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Thermodynamic Equations

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Thermodynamic equations

From Wikipedia, the free encyclopedia

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[edit]

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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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[edit]

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

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

Isothermal compressibility

Adiabatic 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[edit]

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

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

originated in the work of German mathematician Carl Gottfried Neumann[1] 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

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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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 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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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

Thermodynamic potentials[edit]

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.

- 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:

Euler integrals[edit]

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[edit]

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.

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[edit]

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[edit]

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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These properties are seen to be the three possible second derivative of the Gibbs free energy with

respect to temperature and pressure.

Notes[edit]

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

References[edit]

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

(PDF). Pure

Balian, Roger (2003). "Entropy A Protean Concept"

Archived from the original

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

Publications, Inc. (reprinted from Oxford University Press, 1978)

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.

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