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DEPENDENCE OF BOILING POINT ON PRESSURE
The normal boiling point of a liquid is defined as the temperature at which the vapor pressure reaches standard atmospheric pressure, 101.325 kPa.
The change in boiling point with pressure may be calculated from the representation of the vapor pressure by the Antoine Equation,
ln p = A1 ¨C A2/(T + A3)
where p is the vapor pressure, T the absolute temperature, and A1, A2, and A3 are constants. This table, which has been calculated using the Antoine
constants in Reference 1, gives values of Dt/Dp for a number of liquids, in units of both ¡ãC/kPa and ¡ãC/mmHg. The correction to the boiling point is
generally accurate to 0.1 to 0.2 ¡ãC as long as the pressure is within 10% of standard atmospheric pressure.
A slightly less accurate estimate of Dt/Dp may be obtained from the Claussius-Clapeyron equation, with the assumption that the change in volume
upon vaporization equals the ideal-gas volume of the vapor. This leads to the equation
Dt/Dp = RTb
2 /p0 DvapH(Tb)
where R is the molar gas constant, p0 is 101.325 kPa, Tb is the normal boiling point temperature (absolute), and DvapH(Tb) is the molar enthalpy of
vaporization at the normal boiling point. Values of the last quantity may be obtained from the table ¡°Enthalpy of Vaporization¡± in Section 6.
REFERENCE
1. Lide, D.R., and Kehiaian, H.V., CRC Handbook of Thermophysical and Thermochemical Data, CRC Press, Boca Raton, FL, 1994, pp. 49-
59.
tb Dt/Dp
Compound ¡ãC ¡ãC/kPa ¡ãC/mmHg
Acetaldehyde 20.1 0.261 0.0348
Acetic acid 117.9 0.324 0.0432
Acetone 56.0 0.289 0.0385
Acetonitrile 81.6 0.316 0.0421
Ammonia -33.33 0.198 0.0264
Aniline 184.1 0.378 0.0504
Anisole 153.7 0.367 0.0489
Benzaldehyde 179.0 0.392 0.0523
Benzene 80.0 0.321 0.0428
Bromine 58.8 0.300 0.0400
Butane -0.5 0.267 0.0356
1-Butanol 117.7 0.278 0.0371
Carbon disulfide 46.2 0.304 0.0405
Chlorine -34.04 0.224 0.0299
Chlorobenzene 131.7 0.365 0.0487
1-Chlorobutane 78.6 0.321 0.0428
Chloroethane 12.3 0.262 0.0349
Chloroethylene -13.3 0.241 0.0321
Cyclohexane 80.7 0.328 0.0437
Cyclohexanol 160.8 0.344 0.0459
Cyclohexanone 155.4 0.382 0.0509
Decane 174.1 0.388 0.0517
Dibutyl ether 140.2 0.363 0.0484
Dichloromethane 39.6 0.276 0.0368
Diethyl ether 34.5 0.278 0.0371
Dimethyl sulfoxide 189.0 0.379 0.0505
1,4-Dioxane 101.5 0.321 0.0428
Dipropyl ether 90.0 0.326 0.0435
Ethanol 78.2 0.249 0.0332
Ethyl acetate 77.1 0.300 0.0400
Ethylene glycol 197.3 0.331 0.0441
Heptane 98.5 0.336 0.0448
Hexafluorobenzene 80.2 0.305 0.0407
Hexane 68.7 0.314 0.0419
1-Hexanol 157.6 0.318 0.0424
Hydrogen fluoride 20.1 0.276 0.0368
Iodomethane 42.5 0.291 0.0388
Isobutane -11.7 0.254 0.0339
Methanol 64.6 0.251 0.0335
Methyl acetate 56.8 0.282 0.0376
Methyl formate 31.7 0.582 0.0776
N-Methylaniline 196.2 0.396 0.0528
N-Methylformamide 199.5 0.371 0.0495
Nitrobenzene 210.8 0.418 0.0557
Nitromethane 101.1 0.320 0.0427
1-Octanol 195.1 0.360 0.0480
Pentane 36.0 0.289 0.0385
1-Pentanol 137.9 0.296 0.0395
Phenol 181.8 0.349 0.0465
Propane -42.1 0.224 0.0299
1-Propanol 97.2 0.261 0.0348
2-Propanol 82.3 0.247 0.0329
Pyridine 115.2 0.340 0.0453
Pyrrole 129.7 0.330 0.0440
Pyrrolidine 86.5 0.309 0.0412
Styrene 145.1 0.369 0.0492
Sulfur dioxide -10.05 0.221 0.0295
Tetrachloroethylene 121.3 0.354 0.0472
Tetrachloromethane 76.8 0.325 0.0433
Toluene 110.6 0.353 0.0471
Trichloroethylene 87.2 0.330 0.0440
Trichloromethane 61.1 0.302 0.0403
Trimethylamine 2.8 0.248 0.0331
Water 100.0 0.276 0.0368
o-Xylene 144.5 0.373 0.0497
m-Xylene 139.1 0.368 0.0491
p-Xylene 138.3 0.369 0.0492

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