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State Function

A state function in thermodynamics is a property of a system that depends only on the current thermodynamic state of the system and not on how that state was reached. State functions include internal energy, enthalpy, and entropy, while non-state functions like work and heat depend on the path between states. Examples of state functions are energy, enthalpy, internal energy, Gibbs free energy, Helmholtz free energy, and entropy.

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193 views

State Function

A state function in thermodynamics is a property of a system that depends only on the current thermodynamic state of the system and not on how that state was reached. State functions include internal energy, enthalpy, and entropy, while non-state functions like work and heat depend on the path between states. Examples of state functions are energy, enthalpy, internal energy, Gibbs free energy, Helmholtz free energy, and entropy.

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State function

In thermodynamics, a state function or


function of state is a function defined for a
system relating several state variables or
state quantities that depends only on the
current equilibrium state of the system.[1]
State functions do not depend on the path
by which the system arrived at its present
state. A state function describes the
equilibrium state of a system.
For example, internal energy, enthalpy, and
entropy are state quantities because they
describe quantitatively an equilibrium
state of a thermodynamic system,
irrespective of how the system arrived in
that state. In contrast, mechanical work
and heat are process quantities or path
functions, because their values depend on
the specific transition (or path) between
two equilibrium states. The mode of
description breaks down for quantities
exhibiting hysteresis effects.[2]

History
It is likely that the term “functions of state”
was used in a loose sense during the
1850s and 60s by those such as Rudolf
Clausius, William Rankine, Peter Tait,
William Thomson, and it is clear that by
the 1870s the term had acquired a use of
its own. In 1873, for example, Willard
Gibbs, in his paper “Graphical Methods in
the Thermodynamics of Fluids”, states:
“The quantities V, B, T, U, and S are
determined when the state of the body is
given, and it may be permitted to call them
functions of the state of the body.[3]

Overview
A thermodynamic system is described by
a number of thermodynamic parameters
(e.g. temperature, volume, pressure) which
are not necessarily independent. The
number of parameters needed to describe
the system is the dimension of the state
space of the system (D). For example, a
monatomic gas having a fixed number of
particles is a simple case of a two-
dimensional system (D = 2). In this
example, any system is uniquely specified
by two parameters, such as pressure and
volume, or perhaps pressure and
temperature. These choices are
equivalent. They are simply different
coordinate systems in the two-
dimensional thermodynamic state space.
Given pressure and temperature, the
volume is calculable from them. Likewise,
given pressure and volume, the
temperature is calculable from them. An
analogous statement holds for higher-
dimensional spaces, as described by the
state postulate.

Quite generally, a state function is of the


form

where P denotes pressure, T denotes


temperature, V denotes volume, and the
ellipsis denotes other possible state
variables like particle number N and
entropy S. If the state space is two-
dimensional as in the above example, one
may visualize the state space as a three-
dimensional graph (a surface in three-
dimensional space). The labels of the axes
are not generally unique, since there are
more state variables than three in this
case, and any two independent variables
suffice to define the state.

When a system changes state


continuously, it traces out a "path" in the
state space. The path can be specified by
noting the values of the state parameters
as the system traces out the path, perhaps
as a function of time, or some other
external variable. For example, we might
have the pressure and the volume
as functions of time from time to
. This will specify a path in our two
dimensional state space example. We can
now form all sorts of functions of time
which we may integrate over the path. For
example, if we wish to calculate the work
done by the system from time to time
we calculate

It is clear that in order to calculate the


work W in the above integral, we will have
to know the functions and at
each time , over the entire path. A state
function is a function of the parameters of
the system which only depends upon the
parameters' values at the endpoints of the
path. For example, suppose we wish to
calculate the work plus the integral of
over the path. We would have:

It can be seen that the integrand can be


expressed as the exact differential of the
function and that therefore, the
integral can be expressed as the
difference in the value of at the
end points of the integration. The product
is therefore a state function of the
system.

By way of notation, we will specify the use


of d to denote an exact differential. In
other words, the integral of will be
equal to . The symbol δ
will be reserved for an inexact differential,
which cannot be integrated without full
knowledge of the path. For example,
will be used to denote an
infinitesimal increment of work.
It is best to think of state functions as
quantities or properties of a
thermodynamic system, while non-state
functions represent a process during
which the state functions change. For
example, the state function is
proportional to the internal energy of an
ideal gas, but the work is the amount of
energy transferred as the system performs
work. Internal energy is identifiable, it is a
particular form of energy. Work is the
amount of energy that has changed its
form or location.

List of state functions


The following are considered to be state
functions in thermodynamics:
Mass
Energy (E)
Enthalpy (H)
Internal energy (U)
Gibbs free energy (G)
Helmholtz free energy (F)
Exergy (B)
Entropy (S)
Pressure (P)
Temperature (T)
Volume (V)
Chemical composition
Specific volume (v) or its reciprocal
Density (ρ)
Fugacity
Altitude
Particle number (ni)

See also
Markov property
Conservative vector field
Nonholonomic system
Equation of state

Notes
1. Callen 1985, pp. 5,37
2. Mandl 1988, p. 7
3. Gibbs 1873, pp. 309–342
References
Callen, Herbert B. (1985).
Thermodynamics and an Introduction to
Thermostatistics. Wiley & Sons.
ISBN 978-0-471-86256-7.
Gibbs, Josiah Willard (1873). "Graphical
Methods in the Thermodynamics of
Fluids". Transactions of the Connecticut
Academy. II. ASIN B00088UXBK .
Mandl, F. (1988). Statistical physics
(second ed.). Wiley & Sons. ISBN 978-0-
471-91533-1.

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