W. G.

Breck
Queen's University
Kingston, Ontario, Canada

A Simple Approach to the Second Law

W h a t follows presupposes that the first

law of thermodynamirs has been discussed with students and that ideas of reversible processes, heat, and
work have hren introduced. It is assumed that entropy has not been introduced by definition, although
el-en then the exercise is of value.
I t is common practice to carry out a reversible Carnot
ryde for one nlole of ideal gas (whose mode of working is
wrll nnderstood) with the proresses presented on a PV
graph or "work diagram." I t is found t,hat the effi,
by,
rirnry Z w l ~ is~ given

where T,, and T , refer to the hot and rold temperatures

on t,he ideal gas scale.
I t is also instrurtive to consider a cycle for any system
(whose mode of working is, in general, not understood)
operating reversibly with the proresses shown on a
graph of T against q,,,./T or "heat diagram" as in the
drawing:

A R isothermal ( Th)
IIC arli;btic (Th

qr.u =

T,)

CD isothermal (T,)
D.4 ndirthatic (T,

Most of the above is self-evident on the diagram

where, for a beginner, the isothermal processes look
isothermal and the adiabatic processes adiahatie.
Referring again to the drawing, the over-all work done
around the cyrle is equal to the over-all heat transferred
(since AE = O ) , which is the magnitude of the heat from
the source on the outgoing isothermal process (area
ABEF) minus the magnitude of the heat going to the
sink on the returning isothermal process (area DCEF).
Thus area ARCD represents either the over-all heat
transferred or the over-all work done around the cycle.
The effiriencyis:
= ares ABCD - length .4B(Th - l',) _
- -Th - T,
OD

are%ABEF

length AR(Th)

l'b

qh

qrCv = 0
qrev = 10

Th)

6
.
. =0

Around t,hr ryrle the rhange in internal energy, AE, is

Ry definition the effiriency is given by.

Kow define a thermodynamic temperature, 8, proportional to the positive value of the heat flow to or
from t,he system at that temperature. The positive
value of the heat flow to the system a t TI,is q , and the
positive value of the heat flow from the system at T,
is -q, (q, having a negative value). Hence,

and

As the upper temperature is raised, the ratio of the

above areas obviously increases; the efficiency is improved and will approach unity as T , approaches infinity. As the lower temperature is decreased, improved efficiency is again achieved and there is also a
limit. When T, approaches zero, the efficiency again
approaches unity; no heat is rejected a t this temperature, and all the heat absorbed a t the higher temperature is converted into work. To achieve any higher
efficiency than this would violate the law of conservation of energy (first law). In this respect the second
law is a particular ease of the first. Or, considered in
another way, any temperature lower than zero is unattainable.
To be more explicit, the efficiency expression is a
form of the second law which, in the lower limit
(T = 0)becomes,
w = 1, ( A E = 0)

By romparing equations (1) and (4) these thermodynamir temperatures are seen to correspond to temperatuws on the ideal gas scale.
This relation provides justification for the diagram.

and this is a particular statement of the first law. A

similar argument could be applied in the rase of the
upper limit.
Statement of the Second Law. At a sink temperature
of zero on the thermodynamic or ideal gas scales, it is
Volume 40, Number 7, July 1963

353

just theoretically possible to convert heat completely

into work by a cyclic, reversible process; whereas with
the sink a t any higher temperature this is impossible
and for the conversion of some of the heat to work a
price must be paid in the form of heat rejected into the
sink, but it is a bargain price if the process is reversible.
If the process is irreversible, the price is higher for less
work. This complies with experience.
Instructors in thermodynamics will immediately
identify the plot in the drawing as a TS graph. Examples are given in many textbooks and used extensively by engineers, so that nothing original is implied

354 / Journal of Chemical Education

except that by its use in the ahove manner the following are achieved: concepts are presented clearly on a
graph; the first and second laws are correlated; thermodynamic temperatures are introduced and related to the
ideal gas scale; the application to a refrigeration cycle
follows immediately. The student has herein used the
concept of entropy and so it should cause himless alarm
when it is now defined and given further meaning. The
ahove diagram is most adaptable to the presentation of
multiple and elemental Carnot cycles and the properties of q,,,/T as a state funrtion are apparent on the
diagram.