1640. The boiling point of water? It varies from day to day. The
freezing point of water? It is difficult to find ice during most of the year. Furthermore,
there was no reason to believe that materials like water had unique properties that would
be reproducible. Thus, it is understandable that our ancestors turned to phenomeno-
logical references, such as the "warmest water the hand could stand" or the "most severe
winter cold" or the "temperature of the human body." Later, selection of the melting
point of butter or the freezing point of aniseed oil were steps toward objectivity, although
these transition points were not very sharp. It was not until 1694 that the freezing and
boiling points of water gained acceptance.
With the advance of quantitative thermometric experimentation it soon became
apparent that different types of containers had different thermal properties. Hot liquids
would cool less rapidly in mica or wood vessels than in metals. These observations led
to the idealized concept of the adiabatic wall, which could be approached in practice;
thus, the science of calorimetry was born.
If two portions of the same fluid were mixed in a calorimeter, the final temperature
e/could be expressed as a weighted mean of the two initial temperatures 81 and 82:
w1e1 +w202
8 - (l-5)
'f- Wl + W2
The weighting factors w1 or w2 could be mass or volume. Although Eq. (1-5) is of the
form of a conservation Jaw, it is not at all clear wluit is conserved. A simplistic
interpretation would have temperature as the conserved quantity. The conservation law
was given more structure in the mid-1700s, when Eq. (1-5), with mass or volume as
weighting factors, was shown to be invalid when different liquids were mixed. In the
1760s, Joseph Black suggested a modification that was consistent with mixing data for
different fluids. The constants a; in Eq. (1-5) were subdivided into a mass-related
component and an intensity parameter, the specific heat, which was a unique property
of the liquid. This was the first time that it was proposed that matter had distinctive
properties in the thermodynamic sense.
Black's modification indicated that something other than temperature was conserved
in the mixing process. This quantity was called heat or caloric. The interpretAtion went
far beyond the physical observations into the realm of metaphysics. The caloric theory
attempted to define the microscopic nature of the conserved quantity.
Black's ingenious hypothesis led to a flurry of experimentation, during which specific
heats were measured and reported in the then flourishing royal societies. The
conservation law was repeatedly challenged, but by more exacting experimentAtion, the
theory was enlarged to account for the variation of specific heat with temperature, and
later, latent heats were introduced to account for phase transitions.
6 The Scope of Classical Thermodynamics Chapter 1

In the 1780s, no more than 20 years after Black's work, Count Rumford conducted
his exhaustive experiments to show that mechanical work was an inexhaustible source
of caloric. Hence, caloric could not be conserved and could not be of a material nature.
Rumford suggested a revival of the mechanical concept of heat that had been abandoned
SO years earlier. Although we now know that Rumford's suggestion was closer to the
truth, it is understandable why very few of his peers followed his lead. The statistical
concepts necessary to relate micromechanical energy to the macroscopic energy of
calorimetry were not to be introduced until a century later by Maxwell, Boltzmann, and
Gibbs. Rumford's hypothesis failed to produce tangible phenomenological results.
Although the caloric theory remained in use for over 50 years after Rumford's work,
he emphasized the dilemma between conservation and creation (or conversion) which
was to perp Iex the best minds of the nineteenth century. The con version crisis was fi nnl y
established by the work of Mayer and Joule in the 1840s.
In 1824, Carnot offered a partial reconciliation of the conversion and conservation
phenomena with an argument based on the caloric theory (the results of which actually
prolonged the life of the theory). Carnot introduced a step-change in the level of
complexity and sophistication. He put forth a number of new concepts that were essential
to the eventual clarification of preclassical ideas and that later led to the replacement of
the caloric theory by the First and Second Laws. These firsts include the concepts of
heat reservoirs and reversibility, and the requirement of a temperature difference to
generate work from a heat interaction.
Carnot proposed that cyclic operation of an engine working between two heat
reservoirs was analogous to water flowing over a dam. Some quantity, in being
transferred from a high to a low potential, produced work, but the quantity being
transferred was conserved in the process. We know today that Carnot's hypothesis is
incorrect because he assumed that the conserved quantity was caloric. He carried this
reasoning further to prove that there must be a limiting efficiency of heat engines. If
such a limitation did not exist, then two engines could be suitably operated in a cyclic
process in order to bring the heat reservoirs back to their initial states, the net effect being
the production of work. This, Carnot declared, was an impossibility.
We might ask on what basis Carnot ruled out the possibility of what we today call a
"perpetual motion machine of the first kind." It was not until 1847 that Helmholtz
advanced the hypothesis of the conservation of energy. With few notable exceptions,
scientists of the period generally agreed that the basic laws of nature existed a priori and
were indestructible. Thus, over a period of many years, we saw the gradual acceptance
of energy conservation as a basic postulate.
Carnot's engine reconciled both conversion and conservation phenomena-at least
in the reversible limit. But how is this consistent with conservation in the highly
irreversible mixing process of calorimetry, or conversion in the equally irreversible
process of generating heat through friction? Carnot was cognizant of these difficulties
and called for further experimentation and also for reconsideration of the foundations
of the theory.
Section 1.3 The Postulatory Approach 7

The preclassical period drew to a close with the quantitative work of Joule who
established the equivalence of mechanical, electrical, and chemical energy to heat. We
can see that at that time there were a number of concepts yet to be clarified. Caloric had
to be split into heat quantity, energy, and entropy. It remained to be shown that heat and
work were forms of energy transfer and that the interconvertibility was asynunetric. It
is energy that is conserved in the calorimeter, in Carnot's cycle, and in frictional
processes. Entropy is conserved only in the limit of the reversible process.
These further refinements occurred in relatively rapid succession beginning
approximately in 1850 with the genius of Clausius, with important contributions from
Thomson (Lord Kelvin), Maxwell, Rankine, Planck, Duhem, Caratheodory, and
Poincare, and terminating with the brilliance of Gibbs near the end of the century.
Although we cannot cover these events in detail here, one should not underestimate their
historical importance. We will attempt to reconstruct these developments, applying the
insight that we have gained over the last 80 years.

1.3 The Postulatory Approach

Almost all approaches to classical thermodynamics follow one of two extremes: the
historical approach, which parallels closely the chronological development of concepts
and misconceptions, and the postulatory approach, in which axioms that cannot be
proved from first principles are stated. There are merits and drawbacks in each extreme.
Advocates of the historical approach contend that if we are to expect our students to
evolve new concepts and theories, we must expose them to the historical development
of existing theories. Existing postulatory approaches make no reference to historical
developments. The empirical basis for the laws of thermodynamics is impersonally
stated in a small number of postulates that cannot be proved and can only be disproved
by showing that consequences derived from them are in conflict with experimental facts.
The postulates tend to be mathematical and abstract, but the laws of thennodynamics
are derivable from them. Many students are unimpressed because little insight is
provided for the necessity to define new concepts or properties. Figure 1.2 illustrates the
connectivity between the postulates and their applications to engineering practice.
The approach we follow parallels the historical development in many respects. We
begin by assuming the state of mind and body of knowledge available to the seventeenth-
century scientist and proceed from that point to a logical development of a self-consistent
set of rules that applies to the behavior of macroscopic bodies. In the process, we make
use of many of tbe arguments put forth by our ingenious predecessors over the last 300
years, but we use hindsight to avoid the incorrect conclusions that prevailed at many
points in the preclassical period and that resulted in much confusion (some of which is
usually transferred to the student who studies thermodynamics by the historical
approach).
At several junctures in our development we will face obstacles that cannot be obviated
by invoking first principles. Our predecessors overcame these obstacles by trial-and-
8 The Scope of Classical Thennodynamics Chapter 1

[ ENGINEERING APPLICATIONS

BODY OF
EMPIRICAL
OBSERVATIONS
AND
KNOWl£DGE

Figure 1.2 Illustration of interactions when using the postulatory approach.

error experimentation until they amassed a large body of knowledge. In this manner,
generalities were stated and rules established. We clearly identify those principles that
our ancestors learned to accept without proof; these are stated as postulates, but in a form
that could be understood by Black, Lavoisier, Thomson, or Carnot. The ultimate
verification of these postulates lies in the success of the formalism derived from them.
In this vein, Schrodinger' s equation is a basic postulate of quantum mechanics and
Newton's Jaws of motion were basic postulates of classical mechanics. It is conceivable
that, at some later date, new experimental information will be obtained that will
necessitate revision or reformulation of the thermodynamic postulates, just as Newt~n· s
Jaws were found inapplicable to the motion of elementary particles of the atom.
Although the set of postulates presented in this text has the same information content
as those developed in other texts, the phrasing may appear significantly different. There
Section 1.3 The Postulatory Approach 9

are obviously many different sets of postulates that provide equally valid bases for the
theoretical development (see, for example, Callen ( 1985) and Hatsopoulos and Keenan
(1964)). In developing a set of postulates, we have attempted to keep them as real as
possible (as opposed to abstract) while retaining a form that will be readily acceptable
to the chemical engineer.

References and Suggested Readings

Andrade, E. N. DA C. (1935), "Two historical notes-Humphry Davy's experiments on the
frictional development of heat; Newton's early notebook," Nature, 135, p 359.
Bejan, A. (1988), Advanced Engineering Thennodynamics, Wiley, New York. Chap. I and 2.
Bompass, C. (1817),An Essay on the Nature of Heat, light, and Electricity, T & C
Underwood, London.
Caratheodory, C. (1909), "Untersuchungen ilber die Grundlagen der Thermodynamik," Math.
Ann (Berlin) 67, p 355-386 (for an English translation see Kestin, J. (1976). The Second
Law of Thermodynamics, Stroudsburg, PA: Dowden, Hutchinson and Ross part I,
p 229-256)
Callen, H. B. ( 1985), Thermodynamics and an Introduction to Thermostatistics. 2nd ed,
Wiley, New York.
Cardwell, D.S. L. (1971), From Watt to Clausius, Cornell University Press, Ithaca, NY.
Carnot, S. (1824), Reflections on the Morive Power of Fire, and on Machines Fitted to
Develop that Power, Bachelier, Paris.
Clausius, R. (1867), Mechanical Theory of Heat, edited by T. A. Hirst, J. Van Voorst, London.
Gibbs, J. W. (1928), The Collected Works of J. Willard Gibbs, Vol. land 2, Longmans and
Green, New York.
Hatsopoulos, G. W. and J. H. Keenan (1964), Principles of General Thermodynami.cs. Wiley,
New York.
Joule, J.P. (1963), The Scientific Papers of James Prescott Joule, Dawson's, London.
Joule, J. P. ( 1843), "On the calorific effects of magneto-electricity, and on Lhe mechanical
value of heat," Philos. Mag. 23 (3).
Lardner, D. (1833), A Treatise on Heat, Longrnans, Rees, Orme, Brown, Green, and
Longmans, London.
Leslie, J. ( 1804), An Experimental Inquiry into the Nature and Propagation of Heat, I.
Mawman, London.
Mayer, J. R. (1842), "Remarks on the forces of inorganic nature." Ann. Chem. Pharm. 42,
p 233-240.
Metcalfe, S. L. (l 843), Caloric (2 vols.), William Pickering, London.
10 1h e Scope o I Classical Thermodynamics Chapter 1

Planck, M. (1945), Treatise on Thermodynamics, 3rd ed. translated by A. Ogg., Dever, New
York.

Poincare, H. ( 1892), Themwdynamique. Georges Carre, Paris.

Rankine, W. J.M. (1888), A Manual of the Steam Engine and Other Prime Movers, 12 ed.
C. Griffin, London.
Roller, D. (1950), The Early Development of the Concepts of Temperature and Heat, Harvard
Universicy Press. Cambridge, Mass.
Rumford, B. T. (1798), "An experimental inquiry concerning the source of the heat which is
supplied by friction," Philos. Trans., Royal Soc., London, 88, p 80.
Thomson, W. (1840), An Outline of the Sciences of Heat and Electricity, H. Balliere, London.
Tisza, L. (1966), Generalized Thermodynamics, Paper l. MIT Press, Cambridge, Mass.
Tyndall, J. (1880), Heat, A Mode of Motion, Longmans, Green, and Company, London.
Ure, A. (l 818), New Experimental Researches on Some of the Leading Doctrines of Caloric,
William Bulmer and Company, London.