Fundamentals to frontiers
Fundamentals of thermodynamics
BY WILLIAM J. COAD
Virtually all energy consumed passes
through a thermodynamic process
somewhere from its initial form
change to its final use. Thus, to com-
prehend the problem of energy man-
agement, one must understand the
fundamentals of thermodynamics .
This is not to say that everyone
attempting to participate in the en-
ergy management problem must be
a skilled thermodynamicist, but he
must know enough about the science
to understand what is and what is
not possible. Strange as it may seem,
at times some of those who should
have a thorough understanding of
the science of thermodynamics
(physicists and mechanical engi-
neers) appear to overlook the funda-
mentals that separate the possi-
ble from the impossible or, more
constructively, that point to the
areas of probability in the solution
of problems at hand.
This column is intended to serve first law was called the ~ e r o t hl a ~ v .
as a brief review of three of the most
fundamental concepts of ther-
modynamics, called the laws of
thermodynamics. In the realm of
thermodynamics there have been
no scientific breakthroughs in the
past half century of technological
growth. The constraints on energy
systems possibilities that existed
then still exist: the cycles available
to change energy from one form to
another-or to move it from one
place to another-that existed then
still exist. There have been no dis-
coveries of expanded constraints
(new laws or abandonment of old
On this page each motirh, rlre author
shares / l l S engIneerlngp17110Soph4 bJ e.xp~or- be addressed starting with this law.
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McClilre & Associates and rlffillnreprnfes.
so, of mechan~calenpineerinp or ~ ( i s / ~ r n p - of the science of heat transfer, de-
ton L'ni!.ersiry, St. Lortis Lorris. M O .
Heating/Pip~ng/AirConditioning, February 1981
laws) o r of new cycles. T h e
technological advances have been
various types of interface technolo-
gies, notably materials and metal-
lurgy and nuclear source energy
conversion.
In discussing the laws, we will
present a classical statement as well
as a common interpretive statement
(the former for self-defense against
criticism from those skilled in the
science and the latter for clarity).
The classical statements are inten-
tionally worded in rather broad
terms because of the arbitrary na-
ture of some of our commonly held
concepts such as "temperature."
At the time of the formulation of
the first law of thermodynamics in
the latter 19th century, one princi-
ple was assumed to be evident and
was not establishedas ab'law" prior
to wording the first law. This princi-
ple was subsequently worded as a
law of thermodynamics in 1931 and,
being more fundamental than the
The zeroth law of thermodynamics
states:
Tlvo systems in thermal eqlrilib-
rium with a third system are in
t h e r m a l equilibrium tvirlz e a c h
other.
The interpretive statement of this
law might be that heat always flows
from a region of higher temperature
to one of lower temperature and
never from a region of lower tem-
perature to one of higher tempera-
ture. Some might think this fact so
evident that it doesn't warrant clas-
sification as a law, but how many
times haven't we heard reference to
cold energy flowing? The theory of
"heating energy" and "cooling en-
ergy" and their relative values must
The fundamental concept of the
time element of heat flow and its
dependence on finite temperature
differentials, which forms the basis
pends on this law. It is the lack of
properly placed recognition of this
concept that has led unknowledge-
able persons to a false understand-
ing of the potential of such concepts
as active solar energy systems and
cogeneration systems.
The first law of thermodynamics
is founded on the principle of the
conservation of energy and is often
stated as:
If any system undergoes a pro-
cess during ~ , h i c henergy i~ added
t o or remo13edfrom it (in the form of
work or heat), none o f the energy
udded is destroyed within the sys-
t e m , and none qf the energy re-
moi'ed is created ~ . i t h i nthe system.
Again, the interpretive approach
might simplify the statement to
"Energy can neither be created nor
destroyed," or "If the energy enter-
ing a system is not equal to the en-
ergy leaving the system, the dif-
ference is either stored in the sys-
tem o r removed from storage." It
must be remembered that the first
law applies to all energy subsys-
tems-regardless of their simplic-
ity, complexity, o r uniqueness.
Lack of understanding of this sim-
ple principle has led to concepts
such as "free steam" (see Funda-
mentals to Frontiers, HPAC No-
vember 1977) and overly optimistic
beliefs in the potential of direct solar
conversion and in the potential for
heatpumpapplications. Any person
setting about to address an energy
management problem, of any sort,
should initiate the study by defining
an appropriate "system" and then
performing a f?rsr law h u l a n c e ,
which is simply to equate the energy
into the system to the energy out of
the system. Until the first law bal-
ance is successfully completed, any
other effort is meaningless. This is
true for every undertaking from
conducting an energy audit t o
analyzing the most complex inte-
grated energy system to defining a
nation's energy problems (and, we
hope, policies).
81
Fundamentals to Frontiers
There are numerous classical
statements of the second law that
have evolved and been discussedad
infinitum. The second law relates to
two specific types of energy con-
version processes: one is the case
where heat or thermal energy is
converted t o shaft work (and
perhaps subsequently to electric-
ity), called a heat engine; the other
is the case where heat is made to
flow from a region of lower temper-
ature to one of higher temperature,
called a refrigerating process. Clas-
sical statements of the second law
relating to these two cases are:
N o engine whose workingflziid
undergoes a cycle can absorb heat
from a single reservoir, deli\-er an
equi\,ulent amount o f ~ , o r k and
, energy in either of these processes.
produce no otller effect. (Kelvin-
Planck statement.)
N o machine ~ 3 h o s e,t,orking
fluid undergoes a cycle can absorb
hentjronz one system, reject heat to
another at a higher temperature,
a n d produce n o o t h e r e f f e c t .
(Clausins statement.)
In the first case, that of the heat
engine, the "other effect" is found
to be the rejection of heat to a lower
temperature reservoir. I n the
second case, that of the refrigerat-
ing machine, the "other effect" is
the input of energy into the system
from a level or order higher than the
reject sink temperature (work or
shaft energy is a higher order).
Because of their dependence on
the constraints of the second law,
these types of processes (heat
engines and refrigerating machines)
are often referred to as second law
processes. A significant principle is
the Carnot principle, which fixes
the most achievable goals theoreti-
cally possible in the conversion of
The effectiveness of the use of en-
ergy is expressed by the term en-
ergy efficiency, q ~ which
, is the
ratio of work produced t o heat
provided.
The Carnot limits relate the high-
est possible efficiency attainable to
the absolute temperatures of the
HeatingIPipinglAir Conditioning, February 1981
sinks (T = high temperature sink, TO
= low temperature sink). The- Car-
not efficiency is:
qc = (T - To//T
The effectiveness of conversion
for refrigerating machines is ex-
pressed by coefficient of perfor-
mance, COP. If the refrigeration
achieved is the heat removed from
the low temperature sink, COP is
the ratio of refrigeration achieved to
external energy input and, again, if
T and To are the absolute tempera-
tures of the high and low tempera-
ture sinks, the Carnot COP is:
COP, = TJ(T - To)
Much attention has been given to
clever manipulation of second law
machines (heat pumps, cogenera-
tion, etc.) in recent years in an effort
to improve the utilization effective-
ness of energy resources. When
analyzing or trying otherwise to un-
derstand the potential of such con-
cepts or any other thermal energy
concepts, one must apply a n d
satisfy all three of these fundamen-
tal laws of thermodynamics. R