Ideal gas law
The classical Carnot heat engine
The ideal gas law is the equation of state of a hypothetical ideal gas. It is a good approximation to the behaviour of many gases under many conditions, although it has several limitations. It was first stated by Émile Clapeyron in 1834 as a combination of Boyle's law and Charles' law. The ideal gas law is often introduced in its common form:
where P is the absolute pressure of the gas, V is the volume of the gas, n is the amount of substance of gas (measured in moles), T is the absolute temperature of the gas and R is the ideal, or universal, gas constant.
It can also be derived from kinetic theory, as was achieved (apparently independently) by August Krönig in 1856 and Rudolf Clausius in 1857. The universal gas constant was discovered and first introduced into the ideal gas law instead of a large number of specific gas constants by Dmitri Mendeleev in 1874.
- 1 Equation
- 2 Applications to thermodynamic processes
- 3 Deviations from ideal behavior of real gases
- 4 Derivations
- 5 See also
- 6 References
- 7 Further reading
- 8 External links
The state of an amount of gas is determined by its pressure, volume, and temperature. The modern form of the equation relates these simply in two main forms. The temperature used in the equation of state is an absolute temperature: in the SI system of units, kelvin.
The most frequently introduced form is
where P is the pressure of the gas, V is the volume of the gas, n is the amount of substance of gas (also known as number of moles), T is the temperature of the gas and R is the ideal, or universal, gas constant, equal to the product of the Boltzmann constant and the Avogadro constant.
In SI units, P is measured in pascals, V is measured in cubic metres, n is measured in moles, and T in kelvins (273.15 kelvins = 0.00 degrees Celsius). R has the value 8.314 J·K−1·mol−1 or 0.08206 L·atm·mol−1·K−1 if using pressure in standard atmospheres (atm) instead of pascals, and volume in liters instead of cubic metres.
How much gas is present could be specified by giving the mass instead of the chemical amount of gas. Therefore, an alternative form of the ideal gas law may be useful. The chemical amount (n) (in moles) is equal to the mass (m) (in grams) divided by the molar mass (M) (in grams per mole):
By replacing n with m / M, and subsequently introducing density ρ = m/V, we get:
Defining the specific gas constant Rspecific as the ratio R/M,
This form of the ideal gas law is very useful because it links pressure, density, and temperature in a unique formula independent of the quantity of the considered gas. Alternatively, the law may be written in terms of the specific volume v, the reciprocal of density, as
It is common, especially in engineering applications, to represent the specific gas constant by the symbol R. In such cases, the universal gas constant is usually given a different symbol such as R to distinguish it. In any case, the context and/or units of the gas constant should make it clear as to whether the universal or specific gas constant is being referred to.
In statistical mechanics the following molecular equation is derived from first principles:
where P is the absolute pressure of the gas measured in Pascals; n is the number density in the gas measured in 1/(meters cubed); kB is the Boltzmann constant relating temperature and energy; and T is the absolute temperature.
The number density contrasts to the other formulation, which uses N, the number of moles and V, the volume. This relation implies that R=NAkB where NA is Avogadro's constant, and the consistency of this result with experiment is a good check on the principles of statistical mechanics.
and since ρ = m'n, we find that the ideal gas law can be rewritten as:
Applications to thermodynamic processes
The table below essentially simplifies the ideal gas equation for a particular processes, thus making this equation easier to solve using numerical methods.
A thermodynamic process is defined as a system that moves from state 1 to state 2, where the state number is denoted by subscript. As shown in the first column of the table, basic thermodynamic processes are defined such that one of the gas properties (P, V, T, or S) is constant throughout the process.
For a given thermodynamics process, in order to specify the extent of a particular process, one of the properties ratios (listed under the column labeled "known ratio") must be specified (either directly or indirectly). Also, the property for which the ratio is known must be distinct from the property held constant in the previous column (otherwise the ratio would be unity, and not enough information would be available to simplify the gas law equation).
In the final three columns, the properties (P, V, or T) at state 2 can be calculated from the properties at state 1 using the equations listed.
||P2 = P1||V2 = V1(V2/V1)||T2 = T1(V2/V1)|
||P2 = P1||V2 = V1(T2/T1)||T2 = T1(T2/T1)|
||P2 = P1(P2/P1)||V2 = V1||T2 = T1(P2/P1)|
||P2 = P1(T2/T1)||V2 = V1||T2 = T1(T2/T1)|
||P2 = P1(P2/P1)||V2 = V1/(P2/P1)||T2 = T1|
||P2 = P1/(V2/V1)||V2 = V1(V2/V1)||T2 = T1|
(Reversible adiabatic process)
||P2 = P1(P2/P1)||V2 = V1(P2/P1)(−1/γ)||T2 = T1(P2/P1)(γ − 1/γ)|
||P2 = P1(V2/V1)−γ||V2 = V1(V2/V1)||T2 = T1(V2/V1)(1 − γ)|
||P2 = P1(T2/T1)γ/(γ − 1)||V2 = V1(T2/T1)1/(1 − γ)||T2 = T1(T2/T1)|
||P2 = P1(P2/P1)||V2 = V1(P2/P1)(-1/n)||T2 = T1(P2/P1)(n - 1/n)|
||P2 = P1(V2/V1)−n||V2 = V1(V2/V1)||T2 = T1(V2/V1)(1−n)|
||P2 = P1(T2/T1)n/(n − 1)||V2 = V1(T2/T1)1/(1 − n)||T2 = T1(T2/T1)|
^ a. In an isentropic process, system entropy (S) is constant. Under these conditions, P1 V1γ = P2 V2γ, where γ is defined as the heat capacity ratio, which is constant for an ideal gas. The value used for γ is typically 1.4 for diatomic gases like nitrogen (N2) and oxygen (O2), (and air, which is 99% diatomic). Also γ is typically 1.6 for monatomic gases like the noble gases helium (He), and argon (Ar). In internal combustion engines γ varies between 1.35 and 1.15, depending on constitution gases and temperature.
Deviations from ideal behavior of real gases
The equation of state given here applies only to an ideal gas, or as an approximation to a real gas that behaves sufficiently like an ideal gas. There are in fact many different forms of the equation of state. Since the ideal gas law neglects both molecular size and intermolecular attractions, it is most accurate for monatomic gases at high temperatures and low pressures. The neglect of molecular size becomes less important for lower densities, i.e. for larger volumes at lower pressures, because the average distance between adjacent molecules becomes much larger than the molecular size. The relative importance of intermolecular attractions diminishes with increasing thermal kinetic energy, i.e., with increasing temperatures. More detailed equations of state, such as the van der Waals equation, account for deviations from ideality caused by molecular size and intermolecular forces.
Hence the ideal gas law
The ideal gas law can also be derived from first principles using the kinetic theory of gases, in which several simplifying assumptions are made, chief among which are that the molecules, or atoms, of the gas are point masses, possessing mass but no significant volume, and undergo only elastic collisions with each other and the sides of the container in which both linear momentum and kinetic energy are conserved.
Let q = (qx, qy, qz) and p = (px, py, pz) denote the position vector and momentum vector of a particle of an ideal gas, respectively. Let F denote the net force on that particle. Then the time average momentum of the particle is:
By Newton's third law and the ideal gas assumption, the net force on the system is the force applied by the walls of their container, and this force is given by the pressure P of the gas. Hence
where dS is the infinitesimal area element along the walls of the container. Since the divergence of the position vector q is
the divergence theorem implies that
where dV is an infinitesimal volume within the container and V is the total volume of the container.
Putting these equalities together yields
which immediately implies the ideal gas law for N particles:
- Combined gas law
- Van der Waals equation
- Boltzmann constant
- Configuration integral
- Dynamic pressure
- Internal energy
- Clapeyron, E (1834). "Mémoire sur la puissance motrice de la chaleur". Journal de l'École Polytechnique XIV: 153–90. (French) Facsimile at the Bibliothèque nationale de France (pp. 153–90).
- Krönig, A. (1856). "Grundzüge einer Theorie der Gase". Annalen der Physik und Chemie 99 (10): 315–22. Bibcode:1856AnP...175..315K. doi:10.1002/andp.18561751008. (German) Facsimile at the Bibliothèque nationale de France (pp. 315–22).
- Clausius, R. (1857). "Ueber die Art der Bewegung, welche wir Wärme nennen". Annalen der Physik und Chemie 176 (3): 353–79. Bibcode:1857AnP...176..353C. doi:10.1002/andp.18571760302. (German) Facsimile at the Bibliothèque nationale de France (pp. 353–79).
- Mendeleev, D. I. (1874). "О сжимаемости газов (On the compressibility of gases)". Russian Journal of Chemical Society and the Physical Society 6: 309–352. (Russian) (From the Laboratory of the University of St. Petersburg).
- Mendeleev, D. I. (1875). Об упругости газов (On the elasticity of gases). (Russian) Facsimile at the Bibliothèque nationale de France
- Mendeleef D. (1877). "Researches on Mariotte's Law". Nature. 15 (388): 498–500. Bibcode:1877Natur..15..498D. doi:10.1038/015498a0. doi: 10.1038/015498a0.
- "Equation of State".
- Moran and Shapiro, Fundamentals of Engineering Thermodynamics, Wiley, 4th Ed, 2000
- Davis and Masten Principles of Environmental Engineering and Science, McGraw-Hill Companies, Inc. New York (2002) ISBN 0-07-235053-9
- Website giving credit to Benoît Paul Émile Clapeyron, (1799–1864) in 1834
- Ideal Gas Law Calculator
- Configuration integral (statistical mechanics) where an alternative statistical mechanics derivation of the ideal-gas law, using the relationship between the Helmholtz free energy and the partition function, but without using the equipartition theorem, is provided.