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State function
From Wikipedia, the free encyclopedia
In thermodynamics, a state function, function of state, state quantity, or state variable is a property of a system
that depends only on the current state of the system, not on the way in which the system acquired that state
(independent of path). 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 because their values depend on the specific transition
(or path) between two equilibrium states.
Contents
1 History
2 Overview
3 List of state functions
4 See also
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.
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 ( ). For example, a monatomic gas with a fixed number of particles is a simple case of a
two-dimensional system ( ). 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. An analogous statement holds for higher-
dimensional spaces, as described by the state postulate.
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
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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 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 ()
Fugacity
Altitude
Particle number (n
i
)
See also
Markov property
8/9/2014 State function - Wikipedia, the free encyclopedia
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Conservative vector field
Nonholonomic System
Equation of state
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Categories: Thermodynamics State functions
This page was last modified on 12 April 2014 at 02:36.
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