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McGlashan
University
of
Exeter
Exeter, England
LUWS of Thermodynamics
Another source of pedagogic muddle is the widelyheld misconception that thermodynamics approaches
closely the ideal of a purely deductive science, deducible
like Euclidean geometry from a small number of axioms
which can he expressed in words, though much
progress has been made toward the axiomatization of
thermodynamic^,^ the mathematical structure has
still not been completely separated from the physical
content. But none of that need concern the undergraduate. Provided that having made our entry, we
then rely quite formally on deduction, we may choose
to enter the subject at any level of sophistication, just
as we commonly choose to introduce mechanics to
students for the first time through Newton's laws
of motion rather than through the principle of least
action. A rare undergraduate may some day want to
interest himself in the logical foundations of thermodynamics. I n the meantime he will come to no harm
while he listens to us teaching the others, and him, how
to use thermodynamics in his chemistry. At least
in this university I hope that thermodynamics will
always he taught as part of an experimental science and
never as muddled metaphysics nor bogus history.
Now what is thermodynamics? One way of answering that question is by a comparison of thermodynamics
with mechanics. I n mechanics one deals with three
independent basic quantities: mass, length, and time.
In electromechanics, by which I mean mechanics plus
electricity and magnetism, that number is expanded to
four: mass, length, time, and electric current. Thermodynamics includes the whole of electromechanics hut
Briefly,
AU=w+p
Assume that a substance exists for which simultaneously:
(1): P V = nRT
and
i.e., (Za): (aU/aV),
(2): dU = CvdT
0 and (2b): (aUlbT)v
Cv = Cv(7')
Thn:
q/T
dU/Y - w/T
Cv(T)dT/T
prer/T = Cv(T)dT/T
nRdVIV
Therefore for the reversible expansion of a substance defined by
hoth (1) and (Z), p/T depends only on the initial and find temperatures, and an the initial and final volumes, and so for a
closed cycle Z(q/T) = 0.
' GUQGENHEIM,
E. A,, Bullet& of the Institute of Physics,
June 1955.
3 LANDSBERG,
P. T., "Thermod~amics," Interscience
Publishers, s. division of John Wiley & Sons, New York, 1961.
226
where q' is the heat leak, which is kept as small as possible. We now cool the calorimeter back to 25C
and then use ordinary electromechanical methods to
measure the work w needed to increase the temperature
by 68 so that:
Up(25'C
where q is the flow of heat into the body from any bodies
a t different temperatures with which it is in contact,
(its surroundings), and where we have distinguished the
old electromechanical energy E from the thermodynamic energy U . It is only when E is independent of
temperature that E and U are the same.
Equation (1) expresses the first law. It is just the
law of conservation of energy expanded so as to include
energy changes caused by temperature diierences. But
is is incomplete until we learn how to measure the qnantities in our equation. In thermodynamics we add to
the electromechanical armory of measuring devices or
meters, such as cathetometers, dynamometers, manometers, and potentiometers, two new ones: thermometers which are used to measure temperature, and
calorimeters.
Expositions of calorimetry, especially in textbooks of
physics, are still hedged about with antique concepts
like the so-called mechanical equivalent of heat which
belong, like phlogiston, to the time when the first law
of thermodynamics was not yet understood. It is
commonly, hut wrongly, supposed that in calorimetry
one measures heat. On the contrary, the whole art
of calorimetry depends on making the heat q as small as
possible, or at least as reproducible as possible, and
preferably both. I n a calorimetric experiment one
measures only changes of temperature and amounts of
work, and then uses the first law to derive values for
energy changes. The key to understanding calorimetry
is, as usual in science, to think about exactly what one
does in a real experiment in a real laboratory.
Let us use a calorimeter to measure the difference
AU = UP
- Up,
+ *'(leak) = 0
+ qU(leek)
.
I
+ (q' - q")
-w
227
where we have assumed that any work is pressure (P) volume ( V )work,' where T is called the thermodynamic
temperature and is here introduced for the first time
along with S which is called the entropy, and where ,A*
is called the chemical potential of the substance i and
n, is the amount of that substance, and we have
summed over all substances present.
Of these quantities P and V can be measured by
ordinary mechanical methods and n, by ordinary chemical methods. But are T, S, and pr completely and
independently defined by this equation? They are if,
and only if, we can derive from the equation a recipe
for the measurement of each. We find that we can
derive recipes for measuring ratios of thermodynamic
temperatures T, by means of a special kind of thermometer called a gas thermometer, and for measuring
differencesof entropy or of chemical potential by means
of electromechanical, thermometric, and calorimetric
measurements.
It turns out to he convenient to make some new definitions:
H=U+PV
A=U-TS
G=H-TS
VadPCI
dS( = Z',dSm) 2 0
( U and V constant)
(2b)
>, 0
( H and P constant)
<0
dG < 0
( T and V constant)
dS
dA
(Tand P constant)
Work
Matter
Pressure
Chemical
potentiai
Temperature
+ TcdSm + Z&dnie
These equations, though convenient, of course contain nothing new. We might note in passing, however,
that the quantity called "energy" in textbooks of
physics, such as the "energy" E = Q21/2eA of charging
a condenser is actually a change in free energy and not
of energy. The free energy turns out to be the thermodynamic analogue of the electromechanical potential
energy, and is both a more familiar and less complicated
quantity than the energy U.
We must now complete our statement of the second
law. Any body can be regarded as being made up of
one or more phases. We must now distinguish between
such a body which is in internal equilibrium and one
which is not. If the body consists of a cup of water with
a spoonful of sugar lying a t the bottom it is not in internal equilibrium because, without any help from us,
the sugar will dissolve in the water. If one part of a
body is hot and another cold, the body is not in internal
equilibrium because, without any help from us, the hot
part will cool and the cold part will warm up. If the
body consists of a beaker containing a solution of
acidified permangauate a t room temperature to which
an excess of a solution of an oxalate has just been added
then the body is not in internal equilibrium because,
without any help from us, a chemical reaction will occur
and go on until virtually all the permauganate has been
reduced to manganous ion.8
228
Figure 1 b
Wall permeobie to
the substance i
Figure l c
(Clapeyron's relation)
throttle
Figure 2.
I P. S
.
I pa
Second example:
A,vU zz A d l
- T(a/n)AdV
Another statistical mechanical theory of liquid mixtures leads to predictions about the energy of mixing
AmpU a t constant total volume. This is a difficult quantity to measure. When liquids mix, the total volume
changes. Not, i t is true, by much, but the pressures
needed to prevent such changes are nevertheless often
hundreds of atmospheres. I n other words we should
need a very strong calorimeter to measure A,,U directly. The quantity we can and do measure is
AdU the energy of mixing at constant pressure. Provided we know also the expansivity cu and compressibility K and the volume change on mixing a t constant
pressure A-V, a11 of which quantities are relatively
easy to measure, then we can use the equation to calculate values of A,,U which we can then compare with
the t h e ~ r y . ~
Third example:
V - T ( b v / h T ) ~= (bH/bP)7
-/
b - a/&
+E
Here we start with amounts a, b, and c of nitrogen, hydrogen, and ammonia respectively, and suppose that a t
a time t after the introduction of a catalyst the amount
of ammonia has been increased by the chemical reaction
ehown from c to c f. What if anything does thermodynamics tell us about the equilibrium value of f?
' O FRANCIS,
P. G., MCGLASAAN,
M. L., AND WORMALD,
C. J.,
NEI, Reporl, 1963, no. 122: and forthcoming publications.
229
(4)
- ASYT
0)
plus one calorimetrically measured macroscopic quantity. The need for this one calorimetric quantity arises
because, in the case of enthalpies, in contrast to entropies, we do not have a reliable way of calculating the
difference of enthalpy from the enthalpies of the separate substances each measured from some "base
camp."
For the reaction 1 / 2 N ~ 3/zHz NH3 the formula
takes the form:
T*
A,H(T',PJ-= 1 a h )
RT*
i =1
e/T'
3
a/T*
+ + {exp(B/T*) - l l N , + ~ ] e x p ( B / T * )- I 1 m l
harmonic, and the omission of contributions from electronic and nuclear modes. He would then have to
examine the difference to be expected between values of
K measured on the real gas mixture a t 10 atm and those
for an ideal gas mixture. Finally he would have to
examine critically the accuracy of the measured spectroscopic quantities, of the calorimetric quantity
(which is probably the main culprit), and of Larson and
Dodge's direct measurements of the equilibrium constant. If he has a good grasp of both the theoretical
and the experimental aspects of chemical thermodynamics and statistical mechanics he will be able to make
a good job of this, but not otherwise.
The answers to the two questions we asked about
chemical equilibrium constants form the principal
achievement of thermodynamics and statistical mechanics in chemistry.
What Entropy Does Not Mean
231
Figure 4
232
will lead to quitc different values and cvcn signs for the
entropy changes of ordinary reactions.
Some of this kind of misunderstanding has even
rubbed off on the layman. I suspect that Lord Snow's
choice of the second law of thermodynamics as a test
of scientific literacy for the humanist (he said14 it was
"about the scientific equivalent of: Have you read a
work of Shakespeare's?") derives from just such a misunderstanding about the meaning of entropy, and especially from its supposed implications with respect to
the Fate of the Universe.
Since I regard these supposed implications as nonsensical I can hardly be expected to give a coherent account of them, but I think the argument runs something
like this. Any process which actually takes place in
the universe increases the entropy of the universe.
Increase of entropy implies increase of mixed-upness.
Ergo the inevitable fate of the universe is a state of
more and more mixed-upness. I n the end there would
be neither sea nor dry land, but I suppose a kind of porridge. But then there would be no earth and no
heavens but just some species of strnctureless particle
distributed uniformly throughout space. Then the
universe would have suffered the so-called "heat-death,"
and chaos would be come again.
Now I suppose that if thermodynamics could bc
shown (but how?) to be applicable to the universe, and
if the universe were known to he a bounded and isolated body (whatever that might mean in the case of
the universe), then we might deduce that the universe
would eventually reach a state of complete thermal,
mechanical, and chemical equilibrium. But there is
no scientific reason to suppose that the universe is
a hounded isolated hody. Isolated? Isolated from
what indeed? And even if it were, there is no reason
to suppose that thermodynamics, which is an experimental science, can be applied to bodies as large as the
universe. Clausius's famous statement: "Die Entropie
der Welt strebt einem Maximum zu" is, to say the
lea&, misleading. The pessimistic idea that the fate
of the universe is chaos no doubt has an appeal to a
certain kind of mind but it is a matter of faith which has
no support from the science of thermodynamics.
Acknowledgmenf