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Inexact dierential
From Wikipedia, the free encyclopedia

An inexact dierential or imperfect dierential is a specic type of

dierential used in thermodynamics to express the path dependence of a
particular dierential. It is contrasted with the concept of the exact dierential
in calculus, which can be expressed as the gradient of another function and is
therefore path independent. Consequently, an inexact dierential cannot be
expressed in terms of its antiderivative for the purpose of integral calculations;
i.e. its value cannot be inferred just by looking at the initial and nal states of a
given system.[1] It is primarily used in calculations involving heat and work
because they are path functions, not state functions.

Contents
1 Denition
2 First law of thermodynamics
3 Examples
3.1 Total distance
3.2 Heat and work
4 Integrating factors
5 See also
6 References
7 External links

Denition
An inexact dierential is commonly dened as a dierential form dx where

there is no corresponding function x such that: . More precisely, an

inexact dierential is a dierential form that cannot be expressed as the

dierential of a function. In the language of calculus, for a given vector eld F,
is an inexact dierential if there is no function f such that

The fundamental theorem of calculus for line integrals requires path

independence in order to express the values of a given vector eld in terms of
the partial derivatives of another function that is the multivariate analogue of
the antiderivative. This is because there can be no unique representation of an
antiderivative for inexact dierentials since their variation is inconsistent along
dierent paths. This stipulation of path independence is a necessary addendum
to the fundamental theorem of calculus because in one-dimensional calculus
there is only one path in between two points dened by a function.

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First law of thermodynamics

Inexact dierentials are known especially for their presence in the rst law of
thermodynamics:

Q = dU + W

The symbol instead of the plain d, which originated from the 19th century
work of German mathematician Carl Gottfried Neumann,[2] indicates that Q
(heat) and W (work) are path-dependent.

Internal energy U is a state function, meaning its change can be inferred just
by comparing two dierent states of the system (not its transition path), which
we can therefore indicate with U1 and U2. Since we can go from state U1 to
state U2 either by providing heat Q = U2U1 or work W=U2U1, such a
change of state does not identify uniquely the values of provided W and Q, but
only the change in internal energy U.

Examples
Although diicult to express mathematically, the inexact dierential is very
simple conceptually. There are many everyday examples that are much more
relevant to inexact dierentials in the actual context in which it is used.

Total distance

The easiest example is the dierence between net distance and total distance.
For example, in walking from Point A to Point B along a straight line, one
covers a net distance BA that is equal to the total distance. If one then
returns to Point A, however, net distance is now 0 while total distance covered
is 2*(BA). This example captures the essential idea behind the inexact
dierential in one dimension.

Precisely, the dierential of net distance is simply the exact one form
with corresponding function . It is exact because 1
has antiderivative x everywhere on the real line. On the other hand, the
dierential of total distance is the inexact one form (i.e. the
sign function). It is inexact because sgn(x) has antiderivative |x| which is not
dierentiable at x = 0. Therefore and instead we must look at
the path dependence. In our example, in the rst leg of the journey, sgn(dx) is 1
since x is increasing. In the second leg, sgn(dx) is 1 since x is decreasing. We
can then evaluate the total distance as:

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Heat and work

A re requires heat, fuel, and an oxidizing agent. The energy required to

overcome the activation energy barrier for combustion is transferred as heat
into the system, resulting in changes to the systems internal energy. In a
process, the energy input to start a re may comprise both work and heat, such
as when one rubs tinder (work) and experiences friction (heat) to start a re.
The ensuing combustion is highly exothermic, which releases heat. The overall
change in internal energy does not reveal the mode of energy transfer and
quanties only the net work and heat. The dierence between initial and nal
states of the systems internal energy does not account for the extent of the
energy interactions transpired. Therefore, internal energy is a state function
(i.e. exact dierential), while heat and work are path functions (i.e. inexact
dierentials) because integration must account for the path taken.

Integrating factors
It is sometimes possible to convert an inexact dierential into an exact one by
means of an integrating factor. The most common example of this in
thermodynamics is the denition of entropy:

In this case, Q is an inexact dierential, because its eect on the state of the
system can be compensated by W. However, when divided by the absolute
temperature and when the exchange occurs at reversible conditions (therefore
the rev subscript), it produces an exact dierential: the entropy S is also a state
function.

See also
Closed and exact dierential forms for a higher-level treatment
Dierential (mathematics)
Exact dierential
Exact dierential equation
Integrating factor for solving non-exact dierential equations by making
them exact
Conservative vector eld

References
1. Laider, Keith, J. (1993). The World of Physical Chemistry. Oxford University
Press. ISBN 0-19-855919-4.
2. Carl G. Neumann, Vorlesungen ber die mechanische Theorie der Wrme, 1875.

External links

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Inexact dierential - Wikipedia https://en.wikipedia.org/w/index.php?title=Inex...

Inexact Dierential (http://mathworld.wolfram.com

/InexactDierential.html) from Wolfram MathWorld
Exact and Inexact Dierentials (http://www.chem.arizona.edu/~salzmanr
/480a/480ants/e&idi/e&idi.html) University of Arizona
Exact and Inexact Dierentials (http://farside.ph.utexas.edu/teaching
/sm1/lectures/node36.html) University of Texas
Exact Dierential (http://mathworld.wolfram.com/ExactDierential.html)
from Wolfram MathWorld

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Categories: Thermodynamics Multivariable calculus

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