Internal energy

The internal energy of a thermodynamic system is the energy of

the system as a state function, measured as the quantity of energy Internal energy
necessary to bring the system from its standard internal state to its Common U
present internal state of interest, accounting for the gains and losses symbols

of energy due to changes in its internal state, including such SI unit J

quantities as magnetization. [1][2] It excludes the kinetic energy of In SI base units m2⋅kg/s2
motion of the system as a whole and the potential energy of position Derivations
of the system as a whole, with respect to its surroundings and from
external force fields. It includes the thermal energy, i.e., the other quantities
constituent particles' kinetic energies of motion relative to the
motion of the system as a whole. The internal energy of an isolated system cannot change, as expressed in the law
of conservation of energy, a foundation of the first law of thermodynamics.[3] The notion has been introduced to
describe the systems characterized by temperature variations, temperature being added to the set of state
parameters, the position variables known in mechanics (and their conjugated generalized force parameters), in a
similar way to potential energy of the conservative fields of force, gravitational and electrostatic. Its author is
Rudolf Clausius. Internal energy changes equal the algebraic sum of the heat transferred and the work done. In
systems without temperature changes, potential energy changes equal the work done by/on the system.

The internal energy cannot be measured absolutely. Thermodynamics concerns changes in the internal energy,
not its absolute value. The processes that change the internal energy are transfers, into or out of the system, of
substance, or of energy, as heat, or by thermodynamic work.[4] These processes are measured by changes in the
system's properties, such as temperature, entropy, volume, electric polarization, and molar constitution. The
internal energy depends only on the internal state of the system and not on the particular choice from many
possible processes by which energy may pass into or out of the system. It is a state variable, a thermodynamic
potential, and an extensive property.[5]

Thermodynamics defines internal energy macroscopically, for the body as a whole. In statistical mechanics, the
internal energy of a body can be analyzed microscopically in terms of the kinetic energies of microscopic motion
of the system's particles from translations, rotations, and vibrations, and of the potential energies associated with
microscopic forces, including chemical bonds.

The unit of energy in the International System of Units (SI) is the joule (J). The internal energy relative to the
mass with unit J/kg is the specific internal energy. The corresponding quantity relative to the amount of
substance with unit J/mol is the molar internal energy.[6]

Cardinal functions
The internal energy of a system depends on its entropy S, its volume V and its number of massive particles:
U(S,V,{Nj}). It expresses the thermodynamics of a system in the energy representation. As a function of state,
its arguments are exclusively extensive variables of state. Alongside the internal energy, the other cardinal
function of state of a thermodynamic system is its entropy, as a function, S(U,V,{Nj}), of the same list of
extensive variables of state, except that the entropy, S, is replaced in the list by the internal energy, U. It expresses
the entropy representation.[7][8][9]
Each cardinal function is a monotonic function of each of its natural or canonical variables. Each provides its
characteristic or fundamental equation, for example U = U(S,V,{Nj}), that by itself contains all thermodynamic
information about the system. The fundamental equations for the two cardinal functions can in principle be
interconverted by solving, for example, U = U(S,V,{Nj}) for S, to get S = S(U,V,{Nj}).

In contrast, Legendre transformations are necessary to derive fundamental equations for other thermodynamic
potentials and Massieu functions. The entropy as a function only of extensive state variables is the one and only
cardinal function of state for the generation of Massieu functions. It is not itself customarily designated a
'Massieu function', though rationally it might be thought of as such, corresponding to the term 'thermodynamic
potential', which includes the internal energy.[8][10][11]

For real and practical systems, explicit expressions of the fundamental equations are almost always unavailable,
but the functional relations exist in principle. Formal, in principle, manipulations of them are valuable for the
understanding of thermodynamics.

Description and definition

The internal energy of a given state of the system is determined relative to that of a standard state of the
system, by adding up the macroscopic transfers of energy that accompany a change of state from the reference
state to the given state:

where denotes the difference between the internal energy of the given state and that of the reference state,
and the are the various energies transferred to the system in the steps from the reference state to the given
state. It is the energy needed to create the given state of the system from the reference state. From a non-
relativistic microscopic point of view, it may be divided into microscopic potential energy, , and
microscopic kinetic energy, , components:

The microscopic kinetic energy of a system arises as the sum of the motions of all the system's particles with
respect to the center-of-mass frame, whether it be the motion of atoms, molecules, atomic nuclei, electrons, or
other particles. The microscopic potential energy algebraic summative components are those of the chemical and
nuclear particle bonds, and the physical force fields within the system, such as due to internal induced electric or
magnetic dipole moment, as well as the energy of deformation of solids (stress-strain). Usually, the split into
microscopic kinetic and potential energies is outside the scope of macroscopic thermodynamics.

Internal energy does not include the energy due to motion or location of a system as a whole. That is to say, it
excludes any kinetic or potential energy the body may have because of its motion or location in external
gravitational, electrostatic, or electromagnetic fields. It does, however, include the contribution of such a field to
the energy due to the coupling of the internal degrees of freedom of the system with the field. In such a case, the
field is included in the thermodynamic description of the object in the form of an additional external parameter.

For practical considerations in thermodynamics or engineering, it is rarely necessary, convenient, nor even
possible, to consider all energies belonging to the total intrinsic energy of a sample system, such as the energy
given by the equivalence of mass. Typically, descriptions only include components relevant to the system under
study. Indeed, in most systems under consideration, especially through thermodynamics, it is impossible to
calculate the total internal energy.[12] Therefore, a convenient null reference point may be chosen for the internal
energy.
The internal energy is an extensive property: it depends on the size of the system, or on the amount of substance it
contains.

At any temperature greater than absolute zero, microscopic potential energy and kinetic energy are constantly
converted into one another, but the sum remains constant in an isolated system (cf. table). In the classical picture
of thermodynamics, kinetic energy vanishes at zero temperature and the internal energy is purely potential
energy. However, quantum mechanics has demonstrated that even at zero temperature particles maintain a
residual energy of motion, the zero point energy. A system at absolute zero is merely in its quantum-mechanical
ground state, the lowest energy state available. At absolute zero a system of given composition has attained its
minimum attainable entropy.

The microscopic kinetic energy portion of the internal energy gives rise to the temperature of the system.
Statistical mechanics relates the pseudo-random kinetic energy of individual particles to the mean kinetic energy
of the entire ensemble of particles comprising a system. Furthermore, it relates the mean microscopic kinetic
energy to the macroscopically observed empirical property that is expressed as temperature of the system. While
temperature is an intensive measure, this energy expresses the concept as an extensive property of the system,
often referred to as the thermal energy,[13][14] The scaling property between temperature and thermal energy is
the entropy change of the system.

Statistical mechanics considers any system to be statistically distributed across an ensemble of microstates. In
a system that is in thermodynamic contact equilibrium with a heat reservoir, each microstate has an energy
and is associated with a probability . The internal energy is the mean value of the system's total energy, i.e., the
sum of all microstate energies, each weighted by its probability of occurrence:

This is the statistical expression of the law of conservation of energy.

Internal energy changes Interactions of thermodynamic systems

Thermodynamics is chiefly concerned with the changes in internal Type of system Mass flow Work Heat
energy . Open

For a closed system, with mass transfer excluded, the changes in Closed
internal energy are due to heat transfer and due to Thermally isolated
thermodynamic work done by the system on its Mechanically isolated
surroundings.[note 1] Accordingly, the internal energy change
Isolated
for a process may be written

When a closed system receives energy as heat, this energy increases the internal energy. It is distributed between
microscopic kinetic and microscopic potential energies. In general, thermodynamics does not trace this
distribution. In an ideal gas all of the extra energy results in a temperature increase, as it is stored solely as
microscopic kinetic energy; such heating is said to be sensible.

A second kind of mechanism of change in the internal energy of a closed system changed is in its doing of work on
its surroundings. Such work may be simply mechanical, as when the system expands to drive a piston, or, for
example, when the system changes its electric polarization so as to drive a change in the electric field in the
surroundings.
If the system is not closed, the third mechanism that can increase the internal energy is transfer of substance into
the system. This increase, cannot be split into heat and work components.[4] If the system is so set up
physically that heat transfer and work that it does are by pathways separate from and independent of matter
transfer, then the transfers of energy add to change the internal energy:

If a system undergoes certain phase transformations while being heated, such as melting and vaporization, it may
be observed that the temperature of the system does not change until the entire sample has completed the
transformation. The energy introduced into the system while the temperature does not change is called latent
energy or latent heat, in contrast to sensible heat, which is associated with temperature change.

Internal energy of the ideal gas

Thermodynamics often uses the concept of the ideal gas for teaching purposes, and as an approximation for
working systems. The ideal gas consists of particles considered as point objects that interact only by elastic
collisions and fill a volume such that their mean free path between collisions is much larger than their diameter.
Such systems approximate monatomic gases such as helium and other noble gases. For an ideal gas the kinetic
energy consists only of the translational energy of the individual atoms. Monatomic particles do not possess
rotational or vibrational degrees of freedom, and are not electronically excited to higher energies except at very
high temperatures.

Therefore, the internal energy of an ideal gas depends solely on its temperature (and the number of gas particles):
. It is not dependent on other thermodynamic quantities such as pressure or density.

The internal energy of an ideal gas is proportional to its amount of substance (number of moles) and to its
temperature

where is the isochoric (at constant volume) molar heat capacity of the gas; is constant for an ideal gas. The
internal energy of any gas (ideal or not) may be written as a function of the three extensive properties , ,
(entropy, volume, number of moles). In case of the ideal gas it is in the following way [15]

where is an arbitrary positive constant and where is the universal gas constant. It is easily seen that is a
linearly homogeneous function of the three variables (that is, it is extensive in these variables), and that it is
weakly convex. Knowing temperature and pressure to be the derivatives the ideal gas law

immediately follows as below:

Internal energy of a closed thermodynamic system
The above summation of all components of change in internal energy assumes that a positive energy denotes heat
added to the system or the negative of work done by the system on its surroundings.[note 1]

This relationship may be expressed in infinitesimal terms using the differentials of each term, though only the
internal energy is an exact differential.[16]: 33 For a closed system, with transfers only as heat and work, the change
in the internal energy is

expressing the first law of thermodynamics. It may be expressed in terms of other thermodynamic parameters.
Each term is composed of an intensive variable (a generalized force) and its conjugate infinitesimal extensive
variable (a generalized displacement).

For example, the mechanical work done by the system may be related to the pressure and volume change .
The pressure is the intensive generalized force, while the volume change is the extensive generalized
displacement:

This defines the direction of work, , to be energy transfer from the working system to the surroundings,
indicated by a positive term. [note 1] Taking the direction of heat transfer to be into the working fluid and
assuming a reversible process, the heat is

where denotes the temperature, and denotes the entropy.

The change in internal energy becomes

Changes due to temperature and volume

The expression relating changes in internal energy to changes in temperature and volume is

(1)

This is useful if the equation of state is known.

In case of an ideal gas, we can derive that , i.e. the internal energy of an ideal gas can be written as a
function that depends only on the temperature.

Proof of pressure independence for an ideal gas

The expression relating changes in internal energy to changes in
temperature and volume is
The equation of state is the ideal gas law

Solve for pressure:

Substitute in to internal energy expression:

Take the derivative of pressure with respect to temperature:

Replace:

And simplify:

Derivation of dU in terms of dT and dV

To express in terms of and , the term

is substituted in the fundamental thermodynamic relation

This gives

The term is the heat capacity at constant volume

The partial derivative of with respect to can be evaluated if

the equation of state is known. From the fundamental
thermodynamic relation, it follows that the differential of the
Helmholtz free energy is given by

The symmetry of second derivatives of with respect to and

yields the Maxwell relation:
This gives the expression above.

Changes due to temperature and pressure

When considering fluids or solids, an expression in terms of the temperature and pressure is usually more useful:

where it is assumed that the heat capacity at constant pressure is related to the heat capacity at constant volume
according to

Derivation of dU in terms of dT and dP

The partial derivative of the pressure with respect to temperature
at constant volume can be expressed in terms of the coefficient of
thermal expansion

and the isothermal compressibility

by writing

(2)

and equating dV to zero and solving for the ratio dP/dT. This gives

(3)

Substituting (2) and (3) in (1) gives the above expression.

Changes due to volume at constant temperature

The internal pressure is defined as a partial derivative of the internal energy with respect to the volume at
constant temperature:
Internal energy of multi-component systems
In addition to including the entropy and volume terms in the internal energy, a system is often described also
in terms of the number of particles or chemical species it contains:

where are the molar amounts of constituents of type in the system. The internal energy is an extensive
function of the extensive variables , , and the amounts , the internal energy may be written as a linearly
[17]
homogeneous function of first degree:

where is a factor describing the growth of the system. The differential internal energy may be written as

which shows (or defines) temperature to be the partial derivative of with respect to entropy and pressure
to be the negative of the similar derivative with respect to volume ,

and where the coefficients are the chemical potentials for the components of type in the system. The chemical
potentials are defined as the partial derivatives of the internal energy with respect to the variations in
composition:

As conjugate variables to the composition , the chemical potentials are intensive properties, intrinsically
characteristic of the qualitative nature of the system, and not proportional to its extent. Under conditions of
constant and , because of the extensive nature of and its independent variables, using Euler's homogeneous
function theorem, the differential may be integrated and yields an expression for the internal energy:

The sum over the composition of the system is the Gibbs free energy:
that arises from changing the composition of the system at constant temperature and pressure. For a single
component system, the chemical potential equals the Gibbs energy per amount of substance, i.e. particles or
moles according to the original definition of the unit for .

Internal energy in an elastic medium

For an elastic medium the potential energy component of the internal energy has an elastic nature expressed in
terms of the stress and strain involved in elastic processes. In Einstein notation for tensors, with
summation over repeated indices, for unit volume, the infinitesimal statement is

Euler's theorem yields for the internal energy:[18]

For a linearly elastic material, the stress is related to the strain by

where the are the components of the 4th-rank elastic constant tensor of the medium.

Elastic deformations, such as sound, passing through a body, or other forms of macroscopic internal agitation or
turbulent motion create states when the system is not in thermodynamic equilibrium. While such energies of
motion continue, they contribute to the total energy of the system; thermodynamic internal energy pertains only
when such motions have ceased.

History
James Joule studied the relationship between heat, work, and temperature. He observed that friction in a liquid,
such as caused by its agitation with work by a paddle wheel, caused an increase in its temperature, which he
described as producing a quantity of heat. Expressed in modern units, he found that c. 4186 joules of energy were
needed to raise the temperature of one kilogram of water by one degree Celsius.[19]

Notes
1. This article uses the sign convention of the mechanical work as often defined in engineering, which is different
from the convention used in physics and chemistry; in engineering, work performed by the system against the
environment, e.g., a system expansion, is taken to be positive, while in physics and chemistry, it is taken to be
negative.

See also
Calorimetry
Enthalpy
Exergy
Thermodynamic equations
Thermodynamic potentials
Gibbs free energy
Helmholtz free energy

References
1. Crawford, F. H. (1963), pp. 106–107.
2. Haase, R. (1971), pp. 24–28.
3. E.I. Franses (2014), "Internal energy, the First Law, heat, conservation of total energy, mass and energy
balances, enthalpy, and heat capacities" (https://dx.doi.org/10.1017/cbo9781107707009.006),
Thermodynamics with Chemical Engineering Applications, Cambridge University Press, pp. 70–102, retrieved
2024-09-08
4. Born, M. (1949), Appendix 8, pp. 146–149 (https://archive.org/stream/naturalphilosoph032159mbp#page/n15
7/mode/2up).
5. "Thermodynamics - Heat Capacity, Internal Energy | Britannica" (https://www.britannica.com/science/thermody
namics/Heat-capacity-and-internal-energy). www.britannica.com. 2024-07-29. Retrieved 2024-09-08.
6. International Union of Pure and Applied Chemistry. Physical and Biophysical Chemistry Division (2007).
Quantities, units, and symbols in physical chemistry (https://iupac.org/wp-content/uploads/2019/05/IUPAC-GB
3-2012-2ndPrinting-PDFsearchable.pdf) (PDF) (3rd ed.). Cambridge, UK: RSC Pub. ISBN 978-1-84755-788-
9. OCLC 232639283 (https://search.worldcat.org/oclc/232639283).
7. Tschoegl, N.W. (2000), p. 17.
8. Callen, H.B. (1960/1985), Chapter 5.
9. Münster, A. (1970), p. 6.
10. Münster, A. (1970), Chapter 3.
11. Bailyn, M. (1994), pp. 206–209.
12. I. Klotz, R. Rosenberg, Chemical Thermodynamics - Basic Concepts and Methods, 7th ed., Wiley (2008), p.39
13. Leland, T. W. Jr., Mansoori, G. A., pp. 15, 16.
14. Thermal energy (http://hyperphysics.phy-astr.gsu.edu/hbase/kinetic/eqpar.html#c2) – Hyperphysics.
15. Grubbström, Robert W. (1985). "Towards a Generalized Exergy Concept". In van Gool, W.; Bruggink, J.J.C.
(eds.). Energy and time in the economic and physical sciences. North-Holland. pp. 41–56. ISBN 978-
0444877482.
16. Adkins, C. J. (Clement John) (1983). Equilibrium thermodynamics (3rd ed.). Cambridge [Cambridgeshire]:
Cambridge University Press. ISBN 0-521-25445-0. OCLC 9132054 (https://search.worldcat.org/oclc/913205
4).
17. Landau, Lev Davidovich; Lifshit︠ s︡ , Evgeniĭ Mikhaĭlovich; Pitaevskiĭ, Lev Petrovich; Sykes, John Bradbury;
Kearsley, M. J. (1980). Statistical physics. Oxford. p. 70. ISBN 0-08-023039-3. OCLC 3932994 (https://search.
worldcat.org/oclc/3932994).
18. Landau & Lifshitz 1986, p. 8.
19. Joule, J.P. (1850). "On the Mechanical Equivalent of Heat". Philosophical Transactions of the Royal Society.
140: 61–82. doi:10.1098/rstl.1850.0004 (https://doi.org/10.1098%2Frstl.1850.0004). S2CID 186209447 (http
s://api.semanticscholar.org/CorpusID:186209447).

Bibliography of cited references

Adkins, C. J. (1968/1975). Equilibrium Thermodynamics, second edition, McGraw-Hill, London, ISBN 0-07-
084057-1.
Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-
88318-797-3.
Born, M. (1949). Natural Philosophy of Cause and Chance (https://archive.org/details/naturalphilosoph032159
mbp), Oxford University Press, London.
Callen, H. B. (1960/1985), Thermodynamics and an Introduction to Thermostatistics, (first edition 1960),
second edition 1985, John Wiley & Sons, New York, ISBN 0-471-86256-8.
Crawford, F. H. (1963). Heat, Thermodynamics, and Statistical Physics, Rupert Hart-Davis, London, Harcourt,
Brace & World, Inc.
Haase, R. (1971). Survey of Fundamental Laws, chapter 1 of Thermodynamics, pages 1–97 of volume 1, ed.
W. Jost, of Physical Chemistry. An Advanced Treatise, ed. H. Eyring, D. Henderson, W. Jost, Academic Press,
New York, lcn 73–117081.
Thomas W. Leland Jr., G. A. Mansoori (ed.), Basic Principles of Classical and Statistical Thermodynamics (htt
p://www.uic.edu/labs/trl/1.OnlineMaterials/BasicPrinciplesByTWLeland.pdf) (PDF).
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 978-0-7506-2633-0.
Münster, A. (1970), Classical Thermodynamics, translated by E. S. Halberstadt, Wiley–Interscience, London,
ISBN 0-471-62430-6.
Planck, M., (1923/1927). Treatise on Thermodynamics, translated by A. Ogg, third English edition, Longmans,
Green and Co., London.
Tschoegl, N. W. (2000). Fundamentals of Equilibrium and Steady-State Thermodynamics, Elsevier,
Amsterdam, ISBN 0-444-50426-5.

Bibliography
Alberty, R. A. (2001). "Use of Legendre transforms in chemical thermodynamics" (http://www.iupac.org/publica
tions/pac/2001/pdf/7308x1349.pdf) (PDF). Pure Appl. Chem. 73 (8): 1349–1380.
doi:10.1351/pac200173081349 (https://doi.org/10.1351%2Fpac200173081349). S2CID 98264934 (https://api.
semanticscholar.org/CorpusID:98264934).
Lewis, Gilbert Newton; Randall, Merle: Revised by Pitzer, Kenneth S. & Brewer, Leo (1961). Thermodynamics
(2nd ed.). New York, NY USA: McGraw-Hill Book Co. ISBN 978-0-07-113809-3.

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