Helmholtz free energy

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In thermodynamics, the Helmholtz free energy (or Helmholtz energy) is a

thermodynamic potential that measures the useful work obtainable from a closed
thermodynamic system at a constant temperature (isothermal). The change in the
Helmholtz energy during a process is equal to the maximum amount of work that
the system can perform in a thermodynamic process in which temperature is held
constant. At constant temperature, the Helmholtz free energy is minimized at
equilibrium.

In contrast, the Gibbs free energy or free enthalpy is most commonly used as a
measure of thermodynamic potential (especially in chemistry) when it is
convenient for applications that occur at constant pressure. For example, in
explosives research Helmholtz free energy is often used, since explosive
reactions by their nature induce pressure changes. It is also frequently used to
define fundamental equations of state of pure substances.

The concept of free energy was developed by Hermann von Helmholtz, a German
physicist, and first presented in 1882 in a lecture called "On the thermodynamics
of chemical processes".[1] From the German word Arbeit (work), the International
Union of Pure and Applied Chemistry (IUPAC) recommends the symbol A and the
name Helmholtz energy.[2] In physics, the symbol F is also used in reference to
free energy or Helmholtz function.

Definition[edit]

The Helmholtz free energy is defined as[3]

𝐹≡𝑈−𝑇𝑆,

where

● F is the Helmholtz free energy (sometimes also called A, particularly in

the field of chemistry) (SI: joules, CGS: ergs),
● U is the internal energy of the system (SI: joules, CGS: ergs),
● T is the absolute temperature (kelvins) of the surroundings, modelled as
a heat bath,
 ● S is the entropy of the system (SI: joules per kelvin, CGS: ergs per
kelvin).

The Helmholtz energy is the Legendre transformation of the internal energy U, in

which temperature replaces entropy as the independent variable.

Formal development[edit]

The first law of thermodynamics in a closed system provides

d𝑈=𝛿𝑄 +𝛿𝑊,

where

is the internal energy,

𝛿𝑄

is the energy added as heat, and

𝛿𝑊

is the work done on the system. The second law of thermodynamics for a
reversible process yields

𝛿𝑄=𝑇d𝑆

. In case of a reversible change, the work done can be expressed as

𝛿𝑊=−𝑝d𝑉

(ignoring electrical and other non-PV work) and so:

 d𝑈=𝑇d𝑆−𝑝d𝑉.

Applying the product rule for differentiation to

d(𝑇𝑆)=𝑇d𝑆+𝑆d𝑇

, it follows

d𝑈=d(𝑇𝑆)−𝑆d𝑇−𝑝d𝑉,

and

d(𝑈−𝑇𝑆)=−𝑆d𝑇−𝑝d𝑉.

The definition of

𝐹=𝑈−𝑇𝑆

enables to rewrite this as

d𝐹=−𝑆d𝑇−𝑝d𝑉.

Because F is a thermodynamic function of state, this relation is also valid for a

process (without electrical work or composition change) that is not reversible.

Minimum free energy and maximum work principles[edit]

The laws of thermodynamics are only directly applicable to systems in thermal

equilibrium. If we wish to describe phenomena like chemical reactions, then the
best we can do is to consider suitably chosen initial and final states in which the
system is in (metastable) thermal equilibrium. If the system is kept at fixed
volume and is in contact with a heat bath at some constant temperature, then we
can reason as follows.

Since the thermodynamical variables of the system are well defined in the initial
state and the final state, the internal energy increase

Δ𝑈

, the entropy increase

Δ𝑆

, and the total amount of work that can be extracted, performed by the system,

, are well defined quantities. Conservation of energy implies

Δ𝑈bath+Δ𝑈+𝑊=0.

The volume of the system is kept constant. This means that the volume of the
heat bath does not change either, and we can conclude that the heat bath does
not perform any work. This implies that the amount of heat that flows into the
heat bath is given by

𝑄bath=Δ𝑈bath=−(Δ𝑈+𝑊).

The heat bath remains in thermal equilibrium at temperature T no matter what the
system does. Therefore, the entropy change of the heat bath is

Δ𝑆bath=𝑄bath𝑇=−Δ𝑈+𝑊𝑇.
The total entropy change is thus given by

Δ𝑆bath+Δ𝑆=−Δ𝑈−𝑇Δ𝑆+𝑊𝑇.

Since the system is in thermal equilibrium with the heat bath in the initial and the
final states, T is also the temperature of the system in these states. The fact that
the system's temperature does not change allows us to express the numerator as
the free energy change of the system:

Δ𝑆bath+Δ𝑆=−Δ𝐹+𝑊𝑇.

Since the total change in entropy must always be larger or equal to zero, we
obtain the inequality

𝑊≤−Δ𝐹.

We see that the total amount of work that can be extracted in an isothermal
process is limited by the free-energy decrease, and that increasing the free
energy in a reversible process requires work to be done on the system. If no work
is extracted from the system, then

Δ𝐹≤0,

and thus for a system kept at constant temperature and volume and not capable
of performing electrical or other non-PV work, the total free energy during a
spontaneous change can only decrease.

This result seems to contradict the equation dF = −S dT − P dV, as keeping T and

V constant seems to imply dF = 0, and hence F = constant. In reality there is no
contradiction: In a simple one-component system, to which the validity of the
equation dF = −S dT − P dV is restricted, no process can occur at constant T and
V, since there is a unique P(T, V) relation, and thus T, V, and P are all fixed. To
allow for spontaneous processes at constant T and V, one needs to enlarge the
thermodynamical state space of the system. In case of a chemical reaction, one
must allow for changes in the numbers Nj of particles of each type j. The
differential of the free energy then generalizes to

𝑑𝐹=−𝑆𝑑𝑇−𝑃𝑑𝑉+∑𝑗𝜇𝑗𝑑𝑁𝑗,

where the

𝑁𝑗

are the numbers of particles of type j and the

𝜇𝑗

are the corresponding chemical potentials. This equation is then again valid
for both reversible and non-reversible changes. In case of a spontaneous change
at constant T and V, the last term will thus be negative.

In case there are other external parameters, the above relation further generalizes
to

𝑑𝐹=−𝑆𝑑𝑇−∑𝑖𝑋𝑖𝑑𝑥𝑖+∑𝑗𝜇𝑗𝑑𝑁𝑗.

Here the

𝑥𝑖

are the external variables, and the

𝑋𝑖

the corresponding generalized forces.

Relation to the canonical partition function[edit]

A system kept at constant volume, temperature, and particle number is described

by the canonical ensemble. The probability of finding the system in some energy
eigenstate r, for any microstate i, is given by

𝑃𝑟=𝑒−𝛽𝐸𝑟𝑍,

where

● 𝛽=1𝑘𝑇,

●
● 𝐸𝑟
● is the energy of accessible state
● 𝑟
●
● 𝑍=∑𝑖𝑒−𝛽𝐸𝑖.
●

Z is called the partition function of the system. The fact that the system does not
have a unique energy means that the various thermodynamical quantities must
be defined as expectation values. In the thermodynamical limit of infinite system
size, the relative fluctuations in these averages will go to zero.

The average internal energy of the system is the expectation value of the energy
and can be expressed in terms of Z as follows:

𝑈≡⟨𝐸⟩=∑𝑟𝑃𝑟𝐸𝑟=∑𝑟𝑒−𝛽𝐸𝑟𝐸𝑟𝑍=∑𝑟−∂∂𝛽𝑒−𝛽𝐸𝑟𝑍=−∂∂𝛽∑𝑟𝑒−𝛽𝐸𝑟𝑍=−∂log⁡𝑍∂𝛽.

If the system is in state r, then the generalized force corresponding to an external

variable x is given by
 𝑋𝑟=−∂𝐸𝑟∂𝑥.

The thermal average of this can be written as

𝑋=∑𝑟𝑃𝑟𝑋𝑟=1𝛽∂log⁡𝑍∂𝑥.

Suppose that the system has one external variable

. Then changing the system's temperature parameter by

𝑑𝛽

and the external variable by

𝑑𝑥

will lead to a change in

log⁡𝑍

𝑑(log⁡𝑍)=∂log⁡𝑍∂𝛽𝑑𝛽+∂log⁡𝑍∂𝑥𝑑𝑥=−𝑈𝑑𝛽+𝛽𝑋𝑑𝑥.

If we write

𝑈𝑑𝛽
 as

𝑈𝑑𝛽=𝑑(𝛽𝑈)−𝛽𝑑𝑈,

we get

𝑑(log⁡𝑍)=−𝑑(𝛽𝑈)+𝛽𝑑𝑈+𝛽𝑋𝑑𝑥.

This means that the change in the internal energy is given by

𝑑𝑈=1𝛽𝑑(log⁡𝑍+𝛽𝑈)−𝑋𝑑𝑥.

In the thermodynamic limit, the fundamental thermodynamic relation should hold:

𝑑𝑈=𝑇𝑑𝑆−𝑋𝑑𝑥.

This then implies that the entropy of the system is given by

𝑆=𝑘log⁡𝑍+𝑈𝑇+𝑐,

where c is some constant. The value of c can be determined by considering the

limit T → 0. In this limit the entropy becomes

𝑆=𝑘log⁡Ω0

, where
Ω0

is the ground-state degeneracy. The partition function in this limit is

Ω0𝑒−𝛽𝑈0

, where

𝑈0

is the ground-state energy. Thus, we see that

𝑐=0

and that

𝐹=−𝑘𝑇log⁡𝑍.

Relating free energy to other variables[edit]

Combining the definition of Helmholtz free energy

𝐹=𝑈−𝑇𝑆

along with the fundamental thermodynamic relation

𝑑𝐹=−𝑆𝑑𝑇−𝑃𝑑𝑉+𝜇𝑑𝑁,

one can find expressions for entropy, pressure and chemical potential: [4]

𝑆=−(∂𝐹∂𝑇)|𝑉,𝑁,𝑃=−(∂𝐹∂𝑉)|𝑇,𝑁,𝜇=(∂𝐹∂𝑁)|𝑇,𝑉.
These three equations, along with the free energy in terms of the partition
function,

𝐹=−𝑘𝑇log⁡𝑍,

allow an efficient way of calculating thermodynamic variables of interest given

the partition function and are often used in density of state calculations. One can
also do Legendre transformations for different systems. For example, for a
system with a magnetic field or potential, it is true that

𝑚=−(∂𝐹∂𝐵)|𝑇,𝑁,𝑉=(∂𝐹∂𝑄)|𝑁,𝑇.

Bogoliubov inequality[edit]

Computing the free energy is an intractable problem for all but the simplest
models in statistical physics. A powerful approximation method is mean-field
theory, which is a variational method based on the Bogoliubov inequality. This
inequality can be formulated as follows.

Suppose we replace the real Hamiltonian

of the model by a trial Hamiltonian

𝐻~

, which has different interactions and may depend on extra parameters that are
not present in the original model. If we choose this trial Hamiltonian such that
 ⟨𝐻~⟩=⟨𝐻⟩,

where both averages are taken with respect to the canonical distribution defined
by the trial Hamiltonian

𝐻~

, then the Bogoliubov inequality states

𝐹≤𝐹~,

where

is the free energy of the original Hamiltonian, and

𝐹~

is the free energy of the trial Hamiltonian. We will prove this below.

By including a large number of parameters in the trial Hamiltonian and minimizing

the free energy, we can expect to get a close approximation to the exact free
energy.

The Bogoliubov inequality is often applied in the following way. If we write the
Hamiltonian as

𝐻=𝐻0+Δ𝐻,

where

𝐻0
 is some exactly solvable Hamiltonian, then we can apply the above inequality
by defining

𝐻~=𝐻0+⟨Δ𝐻⟩0.

Here we have defined

⟨𝑋⟩0

to be the average of X over the canonical ensemble defined by

𝐻0

. Since

𝐻~

defined this way differs from

𝐻0

by a constant, we have in general

⟨𝑋⟩0=⟨𝑋⟩.

where

⟨𝑋⟩

is still the average over

𝐻~

, as specified above. Therefore,

 ⟨𝐻~⟩=⟨𝐻0+⟨Δ𝐻⟩⟩=⟨𝐻⟩,

and thus the inequality

𝐹≤𝐹~

holds. The free energy

𝐹~

is the free energy of the model defined by

𝐻0

plus

⟨Δ𝐻⟩

. This means that

𝐹~=⟨𝐻0⟩0−𝑇𝑆0+⟨Δ𝐻⟩0=⟨𝐻⟩0−𝑇𝑆0,

and thus

𝐹≤⟨𝐻⟩0−𝑇𝑆0.

Proof of the Bogoliubov inequality[edit]

For a classical model we can prove the Bogoliubov inequality as follows. We
denote the canonical probability distributions for the Hamiltonian and the trial
Hamiltonian by

𝑃𝑟

and

𝑃~𝑟

, respectively. From Gibbs' inequality we know that:

∑𝑟𝑃~𝑟log⁡(𝑃~𝑟)≥∑𝑟𝑃~𝑟log⁡(𝑃𝑟)

holds. To see this, consider the difference between the left hand side and the
right hand side. We can write this as:

∑𝑟𝑃~𝑟log⁡(𝑃~𝑟𝑃𝑟)

Since

log⁡(𝑥)≥1−1𝑥

it follows that:

∑𝑟𝑃~𝑟log⁡(𝑃~𝑟𝑃𝑟)≥∑𝑟(𝑃~𝑟−𝑃𝑟)=0
where in the last step we have used that both probability distributions are
normalized to 1.

We can write the inequality as:

⟨log⁡(𝑃~𝑟)⟩≥⟨log⁡(𝑃𝑟)⟩

where the averages are taken with respect to

𝑃~𝑟

. If we now substitute in here the expressions for the probability distributions:

𝑃𝑟=exp⁡[−𝛽𝐻(𝑟)]𝑍

and

𝑃~𝑟=exp⁡[−𝛽𝐻~(𝑟)]𝑍~

we get:

⟨−𝛽𝐻~−log⁡(𝑍~)⟩≥⟨−𝛽𝐻−log⁡(𝑍)⟩

Since the averages of

and
𝐻~

are, by assumption, identical we have:

𝐹≤𝐹~

Here we have used that the partition functions are constants with respect to
taking averages and that the free energy is proportional to minus the logarithm of
the partition function.

We can easily generalize this proof to the case of quantum mechanical models.
We denote the eigenstates of

𝐻~

by

|𝑟⟩

. We denote the diagonal components of the density matrices for the canonical
distributions for

and

𝐻~

in this basis as:

𝑃𝑟=⟨𝑟|exp⁡[−𝛽𝐻]𝑍|𝑟⟩

and
 𝑃~𝑟=⟨𝑟|exp⁡[−𝛽𝐻~]𝑍~|𝑟⟩=exp⁡(−𝛽𝐸~𝑟)𝑍~

where the

𝐸~ 𝑟

are the eigenvalues of

𝐻~

We assume again that the averages of H and

𝐻~

in the canonical ensemble defined by

𝐻~

are the same:

⟨𝐻~⟩=⟨𝐻⟩

where

⟨𝐻⟩=∑𝑟𝑃~𝑟⟨𝑟|𝐻|𝑟⟩

The inequality
 ∑𝑟𝑃~𝑟log⁡(𝑃~𝑟)≥∑𝑟𝑃~𝑟log⁡(𝑃𝑟)

still holds as both the

𝑃𝑟

and the

𝑃~𝑟

sum to 1. On the l.h.s. we can replace:

log⁡(𝑃~𝑟)=−𝛽𝐸~𝑟−log⁡(𝑍~)

On the right-hand side we can use the inequality

⟨exp⁡(𝑋)⟩𝑟≥exp⁡(⟨𝑋⟩𝑟)

where we have introduced the notation

⟨𝑌⟩𝑟≡⟨𝑟|𝑌|𝑟⟩

for the expectation value of the operator Y in the state r. See here for a proof.
Taking the logarithm of this inequality gives:

log⁡[⟨exp⁡(𝑋)⟩𝑟]≥⟨𝑋⟩𝑟

This allows us to write:

 log⁡(𝑃𝑟)=log⁡[⟨exp⁡(−𝛽𝐻−log⁡(𝑍))⟩𝑟]≥⟨−𝛽𝐻−log⁡(𝑍)⟩𝑟

The fact that the averages of H and

𝐻~

are the same then leads to the same conclusion as in the classical case:

𝐹≤𝐹~

Generalized Helmholtz energy[edit]

In the more general case, the mechanical term

𝑝d𝑉

must be replaced by the product of volume, stress, and an infinitesimal

strain:[5]

d𝐹=𝑉∑𝑖𝑗𝜎𝑖𝑗d𝜀𝑖𝑗−𝑆d𝑇+∑𝑖𝜇𝑖d𝑁𝑖,

where

𝜎𝑖𝑗

is the stress tensor, and

𝜀𝑖𝑗
 is the strain tensor. In the case of linear elastic materials that obey Hooke's
law, the stress is related to the strain by

𝜎𝑖𝑗=𝐶𝑖𝑗𝑘𝑙𝜀𝑘𝑙,

where we are now using Einstein notation for the tensors, in which repeated
indices in a product are summed. We may integrate the expression for

d𝐹

to obtain the Helmholtz energy:

𝐹=12𝑉𝐶𝑖𝑗𝑘𝑙𝜀𝑖𝑗𝜀𝑘𝑙−𝑆𝑇+∑𝑖𝜇𝑖𝑁𝑖=12𝑉𝜎𝑖𝑗𝜀𝑖𝑗−𝑆𝑇+∑𝑖𝜇𝑖𝑁𝑖.

Application to fundamental equations of state[edit]

The Helmholtz free energy function for a pure substance (together with its partial
derivatives) can be used to determine all other thermodynamic properties for the
substance. See, for example, the equations of state for water, as given by the
IAPWS in their IAPWS-95 release.

Application to training auto-encoders[edit]

Hinton and Zemel[6] "derive an objective function for training auto-encoder based
on the minimum description length (MDL) principle". "The description length of
an input vector using a particular code is the sum of the code cost and
reconstruction cost. They define this to be the energy of the code. Given an input
vector, they define the energy of a code to be the sum of the code cost and the
reconstruction cost." The true expected combined cost is
 𝐹=∑𝑖𝑝𝑖𝐸𝑖−𝐻,

"which has exactly the form of Helmholtz free energy".

See also[edit]

● Gibbs free energy and thermodynamic free energy for thermodynamics

history overview and discussion of free energy
● Grand potential
● Enthalpy
● Statistical mechanics
● This page details the Helmholtz energy from the point of view of thermal
and statistical physics.
● Bennett acceptance ratio for an efficient way to calculate free energy
differences and comparison with other methods.

References[edit]

● ^ von Helmholtz, H. (1882). Physical memoirs, selected and translated from foreign
sources. Taylor & Francis.
● ^ Gold, Victor, ed. (2019). Gold Book. IUPAC. doi:10.1351/goldbook. Retrieved 2012-08-
19.
● ^ Levine, Ira. N. (1978). "Physical Chemistry" McGraw-Hill: University of Brooklyn.
● ^ "4.3 Entropy, Helmholtz Free Energy and the Partition Function".
theory.physics.manchester.ac.uk. Retrieved 2016-12-06.
● ^ Landau, L. D.; Lifshitz, E. M. (1986). Theory of Elasticity (Course of Theoretical Physics
Volume 7). (Translated from Russian by J. B. Sykes and W. H. Reid) (Third ed.). Boston,
MA: Butterworth Heinemann. ISBN 0-7506-2633-X.
● ^ Hinton, G. E.; Zemel, R. S. (1994). "Autoencoders, minimum description length and
Helmholtz free energy" (PDF). Advances in Neural Information Processing Systems: 3–
10.

Further reading[edit]

● Atkins' Physical Chemistry, 7th edition, by Peter Atkins and Julio de

Paula, Oxford University Press
● HyperPhysics Helmholtz Free Energy Helmholtz and Gibbs Free
Energies
 show

● V
● T
● E

Statistical mechanics

Authority control
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databases: National

Categories:

Physical quantities
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State functions
Thermodynamic free energy
This page was last edited on 14 October 2023, at 01:50 (UTC).

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