Ind. Eng. Chem. Process Des. Dev.

1083, 22, 313-322

313

Correlation and Prediction of the Vapor Pressures of Pure Liquids

over Large Pressure Ranges
Jack McGerry
Department of Chemical Engineering, University of Saiford, Salford A45 4wT, England

Liquid vapor pressures of 72 substances are available over pressure ranges extending from about 1 kPa up to
the particular critical pressure. For correlation of these data the Wagner equation yields an average root mean
square percentage error of 0.09 % . The results obtained allow the formulation of constraints applying to the behavior
of vapor pressure for values of the reduced temperature in the range 0.5 to 1.O. Using these constraints Wagner
coefficients were generated and are presented for a further 179 pure substances for which only limited range data
are available (the limits are usually about TR = 0.55 and 0.65). It is considered that these coefficients will yield
vapor pressures in the range TR = 0.5 to 1.0 which are suitable for process design work.

Introduction
The calculation of accurate liquid vapor pressures is vital
for the success of many chemical engineering design
techniques. Numerous equations have been proposed for
thia purpose, and eight of these together with modifications
of four of them are considered in this paper.
The widely used Frost-Kalkwarf equation (Frost and
Kalkwarf, 1953) is not included in these eight because it
is not explicit in vapor pressure. It may be worth mentioning, however, that this equation was fitted to the 14
sets of full range data initially involved with an average
% RMS error of 0.12.
The selected eight equations may be divided into two
groups on the basis of the method by which the constants
(coefficients) of the equations are calculated. (Group I):
Constanta are calculated by the regression of experimental
vapor pressure. The Antoine, Wagner, and Thomas
equations belong to this group (Antoine, 1888 Wagner,
1973: Thomas, 1976). Representation by Chebyshev
polynomials also falls into this group (Ambrw et al., 1970).
(Group 11): Constants are calculated from critical temperature and pressure together with one or two further
basic data. The Riedel, Miller, Thek-Stiel, and GomezThodos equations belong to this group (Riedel, 1954:
Miller, 1965: Thek and Stiel, 1966: Gomez-Nieto and
Thodos,1977). It seems obvious that it could be beneficial
to use regression of data for evaluation of the constants
of the equations of the second group.
The Equations Involved
Antoine Equation.

In P = A - T+C
This equation can yield highly accurate values of vapor
pressure in a pressure range of about 1to 200 P a . Values
of constants valid for this range and yielding vapor pressure in millimeters of mercury are available for many
substances (Reid et al., 1977; Boublik et al., 1973). The
equation was developed from the Clausius-Clapepon
equation and is used extensively.
Wagner Equation.
1
In PR = -[A(1 - TR) + B(l - TR)'" C(l - T R ) ~
TR
D(1 - T R ) ~(2)
]
Statistical considerationswere involved in the development
of this equation, which was initially derived to describe
the vapor pressures of argon and nitrogen from the triple

point to the critical temperature (Wagner, 1973).

Thomas Equation.
p=- 253312
(3)
ex - C
where
In X = A - B In T
(4)
Equation 3 is based on the observation that "the ratio of
the value of RT d(ln P)/dT for any nonassociated compound to the value of the function for any other such
compound at the same vapor pressure is constant over a
range from a few millimeters" of mercury to the critical
pressure (Thomas, 1976).
Chebyshev Polynomials. Vapor pressures of liquids
from triple points to critical temperatures may be described with high accuracy by (Ambrose et al., 1970)

where

EJx) = cos (s cos-' x )

(6)
(7)

The Chebyshev polynomials (E,(x)) are related by the

recurrence relation
E,+,(x) - 2xE,(x) + E,-,(x) = 0
(8)
It is easily shown that
E,(x) = x
(9)
E&) = 2x2 - 1
(10)
and then eq 8 allows calculation of the higher polynomials.
The use of up to a total of six polynominals gives excellent
agreement with data; i.e., up to seven constants (ao,...,a,)
are used.
Although the number of constants is higher than that
used by any other method discussed here, standard computer programs allow easy generation of the constants and
evaluation of vapor pressures.
Riedel Equation.
B
In PR= A - - C In T R DTR6
(11)
TR
where
A = -35Q

019~-4305ia3ii
122-0313$01.50io @ 1983 American Chemlcal Society

314

Ind. Eng. Chem. Process Des. Dev., Voi. 22,

No. 2, 1983

B = -36Q
C = 42Q + a,
D = -Q
Q = 0.0838(3.758 - a,)

Table I. Input Data Normally Required for Eq 1, 2, 3,

5 , 11, 16,20,and 25
equation

(12)
where a, is called the Riedel parameter and is defined by
a, = d (In PR)/d (In TR) at TR = 1
(13)

The value of a, is best obtained (Reid et al., 1977) from

a knowledge of the normal boiling point (TB). Substitution
of eq 12 into eq 11 yields
0.3149f(T~~)
- In (1O1.325/Pc)
a, =
(14)
0.0838f(TBR)- In TBR

Antoine
Wagner
Thomas
Chebyshev
Riedel
Miller
Thek-Stiel
Gomez-Thodos

eq no.

1
2

3
5

TC,pC,

20
25

Miller Equation. This equation is referred to by Reid

et al. (1977) as the Reidel-Plank-Miller equation

where

A = 0.4835 + 0.4605h
TBR In (1O1.325/Pc)
h=
1 - TBR

(17)
(18)

Thek-Stiel Equation.

where

f(TR) =
1
1.14893 - - - 0.11719TR-0.03174T~~
- 0.375 In TR
TR

(22)
(23)
(24)
a, is again obtained from a knowledge of normal boiling
temperature, and h is given by eq 18.
Gomez-Thodos Equation.

B = 1 . 0 4 2 ~- ~0.462844
~
C = 5.2691 + 2.0753A - 3.1738h

(25)
where
7.0109

380900

C = 2.4186 - h
he(123.21/h)
+

DE-

a,

A = -(B

(26)

+ BC
7

+ D)

(29)

TB

Tc, P c , TB,AHB
Tc, P c , TB,LY,

Table 11. Modified Input Data

equation
Wagner
Riedel
Miller
Thek-Stiel
Gomez-Thodos

where

fitted constants A , B, C
Tc, Pc, fitted constants A , B, C, D
fitted constants A , B, C
TL,TH,fitted constants a, to as
Tc,P c , TB

T,,
T,,
T,,
T,,
T,,

fitted constants Po A , B,
P,, fitted constants A , B,
fitted constants Po A, B
fitted constants Pc, A , B,
P,, fitted constants A , B,

C, D
C, D

C, D
C, D

and h is given by eq 18.

Gomez-Nieto and Thodos (1977) give values of a, for use
in eq 28 for 138 substances. The Riedel, Miller, and
Thek-Stiel equations are all based on the integration of
the Clausius-Clapeyron equation using various relationships for enthalpy of vaporization and the difference between saturated vapor and liquid compressibilities. The
data input for the above eight equations are summarized
in Table I.
Adjustment of P, and Modification of Group I1
Met hods
Ambrose (1978) has pointed out that measured values
of critical pressures are usually of lower accuracy than the
related critical temperatures. He therefore proposed that
In P, should be treated as an adjustable constant in the
Wagner equation and the resultant value used to obtain
critical pressure for use with this equation. This procedure
is followed here and, while generating critical pressures
very close to the measured ones, allows significantly better
data correlation.
Equations 11, 16, 20, and 25, in addition to being used
in the normal manner, were also used as models for regression of vapor pressure data. For eq 16 and 20 the value
of Pc was again treated as an adjustable constant. There
is no advantage to be gained by this treatment of eq 11
and 25, since in both cases In Pc would merely be merged
with the adjustable constant A.
The Thek-Stiel eq 20 was further modified by replacement of the constant 0.04 by an adjustable value. It
is only to be expected that constants obtained by data
regression will yield better results than those obtained from
critical properties. The modified input data are summarized in Table 11.
Processing the Data
Highly accurate vapor pressure data for 12 liquids exist
in the range -5 kPa to the critical pressure. Similar data
for two light gases are available over a range extending
from the triple point to the critical point. These 14 substances and their data sources are listed in Table 111.
The equation constants obtained for these substances
were those which minimized the sum of the squares of the
fractional deviation at each data point, the fractional deviation being given by (experimental vapor pressure calculated value) i(experimental vapor pressure). With
the exception of Chebyshev polynomial representation this
minimization was carried out by a computer program
based on algorithm E04GAF of the Numerical Algorithms
Group, Oxford, England. For the exception the algorithms

Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 2, 1983 315
Table 111. Sources of High Accuracy Data in Range

5 kPa to PC

ID

source

benzene

toluene

ethylbenzene
o-xylene

3
4

m-xylene
p-xylene
diethyl ether
acetone
cyclohexane

5
6
7
8
9

Willingham et al. (1945)

Bender et al. (1952)
Ambrose et al. (1967)
Willingham et al. (1945)
API 44 Tables (1966)
Ambrose et al. (1967)
as for toluene
Willingham et al. (1945)
Ambrose et al. (1967)
as for o-xylene
as for m-xylene
Ambrose et al. (1972)
Ambrose et al. (1974)
Willingham et al. (1945)
Kerns et al. (1974)
Hugill and McGlashan (1978)
E.R.A. 1967 Steam Tables
Skaates and Kay (1964)
Ambrose and Sprake (1970)
Ambrose et al. (1975)
Ambrose and Sprake (1970)
Ambrose et al. (1975)
Wagner (1973)
Wagner (1973)

substance

water
methanol

10
11

ethanol

12

nitrogen
argon

13
14

EO2ADF and EO2AEE were used. In all cases iteration

continued until the first five significant figures for all
adjustable constants remained unchanged.
The results for each of the fourteen substances are given
in Table IV, which is submitted together with Tables V
and VI as Supplementary Material. (Seeparagraph at end
of paper regarding this material.) Average root mean
square percentage deviations resulting from eq 1 , 2 , 3 , 5 ,
11, 16, 20, and 25 were 0.74, 0.046, 0.95, 0.040, 0.15, 0.41,
0.055, and 0.090, respectively. In all cases the constants
were obtained by iteration. Values of TB and AHB were
obtained from the book by Reid et al. (19771, while values
of Pc and Tc were given with the data.
It is clear from Table IV that the data are most closely
represented by Chebyshev polynomials. However, the
Wagner equation gives results which are not significantly
different. Since the representation by Chebyshev polynomials requires seven coefficients for the above performance it was decided to use the more tractable Wagner
equation for correlation of full range data, and Chebyshev
polynomials take no further part in this discussion.
Table V (Supplementary Material) summarizes the
results obtained by eq 11, 16, 20, and 25 when the constants were calculated from the input data indicated in
Table I, as opposed to the use of regression of vapor
pressure data. The average root-mean-square percentage
deviations resulting from eq 11, 16, 20, and 25 were 1.90,
1.31, 0.85, and 2.93 respectively.
The Wagner coefficients for seventy two compounds are
presented in Table VII. These compounds include the
14 substances referenced in Table In, the remainder being
compounds for which full range data of mixed precision
are available. The values of Tc and Pc are those to be used
in the Wagner equation.
Data for oxygen, carbon monoxide, helium, hydrogen,
and neon were taken from the W.A.D.D. Technical Report
60-56 (1961),while the data of Kemp and Giauque (1937)
and of Robinson and Senturk (1979) were used for carbonyl sulfide.
The work of Mastroianni et al. (1978) is the source of
data for trifluorotrichloroethane,and the data of Ambrose
(1968) and Ambrose et al. (1975) were used for the fluorobenzenes and pentafluorotoluene.

no. of
data points

total
data points

19
19
9
20
4
9

47

20
9

17
9
12
12
20
12
25
23

33
33
29
29
29
40
47
38
49
44
48
49
49

Data for the remaining compounds were generated from

Chebyshev coefficients published by the Engineering
Sciences Data Unit, London (1972,1973,1974,1975,1976,
1977,1978). In all cases the value of Pc was taken to be
adjustable.
The Pitzer acentric factor (w) is extensively used to
quantify the nonideal behavior of gases and is easily calculated from the Wagner coefficients of a substance as
given in Table VII.
w =

-1.0 - 0.620417[0.34 + (0.3)B

+ (0.3)3C+(0.3)60]

(30)
Unconstrained Fit to Limited Ranges of Data
There are many substances for which data only exist
over a small range of pressure, the usual upper limit lying
in the range 100 to 200 kPa. The use of such data for
successful prediction of vapor pressures outside the particular range is obviously desirable.
Consequently, data were extracted from the lower ends
of the full ranges of data for the substances of Table 111,
and equation constants were obtained by regression on
these samples of data. Since no data near the critical
points are involved, it w i l l be evident that critical pressures
should not be subjects of iteration in eq 2, 16 and 20. By
use of these sample constants, vapor pressures were calculated for the full range of data and the root mean square
percentage deviations were obtained. The results are
presented in Table VI (Supplementary Material).
Outstandingly poor results are obtained for argon, and
this is due to the fact that the temperature range yielding
vapor pressures up to about 100 P a is too small a fraction
of the range up to the critical pressure (0.06 compared with
about one quarter for the other substances). Excluding
argon, the average root-mean-square percentage deviations
resulting from eq 1, 2 , 3 , 11, 16, 20, and 25 were 2.3, 0.3,
71.0, 9.1, 0.75, 0.20, and 8.0 respectively.
When generating Thek-Stiel eq 20 constants from the
samples of data, it was necessary to stop the iteration
procedure prematurely to avoid excessive computation.
This had the effect of preventing the equation fitting the
sample data more accurately but gave a better fit over the
full range. In consequence, the percentage deviations given

316

Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 2, 1983

Table VII. Wagner Coefficients from Full Range Data

formula
Ar

name

argon
-5.90501
1.12627
-0.767869
co
carbon
-6.20798
1.27885
-1.34533
monoxide
carbon dioxide -6.95626
1.19695
-3.12614
CO,
cos
carbonyl sulfide -6.40952
1.21015
-1.54976
fluorine
-6.18224
1.18062
-1.16555
F,
He
helium
-3.97466
1.00074
1.50056
hydrogen
-5.57929
2.60012
-0.855060
HZ
water
-7.76451
1.45838
-2.77580
HZ 0
Ne
neon
-6.07686
1.59402
-1.06092
nitrogen
-6.09676
1.13670
-1.04072
NZ
oxygen
-6.28275
1.73619
-1.81349
0 2
CCl,F,
dichlorodi-7.01657
1.73224
-2.97909
fluoromethane
CC1,
carbon
-7.07139
1.71497
-2.89930
tetrachloride
CHClF, chlorodi-6.99913
1.23014
-2.49377
fluoromethane
CHC1,
chloroform
-6.95546
1.16625
-2.13970
CHF,
trifluoro-7.41994
1.65884
-3.14962
methane
difluoromethane -7.44206
1.51914
-2.75319
CHZFZ
CH3C1 methyl chloride -6.86672
1.5227 3
-1.92919
methyl fluoride -6.78099
CH-F
0.828379
-1.41137
CH;
methane
-6.00435
1.18850
-0.834082
CH,O
methanol
-8.547 96 0.769817
-3.10850
CH,N
methylamine
-7.527 7 2 1.81615
-4.20677
trichlorotri-7.36666
1.81971
-3.94233
C2C13F3
fluoroethane
ethylene
-6.32055
1.16819
-1.55935
1,2-dichloro-7.36864
1.767 27
-3.34295
ethane
ethane
-6.34307
1.01630
-1.19116
'ZH6
ethanol
-8.51838
0.341626
-5.73683
'ZH6'
ethyiamine
-7.20059
C,H,N
1.20679
-3.71972
dimethy lamine -7.9 02 9 5 2.81577
-6.31338
propylene
-6.64231
-1.81005
1.21857
acetone
-7.45514
1.20200
-2.43926
prop an e
-6.67833
1.15437
-1.64984
1-propanol
-8.05594
4.25183E-2 -7.51296
2-propanol
-8.1 6927 -9.4321 3E-2 -8.10040
propylamine
-7.23587
1.22853
-3.75004
trimethylamine -6.88066
1.15962
-2.18332
butene
-6.88204
1.27051
-2.26284
isobutene
-6.95542
1.35673
-2.45222
methyl ethyl
-7.71476
1.71061
-3.68770
ketone
butane
-6.88709
1.151 57
-1.99873
isobu tane
-6.95579
1.50090
-2.52717
diethyl ether
-7.29916
1.24828
-2.91931
1-butanol
-8.007 56 0.537 826
-9.34240
2-butanol
-7.80578
0.324557
-9.41265
diethylamine
-7.267 96 1.15810
-3.91125
1-pentene
-7.04875
1.17813
-2.45105
pentane
-7.28936
1.53679
-3.08367
isopentane
-7.12727
1.38996
-2.54302
2,2-dimethyl-6.89153
1.25019
-2.28233
propane
1-pentanol
-8.97725
2.99791
-12.9596
chloropenta-8.0217 2 1.54665
-3.78361
fluorobenzene
pentafluoro-7.79730
1.35271
-3.50409
benzene
1,2,4,5-tetra-7.79740
1.57406
-3.82060
fluorobenzene
benzene
-6.94739
1.25253
'6
H6
-2.53686
cyclohexane
-6.96009
1.31328
-2.75683
hexane
-7.51650
1.54797
-3.38541
isohexane
-7.28750
1.29015
C6H14
-2.97853
3-methyl-7.27084
1.26113
6'
-2.81741
pentane
2,2-dimethyl-7.25933
1.69602
-3.18124
butane
2,3-dimethyl-7.27870
1.56349
-3.05387
butane

C~HIN

D
-1.62721
-2.56842
2.99448
-2.10074
-1.50167
-0.430197
1.70503
-1.23303
4.06656
-1.93306
-2.536453-2
-0.377232

pc

4857.99
3501.15
7374.99
6346.45
5214.72
230.029
1309.60
22122.3
2724.55
3399.61
5089.87
4132.03

Tc

rms %
error

150.651 0.023
132.91 0.28

approx
lowest data

69
26

84
71

304.15
378.8
144.31
5.20
33.19
647.35
44.38
126.200
154.7
384.95

0.011 530
0.18
2
0.012
4
0.26
5
7
0.27
0.026
0.7
0.57
43
0.025 1 3
0.28
0.2
0.038
0.2

217
162
64
2
14
275
25
63
54
155

-2.49466

4550.78

556.40

0.027

250

-2.21052

4983.31

369.30

0.042

170

-3.44421
-0.849379

5365.76
4840.92

536.40
299.06

0.14
0.075

0.1 215
0.2 125

-0.979495
-2.61459
-2.41700
-1.22833
1.54481
-1.22275
0.625601

5826.99
6697.18
5557.36
4596.42
8 0 8 5.0 5
7433.32
3425.71

351.54
416.27
315.0
190.53
512.64
430.0
487.7

0.066
0.11
0.079
0.019
0.12
0.073
0.32

-1.83552
-1.43530

5050.88
5362.00

282.55
566.00

0.034
0.071

0.1 1 0 5
1
260

-2.03539
8.32581
-4.33511
-0.224073
-2.48212
-3.35590
-2.70017
6.89004
7.85000
-4.33990
-2.94707
-2.61632
-1.46110
-0.751692

4869.71
6130.87
5641.37
5308.28
4605.23
4699.93
4255.76
5151.11
4742.44
4806.74
4083.96
4017.60
4007.06
4221.77

305.42
513.92
456.35
437.70
364.85
508.10
369.82
536.78
508.30
497.0
433.30
419.57
417.90
536.78

0.13
0.077
0.089
0.043
0.018
0.086
0.043
0.19
0.22
0.086
0.073
0.094
0.086
0.11

2
6
1
1
0.1
4
0.2
0.2
0.1
1
1
0.2
0.2
1

133
293
215
240
140
259
145
260
250
235
200
170
170
255

-3.13003
-1.49776
-3.36740
6.68692
2.64643
-1.17981
-2.21727
-1.02456
-2.45657
-4.74891

3790.62
3658.01
3646.10
4412.63
4189.75
3705.40
3536.85
3378.62
3385.90
3197.88

425.18
408.14
466.74
563.05
536.01
496.45
464.78
469.74
460.43
433.77

0.11
0.092
0.072
0.14
0.10
0.043
0.095
0.074
0.039
0.036

0.1
0.2
7
2
0.2
1
0.1
0.1
2
41

170
165
250
275
265
240
190
195
220
260

8.84205
-2.99849

3909.45
3235.98

588.15
570.81

0.096
0.024

-3.76856

3535.63

530.97

0.012

27

322

-2.45398

3801.01

543.35

0.017

294

-3.49284
-2.45491
-2.36767
-2.17234
-2.17642

4895.60
4075.26
3036.17
3032.52
3121.71

562.10
553.640
507.90
498.10
504.40

0.084
0.051
0.028
0.046
0.037

-0.805183

31 12.72

489.40

0.065

225

-1.57752

3145.80

500.30

0.066

235

0.6
0.8
0.7
12
10
1
2

155
175
135
91
288
200
238

0.2 290
4
309

8
288
10
293
0.2 220
1
240
1
235

Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 2, 1983 317
Table VI1 (Continued)
approx
rms % lowest data
formula
C,H,F,
C,H,
C,H,,
C,H,,
C,H,,
C,H,,
C,H,,
C,H,,
C,H,,
C,H,,
C,H,,
C,H,,O

3123.89

566.52

0.019

313

-2.79168
-3.20243
-2.42625
-1.10598

4106.45
2732.37
2891.48
2949.13

591.72
540.10
540.64
531.17

0.038
0.063
0.022
0.057

6
0.1
1
1

309
240
265
250

-2.23048
-2.85992
-2.40376
-2.78710
-4.44565
-2.22001

3601.90
3732.98
3536.78
3513.00
2482.82
2561.55

617.12
630.25
616.97
616.15
568.81
543.96

0.041
0.026
0.014
0.021
0.10
0.11

6
6
6
6
0.1
1

330
337
332
331
260
265

-3.59254

2873.76

652.5

0.13

0.1 325

pentafluorotoluene
toluene
heptane
3-ethylpentane
2,2,3-trimethylbutane
ethylbenzene
o-xylene
m-xylene
p-xylene
octane
2,2,4-trimethylpentane
1-octanol

-8.04616

1.43971

-3.76736

-3.00179

-7.28607
-7.67468
-7.58305
-7.22017

1.38091
1.37068
1.58587
1.44914

-2.83433
-3.53620
-3.567 3 2
-3.11808

-7.48645
-7.53357
-7.592 22
-7.63495
-7.87867
-7.38890

1.45488
1.40968
1.39441
1.50724
1.32514
1.25294

-3.37538
-3.10985
-3.22746
-3.19678
-3.78494
-3.16606

-9.71763

4.22514

in Table VI (SupplementaryMaterial) for eq 20 are in fact

the results of a crudely constrained fit to the sample data.
Furthermore, the worst percentage deviation for eq 20 was
2.28 while that for the Wagner eq 2 was only 0.7 (excluding
argon). Bearing these facts in mind and reflecting that the
Wagner equation has been chosen to represent full range
data, it was decided to use the Wagner equation for the
constrained fitting of limited data.
A further point in favor of the Wagner equation is that
the adjusted values of Pc involved in compiling Table IV
(Supplementary Material) show equal numbers of small
positive and negative deviations from the measured values,
while the Thek-Stiel model yields 13 small negative ones
and one positive one.
It will be seen from Table VI (SupplementaryMaterial)
that the unconstrained fitting of the Wagner equation to
the limited range data gives good results when the range
of the data is not too small. It is also evident that the
unconstrained fitting of the Wagner equation yields more
accurate vapor pressures than any of the generalized
equations whose results are given in Table V (Supplementary Material).
Constrained Fit to Limited Range Data
First Constraint. The Clausius-Clapeyron equation
rigorously relates liquid vapor pressure to latent heat of
vaporization, temperature, and volume change accompanying vaporization. It may be written
d (In P) AH
-(31)
dT
RP(Zv-ZL)
Rearranging

Waring (1954) observed that for a wide variety of substance a plot of the left-hand side of eq 32 against reduced
temperature exhibits a minimum value at a value of TR
in the range 0.80 to 0.85. Ambrose et al. (1978) observed
that the minimum occurs at a somewhat lower value of TR
for very low-boiling substances and at about TR = 0.95 for
alcohols.
Differentiation of the left-hand side of eq 32 and
equating the result to zero will yield the minimizing value
of TR. If the Wagner equation is used, the following
equation is obtained for the minimizing value of TR
0.75B(1 - T R ) ~ 'i
. '6C(1 - TR) 300(1 - T R )=~0 (33)

Using eq 33, minimizing values of T R for each of the 72

substances of Table VI1 were obtained, and it was found

error

-12.9222

Tc

name

PC

Table VIII. Full Range Deviations from Constrained Fit

of Wagner Equation t o Limited Sample of Data

frattional
temp, temp
value
K - range
max % dev

rms % dev
substance ID

sample

all

1
2
3
4
5
6
7
8
9
10
11
12
13
14*
14
av value
(excluding 14*)

0.002
0.019
0.016
0.014
0.010
0.006
0.028
0.017
0.015
0.014
0.018
0.015
0.043
0.023
0.028
0.018

0.29
0.13
0.05
0.11
0.12
0.07
0.23
0.11
0.12
0.19
0.50
0.20
0.10
0.99
0.21
0.17

-0.55
-0.34
-0.22
-0.24
0.30
-0.17
0.33
0.43
0.33
-0.33
-1.1
-0.54
-0.12
-1.6
-0.42

500
480
600
500
560
500
400
480
470
490
480
490
120
130
140

0.24
0.27
0.28
0.28
0.28
0.29
0.27
0.28
0.24
0.26
0.22
0.27
0.23
0.06
0.24

that the values fell into quite narrow ranges. With the
exception of alcohols, it was possible to classify the ranges
of TR according to the normal boiling temperatures (TB)
of the substances. In fact, for 50 K C TB C 100 K the range
is 0.70 to 0.77; 100 K C TB C 273 K, 0.78 to 0.85; 273 K
C TB, 0.82 to 0.88; and for alcohols, 0.90 to 0.98. Substances with values of TB below 50 K do not exhibit such
minima.
When fitting the Wagner equation to limited range data,
the values of the coefficients were restricted to those sets
yielding a solution for eq 33 that lies within the appropriate
range for the substance.
Second Constraint. At low pressures the term LvI/(Zv
- 2,) in eq 31 and 32 varies only weakly with temperature.
Assuming this function is constant and integrating eq 31
yields
In P34= A - (B/T)
(34)
The constants A and B may be obtained from vapor
pressure data at T = TCand T = 0.7Tc. Ambrose et al.
(1978) show that In
evaluated at TR = 0.95 falls
into a narrow range for many substances. Making use of
the Pitzer acentric factor (w), eq 34 becomes
In ( P 3 4 / P ~
= )- 0.28278 (1 w ) for TR = 0.95
(35)

Equations 2 and 35 were used to calculate the value of In

(PIPa)at TR = 0.95 for the seventy two substances of
Table VII.

318

Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 2, 1983

Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 2, 1983 319

320

Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 2, 1983

a)

E
0

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""C
cow

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0 c
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0 E
0

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0 0
E
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rr-l"cjc
0 E
0 c
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rirrNC\l

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Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 2, 1983

wwwwwaww~wwwwwwwwwwmwwoF

@I

Values of w were largely taken directly from the book

by Reid et al. (1977). In a small number of cases the
Antoine constants presented in the same book were valid
for the value of TR relating to the acentric factor; these
constants were therefore used to calculate w.
The values of In
at TR = 0.95 fell into the following ranges: for TB < 100 K, the range is -0.024 to
4.018; 100 K C TB C 273 K, -0.017 to -0.006; 273 K C TB,
-0.020 to 4.001; and for alcohols, +0.007 to +0.040. The
only exception is hydrogen, which exhibited a value of
-0.043. The above ranges constitute the second restraint
when fitting the Wagner equation to limited range data.
Third Constraint. The Watson correlation (1943) may
be written

Since A H B and TBR are constants

AH = g(1 - T R ) " ~ ' ~

FJ

5-

+.a

.-0
Y

w w a w

9999

42

.
I

2
2

2
'i
.Y

.y,
.w

42

I
U

(37)

where g is a constant.
At low values of TR vapor pressures are low and eq 32
approximates to
d(ln P )
RP-=AH
dT
Combining eq 37 and 38
RP
d(ln PR)
(39)
g = 1 - TR)0.375 dT
In terms of Wagner coefficients this becomes
-R Tc
[A BV"(1.5 - 0.5Y) + CV(3 g=
(1 - T R ) ~ ' ~ ~ ~
2Y) + D P ( 6 - 5Y)] (40)
where Y = 1 - TR.
Ambrose et al. (1978) suggest that the coefficients of a
vapor pressure equation should be restricted to those sets
which yield little differences in g at TR = 0.5 and 0.6. The
constants of the fitted Wagner equation were used to
calculate the value of g at these values of TRfor the 72
substances of Table VII.
The ratios g(TR= 0.5) to g(TR = 0.6) fell into the following narrow ranges which constitute the third constraint
employed for fitting the Wagner equation to limited range
data. For TB C 100 K, the range is 1.06 to 1.20; 100 K C
TB C 273 K, 1.01 to 1.06; 273 K C TB, 0.99 to 1.03; for
alcohols, 0.98 to 1.06. There were no exceptions to these
ranges.
By use of the same samples of data that were involved
in Table VI and the three constraints detailed above,
values of the Wagner equation constants were obtained
by a computer program utilizing NAG routine E04VBF
for constrained minimization of an objective function.
These constants were then used to calculate vapor pressures up to the critical pressure, and the root mean square
percentage deviations from the full range data were obtained. The results are given in Table VIII.
The last entry in the table relates to an argon data
sample which represenb a fraction of the full-range data
having a similar size to the other entries. While the constraints caused a dramatic reduction of the overall deviation obtained from the smaller sample (0.99 cf. 81) the
larger sample yielded an overall deviation (0.21) more in
keeping with those of the other substances.
It will be seen from Tables VI (Supplementary Material)
and VI11 that the use of constraints improves full range
prediction using only limited range data. The uncon-

c,

321

322 Ind. Eng. Chem. Process Des. Dev., Vol. 22, No. 2, 1983

strained fit of the Wagner equation yielded an average

RMS % deviation of 0.30 for the whole range while the
constrained fit yields a value of 0.17.
The publication of Boublik et al. (1973) was used as the
main source of vapor pressure data for constrained regression of Wagner coefficients. The data of Sheft et al.
(1973), Oguchi et al. (1975), and Messerly et al. (1975) were
used to obtain coefficients for hydrogen fluoride, chlorotrifluoromethane, and ethylenediamine. Antoine coefficients presented by Reid et al. (1977)were used to generate
data for propionaldehyde.
Since the Wagner equation requires a knowledge of the
critical temperature and pressure of a substance, constrained generation of coefficients was limited to substances for which these are known; values were taken from
the work of Reid et al. (1977).
The resultant Wagner coefficients for 179 substances are
given in Table IX. Values of Pc and Tc are also given and
these are to be used in the Wagner equation. For comparison purposes unconstrained regression was also carried
out in each case.
In most cases the fitting of the data involved all three
constraints and only in the cases of methyl iodide and
acetaldehyde were all three active at the solution. However, when the data covered the values of TRrelating to
one or more constraints, then such constraints were totally
relaxed. Furthermore, in five cases (marked with an asterisk in Table IX)where normal boiling temperatures are
not much higher than 273 K, it was considered permissible
to improve results by relaxing the constraints to those
relating to substances with TBin the range 100 to 273 K.
Fifteen substances in Table M yielded very poor results
when compared with those obtained by unconstrained
regression and it was concluded that these substances
constituted marked exceptions to the constraints. For
these substances, therefore, the Wagner coefficients
presented are those resulting from unconstrained regression. They are identified by two asterisks in Table E.In
all cases of course, the percentage root mean square deviations given in Table IV can only relate to the actual
limited range data.
Summary
Liquid vapor pressures of high accuracy are currently
available for 14 pure substances over a pressure range
extending from about 5 kPa up to the particular critical
pressure. The abilities of eight equations to correlate these
data are investigated. The Wagner equation is selected
for processing the data for a further 58 substances for
which vapor pressures up to the particular critical value
have been reported. Wagner coefficients presented represent the data for all 72 substances with an average
root-mean-square percentage deviation of 0.09.
Vapor pressure data for many more liquids exist but are
usually limited to the approximate range 10 to 150 kPa.
Analysis of the results obtained by correlation of full-range
data indicates that vapor pressures of a substance are
usually circumscribed by three constraints selected according to normal boiling point. Wagner coefficients are
then obtained by constrained regression of limited range
data for 179 substances. The coefficients in Tables VI1
and IX, therefore, allow correlation and prediction of vapor
pressures up to the particular critical value for a total of
251 substances.
Nomenclature
A , B, C, D = coefficients (constants) in vapor pressure
equations
ao, a, = coefficients in eq 5
g = constant in eq 37

AH = enthalpy of vaporization, J mol-

AHB= enthalpy of vaporization at the normal boiling point,
J mol-
P = vapor pressure, kPa
P, = critical pressure, kPa
PR = reduced pressure, PIPc
= vapor pressure as calculated by eq 34, kPa
R = universal gas constant, 8.3144 J K- mol-
T = absolute temperature, K
TB= normal boiling point, K (boiling point at 101.325 kPa)
TBR= reduced normal boiling point, TB/Tc
T , = critical temperature, K
TH= highest data temperature, K
T L = lowest data temperature, K
T R = reduced temperature, TIT,
X = variable defined by eq 4
Z, = compressibility of saturated vapor
Z, = compressibility of saturated liquid
Greek Letters
a, = Riedel parameter, defined by eq 13, K

= Pitzer acentric factor

Literature Cited

Ambrose. D. J . Chem. Soc. A . 1988, 1381.

Ambrose. D. J . Chem. 7hs@m. 1978, 10, 765.
Ambrose, D.; Broderick, 8. E.; Townsend. R. J . Chem. Soc. A 1987, 633.
Ambrose, D.; Counseii, J. F.; Davenport, A. J. J . Chem. Thermodyn. 1970,
2 . 283.
Ambrose, D.; Counsell, J. F.; Hicks, C. P. J . Chem. ?hrmo@yn. 1978, 10,
771.
Ambrose, D.; Sprake, C. H. S. J . Chem. o d y n . 1970, 2 , 631.
Ambrose, D.; Sprake, C. H. S.; Townsend, R. J . Chem. Thermodyn. 1972,
4 , 247.
Ambrose. D.; Sprake, C. H. S.; Townsend. R. J . Chem. lhmrwdyn. 1974,
6 , 893.
Ambrose, D.; Sprake. C. H. S.; Townsend, R. J . Chem. Themrodyn. 1975,
7, 185.
Antoine, C. C . R . Acad. Sei. 1888, 107, 681, 836, 1143.
API 44 Tables-Sekcted Values of Properties of Hybocarbons and Related
compwnds,
Thermodynamics Research Center, Texas A 8 M Universlty,
1968; Vol IV.
Bender, P.; Furukuwa, (3. T.; Hyndman, J. R. Ind. ng. Chem. 1952, 44,
387.
Boubk, T.; Fried, V.; Hale, E. The Vapour Pressure of Pure Substances;
E l s e v k New Yo&, 1973; p 7.
Electrical Research Association. 1967 Steam Tables; Edward Arnold Ltd.:
London, 1987; pp 2-9.
Engineering Sciences Data Unk, Physlcal Data; London, 1972-1978; Voi.
5.
Frost, A. A.; Kakwarf, D. R. J . Chem. h y s . 1953. 21, 264.
Oamz-Nieto, M.; Thodos, 0. AIChE J . 1977, 23, 904.
Hugill. J. A.; McQlashan. M. L. J . Chem. Thermodyn. 1978, 10, 95.
Kemp, J. D.; Giauque, W. F. J . Am. Chem. SOC. 1937, 59, 79.
Kerns, W. J.; Anthony, R. G.; Eubank, P. T. A I C M Symp. S e r . No. 140
1974, 70, 14.
Mastrdennl, M. J.; Stahi, R. F.; Sheldon, P. N. J . chem. Eng. Data. 1978,
23, 113.
Messeriy, J. F.; Finke, H. L.; Osbwn, A. G.; Douslin, D. R. J . Chem. Thennodyn. 1975, 7, 1029.
Miller, D. G. J . Fhys. Chem. 1985, 69, 3209.
Oguchi. K.; Tanishita, I.; Watanabe, K.; Yamaguchi. 1.;Sasayama, A. BUN.
JSME 1975, 18, 1456.
Reid, R. C.; Prausnitz, J. M.; Sherwood, T. K.. Properties of Gases and
Liquids, 3rd ed.; McGraw-Hili: New York, 1977; Appendix A, pp
829-665.
Rledei, L. Chem. Ing. Tech. 1954, 26, 83.
Robinson, D. B.; Senturk, N. H. J . Chem. Thennodyn. 1879, 1 1 . 461.
Sheft, I.; Perklns, A. J.; Hymn, H. H. J . Inorg. Nud. Chem. 1973, 35,
3677.
Skaates, J. M.; Kay, W. B. Chem. fng. Sci. 1984, 19, 431.
Thek, R. E.; Sttel, L. I . A I M J . 1988, 12, 599.
momas, L. H. Chem. Eng. J . 1078, 1 1 , 191.
WADD Technical Report 60-56; Wright Air Development Division: Ohio,
1981; Part I, Chapter 6.
Wagner, W. Cryogenics 1973, 13, 470.
Warlng. W. I n d . Eng. Chem. 1954, 4 6 , 762.
Watson, K. M. Ind. Eng. Chem. 1943, 35, 390.
WiHimgham, C. J.; Taylor, W. J.; Plgnocco. J. M.; Rossini, F. D. J . Res. Net/.
Bur. Stand. 1945, 35. 219.

Receiued for review October 22, 1980

Reuised manuscript received August 9, 1982
Accepted September 10, 1982

Supplementary Material Available: Tables IV, V, and

VI (vapor pressure data) are presented as supplementary
material (3 pages). Ordering information is given on any
current masthead page.