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== '''[[Volatility (chemistry)]]''' ==
== '''[[Ideal gas law]]''' ==
''by  [[User:Milton Beychok|Milton Beychok]] (and [[User:Anthony.Sebastian|Anthony.Sebastian]])
''by  [[User:Milton Beychok|Milton Beychok]] and [[User:Paul Wormer|Paul Wormer]] (and [[User:Daniel Mietchen|Daniel Mietchen]] and [[User:David E. Volk|David E. Volk]])


----
----
{{Image|Vapor Pressure Chart2.png|right|250px|Example vapor pressure graphs of various liquids.}}
{| class="wikitable" style="float: right;"
! Values of ''R''
! Units
|-
| 8.314472
|  [[Joule|J]]·[[Kelvin|K]]<sup>-1</sup>·[[Mole (unit)|mol]]<sup>-1</sup>
|-
| 0.082057
| [[Liter|L]]·[[atmosphere (unit)|atm]]·K<sup>-1</sup>·mol<sup>-1</sup>
|-
| 8.205745 × 10<sup>-5</sup>
| [[metre|m]]<sup>3</sup>·atm·K<sup>-1</sup>·mol<sup>-1</sup>
|-
| 8.314472
| L·k[[Pascal (unit)|Pa]]·K<sup>-1</sup>·mol<sup>-1</sup>
|-
| 8.314472
| m<sup>3</sup>·Pa·K<sup>-1</sup>·mol<sup>-1</sup>
|-
| 62.36367
| L·[[mmHg]]·K<sup>-1</sup>·mol<sup>-1</sup>
|-
| 62.36367
| L·[[torr]]·K<sup>-1</sup>·mol<sup>-1</sup>
|-
| 83.14472
| L·m[[Bar (unit)|bar]]·K<sup>-1</sup>·mol<sup>-1</sup>
|-
| 10.7316
| [[Foot (unit)|ft]]<sup>3</sup>·[[Psi (unit)|psi]]· [[Rankine scale|°R]]<sup>-1</sup>·[[lb-mol]]<sup>-1</sup>
|-
| 0.73024
| ft<sup>3</sup>·atm·°R<sup>-1</sup>·lb-mol<sup>-1</sup>
|}


In [[chemistry]] and [[physics]], '''volatility''' is a term used to characterize the tendency of a substance to vaporize.<ref>'''Note:''' To vaporize means to become a [[vapor]], the gaseous state of the substance.</ref> It is directly related to a substance' s [[vapor pressure]]. At a given [[temperature]], a substance with a higher vapor pressure will vaporize more readily than a substance with a lower vapor pressure.<ref>[http://www.bae.uky.edu/~snokes/BAE549thermo/gasesvapor.htm Gases and Vapor] ([[University of Kentucky]] website)</ref><ref>{{cite book|author=James G. Speight|title=The Chemistry and Technology of Petroleum|edition=4th Edition|publisher=CRC Press|date=2006|isbn=0-8493-9067-2}}</ref><ref name=Kister>{{cite book|author=Kister, Henry Z.|title=[[Distillation Design]]|edition=1st Edition|publisher=McGraw-Hill|year=1992|isbn=0-07-034909-6}}</ref> In other words, at a given temperature, the more volatile the substance the higher will be the pressure of the vapor in dynamic equilibrium with its vaporizing substance&mdash;i.e., when the rates at which molecules escape from and return into the vaporizing substance are equal.
The '''[[ideal gas law]]''' is the [[equation of state]] of an '''ideal gas''' (also known as a '''perfect gas''') that relates its [[Pressure#Absolute pressure versus gauge pressure|absolute pressure]] ''p'' to its [[temperature|absolute temperature]] ''T''. Further parameters that enter the equation are the [[volume]] ''V'' of the container holding the gas and the [[amount of substance|amount]] ''n'' (in [[mole (unit)|moles]]) of gas contained in there. The law reads
:<math> pV = nRT \,</math>
where ''R'' is the [[molar gas constant]], defined as the product of the [[Boltzmann constant]] ''k''<sub>B</sub> and  [[Avogadro's constant]] ''N''<sub>A</sub>
:<math>
R \equiv N_\mathrm{A} k_\mathrm{B}
</math>
Currently, the most accurate value of R is:<ref>[http://physics.nist.gov/cgi-bin/cuu/Value?r Molar gas constant] Obtained from the [[NIST]] website. [http://www.webcitation.org/query?url=http%3A%2F%2Fphysics.nist.gov%2Fcgi-bin%2Fcuu%2FValue%3Fr&date=2009-01-03 (Archived by WebCite® at http://www.webcitation.org/5dZ3JDcYN on Jan 3, 2009)]</ref> 8.314472 ± 0.000015 J·K<sup>-1</sup>·mol<sup>-1</sup>.


In common usage, the term applies primarily to [[liquid]]s. However, it may also be used to characterize the process of  [[Sublimation (chemistry)|sublimation]] by which certain [[solid]] substances such as [[ammonium chloride]] (NH<sub>4</sub>Cl) and [[dry ice]], which is solid [[carbon dioxide]] (CO<sub>2</sub>), change directly from their solid form to a vapor without becoming a liquid.
The law applies to ''ideal gases'' which are hypothetical gases that consist of [[molecules]]<ref>Atoms may be seen as mono-atomic molecules.</ref> that do not interact, i.e., that move through the container independently of each other. In contrast to what is sometimes stated (see, e.g., Ref.<ref>[http://en.wikipedia.org/w/index.php?oldid=261421829 Wikipedia: Ideal gas law] Version of January 2, 2009</ref>) an ideal gas does not necessarily consist of [[point particle]]s without internal structure, but may be formed by polyatomic molecules with internal rotational, vibrational, and electronic [[degrees of freedom]]. The ideal gas law describes the motion of the [[center of mass|centers of mass]] of the molecules and, indeed, mass centers may be seen as structureless point masses. However, for other properties of ideal gases, such as [[entropy (thermodynamics)|entropy]], the internal structure may play a role.


Any substance with a significant vapor pressure at temperatures of about 20 to 25 °[[Celsius (unit)|C]] (68 to 77 °[[Fahrenheit (unit)|F]]) is very often referred to as being ''volatile''.
The ideal gas law is a useful approximation for calculating temperatures, volumes, pressures or amount of substance for many gases over a wide range of values, as long as the temperatures and pressures are far from the values where [[condensation]] or [[sublimation]] occur.


=== Vapor pressure, temperature and boiling point ===
Real gases deviate from ideal gas behavior because the intermolecular attractive and repulsive forces cause the motions of the molecules to be correlated.  The deviation is especially significant at low temperatures or high pressures, i.e., close to condensation.  A conventional measure for this deviation is the [[Compressibility factor (gases)|compressibility factor]].


The vapor pressure of a substance is the pressure at which its gaseous (vapor) phase is in equilibrium with its liquid or solid phase. It is a measure of the tendency of [[molecule]]s and [[atom]]s to escape from a liquid or solid.  
There are many equations of state available for use with real gases, the simplest of which is the [[van der Waals equation]].


At [[atmospheric pressure]]s, when a liquid's vapor pressure increases with increasing temperatures to the point at which it equals the atmospheric pressure, the liquid has reached its [[boiling point]], namely, the temperature at which the liquid changes its state from a liquid to a gas throughout its bulk. That temperature is very commonly referred to as the liquid's ''normal boiling point''.
=== Historic background ===


Not surprisingly, a liquid's normal boiling point will be at a lower temperature the greater is the tendency of its molecules to escape from the liquid, namely, the higher is its vapor pressure. In other words, the higher is the vapor pressure of a liquid, the higher is the volatility and the lower is the normal boiling point of the liquid. The adjacent vapor pressure chart graphs the dependency of vapor pressure upon temperature for a variety of liquids<ref name=Perry>{{cite book|author=R.H. Perry and D.W. Green (Editors)|title=Perry's Chemical Engineers' Handbook | edition=7th Edition|publisher=McGraw-Hill|year=1997|id=ISBN 0-07-049842-5}}</ref> and also confirms that liquids with higher vapor pressures have lower normal boiling points.
The early work on the behavior of gases began in pre-industrialized [[Europe]] in the latter half of the 17th century by [[Robert Boyle]] who formulated ''[[Boyle's law]]'' in 1662 (independently confirmed by [[Edme Mariotte]] at about the same time).<ref name=Savidge>[http://www.ceesi.com/docs_techlib/events/ishm2003/Docs/1040.pdf Compressibility of Natural Gas] Jeffrey L. Savidge, 78th International School for Hydrocarbon Measurement (Class 1040), 2003. From the website of the Colorado Engineering Experiment Station, Inc. (CEESI).</ref>  Their work on air at low pressures established the inverse relationship between pressure and volume, ''V'' = constant / ''p'' at constant temperature and a fixed amount of air. ''Boyle's Law'' is often referred to as the ''Boyles-Mariotte Law''.  


 
''[[Ideal gas law|.... (read more)]]''
''[[Volatility (chemistry)|.... (read more)]]''


{| class="wikitable collapsible collapsed" style="width: 90%; float: center; margin: 0.5em 1em 0.8em 0px;"
{| class="wikitable collapsible collapsed" style="width: 90%; float: center; margin: 0.5em 1em 0.8em 0px;"

Revision as of 23:26, 13 January 2012

Ideal gas law

by Milton Beychok and Paul Wormer (and Daniel Mietchen and David E. Volk)


Values of R Units
8.314472 J·K-1·mol-1
0.082057 L·atm·K-1·mol-1
8.205745 × 10-5 m3·atm·K-1·mol-1
8.314472 L·kPa·K-1·mol-1
8.314472 m3·Pa·K-1·mol-1
62.36367 mmHg·K-1·mol-1
62.36367 torr·K-1·mol-1
83.14472 L·mbar·K-1·mol-1
10.7316 ft3·psi· °R-1·lb-mol-1
0.73024 ft3·atm·°R-1·lb-mol-1

The ideal gas law is the equation of state of an ideal gas (also known as a perfect gas) that relates its absolute pressure p to its absolute temperature T. Further parameters that enter the equation are the volume V of the container holding the gas and the amount n (in moles) of gas contained in there. The law reads

where R is the molar gas constant, defined as the product of the Boltzmann constant kB and Avogadro's constant NA

Currently, the most accurate value of R is:[1] 8.314472 ± 0.000015 J·K-1·mol-1.

The law applies to ideal gases which are hypothetical gases that consist of molecules[2] that do not interact, i.e., that move through the container independently of each other. In contrast to what is sometimes stated (see, e.g., Ref.[3]) an ideal gas does not necessarily consist of point particles without internal structure, but may be formed by polyatomic molecules with internal rotational, vibrational, and electronic degrees of freedom. The ideal gas law describes the motion of the centers of mass of the molecules and, indeed, mass centers may be seen as structureless point masses. However, for other properties of ideal gases, such as entropy, the internal structure may play a role.

The ideal gas law is a useful approximation for calculating temperatures, volumes, pressures or amount of substance for many gases over a wide range of values, as long as the temperatures and pressures are far from the values where condensation or sublimation occur.

Real gases deviate from ideal gas behavior because the intermolecular attractive and repulsive forces cause the motions of the molecules to be correlated. The deviation is especially significant at low temperatures or high pressures, i.e., close to condensation. A conventional measure for this deviation is the compressibility factor.

There are many equations of state available for use with real gases, the simplest of which is the van der Waals equation.

Historic background

The early work on the behavior of gases began in pre-industrialized Europe in the latter half of the 17th century by Robert Boyle who formulated Boyle's law in 1662 (independently confirmed by Edme Mariotte at about the same time).[4] Their work on air at low pressures established the inverse relationship between pressure and volume, V = constant / p at constant temperature and a fixed amount of air. Boyle's Law is often referred to as the Boyles-Mariotte Law.

.... (read more)