PHYSICAL PROPERTIES OF LIQUIDS AND GASES
-3
n important but time-consuming factor
A in practically every design situation and
in development of flowsheets is the collection
and assembly of physical property data for the
components of the system in question. Often it is not
sufficient to obtain single data points from various
tables, since many designs cover rather wide ranges of
temperature and pressure, and the effects of these on the
properties must be taken into account.
Data may be located in many useful handbooks 11-41
as well as published technical papers and company
compilations. However, experience indicates that
extensive literature searches may be necessary to locate
specific data on a particular compound. It is surprising to
find so many common compounds for which the data are
incomplete and sometimes inaccurate. Empirical
correlations must often be utilized, sometimes to
generate a value and sometimes to check a questionable
literature value.
Therefore, when developing an estimate of process
engineering it is important to recognize the amount of
effort that may be necessary to collect physical property
data before the flowsheet calculations can commence.
This same concern exists when evaluating K values and
activity coefficient data for phase equilibrium.
3.1 DENSITY OF LIQUIDS
Liquid density data are essential in process engineering design
such as sizing of storage vessels that contain the basic raw mate-
rials and products for a plant, in process piping design involving
either single-phase incompressible fluids, compressible fluids or
two-phase flow mixtures. In distillation, absorption, or stripping,
liquid density data are required in the determination of flooding
and sizing of column diameter. Additionally, liquid density usage is
encountered in various heat-, mass-, and momentum-transfer oper-
ations. Saturated liquid densities at any temperature are based upon
the modified form of the Rackett equation as [ 5 ]
Density = AB (3-1)
where
Density = saturated liquid density, g/mL
A , B , and n =regression coefficients for chemical
compound
T =temperature, K
TC = critical temperature, K
Tr = Reduced temperature, T/Tc.
Appendix C gives tabulated values of the correlation constants and
results for saturated liquid density between the minimum and the
maximum temperature ranges for which the equation is applicable,
and denoted by T,, and T,,. For many of the compounds, the
temperature range corresponds to the freezing point and critical
103
Physical property data of compounds are frequently
required for pilot plant studies or for the design of large
process plants. These data are not readily available
except in some simulation design packages or in the
largest libraries. The data can, of course, be obtained by
conducting experiments to measure the properties of
individual substances or of mixtures, which may exhibit
non-ideal behavior. However, this is often
time-consuming and expensive. Therefore
the process engineer may resort to correlations and
interpolations to obtain data of sufficient accuracy for
design purposes. Thermodynamic data of this type are
required in most calculations such as sizing vessels,
process pipeline sizing, and separation of
multicomponents, gas absorption, and chemical
reactor design.
Many predictions and correlations of thermodynamic
physical data have been published. This chapter
reviews physical property data for liquids and gases
and presents the Excel spreadsheet programs for
determining these properties for a range of
temperature and correlation constants, which can
be downloaded from the companion website.
Appendix C provides tables of some selected physical
property data.
point. Values for liquid density at 25°C are provided in the last
column. The Excel spreadsheet program from the companion
website (density-of-1iquid.xls) provides calculations for the density
of saturated liquids and plots with given correlation constants,
temperatures, and at their critical temperatures. Table C-1 in
Appendix C lists the density of chemical compounds, and
Figure 3-1 shows the plot for saturated liquid density of methanol
as a function of temperature.
-100 -50 0 50 100 150 200 250
Temperature, C
Figure 3-1 Saturated liquid density of Methanol (CH,OH).
104 PHYSICAL PROPERTIES OF LIQUIDS AND GASES

EXAMPLE
3-1
Calculate the liquid density of methanol (CH,OH) at a temper-
ature of 120" C (393.15 K).
%-
ai
c
ra
Solution Q.
Substituting the regression coefficients (A and B ) from Table C-1 ea
in Appendix C, and the temperature at 393.15 K into the equation L
0
for liquid density yields >
m
-(I- I'):
8L?
density = AB >
-( ,- 2331
= (0.27197) (0.27192) -1 00 0 100 200 300 400 500
Temperature, C
= 0.69 g/mL
Figure 3-2 Viscosity of propane (C,H,)

3.2 VISCOSITY OF GAS EXAMPLE

3-2
Calculate the gas viscosity of propane (C,H,) at a temperature
Gas phase viscosity data, pG,are used in the design of compressible of 350 K.
fluid flow and in unit operations. For example, the viscosity of a
gas is required to determine the maximum permissible flow through Solution
a given process pipe size. Alternatively, the pressure loss of a Substituting the regression coefficients ( A , B, and C ) from
given flow rate can be calculated. Gas viscosity data are needed Table C-2 in Appendix C, and the temperature at 350K into the
for the design of process equipment involving heat-, momentum-, correlating equation for the gas viscosity yields
and mass-transfer operations. The correlation for gas viscosity as a
function of temperature is expressed by [ 2 ] : pG= (-5.462) + (0.32722) (350) + (-1.0672 x lo-') (350)'

pLc= A + BT + C T ? (3-2) pG = 95.99 p P

where
* pLc= viscosity of gas, micropoise (p.P)
A. B , and C =regression coefficients for chemical
compound
T = temperature, K.
The Herning-Zipperer correlation for the calculation of gas mixture
viscosity at low pressure is [ 5 ] :
(3-3)
where
* pLm= gas mixture viscosity, micropoise (pP)
MF, = mole fraction of component i
p , = gas viscosity of component i, micropoise (pP)
MW, = molecular weight of component i.
Reid et al. [6] have reviewed other correlation methods for deter-
mining pLcat low pressure. The Excel spreadsheet program from
the companion website (viscosity-of-gas,xls) calculates the gas
viscosity between the range of the minimum and the maximum
temperatures denoted by T,,, and T,,, for any chemical compound.
Table C-2 in Appendix C lists the gas viscosity of compounds, and
Figure 3-2 shows the graph for viscosity of propane as a function of
temperature. The plot gives a linear relationship between viscosity
and temperature. Low pressure gas viscosities (Le., at about 1 bar)
vary in a nearly linear manner with temperature.
3.3 VISCOSITY OF LIQUIDS
Liquid viscosity data are important in many engineering applica-
tions in the petroleum refining and petrochemical industries. It can
be applied in fluid mixing: fluid flow, heat- and momentum-transfer
operations. The viscosities of liquids are larger than those of gases
at the same temperature. Daubert et al. [7] and Yaws et al. [8, 91
have compiled tabulations of constants that allow estimation of liquid
viscosities. When these constants are derived from experimental
data, they can be used with confidence; otherwise, caution should
be exercised when based on estimated viscosities. The correlation for
liquid viscosity as a function of temperature is given by
B
iOg,, pL = A + -
T
+a+
DT' (3-4)
where
* p L = viscosity of liquid, centipoises (cP)
A , B , C, and D =regression coefficients for chemical
compound
T =temperature, K.
The Excel spreadsheet program from the companion website
(viscosity-of-1iquid.xls) calculates liquid viscosity of compounds
between the range of the minimum and the maximum tempera-
tures, and denoted by T,,, and T,,,,,, and at 25°C. Table C-3 in
Appendix C shows the viscosity of liquid, and Figure 3-3 shows

:: Conversion factor
li Con\ ersion factor *Conversion factor
 3.4 HEAT CAPACITY OF GAS 105
chemical reactions, the heat capacity is required to determine the
2 energy (heat) necessary to bring the chemical reactants up to reac-
1.8
tion temperature. The heat capacity Cp is also used in the rating of
heat exchangers and energy balance computations. The heat capacity
% 1.6
of a mixture of gases may be found from the heat capacities of
6 1.4
the individual components contained in the mixture. The correlation
5
.-- 1.2
for heat capacity of the ideal gas is expressed by Yaws et al. [ 101:
+
0 1
.g 0.8 Cp = A + B T + CT2 + D T 3 + E T 4
v)
8 0.6 (3-5)
5 0.4 where
0.2
0
Cp=heat capacity of ideal gas, J/(mol K)
0 50 100 150 200 250 300 350 400 A , B , C, D , and E =regression coefficients for chemical
Temperature, C compound
T = temperature, K.
Figure 3-3 Viscosity of water (H,O). The results for heat capacity of gaseous compounds as given in
the plot of viscosity of water between 273.15 and 643K, and it Table C-4 of Appendix C are based on regression experimental data,
decreases as the temperature increases. and estimates from an extensive literature search. The numerous
Since viscosity is defined as a shearing stress per unit area data points were processed with a generalized least-squares computer
divided by a velocity gradient, its dimension is (force)(time)/ program for minimizing the deviations. The developed Excel
(length)* or mass/(length)(time). Both dimensional groups are used, spreadsheet program from the companion website (heat-capacity-
although for most scientific work, viscosities are expressed in of-gas.xls) calculates the heat capacity of gas between the range of
poises, centipoises, micropoises, and so on. A poise (P) denotes a the minimum and the maximum temperatures, and denoted by Tminto
viscosity of 0.1 N s/m2 and 1.OcP = 0.01 P. The following conver- T,,, for various components. Figure 3-4 shows a plot of the heat
sion factors apply to viscosity units: capacity of 1-butene (C,H,) as a function of temperature.

1 P = lOOcP= 1 . 0 1~0 6 p P = 0 . 1 N s / m 2
= 1 g/(cm s) = 0.01 Pas EXAMPLE 3-4
Calculate the heat capacity of 1-butene at a temperature of
= 6.72 x lo-* lb-mass/(ft s) = 2421b-mass/(ft h) 200°C (473.15K).
1 c P = 1mPas
Solution
The kinematic viscosity is the ratio of the viscosity to the density. Substituting the coefficients (A, B , C, D, and E ) from Table C-4 in
For example, if viscosity is in poise, and the density in grams per Appendix C and the temperature into the heat capacity gives
cubic centimeter, the unit of kinematic viscosity is the stoke, having
the unit square centimeters per second (cm2/s). In SI system of Cp = 24.915 + (0.20648) (473.15) + (5.9828 x lo-') (473.15')
units, viscosities are expressed in Ns/m2 or (Pas) and kinematic
viscosities in either m2/s or cm2/s. + (-1.4166 x (473.153)
+ (4.7053 x lo-'') (473.154)
= 123.36J/(molK)
EXAMPLE 3-3
Calculate the liquid viscosity of water at a temperature of
250°C (523.15K).

Solution
Substituting the regression coefficients (A, B , C, and D ) from
Table C-3 in Appendix C, and the temperature at 523.15 K into the
correlation equation gives
1792.5
+
lOg,,-,pL= (-10.2158)+ - (0.01773) (523.15)
--
Y

+ (-1.2631
523.15
x (523.15)*
-E
%
= 10-09709 .-s
w

scl
= 0.1069cP 5
w
m
I"
3.4 HEAT CAPACITY OF GAS -100 100 300 500 700 900 1100 1300
The heat capacity of gases Cpis essential for some process engineering Temperature, " C
design, for example, in the design of air-cooled heat exchanger
and in the engineering design of chemical processes. In gas-phase Figure 3-4 Heat capacity of 1-butene (C4H8).
106 PHYSICAL PROPERTIES OF LIQUIDS A N D GASES

EXAMPLE 3-5
Calculate the energy required to heat gaseous ethyl chloride
(C,H,CI) from 250 to 500 K.

Solution
From thermodynamic property, the change in enthalpy AH, at
constant pressure is

AH = / C,dT = ;(A + BT + CT2 + DT3 + ET4)dT I n l I I I I I I

TI -100 -50 0 50 100 150 200 250 300
(3-6) Temperature, C O

Figure 3-5 Heat capacity of ethylbenzene (C,H,C,H,).

= 35.946 (500 - 250) + 0.052294

~

2
(5002 - 2502) EXAMPLE 3-6
Calculate the liquid heat capacity of ethylbenzene (C,H,C2H,)
+-0.000203
3
(5003- 2503)
at a temperature of 298.15 K.

Solution
(-2.28 x IO-’) (5004 - 2504)
+ 4
Substituting the coefficients from Table C-5 in Appendix C, and
at a temperature of 298.15 K into the correlating equation for heat
(6.9123 x IO-”) (5005 - 2505) capacity yields
+ 5 C,, = 102.11 + (0.55959) (298.15)+ (-1.5609 x (298.15),
= 18368.8 J/mol.
+ (2.0149 x (298.15)3
= 183.59 J/mol K.

3.5 HEAT CAPACITY OF LIQUID

Heat capacity data for liquids are relevant in process design of heat EXAMPLE 3-7
exchanger equipment and chemical reactors. In liquid-phase chem- Calculate the energy required to heat liquid toluene (C,H,)
ical reactions, the liquid heat capacity is required to determine the from 350 to 600 K.
energy (heat) necessary to bring the liquid chemical reactants up to
reaction temperature. Alternatively, they are essential when sizing Solution
reboilers and condensers for distillation plant and when rating heat From thermodynamics, the change in enthalpy, AH at constant
exchangers in general, and for energy balance design calculations. pressure is
The correlation for heat capacity of liquid is expressed in
polynomial of the form [2]:
AH = / C,dT =r ( A + BT + CT2 + DT3)dT (3-9)
350
C, = A + B T + C T 2 + D T 3 (3-8)
Integrating between the temperatures at 350 and 600 K gives
where B C D
AH = AAT -AT2
2
+ -AT3
3
+ -AT4
4
+ (3-10)
C, =heat capacity of saturated liquid,
J/mol K Substituting the coefficients from Table C-5 in Appendix C, and
A , B , C , and D =correlation constants for chemical the temperature limits into the equation yields
compound
T = temperature, K. AH = (83.703) (600 - 350) + -21 (0.51666) (6002- 3502)
The Excel spreadsheet program from the companion website (heat-
capacity-of-1iquid.xls) calculates the heat capacity of liquid as a
+ 31 (-1.491
- x (6003 -3503)
function of temperature between the range of the minimum and the
maximum temperatures denoted by Tminand T,,,, and at 25” C in + -41 (1.9725 x IO-,) (6004- 3504)
Appendix C. Table C-5 in Appendix C lists the liquid heat capacity
of compounds, and Figure 3-5 shows a plot for the heat capacity AH = 52745.04Jfmol.
of ethylbenzene (C,H,C,H,) as a function of temperature.
 3 7 THERMAL CONDUCTIVITY OF LIQUIDS AND SOLIDS 107
3.6 THERMAL CONDUCTIVITY OF GAS 3.7 THERMAL CONDUCTIVITY OF LIQUIDS
The thermal conductivity, k,, of low pressure gases increases with AND SOLIDS
temperature. In small temperature ranges, k , represents some form Thermal conductivity of liquids and solids is essential in many
of linear relation. However, over wide temperature ranges, k, chemical and process engineering applications where heat transfer
increases significantly more rapidly with temperature than implied is prevalent. The liquid thermal conductivity is required to calculate
by a linear function. Gas thermal conductivity data are used, for the Nusselt number, hdlk, and the Prandtl number, c p / k , and in
example, in the design of process equipment and unit operations correlations to predict the idealized condensing film coefficient
involving heat transfer, such as the rating of heat exchangers based upon laminar liquid flow over a cooled surface.
and fluidized bed operations handling gases. Tsederberg [ 111 has For many simple organic liquids, the thermal conductivities
compiled thermal conductivity data for pure gases; Daubert et al. [7] are between 10 and 100 times larger than those of the low pres-
and Yaws [12, 131 have provided constants that estimate thermal sure gases at the same temperatures, and the effect of pressure
conductivities at different temperatures. Thermal conductivity of a
is minimal. Additionally, increasing the temperature invariably
gas can be correlated as a function of temperature as [2]:
decreases the thermal conductivities, which is characteristic of those
k,=A+BT+CT2 (3-1 1) noted for liquid viscosities. Although the temperature dependence
of the latter is noticeable and nearly exponential, that for thermal
where conductivities is weak and nearly linear [ 11. Values of kllq for most
common organic liquid range between 0.10 and 0.17 W/(m K) at
k, =thermal conductivity of gas, W/(m K) temperatures below the normal boiling point, but water, ammonia,
A, B, and C =regression coefficients for chemical and highly polar molecules are of values which are several times
compound as large.
T = temperature, K. Liquid thermal conductivity data have been compiled by
Jameison et al. [14] and Liley et al. [15], and constants that may be
The Excel spreadsheet program from the companion website used to calculate k, for pure liquids at different temperatures are
(thermal-conductivity-of-gas.xls) calculates the gas thermal tabulated in Daubert et al. [ 7 ] ,Miller et al. [16], and Yaws [13].
conductivity for chemical compounds over the range of the For inorganic compounds, the correlation for thermal conduc-
minimum and the maximum temperatures denoted by T,, and tivity of liquid and solid as a function of temperature is [2]:
T,,,,,. Table C-6 in Appendix C lists the gas thermal conductivity
of chemical compounds, and Figure 3-6 shows the thermal conduc- k = A + B T + CT2 (3-12)
tivity of propane (C,H,) as a function of temperature.
where
EXAMPLE
3-8 k =thermal conductivity of liquid or
Calculate the gas thermal conductivity of propane at a temper- solid, W/(m K)
ature of 500 K. A , B , and C =regression coefficients for chemical
compound
Solution T =temperature, K.
Substituting the correlation coefficients from Table C-6 in
Appendix C and temperature of 500 K into the correlation equation
gives For organic compounds, the correlation for thermal conductivity of
liquid as a function of temperature is [2]:
k, = (-0.00869) + (6.6409 x (500)
+ (7.8760 x lo-') (500)' (3-13)
= 0.0442W/(mK).
where
kllq=thermal conductivity of liquid, W/(mK)
A , B , and C =regression coefficients for chemical
compound
T =temperature, K.
P
E Very limited experimental data for liquid thermal conductivi-
g ties are available at temperatures in the region of the melting
9
.-
point. Additionally, there are very few reliable data at tempera-
I
tures above a reduced temperature of T, = 0.65. Therefore, the
Y values in the regions of melting point and reduced tempera-
2
8 tures above a reduced 0.65 should be considered rough approx-
-5 imations. The values in the intermediate region (above melting
E
S
z point and below reduced temperature of 0.65) are more accu-
I- rate. The Excel spreadsheet program from the companion website
-1co 0 100 200 300 400 500 (liquid-thermal-conductivity.xls)calculates the liquid and solid
Temperature, C thermal conductivities of compounds between the range of the
minimum and the maximum temperatures denoted by T,,, and
Figure 3-6 Thermal conductivity of propane (C,H,) T,,,,,, and at 25°C. Table C-7 in Appendix C lists the liquid
108 PHYSICAL PROPERTIES OF LIQUIDS AND GASES
thermal conductivity of chemical compounds, and Figures 3-7a,
3-7b and 3-7c show plots for thermal conductivity of benzene EXAMPLE 3-9
(C,H,), water (H,O), and iron (Fe) respectively as a function of Determine the liquid thermal conductivity of benzene (C&)
temperature. at a temperature of 340K.

Solution
Substituting the correlation coefficients from Table C-7 in
Appendix C, and the temperature of 340K into the correlation
0.16 equation yields
0.14
0.12 loglo k,i, = (-1.6846) + (1,052) (1 - -
s:;:6)217
0.1
k - 10-087770
0.08 liq -

::::J
0.06 = 0.1325W/(mK)

0
0 50 100 150 200 250 300
Temperature,"C EXAMPLE 3-10
Calculate the liquid thermal conductivity of water (H,O) at a
Figure 3-7a Thermal conductivity of benzene (C,H,). temperature of 320 K.

Solution
Substituting the correlation coefficients from Table C-7 in
Appendix C and the temperature of 320 K in the correlation equa-
rn tion yields
I t I I I I I I
E 0.7 k = (-0.2758) + (4.612 x (320)

s
0.6 + (-5.5391 x lo-,) (320')
e
'5 0.5
._
e = 0.6328 W/(mK).
0.4
-0
0.3 Conversion
0 The units used for thermal conductivity are W/(m K). Conversion
5 0.2
of these to Imperial or cgs units is as follows.
$ 0.1
s o0 T

50 100 150 200 250 300 350 400

W/(mK) x 0.5778 = Btu/(hft"R)

Temperature,"C
W/(mK) x 0.8604 = kcal/(cmhK)
W/(mK) x 2.390 x = cal/(cmsK)
Figure 3-7b Thermal conductivity of water (H,O).
or

Btu/(hft"R) x 1.731 = W/(mK)

kcal/(cmhK) x 1.162 = W / ( m K )
cal/(cmsK) x 4 1 8 . 4 = W/(mK).

3.8 SURFACE TENSION

As the temperature is raised, the surface tension of a liquid (u)in
equilibrium with its own vapor decreases and becomes zero at the
critical point [ 11. In the reduced-temperature range of 0.45-0.65,
r for most organic liquids ranges from 20 to 40dydcm. For low
molecular weight dense liquids the u range is as follows: fonnalde-
n J hyde has u > SOdyn/cm; water, u = 72.8 dyn/cm at 293 K; and
-90 10 110 210 310 410 510 610 710 for liquid metals u is between 300 and 600dydcm. Useful tech-
Temperature, " C niques for estimating the surface tension of a liquid are empirical,
and critical evaluations have been prepared by Jasper [17], Riddick
Figure 3-7c Thermal conductivity of iron (Fe). et al. [18], Timmermans [19], and Vargaftik 1201.
 3.9 VAPOR PRESSURE 109
Surface tension data of liquids are important in many process
design calculations for situations where there is a two-phase inter-
face, for example, two-phase flow in process piping, distillation
40 , I I I 1 I I 1 1
columns, absorption, and heat exchangers. Surface tension correla- 35
E
tion as a function of temperature is based upon a modified Othmer $ 30
relation, and expressed by [ 11 z1
U
i 25
0
'2 20
u = A (1 - (3-14)
-
al
0
0
15
where
f 10
u = surface tension, dydcm v,
5
A, Tc, and n =regression coefficients for chemical
0
compound
0 50 100 150 200 250 300 350 400
T =temperature, K.
Temperature, C
The Excel spreadsheetprogram from the companion website (surface-
tension-1iquid.xls) calculates the surface tension of compounds Figure 3-8a Surface tension of monochlorobenzene (C6H,C1)
between the range of the minimum and the maximum temperatures,
which is denoted by T,,, and T,,, . The surface tension has been corre-
lated with other physical parameters such as liquid compressibility,
viscosity, molar fractions, and the refractive index. Sastri and Rao
[21] developed a linear relationship between the surface tension at
normal boiling point (log ub)and the reduced boiling point (Tbr).
Hadden [22] presented a monograph for hydrocarbons that enables
rapid calculation for cr. For cryogenic liquids, Sprow and Prausnitz 90
[23] introduced the equation:
80
u = a, (1 - T,)P (3-15) E
$ 70
where 2 60

u = surface tension, dydcm 5

.- 50
T, =reduced temperature, TIT,
uo and p were determined by a least square
-(0
5 40

analysis of the measured data.

20 - \
For water, the temperature range for which the surface tension is 10 - \
valid is as follows.
Temperature range 0" c-100" C u = 7 I .97
Temperature range 100°C-374.2" C u = 58.91.

Table C-8 in Appendix C lists the surface tension of organic Figure 3-8b Surface tension of water (H,O).
liquids, and Figures 3-8a and 3-8b show plots of surface tension
of monochlorobenzene (C,H,Cl) and water (H,O) respectively as
a function of temperature.

EXAMPLE 3-11 3.9 VAPOR PRESSURE

Determine the surface tension of methanol at a temperature of
350 K. Vapor pressure data, Pv, of pure components are important in
calculations relating to vapor-liquid phase equilibria, for example,
Solution in the simplest case to predict the pressure in a closed vessel
Substituting the correlation coefficients from Table C-8 in containing a specific liquid or mixture of liquids. The P, data
Appendix C and the temperature of 350 K into the correlation equa- are required for bubble point and most dew point computations.
tion gives These values are used in flash calculations involving mass-transfer
operations. Clearly the design of pressure requirements for storage
u = 68.329 (1 - &) 1.2222
equipment requires knowledge of the vapor pressure of the compo-
nents as does the design of appropriate pressure relief systems. The
= 16.79dynlcm vapor pressure of the saturated liquid as a function of temperature
is [2]:
Conversion
1 dyn = lo-, N
log,, P, = A + -BT + Clog,, T + DT + E T 2 (3-16)
110 PHYSICAL PROPERTIES OF LIQUIDS AND GASES

where
100,000
P, = vapor pressure, mm Hg
A, B. C, D , and E = regression coefficients for chemical
compound m 10,000
I
T =temperature, K. E
E 1,000
An equation often used to estimate the vapor pressure is the Antoine ?-
3
equation.
B
In P,, = A - __ (3-17)
T+C
The constants A. B, and C for many compounds are in the data
bank of some simulation design packages. Alternatively, these are I I I
I I
found in texts such as Reid et al. [6]. Equation (3-17) is only 0 50 100 150 200 250
applicable for pressures ranging from 10 to 1500mmHg (0.01 to Temperature, C
2 bar). The Antoine equation should never be used outside the stated
temperature limits, as extrapolation beyond these limits may lead Figure 3-9a Vapor pressure of n-pentane (C,H,?)
to incorrect results. The constants A, B , and C form a set, implying
that constants are never used from different tabulations.
Vapor pressures have been measured for many substances, and
when reliable measurements are available, they are preferred over
results from estimation methods. Boublik et al. [24] have compiled 1,000,000
tabulations of experimental data, and Yaws [25] has conducted
literature search involving both experimental and parameter values r" 100,000
c
of organic and inorganic compounds. Reid et al. [6] and Beaton and C I ! ! ! ! ! ! ! ! ! I #1 I
! ! !
! ! I 1
E ioooo
Hewitt [3] have discussed other methods in estimating vapor pres-
sure of compounds but none appears to offer any specific advan- E
2 1,000
tage. The Excel spreadsheet program from the companion website %
r I ! ! !.' ! ! ! ! ! ! , ! ! ' ! ! ! ! ,
(vapor-pressure.xls) calculates the vapor pressure of compounds
~

between the range of the minimum and the maximum temperatures,

denoted by Tmlnand T,,,. Table C-9 in Appendix C lists the vapor
pressure of compounds, and Figures 3-9a and 3-9b show plots of
vapor pressure of n-pentane (C,H,J and water as a function of
temperature respectively.

EXAMPLE 3-12 Figure 3-9b Vapor pressure of water

Calculate the vapor pressure of methylchloride (CH,Cl) at a
temperature of 410K. temperature. The enthalpy of vaporization data is used in process
calculations such as the design of relief systems involving volatile
Sol~itioa
compounds. In distillation, heat of vaporization values are needed
Substituting the regression coefficients from Table C-9 in Appendix
to find the heat loads for the reboiler and condenser, and knowledge
C and the temperature of 410K into the correlation equation gives
of the enthalpy of vaporization is required in the design of heat
exchangers for vaporizing liquids. A modified Watson equation
log,, P, = 25.7264+ (- 1.7503
410
x lo3)
for the enthalpy of vaporization as a function of temperature is as
follows.
+ (-6.7151) (log,,410) + (-1.2956
+ (4.4341 x (410')
x lo-') (410)
AH, = A (I - 5)" (3-18)

where where
log,, P, =4.6576 AH, = enthalpy of vaporization, kJ/mol
p, = 1016576
A. Tc, and n =regression coefficients for chemical
= 45,456.9mmHg. compound
T =temperature, K.

Many experimental values of AH, have shown from calculation

3.10 ENTHALPY OF VAPORIZATION
The enthalpy of vaporization, AH,, is also termed the "latent heat
of vaporization." And AH\ is the difference between the enthalpy
of the saturated vapor and that of the saturated liquid at the same
that AH, is related to the slope of the vapor pressure-temperature
curve. Majer and Svoboda [26] have provided a comprehensive and
critical compilation of experimental values of AH, measured for
organic compounds. Tamir et al. [27] have given further compi-
lations of heat of vaporization: however, it is often essential to
supplement data with results, calculated or extrapolated by some
 3.11 ENTHALPY OF FORMATION 111
If AH, < 0, then the chemical reaction is exothermic and cooling
is needed to maintain the reaction temperature. Alternatively, if
AH, > 0, the reaction is endothermic and heating is required to
C" conduct the chemical reaction. The correlation of enthalpy of forma-
.-0 tion for an ideal gas is based on a series expansion temperature and
w
I

.- is expressed by [2]:
8,
?{ AH, = A + BT+CT2 (3-20)
%a
-n
m
where
5
W AHf = enthalpy of formation of ideal gas, kJ/mol
A , B, and C =regression coefficients for chemical
compound
-200 -100 0 100 200 300 400 T = temperature, K.
Temperature, "C
The enthalpy of formation can also be found from measured heats
Figure 3-10 Enthalpy of vaporization of toluene (C,H,) of combustion, AH,, or from an experimental enthalpy of reaction,
AH,. Domalski and Herring [29] reviewed values of AH,,,,,, and
AH,,,,. for several hundreds of organic compounds. For organic
method. Majer et al. [28] present a comprehensive description of compounds, the range of application for the respective minimum
the many methods that have been used to determine AHv. and maximum temperatures are denoted by T,,, and T,, from
The Excel spreadsheet program from the companion website Table C-11 in Appendix C. The Excel spreadsheet program from the
(enthalpy-of-vaporization.xls) calculates the enthalpy of vaporiza- companion website (enthalpy-formation.xls) calculates the enthalpy
of formation of organic compounds. Figure 3-11 shows the plot
tion of compounds between the range of the minimum and the
for the enthalpy of formation of ethane (C2H,) as a function of
maximum temperatures, denoted by T,, and T,,,. Table C-10 in
temperature.
Appendix C lists the enthalpy of vaporization of compounds, and
Figure 3-10 shows the enthalpy of vaporization of toluene (C,H,)
as a function of temperature.
EXAMPLE
3-14
Determine the heat of formation of ethane (C,H,) as an ideal
EXAMPLE
3-13 gas at 500 K.
Calculate the enthalpy of vaporization of toluene (C,H,) at a
temperature of 400 K. Solution
Substituting the correlation coefficients from Table C- 11 in
Appendix C and the temperature of 500 K into the correlation equa-
Solution tion yields
Substituting the regression coefficients from Table C-10 in
Appendix C and the temperature at 400 K into the correlation equa- AH, = (-66.735) + (-6.9337 x (500)
tion yields
+ (3.0379 x (500)2
= -93.81 kJ/mol.
(
AH,, = (50.139) 1 - -
5;;;9)0'333
= 32.57 kJ/mol.

3.11 ENTHALPY OF FORMATION -0 2 0

.g -85
The enthalpy of formation (AH,) is defined as the enthalpy change Y
7

to form a species from chemical elements in their standard states $ -90

.-
by an isothermal reaction. In such a reaction scheme, the elements +-
m
are assumed initially to be at the reaction temperature at 1 atm, E -95
and in their most stable phase, for example, diatomic oxygen as an c
0
c
ideal gas and carbon as a solid in the form of P-graphite. Methods
of determining AHf are provided by Poling et al. [I]. -2 -loo
m
The enthalpy of formation AHf for individual compounds in
chemical reactions is required to determine the heat of reaction
AH, and associated heating and cooling requirements:
E -110 1
I
1
I
I
I
1
I
I
I
I
I
I
I 1
I I
Temperature, K

(3-19) Figure 3-11 Enthalpy of formation of ethane (C,H,)

112 PHYSICAL PROPERTIES OF LIQUIDS AND GASES
the following rough criteria are useful for quick screening of chem-
ical reactions:
EXAMPLE 3-15
AGr < 0 kJ/mol (reaction favorable)
Calculate the heat of the reaction for the dehydrogenation of (reaction possibly favorable)
0 < AG, < 50 kJ/mol
ethane to ethylene at a reaction temperature 860 K. AGr =. 50 kJ/mol (reaction not favorable).

The correlation for Gibbs energy of formation is

AG,=A+BT+CT~ (3-22)
Solution
The heat of the reaction may be determined from enthalpy of where
formation at 860 K for the products and reactants. Using regression
coefficients for ethane and ethylene from Table C- 11 in Appendix AGf = Gibbs energy of formation of ideal gas.
C. and the equation for enthalpy of formation, we obtain kJ/mol
A , B, and C =regression coefficients for chemical
compounds
= (-66.735)
AHf,C2H6 + (-6.9337 x (860) T = temperature, K.
+ (3.0379 x (860)*
The Excel spreadsheet program from the companion website
= -103.897kJ/mol (Gibbs-Energy-of-Formation.xls)calculates Gibbs energy of forma-
tion for a range of temperatures between minimum and maximum,
AHf,H2 = 0 as denoted by T,,, and T,, in Table C-12 in Appendix C.
= 63.053
AHf,C2H4 + (-4.1076 x lo-') (860) Figure 3-12 shows the plot for Gibbs free energy of formation of
ethanol (C,H,OH).
+ (1.6598 x lo-') (8602)
= 40.0kJ/mol.

Substituting AH, values at 860K into the equation for the heat of EXAMPLE 3-16
the reaction yields Calculate the Gibbs free energy of formation of ethylene
(C,H,) as a low pressure gas at 500 K.
AHTeaCtlon
=40+O- (-103.897)
Solution
= 143.89 kJ/mol. Correlation constants ( A , B, C) for ethylene from Table C-12 in
Appendix C are substituted into the equation at a temperature of
500 K.
> 0, the reaction is endothermic, and would require
Since AHreacrlon
heating to maintain the reaction temperature. AGY = 51.752+ (4.9338 x lo-*) (500)
+ (1.7284 x (500)*
= 80.74 kJ/mol.
3.12 GlBBS ENERGY OF FORMATION
Gibbs energy of formation is important in the analysis of chemical
reactions. Values for individual compounds (reactants and prod-
ucts) are required to determine the change in Gibbs energy for
the reaction. This change is significant because of the associated
chemical equilibrium for the reaction. The following criteria are
generally true for the feasibility of chemical reaction. If the change 0
in Gibbs energy is negative, the thermodynamics for the reaction
are favorable. However, if the change in Gibbs energy is highly
positive, the thermodynamics for the reaction are not favorable. The
chemical equilibrium for a reaction is associated with the change
in Gibbs free energy (AG,) for the reaction:

The changes in Gibbs energy for a reaction may be used in Temperature, K

preliminary work to determine if a reaction is thermodynamically
favorable at a given temperature. For thermodynamic equilibrium, Figure 3-12 Gibbs free energy of formation of ethanol (C2H,0H).
 3.13 SOLUBILITY IN WATER CONTAINING SALT 113

EXAMPLE 3-17
1,3-Butadiene is prepared by the gas phase catalytic dehydro- AG498 15,H2 =
genation of 1-butene AG& 15,C4H8 = (- 1.692) + (0.23442) (298.15)
C&g) -+ C'IH,(,) + H2 + (3.1582 x (298.15)'
Calculate the standard state Gibbs free energy of reaction at 298 K
= 71.007kJ/mol.
Solution
The change in Gibbs free energy of reaction may be deter-
Substituting AG, values into the equation for Gibbs free energy
mined from Gibbs free energy of formation for the products and
reactants. gives

A G ~ e a c t ~ ~=
n AGf,C4H6 + AGf,H2 - AGf,C,H8
= a G f . c 4 H 6 -I- AGf,H2 - AGf,C4Hg
AGreaCtiOn
Using correlation constants (A, B, and C) from Table C-12 in
Appendix C at a temperature of 298.15 K, we obtain AG,,,,,,,, = 150.5 + o - 71.007

AG& = 109.172+ (0.13296) (298.15) = 79.49 kJ/mol.

+ (1.9003 x lo-') (298.15)2

Since the change in Gibbs free energy for the reaction is AGf >
= 150.50kJ/mol. 50 kJ/mol, the thermodynamics for the reaction are unfavorable.

EXAMPLE 3-18 AG& ;5,CAH8 = (-1.692) + (0.23442) (900)

Calculate the Gibbs free energy for the gas phase catalytic
dehydrogenation of butane to butadiene at 900 K and 1 bar. + (3.1582 x (900)2
= 234.867kJ/mol.
Solution
Using correlation constants ( A , B, and C) from Table C-12 in Substituting AG, values into the equation for Gibbs free energy
Appendix C at a temperature of 900 K yields gives

AG&, 15,C4H6 = 109.172+ (0.13296) (900) = 244.228 + O - 234.867

AGIeactIOn

+ (1.9003 x (900)2 = 9.361 kJ/mol.

= 244.228 kJ/mol The result shows that by increasing the temperature to 900 K,
AGf < 50kJ/mol, and the thermodynamics for the reaction are
AG;98 15,H2 = favorable.

3.13 SOLUBILITY IN WATER CONTAINING SALT A , B, and C = correlation constants, and determined from
regression data of water solubility.
The solubility of hydrocarbons in water containing salt is intended
for initial engineering and environmental applications, such as the
distribution of a hydrocarbon spill upon its contact with sea water. The correlation constants from Table C-13 in Appendix C were
The correlation is based on a series expansion in salt concentration, determined from regression of the data from sources for water
and is expressed by [2] solubility. The tabulated values for solubility of hydrocarbons in
water apply to conditions of saturation in which the hydrocarbon
is in equilibrium with water. For saturation, the system pressure is
log,, S = A + BX +CX2 (3-23) approximately equal to the sum of the vapor pressures of hydro-
carbon and water. The correlation is applicable to a wide variety
of hydrocarbons (e.g., alkanes, naphthenes, and aromatics with no
where single and multiple substitutions). The Excel spreadsheet program
S = solubility in salt water at 25" C, parts per million by from the companion website (solubility-in-salt-water.xls) calculates
weight, ppm (wt) the solubility in salt water with the range of salt concentration
X = concentration of salt (NaCl) in water, parts per million between 0 and 35.000ppm (wt). Figure 3-13 shows the solubility
by weight, ppm (wt) of benzene in salt water.
114 PHYSICAL PROPERTIES OF LIQUIDS AND GASES

1- 7,000
p 1,800
E 1,600 6,000
8 1,400 5,000
$ 1.200
c
a
3 1,000
4,000
-
c

a
c
800
600
3,000
._ 2,000
5
._
-
.- 400
<- 200 1,000

$ 0 0
0 50,000 1,00,000 1,50,000 2,00,000 2,50,000 3,00,000 3,50,000 20 40 60 80 100 120 140
Salt concentration in water, ppm (wt) Temperature, O C

Figure 3-13 Solubility of benzene (C,H,) in salt water Figure 3-14 Solubility of benzene (C,H,) in water

EXAMPLE 3-20
EXAMPLE 3-19 Determine the solubility of hexane (C6HI4) in water at a
Calculate the solubility of pentane (C,HI2) in salt water with temperature of 370 K.
concentration of salt (NaCl) in water being 100,000ppm (wt).
Solution
Solution Substituting the correlation constants ( A , B, and C) from
Correlation constants ( A , B, and C) for pentane from Table C-13 in Table C- 14 in Appendix C for hexane into the equation at a temper-
Appendix C are substituted into the equation at salt concentration ature of 370 K gives
100,000ppm (wt):

+
log,, S = 1.5966 (-4.5956 x (100,000)
log,, S = 10.992 + (-5969.484)
370
+ (8.89453 x lo5)
3702

+ (2.2978 x (100,000)2 = 1.3553

s = 101.I6O s = 101.3553
= 14.5 = 22.66ppm (wt).

3.14 SOLUBILITY IN WATER AS A FUNCTION 3.15 HENRY'S LAW CONSTANT FOR GASES
OF TEMPERATURE IN WATER

The water solubility of hydrocarbons is applicable in air- and steam- Henry's law constant and the solubility of gases in water are impor-
stripping operations, within the temperature range of 25-121" C. tant parameters that affect health, safety, and environmental consid-
The correlation of water solubility of hydrocarbons is expressed erations in the chemical process industries. Very low concentrations
of gases in water can provide concentrations in air at the air-water
by PI:
interface that exceed the threshold limit value (TLV) for human
exposure, and the lower flammability limit (LFL) for flammability
log,, S = A + -BT + -
C
T2
(3-24) [301.

where HENRY'S LAW CONSTANT EQUATION

The correlation for Henry's law constant for gases in water as a
S = solubility in water, pprn (wt) function of temperature can be expressed by [3 11
T = temperature, K
A , B , and C = correlation constants.
loglo H = A + -BT + C log10 T + 0 7 (3-25)

The Excel spreadsheet program from the companion website where

(solubility-in-water.xls) calculates the water solubility of hydro-
carbons as a function of temperature. Table C-14 in Appendix H =Henry's law constant at pressure of 1 atm
C lists water solubility of organic compounds, and Figure 3-14 (101,325 @a), a t d m o l fraction
shows the plot of solubility of benzene in water as a function of A, B , C , and D = regression coefficients for gas
temperature. T = temperature, K.
 3.16 SOLUBILITY OF GASES IN WATER 115
The Excel spreadsheet program from the companion website
(Henry’s-law-constant.xls)calculates the Henry’s law constant for
the respective minimum and maximum temperatures denoted by Series 3 - Methane
T,, and Tmax.Table C-15 in Appendix C lists Henry’s Law
Constant for gases in water, and Figure 3-15 shows the variation 100,000
of Henry’s law constant with temperature of propane, ethylene,
methane, and propylene. These plots demonstrate that Henry’s law
constant increases with temperature.

10,000

EXAMPLE 3-21
Calculate the Henry’s Law constant of propylene (C3H,) in
water at a temperature of 320 K
1,000
Solution 0 10 20 30 40 50 60 70 80 90 100
Substituting the correlation constants ( A , B, C, and D ) for propy- Temperature, C
lene from Table C- 15 in Appendix C into the equation at a temper-
ature of 320 K gives Figure 3-15 Henry’s law constant of gases as a function of temperature.

log H = (-2570.0227) + (6.86740

320
x lo4)
3.16 SOLUBILITY OF GASES IN WATER
+ (1.03384 x IO3) (log 320) The correlation for the solubility of gases in water as a function of
temperature can be expressed by [311
+ (-0.719694) (320)
B
log,, H = 4.2057 log,, X W=
~ A + -
T
+ C logT+DT (3-26)
H = 104.2057
where
= 16058.3atm/mol fraction.
xwt = solubility in water at pressure of 1 atm
(101.325 Wa), weight fraction
A , B, C, and D = regression coefficients for gas
T = temperature, K.

EXAMPLE 3-22 (6.8674 x lo4)

Propylene (C,H6) is in contact with water at 25“ C (298.15 K) log,, H = (-2570.0227) + 298.125
and 1 atm in an industrial process. The concentration of propylene
in the liquid at the surface of the water is 15 ppm on a mol basis.
+ (1.03384 x IO3) (log 298.15)
Determine the concentration of propylene in the air at the surface + (-0.71964) (298.15)
of the water. H = 103.903946

= 8015.783 atm/mol fraction.

Solution
From the thermodynamics at low pressure, the partition coefficient
Ki is given by The partition coefficient Ki = ____ - 8015.783
8015.783 -
1.o
Since the vapor concentration is given by
Ki = H , / P ,
Y , = K,x,,
where substituting the value of K , and the liquid concentration
( x , = 15ppm) yields
Pt =total pressure, atm
Hi =Henry’s law constant, a t d m o l fraction at pressure of y , = (8015.783) (15)
1 atm.
= 120236.76ppm(mol)
Substituting the coefficients (A, B , C, and D ) from Table (1-15 in = 12.02%.
Appendix C and at a temperature of 298.15 K into the correlation
equation gives
 Next Page

116 PHYSICAL PROPERTIES OF LIQUIDS AND GASES

water solubility of sulfur compounds based on the boiling point is
expressed by [31]
log,, S = A + BT, + CT; + DT; (3-27)
0.0005
0.00045 where
h

Ecn
0.0004
._ S =solubility in water at 25" C, ppm (wt)
0.00035
B TB=boiling point of compound, K.
0.0003
2 0.00025 Estimation of solubility of hydrocarbons and organic oxygen
5
._ 0.0002 compounds is dependent on the following regression coefficients.
0.00015
-0 00001 A = -6.9000 (mercaptans)
CT)
0.00005 A = -6.8500 (thiophenes)
0
A = -6.5389 (sulfides)
0 20 40 60 80 100 120 B = +1.005 x lo-'
Temperature, C C = -2.7288 x lo-'
D = $1.9987 x
Figure 3-16 Solubilities of selected gases in water as a function of
temperature. The correlation constants A , B , C. and D apply to mercaptans.
thiophenes, and sulfides in water, with the range for boiling point
between 310 and 600 K. The regression coefficients for estimating
The Excel spreadsheet program from the companion website the solubility of hydrocarbons and organic oxygen compounds
(Henry's-law-constant.xls)calculates the solubility of gases in are listed in Table C-17 in Appendix C. The Excel spreadsheet
water between the range of the minimum and the maximum temper- program from the companion website (solubility-of-sulfur-compds-
atures, denoted by T,,, and T,,, in Table C-16 in Appendix C. in-water.xls) calculates the solubility of sulfur compounds in water.
Figure 3-16 shows the variation of water solubility with temper- Figures 3-17a and 3-17b show plots of solubility of sulfur and
ature for ethylene, propane, methane, and propylene. These plots aromatic compounds as a function of boiling point.
show that solubility decreases with temperature.

EXAMPLE 3-24
EXAMPLE 3-23 Determine the solubility of ethyl mercaptans (C,H,S) in water
Calculate the concentration of propylene (C,H,) in water at a at a saturation temperature of 308.15 K.
temperature of 360 K and 1 atm.
Solution
Solcctioiz Substituting the regression coefficients (A, B , C. and D ) mentioned
Substituting the coefficients (A, B , C , and D ) from Table C-16 in above and the boiling point of 308.15 K into the correlation equation
Appendix C. and at a temperature at 360K into the correlation yields
equation yields

x IO2)
10g,o S = (-6.9) + (O.lO05 x 308.15)
log,, ,xwT = (-39.4402) + (6.34551
360 + (-2.7288 x IO-' x 308.15')
+ (1.7542 x 10 x log 360) + (1.9987 x lo-' x 308.15')
+ (-3.24155 x (360) s = 104 0057
= 10132ppm (wt),
= 31.29ppm(wt).

3.17 SOLUBILITY AND HENRY'S LAW CONSTANT
FOR SULFUR COMPOUNDS IN WATER
Sulfur emissions are important safety, health, and environmental
concerns in the chemical process industries. As part of a compre-
hensive national program to reduce emissions from non-road diesel
engines. the U S . Environmental Protection Agency (EPA) has
embarked on a program to further reduce the currently allowable
level of sulfur in non-road diesel fuel by more than 99%. At low
levels. sulfur can yield concentrations in air at the air-water inter-
face that either exceed the TLV for human exposure, the lower
explosion limit (LEL) for flammability, or both. A correlation of
3.18 SOLUBILITY OF NAPHTHENES IN WATER
Naphthenes (e.&.,cycloalkanes) are a major component of unrefined
fuels. Like other hydrocarbons such as paraffins and aromatics,
solubility in water is essential in view of the environmental hazard
they present when spilled in water. The correlation of naphthenes'
water solubility as a function of temperature can be expressed by
Eq. 3-24 [31].
Table C-18 in Appendix C lists the correlation constants
and solubilities of naphthenes at 25 and 100°C. The Excel
spreadsheet program from the companion website (solubility-
of-naphthene-compds-in-water.xls)calculates the solubility of