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1. Introduction
2. The Authors
Thermodynamics was published by McGraw-Hill of Table 1. Early monographs dealing with the theory of
New York in 1923 using the same characteristic brown chemical thermodynamics.
cover and black and gold spine label that would later
become the hallmark of its International Chemical Date Author Title Approach
Series. The book, in sharp contrast to Lewiss much
shorter monograph on Valence, was 653 pages in 1884 vant Hoff Etudes de dynamique Arbeit or
length and consisted of 42 chapters and four appendi- chimique affinity
ces. It was the culmination of a research program un-
dertaken by Lewis in 1899 which was directed at the 1885 Liveing Chemical Equilibrium energy
clarification and quantification of chemical thermody- the Result of Dissipa- dissipation
namics as summarized in a 55-item bibliography of the tion of Energy
publications of Lewis and his students appended to the
1886 Duhem Le potential thermo- chemical
book.
dynamique potential
4. The Context 1893 Nernst Theoretische Chemie Arbeit or
affinity
In chapter 1 Lewis noted that the development of
chemical thermodynamics was characterized by three 1893 van Laar Die Thermodynamik total
distinct periods: in der Chemie entropy
1.
The establishment of the basic laws of thermody- 1897 Planck Vorlesung ber total
namics (1842-1865). Thermodynamik entropy
3.
The quantification of chemical thermodynamics via
a fusion of theory with experimental data (1905-1923).
The foundations of the third period were actually
laid nearly a half century before the formal develop-
The first of these periods began with the enuncia- ment of thermodynamics itself with the first measure-
tion of the first law of thermodynamics by Mayer ments of heats of combustion by Lavoisier and Laplace
(1842), Joule (1843), and Helmholtz (1847) in the (1783) and with the extensive measurements of heats
1840s and the equally important enunciation of the of reaction and specific heats within context of the ca-
second law by Clausius (1850) and Kelvin (1852) in loric theory during the period 1840-1854 by such
the 1850s. It was completed in 1865 when Clausius thermochemists as Hess, Andrews, and the French
explicitly reformulated the second law in terms of his team of Favre & Silbermann, leading to the enuncia-
famous entropy function. tion of the law of constant heat summation by Hess in
The second period began with the first application 1840. These results were translated into the context of
of the entropy function to the phenomenon of chemical the first law of thermodynamics and greatly augmented
equilibrium by Horstmann in 1873, followed by its by the work of Thomsen (1882-1884), and Berthelot
application to heterogeneous phase equilibria, the in- (1879, 1897) during the last half of the 19th century.
troduction of the phase rule, and the introduction of
Thus, by the turn of the 20th century there already
both the chemical potential and free-energy functions existed an extensive data bank of quantitative enthalpy
by Gibbs in the period 1874-1878. Of equal impor- values. However, this remained largely localized in a
tance was the further elaboration of the Arbeit and free separate literature dealing with thermochemistry rather
energy concepts by Helmholtz (1882) in the 1880s and than with chemical thermodynamics proper, and the
the translation of Gibbs work into both German (Ost- books listed in Table 1 remained primarily theoretical,
wald 1892) and French (Le Chatelier 1899) in the rather than practical, in their orientation, in large part
1890s. because that theory showed that what was important in
2
THE QUANTIFICATION OF 20TH-CENTURY CHEMICAL THERMODYNAMICS
A = Q[(Teq - T)/Teq]
Figure 4. Fritz Haber (1868-1934).
in which S appeared only as Q/Teq, whereas Nernst
methods may spare other workers in this field much of always used the temperature dependency of the Arbeit,
the arduous labor which we ourselves have spent. (dA/dT), in place of -S when writing the equation for
Helmholtz free energy:
And lastly, it became apparent that these purely techni-
cal aspects were best appreciated if they were first A = U + T(dA/dT) = Q + T(dA/dT)
prefaced by an introductory overview of the underlying
principles of thermodynamics: In keeping with these preferences, an informal survey
of 17 physical chemistry texts published during this
Finally, these methods themselves require a fuller un- period showed that 11 or 65% did not list entropy as a
derstanding of the underlying principles of thermody- index entry, whereas 5 of the remaining 6, though list-
namics than most elementary treatises afford... Partly ing it once, devoted little more than a paragraph to the
for this reason, and partly perhaps because of a temp- subject. Likewise, the 1921 text by MacDougall has
tation to present in a somewhat novel manner the basic only three index entries for free energy, two of which
principles of thermodynamics, we devote the first part refer to Helmholtz free energy and only one to Gibbs
of our book to a presentation of the elements of ther- free energy.
modynamic theory.
In sharp contrast, the Lewis-Randall text is firmly
and unambiguously based on the Gibbs free-energy
In keeping with this plan, Chapters 1-26 of the final function (symbolized as F rather than as G) and
book dealt with theory and chapters 27-42 with meth- formulated in terms of explicit enthalpy and entropy
ods and data. terms:
5. Innovations F = H - TS + RTlnQ
4
THE QUANTIFICATION OF 20TH-CENTURY CHEMICAL THERMODYNAMICS
partial molal properties in discussing the thermody- tated Thermodynamics to his coauthor and, not unex-
namics of solutions, whereas this topic is missing from pectedly, like his monograph on Valence, it contains
the MacDougall text. many superb examples of the Lewis style in techni-
cal writing, of which I have time to quote only a few
2.
The Lewis-Randall text extends the concept of representative examples:
standard states (X vs X) beyond the Nernst equa-
tion (E vs E) so as to also include the free energy, 1.
On the quality of the thermodynamic literature:
enthalpy and entropy functions. The MacDougall text
does not. We have seen cyclical processes limping about ec-
centric and not quite completed cycles, we have seen
3.
Building on the thermochemical tradition of the exact laws of thermodynamics uncritically joined to
Berthelot (1879, 1897) and Nauman (1882), the Lewis- assumptions comprising half truths or no truth at all,
Randall text essentially perfects our current suffix con- and worst of all we have seen ill-begotten equations
ventions for indicating physical states (e.g. CO2(g), supported by bad data.
H2O(l) Fe(s)). The MacDougall text does not.
2.
On the question of thermodynamic nomenclature:
4.
The Lewis-Randall text deals with the issue of
nonideality through the introduction of such concepts We presume that every author regards his own as the
as fugacity (1901), activity (1907), and ionic strength best of all possible notations. While we may privately
(1921). The MacDougall text mentions activity but be victims of some such hallucination, all that we care
neither fugacity nor ionic strength. to claim publicly is that our system of nomenclature
and notation is one which has gradually developed
5.
In sharp contrast to the Lewis-Randall text, the through many years of practical work and the teaching
Haber-Nernst tradition deals with the quantification of of many types of students, and that it has proved satis-
affinity in terms of a power expansion of the tempera- factory.
ture dependency of either the Arbeit function or the
integrated vant Hoff isochore: 3.
On the intended uses of the book:
InK = Q0/RT + (/R)lnT + (/R)T + ... I/R Our work is not a textbook in the ordinary sense of the
term. A textbook is a sort of table dhote to which any-
rather than in terms of explicit tabulations of F, H one may sit down and satisfy his hunger for informa-
and S values. tion with no thought of the complex agricultural proc-
esses which gave rise to the raw materials, nor of the
6.
The Lewis-Randall text contains a table of S val- mills which converted these raw materials into food-
ues at 298 K for 75 elements and a table of F values stuffs, nor of the arts of cookery responsible for the
at 298 K for 140 ions and compounds. The Mac- well-prepared meal which has been set before him. It
Dougall text contains no entropy or free energy data, has not been our desire to offer such a repast to the
only tables of heats of formation and various phase reader.
diagrams a topic that is completely missing from the
Lewis-Randall text. 4.
And, most famous of all, the opening paragraphs of
the books preface:
Points 5 and 6 represent the most defining feature
of the Lewis-Randall text and are what distinguish it There are ancient cathedrals which, apart from their
from all of its predecessors. Whereas the primary consecrated purpose, inspire solemnity and awe. Even
contact with experimental data, if any, for most ther- the curious visitor speaks of serious things, with
modynamic texts written in the period 1884-1922 was hushed voice, and as each whisper reverberates
via the phase rule and various phase diagrams, for the through the vaulted nave, the returning echo seems to
Lewis-Randall text this contact was made for the first bear a message of mystery. The labor of generations of
time via the use of tabulated free energy and entropy architects and artisans has been forgotten, the scaf-
values. folding erected for their toil has been removed, their
mistakes have been erased or have become hidden by
6. Prose Style the dust of centuries. Seeing only the perfection of the
completed whole, we are impressed as if by some su-
As with many of his papers and reviews, Lewis dic- pernatural agency. But sometimes we enter such an
5
WILLIAM B. JENSEN
7. The Legacy
6
THE QUANTIFICATION OF 20TH-CENTURY CHEMICAL THERMODYNAMICS
7
WILLIAM B. JENSEN
2.
G. N. Lewis, M. Randall, Thermodynamics and the
9.
W. Latimer, The Oxidation States of the Elements and
Free Energy of Chemical Substances, McGraw-Hill: New their Potentials in Aqueous Solutions, Prentice-Hall: New
York, NY, 1923. York, NY, 1938.
3.
W. L. Jolly, From Retorts to Lasers: The Story of
10.
F. R. Bichowsky, F. D. Rossini, The Thermochemis-
Chemistry at Berkeley, College of Chemistry, University of try of Chemical Substances, Reinhold: New York, NY, 1936.
California: Berkeley, 1987, pp. 99-101.
11.
F. D. Rossini, D. D. Wagman, W. H. Evans, S.
4.
Specific quotes from reference 2, pp. vii, viii, ix, xi, Levine, I. Jaffe, Selected Values of Chemical Thermodynamic
2, 5. Properties, NBS Circular 500, U. S. Government Printing
5.
G. N. Lewis, M. Randall, Thermodynamik und die Office: Washington, DC., 1952.
freie Energie chemischer Substanzen, Springer: Wein, 1927.
6.
A. Lachman, Borderland of the Unknown: The Life Update
Story of Gilbert Newton Lewis, Pageant Press: New York,
NY, 1955. I have only recently become aware of the 1996 study by
7.
G. N. Lewis, M. Randall, K. Pitzer, L. Brewer, Ther- Helge Kragh and Stephen Weininger (Sooner Silence than
modynamics, 2nd. ed., McGraw-Hill: New York, NY, 1961. Confusion: The Tortuous Entry of Entropy into Chemistry,
8.
M. Randall, Free Energy of Chemical Substances, Hist. Stud. Phy. Bio. Sci., 1997, 27, 91-130) which provides
Activity Coefficients, Partial Molal Quantities, and Related an even more detailed context for the emergence of Lewis
Quantities, in E. W. Washburn, Ed., International Critical textbook and independently reaches many of the same con-
Tables of Numerical Data, Physics, Chemistry, and Technol- clusions as I have in this and other papers dealing with the
ogy, Vol. 7, McGraw-Hill: New York, NY, 1930, pp. 224- history of chemical thermodynamics.
313.