Vapor pressure

From Wikipedia, the free encyclopedia

The picture shows the particle transition, as a result of their vapor pressure, from the liquid phase to the
gas phase and converse.

Vapor pressure or equilibrium vapor pressure is defined as the pressure exerted by

a vapor in thermodynamic equilibrium with itscondensed phases (solid or liquid) at a given
temperature in a closed system. The equilibrium vapor pressure is an indication of a
liquid'sevaporation rate. It relates to the tendency of particles to escape from the liquid (or a
solid). A substance with a high vapor pressure at normal temperatures is often referred to
as volatile. The pressure exhibited by vapor present above a liquid surface is known as vapor
pressure. As the temperature of a liquid increases, the kinetic energy of its molecules also
increases. As the kinetic energy of the molecules increase the number of molecules transitioning
into a vapor also increases, thereby increasing the vapor pressure.
The vapor pressure of any substance increases non-linearly with temperature according to
the ClausiusClapeyron relation. Theatmospheric pressure boiling point of a liquid (also known
as the normal boiling point) is the temperature at which the vapor pressure equals the ambient
atmospheric pressure. With any incremental increase in that temperature, the vapor pressure
becomes sufficient to overcome atmospheric pressure and lift the liquid to form vapor bubbles
inside the bulk of the substance. Bubble formation deeper in the liquid requires a higher
pressure, and therefore higher temperature, because the fluid pressure increases above the
atmospheric pressure as the depth increases.
The vapor pressure that a single component in a mixture contributes to the total pressure in the
system is called partial pressure. For example, air at sea level, and saturated with water vapor at
20 C, has partial pressures of about 2.3 kPa of water, 78 kPa of nitrogen, 21 kPa of oxygen and
0.9 kPa of argon.

Contents
[hide]

1 Measurement and units

2 Estimating vapor pressures with Antoine equation

3 Relation to boiling point of liquids

4 Liquid mixtures

5 Solids

6 Boiling point of water

7 Dhring's rule

8 Examples

9 Estimating vapor pressure from molecular structure

10 Meaning in meteorology

11 See also

12 References

13 External links

Measurement and units[edit]

Vapor pressure is measured in the standard units of pressure. The International System of
Units (SI) recognizes pressure as a derived unit with the dimension of force per area and
designates the pascal (Pa) as its standard unit. One pascal is one newton per square
meter (Nm2 or kgm1s2).
Experimental measurement of vapor pressure is a simple procedure for common pressures
between 1 and 200 kPa.[1] Most accurate results are obtained near the boiling point of substances
and large errors result for measurements smaller than 1kPa. Procedures often consist of
purifying the test substance, isolating it in a container, evacuating any foreign gas, then
measuring the equilibrium pressure of the gaseous phase of the substance in the container at
different temperatures. Better accuracy is achieved when care is taken to ensure that the entire
substance and its vapor are at the prescribed temperature. This is often done, as with the use of
an isoteniscope, by submerging the containment area in a liquid bath.

Estimating vapor pressures with Antoine equation[edit]

The Antoine equation [2][3] is a mathematical expression of the relation between the vapor
pressure and the temperature of pure liquid or solid substances. The basic form of the equation
is:

and it can be transformed into this temperature-explicit form:

where:

is the absolute vapor pressure of a substance

is the temperature of the substance

and

parameters)
is typically either

are substance-specific coefficients (i.e., constants or

or

[3]

A simpler form of the equation with only two coefficients is sometimes used:

which can be transformed to:

Sublimations and vaporizations of the same substance have

separate sets of Antoine coefficients, as do components in mixtures.
[2]
Each parameter set for a specific compound is only applicable
over a specified temperature range. Generally, temperature ranges
are chosen to maintain the equation's accuracy of a few up to 8-10
percent. For many volatile substances, several different sets of
parameters are available and used for different temperature ranges.
The Antoine equation has poor accuracy with any single parameter
set when used from a compound's melting point to its critical
temperature. Accuracy is also usually poor when vapor pressure is
under 10 Torr because of the limitations of the apparatus used to
establish the Antoine parameter values.

The Wagner Equation[4] gives "one of the best"[5] fits to experimental

data but is quite complex. It expresses reduced vapor pressure as a
function of reduced temperature.

Relation to boiling point of liquids[edit]

Further information: Boiling point

A typical vapor pressure chart for various liquids

As a general trend, vapor pressures of liquids at ambient

temperatures increase with decreasing boiling points. This is
illustrated in the vapor pressure chart (see right) that shows graphs
of the vapor pressures versus temperatures for a variety of
liquids.[6]
For example, at any given temperature, methyl chloride has the
highest vapor pressure of any of the liquids in the chart. It also has
the lowest normal boiling point (24.2 C), which is where the vapor
pressure curve of methyl chloride (the blue line) intersects the
horizontal pressure line of one atmosphere (atm) of absolute vapor
pressure.
Although the relation between vapor pressure and temperature is
non-linear, the chart uses a logarithmic vertical axis to produce
slightly curved lines, so one chart can graph many liquids. A nearly
straight line is obtained when the logarithm of the vapor pressure is

plotted against 1/(T+230)[7] where T is the temperature in degrees

Celsius. The vapor pressure of a liquid at its boiling point equals the
pressure of its surrounding environment.

Liquid mixtures[edit]
Raoult's law gives an approximation to the vapor pressure of
mixtures of liquids. It states that the activity (pressure orfugacity) of
a single-phase mixture is equal to the mole-fraction-weighted sum
of the components' vapor pressures:

where p tot is the mixture's vapor pressure, i is one of the

components of the mixture and i is the mole fraction of that
component in the liquid mixture. The term pii is the partial
pressure of component i in the mixture. Raoult's Law is
applicable only to non-electrolytes (uncharged species); it is
most appropriate for non-polar molecules with only weak
intermolecular attractions (such as London forces).
Systems that have vapor pressures higher than indicated by the
above formula are said to have positive deviations. Such a
deviation suggests weaker intermolecular attraction than in the
pure components, so that the molecules can be thought of as
being "held in" the liquid phase less strongly than in the pure
liquid. An example is the azeotrope of approximately 95%
ethanol and water. Because the azeotrope's vapor pressure is
higher than predicted by Raoult's law, it boils at a temperature
below that of either pure component.
There are also systems with negative deviations that have
vapor pressures that are lower than expected. Such a deviation
is evidence for stronger intermolecular attraction between the
constituents of the mixture than exists in the pure components.
Thus, the molecules are "held in" the liquid more strongly when
a second molecule is present. An example is a mixture of
trichloromethane (chloroform) and 2-propanone (acetone),
which boils above the boiling point of either pure component.
The negative and positive deviations can be used to
determine thermodynamic activity coefficients of the
components of mixtures.

Solids[edit]

Vapor pressure of liquid and solid benzene

Equilibrium vapor pressure can be defined as the pressure

reached when a condensed phase is in equilibrium with its own
vapor. In the case of an equilibrium solid, such as a crystal, this
can be defined as the pressure when the rate of sublimationof a
solid matches the rate of deposition of its vapor phase. For
most solids this pressure is very low, but some notable
exceptions are naphthalene, dry ice (the vapor pressure of dry
ice is 5.73 MPa (831 psi, 56.5 atm) at 20 degrees Celsius,
which causes most sealed containers to rupture), and ice. All
solid materials have a vapor pressure. However, due to their
often extremely low values, measurement can be rather difficult.
Typical techniques include the use of thermogravimetry andgas
transpiration.
There are a number of methods for calculating the sublimation
pressure (i.e., the vapor pressure) of a solid. One method is to
estimate the sublimation pressure from extrapolated liquid
vapor pressures (of the supercooled liquid), if the heat of
fusion is known, by using this particular form of the Clausius
Clapeyron relation:[8]

with:

= Sublimation pressure of the solid component at the tem

= Extrapolated vapor pressure of the liquid component at

temperature

= Heat of fusion
= Gas constant
= Sublimation temperature
= Melting point temperature

This method assumes that the heat of fusion is

temperature-independent, ignores additional transition
temperatures between different solid phases, and it gives a
fair estimation for temperatures not too far from the melting
point. It also shows that the sublimation pressure is lower
than the extrapolated liquid vapor pressure (Hm is positive)
and the difference grows with increased distance from the
melting point.

Boiling point of water[edit]

Graph of water vapor pressure versus temperature. At the normal

boiling point of 100 C, it equals the standard atmospheric
pressure of 760Torr or 101.325 kPa.

Main article: Vapor pressure of water

Like all liquids, water boils when its vapor pressure reaches
its surrounding pressure. In nature, the atmospheric
pressure is lower at higher elevations and water boils at a
lower temperature. The boiling temperature of water for
atmospheric pressures can be approximated by the Antoine
equation:

or transformed into this temperature-explicit form:

where the temperature

is the boiling point

in degrees Celsius and the pressure

is

in Torr.

Dhring's rule[edit]
Main article: Dhring's rule
Dhring's rule states that a linear relationship exists
between the temperatures at which two solutions
exert the same vapor pressure.

Examples[edit]
The following table is a list of a variety of
substances ordered by increasing vapor pressure
(in absolute units).

Substance

Vapor
Pressure
(SI units)

Vapor
Pressure
(Bar);

Vapo
Pressu
(mmH

Tungsten

100 Pa

0.001

0.75

Ethylene glycol

500 Pa

0.005

3.75

Xenon difluoride

600 Pa

0.006

4.50

Water (H2O)

2.3 kPa

0.023

17.5

Propanol

2.4 kPa

0.024

18.0

Ethanol

5.83 kPa

0.0583

Methyl isobutyl
ketone

2.66 kPa

0.0266

Freon 113

37.9 kPa

0.379

284

Acetaldehyde

98.7 kPa

0.987

740

Butane

220 kPa

2.2

1650

Formaldehyde

435.7 kPa

4.357

3268

Propane[9]

997.8 kPa

9.978

7584

Carbonyl sulfide

1.255 MPa

12.55

9412

Nitrous oxide[10]

5.660 MPa

56.60

4245

Carbon dioxide

5.7 MPa

57

4275

Estimating vapor pressure from

molecular structure[edit]
Several empirical methods exist to estimate liquid
vapor pressure from molecular structure for organic
molecules. Some examples are SIMPOL,[11] the
method of Moller et al.,[8]and EVAPORATION.[12][13]

Meaning in meteorology[edit]
In meteorology, the term vapor pressure is used to
mean the partial pressure of water vapor in the
atmosphere, even if it is not in equilibrium,[14] and
the equilibrium vapor pressure is specified
otherwise. Meteorologists also use the
term saturation vapor pressure to refer to the

43.7

19.9

equilibrium vapor pressure of water or brine above

a flat surface, to distinguish it from equilibrium
vapor pressure, which takes into account the shape
and size of water droplets and particulates in the
atmosphere.[15]

See also[edit]

Absolute humidity

Lee-Kesler method

Reid vapor pressure

Relative humidity

Relative volatility

Saturation vapor density

Triple point

True vapor pressure

Vaporliquid equilibrium

Vapor pressures of the elements (data page)

References[edit]
1.

Jump up^ K. Rika, M. Fulem, V.

Rika. "Vapor Pressure of Organic
Compounds. Measurement and
Correlation" (PDF).

2.

^ Jump up to:a b What is the Antoine

Equation? (Chemistry Department, Frostburg
State University, Maryland)

3.

^ Jump up to:a b R.K.Sinnot (2005). Chemical

Engineering Design (4th ed.). ButterworthHeinemann. p. 331. ISBN 0-7506-65386. External link in |title= (help)

4.

Jump up^ Wagner, W. (1973), "New vapour

pressure measurements for argon and nitrogen
and a new method for establishing rational
vapour pressure equations", Cryogenics 13 (8):
470482,Bibcode:1973Cryo...13..470W, do
i:10.1016/0011-2275(73)90003-9

5.

Jump up^ Perry's Chemical Engineers'

Handbook, 7th Ed. pg 4-15

6.

Jump up^ Perry, R.H. and Green, D.W.

(Editors) (1997). Perry's Chemical Engineers'
Handbook (7th ed.). McGraw-Hill. ISBN 0-07049841-5.

7.

Jump up^ Dreisbach, R. R. and Spencer, R. S.

(January 1949). "Infinite Points of Cox Chart
Families and dt/dP Values at any
Pressure". Industrial and Engineering
Chemistry, 41 (1). p. 176.

8.

^ Jump up to:a b Moller B., Rarey J.,

Ramjugernath D., "Estimation of the vapour
pressure of non-electrolyte organic compounds
via group contributions and group interactions ",
J.Mol.Liq., 143(1), 52-63, 2008

9.

Jump up^ "Thermophysical Properties Of

Fluids II Methane, Ethane, Propane,
Isobutane, And Normal Butane" (page 110 of
PDF, page 686 of original document), BA
Younglove and JF Ely.

10. Jump up^ "Thermophysical Properties Of

Nitrous Oxide" (page 14 of PDF, page 10 of
original document), ESDU.
11. Jump up^ J. F. Pankow; et al.
(2008). "SIMPOL.1: a simple group contribution
method for predicting vapor pressures and
enthalpies of vaporization of multifunctional
organic compounds". Atmos. Chem. Phys. 8:
27732796. doi:10.5194/acp-8-2773-2008.
12. Jump up^ "Vapour pressure of pure liquid
compounds. Estimation by EVAPORATION"
13. Jump up^ S. Compernolle; et al.
(2011). "EVAPORATION: a new vapour
pressure estimation method for organic
molecules including non-additivity and
intramolecular interactions". Atmos. Chem.
Phys. 11: 9431
9450. Bibcode:2011ACP....11.9431C. doi:10.51
94/acp-11-9431-2011.
14. Jump up^ Glossary (Developed by
the American Meteorological Society)
15. Jump up^ A Brief Tutorial (An article about the
definition of equilibrium vapor pressure)

External links[edit]

Fluid Characteristics Chart

Hyperphysics

MSDS Vapor Pressure

Online vapor pressure calculation tool

(Requires Registration)

Prediction of Vapor Pressures of Pure Liquid

Organic Compounds
Authority
control

NDL: 00575023

Categories:

Thermodynamic properties

Engineering thermodynamics

Basic meteorological concepts and phenomena

Gases

Pressure

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