II.

THE PRINCIPLE OF CONSERVATION OF ENERGY

Critical studies that led to establish equivalence between mechanical work and h
eat were made in 1840 by James Joule in Great Britain. These studies were inspir
ed by the work Rumford had conducted nearly fifty years earlier and described in
the previous chapter. In a paper entitled EI mechanical equivalent of heat, whi
ch dates from 1843 and which was published in 1850, Joule presented unequivocal
evidence justifying the conclusions of Rumford. He wrote:
It has long been a favorite hypothesis that heat consists of a force or power be
longing to the bodies, but was reserved for the Count Rumford to conduct the fir
st experiments strongly in favor of this idea. The natural philosopher justly fa
mous for his ingenious experiments demonstrated that the large quantity of heat
excited by the piercing of a royalty can not be associated with a change that ta
kes place in the heat capacity of metal, so he concludes that the movement of th
e drill transmitted to the metal particles, thus producing the phenomenon of hea
t.
He pointed out also that if in the experiment of Rumford (see Chapter I) assumes
that the speed with which work is supplied (power) is, as Rumford, from one hor
sepower can be estimated that the work required to raise a pound (454 g) of wate
r, 1 F (18 º C) is approximately equal to 1000 ft. lb (1356 joules) which is not
very different from the value obtained in their own experiments, 772 ft-lb (104
6 joules). Joule's experiment was a feat of precision and ingenuity considering
the resources made available at that time. The device (Fig. 4) consisted essenti
ally of a rotating shaft with a series of blade, made eight arms revolving, rota
ting between four sets of stationary blades. The purpose of these vanes was stir
the liquid that was placed in the space between them. The shaft was connected t
hrough a system of pulleys and ropes to a couple very fine mass of known weight.
The experiment was to wrap the rope holding the masses on pulleys to put them a
t a certain height above the ground. When dropped the masses, the revolving shaf
t which in turn generated a rotation of the revolving arm shaking the liquid in
the container.
Figure 4. Apparatus used by Joule in measuring the mechanical equivalent of heat
. The known masses m are wound through the crank on the reel. The rope passes ov
er two pulleys P perfectly well greased. The height of the masses on the ground
is known, and the water temperature is controlled by the thermometer. This proce
ss was repeated twenty times and measured the final temperature of the liquid ag
itated. The walls of the vessel containing the fluid were sealed and were made o
f a thick wood properly treated to minimize any heat loss by convection and radi
ation. After a careful repetition of these experiments Joule concluded that: 1)
The amount of heat produced by friction between bodies, whether liquid or solid
is always proportional to the amount of mechanical work supplied. 2) The amount
of heat capable of increasing the temperature of 1 pound of water (weighed in a
vacuum and taken to a temperature between 55 º and 60 º F) by 1.8 º C (1 F) requ
ired to evolve the action of a mechanical force represented by the fall of 772 l
b (350.18 kg) for a distance of l foot (30.48 cm). Between 1845 and 1847 repeate
d these experiments using water, whale oil and mercury, obtaining that for every
pound of these compounds, mechanical equivalents were respectively equal to 781
.5, 782.1 and 787.6 lb, respectively. It concluded that:
These results, other previously electromagnetic existence of each other so close
ly coinciding with elastic fluids obtained and a machine left no doubt in my min
d about the relationship between force and work equivalent.
Joule's results are indeed the basis of what is known today as the first thermos
tat. In fact, what they do see is isolated from the outside, and supplied the sa
me amount of mechanical energy in different ways, the observed change in the sys
tem
is the same. In the case of Joule experiment this change is recorded by varying
the temperature of the system. Isolated from the outside systems are those that
are enclosed in containers whose walls totally prevent thermal interaction with
the surroundings, these walls are called ideal adiabatic walls. Note that in the
se experiments the system moves, its kinetic energy is zero,€or moving about at
ground level, its potential energy remains constant and yet the system has absor
bed a certain amount of energy! The key to the answer to this question is that i
f you believe in the principle of conservation of energy, the energy supplied is
converted into another type of energy. At this energy we call the internal ener
gy of the system. Joule's experiences served to extend this observation to any t
hermodynamic system and postulate that if any isolated system, ie no heat or mas
s exchange with its surroundings, we provide a certain amount of mechanical ener
gy W, it only causes a increase the system's internal energy U in an amount such
that ΔU:
ΔU = Wad
(1)
This equality, where the index "d" in W only serves to point out that the mechan
ical energy supplied to the system should be done only when this is isolated fro
m its surroundings, is the definition of internal energy U. The existence of thi
s quantity for any system, is the postulate known as the first law of the thermo
stat. It is important to stress that equation (1) proposed here is valid for any
system, water, oil, a metal, a gas, a piece of magnet, etc.. is an extrapolatio
n from the experiments of Joule, who verified it, as we have seen, only a few su
bstances. Moreover, we have written to invoke the principle of conservation of e
nergy, which essentially allows us to define what we mean by Δ U. It is worth no
ting that ΔU is a symbol that represents the change in internal energy between t
he initial state (eg water at 55 º F in the experiment of Joule) can be called U
i and internal energy in the final state (eg the water temp. final) denoted by U
f. Then, ΔU º Uf - Ui. Moreover, we have seen in Chapter I that if the system on
which we are conducting our experiments is at a different temperature than the
environment will be a natural tendency to establish a flow of heat between them.
In short if the experiments of Joule or similar on other systems will be carrie
d out without taking the precaution of isolating the system from its surrounding
s, observe that:
-W ΔU ≠ 0 The simplest example to which the reader can use is to heat the same q
uantity of water used by Joule, but putting it directly into the fire to get the
same variation in temperature. Taking the necessary precautions so that neither
the volume or pressure or other property of water change, we must conclude that
the same energy W that produced the change in U in the experiments of Joule, wa
s now supplied by the fire, ie, is a amount of heat Q. And in the case of mechan
ical energy is supplied under the conditions that displays the equation (2), it
is clear that the energy shortage, according to Carnot, to be taken into account
by the "loss" of heat caused by heat flux body or outside systems. Combining th
ese results we can write that:
(2)
ΔU - W = Q that is, energy is conserved in all sproceso if one takes into accoun
t the heat. This simple equation is nothing more than the expression of the prin
ciple of conservation of energy for thermostatic process requires several import
ant comments that show both their significance to his nature. The first comment
concerns the design of Q in equation (3). According to the experiments of Rumfor
d and Joule corresponds to a non-mechanical energy, just the one that is release
d by friction. In fact, Joule's own experiences show that the amount of heat Q d
efined in (3) only differs by a numerical factor of the traditional definition.
A calorie is defined as the amount of heat required to raise 1 g of water from 1
5.5 º C to 16.5 º C. But according to Joule, the amount of heat is equivalent to
mechanical work in units of 4187 joules MKS.2 Then, a calorie is equal to 4187
joules and the conversion factor from one unit to another is known as the mechan
ical equivalent of heat, often represented by J. Thus,
(3)
J = 4187 joules / calorie
The second comment concerns the origin of the equation (3). To get there we have
invoked the validity Unversal the principle of conservation of energy. So this
equation only summarizes the experiences of Rumford, Joule and Carnot. It is the
first law of the thermostat as is often claimed. But we insist, to discuss ener
gy conservation requires an operational definition of energy for any system. Thi
s definition, given by equation (1) and extends the experience of Joule to any s
ystem€is the first law of termostática.i The third comment concerns the nature o
f the terms in equation (3). First, ΔU corresponds, by definition, an amount tha
t does not depend on the nature of the process used to measure it. In this sense
has a hierarchy similar to other variables such as pressure p,
volume V, temperature T, etc. We say that a variable is able to describe the sta
te of a system or simply a state variable. It is therefore a quantity intrinsic
to the nature of the system that is chosen for study. Note that the definition (
1) only allows us to measure differences in internal energy which indicates that
similarly to the case of potential energy into mechanical or electrostatic pote
ntial, we can arbitrarily choose a reference point, ie, a state which we can ass
ign arbitrary a U value determined and can be zero. The other two terms Q and W
are of a totally different U. Only intervene in a system when we took him for a
given process which can make or receive or assign work and absorb heat. Clearly
the values of Q and W depend on the process in question and therefore neither is
a state variable. A pedestrian analogy may help understand the situation. In te
rms of a bank account, the financial solvency of a person can only be determined
by funds which has in it, that is, the money deposited in the bank. This quanti
ty describes or indicates the financial statement as to your available funds are
concerned, to that person. When this process occurs can be seen as turning or d
eposit checks or deposit bank and draw cash. At the end of the process the chang
e in its funds shall be the net sum of the amounts involved in handling checks a
nd cash. These two play the roles of W and Q whereas the money in the account is
U. (Here the reference state is obvious since U = O corresponds to have the acc
ount to zero.) So, in short, U is a state variable, Q and W have meaning only on
the scene and if there is a process. Often, even after all these considerations
, it is often heard the question: What is e1 heat? The answer is now obvious: it
is a form of energy that appears in a process whose origin is not mechanical. T
he continuous friction between two bodies, as noted Rumford, generates "heat." I
t is true that to produce that require rubbing of an external agent, is the musc
ular effort of the one who rubs the horse that was turning the drill in the expe
riment of Rumford, etc. But the very act of rubbing occurs as shown by Carnot en
ergy can not be converted into useful work fully. However, its inclusion in the
overall description of a process, in terms of energy balance is concerned, it is
imperative to be consistent with the principle of conservation of energy. Heat
is thus a form of energy in transit. Although it is common to use the term heat
in ways that appear to contradict the above. We say that heat "flows" from a hot
body to a cold as if it were a fluid. This is wrong and exactly what we should
rule for a proper understanding of equation (3). As in the case of the lighter d
iscussed in connection with the experiments of Joule, ΔU = Q represents the chan
ge in internal energy of the system formed by the two
(Or more) bodies as by differences in temperature between them occurs an exchang
e of mechanical energy of nature. Prior to its end this discussion of energy con
servation and the first law of the thermostat should be noted that despite his b
rilliant experience and the most obvious fact that equation (3) was behind all r
esults Joule was the first to reach this conclusion. Equation (3) was actually t
he product of deeper analysis than on the experiences of Joule, Carnot, and othe
rs did Sir William Thomson, later Lord Kelvin, Rudolf Clausius and early in the
second half of the nineteenth century. But even more curious than a year before
Joule had issued its findings in England, a young Native Medical Heilbronn, Germ
any. Julius Robert Mayer in 1842 suggested a general equivalence between the con
servation of all forms of energy. In his essay comments on the energies of inorg
anic nature using what we now call "thought experiments" pointed out that starti
ng from the principle that a cause is equal to its effect and considering that t
he energies are causes can take many forms, energies are indestructible and inte
rconvertible entities.€Although Mayer's method is entirely different from Joule
therefore had no opportunity to do experiments, their conclusions are very simil
ar. Mayer notes that there are forms of energy in nature that are not necessaril
y associated with movement (kinetic energy) or the lowering or raising of a body
(potential energy) and raises based on their first proposition, the problem on
other forms that energy can take. It shows that, as heat can be generated by fri
ction, must be a form of movement and therefore equivalent to a kinetic or poten
tial energy. Finally, the question arises about how to calculate the amount of h
eat for a given amount of kinetic or potential energy (the mechanical equivalent
of heat?). At this crucial point, Mayer presents a "thought experiment" and out
lines a calculation by which shows that J = 4200 J / Kcal, which considering the
imprecision of a method, is very reasonable when compared with equation (4) . H
owever, his work went unnoticed and did not receive any credit in the subsequent
20 years. To complete the list of distinguished and outstanding researchers who
claim paternity of the physical content of equation (3) we can not stop quoting
H. von Helmholtz who on July 23, 1847 read before the Berlin Physical Society a
paper entitled "Conservation of force." In this work, purely mathematical, it s
hows that the energy (work force) is preserved and that heat is a form of energy
, once again, the basic propositions behind the familiar equation (3). Thus, for
1847-1850, when the locomotive traveled great distances, rivers and lakes were
crossed by steamboat and the steam engine was in common use, just set out the th
eoretical basis of the equivalence between heat and mechanical work was banished
as the last remnants of the caloric theory and the concept was based
"Internal energy" as a postulate now called the first law of the thermostat. Rem
ained unanswered, however a second question raised by Sadi Carnot in 1824: What
fraction of heat transferred to a heat engine is good enough? His answer led to
physicists of the time or the second law of thermostatic and the still controver
sial and elusive concept of entropy.
NOTES
2 The results of Joule for water is about 780 ft-1b for 1lb (H2O = 453.6 g) by 1
° F = 1.8 º C. Since July 1 = 0.7376 ft-lb in the MKS system is mechanical ener
gy.