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R. H. WRIGHT
..
TEMPERATURE
When the two bodies which are at different temperatures are brought together, it is generally observed
that their temperatures change in such a way as eventually to become equal. From this we infer that something has passed from one body to the other. This
"something" is not temperature, for the change in
temperature of one body is not generally the same as
the change in temperature of the other. We caSl this
something heat.
If, in order to measure heat, we take as a unit that
quantity of the "something" which is required to raise
the temperature of one gram of water one Centigrade
degree, than the quantity of heat lost by the hotter
body and gained by the colder body can be measured.
I t is found that the two quantities are equal. While
we have defined a unit in which quantities of heat may
be measured and expressed, we have made no suggestion as to the nature of the thing called "heat."
So far it is simply sometliing whose entry into or
withdrawal from a system at constant volume will
cause its temperature to change, provided no new
phase appears during the addition and the relative
masses of the phases already present are unaltered.
,
The First Law of Thermodynamics is a generalization of the observed proportionality between heat and
the various forms of energy-kinetic, potential, electrical, and so forth. Regarding heat as a form of energy, the F i s t Law states that energy must be couserved in all processes, providing only that there is no
altefation in mass. From the First Law in this general
form, various laws (for example, those relating to
thermochemistry) may be deduced.
But while the First Law prescribes certain conditions
which must be fulfilledif a process should occur, it has
nothing to say about whether that process will in f a d
take place. The F i s t Law is, of course, not unique
in this. All the laws of physical and chemical science
with one exception are similar: they begin with the
word "whenever" and go on to describe what happens
afterward. They take the "when" for granted and are
silent about the "whether." The only law that enables us to predict whether or not a process which is
26i3
0, Q? = T I - T?
Ql
T,
where Q is the heat absorbed a t the higher temperature T I ,and Qz the heat absorbed a t the lower temperature Tz. At T I ,Q1is a positive number, heat entering
the gas; a t Tz,Qz is a negative number because the gas
gives up heat to the surroundings.
The d c i e n c y of a heat engine is defined as the
ratio of the heat converted into work to the heat supplied to the machine. Denoting efficiency by ?, then
the efficiencyof the Carnot cycle for a perfect gas is, by
definition,
= -
T'
CLAUSIUS' THEOREM
'&+a=0
..
T , T*
it follows that for all the Carnot cycles,
c(=)
then
= a constant
+ ds'
= 0
I t is not so easy to see how the entropy of systemplus-environment varies as a result of irreversible
changes originating in the system, and as the problem
is seldom adequately treated in textbooks it will be
examined in some detail here. Consider a system
which as a result of some irreversible process taking
place within it absorbs an amount of heat Q' from
surroundings a t a uniform temperature T'. (The
environment is assumed to be at a uniform temperature so that it will not undergo any changes except
as a result of something happening in the system.)
Because the environment is at a uniform temperature,
any heat entering or leaving it does so because of a
temperature gradient existing in the system. In such
a temperature gradient, the parts of the system immediately adjacent to the environment will be a t a
temperature only infinitesimally different from that of
the environment, and therefore any heat which enters
or leaves the environment does so reversibly. Hence
the change in entropy of the environment due to absorption of heat Q' by the system is,
..
ds = Q
T
so that
Q' = d U
The units in which such changes in entropy are expressed have the dimensions of energy divided by
temperature, usually calories per degree.
THE MOST GENERAL FORM OF THE SECOND LAW
and
Q = dU
+ W = beat absorbed
by system during the equivalent
reversible ehanp.
-$ W' (environment)
T1(dU
+ W ) - T ( d U + W')
TT'
T'(dU
+ W ) - T(dU + W')
and
dS
Insofar as a pure mechanical use of the entropy function in solving problems is concerned, the question of
what entropy is does not need to be answered. Nevertheless, it is desirable that the question be considered
because beginners, accustomed to conservation laws
of mass and energy, are often bewildered by a quantity which is far from being conserved and grows ever
larger.
I t will be remembered that while a given quantity of
work may always be completely converted into heat,
the converse is not necessarily true. The one-way increase in entropy in natural, irreversible processes is
merely a generalization of this one-sided convertibility
of work and heat. The kinetic theory regards heat
energy as residing in the unordered motion of molecules. On the other hand, those other forms of energy
which are called work are obtainable only when molecules possess some orderly motion or arrangement,
giving rise to kinetic or potential energy. The transformation of work into heat therefore involves a change
from ordered motion or arrangement to the disorderly
motion and chaotic arrangement known as thermal
agitation. It is not difficult to see in a general way
that the change from order to disorder should take
place naturally and spontaneously while the converse
should not.
Boltzmann approached the problem from this viewpoint and was able to show that the entropy of a given
system was a function of its probability, such that the
greater the entropy the greater is the probability.
Thus changes which increase the entropy of the world
involve a change from a molecular arrangement of
smaller probability to one of greater probability.
According to A. S. Eddiugton, "the practical measure of the random element which can increase in the
universe but can never decrease is called entropy."
THE IMPORTANCE OF ENTROPY TO CHEMISTRY
Universe, he
is only one law of nature which would
us to decide which was taken first: the later
picture is the One in which the entropy is greater.
Eddington uses the phrase "time's arrow" to express
this one-way property of time which enters the conceptud
scheme ,.died
science through the second L~~
of Thermodynamics only.
w e cannot do better than close this account of the
Second Law With the follo~ingquotation from Eddington's book.
ing it have been found. The chain of deductions from this simple
law have been almost illimitable; and it has been equally succesful in connection with the most recondite problems of theoretical
physics and the practical tasks of the engineer. Its special
feature is that the conclusions drawn are independent of the
nature of the microscopical processes that are going on. It is not
concerned with the nature of the individual; it is interested in
him only as a component of a crowd. Therefore the method is
applicable in fields of research where our iporsnce has scarcely
begun to lift, and we have no hesitation in applying it t o problems
of the quantum theory, although the mechanism of the individual
quantum process is unknown and at present unimaginable."~
"I wish I could convey to you the amazing power of this conception of entropy in sdentific research. From the Property
that entropy must always increase, practical methods of measur-
I E
~
~ - ~ nature
h N ~ of
~ the~physical
~
~
, lst ed.,
The Macmillan Co., Inc., New York City; Cambridge University
Press. Cambridge, England, 1928, p. 75.