Vapor Pressure PDF
Vapor Pressure PDF
Vapor Pressure PDF
Vapor pressure
From Wikipedia, the free encyclopedia
Contents
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 Dühring's rule
8 Examples
9 Estimating vapor pressure from molecular structure
10 Meaning in meteorology
11 See also
12 References
13 External links
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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 1 kPa. 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.
A simpler form of the equation with only two coefficients is sometimes used:
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
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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.
where p tot is the mixture's vapor pressure, i is one of the components of the mixture and Χi is the mole fraction of
that component in the liquid mixture. The term piΧi 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).
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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.
Solids
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
sublimation of 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 and gas transpiration.
with:
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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 (ΔHm is positive) and
the difference grows with increased distance from the melting point.
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:
where the temperature is the boiling point in degrees Celsius and the pressure is in Torr.
Dühring's rule
Main article: Dühring's rule
Dühring's rule states that a linear relationship exists between the temperatures at which two solutions exert the same
vapor pressure.
Examples
The following table is a list of a variety of substances ordered by increasing vapor pressure.
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Meaning in meteorology
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,[12] and the equilibrium vapor pressure is specified otherwise. Meteorologists also
use the term saturation vapor pressure to refer to the 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.[13]
See also
Absolute humidity
Clausius-Clapeyron relation
Partial pressure
Relative humidity
Relative volatility
Raoult's law
Saturation vapor density
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Triple point
Vapor-liquid equilibrium
Vapor pressure of water
Volatility
Reid vapor pressure
True vapor pressure
Vapor pressures of the elements (data page)
References
1. ^ K. Růžička, M. Fulem, V. Růžička. "Vapor Pressure of Organic Compounds. Measurement and Correlation"
(http://www.capec.kt.dtu.dk/documents/overview/Vapor-pressure-Ruzicka.pdf).
2. ^ a b What is the Antoine Equation? (http://antoine.frostburg.edu/chem/senese/101/liquids/faq/antoine-vapor-
pressure.shtml) (Chemistry Department, Frostburg State University, Maryland)
3. ^ a b R.K.Sinnot (2005). Chemical Engineering Design (http://books.google.ca/books?
id=DJaxUL3numgC&pg=PA331&lpg=PA331&dq=antoine+equation+constants&source=bl&ots=2c0cqzbR0t&si
g=YPuvrW2kWnWP2s4QvY9TTpxGgNM&hl=en&sa=X&ei=widrUcu9Cce0qgHq24CgCA&ved=0CGcQ6AEwBzg
K#v=onepage&q=antoine%20equation%20constants&f=false) (4th ed.). Butterworth-Heinemann. p. 331. ISBN 0-
7506-6538-6.
4. ^ Wagner, W. (1973), "New vapour pressure measurements for argon and nitrogen and an new method for
establishing rational vapour pressure equations", Cryogenics 13 (8): 470–482
5. ^ Perry's Chemical Engineers' Handbook, 7th Ed. pg 4-15
6. ^ Perry, R.H. and Green, D.W. (Editors) (1997). Perry's Chemical Engineers' Handbook (7th ed.). McGraw-Hill.
ISBN 0-07-049841-5.
7. ^ 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. ^ 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. ^ 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" (http://www.atmos-chem-
phys.net/8/2773/2008/acp-8-2773-2008.html). Atmos. Chem. Phys. 8: 2773–2796.
10. ^ "Vapour pressure of pure liquid compounds. Estimation by EVAPORATION"
(http://tropo.aeronomie.be/models/evaporation_run.htm)
11. ^ S. Compernolle et al. (2011). "EVAPORATION: a new vapour pressure estimation method for organic molecules
including non-additivity and intramolecular interactions" (http://www.atmos-chem-phys.net/11/9431/2011/acp-11-
9431-2011.html). Atmos. Chem. Phys. 11: 9431–9450.
12. ^ Glossary (http://amsglossary.allenpress.com/glossary/search?id=vapor-pressure1) (Developed by the American
Meteorological Society)
13. ^ A Brief Tutorial (http://fermi.jhuapl.edu/people/babin/vapor/index.html) (An article about the definition of
equilibrium vapor pressure)
External links
Fluid Characteristics Chart (http://www.engineersedge.com/fluid_flow/fluid_data.htm)
Hyperphysics (http://hyperphysics.phy-astr.gsu.edu/hbase/kinetic/vappre.html#c2)
MSDS Vapor Pressure (http://www.ilpi.com/msds/ref/vaporpressure.html)
Online vapor pressure calculation tool (Requires Registration) (http://www.envmodels.com/freetools.php?
menu=pression)
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