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Presin de vapor

Grfico de la presin del vapor de agua.


La presin de vapor es la presin de la fase gaseosa o vapor de un slido o un lquido sobre
la fase lquida, para una temperatura determinada, en la que la fase lquida y el vapor se
encuentran en equilibrio dinmico; su valor es independiente de las cantidades de lquido y
vapor presentes mientras existan ambas. Este fenmeno tambin lo presentan los slidos;
cuando un slido pasa al estado gaseoso sin pasar por el estado lquido (proceso
denominadosublimacin o el proceso opuesto, llamado sublimacin inversa) tambin
hablamos de presin de vapor. En la situacin de equilibrio, las fases reciben la denominacin
de lquido saturado y vapor saturado. Esta propiedad posee una relacin inversamente
proporcional con las fuerzas de atraccin intermoleculares, debido a que cuanto mayor sea el
mdulo de las mismas, mayor deber ser la cantidad de energa entregada (ya sea en forma
de calor u otra manifestacin) para vencerlas y producir el cambio de estado.
Inicialmente slo se produce la evaporacin, ya que no hay vapor; sin embargo, a medida que
la cantidad de vapor aumenta ,y por tanto la presin en el interior de la ampolla, se va
incrementando tambin la velocidad de condensacin, hasta que transcurrido un cierto tiempo
ambas velocidades se igualan. Llegado este punto se habr alcanzado la presin mxima
posible en la ampolla (presin de vapor o de saturacin), que no podr superarse salvo que se
incremente la temperatura.
El equilibrio dinmico se alcanzar ms rpidamente cuanto mayor sea la superficie de
contacto entre el lquido y el vapor, pues as se favorece la evaporacin del lquido; del mismo
modo que un charco de agua extenso pero de poca profundidad se seca ms rpido que uno
ms pequeo pero de mayor profundidad que contenga igual cantidad de agua. Sin embargo,
el equilibrio se alcanza en ambos casos para igual presin.
El factor ms importante que determina el valor de la presin de saturacin es la propia
naturaleza del lquido, encontrndose que en general entre lquidos de naturaleza similar, la
presin de vapor a una temperatura dada es tanto menor cuanto mayor es el peso
molecular del lquido.
Por ejemplo, el aire al nivel del mar saturado con vapor de agua a 20 C, tiene una presin
parcial de 23 mbar de agua y alrededor de 780 mbar de nitrgeno, 210 mbar de oxgeno y 9
mbar de argn.

ndice
[ocultar]

1Medicin y unidades
2Presin de vapor y punto de ebullicin de un lquido
3Variacin de la presin de vapor con la temperatura
4Importancia para el Derecho Ambiental
5Vase tambin

Medicin y unidades[editar]
La presin de vapor es medida en unidades estndar de presin. El Sistema Internacional de
Unidades (SI) reconoce la presin como una unidad derivada de la fuerza ejercida a travs de
un rea determinada; a esta unidad se le conoce por el nombre de pascal (Pa). Un pascal es
equivalente a un newton por metro cuadrado (Nm-2 kgm-1s-2).
La medicin experimental de la presin de vapor es un procedimiento simple para presiones
similares que estn entre 1 y 200 kPa. Resultados ms exactos son obtenidos cerca del punto
de ebullicin de cada sustancia en particular y con ndice de error ms significativo en
mediciones menores a 1 kPa. Con frecuencia, algunos procedimientos consisten en purificar
las sustancias que son analizadas, aislando la sustancia deseada en un contenedor, evitando
cualquier gas indeseado y midiendo la presin de equilibrio de la fase gaseosa de la sustancia
en el sistema cerrado a distintas temperaturas. El uso de herramientas, como un isoteniscopio,
genera una mayor exactitud en el proceso.

Presin de vapor y punto de ebullicin de un lquido[editar]


Un lquido est, a cualquier temperatura, en equilibrio con su propio vapor cuando las
molculas de ste estn presentes en una cierta concentracin. La presin que corresponde a
esta concentracin de molculas gaseosas se llama presin de vapor del lquido a la
temperatura dada. La presin de vapor de cada lquido aumenta con la temperatura. La
temperatura para la cual la presin de vapor de un lquido iguala a la presin externa se
denomina punto de ebullicin del lquido. A esta temperatura aparecen en el lquido burbujas
de vapor que escapan de la superficie.

Variacin de la presin de vapor con la temperatura[editar]


Presin de vapor versus temperatura.
Como una tendencia general, la presin de vapor de los lquidos a presin atmosfrica se
incrementa con el aumento en la temperatura de ebullicin. Este fenmeno es ilustrado en el
diagrama adjunto, que muestra, para varios lquidos, el comportamiento de su presin de
vapor versus la temperatura. Por ejemplo, a cualquier temperatura, el cloruro de metileno tiene
la ms alta presin de vapor de todos los lquidos expuestos en el grfico. Tambin se
observa la baja temperatura de ebullicin del propano, cuya curva de presin de vapor (lnea
cian) se interseca con la lnea horizontal correspondiente a 1 atmsfera en -41 C.
Aunque la relacin entre la presin de vapor y la temperatura no es lineal, el grfico usa un eje
logartmico vertical para obtener una lnea poco curva y as poder representar en un solo
grfico el comportamiento de varios lquidos.

Importancia para el Derecho Ambiental[editar]


El ndice de peligrosidad (Ip) de una sustancia est determinado por el cociente entre la
presin de vapor de la sustancia y su CMP (concentracin mxima permitida) en condiciones
estndar (25 C y 1 atm), por lo que esta propiedad nos permite analizar la viabilidad del uso
de una sustancia para actividades determinadas, debido a que indica la probabilidad de que la
misma se volatilice.

Vapor pressure
From Wikipedia, the free encyclopedia
The picture shows the particle transition, as a result of their vapor gas,
from the liquid phase to the gas phase and converse.
The "Pistol Test Tube" experiment. The tube contains alcohol and is
closed with a piece of cork. By heating the alcohol, the vapors fill in the
space, increasing the pressure in the tube to the point of the cork popping
out.
Vapor pressure or equilibrium vapor pressure is defined as the pressure exerted by
a vapor inthermodynamic equilibrium with its condensed phases (solid or liquid) at a given
temperature in aclosed system. The equilibrium vapor pressure is an indication of a
liquid's evaporation 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 increases, 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
theClausiusClapeyron relation. The atmospheric pressure boiling point of a liquid (also known
as thenormal 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. More important at shallow depths is the higher
temperature required to start bubble formation. The surface tension of the bubble wall leads to
an overpressure in the very small, initial bubbles. Thus, thermometer calibration should not rely
on the temperature in boiling water.
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, totaling 102.2 kPa, making the basis for standard atmospheric
pressure.

Contents
[hide]

1Measurement and units


2Estimating vapor pressures with Antoine equation
3Relation to boiling point of liquids
4Liquid mixtures
5Solids
6Boiling point of water
7Dhring's rule
8Examples
9Estimating vapor pressure from molecular structure
10Meaning in meteorology
11See also
12References
13External 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 unitwith 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.
Very low vapor pressures of solids can be measured using the Knudsen effusion cell method.
In a medical context, vapor pressure is sometimes expressed in other units,
specifically millimeters of mercury (mmHg). This is important for volatile anesthetics, most of
which are liquids at body temperature, but with a relatively high vapor pressure. Anesthetics
with a higher vapor pressure at body temperature will be excreted more quickly, as they are
exhaled from the lungs.

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


parameters)

is typically either 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 810 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 log-lin 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 thevapor 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 or fugacity)
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
acrystal, 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.
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 ClausiusClapeyron relation:[8]

with:

= Sublimation pressure of the solid


component at the temperature
= Extrapolated vapor pressure of the
liquid component at the
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).

Vap Vap Vap


Substa Tempe
or or or
nce Pres Pres Pres rature
sure sure sure
(SI (Bar (mm
unit ) Hg)
s)

Tungste 100 0.00 3203


0.75
n Pa 1 C

Ethylen 500 0.00


3.75 20 C
e glycol Pa 5

Xenon
600 0.00
difluori 4.50 25 C
Pa 6
de

Water ( 2.3 0.02


17.5 20 C
H2O) kPa 3

Propan 2.4 0.02


18.0 20 C
ol kPa 4

5.83 0.05
Ethanol 43.7 20 C
kPa 83

Methyl
2.66 0.02 19.9
isobutyl 25 C
kPa 66 5
ketone

Freon 37.9 0.37 284 20 C


113 kPa 9

Acetald 98.7 0.98


740 20 C
ehyde kPa 7

220
Butane 2.2 1650 20 C
kPa

435.
Formal 4.35
7 3268 20 C
dehyde 7
kPa

997.
Propan 9.97 26.85
8 7584
e[9] 8 C
kPa

Carbon 1.25
12.5
yl 5 9412 25 C
5
sulfide MPa

5.66
Nitrous 56.6 4245
0 25 C
oxide[10] 0 3
MPa

Carbon 5.7 4275


57 20 C
dioxide MPa 3

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
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]
Vapour pressure of water
Absolute humidity
LeeKesler 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^ Rika, K.; Fulem,
M. & Rika, V. "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 Sinnot, R.K.
(2005). Chemical Engineering
Design] (4th ed.). Butterworth-
Heinemann. p. 331. ISBN 0-
7506-6538-6.
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):
470
482, Bibcode:1973Cryo...13..47
0W,doi:10.1016/0011-
2275(73)90003-9
5. Jump up^ Perry's Chemical
Engineers' Handbook, 7th Ed.
pp. 415
6. Jump up^ Perry, R.H.; Green,
D.W., eds. (1997). Perry's
Chemical Engineers'
Handbook (7th ed.). McGraw-
Hill. ISBN 0-07-049841-5.
7. Jump up^ Dreisbach, R. R. &
Spencer, R. S. (1949). "Infinite
Points of Cox Chart Families
and dt/dP Values at any
Pressure". Industrial and
Engineering Chemistry,. 41 (1).
p. 176. doi:10.1021/ie50469a04
0.
8. ^ Jump up to:a b Moller B.;
Rarey J.; Ramjugernath D.
(2008). "Estimation of the
vapour pressure of non-
electrolyte organic compounds
via group contributions and
group interactions". Journal of
Molecular Liquids. 143:
52.doi:10.1016/j.molliq.2008.04.
020.
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^ Pankow, J. F.;
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 (10): 2773
2796. doi:10.5194/acp-8-2773-
2008.
12. Jump up^ "Vapour
pressure of pure liquid
compounds. Estimation by
EVAPORATION".
tropo.aeronomie.be
13. Jump up^ Compernolle,
S.; et al.
(2011). "EVAPORATION: a
new vapour pressure estimation
method for organic molecules
including non-additivity and
intramolecular
interactions". Atmos. Chem.
Phys. 11 (18): 9431
9450.Bibcode:2011ACP....11.9
431C. doi:10.5194/acp-11-
9431-2011.
14. Jump
up^ Glossary (Developed by
the American Meteorological
Society)
15. Jump up^ A Brief
Tutorial. jhuapl.edu (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