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First law of thermodynamics

From Wikipedia, the free encyclopedia

The first law of thermodynamics is a version of the law of conservation of energy, specialized for thermodynamical systems. It is usually
formulated by stating that the change in the internal energy of a closed system is equal to the amount of heat supplied to the system, minus
the amount of work performed by the system on its surroundings. The law of conservation of energy can be stated: The energy of an
isolated system is constant.

Contents
1 Original statements
2 Description
3 Evidence for the first law of thermodynamics
3.1 Adiabatic processes
3.2 Isothermal diabatic processes
3.3 Combination of adiabatic and isothermal diabatic processes
4 State functional formulation
5 Spatially inhomogeneous systems
6 History
7 See also
8 References
9 Further reading
10 External links

Original statements
The first explicit statement of the first law of thermodynamics, by Rudolf Clausius in 1850, referred to cyclic thermodynamic processes.

"In all cases in which work is produced by the agency of heat, a quantity of heat is consumed which is proportional to the
work done; and conversely, by the expenditure of an equal quantity of work an equal quantity of heat is produced."[1]

Clausius stated the law also in another form, this time referring to the existence of a function of state of the system called the internal energy,
and expressing himself in terms of a differential equation for the increments of a thermodynamic process. This equation may be translated
into words as follows:

In a thermodynamic process, the increment in the internal energy of a system is equal to the difference between the
increment of heat accumulated by the system and the increment of work done by it.[2]

Description
The first law of thermodynamics was expressed in two ways by Clausius. One way referred to cyclic processes and the inputs and outputs
of the system, but did not refer to increments in the internal state of the system. The other way referred to any incremental change in the
internal state of the system, and did not expect the process to be cyclic. A cyclic process is one which can be repeated indefinitely often
and still eventually leave the system in its original state.

In each repetition of a cyclic process, the work done by the system is proportional to the heat consumed by the system. In a cyclic process
in which the system does work on its surroundings, it is necessary that some heat be taken in by the system and some be put out, and the
difference is the heat consumed by the system in the process. The constant of proportionality is universal and independent of the system and
was measured by Joule in 1845 and 1847.

In any incremental process, the change in the internal energy is considered due to a combination of heat added to the system and work
done by the system. Taking as an infinitesimal (differential) change in internal energy, one writes

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where and are infinitesimal amounts of heat supplied to the system and work done by the system, respectively. Note that the
minus sign in front of indicates that a positive amount of work done by the system leads to energy being lost from the system. This is
the sign convention used in many textbooks on physics.

(An alternate sign convention is to consider the work performed on the system by its surroundings. This leads to a change in sign of the
work, so that . This is the convention adopted by many modern textbooks of physical chemistry, such as those by
Peter Atkins and Ira Levine.)

When a system expands in a quasistatic process, the work done on the environment by the system is the product of pressure (P) and
volume (V) change, i.e. P dV, whereas the work done on the system is -P dV. With either sign convention for the work, the change in
internal energy of the system is:

Work and heat are expressions of actual physical processes which add or subtract energy, while U is a mathematical abstraction that keeps
account of the exchanges of energy that befall the system. Thus the term heat for means that amount of energy added as the result of
heating, rather than referring to a particular form of energy. Likewise, work energy for means "that amount of energy lost as the result
of work". Internal energy is a property of the system whereas work done and heat supplied are not. A significant result of this distinction is
that a given internal energy change can be achieved by, in principle, many combinations of heat and work.

The internal energy of a system is not uniquely defined. It is defined only up to an arbitrary additive constant of integration, which can be
adjusted to give arbitrary reference zero levels. This non-uniqueness is in keeping with the abstract mathematical nature of the internal
energy.

Evidence for the first law of thermodynamics

The first law of thermodynamics is induced from empirically observed evidence. The original discovery of the law was gradual over a period
of perhaps half a century or more, and was mostly in terms of cyclic processes.[3] The following is an account in terms of changes of state
through compound processes that are not necessarily cyclic, but are composed of segments of two special kinds, adiabatic and isothermal
diabatic.

Adiabatic processes

It can be observed that, given a system in an initial state, if work is exerted on the system in an adiabatic (i.e. no heat transfer) way, the final
state is the same for a given amount of work, irrespective of how this work is performed.

For instance, in Joule's experiment, the initial system is a tank of water with a paddle wheel inside. If we isolate thermally the tank and move
the paddle wheel with a pulley and a weight we can relate the increase in temperature with the height descended by the mass. Now the
system is returned to its initial state, isolated again, and the same amount of work is done on the tank using different devices (an electric
motor, a chemical battery, a spring,...). In every case, the amount of work can be measured independently. The evidence shows that the
final state of the water (in particular, its temperature) is the same in every case. It's irrelevant if the work is electrical, mechanical,
chemical,... or if done suddenly or slowly, as long as it is performed in an adiabatic way.

This evidence leads to a statement of one aspect of the first law of thermodynamics

For all adiabatic processes between two specified states of a closed system, the net work done is the same regardless of the
nature of the closed system and the details of the process.

This affirmation of path independence is one aspect of the meaning of the state function that is called internal energy, . In an adiabatic
process, adiabatic work takes the system from a reference state with internal energy to an arbitrary eventual one with internal
energy :

where, following IUPAC convention we take as positive the work done on the system.

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To go from a state A to a state B we can take a path that goes through the reference state, since the adiabatic work is independent of the
path

Isothermal diabatic processes

See also: Thermodynamic processes

A complementary observable aspect of the first law is about heat transfer.

When the system does not evolve adiabatically, the work exerted on the system is not equal to the increase in its internal energy:

The difference is due to the transfer of heat into the system. Heat transfer can be measured by calorimetry.

If the system is at constant temperature during the heat transfer, the transfer is called isothermal diabatic, and we may write .

Combination of adiabatic and isothermal diabatic processes

Putting the two complementary aspects together, adiabatic and isothermal diabatic, the inequality can be transformed into an equality as

This combined statement is the expression the first law of thermodynamics for finite processes composed of distinct adiabatic and
isothermal diabatic segments.

In particular, if no work is exerted on a thermally isolated system we have

This is one aspect of the law of conservation of energy and can be stated:

The internal energy of an isolated system remains constant.

State functional formulation

The infinitesimal heat and work in the equations above are denoted by δ, rather than exact differentials denoted by "d", because they do not
describe the state of any system. The integral of an inexact differential depends upon the particular path taken through the space of
thermodynamic parameters while the integral of an exact differential depends only upon the initial and final states. If the initial and final states
are the same, then the integral of an inexact differential may or may not be zero, but the integral of an exact differential will always be zero.
The path taken by a thermodynamic system through a chemical or physical change is known as a thermodynamic process.

For homogeneous systems, with a well-defined temperature and pressure, the expression for dU can be written, in terms of exact
differentials by realizing that the work that a system does is equal to its pressure times the infinitesimal increase in its volume. Here one
implicitely assumes that the changes are quasistatic, as any change at a finite rate will cause the assumption of thermal equilibrium to break
down. In other words δW = PdV where P is pressure and V is volume. As such a quasistatic process in a homogeneous system is
reversible, the total amount of heat added to a closed system can be expressed as δQ =TdS where T is the temperature and S the entropy
system. Therefore, for closed, homogeneous systems:

The above equation is known as the fundamental thermodynamic relation. While this has been derived for quasistatic changes, it is valid in
general, as U can be considered as a thermodynamic state function of the independent variables S and V.

E.g., suppose that the system is intitially in a state of thermal equilibrium defined by S and V, and then the system is suddenly perturbed so
that thermal equilibrium breaks down and no temperature and pressure can be defined. Then the system settles down again to a state of
thermal equilibrium, defined by an entropy and a volume which differ infinitessimally from the initial values. The infinitesimal difference in
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internal energy between the intitial and final state will then satisfy the above equation. The work done and heat added to the system will then
not satisfy the above expressions, they will instead satisfy the inequalities: δQ < TdS' and δW < PdV'.

In the case where the number of particles in the system is not necessarily constant and may be of different types, the expression for dU
becomes:

where dNi is the (small) amount of type-i particles added to the system, and μi is known as the chemical potential of the type-i particles in
the system. If dNi is expressed in kg then μi is expressed in J/kg. The statement of the first law, using exact differentials is now:

If the system has more external variables than just the volume that can change, the fundamental thermodynamic relation generalizes to:

Here the Xi are the generalized forces corresponding to the external variables x i. The parameters Xi are independent of the size of the
system and are called intensive parameters and the x i are proportional to the size and called extensive parameters.

A useful idea from mechanics is that the energy gained by a particle is equal to the force applied to the particle multiplied by the
displacement of the particle while that force is applied. Now consider the first law without the heating term: dU = -PdV. The pressure P
can be viewed as a force (and in fact has units of force per unit area) while dVis the displacement (with units of distance times area). We
may say, with respect to this work term, that a pressure difference forces a transfer of volume, and that the product of the two (work) is the
amount of energy transferred out of the system as a result of the process. If one were to make this term negative then this would be the
work done on the system.

It is useful to view the TdS term in the same light: here the temperature is known as a "generalized" force (rather than an actual mechanical
force) and the entropy is a generalized displacement.

Similarly, a difference in chemical potential between groups of particles in the system forces a transfer of particles, and the corresponding
product is the amount of energy transferred as a result of the process. For example, consider a system consisting of two phases: liquid
water and water vapor. There is a generalized "force" of evaporation which drives water molecules out of the liquid. There is a generalized
"force" of condensation which drives vapor molecules out of the vapor. Only when these two "forces" (or chemical potentials) are equal will
there be equilibrium, and the net transfer will be zero.

The two thermodynamic parameters which form a generalized force-displacement pair are termed "conjugate variables". The two most
familiar pairs are, of course, pressure-volume, and temperature-entropy.

Spatially inhomogeneous systems

Classical thermodynamics is focused on homogeneous systems (e.g. Planck 1897/1903[4]), which might be regarded as 'zero-dimensional'
in the sense that they have no spatial variation. But it is desired to study also systems with distinct internal motion and spatial inhomogeneity.
For such systems, the principle of conservation of energy is expressed in terms not only of internal energy as defined for homogeneous
systems, but also in terms of kinetic and potential energies.[5] How the total energy of a system is allocated between these three more
specific kinds of energy varies according to the purposes of different writers; this is because these components of energy are to some extent
mathematical artefacts rather than actually measured physical quantities. If denotes the total energy of a system, one may write

where and denote respectively the kinetic and potential energies internal to the system.[6]

Potential energy can be exchanged with the surroundings of the system when the surroundings impose a force field, such as gravitational or
electromagnetic, on the system.

The distinction between internal and kinetic energy is hard to make in the presence of turbulent motion within the system, as friction
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gradually dissipates macroscopic kinetic energy of localised bulk flow into molecular random motion of molecules that is classified as
internal energy. The rate of dissipation by friction of kinetic energy of localised bulk flow into internal energy,[7][8][9] whether in turbulent or
in streamlined flow, is an important quantity in non-equilibrium thermodynamics. This is a serious difficulty for attempts to define entropy for
time-varying spatially inhomogeneous systems.

History
The discovery of the first law of thermodynamics was by way of many tries and mistakes of investigation, over
a period of about half a century. The first full statements of the law were made by Clausius in 1850 as noted
above, and by Rankine also in 1850; Rankine's statement was perhaps not quite as clear and distinct as was
Clausius'.[3] A main aspect of the struggle was to deal with the previously proposed caloric theory of heat.

Germain Hess in 1840 stated a conservation law for so-called 'heat of reaction' for chemical reactions,[10] but
this was not explicitly concerned with the relation between energy exchanges by heat and work.

According to Truesdell (1980), Julius Robert von Mayer in 1841 made a statement that meant that "in a
process at constant pressure, the heat used to produce expansion is universally interconvertible with work", but Julius Robert von
this is not a general statement of the first law.[11][12] Mayer

See also
Laws of thermodynamics
Entropy production
Perpetual motion
Relativistic heat conduction

References
1. ^ Clausius, R. (1850). Ueber die bewegende Kraft der Wärme und die Gesetze, welche sich daraus für die Wärmelehre selbst ableiten lassen,
Annalen der Physik und Chemie (Poggendorff, Leipzig), 155 (3): 368-394, particularly on page 373 [1]
(http://gallica.bnf.fr/ark:/12148/bpt6k15164w/f389.image) , translation here taken from Truesdell, C.A. (1980). The Tragicomical History of
Thermodynamics, 1822-1854, Springer, New York, ISBN 0-387-90403-4, pages 188-189.
2. ^ Clausius, R. (1850). Ueber die bewegende Kraft der Wärme und die Gesetze, welche sich daraus für die Wärmelehre selbst ableiten lassen,
Annalen der Physik und Chemie (Poggendorff, Leipzig), 155 (3): 368-394, page 384 [2]
(http://gallica.bnf.fr/ark:/12148/bpt6k15164w/f400.image) .
3. ^ a b Truesdell, C.A. (1980). The Tragicomical History of Thermodynamics, 1822-1854, Springer, New York, ISBN 0-387-90403-4.
4. ^ Planck, M. (1897/1903). Treatise on Thermodynamics, translated by A. Ogg, Longmans, Green & Co., London. [3]
(http://www.onread.com/reader/145819)
5. ^ Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318-797-3, pages 162-163,
254-256.
6. ^ Glansdorff, P., Prigogine, I. (1971). Thermodynamic Theory of Structure, Stability and Fluctuations, Wiley, London, ISBN 0-471-30280-
5, page 8.
7. ^ Thomson, William (1852 a). "On a Universal Tendency in Nature to the Dissipation of Mechanical Energy
(http://zapatopi.net/kelvin/papers/on_a_universal_tendency.html) " Proceedings of the Royal Society of Edinburgh for April 19, 1852 [This
version from Mathematical and Physical Papers, vol. i, art. 59, pp. 511.]
8. ^ Thomson, W. (1852 b). On a universal tendency in nature to the dissipation of mechanical energy, Philosophical Magazine 4: 304-306.
9. ^ Helmholtz, H. (1869/1871). Zur Theorie der stationären Ströme in reibenden Flüssigkeiten, Verhandlungen des naturhistorisch-
medizinischen Vereins zu Heidelberg, Band V: 1-7. Reprinted in Helmholtz, H. (1882), Wissenschaftliche Abhandlungen, volume 1, Johann
Ambrosius Barth, Leipzig, pages 223-230 [4] (http://echo.mpiwg-berlin.mpg.de/ECHOdocuViewfull?
url=/mpiwg/online/permanent/einstein_exhibition/sources/QWH2FNX8/index.meta&start=231&viewMode=images&pn=237&mode=texttool)
10. ^ Hess, H. (1840). Thermochemische Untersuchungen, Annalen der Physik und Chemie (Poggendorff, Leipzig) 126(6): 385-404 [5]
(http://gallica.bnf.fr/ark:/12148/bpt6k151359/f397.image.r=Annalen%20der%20Physik%20(Leipzig)%20125.langEN) .
11. ^ Truesdell, C.A. (1980). The Tragicomical History of Thermodynamics, 1822-1854, Springer, New York, ISBN 0-387-90403-4, pages
157-158.
12. ^ Mayer, Robert (1841). Paper: 'Remarks on the Forces of Nature"; as quoted in: Lehninger, A. (1971). Bioenergetics - the Molecular Basis
of Biological Energy Transformations, 2nd. Ed. London: The Benjamin/Cummings Publishing Company.

Further reading
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Goldstein, Martin, and Inge F. (1993). The Refrigerator and the Universe. Harvard University Press. ISBN 0-674-75325-9.
OCLC 32826343 (//www.worldcat.org/oclc/32826343) . Chpts. 2 and 3 contain a nontechnical treatment of the first law.

Çengel Y.A. and Boles M. (2007). Thermodynamics: an engineering approach. McGraw-Hill Higher Education. ISBN 0-07-
125771-3. Chapter 2.

Atkins P. (2007). Four Laws that drive the Universe. OUP Oxford. ISBN 0-19-923236-9.

External links
MISN-0-158, The First Law of Thermodynamics (http://35.9.69.219/home/modules/pdf_modules/m158.pdf) (PDF file) by Jerzy
Borysowicz for Project PHYSNET (http://www.physnet.org) .
First law of thermodynamics (http://web.mit.edu/16.unified/www/FALL/thermodynamics/notes/node8.html) in the MIT Course
Unified Thermodynamics and Propulsion (http://web.mit.edu/16.unified/www/FALL/thermodynamics/notes/notes.html) from Prof.
Z. S. Spakovszky

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