Loschmidt constant

The Loschmidt constant (symbol: "n"₀) is the number of particles (atoms or molecules) of an ideal gas in a given volume (the number density). It is usually quoted at standard temperature and pressure, and the 2006 CODATA recommended value [CODATA2006|url=http://physics.nist.gov/cgi-bin/cuu/Value?n0] is 2.686 7774(47)e|25 per cubic metre at 0 °C and 1 atm. It is named after the Austrian physicist Johann Josef Loschmidt, who was the first to estimate the physical size of molecules in 1865. [cite journal | first = J. | last = Loschmidt | authorlink = Johann Josef Loschmidt | title = Zur Grösse der Luftmoleküle | journal = Sitzungsberichte der kaiserlichen Akademie der Wissenschaften Wien | volume = 52 | issue = 2 | pages = 395–413 | year =1865 [http://dbhs.wvusd.k12.ca.us/webdocs/Chem-History/Loschmidt-1865.html English translation] .] The term "Loschmidt constant" is also sometimes (incorrectly) used to refer to the Avogadro constant, particularly in German texts.

The Loschmidt constant is given by the relationship::$n\_0\; =\; frac\{p\_0\}\{k\_\{\; m\; B\}T\_0\}$where "p"₀ is the pressure, "k"_B is the Boltzmann constant and "T"₀ is the thermodynamic temperature. It is related to the Avogadro constant, "N"_A, by::$n\_0\; =\; frac\{p\_0N\_\{\; m\; A\{RT\_0\}$where "R" is the gas constant.

Being a measure of number density, the Loschmidt constant is used to define the amagat, a practical unit of number density for gases and other substances::1 amagat = "n"₀ = 2.6867774×10²⁵ m⁻³ ,such that the Loschmidt constant is exactly 1 amagat.

Modern determinations

In the CODATA set of recommended values for physical constants, the Loschmidt constant is calculated from the gas constant and the Avogadro constant: [CODATA2002] :$n\_0\; =\; frac\{N\_\{\; m\; A\{R\}frac\{p\_0\}\{T\_0\}\; =\; frac\{A\_\{\; m\; r\}(\{\; m\; e\})M\_\{\; m\; u\}calpha^2\}\{2R\_\{infty\}h\}frac\{p\_0\}\{T\_0\}$where "A"sub|r(e) is the relative atomic mass of the electron, "M"sub|u is the molar mass constant, "c" is the speed of light, "α" is the fine structure constant, "R"sub|∞ is the Rydberg constant and "h" is the Planck constant. The pressure and temperature can be chosen freely, and must be quoted with values of the Loschmidt constant. The precision to which the Loschmidt constant is currently known is limited entirely by the uncertainty in the value of the gas constant.

First determinations

Loschmidt did not actually calculate a value for the constant which now bears his name, but it is a simple and logical manipulation of his published results. James Clerk Maxwell described the paper in these terms in a public lecture eight years later:cite journal | last = Maxwell | first = James Clerk | authorlink = James Clerk Maxwell | url = http://web.lemoyne.edu/~giunta/maxwell.html | title = Molecules | journal = Nature | volume = 8 | pages = 437–41 | year = 1873]

Loschmidt has deduced from the dynamical theory the following remarkable proportion:—As the volume of a gas is to the combined volume of all the molecules contained in it, so is the mean path of a molecule to one-eighth of the diameter of a molecule.

To derive this "remarkable proportion", Loschmidt started from the Maxwell's own definition of mean free path::$ell\; =\; frac\{3\}\{4n\_0pi\; d^2\}$where "n"sub|0 has the same sense as the Loschmidt constant, that is the number of molecules per unit volume, and "d" is the effective diameter of the molecules (assumed to be spherical). This rearranges to:$frac\{1\}\{n\_0\}\; =\; frac\{16\}\{3\}frac\{piell\; d^2\}\{4\}$where 1/"n"sub|0 is the volume occupied by each molecule in the gas phase and "π"ℓ"d"sup|2/4 is the volume of the cylinder made by the molecule in its trajectory between two collisions. However, the true volume of each molecule is given by "πd"sup|3/6, and so "n"sub|0"πd"sup|3/6 is the volume occupied by all the molecules not counting the empty space between them. Loschmidt equated this volume with the volume of the liquified gas. Dividing both sides of the equation by "n"sub|0"πd"sup|3/6 has the effect of introducing a factor of "V"sub|liquid/"V"sub|gas, which Loschmidt called the "condensation coefficient" and which is experimentally measurable. The equation reduces to:$d\; =\; 8frac\{V\_\{\; m\; l\{V\_\{\; m\; gell$relating the diameter of a gas molecule to measurable phenomena.

The number density, the constant which now bears Loschmidt's name, can be found by simply subsituting the diameter of the molecule into the definition of the mean free path and rearranging::$n\_0\; =\; left\; (frac\{V\_\{\; m\; g\{V\_\{\; m\; l\; ight\; )^2\; frac\{3\}\{256piell^3\}$Instead of taking this step, Loschmidt decided to estimate the mean diameter of the molecules in air. This was no minor undertaking, as the condensation coefficient was unknown and had to be estimated–it would be another twelve years before Pictet and Cailletet would liquify nitrogen for the first time. The mean free path was also uncertain. Nevertheless, Loschmidt arrived at a diameter of about one nanometre, of the correct order of magnitude.

Loschmidt's estimated data for air give a value of "n"sub|0 = 1.81e|24 msup|3. Eight years later, Maxwell was citing a figure of "about 19 million million million" per cmsup|3, or 1.9e|25 msup|3.

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