SECTION 23

Physical Properties
Thi s secti on contai ns a number of charts, correlations, and
cal cul ati on procedures to be used for predi cti ng physi cal prop-
erti es of hydrocarbons and components found wi th them.
Fi g. 23-1 shows the nomenclature used i n thi s section.
Fig. 23-2 i s a tabl e contai ning frequentl y used physi cal prop-
erti es for a number of hydrocarbons and other sel ected com-
ponents. I mmedi atel y fol l owing i s a detai l ed l i st of references
and footnoted explanati on for the values i n Fi g. 23-2.
Physical properti es for eighteen sel ected compounds can be
found i n GPA Standard 2145, "Tabl e of Physi cal Constants of
Paraffi n Hydrocarbons and Other Components of Natural
Gas."
B = second vi rial coeffi ci ent for a gas mi xture,
[kPa (abs)]
-1
B = mole fracti on H
2
S i n sour gas stream, Eq 23-6
B
i i
= second vi rial coeffi ci ent for component i
B
i j
= second cross vi ri al coeffici ent for components i
and j
b
i
1/2
= summati on factor for component i
CABP = cubic average boi l i ng poi nt, C
d = densi ty, g/cc
G = rel ati ve densi ty (gas densi ty)
G
i
= rel ati ve densi ty (gas gravi ty) of i deal gas, MW/MW
a
G
i
i d
= molecul ar mass rati o of component i i n mi xture
H
v
= gross heati ng val ue per uni t vol ume of i deal gas,
MJ/m
3
K
w
= Watson characteri zati on factor, Fi g. 23-12
k = thermal conducti vi ty, W/(m C)
k
a
= thermal conducti vi ty at one atmosphere, W/(m C)
M = mass fracti on
m = mass, kg
MW = molecul ar mass, g mol e
MABP = molal average boi l i ng poi nt, C or K
MeABP = Mean average boil i ng poi nt, C or K
n = number of mol es (mass/mol e wei ght)
P = pressure, kPa (abs)
P
c
= pseudocri ti cal pressure adjusted for aci d gas
composi ti on, kPa (abs)
P
vp
= vapor pressure at a reduced temperature of 0.7
P
w
o
= vapor pressure of water, 7.3811 kPa (abs) at 40C
R = gas constant, 8.3145 [kPa (abs) m
3
]/(K kg mole)
for al l gases (see Section 1 for R i n other uni ts)
S = rel ati ve densi ty at 15/15C
T = absol ute temperature, K
t = ASTM D-86 di sti ll ati on temperature, C or K,
Eq 23-11
T
c
= pseudocri ti cal temperature adjusted for acid gas
composi ti on, K
V = vol ume, m
3
VABP = vol umetri c average boil i ng poi nt, C
W = mass, kg
WABP = wei ght average boi li ng poi nt, C
y
i
= mole fracti on of component i from anal ysi s on dry
basi s, Eq 23-37
x = mole fracti on in l i qui d phase
y
i
w
= mole fracti on of component i adjusted for water
content
y = mol e fracti on i n gas phase
Z = compressi bi li ty factor
Greek
= pseudocri ti cal temperature adjustment factor,
Eq 23-6
= MeABP/T
pc
= densi ty, kg/m
3
= vi scosi ty at operati ng temperature and pressure,
centipoise

A
= viscosi ty at 101.325 kPa (abs) (1 atm) and operati ng
temperature, centipoise
= factor defi ned by Eq 23-20
= surface tensi on, dynes/cm
= acentri c factor
= ki nematic vi scosity, centi stokes
Subscripts
a = ai r
b = boi l ing
c = criti cal
i = component i
L = li quid
m = mi xture
pc = pseudocri ti cal
r = reduced state
V = vapor
v = vol ume
w = water
Superscripts
i d = ideal gas
w = water
o
= reference state
FIG. 23-1
Nomenclature
23-1



See Note No.
Compound
Methane
Ethane
Propane
lsobutane
n-Butane
Isopentane
n-Pentane
Neopentane
n-Hexane
2-Methylpentane
3-Methylpentane
Neohexane
2,3-Dimethylbutane
n-Heptane
2-Methylhexane
3-Methylhexane
3-Ethylpentane
2,2-Dimethylpentane
2,4-Dimethylpentane
3,3-Dimethylpentane
Triptane
n-Octane
Diisobutyl
Isooctane
n-Nonane
n-Decane
Cyclopentane
Methylcyclopentane
Cyclohexane
Methylcyclohexane
Ethene(Ethylene)
Propene(Propylene)
1-Butene(Butylene)
cis-2-Butene
trans-2-Butene
Isobutene
1-Pentene
1,2-Butadiene
1,3-Butadiene
Isoprene
Ethylbenzene
o-Xylene
m-Xylene
p-Xlyene
Isopropylbenzene
Methyl alcohol
Ethyl alcohol
Carbon monoxide
Carbon dioxide
Hydrogen sulfide
Sulfur dioxide
Ammonia
Air
Hydrogen
Oxygen
Nitrogen
Chlorine
Water
Helium
Hydrogen chloride
16.043 -161.51
30.070 -88.59
44.097 -42.07
58.123 -11.79
58.123 -0.51
(35000)*
1369.8
530.89
379.61
-182.45* 4599.
-182.79* 4880.
-187.62" 4240.
-159.59 3640.
-138.35 3784.
72.150 27.83 151.31
114.70
-159.89 3381.
72.150 36.05 -129.71
270.0
3365.
72.150 9.50 -16.58 3199.
86.177 68.72
86.177 60.24
86.177 63.26
86.177 49.72
86.177 57.96
37.297 -95.31
50.68
45.73
-153.67
-162.89
73.41
55.34
-99.825
-128.53
3030.
3010.
3120.
3080.
3130.
100.204 98.37
12.342
100.204 90.03
17.226
100.204 91.85
16.155
100.204 93.47
15.265
100.204 79.17
26.32
100.204 80.47
24.85
100.204 86.04
20.94
100.204 80.86
25.41
-90.55
-118.26
-118.58
-123.78
-119.21
-134.44
-24.56
2740.
2730.
2810.
2890.
2770.
2740.
2950.
2950.
114.231 125.65
114.231 109.08
114.231 99.21
128.258 150.78
142.285 174.11
70.134 49.22
84.161 71.83
84.161 80.78
98.188 100.94
4.146 -56.76
8.417
12.966
-91.160
-107.35
1.358 -53.48
0.4814 -29.63
73.99 -93.827
33.75 -142.43
24.64 6.550
12.211 -126.59
2490.
2490.
2570.
2280.
2100.
425.
4508.
3784.
4073.
3471.
28.054 -103.73
42.081 -47.68
56.108 -6.23
56.108 3.72
56.108 0.88
56.108 -6.91
70.134 29.95
54.092 10.84
54.092 -4.41
68.119 34.05
(9700)
459.0
338.3
366.5
477.4
141.65
269.
436.1
123.8
-169.15*
-185.25*
-185.35*
-138.90
-105.54
-140.34
-165.21
-136.19
-108.89
-145.95
5040.
4665.
4043.
4243.
3964.
4000.
3513.
(4502)
(3856)
26.038 -84.01*
78.114 80.07
92.141 110.60
106.167 136.17
106.167 144.39
106.167 139.09
106.167 138.32
104.152 145.23
120.194 152.38
24.38
7.895
2.873
2.051
2.528
2.648
2.00
1.47
-80.8"
5.532
-94.98
-94.963
-25.18
-47.86
13.26
30.63
-96.021
6139. 308.31 0.00432
4898. 562.12 0.00332
4106. 591.76 0.00343
3606. 617.16 0.00352
3734. 630.29 0.00348
3536. 617.01 0.00354
3511. 616.19 0.00357
4050.
3209.
(646)* 0.00333
0.00355
32.042 64.67
46.069 78.26
28.010 -191.45
44.010 -78.464*
34.082 -60.266
64.065 -9.94
35.44
17.903

2859.7
630.2
-97.65 8097.
-114.1 6148.
-204.99* 3494.
-56.56* 7374.
-85.48* 8963.
-75.47* 7884.
17.0305 -33.32
28.9625 -194.34
2.0159 -252.850*
31.9986 -182.954*
28.0134 -195.798
70.9054 -33.95
18.0153 99.974*
4.0026 -268.95
36.461 -85.14
1555.

1146.
7.3849
6547.
-77.69*
-259.347*
-218.792*
-209.997*
-100.95
0.000
-114.17*
11350.
3771.
1293.
5043.
3398.
7977.
22064.
227.5
8310.
PHYSICAL CONSTANTS
*See the Table of Notes and References
Critical constants
190.56 0.00617
305.41 0.00489
369.77 0.00454
407.82 0.00446
425.10 0.00439
460.35 0.00427
469.65 0.00434
433.71 0.00420
506.4 0.00429
497.46 0.00426
504.4 0.00426
488.66 0.00417
499.86 0.00415
539.2 0.00426
530.06 0.00420
535.16 0.00403
540.46 0.00415
520.36 0.00415
519.66 0.00417
536.26 0.00413
531.06 0.00397
568.4 0.00420
549.96 0.00422
543.86 0.00410
594.7 0.00433
617.7 0.00439
511.6 0.00371
532.75 0.00379
553.5 0.00366
572.15 0.00375
282.34 0.00466
365.55 0.00448
419.92 0.00426
435.54 0.00417
428.59 0.00424
417.86 0.00425
464.74 0.00421
(444)* (0.0043)*
(484)
0.00407
(0.0041)*
512.60 0.00368
513.88 0.00362
132.86 0.00329
304.11 0.00214
373.37 0.00288
430.8 0.00190
405.5 0.00425
132.43 0.00323
33.0 0.03185*
154.59 0.00229
126.21 0.00318
416.86 0.00175
647.10 0.003102
5.20 0.01436
324.68 0.00222
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
(6000)*

4277.
Acetylene
Benzene
Toluene
1691.

Styrene

631.1
1.00040*
1.21403*
1.29558*
1.3251*
1.33631*
1.35658
1.36024
1.345*
1.37746
1.37417
1.37918
1.37157
1.37759
1.39017
1.38743
1.39119
1.39594
1.38475
1.38408
1.39342
1.39196
1.39981
1.39488
1.39392
1.40773
1.41411
1.40927
1.41240
1.42892
1.42566
(1.241)*
1.313*
1.351*
1.368*
1.359*
1.358*
1.3746

1.4253

1.5043
1.49960
1.49856
1.50795
1.49980
1.49839
1.5496
1.49400
1.33028
1.36345
1.00036*
1.00049*
1.00061*
1.00062*
1.00036*
1.00028*
1.00013*
1.00027*
1.00028*
1.3878*
1.33347
1.00003*
1.00042
F
o
r
m
u
l
a
N
u
m
b
e
r
M
o
l
a
r

m
a
s
s
(
M
o
l
e
c
u
l
a
r

w
e
i
g
h
t
)
B
o
i
l
i
n
g

P
o
i
n
t
,

C
1
0
1
.
3
2
5
0

k
P
a
(
a
b
s
)
V
a
p
o
r

p
r
e
s
s
u
r
e
,
k
P
a
(
a
b
s
)
,

4
0

C
NOTE: Numbers in this table do not have accuracies greater
than 1 part in 1000; in some cases extra digits have been added
to calculated values to achieve internal consistency or to permit
recalculation of experimental values.
A. B. C. D.
F
r
e
e
z
i
n
g

p
o
i
n
t
,

C
1
0
1
.
3
2
5
0

k
P
a
(
a
b
s
)
R
e
f
r
a
c
t
i
v
e

i
n
d
e
x
,

n
D

1
5

C
P
r
e
s
s
u
r
e
,
k
P
a
(
a
b
s
)
T
e
m
p
e
r
a
t
u
r
e
,

K
V
o
l
u
m
e
,

m
3
/
k
g
C H
4 10
C H
3 8
C H
4 10
C H
2 6
C H
4
C H
5 12
C H
5 12
C H
5 12
C H
5 10
C H
6 14
C H
6 14
C H
6 14
C H
6 14
C H
6 12
C H
7 16
C H
7 16
C H
7 16
C H
7 16
C H
7 16
C H
7 16
C H
7 16
C H
7 16
C H
8 18
C H
8 18
C H
8 18
C H
9 20
C H
7 14
C H
2 4
C H
3 6
C H
4 8
C H
4 8
C H
4 8
C H
4 8
C H
5 10
C H
4 6
C H
4 6
C H
5 8
C H
2 2
C H
6 6
C H
7 8
C H
8 10
8 10
8 10
8 10
C H
C H
C H
C H
8 8
C H
9 12
C H
6 14
C H
6 12
10 22
C H
CH O
4
2 6
C H O
CO
CO
2
HCl
H S
2
SO
2
He
Cl
2
H O
2
O
2
H
2
N
2
N
2
O
2
+
NH
3
5/99
N
u
m
b
e
r
FIG. 23-2
Physical Constants
Revi sed (5-99)
23-2
FIG. 23-2 (Contd)
Physical Constants
23-3
FIG. 23-2 (Contd)
Physical Constants
23-4
FIG. 23-2 (Contd)
Notes and References for the Table of Physical Constants
23-5
FIG. 23-2 (Contd)
Notes and References for the Table of Physical Constants
23-6
FIG. 23-2 (Contd)
Notes and References for the Table of Physical Constants
23-7
a. Val ues i n par entheses ar e esti mated val ues.
b. The temper atur e i s above the cr i ti cal poi nt.
c. At satur ati on pr essur e (tr i pl e poi nt).
d. Subl i mati on poi nt.
e. The + si gn and number fol l owi ng speci fy the number of cm
3
of
TEL added per gal l on to achi eve the ASTM octane number of
100, whi ch cor r esponds to that of I sooctane (2,2,4-
Tri methyl pentane).
f. These compounds for m a gl ass.
g. Average val ue from octane numbers of more than one sampl e.
h. Satur ati on pressure and 15C.
i . I ndex of refr acti on of the gas.
j. Densi ti es of the l i qui d at the nor mal boi l i ng poi nt.
k. Heat of subl i mati on.
m. Equati on 2 of the r efer ence was r efi tted to gi ve:
a = 0.7872957; b = 0.1294083; c = 0.03439519.
n. Nor mal hydrogen (25% par a, 75% or tho).
p. An extr apol ated val ue.
q. Gas at 15C and the l i qui d at the normal boi l i ng poi nt.
r . Fi xed poi nts on the 1968 I nternati onal Pr acti cal Temperatur e
Scal e (I PTS-68).
s. Fi xed poi nts on the 1990 I nter nati onal Temper ature Scal e
(I TS-90).
t. Densi ti es at the nor mal boi l i ng poi nt ar e: Ethane, 554.0 [29];
Propane, 581.0 [28]; Pr opene, 609.1 [5]; Hydr ogen Chl or i de,
1192 [43]; Hydrogen Sul fi de, 949.0 [25]; Ammoni a, 681.6 [43];
Sul fur Di oxi de, 1462 [43].
u. Techni cal l y, water has a heati ng val ue i n two cases: net
((2.466 MJ/kg) when water i s l i qui d i n the reactants, and gr oss
(+1.879 MJ/m3) when water i s gas i n the reactants. The val ue
i s the i deal heat of vapor i zati on (enthal py of the i deal gas l ess
the enthal py of the satur ated l i qui d at the vapor pressure).
Thi s i s a matter of defi ni ti on; water does not bur n.
v. Extr eme val ues of those r eported by r efer ence 19.
A. Mol ar mass (mol ecul ar mass) i s based upon the fol l owi ng
atomi c wei ghts: C = 12.011; H = 1.00794; O = 15.9994; N =
14.0067; S = 32.066; Cl = 35.4527. The val ues wer e r ounded
off after cal cul ati ng the mol ar mass usi ng al l si gni fi cant fi gures
i n the atomi c wei ghts.
B. Boi l i ng poi nt: the temper atur e at equi l i bri um between the l i q-
ui d and vapor phases at 101.3250 kPa.
C. Freezi ng poi nt: the temperature at equi l i bri um between the crys-
tal l i ne phase and the ai r saturated l i qui d at 101.3250 kPa.
D. The refr acti ve i ndex r eported r efers to the l i qui d or gas and i s
measured for l i ght of wavel ength corr espondi ng to the sodi um
D-l i ne (589.26 nm).
E. The rel ati ve densi ty: (l i qui d, 15C)/(water, 15C). The den-
si ty of water at 15C i s 999.10 kg/m
3
.
F. The temper atur e coeffi ci ent of densi ty i s r el ated to the expan-
si on coeffi ci ent by: (/T)P/ = (V/T)P/V, i n uni ts of 1/T.
G. Pi tzer acentr i c factor : = l og10(P/Pc) 1, P at T = 0.7 Tc
H. Compressi bi l i ty factor of the real gas, Z = PV/RT, i s cal cul ated
usi ng the second vi r i al coeffi ci ent.
I . The densi ty of an i deal gas r el ati ve to ai r i s cal cul ated by di -
vi di ng the mol ar mass of the of the gas by 28.9625, the cal cu-
l ated aver age mol ar mass of ai r. See ref. 34 for the average
composi ti on of dr y ai r. The speci fi c vol ume of an i deal gas i s
cal cul ated from the i deal gas equati on. The vol ume r ati o i s:
V(i deal gas)/V(l i qui d i n vacuum).
J. The l i qui d val ue i s not r i gorousl y CP, but r ather i t i s the heat
capaci ty al ong the satur ati on l i ne CS defi ned by: CS = CP T
(V/T)P(P/T)S. For l i qui ds far from the cr i ti cal poi nt, CS
CP.
K. The heati ng val ue i s the negati ve of the enthal py of combusti on
at 15C and 101.3250 kPa (abs.) i n an i deal reacti on (one wher e
al l gasses are i deal gasses). For an ar bi trar y or gani c com-
pound, the combusti on r eacti on i s:
CnHmOhSjNk (s,l ,or,g) + (n + m/4 h/2 + j) O2(g)
n CO2(g) + m/2 H2O (g or l ) + k/2 N2(g) + j SO2(g),
wher e s, l and g denote r especti vel y sol i d, l i qui d and i deal gas.
For gr oss heati ng val ues, the water for med i s l i qui d; for net
heati ng val ues, the water for med i s i deal gas. Val ues r epor ted
ar e on a dry basi s. To account for water i n the heati ng val ue,
see GPA 2172. The MJ/kg l i qui d col umn assumes a reacti on
wi th the fuel i n the l i qui d state, whi l e the MJ/m
3
i deal gas
col umn assumes the gas i n the i deal gas state. Ther efor e, the
val ues ar e not consi stent i f used i n the same cal cul ati on, e.g. a
gas pl ant bal ance.
L. The heat of vapor i zati on i s the enthal py of the saturated vapor
at the boi l i ng poi nt at 101.3250 kPa mi nus the enthal py of the
satur ated l i qui d at the same condi ti ons.
M. Ai r r equi r ed for the combusti on of i deal gas for compounds of
for mul a CnHmOhSjNk i s:
V(ai r)/V(gas) = (n + m/4 - h/2 + j)/0.20946.
COMMENTS
Uni ts: repor ted val ues ar e i n SI uni ts based on the fol l owi ng:
mass: ki l ogr am, kg
l ength: meter, m
temper atur e: I nter nati onal Temper ature of 1990
(I TS-90), wher e 0C = 273.15 K.
Other der i ved uni ts ar e:
vol ume: cubi c meter, m
3

pressure: Pascal , Pa (1 Pa = N/m
2
)
ener gy: Joul e, J
Gas constant, R:
8.314510 J/(Kmol )
0.008314510 m
3
(kPa/(Kmol )
1.987216 cal th/(Kmol )
1.985887 Btu(I .T.)/(R(l bmol )
Conver si on factor s:
1 m
3
= 35.31467 ft
3
= 264.1721 gal .(U.S.)
1 kg = 2.204623 l bm
1 kg/m
3
= 0.06242795 l bm/ft
3
=0.001 g/cm
3
1 kPa = 0.01 bar = 0.009869233 atm = 0.1450377 psi a
1 atm = 101.3250 kPa = 14.69595 psi a = 760 Tor r
1 k J = 0.2390057 kcal th = 0.2388459 kcal (I .T.)
= 0.9478172 Btu (I .T.)
FIG. 23-2 (Contd)
Notes for the Table of Physical Constants
Revi sed (5-99)
23-8
1. Ambrose, D., Nati onal Physi cal Labor ator y, Teddi ngton,
Mi ddl esex, Engl and: Feb. 1980, NPL Repor t Chem 107.
2. Ambrose, D.; Hal l , D. J.; Lee, D. A.; Lewi s, G. B.; Mash, C. J.,
J. Chem. Ther mo., 11, 1089 (1979).
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i de. I nter nati onal Thermodynami c Tabl es of the Fl ui d State-3,"
Per gamon Press: Oxfor d, 1976.
4. Angus, S.; Ar mstrong, B.; de Reuck, K. M., Eds. "Methane. I n-
ter nati onal Ther modynami c Tabl es of the Fl ui d State-5," Per -
gamon Pr ess: Oxford, 1978.
5. Angus, S.; Ar mstrong, B.; de Reuck, K. M., "Pr opyl ene
(Propene). I nter nati onal Thermodynami c Tabl es of the Fl ui d
State-7," Per gamon Pr ess: Oxfor d, 1980.
6. Angus, S.; de Reuck, K. M.; Armstr ong, B., Eds. "Ni tr ogen. I n-
ter nati onal Ther modynami c Tabl es of the Fl ui d State-6," Per -
gamon Pr ess: Oxford, 1979.
7. Angus, S.; de Reuck, K. M.; McCarthy, R. D., Eds. "Hel i um.
I nternati onal Ther modynami c Tabl es of the Fl ui d State-4,"
Per gamon Press: Oxfor d, 1977.
8. Armstr ong, G. T.; Jobe, T. L., "Heati ng Val ues of Natur al Gas
and i ts Components," NBSI R 82-2401, May 1982.
9. Aston, J. G.; Szasz, G. J.; Fi nke, H. L., J. Am. Chem. Soc., 65,
1135 (1943).
10. Bar ber, C. R., Metrol ogi a 5, 35 (1969).
11. Boundy, R. H.; Boyer, R. F., (Eds.), "Styr ene, I ts Pol ymers, Co-
pol ymer s and Deri vati ves," A.C.S. monogr aph No. 115, Rei n-
hol t, N.Y., 1952.
12. Chai yavech, P.; Van Wi nkl e, M., J. Chem. Eng. Data, 4, 53
(1959).
13. Chao, J.; Hal l , K. R.; Yao, J., Ther mochi mi ca Acta, 64, 285
(1983).
14. CODATA Task Gr oup on Key Val ues for Thermodynami cs, CO-
DATA Speci al Repor t No. 7, 1978.
15. Commi ssi on on Atomi c Wei ghts and I sotopi c Abundances, Pur e
and Appl . Chem. 63, 975 (1991).
16. Dean, J. W., "A Tabul ati on of the Proper ti es of Nor mal Hydr o-
gen fr om Low Temper atur e to 300 K and fr om 1 to 100 Atmos-
pher es," NBS Tech. Note 120, November 1961.
17. Dousl i n, D. R.; Huffman, H. M., J. Am. Chem. Soc., 68, 1704
(1946).
18. Edwar ds, D. G., "The Vapor Pr essur e of 30 I nor gani c Li qui ds
Between One Atmosphere and the Cr i ti cal Poi nt," Uni v. of
Cal i f., Lawr ence Radi ati on Labor atory, UCRL-7167. June 13,
1963.
19. Engi neer i ng Sci ences Data Uni t, "EDSU, Engi neer i ng Sci -
ences Data," EDSU I nter nati onal Ltd., London.
20. Fl ebbe, J. L.; Barcl ay, D. A.; Manl ey, D. B., J. Chem. Eng. Data,
27, 405 (1982).
21. Franci s, A. W., J. Chem. Eng. Data, 5, 534 (1960).
22. Gi nni ngs, D. C.; Fur ukawa, G. T., J. Am. Chem. Soc. 75, 522
(1953).
23. Gi r ar d, G., "Recommended Refer ence Mater i al s of the Real i za-
ti on of Physi cochemi cal Pr oper ti es," Chapter 2, Mar sh, K. N.
Ed.; Bl ackwel l Sci . Pub.: London, 1987.
24. Gl asgow, A. R.; Murphy, E. T.; Wi l l i ngham, C. B.; Rossi ni , F. D.,
J. Res. NBS, 37, 141 (1946).
25. Goodwi n, R. D., "Hydr ogen Sul fi de Pr ovi si onal Ther mochemi -
cal Pr oper ti es fr om 188 to 700 K at Pr essur es to 75 MPa,"
NBSI R 83-1694, October 1983.
26. Goodwi n, R. D.; Haynes, W. M., "Ther mophysi cal Pr oper ti es of
I sobutane from 114 to 700 K at Pr essur es to 70 MPa," NBS
Tech. Note 1051, Januar y 1982.
27. Goodwi n, R. D.; Haynes, W. M., "Ther mophysi cal Pr oper ti es of
Nor mal Butane from 135 to 700 K at Pr essur es to 70 MPa,"
NBS Monogr aph 169, Apr i l 1982.
28. Goodwi n, R. D.; Haynes, W. M., "Ther mophysi cal Pr oper ti es of
Propane from 85 to 700 K at Pr essur es to 70 MPa," NBS Mono-
gr aph 170, Apr i l 1982.
29. Goodwi n, R. D.; Roder, H. M.; Str aty, G. C.; "Ther mophysi cal
Proper ti es of Ethane, 90 to 600 K at Pr essur es to 700 bar," NBS
Tech. Note 684, August 1976.
30. Guthri e, G. B.; Huffman, H. M., J. Am. Chem. Soc., 65, 1139
(1943).
31. Haar, L.; Gal l agher, J. S.; Kel l , G. S., "NBS/NRC Steam Tabl es,"
Hemi sphere Publ i shi ng Corporati on, Washi ngton, 1984.
32. Huffman, H. M.; Par k, G. S.; Thomas, S. B., J. Am. Chem. Soc.,
52, 3241 (1930).
33. Hust, J. G.; Stewar t, R. B., "Ther modynami c Pr oper ty Val ues
for Gaseous and Li qui d Car bon Monoxi de fr om 70 to 300 At-
mospheres," NBS Techni cal Note 202, Nov. 1963.
34. Jones, F. E., J. Res. NBS, 83, 419 (1978).
35. Keenan, J. H.; Chao, J.; Kaye, J. "Gas Tabl es: (SI Uni ts)," John
Wi l ey and Sons, I nc.: New York, 1983.
36. "The Matheson Unabr i dged Gas Data Book," Matheson Gas
Products; New York, 1974.
37. McCar ty, R. D.; Weber, L. A., "Ther mophysi cal Pr oper ti es of
Oxygen from the Fr eezi ng Li qui d Li ne to 600 R for Pressures
to 5000 Psi a," NBS Techni cal Note 384, Jul y 1971.
38. Messer l y, J. F.; Guthr i e, G. B.; Todd, S. S.; Fi nke, H. L., J. Chem.
Eng. Data, 12, 338 (1967).
39. Messer l y, J. F.; Todd, S. S.; Guthr i e, G. B., J. Chem. Eng. Data,
15, 227 (1970).
40. Ohe, S., "Computer Ai ded Data Book of Vapor Pr essur e," Data
Book Publ i shi ng Co., Tokyo, Japan, 1976.
41. Roder, H. M., "Measur ements of the Speci fi c Heats, Cs, and Cv,
of Dense Gaseous and Li qui d Ethane," J. Res. Nat. Bur. Stand.
(U.S.) 80A, 739 (1976).
42. Scott, R. B.; Meyer s, C. H.; Rands, R. D.; Br i ckwedde, F. G.;
Bekkedahl , N., J. Res. NBS, 35, 39 (1945).
43. Stul l , D. R.; Westr um, E. F.; Si nke, G. C., "The Chemi cal Ther -
modynami cs of Or gani c Compounds," John Wi l ey & Sons, I nc.,
New Yor k, 1969.
44. "TRC Ther modynami c Tabl es (Hydr ocar bons)," Thermody-
nami cs Resear ch Center, Texas A&M Uni ver si ty System: Col -
l ege Stati on, Texas.
45. "TRC Ther modynami c Tabl es (Non-Hydr ocarbons)," Ther mo-
dynami cs Resear ch Center, Texas A&M Uni ver si ty System:
Col l ege Stati on, Texas.
46. Var gafti k, N. B.; "Tabl es on the Thermophysi cal Pr oper ti es of
Li qui ds and Gases," Hemi spher e Publ i shi ng Cor porati on,
Washi ngton D.C., 1975.
47. Weast, R. C., "Handbook of Chemi str y and Physi cs," The
Chemi cal Rubber Co: Cl evel and, Ohi o, 1969.
FIG. 23-2 (Contd)
References for the Table of Physical Constants
23-9
The table in Fi g. 23-2 is fol l owed by procedures for esti mat-
i ng compressi bi li ty for gases. Additi onal materi al fol l ows on
hydrocarbon fl ui d densiti es, boi l ing poi nts, ASTM disti l lation,
cri ti cal properties, acentri c factors, vapor pressures, vi scosity,
thermal conducti vi ty, surface tensi on and gross heati ng val ue.
COMPUTER PREDICTION METHODS
Computer methods for predi cti ng physi cal and thermody-
nami c properti es for l ight hydrocarbons and natural gas con-
sti tuents are wi del y avai labl e. They are routinel y used by
many i nvol ved in the desi gn and operati on of natural gas proc-
essi ng faci l i ti es. This secti on emphasi zes hand cal cul ati on
methods that gi ve rel i abl e esti mates of physical properti es.
They should be used when a number i s requi red quickl y, for
an "order of magni tude" check when eval uating a more de-
tai l ed procedure, or when a computer i s not avai l abl e.
There wil l be presentati on of some computer resul ts. The
use of equations of state for property predi cti ons i s conveni ent
and easy, but they do not apply equal l y well for all properti es.
Gas phase densi ti es, vol umes and compressi bi l i ti es are pre-
dicted accuratel y and rel iabl y. Li quid vol umes and densi ti es
are less accurate but stil l can be expected to generall y be as
rel i abl e as predi cti ons by hand methods. Thermal conducti vi -
ties, vi scosi ties and surface tensi ons are not wel l predi cted by
PVT equati ons of state. Computer programs cited or used are
sel ected exampl es of those wi del y avai l abl e for predi ction of
physical and thermodynamic properti es. I ncl usion here does
not represent GPA and/or GPSA endorsement of the pro-
gram(s). A good, rel i abl e equation of state properl y pro-
grammed and appl ied wil l always be the most conveni ent
method for obtai ning engineeri ng accuracy gas phase proper -
ties. Unfortunately, widespread avai l abi l i ty and/or ease of use
are not sui tabl e cri teri a for choi ce of an equati on of state pro-
gram. The methods detai l ed here are for hand cal culati on of
physical properties.
COMPRESSIBILITY OF GASES
Pure Gases
When deal i ng wi th gases at very low pressure, the i deal gas
rel ati onship is a conveni ent and general l y sati sfactory tool .
For measurements and cal cul ati ons for gases at el evated pre-
sure, the use of the ideal gas rel ati onship may l ead to errors
as great as 500%, as compared to errors of 2 or 3% at atmos-
pheric pressure.
The many PVT equati ons of state that have been proposed
(see Secti on 25) for representi ng the pressure-vol ume-tem-
perature rel ati onshi p of gases are compli cated and requi re a
computer or programmabl e cal cul ator to solve in a reasonable
l ength of ti me. A generali zed correspondi ng states correl ati on
of compressi bi l i ty factors i s reasonabl y conveni ent and suffi -
cientl y accurate for normal engi neering requi rements. The
procedure provi des a correcti on factor, Z, by whi ch the volume
computed from the i deal gas equati on i s converted to the cor -
rect vol ume for the real gas.
PV ZmRT / MW Zn RT Eq 23-1
The compressi bi l ity factor Z i s a di mensi onl ess parameter
i ndependent of the quanti ty of gas and determi ned by the
characteristi cs of the gas, the temperature, and pressure.
Once Z i s known or determined, the cal cul ati on of pressure-
vol ume-temperature rel ati onshi ps may be made wi th as much
ease at hi gh pressure as at l ow pressure.
The equati on used to calculate gas densi ty is:

MW P
8.3145 T Z
Eq 23-2
The val ue 8.3145 for R is used when pressure i s i n kPa (abs),
vol ume i n cubi c meters, quanti ty of gas i n kg mol es, and tem-
perature i n K. Val ues of R for other combi nati ons of uni ts are
gi ven in Section 1.
Accordi ng to the theorem of correspondi ng states, the devi a-
tion of any actual gas from the i deal gas l aw i s proportionall y
the same for di fferent gases when at the same corresponding
state. The same correspondi ng states are found at the same
fracti on of the absol ute criti cal temperature and pressure,
whi ch, for pure gases, are known as the "reduced conditi ons."
Component
Mole
Fraction,
yi
Component
Critical
Temperature,
Tci, K
Component
Critical
Pressure,
Pci, kPa
Component
Molecular
Mass,
MWi
Pseudocritical
Temperature
yiTci, K
Pseudocritical
Pressure
yiPci, kPa
Mixture
Molecular
Mass
y
i
MWi
Methane 0.8319 190.6 4599 16.043 158.560 3825.908 13.346
Ethane 0.0848 305.4 4880 30.070 25.898 413.824 2.550
Pr opane 0.0437 369.8 4240 44.097 16.160 185.288 1.927
i -Butane 0.0076 407.8 3640 58.123 3.099 27.664 0.442
n-Butane 0.0168 425.1 3784 58.123 7.142 63.571 0.976
i -Pentane 0.0057 460.4 3381 72.150 2.624 19.272 0.411
n-Pentane 0.0032 469.6 3365 72.150 1.503 10.768 0.231
n-Hexane 0.0063 507.5 3012 86.177 3.197 19.976 0.543
1.0000 218.184 = Tc 4565.271 = Pc 20.426 = MW
G = 20.246/28.9625 = 0.705
FIG. 23-3
Calculation of Pseudocritical Temperature, Pressure and Average Molecular Mass for a Natural Gas Mixture
23-10
Reduced Temperature, T
r
T/T
c
Eq 23-3
Reduced Pressure, P
r
P/P
c
Eq 23-4
For gas mixtures, the reduced conditi ons are determined us-
i ng pseudocri tical val ues i nstead of the true cri ti cal s:
Reduced Temperature, T
r
T/(y
i
T
ci
) T/T
pc
Eq 23-3a
Reduced Pressure, P
r
P/(y
i
P
ci)
P/P
pc
Eq 23-4a
Any uni ts of temperature or pressure may be used to deter -
mi ne reduced condi ti ons provi ded that the same absol ute
units are used for T as for T
c
(T
pc
) and for P as for P
c
(P
pc
).The
"average molecul ar weight" for a gas mi xture is defi ned the
same way MW
avg
= (y
i
MW
i
). Cal cul ati on of pseudo criti -
cal s and MW
avg
for a typi cal natural gas i s i ll ustrated in Fi g.
23-3. Cri tical temperature and pressure for the hexanes and
heavi er or heptanes and heavi er fracti on can be estimated
from mol ecul ar mass and relative density or average boi l ing
poi nt and rel ati ve densi ty usi ng procedures presented i n thi s
secti on.
Attempts to prepare a general i zed pl ot sui tabl e for appl ica-
tion to the low molecul ar mass hydrocarbons, i ncl udi ng meth-
ane, ethane, and propane, i ndi cate that an error frequentl y in
excess of 2 to 3% was unavoi dabl e due to thei r departure from
the theorem of corresponding states. Fi g. 23-4, prepared using
pure component and gas mi xture data, can be used to esti mate
Z (2-3% error) for pure hydrocarbon gases for thi s appl i cation.
Reduced temperature and pressure are used i nstead of
pseudoreduced val ues. At l ow pressures, the di fferent com-
pounds appear to conform more closel y. The compressi bi l i ty
factor may be assumed equal to 1.0 at l ow pressure. Errors
generall y wi ll be 2-3% for pressures of 200 kPa (abs) or less so
l ong as the gas i s 10C or more above i ts saturati on tempera-
tur e at the pressure of concern.
P-H di agrams l ike those i n Secti on 24, Thermodynami c
Properties, can be used to determi ne gas volumes, densi ti es
and compressibi l iti es for pure hydrocarbon and nonhydrocar -
bon vapors. I nterpol ati on between speci fic vol ume curves on
a P-H di agram does not yi el d resul ts of high accuracy. Pure
component PVT properti es are more accuratel y obtai ned from
an equati on of state, parti cul arl y if that equation has been
fitted to vol umetri c data for the speci fi c component. Tabul a-
tions of properti es obtai ned in thi s way can be found i n the
l i terature.
12
Example 23-1 Pure component properties
Usi ng Fi g. 24-25, the P-H diagram for propane, calculate the
densi ty of propane vapor at 110C and 2000 kPa (abs).
Solution
On the P-H di agr am at the i nter secti on of the T = 110C,
P = 2000 kPa (abs) li nes read v = 0.03 m
3
/kg. Then:
1/0.03 33.33 kg/m
3
Usi ng the EZ*THERMO
90
versi on of the SRK
91
equati on of
state, i s cal cul ated to be 32.83 kg/m
3
, from which v = (1/32.83)
= 0.03 m
3
/kg.
For propane at 110C and 2000 kPa (abs) using data from
Fi g. 24-25:
Z
MW P
R T

(44.10) (2000)
(8.3145) (273 + 110) (33.33)
0.831
The SRK cal cul ati on gi ves = 32.93 kg/m
3
, and Z = 0.842.
Gas Mixtures
Additi onal i nformation regardi ng the cal cul ati on of com-
pressi bi li ty factors for mi xtures at pressures below
1000 kPa (abs) can be obtai ned from GPA Standard 2172,
"Cal cul ati on of Gross Heati ng Val ue, Relative Densi ty and
Compressi bi li ty Factor for Natural Gas Mi xtures from Com-
positi onal Anal ysi s."
Minor Amounts of Nonhydrocarbons Fi g. 23-4
1
shows compressi bi l i ty factors for typical sweet natural gases.
Use of compressibility factors from Fig. 23-4 should yield mixture
volumes (densities) within 2 to 3% of the true values from a re-
duced temperature slightly greater than 1.0 to the limits of the
chart for both temperature and pressure. The chart was prepared
from data for binary mixtures of methane with ethane, propane
and butane and data for natural gases. No mixtures having av-
erage molecular weights greater than 40 were used, and all gases
contained less than 10% nitrogen and less than 2% combined
hydrogen sulfide and carbon dioxide. Fig. 23-4 is applicable for
temperatures 10C or more above saturation and to pressures as
high as 70 000 kPa.
Appreciable Amount of Nonhydrocarbons
Fi g. 23-4 does not appl y for gases or vapors with more than
2% H
2
S and/or CO
2
or more than 10% ni trogen. For gas or
vapors that have composi ti ons atypi cal of natural gases, or for
mi xtures contai ning si gni fi cant amounts of water and/or aci d
gases, and for all mixtures as saturated flui ds, other methods
should be empl oyed.
Reasonabl y accurate gas compressibi l ity factors for natural
gases with hi gh nitrogen content, up to 50% ni trogen or even
hi gher, can be obtained usi ng Fi g. 23-4 i f the molar average
pseudocriti cal s from Eqs 23-3a and 23-4a are empl oyed. Thi s
same approach i s recommended for gas condensate flui ds con-
tai ni ng appreci able amounts of heptanes and heavier compo-
nents. Cri ti cal temperature and pressure for the heptane and
heavi er fracti on or fractions can be esti mated from mol ecul ar
mass and rel ati ve densi ty, or average boil i ng poi nt and rel a-
tive density, usi ng correl ati ons presented i n thi s section.
Figs. 23-5, 23-6 and 23-7 provide compressi bi li ty factors for
l ow mol ecular mass natural gases. These fi gures cover a wi de
range of molecul ar masses (15.95 to 26.10), temperatures (70
to 500C), and pressures [up to 35 000 kPa (abs)]. For gases
wi th mol ecul ar masses between the mol ecul ar masses shown
i n Fi gs. 23-5 through 23-7, l inear interpol ati on between adja-
cent charts shoul d be used to compute the compressi bi li ty.
I n general , compressi bi li ties for gases wi th l ess than 5%
noncondensabl e hydrocarbons, such as ni trogen, carbon di ox-
i de, and hydrogen sul fi de, are predicted wi th less than 2% er -
ror. When mol ecular mass is above 20 and compressi bi li ty i s
below 0.6, errors as l arge as 10% may occur.
Effect of Acid Gas Content Natural gases that con-
tai n H
2
S and/or CO
2
exhibi t di fferent compressi bil i ty factor
behavi or than do sweet gases. Wichert and Azi z
3
present a
cal cul ati onal procedure to account for these di fferences. The
method uses the standard gas compressi bi li ty factor chart
(Fig. 23-4) and provides accurate sour gas compressi bi l i ti es for
gas composi ti ons that contai n as much as 85% total aci d gas.
Wichert and Azi z define a "criti cal temperature adjustment
factor," , that i s a function of the concentrati ons of CO
2
and
H
2
S in the sour gas. Thi s correction factor i s used to adjust the
pseudocriti cal temperature and pressure of the sour gases ac-
cordi ng to the equati ons:
T
c
T
c
Eq 23-5
23-11
FIG. 23-4
Compressibility Factors for Natural Gas
1
23-12
FIG. 23-5
Compressibility of Low-Molecular-Weight Natural Gases
11
23-13
FIG. 23-6
Compressibility of Low-Molecular-Weight Natural Gases
11
23-14
FIG. 23-7
Compressibility of Low-Molecular-Weight Natural Gases
11
23-15
P
c

P
c
T
c

T
c
+ B (1 B)
Eq 23-6
The pseudocri ti cal temperature adjustment factor is pl otted
i n Fig. 23-8. To use the factor, the pseudocri ti cal temperature
and pressure are cal cul ated fol l owing the procedure outli ned
earl i er. I n this cal cul ati on, the H
2
S and CO
2
are included as
wel l as hydrocarbon and other nonhydrocarbon constituents.
The pseudocri ti cal temperature adjustment factor i s read
from Fig. 23-8, and used to adjust the values of cri ti cal tem-
perature and pressure. The reduced temperature and reduced
pressure are cal cul ated usi ng the adjusted values. The com-
pressi bi li ty factor is then read from Fi g. 23-4.
Example 23-2 A sour natural gas has the compositi on
shown bel ow. Determi ne the compressibi l ity factor for the gas
at 38C and 6900 kPa (abs).
Solution Steps
The fi rst step is to calculate the pseudocri tical temperature
and pseudocri ti cal pressure for the sour gas.
Comp.
Mole
Fraction
Critical
Temp.
Critical
Press. yi (Tci) yi (Pci)
CO2 0.10 304.1 7374 30.41 737.40
H2S 0.20 373.4 8963 74.68 1792.60
N2 0.05 126.2 3398 6.31 169.90
CH4 0.60 190.6 4599 114.36 2759.40
C2H6 0.05 305.4 4880 15.27 244.00
241.03 5703.30
The pseudocri tical temperature adjustment factor i s read
from Fig. 23-8 to be 16.6C. The adjusted pseudocriti cal tem-
perature i s:
T
c
241.03 16.6 224.43 K
The adjusted pseudocriti cal pressure i s:
P
c

(5703.3) (224.43)
241.03 + 0.2 (1 0.2) 16.6
5253 kPa (abs)
The pseudoreduced temperature and pseudoreduced pres-
sure are:
T
r

38 + 273.15
224.43
1.39 P
r

6900
5253
1.314
Z 0.840 (Fi g. 23-4)
(The EZ*THERMO
90
versi on of the SRK gi ves Z = 0.837)
HYDROCARBON LIQUID DENSITIES
Data and Correlations
Fig. 23-9 presents saturated fl uid densi ti es (l i qui d and va-
por) for hydrocarbons and l iqui d densi ties for some mi xtures.
Fi g. 23-10 i s a plot of rel ati ve densi ty as a functi on of tempera-
ture for petrol eum fracti ons.
Subcooled l i qui d hydrocarbon densi ti es from 20C to +60C
are shown in Fig. 23-11. Corrections to l i qui d hydrocarbon
densi ties due to hi gh pressure are shown i n Fi g. 23-15.
Relative densities of petroleum fractions are given in Fig. 23-12
where temperature ranges from 0 to 550C and pressures
from atmospheri c to 10 000 kPa (abs). The petrol eum fracti on
i s i denti fied wi thi n the center gri d by two of three charac-
teri sti cs API gravity at 15.5C, the Watson characteri zati on
factor, K
w
, or the mean-average boi l i ng poi nt. The mean-av-
erage boil i ng poi nt can be determined from Fi g. 23-18 together
wi th the API gravi ty and an ASTM D-86 disti l lation of the
FIG. 23-8
Pseudocritical Temperature Adjustment Factor
3
, , C
23-16
FIG. 23-9
Hydrocarbon Fluid Densities
2, 3, 19
23-17
FIG. 23-10
Approximate Relative Density of Petroleum Fractions
23-18
FIG. 23-11
Effect of Temperature on Hydrocarbon Liquid Densities
19
23-19
petrol eum fraction. The characterization factor, K
w
, is defined
in the inset example shown to illustrate use of Fig. 23-12.
The rel ati ve densi ty of paraffini c hydrocarbons at their boi l -
i ng poi nt or bubbl e poi nt pressure and temperature can be
obtai ned from Fig. 23-13. The nomograph appli es to mixtures
as wel l as to singl e components. Al i gnment poi nts for paraf-
fini c mi xtures and pure components are l ocated accordi ng to
mol ecul ar mass. Fi g. 23-13 general l y predicts speci fi c gravi -
ties wi thi n 3% of measured val ues for paraffi nic mi xtures.
However, the accuracy is somewhat l ess for mixtures havi ng:
Reduced temperatures above 0.9.
Mol ecul ar masses l ess than 30 (low temperature regi on)
and where methane i s a signi fi cant part of the l i qui d.
Density of Saturated and Subcooled Liquid Mix-
tures A versati le, manual procedure for cal cul ati ng the
densi ty of gas-saturated and subcool ed hydrocarbon l iqui d
mi xtures was presented by Standing and Katz.
1
The basi c
method proposed uses the addi ti ve vol ume approach for pro-
pane and heavi er components at standard conditi ons, then
correcti ng thi s i deal volume using apparent densi ties for the
gaseous components ethane and methane. The resul ting
pseudodensi ty at 15C and 101.325 kPa (abs) is corrected for
pressure usi ng a hydrocarbon l i qui d compressibi l ity chart
(Fig. 23-15), then for temperature usi ng a thermal expansi on
chart (Fi g. 23-17) for hydrocarbon li quids. Experi ence wi th
crude oi l s and rich absorber oi l s shows thi s correl ati on wi ll
predi ct densi ti es wi thi n 1 to 4% of experi mental data.
The ori gi nal correl ati on di d not have a procedure for han-
dli ng si gni fi cant amounts of nonhydrocarbons and had a fai rl y
narrow temperature range of 15C to 115C. The fol lowi ng pro-
cedures and charts are recommended for general appl icabi l i ty
to l i qui ds containi ng components heavi er than pentanes (gas
saturated or subcool ed) at pressures up to 70 000 kPa (abs)
and temperatures from 80C to 320C. Si gni ficant amounts
of nonhydrocarbons can be handled by thi s procedure (up to
20% N
2
, 80% CO
2
, and 30% H
2
S).
FIG. 23-12
Relative Density of Petroleum Fractions
FIG. 23-13
Relative Density of Paraffinic Hydrocarbon Mixtures
23-20
FIG. 23-14
Pseudo Liquid Density of Systems Containing Methane and Ethane
23-21
1. Set up a calculation tabl e as shown i n the foll owi ng ex-
ample.
2. Cal cul ate the densi ty of propane and heavier (C
3
pl us)
or, i f H
2
S i s present, of H
2
S and heavier (H
2
S plus) com-
ponents, assumi ng additi ve vol umes.
Densi ty of C
3
pl us (or H
2
s pl us)

Wei ght C
3
p l u s(or H
2
S pl us) components
Vol C
3
pl us (or H
2
S plus) components
Eq 23-7
3. Determi ne the wei ght percent of (N
2
+ C
2
) i n the
(N
2
+ C
2
plus) fracti on.
Wt % (N
2
+ C
2
)
Wt (N
2
+ C
2
)
Wt (N
2
+ C
2
pl us)
100 Eq 23-8
4. Use Fi g. 23-14 to determine the pseudodensity of the
(N
2
+ C
2
pl us) fracti on. Enter wi th the C
3
plus (or H
2
S
plus) densi ty from Step 2 i n the upper l eft of the chart
and go hori zontal ly to the li ne (interpol ate i f necessary)
representi ng the wei ght % (N
2
+ C
2
) , then l ook up and
read the pseudodensi ty of the (N
2
+ C
2
pl us) al ong the top
of the chart.
At temperatures bel ow 18C, ethane can be included in
Step 2 and onl y N
2
used i n Steps 3 and 4.
5. I f CO
2
i s not present, go to Step 6. I f it is present, then
account for i t on an additi ve vol ume basi s as shown.
Densi ty of CO
2
and (N
2
+ CO
2
pl us)

Wt CO
2
+ Wt (N
2
+ C
2
pl us)
Vol CO
2
+ Vol (N
2
+ C
2
pl us)
Eq 23-9
where
Vol (N
2
+ C
2
pl us)
Wt (N
2
+ C
2
pl us)
Densi ty (N
2
+ C
2
pl us)
6. Cal cul ate the wei ght percent methane,
Wt % methane
Wt methane
total Wt
100 Eq 23-10
7. Enter the top of Fi g. 23-14 wi th the pseudodensi ty from
Step 4 or 5 as appropriate, and drop verti cal l y to the l i ne
(interpol ati on may be requi red) representi ng the wei ght
percent methane. Read the pseudodensi ty of the mi xture
[15C and 101.325 kPa (abs)] on the ri ght si de of the
chart.
8. Correct the pseudodensi ty to the actual pressure usi ng
Fi g. 23-15. Add the correction to the pseudodensi ty from
Step 7.
9. Correct the densi ty at 15C and pressure to the actual
temperature usi ng Fi g. 23-16. Add the correction to the
densi ty from Step 8.
Thi s procedure shoul d not be used i n the cri ti cal region. Mi x-
tures at temperatures greater than 65C that contai n more
than 60 mol e percent methane or more than 80 mol e percent
CO
2
have been demonstrated to be probl em areas. Away from
the near cri tical regi on calculated densi ti es usual l y are within
5% of experi mental data and errors are rarel y greater than
8%. The best accuracy i s obtained for mi xtures contai ning
mostl y C
5
pl us with rel ati vel y smal l amounts of di ssol ved
gaseous components (errors are usuall y l ess than 3%). Note
that densi ties of C
2
pl us, C
3
pl us, CO
2
plus, or C
4
pl us mixtures
can be cal cul ated by thi s procedure at various temperatures
and pressures, and that the gaseous components need not be
present.
FIG. 23-15
Density Correction for Compressibility of Hydrocarbon Liquids
23-22
Example 23-3 Fi g. 23-16 i l l ustrates the procedure outli ned
above to cal cul ate necessary numbers for the foll owi ng exam-
ple.
Densi ty of C
3
pl us
Wt of C
3
pl u s
Vol of C
3
pl u s

44.836 kg
0.0632 m
3
709.5 k g/m
3
Mass % C
2
i n C
2
pl u s
0.567
0.567 + 44.836
100 1.25%
Densi ty of C
2
pl us from Fig. 23-14 = 705 kg/m
3
Densi ty of CO
2
pl us
62.889 kg
0.0845 m
3
744.52 kg/m
3
Mass % CH
4
in Total
3.352
66.241
100 5.1%
Pseudodensi ty of mixture at 15C and 101.325 kPa (abs) from
Fi g. 23-14 = 680 kg/m
3
Pressure correction to 12 000 kPa (abs) from Fig. 23-15 = 12.5
Densi ty at 15C an d 12 000 kPa (abs) 680 + 12.5
692.5 k g/m
3
Temperature correcti on to 50C from Fi g. 23-17 = 30
Densi ty at 50C an d 12 000 kPa (abs) 692.5 30
662.5 kg/m
3
(Densi ty by EZ*THERMO version of SRK usi ng Costal d
92
668 kg/m
3
.
Experimental density
35
at 50C and 12 000 kPa (abs) = 660 kg/m
3
Error (662.5 660)/660 0.0038 0.38%
BOILING POINTS, CRITICAL
PROPERTIES, ACENTRIC FACTOR,
VAPOR PRESSURE
Boiling Points
Fig. 23-18 shows the interconversi on between ASTM D-86
disti l lation 10% to 90% sl ope and the di fferent boil i ng poi nts
used in characteri zing fracti ons of crude oi l to determi ne the
properti es; VABP, WABP, CABP, MeABP, and MABP. On the
basi s of ASTM D-86 di sti l l ati on data, the vol umetri c average
boi l i ng (VABP) poi nt i s defined as:
VABP (t
10
+ t
30
+ t
50
+ t
70
+ t
90
)/5 Eq 23-11
Where the subscri pts 10, 30, 50, 70, and 90 refer to the
vol ume percent recovered duri ng the disti l lation. The 10%
to 90% sl ope used as the absci ssa i n Fi g. 23-18 i s defi ned as:
slope (t
90
t
10
)/(90 10) Eq 23-12
To use the graph, locate the curve for the di sti l l ati on VABP
i n the appropriate set for the type of boi l ing poi nt desi red. For
the known 10-90% sl ope calculated by Eq. 23-12, read a cor -
recti on for the VABP from the sel ected VABP curve.
(1) (2) (3) (4) (5) (6)=(4)/(5)
Component
Mole
Fraction
Molecular
Mass
Mass, kg
Density (15C),
kg/m
3
Volume, m
3
Methane 0.20896 16.043 3.352
Carbon Di oxi de 0.39730 44.010 17.485 821.94 0.02127
Ethane 0.01886 30.070 0.567
Propane 0.02387 44.097 1.053 507.30 0.00207
n-Butane 0.03586 58.123 2.084 584.06 0.00357
n-Pentane 0.02447 72.150 1.766 631.00 0.00280
n-Hexane 0.01844 86.177 1.589 663.89 0.00239
n-Heptane 0.02983 100.204 2.989 687.84 0.00435
n-Octane 0.02995 114.231 3.421 706.54 0.00484
n-Decane 0.18208 142.285 25.907 733.86 0.03530
n-Tetradecane 0.03038 198.394 6.027 765.90 0.00787
Total 1.00000 66.240
Mass C
3
pl us 44.83626684
Vol C
3
pl us 0.063195095132604
Densi ty C
3
pl us 709.48966444182
Mass% C
2
0.012490702499802
Mass CO
2
pl us 62.88856004
Vol CO
2
pl us 0.084468147910179
Den CO
2
pl us 744.52396075825
Mass% CH
4
0.050608385616189
FIG. 23-16
Calculation of Liquid Density of a Mixture at 50C and 12 000 kPa (abs)
23-23
FIG. 23-17
Density Correction for Thermal Expansion of Hydrocarbon Liquids
23-24
Example 23-4 Determine the mean average boi li ng poi nt
(MeABP) and the mol ecul ar mass for a 56.8 API petroleum
fracti on wi th the fol l owing ASTM D-86 di sti ll ati on data.
% Over Temperature, C
I BP 37.8
5 54.4
10 67.2
20 88.3
30 102.8
40 117.8
50 137.8
60 159.4
70 195.6
80 240.0
90 311.1
EP 337.8
I BP i niti al boi li ng poi nt, EP end poi n t
Sl ope (311.1 67.2)/80 3.05
VABP (67.2 + 102.8 + 137.8 + 195.6 + 311.1)/5 162.9C
Refer to Fig. 23-18. Read down from a sl ope of 3.05 to the
i nterpolated curve for 162.9C i n the set drawn with dashed
l i nes (MeABP). Read a correl ati on val ue of 29.5 on the ordi -
nate. Then:
MeABP 162.9 29.5 133.4C
A di scussion of the signi fi cance of the various average boi l -
i ng poi nts, i nterconversion of D-86 and D-1160 ASTM di stil l a-
tions, and the cal cul ati on of true-boi l i ng poi nt and
atmospheri c fl ash curves from ASTM di sti l l ati on data can be
found in Chapters 3 and 4 of the API Techni cal Data Book.
36
Molecular mass can be calculated from Eq 23-13 using MeABP
in K, and S (relative density at 15C) .
MW 204.38

(1.8 T)
0.118
1
]

S
1.88
_
,

e
(0.00392 T 3.075 S
_
,
Eq 23-13
Thi s rel ati onshi p has been eval uated i n the mol ecul ar mass
range of 70 to 720; the MeABP of 36 to 560C; and the API
range of 14 to 93. I ts average error was about 7%. Eq. 23-13
i s best used for mol ecul ar masses above 115, since i t tends to
over-predi ct bel ow thi s val ue.
Example 23-5 Cal cul ati on of mol ecul ar mass.
From Exampl e 23-4:
S 0.7515 for 56.8 API
MeABP 133.4 + 273 406.4 K
Usi ng Eq 23-13,
MW 204.38[(1.8 406.4)
0.118
]
[(0.7515)
1.88
]

e
(0.00392 406.4) (3.075 0.7515)
1
]
127.0
FIG. 23-18
Characterized Boiling Points of Petroleum Fractions (From API Technical Data Book)
23-25
FIG. 23-19
Low-Temperature Vapor Pressures for Light Hydrocarbons
23-26
FIG. 23-20
High-Temperature Vapor Pressures for Light Hydrocarbons
23-27
FIG. 23-21
Viscosities of Hydrocarbon Liquids
FIG. 23-22
Viscosity of Paraffin Hydrocarbon Gases at One Atmosphere
23-28
FIG. 23-23
Hydrocarbon Gas Viscosity
Courtesy Western Suppl y Co., Tul sa
Revi sed (5-99)
23-29
Critical Properties
Cri ti cal properti es are of i nterest because they are com-
monl y used to fi nd reduced conditi ons of temperature and
pressure whi ch are required for correspondi ng states correl a-
tions. Pseudocri ti cal s are used i n many correspondi ng states
correl ati ons for mi xtures.
The fol l owing equations taken from the API Technical Data
Book
36a, b
can be used to estimate pseudo cri ti cal temperature
and pressure for petrol eum fractions (pseudo, or undefi ned
components):
P
pc

5.5303

19
9
_
,
T
2.3125
1
]
S
2.3201
Eq 23-14
T
pc
19.0623 T
0.58848
S
0.3596
Eq 23-15
These equati ons ar e i n ter ms of T = MeABP ( K) and
r el ati ve densi ty (S) at 15C. Both of these cor r el ati ons
have been eval uated over the r ange of 80 to 690 mol ecul ar
mass; 20 to 150C nor mal boi l i ng poi nt; and 6.6 to 95
API .
Example 23-6 Pseudocriti cal temperature and pressure.
Take the previ ous mi xture (from Exampl e 23-4) wi th:
VABP = 166.4C
MeABP = 118.4C
API = 56.8
Mol ecul ar Weight = 127 (Ex. 23-5)
ASTM D-86, 10% to 90% Slope = 3.05
Find i ts pseudocri ti cal temperature.
Solution Steps
From Fig. 23-18 with ASTM D-86 sl ope = 3.05 fi nd a VABP
correcti on of about 65C (extrapolated from the l eft-hand
group).
MABP 166.4 65 101.4C
Use Eq 23-15 to cal cul ate the pseudocri ti cal temperatur e
as:
T
pc
19.0623 (118.4 + 273)
0.58848
(0.7515)
0.3596
577.1 K 304.1C
For thi s 56.8 API flui d, esti mate the pseudocri ti cal pres-
sure, usi ng Eq. 23-14 and MeABP = 118.4C:
P
pc
[5.5303 (10
9
)] (118.4 + 273)
2.3125
(0.7515)
2.3021
2865 k Pa (abs)
Acentric Factor
The acentric factor, , i s frequently used as a third parame-
ter in correspondi ng states correl ati ons. I t i s tabulated for
pure hydrocarbons i n Fi g. 23-2. Note that the acentri c factor
i s a functi on of P
vp
, P
c
, and T
c
.
I t i s arbi trari ly defi ned by
l og (P
vp
/P
c
)
T
r
0.7
1.0 Eq 23-16
Thi s defi ni ti on requi res knowledge of the criti cal (pseudo-
cri ti cal ) temperature, vapor pressure, and cri ti cal (pseudo-
cri ti cal ) pressure.
For a mi xture of known composi ti on, and contai ni ng si mi l ar
components, the acentri c factor may be esti mated, wi th rea-
sonabl e accuracy, as the mol ar average of the indivi dual pure
component acentric factors:
x
i

i
Eq 23-17
I f the vapor pressure i s not known, can be esti mated
38
for
pure hydrocarbons or fracti ons wi th boi l i ng poi nt ranges of
10C or l ess, usi ng Eq. 23-18.

3
7
_

l og P
c
l og 14.7

T
c
T
b
_

,
1
1
1
]
1
1
1.0 Eq 23-18
Example 23-7 Acentri c factor.
A narrow-boi l ing petrol eum fracti on has a VABP of 214.4C,
an ASTM slope of 0.75 and an API gravity of 41. Esti mate its
acentri c factor.
I n order to use Eq 23-18 we need the average boiling point
(MeABP); the pseudocritical temperature (a function of MABP);
and the pseudocritical pressure (a function of MeABP).
Fr om Fi g. 23-18, the cor recti on to VABP for mean average
i s 1.7C; and the correcti on for MABP i s 2.8C. Note that
for narrow-boi l i ng fracti ons, al l boi l i ng poi nts approach the
vol umetri c average. Then, MeABP = 212.7C and MABP i s
211.6C.
From Eq. 23-14, the pseudocri tical pressure i s:
T 212.7 + 273.15 485.85 K
S for 41 API = 141.5/(131.5 + 41) = 0.871
P
pc

5.5303

10
9
_
,
(485.85)
2.3125
1
]
(0.871)
2.3201
P
pc
2460 kPa (abs)
From Eq. 23-15, the pseudocri ti cal temperature i s:
T
pc
19.0623 (485.85)
0.58848
(0.871)
0.3596
T
pc
691.2 K

3
7
_

log (2460) l og (101.325)

691.2
485.85
_

,
1
1
1
]
1
1
1.0 0.505
Vapor Pressure
The vapor pressures of l i ght hydrocarbons and some com-
mon non-hydrocarbons i n the temperature range bel ow 38C
are given i n Fi g. 23-19. Vapor pressures at hi gher tempera-
tures, up to 315C, are given i n Fi g. 23-20 for the same com-
pounds. Note that, except for ethyl ene and propyl ene, the
hydrocarbons are al l normal paraffi ns.
VISCOSITY
Figs. 23-21 through 23-29 gi ve the viscosi ty of hydrocarbon
l i qui ds and vapors, water, steam, and miscel l aneous gases.
Fi g. 23-21 gives data on hydrocarbon li quids. Figs. 23-22, 23-
23 and 23-24 present data on hydrocarbon gases. To correct
for pressure, the gas vi scosi ty from Fi g. 23-22 is adjusted from
atmospheri c pressure values by Fi g. 23-24, or i t can be read
directly from Fig. 23-23. Fi g. 23-24 i s preferred when the re-
duced temperature is greater than 1.0. Fi g. 23-28 gi ves the
vi scosity of hydrocarbon li quids contai ni ng dissolved gases.
Note that Fig. 1-7 gi ves conversion factors for vi scosity.
Calculation of Gas Mixture Viscosity
Example 23-8Determi ne the vi scosi ty of a gas of mol ecu-
l ar mass 22 at 6895 kPa (abs) and 40C. T
c
= 226.9 K,
P
c
= 4885 kPa(abs).
Revi sed (5-99)
23-30
FIG. 23-25
Viscosity of Miscellaneous Gases 101 kPa (abs)
FIG. 23-26
Viscosity of Air
43, 44, 45
FIG. 23-24
Viscosity Ratio For Natural Gases
23-31
Solution Steps
G
i d
22/28.9625 0.760
From Fi g. 23-22 at 40C:

A
0.0105 mPa s
Then:
T
r

40 + 273
226.9
_

,
1.38 P
r

6895
4885
_

,
1.411
Note: Pseudocri tical temperature and pressure should be
cal cul ated as outli ned i n thi s secti on, i f the compositi on of the
gas i s avai l abl e.
Because T
r
> 1.0, Fi g. 23-24 i s preferred over Fi g. 23-23 to
obtai n the correcti on for elevated pressure to the vi scosity at
one atmosphere.
From Fi g. 23-24:

A
1.21
Hence, the vi scosi ty at 6895 kPa (abs) and 40C i s:
(1.21) (0.0105) 0.0127 mPa s
The vi scosi ty of a gaseous mi xture wi th l arge amounts of
nonhydr ocar bons i s best deter mi ned by usi ng the method
of Dean and Sti el .
41
Thi s method i s parti cul arl y useful for
handl i ng natur al gas wi th hi gh CO
2
content. Tested agai nst
30 CO
2
-N
2
mi xtures, i t had an average devi ati on of 1.21%
at pressur es up to 24 300 kPa (abs). I t makes use of a factor,
, defi ned as:
21.74

(T
cm
)
1/6

(y
i
MW
i
)
1/2
(P
cm
)_
,
2/3
1
1
]
1
1
Eq 23-20
I f the reduced temperature, T
r
i s > 1.5, then
(
A
)

166.8 (10
5
)
1
]

(0.1338 T
r
0.0932)
5/9
1
]
Eq 23-21
I f T
r
i s 1.5,
(
A
) 34.0 (10
5
) (T
r
)
8/9
Eq 23-22
I n ei ther case,
A
i s found by di vi di ng (
A
) by .
Equati ons 23-20 through 23-22 wi ll predi ct the vi scosity of
pure gases as wel l as mi xtures. To appl y the Dean and Sti el
method to mi xtures, the pseudocri ti cal vol umes, compressi -
bi li ties, and temperatures are cal cul ated by the Prausni tz and
Gunn
42
rul es:
V
cm
(y
i
V
ci
) Eq 23-23
Z
cm
(y
i
Z
ci
) Eq 23-24
T
cm
(y
i
T
ci
) Eq 23-25
P
cm

Z
cm
R T
cm
V
cm
_

,
Eq 23-26
Example 23-9 For a temperature of 10C and a pressure
of 2000 kPa (abs), esti mate the vi scosi ty of a mixture of 80
mol e percent methane, 15 mol e percent nitrogen, and 5 mol e
percent carbon di oxi de. See Fig. 23-30:
P
cm

Z
cm
R T
cm
V
cm

(0.2871) (8.31) (186.6)
0.0973
4581.8 kPa (abs)
Substi tuti ng from the cal cul ati on tabl e in Fi g. 23-30 i nto
Eq 23-20:

(21.74) (186.6)
1/6
(19.237)
1/2
(4581.8)
2/3
0.043
T
r

T
T
cm

283
186.6
1.52
Because T
r
> 1.5, the expressi on for
A
i s Eq 23-21.

A

166.8 (10
5
)
1
]

(0.1338 T
r
0.0932)
5/9
1
]

166.8 (10
5
)
1
]

(0.1338 1.52 0.0932)

5/9
1
]

A
48.98

10
5
_
,

A
0.01147 mPa s
Usi ng Fi g. 23-22 and correcti ng for the ni trogen and carbon
dioxi de content of thi s mi xture gi ves a
A
of 0.0116 cp. Thi s i s
a good check. Had a 20% N
2
content been chosen for thi s ex-
ample, the N
2
range of Fi g. 23-22 woul d have been exceeded
and use of the Dean and Sti el method woul d have been re-
quired. When the condi tions at hand fal l wi thi n the l i mi ts of
Fig. 23-23, use this figure and not the Dean and Stiel correlation.
FIG. 23-27
Water Viscosity at Saturated Conditions
Revi sed (5-99)
23-32
FIG. 23-28
Liquid Viscosity of Pure and Mixed Hydrocarbons Containing Dissolved Gases at 38C and 101.325 kPa (abs)
23-33
Viscosity of Petroleum Fractions
Mid-Boiling Point Method The vi scosi ty of a crude
oi l or crude oi l fraction can be esti mated using the equations
gi ven bel ow i f the mi d-boi l ing point and gravi ty are known:
Mid-boil ing poi nt is defined as the boi li ng point at 50% vol -
ume di sti ll ed.
A e
B / T
Eq 23-27
A

91.83 T
b
0.175
29.263
_
,

K
w
B
Eq 23-28
l n (B) 4.717 + 0.00526 T
b
Eq 23-29
Example 23-10 At 40C and 100C fi nd the vi scosi ty of a
heavy condensate havi ng a mi d-boi l i ng poi nt of 163C and
a rel ati ve densi ty of 0.7688.
Solution Steps
K
w

3
(163 + 273) 1.8
0.7688
11.99
l n (B) 4.717 + (0.00526) (163 + 273) 7.01
B 1108
A

91.83 (436)
0.175
29.263
1
]

11.99
1108
0.02638
The same constants are employed at 40C and 100C.
0.02638 e
1108
313
0.909 cs at 40C
0.02638 e
1108
373
0.513 cs at 100C
The reported values are 0.93 and 0.52 centi stokes, respec-
tivel y.
THERMAL CONDUCTIVITY
Thermal conducti vi ty for natural gas mi xtures at elevated
pressure can be calcul ated from an atmospheri c value and a
pressure correcti on. Fi gs. 23-31 through 23-34 present l ow
pressure thermal conducti vi ty data of gases devel oped from
publ ished data.
51, 54
The pressure correcti on of Lenoi r et al.
52
shown i n Fig. 23-32 is appl ied to these low pressure data as
i ll ustrated bel ow. The thermal conductivity of li quid paraffi n
hydrocarbons i s pl otted in Fig. 23-35 and the thermal conduc-
ti vity of li quid petrol eum fracti ons in Fig. 23-36.
Example 23-11 Fi nd the thermal conducti vi ty of a 25 mol ecu-
l ar mass natural gas at 4826 kPa (abs) and 140C. Tc = 244 K,
Pc = 4550 kPa (abs)
Solution Steps
From Fi g. 23-31, at 140C:
k
A
0.0445 W/(m C)
T
r
(140 + 273)/244 1.69
P
r
4826/4550 1.06
From Fi g. 23-32:
k/k
A
1.13
k (1.13) (0.0445) 0.0503 W/(m C)
Another method for estimati ng thermal conducti vity i s pre-
sented by Sti el and Thodos.
53
To determi ne the thermal conducti vi ty of a gaseous mi xture
of defi ned components, the thermal conducti vi ty of each com-
ponent at the given temperature i s read from the chart pro-
vi ded and the thermal conducti vi ty of the mi xture i s
FIG. 23-29
Viscosity of Steam
46, 47
Mole
Fraction, y
i
Molecular
Mass, MWi
Pci,
kPa (abs)
Tci, K vci , m
3
/kg
Vci MWi vci
m
3
/kg mole
Zci
Pci Vci
8.31 Tci
CH4 0.80 16.043 4599 190.56 0.00617 0.0990 0.2875
N2 0.15 28.013 3398 126.21 0.00318 0.0891 0.2887
CO2 0.05 44.010 2374 304.11 0.00214 0.0942 0.2749
Mi xture
1.00 19.237

186.59

0.0973 0.2871
MWcm yi MWi Tcm yi Tci Vcm yi Vci Zcm yi Zci
FIG. 23-30
Calculation of Viscosity of a Gas Mixture
Revi sed (5-99)
23-34
determi ned by the "cube root rul e."
56
Thi s rul e is appl i cable
to mi xtures of si mpl e gases; i t does not appl y to mi xtures con-
tai ni ng CO
2
because the thermal conductivi ty goes through a
maxi mum.
k
m

(y
i
k
i

3
MW
i
)
y
i

3
MW
i
Eq 23-30
The cube root rul e was tested
56
against 17 systems wi th an
average devi ati on of 2.7%.
The thermal conducti vi ty of a l i qui d mi xture i s best deter -
mi ned by the method of Li ,
55
based on vol ume fracti ons.
Example 23-12 Find the thermal conductivi ty of the gase-
ous mi xture shown in Fi g. 23-37 at 100C and one atmosphere.
k
m

0.10780
2.822
0.0382 W/(m C)
TRANSPORT PROPERTY REFERENCES
There are no si mpl e correl ati ons for the transport properti es
of vi scosity and thermal conductivi ty, as evi dent from the pre-
cedi ng paragraphs. For pure components, the best approach
i s a compl i cated equati on wi th many constants that must be
fitted to experi mental data, or extensi ve tabl es. Vargaftik
62
and Toul oukian
65
each have extensive col l ecti ons of experi -
mental data.
SURFACE TENSION
The i nteri or molecul es of a li quid exert upon the surface
mol ecul es an i nward force of attracti on whi ch tends to mi ni -
mi ze the surface area of the l iqui d. The work requi red to en-
l arge the surface area by one square centi meter i s cal l ed the
surface free energy. The perpendi cul ar force i n the li quid sur -
face, cal l ed surface tensi on, exerts a force paral l el to the pl ane
of the surface. Surface tensi on, an i mportant property where
wetti ng, foami ng, emul si ficati on, and dropl et formati on are
encountered, i s used i n the desi gn of fracti onators, absorbers,
two-phase pipeli nes, and in reservoi r calculations.
Pure Components
The surface tensi on of pure hydrocarbons as a functi on of
temperature may be obtained from Fi g. 23-38.
Mixtures
Surface tension for bi nari es of known composi ti on at or near
atmospheri c pressure may be cal cul ated
78
usi ng:

1

2

1
x
2
+
2
x
1
Eq 23-31
The presence of inert gases, such as N
2
and CO
2
, in the liquid
phase tends to lower the surface tension of the liquid. Where the
concentration of inert gases in the liquid exceeds 1.0 mole%, es-
timated values of surface tension may be 5 to 20% higher than
actual values for the mixture.
FIG. 23-31
Thermal Conductivity of Natural and Hydrocarbon Gases
at One Atmosphere [101.325 kPa (abs)]
FIG. 23-32
Thermal Conductivity Ratio for Gases
23-35
GROSS HEATING VALUE OF NATURAL
GASES
The gross heati ng value, relative densi ty, and compressibi l -
i ty of a natural gas mixture may be cal cul ated when a compl ete
composi ti onal analysis of the mi xture i s avai l abl e.
Gross Heating Value i s defi ned as the total energy
transferred as heat in an ideal combusti on reacti on at a stand-
ard temperature and pressure in whi ch all water formed ap-
pears as l iqui d. The gross heating val ue can be cal cul ated per
unit vol ume of an i deal gas, or per uni t vol ume of a real gas as
fol l ows:
H
v

y
i
H
v
i
_
,
Eq 23-32
Val ues for H
v
and MW
i
are obtai ned from Fi g. 23-2.
To calculate the i deal gross heati ng value produced or used
for a gi ven peri od of ti me, H
v
must be mul ti pli ed by the ideal
gas vol umetric fl ow rate of gas for the ti me peri od. To employ
a real gas fl ow to cal cul ate the i deal gross heati ng val ue pro-
duced or used for a gi ven period of ti me, the real gas fl ow rate
must be converted to the i deal gas fl ow rate by di vidi ng by the
compressi bi l i ty factor. Often the heati ng val ue H
v
is di vided
by the compressibi l ity factor i n preparati on for mul ti pl yi ng by
the real gas flow rate. Thus H
v
/Z i s gross heati ng value per
unit vol ume of real gas.
Relative Density (al so termed speci fic gravi ty or gas
gravi ty) i s defi ned as the rati o of gas densi ty (at the tem-
perature and pressure of the gas) to the densi ty of dry air (at
the ai r temperature and pressure).
G

s

MW P T
a
Z
a
MW
a
P
a
Z
Eq 23-33
The i deal gas relative density i s the ratio of the mol ecul ar
mass of the gas to the mol ecul ar mass of dry ai r.
G
i d

MW
MW
a
Eq 23-34
For a mi xture
G
i d

y
i
G
i
i d
_
,
Eq 23-35
The rel ati ve densi ty G is measured and i s generall y used to
cal cul ate the mol ecul ar mass rati o G
id
when the gas composi -
tion i s not avai l abl e.
G
i d

MW
MW
a

G (P
a
T Z)
P T
a
Z
Eq 23-36
The temperatures and pressures used must correspond to
actual measurement condi tions or seri ous errors in G
i d
can
occur.
Corrections for Water Content When the gas i s
water saturated but the component anal ysi s i s on a dry basi s,
the component anal ysi s must be adjusted to refl ect the pres-
ence of water. The mole fracti on of water i n the mi xture i s
estimated as:
y
w

P
w
o
p

n
w
(1 + n
w
)
(on a one mole basi s)
FIG. 23-33
Thermal Conductivity of Miscellaneous Gases
at One Atmosphere
59, 60, 61, 62
FIG. 23-34
Thermal Conductivity of Hydrocarbon Gases
at One Atmosphere
67, 68, 69
23-36
FIG. 23-35
Thermal Conductivity of Liquid Paraffin Hydrocarbons
FIG. 23-36
Thermal Conductivity of Liquid Petroleum Fractions
58
23-37
Component
Mole
Fraction
Thermal
Conductivity
W/(m C)
Molecular
Mass
3
MW
i
(y
i

3
MW
i
) (y
i
k
i

3
MW
i
)
CO
2
0.10 0.0225 44.010 3.530 0.3530 0.00794
H
2
S 0.20 0.0240 34.076 3.242 0.6484 0.01556
N
2
0.05 0.0310 28.013 3.037 0.1519 0.00474
CH
4
0.60 0.0410 16.043 2.522 1.5132 0.07474
C
2
H
6
0.05 0.0310 30.070 3.109 0.1555 0.00482
Total 1.00 2.8220 0.10780
FIG. 23-37
Calculation of Thermal Conductivity
FIG. 23-38
Surface Tension of Paraffin Hydrocarbons
85
23-38
The adjusted mole fractions are cal cul ated using the fol l ow-
i ng equati on:
y
i
w
y
i

P
w
o
P
_

,
1
1
]
y
i
(1 y
w
) Eq 23-37
For water saturated gas, water i s added to the component
l i st and the x
i
w
val ues are used i n the gross heati ng val ue and
the gas compressi bi l i ty cal cul ati ons. I f the dry gross heating
val ue is known, the water saturated gross heating val ue can
be cal cul ated by:
H
v
(satd)

1.7051
P
_

,
1
1
]
H
v
(dry) +

1.7051 29.94
P
_

,
Eq 23-38
When the gas i s wet but not water satur ated and the com-
ponent anal ysi s i s on a dry basis, it is necessary to determi ne
the water content and to adjust the mole fractions to reflect
the presence of water. When the water mol e fraction, y
w
, i s
known, the adjusted mole fracti ons can be obtained from Eq
23-37.
The y
i
w
val ues are used i n the gross heati ng val ue and gas
compressi bi l i ty calculations after addi ng water to the compo-
nent l i st. I f the dry gross heating val ue i s known, the effect of
the water content can be cal cul ated using:
H
v
(wet) (1 y
w
) H
v
(dry) + 50.3 y
w
Eq 23-39
Calculations Additional details on these calculational
methods and examples are given in GPA Standard 2172, "Calcu-
lation of Gross Heating Value, Relative Density and Compressi-
bility Factor for Natural Gas Mixtures from Composi ti onal
Analysis." A l i sting of the Basi c source code for a computer
program to perform the calculations i s given i n 2172.
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23-40