Volume One of the Scientific Papers of J. Willard Gibbs, published posthumously in 1906, is devoted to Thermodynamics. Chief among its content is the hugely long and desperately difficult “On the equilibrium of heterogeneous substances (1876, 1878)”, with which Gibbs single-handedly laid the theoretical foundations of chemical thermodynamics.
In contrast to James Clerk Maxwell’s textbook Theory of Heat (1871), which uses no calculus at all and hardly any algebra, preferring geometry as the means of demonstrating relationships between quantities, Gibbs’ magnum opus is stuffed with differential equations. Turning the pages of this calculus-laden work, one could easily be drawn to the conclusion that the writer was not a visual thinker.
But in Gibbs’ case, this is far from the truth.
The first two papers on thermodynamics that Gibbs published, in 1873, were in fact visually-led. Paper I deals with indicator diagrams and their comparative properties, while Paper II shows how the relations between the state variables V, P, T, U, S, given in analytical form by dU=TdS – PdV, may be expressed geometrically by means of a surface.
Indeed Gibbs propels the visual argument further by pointing out that analytical formulae are strictly unnecessary for comprehending relationships between thermodynamic state variables, since they can just as easily be understood by applying graphical methods.
Gibbs’ advocacy of the visual approach found instant favor with Maxwell, who in the fourth edition of Theory of Heat devoted no less than 12 pages to an illustrated discussion of Gibbs’ thermodynamic surface, including the wild diagram shown at the head of this post. Maxwell’s enthusiasm was such that he sculpted a clay model of the surface, from which he made a plaster cast and sent it to Gibbs at Yale in 1874.
Besides his passion for using geometrical constructions to demonstrate connexions between quantities, Maxwell had an influential voice in the scientific world, and it is almost certain that he would have used it to promulgate the geometrical approach to understanding thermodynamic relationships that Gibbs had pioneered. But Maxwell’s death in 1879 at the early age of 48 brought such initiatives to a premature end.
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The exposure that Gibbs’ thermodynamic surface gained through the agency of Maxwell proved to be short-lived; no other contemporary scientist followed Maxwell’s lead. One explanation could be that Gibbs’ visual approach lacked appeal because — for reasons best known to himself — he described it in words, not pictures. Another could be that Maxwell’s illustrations of the surface were found too difficult: a joke reportedly circulated at the time that “only one man lived who could understand Gibbs’ papers. That was Maxwell, and now he is dead.”
Whatever the actual truth, the fact remains that none of the milestone literature in the post-Maxwell period took up Gibbs’ visual approach to understanding relationships between thermodynamic properties. Instead, the approach taken in textbooks by Max Planck (1879), GH Bryan (1909), JR Partington (1913) and most importantly by Lewis & Randall (1923) and Guggenheim (1933), was analytical.
Writing in 1936, the American mathematician Edwin Wilson (who had attended Gibbs’ lectures at Yale in 1901-2) argued that Gibbs’ entropy-temperature diagram in Paper I and the thermodynamic surface in Paper II were both victims of the inevitable choices that science makes as it evolves.
He commented: “Science goes on its way, picking and choosing and modifying. The trend of the last fifty years is not towards Papers I and II. Interesting as they are historically, and important because of the preparation they afforded Willard Gibbs for writing his great memoir III [On the Equilibrium of Heterogeneous Substances], there is no present indication that they are in themselves significant for present or future science.”
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JR Partington’s fascinating Text-book of Thermodynamics (with Special Reference to Chemistry) of 1913, although presenting the subject analytically, nonetheless points out the graphical origins of Gibbs’ early discoveries.
Commenting on Paper II, Partington writes: “In this very important memoir Gibbs shows that the conditions of equilibrium of two parts of a substance in contact can be expressed geometrically in terms of the position of the tangent planes to the volume-entropy-energy surface of the substance, and he finds that the analytical expression of this property is that the value of this function (U–TS+PV) shall be the same for the two states at the same temperature and pressure.”
For those of us educated in the analytical age, it is indeed remarkable to discover that the free energy function was first obtained by Gibbs using purely graphical methods, and that the pressure-temperature equilibrium relation G(α)=G(β) between two phases of a substance in contact was originally derived from geometrical considerations.
In fact the volume-entropy-energy diagram enabled Gibbs to reach a further conclusion of great importance to his future work in thermodynamics: namely that the volume, entropy and energy of a mixture of portions of a substance in different states (whether in equilibrium or not) are the sums of the volumes, entropies and energies of the separate parts. This suggested to Gibbs that mixtures of substances differing in chemical composition, as well as physical state, might be treated in a similar manner.
It was this clue from Paper II that gave Gibbs the conceptual springboard he needed for investigating chemical equilibrium, the subject matter of Paper III – On the Equilibrium of Heterogeneous Substances.
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Ok, so let’s take a closer look at Gibbs’ thermodynamic surface of 1873, realized by Maxwell in 1874. Each point on this surface describes the state of a body (of invariable composition) in terms of its volume, entropy and energy.
Now if we were to slice vertical sections of this surface perpendicular to the energy-volume plane, the curve of section would represent the relation between energy and entropy when the volume is constant; the tangent of the angle of slope of this curve of section is therefore (dU/dS)V. By similar reasoning, the curve of section of the surface perpendicular to the energy-entropy plane represents the relation between energy and volume when the entropy is constant. The tangent of the angle of slope of this curve of section is therefore (dU/dV)S.
From the fundamental thermodynamic relation dU = TdS – PdV, we can identify (dU/dS)V as the absolute temperature T which reckoned from zero is essentially positive, and (dU/dV)S as the pressure P which is reckoned negative when the energy U increases as the volume V increases.
The tangent plane therefore represents the same temperature and pressure at all points. Gibbs used this geometrical property of the model to show that if two points in the surface (such as ε’ and ε”) have a common tangent plane, the states they represent can exist permanently in contact. He then gave the analytical expression of this condition – that what we now know as the Gibbs free energy of states ε’ and ε” are equal. But he did not show the geometrical reasoning by which he reached his conclusion.
Maybe he thought we could work it all out in our heads, who knows. Personally I much prefer to see these things drawn – and especially in this case, for it is a rewarding exercise in solid geometry to see how the answer emerges. CarnotCycle is indebted to Ronald Kriz for making available the following explanatory diagram:
The common tangent plane through states ε’ and ε” cuts the axis of energy at a single point, marked ε. Beginning with the liquid state ε’, the length ε’–ε on the axis of energy is the sum of Δε’η (due to the entropy change) and Δε’v (due to the volume change).
Since the tangent plane defines t’ = Δε’η/η’ and –p’ = Δε’v/v’ we have
ε = ε’ – t’η’ + p’v’
The right hand member of this equation is composed entirely of state variables, and thus denotes a state function associated with the point ε’ on the thermodynamic surface.
Turning to the gas state ε”, the length ε”–ε on the axis of energy is the sum of Δε”η (due to the entropy change) and Δε”v (due to the volume change).
Since the tangent plane defines t” = Δε”η/η” and –p” = Δε”v/v” we have
ε = ε” – t”η” + p”v”
The right hand member of this equation is composed entirely of state variables, and thus denotes a state function associated with the point ε” on the thermodynamic surface.
An identical result will be obtained for all such pairs of points on the so-called node-couple curve, the branches of which unite at the isopycnic or critical point. Since the magnitude of the state function ε–tη+pv (in modern notation U–TS+PV=G) is the same for each pair, it is demonstrated that G(ε’)=G(ε”) is the analytical expression of the condition of coexistent equilibrium of separate states of a substance of invariable composition at the same temperature and pressure.
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