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In
chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a natural science that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, structure, proper ...
and related fields, the molar volume, symbol ''V''m, or \tilde V of a substance is the ratio of the
volume Volume is a measure of occupied three-dimensional space. It is often quantified numerically using SI derived units (such as the cubic metre and litre) or by various imperial or US customary units (such as the gallon, quart, cubic inch). ...
occupied by a substance to the
amount of substance In chemistry, the amount of substance ''n'' in a given sample of matter is defined as the quantity or number of discrete atomic-scale particles in it divided by the Avogadro constant ''N''A. The particles or entities may be molecules, atoms, io ...
, usually given at a given
temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer. Thermometers are calibrated in various temperature scales that historically have relied o ...
and
pressure Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country a ...
. It is equal to the
molar mass In chemistry, the molar mass of a chemical compound is defined as the mass of a sample of that compound divided by the amount of substance which is the number of moles in that sample, measured in moles. The molar mass is a bulk, not molecular, ...
(''M'') divided by the
mass density Density (volumetric mass density or specific mass) is the substance's mass per unit of volume. The symbol most often used for density is ''ρ'' (the lower case Greek letter rho), although the Latin letter ''D'' can also be used. Mathematicall ...
(''ρ''): V_ = \frac . The molar volume has the
SI unit The International System of Units, known by the international abbreviation SI in all languages and sometimes pleonastically as the SI system, is the modern form of the metric system and the world's most widely used system of measurement. ...
of
cubic metre The cubic metre (in Commonwealth English and international spelling as used by the International Bureau of Weights and Measures) or cubic meter (in American English) is the unit of volume in the International System of Units (SI). Its symbol is m ...
s per mole (m3/mol), although it is more typical to use the units cubic decimetres per mole (dm3/mol) for gases, and
cubic centimetre A cubic centimetre (or cubic centimeter in US English) (SI unit symbol: cm3; non-SI abbreviations: cc and ccm) is a commonly used unit of volume that corresponds to the volume of a cube that measures 1 cm × 1 cm × 1 cm. One cu ...
s per mole (cm3/mol) for
liquid A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, ...
s and
solid Solid is one of the four fundamental states of matter (the others being liquid, gas, and plasma). The molecules in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structur ...
s.


Definition

The molar volume of a substance ''i'' is defined as its
molar mass In chemistry, the molar mass of a chemical compound is defined as the mass of a sample of that compound divided by the amount of substance which is the number of moles in that sample, measured in moles. The molar mass is a bulk, not molecular, ...
divided by its density ''ρ''''i''0: V_ = . For an ideal mixture containing ''N'' components, the molar volume of the mixture is the weighted sum of the molar volumes of its individual components. For a real mixture the molar volume cannot be calculated without knowing the density: V_ = \frac. There are many liquid–liquid mixtures, for instance mixing pure
ethanol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a ...
and pure
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...
, which may experience contraction or expansion upon mixing. This effect is represented by the quantity excess volume of the mixture, an example of
excess property In chemical thermodynamics, excess properties are properties of mixtures which quantify the non- ideal behavior of real mixtures. They are defined as the difference between the value of the property in a real mixture and the value that would exist ...
.


Relation to specific volume

Molar volume is related to
specific volume In thermodynamics, the specific volume of a substance (symbol: , nu) is an intrinsic property of the substance, defined as the ratio of the substance's volume () to its mass (). It is the reciprocal of density (rho) and it is related to the m ...
by the product with
molar mass In chemistry, the molar mass of a chemical compound is defined as the mass of a sample of that compound divided by the amount of substance which is the number of moles in that sample, measured in moles. The molar mass is a bulk, not molecular, ...
. This follows from above where the specific volume is the reciprocal of the density of a substance: V_ = = M_i v_i.


Ideal gases

For
ideal gas An ideal gas is a theoretical gas composed of many randomly moving point particles that are not subject to interparticle interactions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is a ...
es, the molar volume is given by the ideal gas equation; this is a good approximation for many common gases at
standard temperature and pressure Standard temperature and pressure (STP) are standard sets of conditions for experimental measurements to be established to allow comparisons to be made between different sets of data. The most used standards are those of the International Union ...
. The ideal gas equation can be rearranged to give an expression for the molar volume of an ideal gas: V_ = \frac = \frac. Hence, for a given temperature and pressure, the molar volume is the same for all ideal gases and is based on the
gas constant The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment per ...
: ''R'' = , or about . The molar volume of an ideal gas at 100  kPa (1 
bar Bar or BAR may refer to: Food and drink * Bar (establishment), selling alcoholic beverages * Candy bar * Chocolate bar Science and technology * Bar (river morphology), a deposit of sediment * Bar (tropical cyclone), a layer of cloud * Bar ( ...
) is : at 0 °C, : at 25 °C. The molar volume of an ideal gas at 1 atmosphere of pressure is : at 0 °C, : at 25 °C.


Crystalline solids

For
crystalline solids A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
, the molar volume can be measured by
X-ray crystallography X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
. The
unit cell In geometry, biology, mineralogy and solid state physics, a unit cell is a repeating unit formed by the vectors spanning the points of a lattice. Despite its suggestive name, the unit cell (unlike a unit vector, for example) does not necessaril ...
volume (''V''cell) may be calculated from the
unit cell In geometry, biology, mineralogy and solid state physics, a unit cell is a repeating unit formed by the vectors spanning the points of a lattice. Despite its suggestive name, the unit cell (unlike a unit vector, for example) does not necessaril ...
parameters, whose determination is the first step in an X-ray crystallography experiment (the calculation is performed automatically by the structure determination software). This is related to the molar volume by V_ = where ''N''A is the
Avogadro constant The Avogadro constant, commonly denoted or , is the proportionality factor that relates the number of constituent particles (usually molecules, atoms or ions) in a sample with the amount of substance in that sample. It is an SI defining ...
and ''Z'' is the number of formula units in the unit cell. The result is normally reported as the "crystallographic density".


Molar volume of silicon

Ultra-pure
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...
is routinely made for the electronics industry, and the measurement of the molar volume of silicon, both by X-ray crystallography and by the ratio of molar mass to mass density, has attracted much attention since the pioneering work at
NIST The National Institute of Standards and Technology (NIST) is an agency of the United States Department of Commerce whose mission is to promote American innovation and industrial competitiveness. NIST's activities are organized into physical sci ...
in 1974. The interest stems from that accurate measurements of the unit cell volume,
atomic weight Relative atomic mass (symbol: ''A''; sometimes abbreviated RAM or r.a.m.), also known by the deprecated synonym atomic weight, is a dimensionless physical quantity defined as the ratio of the average mass of atoms of a chemical element in a giv ...
and mass density of a pure crystalline solid provide a direct determination of the Avogadro constant. The CODATA recommended value for the molar volume of silicon is , with a relative standard uncertainty of


See also

*
Specific volume In thermodynamics, the specific volume of a substance (symbol: , nu) is an intrinsic property of the substance, defined as the ratio of the substance's volume () to its mass (). It is the reciprocal of density (rho) and it is related to the m ...


References


External links


Interactive table of molar volumes
{{Authority control Volume