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Vol. 87 No. 7 July 2010
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Journal of Chemical Education 691
10.1021/ed1001976 Published on Web 05/17/2010
In the Classroom
From Joule to Caratheodory and Born: A
Conceptual Evolution of the First Law of
Thermodynamics
Robert M. Rosenberg
Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113
rmr921@northwestern.edu
Since the first law of thermodynamics was first formulated
in the 19th century, it has had a substantial evolution, mainly in
the definition of heat and in the number of terms requiring
independent definition. This essay describes the course of this
evolution.
The 19th Century Development
The first law arose after almost two centuries of controversy
about the nature of force, heat, motion, energy, kinetic energy,
and potential energy. This era is engagingly described by Rogers
inAnInformal History of the First Lawof Thermodynamics (1).
Our discussion will start withJames Prescott Joule's experiment on
the mechanical equivalent of heat (2).
James Prescott Joule (1818-1889) was a brewer and
physicist who did his experiments in his private laboratory. Joule
carried out his experiments starting in 1843 at a time when the
caloric theory of heat was being challenged, and heat was
beginning to be considered as a form of motion rather than
the substance caloric. He measured the change in temperature
of a water bath when work was performed against friction, by a
falling weight driving a paddle wheel, or by passage of an electric
current through a resistor immersed in the bath. His major
finding is that the change of temperature for a given quantity of
work is the same no matter what kind of work was done. Joule
clearly used the change in temperature as a measure of the
quantity of heat. He concluded that there is a fixed relationship
between the quantity of heat and the quantity of work, hence, the
mechanical equivalent of heat. Unknown to Joule, the concept
had already been propounded by Clapeyron (3) in 1834 and J. R.
Mayer (4) in 1842, but these ideas were ignored. Later, Mayer
applied to the biological world what would later become the first
law of thermodynamics.
When Hermann von Helmholtz (5) and Rudolph Clau-
sius (6) extended the work of Joule to include the concept of
energy of a system, they expressed the first law of thermodynamics
as (in modern form),
dU DQ DW 1
which introduces the concept of the energy of the system, U, in
terms of work, W, and heat, Q. They make the additional
statement that for a given change of state, dU is a constant,
although DQand DWmay vary (the capital Dfor heat and work,
in contrast with the lower case d indicates this distinction
symbolically). In this distinction, they introduced the concept
of a state function, U. The conservation of energy follows from
eq 1, since in the absence of interaction with the environment in
the formof heat or work, dUis equal to zero. All these discussions
of the first law take for granted that the experimental quantities
to be defined are work and heat, with work defined mechanically,
and heat defined in terms of temperature change and heat
capacity.
J. Willard Gibbs, in his classic treatise (7) in 1875, like many
other authors, takes for granted that U is the sum of the heat
exchanged and the work done. But Gibbs gives little considera-
tion to operational definitions of these terms. When, in 1897,
Max Planck (8) reinvented modern thermodynamics without
knowledge of Gibbs' work,
1
he also used heat and work as the
primary experimental quantities, with the statement of the lawof
conservation of energy as
U Q W 2
G. N. Lewis and Merle Randall, in their classic work (9), also take
the conservation of energy as a postulate, with the conclusion that
U is a state function and that eq 2 is a statement of the first law.
An alternative version for the earlier system has been
proposed by Henry Bent (10). He designates the mutually
interacting parts of the universe as (i) the system, (ii) the thermal
surroundings, and (iii) the mechanical surroundings. These three
entities are considered to be isolated fromthe rest of the universe.
He then expresses the total energy change as the sum of the
energy changes in the three entities,
U
total
U

U
wt
3
where represents the system, represents the thermal surround-
ings, and wt represents the mechanical surroundings, essentially a
statement of the conservation of energy. In this convention, U
wt
is determined by measurement of mechanical quantities such as
the change in height of a weight, and U

is determined by a
separate experiment such as Joule's of the mechanical equivalent of
heat that involves only and wt. Thus, Joule's experiment does not
involve a system according to this point of view. Bent defines Q
as -U

and W as -U
wt
, so that
U

Q W 4
essentially the conventional formof the first lawof thermodynamics,
although he prefers not to use the symbols Qand W. In essence, this
convention takes the conservation of energy as a postulate, rather
than using Joule's experiment as evidence that U is a state function.
Modern Developments
Constantin Caratheodory (1873-1950) was Professor of
Mathematics at the University of Munich from 1924 to 1950.
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In the Classroom
In 1909, he (11) tried to unify and simplify the treatment of the
first law of thermodynamics by reducing thermal concepts to
mechanical terms. From this point of view, Joule's experiment is
assumed to be carried out adiabatically because Joule made very
careful corrections for the small quantities of heat transferred
between system and surroundings.
2
The system is defined as the
water in the tank, the device that transfers the work to the system,
and the wall of the tank. The surroundings include the devices
that do work on the system; in this case, the pulley and weights or
the electrical circuit that does electrical work. His results
demonstrate that adiabatic work of a given quantity produces
the same change in temperature no matter how the work is
produced, whether by friction, by turbulent motion of water, by
compression of gas, or electrically. Because the adiabatic work is
independent of the kind of work that is done, it is equal to the
difference between two values of a state function U, which is
named the energy, so that the energy change is defined in
differential form as
dU DW
adiabatic
5
where D is used with W because it is not in general a state
function.
If a change of state is not carried out adiabatically, the work
is no longer equal to dU. The difference between dU and DW is
attributed to the transfer of thermal energy to or from the
surroundings as a result of a difference of temperature across a
thermally conductive boundary, and we call this energy transfer,
heat, DQ.
3
This concept was first put forth by Max Born (12).
Max Born (1873-1970) won the Nobel Prize in Physics in
1954. He defined heat in terms of energy and work as
DQ dU -DW 6
or
DQ DW
adiabatic
-DW 7
The statement that Uis a state function together with eqs 5 and 6
constitute the first law of thermodynamics according to this
point of view. In principle, then, one can map the values of U,
relative to some chosen reference state, by carrying out changes of
state that can be reached by an adiabatic process. It has been
pointed out that it is not possible to go from one adiabat to
another reversibly without violating the second law of thermo-
dynamics, so that eq 1 only describes values of U along a single
adiabat (13). However, it is possible to go from one adiabat to
another irreversibly. If one carries out that change of state in the
spontaneous direction quasi-statically, with infinite slowness,
one can determine W
adiabatic
and hence U in going from one
adiabat to another. Thus, all values of U in the coordinate space
P, V, T, can be mapped (12-17).
The most common method for measuring heat is with a
calorimeter. Most calorimeters are adiabatic, with the system
defined as the calorimeter and the surrounding water bath. The
value of dU is obtained by measuring the quantity of electrical
work that is required to produce the same temperature change in
the system as occurred when the state changed. The measure-
ment is actually one of the adiabatic work, DW
adiabatic
, where the
work is equal to dU or dH, depending on whether the change is
carried out at constant volume or constant pressure,
dU DW
electrical
constant volume 8
where DW
electrical
is the infinitesimal electrical work required to
produce a given infinitesimal change in temperature and therefore a
given change of state. If the calorimeter is held at constant pressure,
dU DW
electrical
-PdV 9
where -PdVis the pressure volume work. Because Pis constant, we
can add -VdP to the right side of eq 9 without its value changing,
and obtain
dU DW
electrical
-PdV -VdP
DW
electrical
-dPV 10
or
dU dPV dU PV DW
electrical
11
The parenthesized sum, (U PV) is a state function, the familiar
enthalpy, H, so that
DW
electrical
dH 12
for a constant pressure calorimeter. Thus, although the name
calorimeter implies the measurement of heat, as a remnant of the
caloric theory of heat, the calorimeter actually measures
W
adiabatic

Z
T
2
T
1
DW
adiabatic
dT
which is equal to U or H.
An important question is: what is the change of state to
which the value of U or H applies? Consider that we are
carrying out the reaction
XY f Z
The change of state that occurs in the calorimeter is
XT
1
YT
1
f ZT
2
reaction A
But we wish to know U for the reaction
XT
1
YT
1
f ZT
1
reaction B
We can obtain Reaction B by adding reaction C to reaction A,
where reaction C is
ZT
2
f ZT
1
reaction C
Therefore,
Ureaction B Ureaction C Ureaction A
because U is a state function. But
Ureaction C
Z
T
1
T
2
DU
Z
DT

V
dT 13
where (U
Z
/T)
V
is the conventional isochoric heat capacity C
V
.
Capacity is a reference to the caloric theory of heat, implying
that heat is contained in a system. The integral in eq 13 is the
electrical work used to change the temperature of Z from T
2
to
T
1
in the calorimeter in which the reaction was carried out. If T
2
is greater than T
1
, then no addition of electrical work will change
the temperature from T
2
to T
1
, and we need to cool the system
from T
2
to T
1
and measure the work required to heat the system
from T
1
to T
2
. Thus, the measurement of heat capacity is also a
measurement of W
adiabatic
.
Some later authors follow Caratheodory in using eq 5 as
their definition of dU, beginning with Born (12) and including
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Vol. 87 No. 7 July 2010
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Journal of Chemical Education 693
In the Classroom
Callen (14); Denbigh (15); Zemansky and Dittman (16); and
Berry, Rice, and Ross (17). Both Callen and Berry, Rice, and Ross
followed Born in calling attention to the use of irreversible
processes to extend the applicability of eq 1 to the whole P, V, T
coordinate space of a system.
As heat transfer engineers, Keenan and Shapiro (18) present
an alternative statement of the first law based on a one variable
definition that uses a no-work rigid wall instead of an adiabatic
wall and uses heat instead of work as the defining variable. That is
dU DQ
no work
14
In this treatment, work is defined as
DW dU -DQ 15
This approach shares the economy of the approach of Caratheod-
ory, but Keenan and Shapiro do not specify an operational
definitionof heat, analogous tothe operational definitions of various
kinds of work provided by mechanics and by electricity and
magnetism, and they ignore that work is defined clearly in mechan-
ical or electrical terms. Heat is usually defined through heat capacity
and temperature change, but that definition seems circular because
heat capacity is measured calorimetrically by measuring W
adiabatic
.
Conclusion
Three approaches to the first law of thermodynamics still
survive, and their proponents still see the merits of each. First, the
historical approach uses work and heat as primary experimental
quantities and energy as a derived quantity, with work measured
mechanically or electrically, and heat measured by temperature
change, with the magnitude obtained from the heat capacity and
temperature change. Energy changes are then calculated with
eq 1, with the understanding that U is a state function and work
and heat depend on the path taken in passing fromstate 1 to state
2. Amajor problemwith this convention is that heat is defined as
DQ C
V
dT 16
and, as pointed out above, C
V
is obtained in an adiabatic
calorimeter, hence, measured by W
adiabatic
.
The second approach, suggested by Keenan and Shapiro,
uses only heat as a primary quantity with both work and energy
change as derived quantities. But, in the heat-based convention,
where heat is defined as
Q
Z
T
2
T
1
C
V
dT 17
the heat capacity is determined in a calorimeter and depends on
measurement of W
adiabatic
. Thus, calculating W from Q is
circular in the second approach.
The third approach based on Caratheodory's proposal uses
only work as the primary quantity, with both energy change and
heat as derived quantities. Uis a state function and heat and work
are path dependent.
All three approaches provide a basis for deriving all the
relationships usually associated with the first law of thermo-
dynamics. Both modern approaches, based on Caratheodory's
suggestion and that proposed by Keenan and Shapiro, provide a
more economical set of assumptions than the historical method,
but Caratheodory's is firmly based on operational definitions of
work and does not use circular reasoning.
Notes
1. Because Gibbs published his work in the Transactions of the
Connecticut Academy, a journal not read by most European
scientists, he had a mailing list of those to whom he sent
reprints. At the time he published his thermodynamics papers,
Planck was not on the list, because he was still a graduate
student. When Gibbs published Statistical Mechanics in 1901,
Planck received a reprint. It is interesting that Planck cited
both earlier and later thermodynamics papers of Gibbs, but
not his primary work on the equilibrium of heterogeneous
substances.
2. Most of us infer from reading textbook descriptions of Joule's
experiment that Joule's water bath was insulated. According to
Joule, it was not.
3. This word has the unfortunate connotation that it is a material
substance, a historical legacy of the caloric theory of heat. Some
have suggested that we should not use the word heat at all, but
its usage is too entrenched in the literature to be ignored.
Literature Cited
1. Rogers, D. W. Chemistry 1976, 49, 1115.
2. Joule, J. P. Philos. Trans. R. Soc. 1850, 140, 6182.
3. Clapeyron, E. J. de l'Ecole Polytechnique, 1834, 14, 153-190.
English translation in Reflections on the Motive Power of Fire;
Mendoza, E., Ed.; Dover Pub.: New York, 1960.
4. Mayer, J. R. Ann Chem. 1842, 42, 233240.
5. Helmholtz, H. v. Sitzung Phys. Ges. zu Berlin 1847, July, 23.
Reprinted in Helmholtz, H. Ueber die Erhaltung der Kraft,
Wissenschafttliche Abhandlungen, Barth, Leipzig, 1882; pp
12-75.
6. Clausius, R. The Mechanical Theory of Heat; Macmillan & Co.:
London, 1879: p 31. An English translation of his original article,
On the Motive Power of Heat, appears in Mendoza, E., Ed.,
Reflections on the Motive Power of Fire, Dover, New York, 1960,
and in Philos. Mag., 1851, Series 4, 2, 1-21, 102-119.
7. Gibbs, J. W. On the Equilibrium of Heterogenous Substances,
Trans. Conn. Acad. 1875, 3, 103-246. Reprinted in The Collected
Works of J. Willard Gibbs; Yale University Press: New Haven, CT,
1948; pp 55-353.
8. Planck, M. Treatise on Thermodynamics; Longmans, Green, and
Co.: NewYork, 1903. Based on the First German edition, 1897,
pp 38-45.
9. Lewis, G. N.; Randall, M. Thermodynamics and the Free Energy of
Chemical Substances; McGraw-Hill Book Co., Inc.: New York,
1923; pp 47-54.
10. Bent, H. A. J. Chem. Educ. 1972, 49, 4446.
11. Caratheodory, C. Math. Ann. 1901, 67, 355386. Redlich, O. Rev.
Mod. Phys. 1968, 40, 556563.
12. Born, M. Phys. Z. 1921, 22, 218.
13. Craig, N. C.; Gislason, E. A. J. Chem. Educ. 2002, 79, 193200.
14. Callen, H. B. Thermodynamics; John Wiley & Sons, Inc.:
New York, 1960; pp 15-21.
15. Denbigh, K. The Principles of Chemical Equilibrium; Cambridge
University Press: Cambridge, 1971; pp 15-19.
16. Zemansky, M. W.; Dittman, R. H. Heat and Thermodynamics; The
McGraw-Hill Book Companies: New York, 1997; pp 72-81.
17. Berry, R. S.; Rice, S. A., Ross, J. Physical Chemistry, 2nd ed.; Oxford
University Press: Oxford, 2000; pp 379-382, pp 454-456.
18. Keenan, J. H.; Shapiro, A. H. Mech. Eng. 1947, 69, 915921.