Vapor Pressure

CEE-PUBH 5730-6730
Lecture 4
Vapor pressure (P
v
)
Pressure exerted when a chemical is in
equilibrium with its own vapor at a specified
temperature.
Can be regarded as the maximum amount or
solubility of the substance in the air phase.
Difference in P
v
for different compounds is due
to differences in molecular-molecular
interactions.
Why is P
v
important/how is it used?
Used with aqueous solubility to calculate
Henry's Law Constants
Used to estimate how rapidly a chemical may
evaporate in a spill situation.
Used to determine the speciation of the
compound (gaseous vs. particulate) in the
atmosphere
Units of Vapor pressure
1Torr = 1 mm Hg = 1.333 ! 10
2
Pa
1 atmosphere = 1.013 ! 10
5
Pa
1 bar = 10
5
Pa
Thermodynamic considerations
Simplified phase diagram
Solid-vapor equilibrium
Liquid-vapor equilibrium
Simplified phase diagram of organic liquids and solid
Liquid-vapor equilibrium (Clausius
Clapeyron)
ln P = - !H
vap
/RT + A = -B/T + A
At temperatures well below the boiling point, H
vap
is relatively
independent of temperature and !H
vap
is assumed to be
constant.
!H
vap
: energy require to convert one mole of liquid to vapor
without increasing the temperature.
This expression can be used to calculate vapor pressures (P)
at any other temperature provided that no other phase change
occurs within the temperature range considered.
Antoine equation
ln P = -B/T+C + A
where C is used to correct for the temperature
dependence of !H
vap
.
Values for A, B, and C are tabulated for a variety
of compounds.
Used to describe the temperature dependence
of Pv
Supplemental Table: Properties of Pure Species
Vapor pressure (P
sat
) by the Antoine Equation: ln P
sat
/kPa = A
B
t /

C +C
Latent heat of vaporization at the normal boiling point (Hn), and normal boiling point (tn)
Parameters for Antoine Eqn. Temp. Range Hn tn
Name Formula A

B C

C kJ/mol

C
Acetone C
3
H
6
O 14.3145 2756.22 228.060 26 77 29.10 56.2
Acetic acid C
2
H
4
O
2
15.0717 3580.80 224.650 24 142 23.70 117.9
Acetonitrile* C
2
H
3
N 14.8950 3413.10 250.523 27 81 30.19 81.6
Benzene C
6
H
6
13.7819 2726.81 217.572 6 104 30.72 80.0
iso-Butane C
4
H
10
13.8254 2181.79 248.870 83 7 21.30 11.9
n-Butane C
4
H
10
13.6608 2154.70 238.789 73 19 22.44 0.5
1-Butanol C
4
H
10
O 15.3144 3212.43 182.739 37 138 43.29 117.6
2-Butanol* C
4
H
10
O 15.1989 3026.03 186.500 25 120 40.75 99.5
iso-Butanol C
4
H
10
O 14.6047 2740.95 166.670 30 128 41.82 107.8
tert-Butanol C
4
H
10
O 14.8445 2658.29 177.650 10 101 39.07 82.3
Carbon tetrachloride CCl
4
14.0572 2914.23 232.148 14 101 29.82 76.6
Chlorobenzene C
6
H
5
Cl 13.8635 3174.78 211.700 29 159 35.19 131.7
1-Chlorobutane C
4
H
9
Cl 13.7965 2723.73 218.265 17 79 30.39 78.5
Chloroform CHCl
3
13.7324 2548.74 218.552 23 84 29.24 61.1
Cyclohexane C
6
H
12
13.6568 2723.44 220.618 9 105 29.97 80.7
Cyclopentane C
5
H
10
13.9727 2653.90 234.510 35 71 27.30 49.2
n-Decane C
10
H
22
13.9748 3442.76 193.858 65 203 38.75 174.1
Dichloromethane CH
2
Cl
2
13.9891 2463.93 223.240 38 60 28.06 39.7
Diethyl ether C
4
H
10
O 14.0735 2511.29 231.200 43 55 26.52 34.4
1,4-Dioxane C
4
H
8
O
2
15.0967 3579.78 240.337 20 105 34.16 101.3
n-Eicosane C
20
H
42
14.4575 4680.46 132.100 208 379 57.49 343.6
Ethanol C
2
H
6
O 16.8958 3795.17 230.918 3 96 38.56 78.2
Ethylbenzene C
8
H
10
13.9726 3259.93 212.300 33 163 35.57 136.2
Ethylene glycol* C
2
H
6
O
2
15.7567 4187.46 178.650 100 222 50.73 197.3
n-Heptane C
7
H
16
13.8622 2910.26 216.432 4 123 31.77 98.4
n-Hexane C
6
H
14
13.8193 2696.04 224.317 19 92 28.85 68.7
Methanol CH
4
O 16.5785 3638.27 239.500 11 83 35.21 64.7
Methyl acetate C
3
H
6
O
2
14.2456 2662.78 219.690 23 78 30.32 56.9
Methyl ethyl ketone C
4
H
8
O 14.1334 2838.24 218.690 8 103 31.30 79.6
Nitromethane* CH
3
NO
2
14.7513 3331.70 227.600 56 146 33.99 101.2
n-Nonane C
9
H
20
13.9854 3311.19 202.694 46 178 36.91 150.8
iso-Octane C
8
H
18
13.6703 2896.31 220.767 2 125 30.79 99.2
n-Octane C
8
H
18
13.9346 3123.13 209.635 26 152 34.41 125.6
n-Pentane C
5
H
12
13.7667 2451.88 232.014 45 58 25.79 36.0
Phenol C
6
H
6
O 14.4387 3507.80 175.400 80 208 46.18 181.8
1-Propanol C
3
H
8
O 16.1154 3483.67 205.807 20 116 41.44 97.2
2-Propanol C
3
H
8
O 16.6796 3640.20 219.610 8 100 39.85 82.2
Toluene C
7
H
8
13.9320 3056.96 217.625 13 136 33.18 110.6
Water H
2
O 16.3872 3885.70 230.170 0 200 40.66 100.0
o-Xylene C
8
H
10
14.0415 3358.79 212.041 40 172 36.24 144.4
m-Xylene C
8
H
10
14.1387 3381.81 216.120 35 166 35.66 139.1
p-Xylene C
8
H
10
14.0579 3331.45 214.627 35 166 35.67 138.3
Based primarily on data presented by B. E. Poling, J. M. Prausnitz, and J. P. OConnell,
The Properties of Gases and Liquids, 5th ed., App. A, McGraw-Hill, New York, 2001.
*Antoine parameters adapted from Gmehling et al. See footnote 2, p. 764.

Antoine parameters A are adjusted to reproduce the listed values of tn.

Temperature
dependence of P
v

Solid-vapor equilibrium
Below the melting point a solid can vaporize without
melting (sublimes)
! H
sub
= ! H
melt
+ !H
vap
(L) of the hypothetical subcooled
liquid (imaginary liquid cooled below its melting pt
without becoming solid)
For solids, the reference state fugacity is the vapor
pressure of the subcooled liquid.
The P
v
for a subcooled liquid is obtained by
extrapolation of P
v
data above the melting point.
Molecular interactions governing vapor
pressure
The stronger the intermolecular attractions, the
lower the vapor pressure.
Electron deficient molecular regions of one
molecule drawn toward electron-rich regions of
neighboring molecules.
Summation of intermolecular forces determines
vapor pressure.
Intermolecular forces
Van der Waals or dispersive attractions
nonpolar molecules-greater the size, greater the
attraction
Polar interactions
dipole:dipole
dipole: induced dipole attraction
hydrogen bonding (i.e. alcohols and amines)
Electronegativities H,C, S, I < N, Br < Cl < O < F
MW Solubility Vapor Press. Vapor Press. H
Chemical g/mol mp, C bp, C (mg/L) Pa (atm) Log Kow (dimensionless)
Trichlorouoromethane 137.4 -111 23.8 1100 9.04E-01 2.53 4.62E+00
n-Hexane 86.2 -95 68 9.5 1.99E-01 4.11 7.40E+01
1,1,1-Trichloroethane 133.4 -32 113 730 1.26E-01 2.47 9.44E-01
Benzene 78.1 5.53 80 1780 1.25E-01 2.13 2.25E-01
Cyclohexane 84.2 6.55 80.7 55 1.25E-01 3.44 7.85E+00
Trichloroethylene 131.4 -73 87 1100 9.74E-02 2.29 4.76E-01
Toluene 92.1 -95 111 515 3.75E-02 2.69 2.74E-01
Chlorobenzene 112.6 -46.5 132 472 1.56E-02 2.84 1.52E-01
p-Xylene 106.2 13.2 138 185 1.15E-02 3.15 2.71E-01
Quinoline 129.2 -15.6 237.7 60000 1.31E-03 2.03 1.16E-04
Phenol 94.1 40.9 181.75 82000 6.97E-04 1.46 3.27E-05
1,2,4-Trichlorobenzene 181.5 17 213.5 34.6 5.98E-04 4.00 1.28E-01
p-Cresol 108.1 34.8 201.9 16800 1.45E-04 1.95 3.81E-05
Naphthalene 128.2 80.2 218 31.7 1.03E-04 3.35 1.70E-02
2-Chlorobiphenyl 188.7 34 374 1.3 2.01E-05 4.54 1.20E-01
2,2'4,4'-Tetrachlorobiphenyl 291.9 83 0.068 1.97E-07 5.90 3.47E-02
Phenanthrene 178.2 101 339 1.29 1.59E-07 4.57 8.98E-04
Pentachlorophenol 266.4 190 310 14 1.45E-07 5.01 1.13E-04
Hexachlorobenzene 284.8 230 322 0.005 2.27E-08 5.50 5.29E-02
2,2',4,4',6,6'-Hexachlorobiphenyl 360.9 114 0.0007 1.58E-08 7.00 3.33E-01
Anthracene 178.2 216.2 340 0.041 7.90E-09 4.63 1.40E-03
Pyrene 202.3 156 360 0.135 5.92E-09 5.22 3.63E-04
2,4-D 221.0 138 215 890 5.53E-10 2.81 5.61E-09
DDT 354.5 108.5 0.0031 1.97E-10 6.19 9.23E-04
Benzo(a)pyrene 252.3 175 0.0038 6.91E-12 6.04 1.88E-05
2,3,7,8-TCDD 322.0 305 0.0193 9.87E-13 6.80 6.73E-07
Physical-Chemical Properties of Selected Organic Chemicals at 25C (Mackay, 1991)
Selected experimental P
v
values
Method for Pv measurement
OECD GUIDELINES FOR THE TESTING OF CHEMICALS
GUIDELINE 104 VAPOR PRESSURE
Exp. determination of P
v

Gas saturation or generator column method
Generate a saturated gas stream by flowing gas
through column containing the volatile solid or liquid
solute coated on a inert packing. Column exit gas is
analyzed for solute concentration.
Burkhard, L. P., D. E. Armstrong, et al. (1984). Vapor
Pressures for Biphenyl, 4-Chlorobiphenyl, 2,2',3,3',5,5',6,6'-
Octachlorobiphenyl, and Decachlorobiphenyl. J. Chem. Eng.
Data 29: 248-250.
Databases of P
v
values
Environmental Fate/Exposure Database
http://www.srcinc.com/what-we-do/efdb.aspx
CRC Handbook of Chemistry and Physics (Lide,
1995)
The Handbook of Physical Properties of Organic
Chemicals (Howard & Meylan, 1997)
The Handbook of Vapor Pressure (Yaws, 1994)
The Illustrated Handbook of Physical-Chemical
Properties and Environmental Fate for Organic
Chemicals (Mackay et al., 1999)
Estimation of Pv
Review article:
Dearden, J C. 2003. QUANTITATIVE STRUCTURE
PROPERTY RELATIONSHIPS FOR PREDICTION OF
BOILING POINT, VAPOR PRESSURE, AND MELTING
POINT. Environmental Toxicology and Chemistry 22:
1696-1709
Estimation of P
v

From T
B
and T
M
- Derivatives of the Clausius-Clapeyron equation
(Antoine equation, modified Watson Correlation)
Assumptions: linear temperature dependence of !H
vap
, !S
vap
is
the same for many organic compounds
ln P = -(4.4 + ln T
B
) x {1.803(T
B
/T - 1) - 0.803 ln (T
B
/T)} - 6.8
(T
M
/T - 1)
where P is vapor pressure in atm, T
B
is the boiling point (K), T
M
is the
melting point (K) and T is the temperature of interest (K). The last term is
used to account for melting of subcooled liquid. This term, that includes
the melting point, is ignored for liquids.
Mackay, D., A. Bobra, et al. (1982). Vapor Pressure Correlations for Low
Volatility Environmental Chemicals. Environ. Sci. Technol. 16: 645-649.
Correlation with GC retention times
Westcott, J. W. and T. F. Bidleman (1981).
Determination of polychlorinated biphenyl
vapor pressures by capillary gas
chromatography. J. Chromatogr. 210: 331-336.
Group Contribution method
Burkhard, L. P. (1985). Estimation of Vapor
Pressures for Halogenated Aromatic
Hydrocarbons by a Group-Contribution
Method. Ind. Eng. Chem. Fundam. 24:
119-120.
UNIversal Functional Activity Coefficient (UNIFAC)
derived variables
UNIFAC is a group contribution method for
estimating activity coefficients
log P
v
= 6.94 - (2.25 Vu + 4.23 log !
C
) -0.577 log
!
R
) - 0.01(mp-25)
Banerjee, S., P. H. Howard, S.S. Lande. 1990.
General structure-vapor pressure relationships
for organics. Chemosphere 21(10-11):
1173-1180.
Computerized methods
MPBPVP from Syracuse Research Corp.
http://www.epa.gov/opptintr/exposure/pubs/
episuite.htm
SPARC from the University of Georgia
http://ibmlc2.chem.uga.edu/sparc/index.cfm
ACD from Advanced Chemistry Development
Effect of environmental variables -
temperature
Pv of any chemical increases with an increase in temperature.
P
v
for a compound may change by more than 10X over an
environmentally relevant temperature range.
For biphenyl:
at T = 5.2 C, Pv = 0.106 Pa
at T = 24.7 C, Pv = 1.15 Pa
The effect of temperature is often modeled by Antoine equation:
ln Pv = A- B/T + C where A and C are empirical constants and B =
!Hvap/R