Thermodynamic free

energy

In thermodynamics, the thermodynamic

free energy is one of the state functions of
a thermodynamic system (the others
being internal energy, enthalpy, entropy,
etc.). The change in the free energy is the
maximum amount of work that the system
can perform in a process at constant
temperature, and its sign indicates
whether the process is thermodynamically
favorable or forbidden. Since free energy
usually contains potential energy, it is not
absolute but depends on the choice of a
zero point. Therefore, only relative free
energy values, or changes in free energy,
are physically meaningful.

The free energy is the portion of any first-

law energy that is available to perform
thermodynamic work at constant
temperature, i.e., work mediated by
thermal energy. Free energy is subject to
irreversible loss in the course of such
work.[1] Since first-law energy is always
conserved, it is evident that free energy is
an expendable, second-law kind of energy.
Several free energy functions may be
formulated based on system criteria. Free
energy functions are Legendre transforms
of the internal energy.

The Gibbs free energy is given by

G = H − TS, where H is the enthalpy, T is
the absolute temperature, and S is the
entropy. H = U + pV, where U is the
internal energy, p is the pressure, and V is
the volume. G is the most useful for
processes involving a system at constant
pressure p and temperature T, because, in
addition to subsuming any entropy change
due merely to heat, a change in G also
excludes the p dV work needed to "make
space for additional molecules" produced
by various processes. Gibbs free energy
change therefore equals work not
associated with system expansion or
compression, at constant temperature and
pressure, hence its utility to solution-phase
chemists, including biochemists.

The historically earlier Helmholtz free

energy is defined in contrast as
A = U − TS. Its change is equal to the
amount of reversible work done on, or
obtainable from, a system at constant T.
Thus its appellation "work content", and
the designation A (from German
Arbeit 'work'). Since it makes no reference
to any quantities involved in work (such as
p and V), the Helmholtz function is
completely general: its decrease is the
maximum amount of work which can be
done by a system at constant temperature,
and it can increase at most by the amount
of work done on a system isothermally.
The Helmholtz free energy has a special
theoretical importance since it is
proportional to the logarithm of the
partition function for the canonical
ensemble in statistical mechanics. (Hence
its utility to physicists; and to gas-phase
chemists and engineers, who do not want
to ignore p dV work.)
Historically, the term 'free energy' has been
used for either quantity. In physics, free
energy most often refers to the Helmholtz
free energy, denoted by A (or F), while in
chemistry, free energy most often refers to
the Gibbs free energy. The values of the
two free energies are usually quite similar
and the intended free energy function is
often implicit in manuscripts and
presentations.

Meaning of "free"
The basic definition of "energy" is a
measure of a body's (in thermodynamics,
the system's) ability to cause change. For
example, when a person pushes a heavy
box a few metres forward, that person
exerts mechanical energy, also known as
work, on the box over a distance of a few
meters forward. The mathematical
definition of this form of energy is the
product of the force exerted on the object
and the distance by which the box moved
(Work = Force × Distance). Because the
person changed the stationary position of
the box, that person exerted energy on that
box. The work exerted can also be called
"useful energy", because energy was
converted from one form into the intended
purpose, i.e. mechanical use. For the case
of the person pushing the box, the energy
in the form of internal (or potential) energy
obtained through metabolism was
converted into work to push the box. This
energy conversion, however, was not
straightforward: while some internal
energy went into pushing the box, some
was diverted away (lost) in the form of
heat (transferred thermal energy).

For a reversible process, heat is the

product of the absolute temperature
and the change in entropy of a body
(entropy is a measure of disorder in a
system). The difference between the
change in internal energy, which is ,
and the energy lost in the form of heat is
what is called the "useful energy" of the
body, or the work of the body performed
on an object. In thermodynamics, this is
what is known as "free energy". In other
words, free energy is a measure of work
(useful energy) a system can perform at
constant temperature.

Mathematically, free energy is expressed

as

This expression has commonly been

interpreted to mean that work is extracted
from the internal energy while
represents energy not available to perform
work. However, this is incorrect. For
instance, in an isothermal expansion of an
ideal gas, the internal energy change is
and the expansion work
is derived exclusively from
the term supposedly not available to
perform work. But it is noteworthy that the
derivative form of the free energy:
(for Helmholtz
free energy) does indeed indicate that a
spontaneous change in a non-reactive
system's free energy (NOT the internal
energy) comprises the available energy to
do work (compression in this case)
and the unavailable energy
.[2][3][4] Similar expression can be
written for the Gibbs free energy
change.[5][3][4]

In the 18th and 19th centuries, the theory

of heat, i.e., that heat is a form of energy
having relation to vibratory motion, was
beginning to supplant both the caloric
theory, i.e., that heat is a fluid, and the four
element theory, in which heat was the
lightest of the four elements. In a similar
manner, during these years, heat was
beginning to be distinguished into different
classification categories, such as "free
heat", "combined heat", "radiant heat",
specific heat, heat capacity, "absolute
heat", "latent caloric", "free" or "perceptible"
caloric (calorique sensible), among others.

In 1780, for example, Laplace and

Lavoisier stated: “In general, one can
change the first hypothesis into the
second by changing the words ‘free heat,
combined heat, and heat released’ into ‘vis
viva, loss of vis viva, and increase of vis
viva.’" In this manner, the total mass of
caloric in a body, called absolute heat, was
regarded as a mixture of two components;
the free or perceptible caloric could affect
a thermometer, whereas the other
component, the latent caloric, could not.[6]
The use of the words "latent heat" implied
a similarity to latent heat in the more usual
sense; it was regarded as chemically
bound to the molecules of the body. In the
adiabatic compression of a gas, the
absolute heat remained constant but the
observed rise in temperature implied that
some latent caloric had become "free" or
perceptible.

During the early 19th century, the concept

of perceptible or free caloric began to be
referred to as "free heat" or "heat set free".
In 1824, for example, the French physicist
Sadi Carnot, in his famous "Reflections on
the Motive Power of Fire", speaks of
quantities of heat ‘absorbed or set free’ in
different transformations. In 1882, the
German physicist and physiologist
Hermann von Helmholtz coined the phrase
‘free energy’ for the expression
, in which the change in A
(or G) determines the amount of energy
‘free’ for work under the given conditions,
specifically constant temperature.[7]: 235

Thus, in traditional use, the term "free" was

attached to Gibbs free energy for systems
at constant pressure and temperature, or
to Helmholtz free energy for systems at
constant temperature, to mean ‘available
in the form of useful work.’[8] With
reference to the Gibbs free energy, we
need to add the qualification that it is the
energy free for non-volume work and
compositional changes.[9]: 77–79

An increasing number of books and

journal articles do not include the
attachment "free", referring to G as simply
Gibbs energy (and likewise for the
Helmholtz energy). This is the result of a
1988 IUPAC meeting to set unified
terminologies for the international
scientific community, in which the
adjective ‘free’ was supposedly
banished.[10][11][12] This standard, however,
has not yet been universally adopted, and
many published articles and books still
include the descriptive ‘free’.

Application
Just like the general concept of energy,
free energy has a few definitions suitable
for different conditions. In physics,
chemistry, and biology, these conditions
are thermodynamic parameters
(temperature , volume , pressure ,
etc.). Scientists have come up with several
ways to define free energy. The
mathematical expression of Helmholtz
free energy is:
This definition of free energy is useful for
gas-phase reactions or in physics when
modeling the behavior of isolated systems
kept at a constant volume. For example, if
a researcher wanted to perform a
combustion reaction in a bomb
calorimeter, the volume is kept constant
throughout the course of a reaction.
Therefore, the heat of the reaction is a
direct measure of the free energy change,
. In solution chemistry, on the
other hand, most chemical reactions are
kept at constant pressure. Under this
condition, the heat of the reaction is
equal to the enthalpy change of the
system. Under constant pressure and
temperature, the free energy in a reaction
is known as Gibbs free energy .

These functions have a minimum in

chemical equilibrium, as long as certain
variables ( , and or ) are held
constant. In addition, they also have
theoretical importance in deriving Maxwell
relations. Work other than p dV may be
added, e.g., for electrochemical cells, or
f dx work in elastic materials and in
muscle contraction. Other forms of work
which must sometimes be considered are
stress-strain, magnetic, as in adiabatic
demagnetization used in the approach to
absolute zero, and work due to electric
polarization. These are described by
tensors.

In most cases of interest there are internal

degrees of freedom and processes, such
as chemical reactions and phase
transitions, which create entropy. Even for
homogeneous "bulk" materials, the free
energy functions depend on the (often
suppressed) composition, as do all proper
thermodynamic potentials (extensive
functions), including the internal energy.

Name Symbol Formula Natural variables

Helmholtz free energy

Gibbs free energy

 is the number of molecules
(alternatively, moles) of type in the
system. If these quantities do not appear,
it is impossible to describe compositional
changes. The differentials for processes at
uniform pressure and temperature are
(assuming only work):

where μi is the chemical potential for the

ith component in the system. The second
relation is especially useful at constant
and , conditions which are easy to
achieve experimentally, and which
approximately characterize living
creatures. Under these conditions, it
simplifies to

Any decrease in the Gibbs function of a

system is the upper limit for any
isothermal, isobaric work that can be
captured in the surroundings, or it may
simply be dissipated, appearing as
times a corresponding increase in the
entropy of the system and/or its
surrounding.
An example is surface free energy, the
amount of increase of free energy when
the area of surface increases by every unit
area.

The path integral Monte Carlo method is a

numerical approach for determining the
values of free energies, based on quantum
dynamical principles.

Work and free energy change

For a reversible isothermal process, ΔS =

qrev/T and therefore the definition of A
results in
 (at constant temperature)

This tells us that the change in free energy

equals the reversible or maximum work for
a process performed at constant
temperature. Under other conditions, free-
energy change is not equal to work; for
instance, for a reversible adiabatic
expansion of an ideal gas,
. Importantly, for a
heat engine, including the Carnot cycle, the
free-energy change after a full cycle is
zero, , while the engine
produces nonzero work. It is important to
note that for heat engines and other
thermal systems, the free energies do not
offer convenient characterizations; internal
energy and enthalpy are the preferred
potentials for characterizing thermal
systems.

Free energy change and spontaneous

processes

According to the second law of

thermodynamics, for any process that
occurs in a closed system, the inequality
of Clausius, ΔS > q/Tsurr, applies. For a
process at constant temperature and
pressure without non-PV work, this
inequality transforms into .
Similarly, for a process at constant
temperature and volume, . Thus,
a negative value of the change in free
energy is a necessary condition for a
process to be spontaneous; this is the
most useful form of the second law of
thermodynamics in chemistry. In chemical
equilibrium at constant T and p without
electrical work, dG = 0.

History
The quantity called "free energy" is a more
advanced and accurate replacement for
the outdated term affinity, which was used
by chemists in previous years to describe
the force that caused chemical reactions.
The term affinity, as used in chemical
relation, dates back to at least the time of
Albertus Magnus.[13]

From the 1998 textbook Modern

Thermodynamics[14] by Nobel Laureate and
chemistry professor Ilya Prigogine we find:
"As motion was explained by the
Newtonian concept of force, chemists
wanted a similar concept of ‘driving force’
for chemical change. Why do chemical
reactions occur, and why do they stop at
certain points? Chemists called the ‘force’
that caused chemical reactions affinity, but
it lacked a clear definition."
During the entire 18th century, the
dominant view with regard to heat and
light was that put forth by Isaac Newton,
called the Newtonian hypothesis, which
states that light and heat are forms of
matter attracted or repelled by other forms
of matter, with forces analogous to
gravitation or to chemical affinity.

In the 19th century, the French chemist

Marcellin Berthelot and the Danish
chemist Julius Thomsen had attempted to
quantify affinity using heats of reaction. In
1875, after quantifying the heats of
reaction for a large number of compounds,
Berthelot proposed the principle of
maximum work, in which all chemical
changes occurring without intervention of
outside energy tend toward the production
of bodies or of a system of bodies which
liberate heat.

In addition to this, in 1780 Antoine

Lavoisier and Pierre-Simon Laplace laid
the foundations of thermochemistry by
showing that the heat given out in a
reaction is equal to the heat absorbed in
the reverse reaction. They also
investigated the specific heat and latent
heat of a number of substances, and
amounts of heat given out in combustion.
In a similar manner, in 1840 Swiss chemist
Germain Hess formulated the principle
that the evolution of heat in a reaction is
the same whether the process is
accomplished in one-step process or in a
number of stages. This is known as Hess'
law. With the advent of the mechanical
theory of heat in the early 19th century,
Hess's law came to be viewed as a
consequence of the law of conservation of
energy.

Based on these and other ideas, Berthelot

and Thomsen, as well as others,
considered the heat given out in the
formation of a compound as a measure of
the affinity, or the work done by the
chemical forces. This view, however, was
not entirely correct. In 1847, the English
physicist James Joule showed that he
could raise the temperature of water by
turning a paddle wheel in it, thus showing
that heat and mechanical work were
equivalent or proportional to each other,
i.e., approximately, dW ∝ dQ. This
statement came to be known as the
mechanical equivalent of heat and was a
precursory form of the first law of
thermodynamics.

By 1865, the German physicist Rudolf

Clausius had shown that this equivalence
principle needed amendment. That is, one
can use the heat derived from a
combustion reaction in a coal furnace to
boil water, and use this heat to vaporize
steam, and then use the enhanced high-
pressure energy of the vaporized steam to
push a piston. Thus, we might naively
reason that one can entirely convert the
initial combustion heat of the chemical
reaction into the work of pushing the
piston. Clausius showed, however, that we
must take into account the work that the
molecules of the working body, i.e., the
water molecules in the cylinder, do on
each other as they pass or transform from
one step of or state of the engine cycle to
the next, e.g., from ( ) to ( ).
Clausius originally called this the
"transformation content" of the body, and
then later changed the name to entropy.
Thus, the heat used to transform the
working body of molecules from one state
to the next cannot be used to do external
work, e.g., to push the piston. Clausius
defined this transformation heat as
.

In 1873, Willard Gibbs published A Method

of Geometrical Representation of the
Thermodynamic Properties of Substances
by Means of Surfaces, in which he
introduced the preliminary outline of the
principles of his new equation able to
predict or estimate the tendencies of
various natural processes to ensue when
bodies or systems are brought into
contact. By studying the interactions of
homogeneous substances in contact, i.e.,
bodies, being in composition part solid,
part liquid, and part vapor, and by using a
three-dimensional volume-entropy-internal
energy graph, Gibbs was able to determine
three states of equilibrium, i.e.,
"necessarily stable", "neutral", and
"unstable", and whether or not changes
will ensue. In 1876, Gibbs built on this
framework by introducing the concept of
chemical potential so to take into account
chemical reactions and states of bodies
that are chemically different from each
other. In his own words, to summarize his
results in 1873, Gibbs states:

If we wish to express in a single

equation the necessary and
sufficient condition of
thermodynamic equilibrium for
a substance when surrounded
by a medium of constant
pressure p and temperature T,
this equation may be written:

δ(ε − Tη + pν) = 0
 when δ refers to the variation
produced by any variations in
the state of the parts of the body,
and (when different parts of the
body are in different states) in
the proportion in which the
body is divided between the
different states. The condition of
stable equilibrium is that the
value of the expression in the
parenthesis shall be a minimum.

In this description, as used by Gibbs, ε

refers to the internal energy of the body, η
refers to the entropy of the body, and ν is
the volume of the body.

Hence, in 1882, after the introduction of

these arguments by Clausius and Gibbs,
the German scientist Hermann von
Helmholtz stated, in opposition to
Berthelot and Thomas’ hypothesis that
chemical affinity is a measure of the heat
of reaction of chemical reaction as based
on the principle of maximal work, that
affinity is not the heat given out in the
formation of a compound but rather it is
the largest quantity of work which can be
gained when the reaction is carried out in
a reversible manner, e.g., electrical work in
a reversible cell. The maximum work is
thus regarded as the diminution of the
free, or available, energy of the system
(Gibbs free energy G at T = constant, P =
constant or Helmholtz free energy A at T =
constant, V = constant), whilst the heat
given out is usually a measure of the
diminution of the total energy of the
system (Internal energy). Thus, G or A is
the amount of energy "free" for work under
the given conditions.

Up until this point, the general view had

been such that: “all chemical reactions
drive the system to a state of equilibrium
in which the affinities of the reactions
vanish”. Over the next 60 years, the term
affinity came to be replaced with the term
free energy. According to chemistry
historian Henry Leicester, the influential
1923 textbook Thermodynamics and the
Free Energy of Chemical Reactions by
Gilbert N. Lewis and Merle Randall led to
the replacement of the term "affinity" by
the term "free energy" in much of the
English-speaking world.

See also
Energy
Exergy
Merle Randall
 Second law of thermodynamics
Superconductivity

References
1. Stoner, Clinton D. (2000). Inquiries into the
Nature of Free Energy and Entropy in
Respect to Biochemical Thermodynamics.
Entropy Vol. 2.
2. Osara, Jude A.; Bryant, Michael D.
(September 2019). "Thermodynamics of
grease degradation" (https://dx.doi.org/10.
1016/j.triboint.2019.05.020) . Tribology
International. 137: 433–445.
doi:10.1016/j.triboint.2019.05.020 (https://
doi.org/10.1016%2Fj.triboint.2019.05.02
0) . ISSN 0301-679X (https://www.worldca
t.org/issn/0301-679X) . S2CID 182266032
(https://api.semanticscholar.org/CorpusID:
182266032) .
3. Callen, Herbert B. (October 1966).
Thermodynamics (http://worldcat.org/oclc/
651933140) . Wiley. ISBN 0-471-13035-4.
OCLC 651933140 (https://www.worldcat.or
g/oclc/651933140) .
4. Kondepudi, Dilip, 1952- (1998). Modern
thermodynamics : from heat engines to
dissipative structures (http://worldcat.org/o
clc/1167078377) . John Wiley. ISBN 0-471-
97393-9. OCLC 1167078377 (https://www.
worldcat.org/oclc/1167078377) .
5. Osara, Jude; Bryant, Michael (3 April 2019).
"A Thermodynamic Model for Lithium-Ion
Battery Degradation: Application of the
Degradation-Entropy Generation Theorem"
(https://doi.org/10.3390%2Finventions4020
023) . Inventions. 4 (2): 23.
doi:10.3390/inventions4020023 (https://do
i.org/10.3390%2Finventions4020023) .
ISSN 2411-5134 (https://www.worldcat.or
g/issn/2411-5134) .
6. Mendoza, E. (1988). Clapeyron, E.; Carnot,
R. (eds.). Reflections on the Motive Power
of Fire – and other Papers on the Second
Law of Thermodynamics. Dover
Publications, Inc. ISBN 0-486-44641-7.
7. Baierlein, Ralph (2003). Thermal Physics (ht
tps://archive.org/details/thermalphysics00r
alp) . Cambridge University Press. ISBN 0-
521-65838-1.
8. Perrot, Pierre (1998). A to Z of
Thermodynamics. Oxford University Press.
ISBN 0-19-856552-6.
9. Reiss, Howard (1965). Methods of
Thermodynamics. Dover Publications.
ISBN 0-486-69445-3.
10. International Union of Pure and Applied
Chemistry Commission on Atmospheric
Chemistry, J. G. (1990). "Glossary of
Atmospheric Chemistry Terms
(Recommendations 1990)" (http://www.iup
ac.org/publications/pac/1990/pdf/6211x2
167.pdf) (PDF). Pure Appl. Chem. 62 (11):
2167–2219.
doi:10.1351/pac199062112167 (https://do
i.org/10.1351%2Fpac199062112167) .
S2CID 53117465 (https://api.semanticscho
lar.org/CorpusID:53117465) . Archived (htt
ps://ghostarchive.org/archive/20221009/ht
tp://www.iupac.org/publications/pac/1990/
pdf/6211x2167.pdf) (PDF) from the
original on 9 October 2022. Retrieved
28 December 2006.
11. International Union of Pure and Applied
Chemistry Commission on
Physicochemical Symbols Terminology and
Units (1993). Quantities, Units and Symbols
in Physical Chemistry (https://archive.org/d
etails/quantitiesunitss0000unse/page/48)
(2nd ed.). Oxford: Blackwell Scientific
Publications. pp. 48 (https://archive.org/det
ails/quantitiesunitss0000unse/page/48) .
ISBN 0-632-03583-8. Retrieved
28 December 2006.
12. Lehmann, H. P.; Fuentes-Arderiu, X.;
Bertello, L. F. (1996). "Glossary of Terms in
Quantities and Units in Clinical Chemistry
(IUPAC-IFCC Recommendations 1996)" (htt
p://www.iupac.org/publications/pac/1996/
pdf/6804x0957.pdf) (PDF). Pure Appl.
Chem. 68 (4): 957–100 0.
doi:10.1351/pac199668040957 (https://do
i.org/10.1351%2Fpac199668040957) .
S2CID 95196393 (https://api.semanticscho
lar.org/CorpusID:95196393) . Archived (htt
ps://ghostarchive.org/archive/20221009/ht
tp://www.iupac.org/publications/pac/1996/
pdf/6804x0957.pdf) (PDF) from the
original on 9 October 2022.
13. Quilez, Juan (July 2019). "A
historical/epistemological account of the
foundation of the key ideas supporting
chemical equilibrium theory" (https://go.gal
e.com/ps/i.do?p=AONE&u=22417_vcpl&id=
GALE%7CA592081896&v=2.1&it=r&sid=ebs
co) . Foundations of Chemistry. 21 (2): 223.
doi:10.1007/s10698-018-9320-0 (https://do
i.org/10.1007%2Fs10698-018-9320-0) .
S2CID 102566121 (https://api.semanticsch
olar.org/CorpusID:102566121) . Retrieved
2 November 2021.
 14. Kondepudi, Dilip; Prigogine, Ilya (1998).
Modern Thermodynamics (https://archive.o
rg/details/modernthermodyna0000kond) .
John Wiley & Sons Ltd. ISBN 978-0-471-
97394-2. Chapter 4, Section 1, Paragraph 2
(page 103)

Retrieved from
"https://en.wikipedia.org/w/index.php?
title=Thermodynamic_free_energy&oldid=1185072
037"

This page was last edited on 14 November 2023,

at 10:47 (UTC). •
Content is available under CC BY-SA 4.0 unless
otherwise noted.