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Internal energy

The internal energy of a thermodynamic system is the energy contained within it, measured as the quantity of energy necessary to bring the system from its standard internal state to its present internal state of interest, accounting for the gains and losses of energy due to changes in its internal state, including such quantities as magnetization.[1][2] It excludes the kinetic energy of motion of the system as a whole and the potential energy of position of the system as a whole, with respect to its surroundings and external force fields. It includes the thermal energy, i.e., the 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.

Internal energy
Common symbols
U
SI unitJ
In SI base unitsm2⋅kg/s2
Derivations from
other quantities

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 matter, or of energy, as heat, or by thermodynamic work.[3] 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.

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.[4]

Cardinal functions edit

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.[5][6][7]

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.[6][8][9]

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 edit

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 object 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.[10] 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,[11][12] 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.

Interactions of thermodynamic systems
Type of system Mass flow Work Heat
Open  Y  Y  Y
Closed  N  Y  Y
Thermally isolated  N  Y  N
Mechanically isolated  N  N  Y
Isolated  N  N  N

Internal energy changes edit

Thermodynamics is chiefly concerned with the changes in internal energy  .

For a closed system, with matter transfer excluded, the changes in internal energy are due to heat transfer   and due to thermodynamic work   done by the system on its surroundings.[note 1] Accordingly, the internal energy change   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 matter into the system. This increase,   cannot be split into heat and work components.[3] 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 edit

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 mass (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, mass). In case of the ideal gas it is in the following way [13]

 

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 edit

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.[14]: 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 edit

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 edit

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 edit

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 edit

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 homogeneous function of first degree:[15]

 

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 edit

For an elastic medium the mechanical energy term of the internal energy is 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:[16]

 

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 edit

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.[17]

Notes edit

  1. ^ a b c 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 edit

References edit

  1. ^ Crawford, F. H. (1963), pp. 106–107.
  2. ^ Haase, R. (1971), pp. 24–28.
  3. ^ a b Born, M. (1949), Appendix 8, pp. 146–149.
  4. ^ International Union of Pure and Applied Chemistry. Physical and Biophysical Chemistry Division (2007). Quantities, units, and symbols in physical chemistry (PDF) (3rd ed.). Cambridge, UK: RSC Pub. ISBN 978-1-84755-788-9. OCLC 232639283.
  5. ^ Tschoegl, N.W. (2000), p. 17.
  6. ^ a b Callen, H.B. (1960/1985), Chapter 5.
  7. ^ Münster, A. (1970), p. 6.
  8. ^ Münster, A. (1970), Chapter 3.
  9. ^ Bailyn, M. (1994), pp. 206–209.
  10. ^ I. Klotz, R. Rosenberg, Chemical Thermodynamics - Basic Concepts and Methods, 7th ed., Wiley (2008), p.39
  11. ^ Leland, T. W. Jr., Mansoori, G. A., pp. 15, 16.
  12. ^ Thermal energy – Hyperphysics.
  13. ^ van Gool, W.; Bruggink, J.J.C., eds. (1985). Energy and time in the economic and physical sciences. North-Holland. pp. 41–56. ISBN 978-0444877482.
  14. ^ Adkins, C. J. (Clement John) (1983). Equilibrium thermodynamics (3rd ed.). Cambridge [Cambridgeshire]: Cambridge University Press. ISBN 0-521-25445-0. OCLC 9132054.
  15. ^ Landau, Lev Davidovich; Lifshit︠s︡, Evgeniĭ Mikhaĭlovich; Pitaevskiĭ, Lev Petrovich; Sykes, John Bradbury; Kearsley, M. J. (1980). Statistical physics. Oxford. p. 70. ISBN 0-08-023039-3. OCLC 3932994.{{cite book}}: CS1 maint: location missing publisher (link)
  16. ^ Landau & Lifshitz 1986, p. 8.
  17. ^ 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. S2CID 186209447.

Bibliography of cited references edit

  • 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, 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 (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 edit

  • Alberty, R. A. (2001). "Use of Legendre transforms in chemical thermodynamics" (PDF). Pure Appl. Chem. 73 (8): 1349–1380. doi:10.1351/pac200173081349. S2CID 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.{{cite book}}: CS1 maint: multiple names: authors list (link)

internal, energy, this, article, needs, additional, citations, verification, please, help, improve, this, article, adding, citations, reliable, sources, unsourced, material, challenged, removed, find, sources, news, newspapers, books, scholar, jstor, november,. This article needs additional citations for verification Please help improve this article by adding citations to reliable sources Unsourced material may be challenged and removed Find sources Internal energy news newspapers books scholar JSTOR November 2015 Learn how and when to remove this template message The internal energy of a thermodynamic system is the energy contained within it measured as the quantity of energy necessary to bring the system from its standard internal state to its present internal state of interest accounting for the gains and losses of energy due to changes in its internal state including such quantities as magnetization 1 2 It excludes the kinetic energy of motion of the system as a whole and the potential energy of position of the system as a whole with respect to its surroundings and external force fields It includes the thermal energy i e the 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 Internal energyCommon symbolsUSI unitJIn SI base unitsm2 kg s2Derivations fromother quantitiesD U i p i E i displaystyle Delta U sum i p i E i D U n C V D T displaystyle Delta U nC V Delta T 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 matter or of energy as heat or by thermodynamic work 3 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 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 4 Contents 1 Cardinal functions 2 Description and definition 2 1 Internal energy changes 3 Internal energy of the ideal gas 4 Internal energy of a closed thermodynamic system 4 1 Changes due to temperature and volume 4 2 Changes due to temperature and pressure 4 3 Changes due to volume at constant temperature 5 Internal energy of multi component systems 6 Internal energy in an elastic medium 7 History 8 Notes 9 See also 10 References 10 1 Bibliography of cited references 11 BibliographyCardinal functions editThe 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 5 6 7 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 6 8 9 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 editThe internal energy U displaystyle U nbsp 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 D U i E i displaystyle Delta U sum i E i nbsp where D U displaystyle Delta U nbsp denotes the difference between the internal energy of the given state and that of the reference state and the E i displaystyle E i nbsp 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 U micro pot displaystyle U text micro pot nbsp and microscopic kinetic energy U micro kin displaystyle U text micro kin nbsp components U U micro pot U micro kin displaystyle U U text micro pot U text micro kin nbsp 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 object 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 10 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 11 12 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 N displaystyle N nbsp microstates In a system that is in thermodynamic contact equilibrium with a heat reservoir each microstate has an energy E i displaystyle E i nbsp and is associated with a probability p i displaystyle p i nbsp 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 U i 1 N p i E i displaystyle U sum i 1 N p i E i nbsp This is the statistical expression of the law of conservation of energy Interactions of thermodynamic systems Type of system Mass flow Work HeatOpen nbsp Y nbsp Y nbsp YClosed nbsp N nbsp Y nbsp YThermally isolated nbsp N nbsp Y nbsp NMechanically isolated nbsp N nbsp N nbsp YIsolated nbsp N nbsp N nbsp NInternal energy changes edit Thermodynamics is chiefly concerned with the changes in internal energy D U displaystyle Delta U nbsp For a closed system with matter transfer excluded the changes in internal energy are due to heat transfer Q displaystyle Q nbsp and due to thermodynamic work W displaystyle W nbsp done by the system on its surroundings note 1 Accordingly the internal energy change D U displaystyle Delta U nbsp for a process may be writtenD U Q W closed system no transfer of matter displaystyle Delta U Q W quad text closed system no transfer of matter nbsp 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 matter into the system This increase D U m a t t e r displaystyle Delta U mathrm matter nbsp cannot be split into heat and work components 3 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 D U Q W D U matter matter transfer pathway separate from heat and work transfer pathways displaystyle Delta U Q W Delta U text matter quad text matter transfer pathway separate from heat and work transfer pathways nbsp 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 editThermodynamics 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 U U N T displaystyle U U N T nbsp It is not dependent on other thermodynamic quantities such as pressure or density The internal energy of an ideal gas is proportional to its mass number of moles n displaystyle n nbsp and to its temperature T displaystyle T nbsp U c V N T displaystyle U c V NT nbsp where c V displaystyle c V nbsp is the isochoric at constant volume molar heat capacity of the gas c V displaystyle c V nbsp 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 S displaystyle S nbsp V displaystyle V nbsp n displaystyle n nbsp entropy volume mass In case of the ideal gas it is in the following way 13 U S V N c o n s t e S c V N V R c V N R c V c V displaystyle U S V N mathrm const cdot e frac S c V N V frac R c V N frac R c V c V nbsp where c o n s t displaystyle mathrm const nbsp is an arbitrary positive constant and where R displaystyle R nbsp is the universal gas constant It is easily seen that U displaystyle U nbsp 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 T U S displaystyle T frac partial U partial S nbsp P U V displaystyle P frac partial U partial V nbsp the ideal gas law P V N R T displaystyle PV NRT nbsp immediately follows as below T U S U c V N displaystyle T frac partial U partial S frac U c V N nbsp P U V U R c V V displaystyle P frac partial U partial V U frac R c V V nbsp P T U R c V V U c V N N R V displaystyle frac P T frac frac UR c V V frac U c V N frac NR V nbsp P V N R T displaystyle PV NRT nbsp Internal energy of a closed thermodynamic system editThe 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 14 33 For a closed system with transfers only as heat and work the change in the internal energy is d U d Q d W displaystyle mathrm d U delta Q delta W nbsp 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 P displaystyle P nbsp and volume change d V displaystyle mathrm d V nbsp The pressure is the intensive generalized force while the volume change is the extensive generalized displacement d W P d V displaystyle delta W P mathrm d V nbsp This defines the direction of work W displaystyle W nbsp to be energy transfer from the working system to the surroundings indicated by a positive term note 1 Taking the direction of heat transfer Q displaystyle Q nbsp to be into the working fluid and assuming a reversible process the heat is d Q T d S displaystyle delta Q T mathrm d S nbsp where T displaystyle T nbsp denotes the temperature and S displaystyle S nbsp denotes the entropy The change in internal energy becomes d U T d S P d V displaystyle mathrm d U T mathrm d S P mathrm d V nbsp Changes due to temperature and volume edit The expression relating changes in internal energy to changes in temperature and volume is d U C V d T T P T V P d V displaystyle mathrm d U C V mathrm d T left T left frac partial P partial T right V P right mathrm d V nbsp 1 This is useful if the equation of state is known In case of an ideal gas we can derive that d U C V d T displaystyle dU C V dT nbsp 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 gasThe expression relating changes in internal energy to changes in temperature and volume is d U C V d T T P T V P d V displaystyle mathrm d U C V mathrm d T left T left frac partial P partial T right V P right mathrm d V nbsp The equation of state is the ideal gas law P V n R T displaystyle PV nRT nbsp Solve for pressure P n R T V displaystyle P frac nRT V nbsp Substitute in to internal energy expression d U C V d T T P T V n R T V d V displaystyle dU C V mathrm d T left T left frac partial P partial T right V frac nRT V right mathrm d V nbsp Take the derivative of pressure with respect to temperature P T V n R V displaystyle left frac partial P partial T right V frac nR V nbsp Replace d U C V d T n R T V n R T V d V displaystyle dU C V mathrm d T left frac nRT V frac nRT V right mathrm d V nbsp And simplify d U C V d T displaystyle mathrm d U C V mathrm d T nbsp Derivation of dU in terms of dT and dVTo express d U displaystyle mathrm d U nbsp in terms of d T displaystyle mathrm d T nbsp and d V displaystyle mathrm d V nbsp the term d S S T V d T S V T d V displaystyle mathrm d S left frac partial S partial T right V mathrm d T left frac partial S partial V right T mathrm d V nbsp is substituted in the fundamental thermodynamic relation d U T d S P d V displaystyle mathrm d U T mathrm d S P mathrm d V nbsp This gives d U T S T V d T T S V T P d V displaystyle dU T left frac partial S partial T right V dT left T left frac partial S partial V right T P right dV nbsp The term T S T V displaystyle T left frac partial S partial T right V nbsp is the heat capacity at constant volume C V displaystyle C V nbsp The partial derivative of S displaystyle S nbsp with respect to V displaystyle V nbsp 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 A displaystyle A nbsp is given by d A S d T P d V displaystyle dA S dT P dV nbsp The symmetry of second derivatives of A displaystyle A nbsp with respect to T displaystyle T nbsp and V displaystyle V nbsp yields the Maxwell relation S V T P T V displaystyle left frac partial S partial V right T left frac partial P partial T right V nbsp This gives the expression above Changes due to temperature and pressure edit When considering fluids or solids an expression in terms of the temperature and pressure is usually more useful d U C P a P V d T b T P a T V d P displaystyle dU left C P alpha PV right dT left beta T P alpha T right V dP nbsp where it is assumed that the heat capacity at constant pressure is related to the heat capacity at constant volume according to C P C V V T a 2 b T displaystyle C P C V VT frac alpha 2 beta T nbsp Derivation of dU in terms of dT and dPThe partial derivative of the pressure with respect to temperature at constant volume can be expressed in terms of the coefficient of thermal expansion a 1 V V T P displaystyle alpha equiv frac 1 V left frac partial V partial T right P nbsp and the isothermal compressibility b T 1 V V P T displaystyle beta T equiv frac 1 V left frac partial V partial P right T nbsp by writing d V V p T d P V T P d T V a d T b T d P dV left frac partial V partial p right T dP left frac partial V partial T right P dT V left alpha dT beta T dP right nbsp 2 and equating dV to zero and solving for the ratio dP dT This gives P T V V T P V P T a b T left frac partial P partial T right V frac left frac partial V partial T right P left frac partial V partial P right T frac alpha beta T nbsp 3 Substituting 2 and 3 in 1 gives the above expression Changes due to volume at constant temperature edit The internal pressure is defined as a partial derivative of the internal energy with respect to the volume at constant temperature p T U V T displaystyle pi T left frac partial U partial V right T nbsp Internal energy of multi component systems editThis section does not cite any sources Please help improve this section by adding citations to reliable sources Unsourced material may be challenged and removed November 2015 Learn how and when to remove this template message In addition to including the entropy S displaystyle S nbsp and volume V displaystyle V nbsp terms in the internal energy a system is often described also in terms of the number of particles or chemical species it contains U U S V N 1 N n displaystyle U U S V N 1 ldots N n nbsp where N j displaystyle N j nbsp are the molar amounts of constituents of type j displaystyle j nbsp in the system The internal energy is an extensive function of the extensive variables S displaystyle S nbsp V displaystyle V nbsp and the amounts N j displaystyle N j nbsp the internal energy may be written as a linearly homogeneous function of first degree 15 U a S a V a N 1 a N 2 a U S V N 1 N 2 displaystyle U alpha S alpha V alpha N 1 alpha N 2 ldots alpha U S V N 1 N 2 ldots nbsp where a displaystyle alpha nbsp is a factor describing the growth of the system The differential internal energy may be written as d U U S d S U V d V i U N i d N i T d S P d V i m i d N i displaystyle mathrm d U frac partial U partial S mathrm d S frac partial U partial V mathrm d V sum i frac partial U partial N i mathrm d N i T mathrm d S P mathrm d V sum i mu i mathrm d N i nbsp which shows or defines temperature T displaystyle T nbsp to be the partial derivative of U displaystyle U nbsp with respect to entropy S displaystyle S nbsp and pressure P displaystyle P nbsp to be the negative of the similar derivative with respect to volume V displaystyle V nbsp T U S displaystyle T frac partial U partial S nbsp P U V displaystyle P frac partial U partial V nbsp and where the coefficients m i displaystyle mu i nbsp are the chemical potentials for the components of type i displaystyle i nbsp in the system The chemical potentials are defined as the partial derivatives of the internal energy with respect to the variations in composition m i U N i S V N j i displaystyle mu i left frac partial U partial N i right S V N j neq i nbsp As conjugate variables to the composition N j displaystyle lbrace N j rbrace nbsp 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 T displaystyle T nbsp and P displaystyle P nbsp because of the extensive nature of U displaystyle U nbsp and its independent variables using Euler s homogeneous function theorem the differential d U displaystyle mathrm d U nbsp may be integrated and yields an expression for the internal energy U T S P V i m i N i displaystyle U TS PV sum i mu i N i nbsp The sum over the composition of the system is the Gibbs free energy G i m i N i displaystyle G sum i mu i N i nbsp 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 N j displaystyle lbrace N j rbrace nbsp Internal energy in an elastic medium editFor an elastic medium the mechanical energy term of the internal energy is expressed in terms of the stress s i j displaystyle sigma ij nbsp and strain e i j displaystyle varepsilon ij nbsp involved in elastic processes In Einstein notation for tensors with summation over repeated indices for unit volume the infinitesimal statement is d U T d S s i j d e i j displaystyle mathrm d U T mathrm d S sigma ij mathrm d varepsilon ij nbsp Euler s theorem yields for the internal energy 16 U T S 1 2 s i j e i j displaystyle U TS frac 1 2 sigma ij varepsilon ij nbsp For a linearly elastic material the stress is related to the strain by s i j C i j k l e k l displaystyle sigma ij C ijkl varepsilon kl nbsp where the C i j k l displaystyle C ijkl nbsp 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 editJames 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 17 Notes edit a b c 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 editCalorimetry Enthalpy Exergy Thermodynamic equations Thermodynamic potentials Gibbs free energy Helmholtz free energyReferences edit Crawford F H 1963 pp 106 107 Haase R 1971 pp 24 28 a b Born M 1949 Appendix 8 pp 146 149 International Union of Pure and Applied Chemistry Physical and Biophysical Chemistry Division 2007 Quantities units and symbols in physical chemistry PDF 3rd ed Cambridge UK RSC Pub ISBN 978 1 84755 788 9 OCLC 232639283 Tschoegl N W 2000 p 17 a b Callen H B 1960 1985 Chapter 5 Munster A 1970 p 6 Munster A 1970 Chapter 3 Bailyn M 1994 pp 206 209 I Klotz R Rosenberg Chemical Thermodynamics Basic Concepts and Methods 7th ed Wiley 2008 p 39 Leland T W Jr Mansoori G A pp 15 16 Thermal energy Hyperphysics van Gool W Bruggink J J C eds 1985 Energy and time in the economic and physical sciences North Holland pp 41 56 ISBN 978 0444877482 Adkins C J Clement John 1983 Equilibrium thermodynamics 3rd ed Cambridge Cambridgeshire Cambridge University Press ISBN 0 521 25445 0 OCLC 9132054 Landau Lev Davidovich Lifshit s Evgeniĭ Mikhaĭlovich Pitaevskiĭ Lev Petrovich Sykes John Bradbury Kearsley M J 1980 Statistical physics Oxford p 70 ISBN 0 08 023039 3 OCLC 3932994 a href Template Cite book html title Template Cite book cite book a CS1 maint location missing publisher link Landau amp Lifshitz 1986 p 8 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 S2CID 186209447 Bibliography of cited references edit 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 Oxford University Press London Callen H B 1960 1985 Thermodynamics and an Introduction to Thermostatistics first edition 1960 second edition 1985 John Wiley amp Sons New York ISBN 0 471 86256 8 Crawford F H 1963 Heat Thermodynamics and Statistical Physics Rupert Hart Davis London Harcourt Brace amp 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 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 Munster 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 editAlberty R A 2001 Use of Legendre transforms in chemical thermodynamics PDF Pure Appl Chem 73 8 1349 1380 doi 10 1351 pac200173081349 S2CID 98264934 Lewis Gilbert Newton Randall Merle Revised by Pitzer Kenneth S amp Brewer Leo 1961 Thermodynamics 2nd ed New York NY USA McGraw Hill Book Co ISBN 978 0 07 113809 3 a href Template Cite book html title Template Cite book cite book a CS1 maint multiple names authors list link Retrieved from https en wikipedia org w index php title Internal energy amp oldid 1206465106, wikipedia, wiki, book, books, library,

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