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Thermodynamic equations

For a quick reference table of these equations, see: Table of thermodynamic equations
Thermodynamics is expressed by a mathematical framework of thermodynamic equations which
relate various thermodynamic quantities and physical properties measured in a laboratory or
production process. Thermodynamics is based on a fundamental set of postulates, that became the
laws of thermodynamics.

Contents
1 Introduction
2 Notation
3 Laws of thermodynamics
4 The fundamental equation
5 Thermodynamic potentials
6 First order equations
6.1 Euler integrals
6.2 GibbsDuhem relationship
7 Second order equations
7.1 Maxwell relations
7.2 Material properties
8 Notes
9 References

Introduction
One of the fundamental thermodynamic equations is the description of thermodynamic work in
analogy to mechanical work, or weight lifted through an elevation against gravity, as defined in
1824 by French physicist Sadi Carnot. Carnot used the phrase motive power for work. In the
footnotes to his famous On the Motive Power of Fire, he states: We use here the expression
motive power to express the useful effect that a motor is capable of producing. This effect can

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## always be likened to the elevation of a weight to a certain height. It has, as we know, as a

measure, the product of the weight multiplied by the height to which it is raised. With the inclusion
of a unit of time in Carnot's definition, one arrives at the modern definition for power:

During the latter half of the 19th century, physicists such as Rudolf Clausius, Peter Guthrie Tait, and
Willard Gibbs worked to develop the concept of a thermodynamic system and the correlative
energetic laws which govern its associated processes. The equilibrium state of a thermodynamic
system is described by specifying its "state". The state of a thermodynamic system is specified by a
number of extensive quantities, the most familiar of which are volume, internal energy, and the
amount of each constituent particle (particle numbers). Extensive parameters are properties of the
entire system, as contrasted with intensive parameters which can be defined at a single point, such
as temperature and pressure. The extensive parameters (except entropy) are generally conserved
in some way as long as the system is "insulated" to changes to that parameter from the outside.
The truth of this statement for volume is trivial, for particles one might say that the total particle
number of each atomic element is conserved. In the case of energy, the statement of the
conservation of energy is known as the first law of thermodynamics.
A thermodynamic system is in equilibrium when it is no longer changing in time. This may happen
in a very short time, or it may happen with glacial slowness. A thermodynamic system may be
composed of many subsystems which may or may not be "insulated" from each other with respect
to the various extensive quantities. If we have a thermodynamic system in equilibrium in which we
relax some of its constraints, it will move to a new equilibrium state. The thermodynamic
parameters may now be thought of as variables and the state may be thought of as a particular
point in a space of thermodynamic parameters. The change in the state of the system can be seen
as a path in this state space. This change is called a thermodynamic process. Thermodynamic
equations are now used to express the relationships between the state parameters at these
different equilibrium state.
The concept which governs the path that a thermodynamic system traces in state space as it goes
from one equilibrium state to another is that of entropy. The entropy is first viewed as an extensive
function of all of the extensive thermodynamic parameters. If we have a thermodynamic system in
equilibrium, and we release some of the extensive constraints on the system, there are many
equilibrium states that it could move to consistent with the conservation of energy, volume, etc.
The second law of thermodynamics specifies that the equilibrium state that it moves to is in fact the
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one with the greatest entropy. Once we know the entropy as a function of the extensive variables
of the system, we will be able to predict the final equilibrium state. (Callen 1985)

Notation
Some of the most common thermodynamic quantities are:
The conjugate variable pairs are the fundamental state variables used to formulate the
thermodynamic functions.
p Pressure

V Volume

T Temperature

S Entropy

## Chemical potential N Particle number

The most important thermodynamic potentials are the following functions:
U Internal energy F Helmholtz free energy H Enthalpy G Gibbs free energy
Thermodynamic systems are typically affected by the following types of system interactions. The
types under consideration are used to classify systems as open systems, closed systems, and
isolated systems.
w infinitesimal amount of Work (W)
q infinitesimal amount of Heat (Q)
m mass
Common material properties determined from the thermodynamic functions are the following:

CV

Cp

## Heat capacity at constant pressure

Isothermal compressibility
Coefficient of thermal expansion

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The following constants are constants that occur in many relationships due to the application of a
standard system of units.
kB Boltzmann constant R Ideal gas constant NA Avogadro constant

Laws of thermodynamics
The behavior of a thermodynamic system is summarized in the laws of thermodynamics, which
concisely are:
Zeroth law of thermodynamics
If A, B, C are thermodynamic systems such that A is in thermal equilibrium with B
and B is in thermal equilibrium with C, then A is in thermal equilibrium with C.
The zeroth law is of importance in thermometry, because it implies the existence of
temperature scales. In practice, C is a thermometer, and the zeroth law says that
systems that are in thermodynamic equilibrium with each other have the same
temperature. The law was actually the last of the laws to be formulated.
First law of thermodynamics
where
system,

is the

## infinitesimal work done by the system.

The first law is the law of conservation of energy. The symbol

## instead of the plain d,

originated in the work of German mathematician Carl Gottfried Neumann and is used
to denote an inexact differential and to indicate that Q and W are path-dependent (i.e.,
they are not state functions). In some fields such as physical chemistry, positive work is
conventionally considered work done on the system rather than by the system, and the
law is expressed as

## Second law of thermodynamics

The entropy of an isolated system never decreases:

for an isolated

system.
A concept related to the second law which is important in thermodynamics is that of
reversibility. A process within a given isolated system is said to be reversible if
throughout the process the entropy never increases (i.e. the entropy remains
unchanged).

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## Third law of thermodynamics

when
The third law of thermodynamics states that at the absolute zero of temperature, the
entropy is zero for a perfect crystalline structure.
Onsager reciprocal relations sometimes called the Fourth law of thermodynamics

The fourth law of thermodynamics is not yet an agreed upon law (many supposed
variations exist); historically, however, the Onsager reciprocal relations have been
frequently referred to as the fourth law.

## The fundamental equation

The first and second law of thermodynamics are the most fundamental equations of
thermodynamics. They may be combined into what is known as fundamental thermodynamic
relation which describes all of the thermodynamic properties of a system. As a simple example,
consider a system composed of a number of k different types of particles and has the volume as its
only external variable. The fundamental thermodynamic relation may then be expressed in terms of
the internal energy as:

Some important aspects of this equation should be noted: (Alberty 2001), (Balian 2003), (Callen
1985)
The thermodynamic space has k+2 dimensions
The differential quantities (U, S, V, Ni) are all extensive quantities. The coefficients of the
differential quantities are intensive quantities (temperature, pressure, chemical potential).
Each pair in the equation are known as a conjugate pair with respect to the internal energy.
The intensive variables may be viewed as a generalized "force". An imbalance in the intensive
variable will cause a "flow" of the extensive variable in a direction to counter the imbalance.
The equation may be seen as a particular case of the chain rule. In other words:

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## from which the following identifications can be made:

These equations are known as "equations of state" with respect to the internal energy. (Note the relation between pressure, volume, temperature, and particle number which is commonly
called "the equation of state" is just one of many possible equations of state.) If we know all
k+2 of the above equations of state, we may reconstitute the fundamental equation and
recover all thermodynamic properties of the system.
The fundamental equation can be solved for any other differential and similar expressions can
be found. For example, we may solve for

## and find that

Thermodynamic potentials
By the principle of minimum energy, the second law can be restated by saying that for a fixed
entropy, when the constraints on the system are relaxed, the internal energy assumes a minimum
value. This will require that the system be connected to its surroundings, since otherwise the
energy would remain constant.
By the principle of minimum energy, there are a number of other state functions which may be
defined which have the dimensions of energy and which are minimized according to the second law
under certain conditions other than constant entropy. These are called thermodynamic potentials.
The four most common thermodynamic potentials are:

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Name

Symbol

http://en.wikipedia.org/wiki/Thermodynamic_equations

Formula

Natural variables

Internal energy
Helmholtz free energy
Enthalpy
Gibbs free energy
After each potential is shown its "natural variables". These variables are important because if the
thermodynamic potential is expressed in terms of its natural variables, then it will contain all of the
thermodynamic relationships necessary to derive any other relationship. In other words, it too will
be a fundamental equation. For the above four potentials, the fundamental equations are expressed
as:

The thermodynamic square can be used as a tool to recall and derive these potentials.

## First order equations

- General system
- Particular systems
Just as with the internal energy version of the fundamental equation, the chain rule can be used on
the above equations to find k+2 equations of state with respect to the particular potential. If is a
thermodynamic potential, then the fundamental equation may be expressed as:

where the

is conjugate to

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equations of state for that potential, one for each set of conjugate variables.

Only one equation of state will not be sufficient to reconstitute the fundamental equation. All
equations of state will be needed to fully characterize the thermodynamic system. Note that what is
commonly called "the equation of state" is just the "mechanical" equation of state involving the
Helmholtz potential and the volume:

## For an ideal gas, this becomes the familiar PV=NkBT.

Euler integrals
Because all of natural variables of the internal energy U are extensive quantities, it follows from
Euler's homogeneous function theorem that

Substituting into the expressions for the other main potentials we have the following expressions
for the thermodynamic potentials:

Note that the Euler integrals are sometimes also referred to as fundamental equations.

GibbsDuhem relationship
Differentiating the Euler equation for the internal energy and combining with the fundamental
equation for internal energy, it follows that:

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which is known as the Gibbs-Duhem relationship. The Gibbs-Duhem is a relationship among the
intensive parameters of the system. It follows that for a simple system with r components, there
will be r+1 independent parameters, or degrees of freedom. For example, a simple system with a
single component will have two degrees of freedom, and may be specified by only two parameters,
such as pressure and volume for example. The law is named after Willard Gibbs and Pierre Duhem.

## Second order equations

There are many relationships that follow mathematically from the above basic equations. See Exact
differential for a list of mathematical relationships. Many equations are expressed as second
derivatives of the thermodynamic potentials (see Bridgman equations).

Maxwell relations
Maxwell relations are equalities involving the second derivatives of thermodynamic potentials with
respect to their natural variables. They follow directly from the fact that the order of differentiation
does not matter when taking the second derivative. The four most common Maxwell relations are:

The thermodynamic square can be used as a tool to recall and derive these relations.

Material properties
Second derivatives of thermodynamic potentials generally describe the response of the system to
small changes. The number of second derivatives which are independent of each other is relatively
small, which means that most material properties can be described in terms of just a few
"standard" properties. For the case of a single component system, there are three properties
generally considered "standard" from which all others may be derived:
Compressibility at constant temperature or constant entropy
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## Coefficient of thermal expansion

These properties are seen to be the three possible second derivative of the Gibbs free energy with
respect to temperature and pressure.

Notes
1. ^ Carl G. Neumann, Vorlesungen ber die mechanische Theorie der Wrme, 1875.

References
Alberty, R. A. (2001). "Use of Legendre transforms in chemical thermodynamics"

(PDF). Pure

## Appl. Chem. 73 (8): 13491380. doi:10.1351/pac200173081349.

Balian, Roger (2003). "Entropy A Protean Concept"
Archived from the original

## Callen, Herbert B. (1985). Thermodynamics and an Introduction to Themostatistics (2nd ed.).

New York: John Wiley & Sons. ISBN 0-471-86256-8.
Atkins, Peter; de Paula, Julio (2002). Physical Chemistry (7th ed.). W.H. Freeman and
Company. ISBN 0-7167-3539-3.
Chapters 1 - 10, Part 1: Equilibrium.
Bridgman, P.W. (1914). Phys. Rev. 3: 273. Bibcode:1914PhRv....3..273B.
doi:10.1103/PhysRev.3.273. Missing or empty |title= (help)
Landsberg, Peter T. (1990). Thermodynamics and Statistical Mechanics. New York: Dover
Lewis, G.N.; Randall, M. (1961). Thermodynamics (2nd ed.). New York: McGraw-Hill Book

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Company.
Schroeder, Daniel V. (2000). Thermal Physics. San Francisco: Addison Wesley Longman.
ISBN 0-201-38027-7.
Silbey, Robert J. et al. (2004). Physical Chemistry (4th ed.). New Jersey: Wiley.
oldid=644669402"
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