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+
=
2
T T
b
c
567 . 0
T
T (3)
T
is the contribution of each functional group to the critical temperature. The values of
T
for each
group is given in Table 1 in section 9.1
Chemical Engineering 317: Additional Notes Properties of Compounds Page 5 of 34
Example: Estimate the critical temperature of cyclohexanol using Lydersens method
OH
T
b
= 434.3 K
T
= 5 * (-CH
2
- cyclic) + (
/
\
C cyclic) + (-OH alcohol)
= 5 * 0.013 + 0.012 + 0.082
= 0.159
From equation 3:
[ ]
K 620
0159 . 159 . 0 567 . 0
3 . 434
T
2
c
=
+
=
The published experimental value is 625 K (Reid and Prausnitz).
The error in the value is thus 1 %
Constantinou and Gani proposed a group contribution method that takes into account both the
structural groups (first order) as well as structural isomerisation (second order). As the second order
contributions are quite complicated, only the first order contributions will be discussed here (For more
accurate predictions, the second order contributions can be considered consult the original article
[1]). The critical temperature can be calculated as follows:
Constantinou and Gani
( )
=
ci
c
nT ln
128 . 181
T
(4)
Where n is the number of functional groups (i) present and T
ci
the contribution of group (i) present. The
values of T
ci
are given in Table 2 in section 9.2.
Example: Estimate the critical temperature of cyclohexane using the method of Constantiou and Gani
There are 5 CH
2
groups, i.e. 5 * 3.4920 = 17.460
There is 1
/
\
C group, i.e. 4.0330
There is 1 OH group, i.e. 9.7292
Therefore the right hand side of equation 4 is 31.2222.
Solving T
c
, the critical temperature is 623 K.
The error less than 0.5 %.
Critical pressure
The critical pressure of organics can be estimated according to the method of Lydersen:
Lydersen:
( )
) Pa (
34 . 0
MW 101325
P
2
p
c
+
= (5)
p
it the contribution of the functional group to the critical pressure and MW is the molar weight in
g/mol. The values of
p
for each group is given in Table 1 in section 9.1.
Chemical Engineering 317: Additional Notes Properties of Compounds Page 6 of 34
Example: Estimate the critical pressure of fluorotrichloromethane according to the method of Lydersen
M = 137.38 g/mol
P
= (Fluoro) + 3 * (Chloro) + (Quatro subst. Carbon)
= 0.224 + 3 * 0.320 + 0.210 = 1.394
From equation 5:
( )
MPa 63 . 4
394 . 1 34 . 0
38 . 137 101325
P
2
c
=
+
=
The published experimental value is 4.41 MPa (Reid and Prausnitz).
The error is thus 5 %
Constantinou and Gani proposed a method to estimate the critical pressure, similar to their method of
estimating the critical temperature:
Constantinou and Gani
) bar ( P n 100220 . 0
3075 . 1 P
1
ci
c
(6)
P
ci
is the contribution of the functional group (i) to the critical pressure and n is the number of groups
(i) present. The values of P
ci
are given in Table 2 in section 9.2.
Example: Estimate the critical pressure of n-butanol according to the method of Constantinou and
Gani
There is 1 OH group, i.e. 0.005148
There are 3 CH
2
groups, i.e. 3 * 0.010558
There is 1 CH
3
group, i.e. 0.019904
The right hand side of equation 6 is 0.056726.
Solving for P
c
the critical pressure is 41.9 bar.
The published value is 44.2 bar (Reid and Prausnitz).
The error is thus 5 %.
The method of Constantinou and Gani, as used, only takes first order interactions into account.
Greater accuracy can be obtained if second order interactions are taken into account, yet, as
previously mentioned, this is beyond the scope of this course.
Critical volume
Methods to calculate the critical volume are similar to those calculating the critical pressure and
temperature. Fedors proposed a method for pure organic compounds:
Fedors
|
\
|
+ =
kmol
m
0266 . 0 v
3
v c
(7)
v
is the contribution of the functional group to the critical volume. The values if
v
is given in Table 4
in section 9.1
Chemical Engineering 317: Additional Notes Properties of Compounds Page 7 of 34
Example: Estimate the critical volume of 2-butanol according to the method of Fedors
The molecular formula is C
4
H
10
O. Therefore:
v
= 4 * (carbon atom) + 10 * (hydrogen atom) + (oxygen atom)
= 4 * 0.034426 + 10 * 0.009172 + 0.018000
= 0.2474
v
c
= 0.0266 + 0.2474 = 0.2740 m
3
/mol.
The published experimental value is 0.2690 m
3
/mol (Perry).
The error is thus 2 %.
Other methods, similar to those shown for the critical temperature and pressure also exist and have
similar accuracy.
Critical properties of mixtures
The critical properties of mixtures are often calculated as the molar average value of the individual
values. For example, the critical temperature of a mixture can be calculated as follows:
= ) n ( T x ) mixture ( T
c c
(8)
Please note that x is the MOLE fraction and T
c
(n) is the critical temperature of pure compound n.
Example: Estimate the critical pressure and temperature of LPG
Composition (mol%): propane = 70 %, iso-butane = 20 %, n-butane = 10 %
Pure component critical temperature:
propane = 369.8 K, iso-butane = 408.2 K, n-butane = 425.2 K
T
c
(LPG) = 0.7 * 369.8 + 0.2 * 408.2 + 0.1 * 425.2 = 383.0 K
Pure component critical pressure:
propane = 42.5 bar, iso-butane = 36.5 bar, n-butane = 38.0 bar
P
c
(LPG) = 0.7 * 42.5 + 0.2 * 36.5 + 0.1 * 38.0 = 40.9 bar
2.2 Normal boiling point
The boiling point is defined as the temperature at which the vapour pressure of the liquid is equal to
the pressure of one atmosphere on the liquid i.e. the temperature at which the vapour pressure is
101325 Pa. However, if two values of vapour pressure close to 1 atm are available, the normal boiling
point can be interpolated or extrapolated. This is discussed in more detail in the section on vapour
pressures.
The normal boiling point is often published together with critical constants. Good sources for the
normal boiling point include:
Perrys Chemical Engineers Handbook, 7
th
Ed. Chapter 2
Properties of Gases and Liquids 4
th
Ed., Appendix A (p 568 et seq.)
CRC Handbook of Physics and Chemistry, Chapter 3 and Chapter 6
In addition, some suppliers of fine chemicals, such as Sigma-Aldrich, often give the melting points of
their compounds in their catalogues. Caution should be exercised when using values from older
sources since the temperatures were often reported at prevailing conditions (0.95 0.97 atm).
Chemical Engineering 317: Additional Notes Properties of Compounds Page 8 of 34
A number of correlations exist linking the critical temperature and the normal boiling point. Some of
these relationships have been discussed in section 2.1 and should the critical temperature be
available, the normal boiling point can be determined.
The normal boiling point can also be determined from the vapour pressure curve by setting the
pressure equal to 101325 Pa and solving the temperature. The vapour pressure curve is discussed in
section 3.
Steil and Thodos proposed a method to calculate the boiling points of normal hydrocarbons:
Steil and Thodos
( )
) K (
N 0742 . 0 1
1163
1209 T
85 . 0
b
+
= (9)
Where N is the number of carbon atoms in the compound.
Example: Normal boiling point of decane (10 carbon atoms) according to the method of Steil and
Thodos
( )
K 446
10 0742 . 0 1
1163
1209 T
85 . 0
b
=
+
=
The experimental value is 447.3 K (Reid and Prausnitz).
The error is thus less than 0.5 %.
The accuracy of correlations such as those of Steil and Thodos are quite good but, as is the case with
the correlation of Steil and Thodos, these types of correlations are often limited to a few compounds.
A number of group contribution methods exist to predict the normal boiling point. Constantinou and
Gani also proposed such a group contribution method, this method being very similar to the ones for
estimating the critical temperature and the critical pressure. The normal boiling point can be estimated
as follows:
Constantinou and Gani
( )
=
bi
b
T n ln
359 . 204
T
(10)
Where T
bi
is the contribution of the functional group (i) and n the number of groups (i) present. The
values of T
bi
are given in Table 2 in section 9.2.
Example: Estimate the normal boiling point of octanoic acid according to the method of Constantinou
and Gani
There 1 CH
3
groups, i.e. 0.8894
There is 6 CH
2
group, i.e. 6 * 0.9225
There is 1 COOH group, i.e. 5.8337
The right hand side of equation 10 is thus 12.2581.
Solving for T
b
in equation 10 the normal boiling point is 512 K.
The published experimental value is 512 K !
2.3 Acentric factor
The acentric factor () is a measure of the shape of a molecule, though it also measures its polarity.
The acentric factor is often used as a parameter in equations of state, hence its importance in
thermodynamics and chemical engineering. By definition, the acentric factor is calculated from the
reduced pressure at a reduced temperature of 0.7:
Chemical Engineering 317: Additional Notes Properties of Compounds Page 9 of 34
( ) ) ensionless (dim 000 . 1 P log
7 . 0 T
sat
r
r
=
=
(11)
Critical pressures and temperatures are estimated according to the aforementioned methods. The
vapour pressure can be predicted according to the methods set out below or obtained experimentally.
For small, spherical molecules the acentric factor is essentially zero and it increases as branching,
molecular weight and polarity increases. For mixtures, the acentric factor is usually taken as the
simple molar average value of the compounds in the mixture:
=
=
n
1 i
i i
x (12)
Example: Calculate the acentric factor of the LPG mixture given above
Composition (mol%): propane = 70 %, iso-butane = 20 %, n-butane = 10 %
Pure component acentric factors:
propane = 0.153, iso-butane = 0.183, n-butane = 0.199
(LPG) = 0.7 * 0.153 + 0.2 * 0.183 + 0.1 * 0.199 = 0.164
The acentric factor is usually published together with the critical constants of a compound.
3 VAPOUR PRESSURE OF LIQUIDS
The vapour pressure at a set temperature is the pressure exerted by a pure component at equilibrium
at this temperature when both liquid and vapour phases exist. The vapour pressure is a continuous
function of temperature and the vapour pressure curve extends from the triple point to the critical
point.
Vapour pressures have been measured extensively, usually as part of thermophysical data of a
compound. Perrys Chemical Engineers Handbook contains a large amount of the thermophysical
data. Another useful source of vapour pressure data is the NIST website. (See section 6).
If the natural logarithm of the vapour pressure (ln(P
sat
)) is plotted as a function of the reciprocal of
temperature (1/T) the relationship is often linear over a limited temperature range. This is shown in
Figure 2.
Chemical Engineering 317: Additional Notes Properties of Compounds Page 10 of 34
-12
-10
-8
-6
-4
-2
0
2
4
6
0.000 0.004 0.008 0.012 0.016
1/T (1/K)
l
n
(
P
s
a
t
)
(
l
n
(
b
a
r
)
)
Ethane
Hexane
Methane
Nitrogen
Water
Figure 2: Relationship between 1/T and ln(P
sat
) for ethane, hexane, methane, nitrogen and water
(Data from NIST Website)
If a linear relationship between ln(P
sat
) and 1/T is assumed, the vapour pressure curve can be
expressed as follows:
( ) c
T
1
m P ln
sat
+ = (13)
This is probably the simplest method for predicting the vapour pressure or for interpolating (and to a
limited extent extrapolating) values. If two values on the vapour pressure curve are know, this method
can be used. Referring to equation 13:
( ) ( )
2 1
sat
2
sat
1
T
1
T
1
P ln P ln
m
= (14)
( )
1
sat
1
T
1
m P ln c = (15)
Using equations 14 and 15, equation 13 can now be used to determine the vapour pressure.
Chemical Engineering 317: Additional Notes Properties of Compounds Page 11 of 34
Example: Estimate the vapour pressure of propane at 0
o
C by interpolating between two values
Given: T
b
= 231.03 K, P
sat
(300.00 K) = 9.9780 bar
At normal boiling point (Conditions 1): ( )
sat
1
P ln = 11.526 and 1/T
1
= 0.004328
At 300.1 K (Conditions 2): ( )
sat
2
P ln = 13.813 and 1/T
2
= 0.003333
2298
003333 . 0 004328 . 0
813 . 13 526 . 11
m =
=
474 . 21 004328 . 0 ) 2298 ( 526 . 11 c = =
Therefore: ( ) 474 . 21
T
1
2298 P ln
sat
+ = , T in K, P in Pa
At 0
o
C, i.e. 273.15 K:
( ) 06 . 13 474 . 21
15 . 273
1
2298 P ln
sat
= + =
P
sat
= 469863 Pa = 4.70 bar.
The NIST website gives the value as 4.75 bar.
The error is thus less than 1.3 %
The Antoine equation is based on the same concept, yet due to the introduction of an additional
parameter is more accurate:
Antoine
( )
C T
B
A P ln
sat
+
+ = (16)
A, B and C are regression constants and are unique to each compound. Table 5 in section 9.4 lists the
parameters for some compounds.
Example: Estimate the vapour pressure of carbon tetrachloride at 37
o
C using the Antoine equation
For carbon tetrachloride with P in mmHg and T in K:
A = 15.8742
B = -2808.19
C = -45.99
At 37
o
C (308 K)
( ) 2375 . 5
99 . 45 310
19 . 2808
8742 . 15 P ln
sat
=
=
Therefore P
sat
= 188.2 mmHg 25.1 kPa
The experimental value is 25.1 kPa !
However, the Antoine equation does not fit the data accurately much above the normal boiling point.
More accurate regression equations are required. These functions usually express the natural
logarithm of the vapour pressure as a function of temperature. Different sources use different
equations. Reid and Prausnitz use three correlations to estimate vapour pressure data for more than
500 compounds. The vapour pressure of these compounds can be expressed by one of three
equations:
Reid and Prausnitz Equation 1
( ) 1 x
Dx Cx Bx Ax
P
P
ln
6 3 5 . 1
c
sat
+ + +
=
|
|
\
|
(17)
where
c
T
T
1 x = (18)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 12 of 34
Reid and Prausnitz Equation 2
( ) ( )
2
sat
sat
T
P D
T ln C
T
B
A P ln
+ + = (19)
Reid and Prausnitz 3
( )
C T
B
A P ln
sat
+
= (20)
The values of A, B and C are given in Properties of Gases and Liquids by Reid and Prausnitz (On
reserve in the Library). The correlations use T in K and P
sat
in bar.
Equation 3 (equation 20) is in essence the Antoine equation. (See above for example). In equation 1
the pressure is calculated explicitly as a complex function of temperature. On the other hand, equation
2 needs to be solved iteratively. Examples of both equations 1 and 2 follow:
Example: Plot the vapour pressure curve from 260 to 430 K for 2,2-Dimethyl-propane using the
correlation in Reid and Prausnitz
Correlation 1: A = -6.89153, B = 1.25019, C = -2.28233, D = -4.74891
Tc = 433.8 K, Pc = 32.0 bar
Using the above the vapour pressure was calculate and plotted: ln(Psat) is
plotted as a function of 1/T and compared to data from the NIST website:
-1
-0.5
0
0.5
1
1.5
2
2.5
3
3.5
0.002 0.0025 0.003 0.0035 0.004
1/T with T in K
l
n
(
P
s
a
t
)
w
i
t
h
P
s
a
t
i
n
b
a
r
Reid and Prausnitz
NIST data
As seen, the data generated with the correlation by Reid and Prausnitz
agrees very well with the data on the NIST website
Chemical Engineering 317: Additional Notes Properties of Compounds Page 13 of 34
Example: Estimate the vapour pressure of trichlorofluoromethane at 400 K using the correlation
published in Reid and Prausnitz
Correlation 2:
A = 42.089, B = 4464.14, C = -4.753, D = 2138 (P in bar, T in K)
T
c
= 471.2 K, P
c
= 44.1 bar
For 400 K:
P guess LHS RHS Ratio Change
20 2.9957 2.7185 1.1020 Increase Guess
25 3.2189 2.7853 1.1557 Decrease Guess
15 2.7081 2.6517 1.0213 Decrease Guess
14 2.6391 2.6383 1.0003 Decrease Guess
13.9 2.6319 2.6370 0.9981 Increase Guess
13.95 2.6355 2.6376 0.9992 Increase Guess
13.98 2.6376 2.6380 0.9998 Increase Guess
13.99 2.6383 2.6382 1.0001 Close enough
The NIST website gives the value as 14.074 bar.
The accuracy is thus 0.6 %.
Perry published a similar correlation for over 230 compounds:
Perry
( ) ( )
5
C
4 3
2
1
sat
T C T ln C
T
C
C P ln + + + = (21)
The values of C
1
, C
2
, C
3
, C
4
and C
5
are given by Perry (page 2-50 2-54 in Table 2-6, 7
th
Edition).
The correlations use T in K and P in Pa.
Example: Plot the vapour pressure curve of hydrogen sulphide between 200 and 350 K using the
correlation in Perry
Parameters: C
1
= 85.584, C
2
= -3839.9, C
3
= -11.199, C
4
= 0.018848, C
5
= 1
Using the above the vapour pressure was calculate and plotted: ln(Psat) is
plotted as a function of 1/T and compared to data from the NIST website:
10
11
12
13
14
15
16
0.0025 0.003 0.0035 0.004 0.0045 0.005
1/T (T in K)
l
n
(
P
s
a
t
)
(
P
s
a
t
i
n
P
a
)
Perry
NIST
As seen, the data generated with the correlation by Perry agrees very well
with the data on the NIST website
The above methods all estimate the vapour pressure by correlating experimental values and fitting
them to a mathematical expression. Lee and Kesler proposed a method to estimate the vapour
Chemical Engineering 317: Additional Notes Properties of Compounds Page 14 of 34
pressure using only the critical temperature and pressure and the acentric factor of the compound as
parameters.
( )
( )
( )
( ) 1
sat
r
0
sat
r
sat
r
P ln P ln P ln + = (22)
Where
( )
( )
6
r r
r
0
sat
r
T 169347 . 0 T ln 28862 . 1
T
09648 . 6
92714 . 5 P ln + = (23)
( )
( )
6
r r
r
1
sat
r
T 43577 . 0 T ln 4721 . 13
T
6875 . 15
2518 . 15 P ln + = (24)
This method can be applied at reduced temperatures above 0.3 or above the melting point, whichever
is higher and below the critical point and is most reliable between reduced temperatures of 0.5 and
0.95.
Example: Estimate the vapour pressure of 1-butene at 98
o
C
Pure component parameters: T
c
= 146.4
o
C, P
c
= 4.02 MPa, = 0.1867
( )
( )
885 . 0
5 . 419
1 . 371
1 . 273 4 . 146
1 . 273 98
T
r
= =
+
+
=
From equation 23:
( )
( )
7227 . 0
885 . 0 169347 . 0 885 . 0 ln 28862 . 1
885 . 0
09648 . 6
92714 . 5 P ln
6
0
sat
r
=
+ =
From equation 24:
( )
( )
6190 . 0
885 . 0 43577 . 0 885 . 0 ln 4721 . 13
885 . 0
6875 . 15
2518 . 15 P ln
6
1
sat
r
=
+ =
From equation 22:
( ) 8383 . 0 6190 . 0 1867 . 0 7227 . 0 P ln
sat
r
= + =
4325 . 0 P
sat
r
=
MPa 74 . 1 02 . 4 4325 . 0
P P P
c
sat
r
sat
= =
=
Perry gives an experimental value of 1.72 MPa.
The error is thus 1.2 %
4 THERMAL PROPERTIES
4.1 Heat capacity / enthalpy
Heat capacity is defined as the amount of energy required to change the temperature of a unit of mass
or mole by one degree. Typical units include J/mol.K and J/kg.K. Heat capacity is usually given either
at constant pressure (C
p
) or at constant volume (C
v
). Although heat capacity at constant volume is
sometimes used, most engineering applications use heat capacity at constant pressure and we will
thus focus on heat capacity at constant pressure.
In thermodynamics and in heat transfer the heat capacity is often used as a function of temperature in
the definition of enthalpy:
dh = C
p
dT (25)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 15 of 34
It is thus very useful if the heat capacity is expressed as a function of temperature.
A number of literature sources publish correlations which can be used to determine the heat capacity.
These sources include but are not limited to:
Perrys Chemical Engineers Handbook, 7
th
Edition, Chapter 2
Properties of Gases and Liquids 4
th
Edition, Appendix A
Basic Principles and Calculations in Chemical Engineering, 6
th
Edition
JANNAF Tables
When using such correlations, one needs to take note of the phase that the correlation refers to as
well as the temperature limits of the correlation.
There are also a number of sources that publish values of the heat capacity and / or enthalpy at
specific temperatures and pressures. The sources include but are not limited to:
Steam Tables
Perrys Chemical Engineers Handbook, 7
th
Edition, Chapter 2
This section focuses on energy changes without phase changes. For the energy associated with
phase changes, please see section 4.2.
Vapour heat capacity at constant pressure
Harrison and Seaton proposed a method, valid from 300 to 1500 K, to calculate the heat capacity of
an ideal gas based in the type and number of atoms in the molecule:
Harrison and Seaton
Other 15 P 14 B 13 Al 12 Si 11 Br 10
I 9 Cl 8 F 7 S 6 N 5 O 4 H 3 C 2 1
ig
p
n a n a n a n a n a n a
n a n a n a n a n a n a n a n a a ) mol / J ( C
+ + + + + +
+ + + + + + + + =
(26)
Where a
1
to a
15
are constant parameters (See section 1.1 in Table 6) and n
i
are the number of atoms
of type i.
Example: Estimate the ideal gas heat capacity of acetone (C
3
H
6
O) at 600 K
ig
p
C =-4.61 + 17.5 * 3 + 10.5 * 6 + 17.5 * 1 = 128 J/mol.K
Daubert et al. reported the experimental value as 121.8 J/mol.K.
The error is thus 5.5 %
However, the method of Harrison and Seaton is limited to ideal gases and does not provide the heat
capacity as an explicit function of temperature. Rihani and Doraiswamy suggested a group
contribution method to determine the heat capacity of vapours as a function of temperature. The heat
capacity has the following temperature functionality:
3 2
p
dT cT bT a C + + + = (27)
Where the parameters a, b, c and d are calculated by a group contribution method:
a n a
i
= (28)
b n b
i
= (29)
=
i
c n c (30)
=
i
d n d (31)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 16 of 34
The group contribution parameters of a
i
, b
i
, c
i
and d
i
are given in Table 7 to Table 12 in section 1.1 for
the unit cal/mol.K. Note the units and that the values are often multiplied by a power of 10 to give
reasonable values in the table.
Example: The vapour heat capacity of 3-methyl-1,2-butaniene as a function of temperature and at 300
K according to the method of Rihani and Doraiswamy
Molecular structure:
C H
2
C C
CH
3
CH
3
There is one
/
\ 3
C C C H = = group and two CH
3
groups.
Therefore
a = 2 * 0.6087 + 2.6308 = 3.8483
b = 2 * 2.1433E-2 + 4.1658E-2 = 8.4524E-2
c = 2 * (-0.0852)E-4 + (-0.2845)E-4 = -0.4549E-4
d = 2 * 0.001135E-6 + 0.007277E-6 = 0.009547E-6
The temperature dependent heat capacity correlation is thus:
3 8 2 4
p
T 10 9547 . 0 T 10 4549 . 0 T 084524 . 0 8483 . 3 C
+ + = (cal/mol.K)
Using the correlation above the heat capacity at 300 K is estimated to be
25.37 cal/mol.K. The literature value (Weast) is 25.3 cal/mol.K. The error is
thus 0.3 %
Liquid heat capacity at constant pressure
Shaw proposed a group contribution method to estimate the liquid heat capacity at constant pressure
at 25
o
C:
Shaw
=
pi p
nC C (32)
Where C
pi
is the contribution of functional group (i) and n the number of groups (i) present. The values
of C
pi
are given in Table 13 in section 9.7.
Example: Estimate the heat capacity of hexane and heptane at 298.15 K using the method of Shaw
Hexane:
Two CH
3
groups, i.e. 8.80 * 2 = 17.60
Four CH
2
groups, i.e. 7.26 * 4 = 29.04
C
p
= 17.60 + 29.04 = 46.6 cal/mol.K
This NIST website gives the value as 46.379 cal/mol.K
The error is thus 0.5 %
Heptane:
Two CH
3
groups, i.e. 8.80 * 2 = 17.60
Four CH
2
groups, i.e. 7.26 * 5 = 36.30
C
p
= 17.60 + 36.30 = 53.9 cal/mol.K
This NIST website gives the value as 53.657 cal/mol.K
The error is thus 0.5 %
The method of Shaw, although simple and quite accurate is limited to 25
o
C. Rika and Domalski
proposed a group contribution method that is able to express the heat capacity of liquids as a second
order polynomial function of temperature. The method is applicable between the melting temperature
Chemical Engineering 317: Additional Notes Properties of Compounds Page 17 of 34
and the normal boiling temperature yet extrapolation of up to 80 K beyond the range has no
considerable effect.
Rika and Domalski
2
p
100
T
d
100
T
b a
R
C
|
\
|
+ + = (33)
Where the parameters a, b and d are calculated by a group contribution method:
a n a
i
= (34)
b n b
i
= (35)
=
i
d n d (36)
The temperature is in K and the unit of C
p
then depends in the unit of R. The values of a
i
, b
i
and d
i
for
linear aliphatic and aromatics hydrocarbons are given in Table 14 in section 9.8. Parameters for
halogen, nitrogen, oxygen and sulphur groups are given in Table 15 in section 9.8. The method can be
extended to include second order interactions. This is beyond the scope of this course. (If required,
please consult the original texts [2,3].)
Example: Determine a temperature dependent correlation for the heat capacity of hexane and
estimate the heat capacity at 298.15 K
There are two CH
3
groups:
a
CH3
= 3.8452 * 2 = 7.6904
b
CH3
= -0.33997 * 2 = -0.67994
d
CH3
= 0.19489 * 2 = 0.38979
There are four CH
2
groups:
a
CH2
= 2.7972 * 4 = 11.1888
b
CH2
= -0.054967 * 4 = -0.219868
d
CH2
= 0.10697 * 4 = 0.42788
Therefore for hexane:
2
p
100
T
81767 . 0
100
T
89981 . 0 879 . 18
R
C
|
\
|
+ =
K . mol
J
100
T
81767 . 0
100
T
89981 . 0 879 . 18 314 . 8 C
2
p
(
(
\
|
+ =
At 298.15 K:
K . mol
J
1 . 195
100
15 . 298
81767 . 0
100
15 . 298
89981 . 0 879 . 18 314 . 8 C
2
p
=
(
(
\
|
+ =
The NIST website gives a value of 194.0 J/mol.K
The error is thus 0.5 %
Heat capacity of mixtures
As a first approximation the heat capacity of mixtures can be approximated by calculating the molar
average of the constituent compounds:
=
=
n
1 i
pi i p
) T ( C x ) T ( C (37)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 18 of 34
This method works similar to the above discussed group contribution methods yet does not take
enthalpy of mixing into account. For accurate approximations, the enthalpy of mixing needs to be
incorporated.
4.2 Enthalpy of phase changes
When a substance changes phase, the enthalpy of the substance changes. This section concerns
itself with the energy associated with phase changes.
Enthalpy (heat) of vapourisation (liquid to vapour)
The enthalpy of vapourisation (h
vap
) is defined as the difference in the enthalpies of a unit of mole or
mass of a saturated vapour and a saturated liquid of a pure component. Basically, the enthalpy of
vapourisation is the energy required to vapourise a unit of mole or mass at the said temperature.
Similarly, the enthalpy of vapourisation is the amount of energy released when a unit mole or mass is
condensed at the said temperature.
Enthalpies of vapourisation are often published together with saturated enthalpies in sources such as
the steam tables and Perry.
Pitzer et al. proposed a method based in the corresponding states approach that only requires the
critical temperature and acentric factor:
Pitzer et al.
( ) ( )
456 . 0
r
354 . 0
r
c
vap
T 1 95 . 10 T 1 08 . 7
RT
h
+ =
(38)
Example: Estimate the enthalpy of vapourisation for propionaldehyde at 350 K using the method of
Pitzer et al.
T
c
= 504.4 therefore T
r
= 0.6939, = 0.2559
From equation 38:
( ) ( ) 289 . 6 6993 . 0 1 2559 . 0 95 . 10 6939 . 0 1 08 . 7
RT
h
456 . 0 354 . 0
c
vap
= + =
Thus:
h
vap
= 6.289 * 8.314 * 504.4 = 2.64 E4 J/mol 26.4 J/kmol
The experimental value is 26.85 (Perry) and the error is thus less than 2 %
Riedel proposed a method of estimating the enthalpy of vapourisation at the normal boiling point:
Reidel
(
(
(
(
(
|
|
\
|
=
c
b
c
c
b
c b , vap
T
T
930 . 0
1
325 . 101
P
ln
T
T
T R 039 . 1 h (39)
In equation 39, the critical pressure is in kPa and the critical temperature in K.
Chemical Engineering 317: Additional Notes Properties of Compounds Page 19 of 34
Example: Estimate the heat of vapourisation at the normal boiling point for ethyl acetate using the
method of Reidel
T
c
= 523.3 K, T
b
= 350.2 K, P
c
= 3880 kPa
Therefore:
mol / kJ 28 . 32 mol / J 4 E 228 . 3
3 . 523
2 . 350
930 . 0
1
325 . 101
3880
ln
3 . 523
2 . 350
3 . 523 314 . 8 039 . 1 h
b , vap
= =
(
(
(
(
\
|
=
The experimental value is 32.23 kJ/mol (Perry).
The error is thus 0.16 %
Constantinou and Gani proposed a group contribution method to calculate the enthalpy of
vapourisation at 298 K:
Constantinou and Gani
+ =
vi K 298 , vap
h n 892 . 6 h (kJ/mol) (40)
Where n is the number of functional groups (i) present and h
vi
the contribution of groups (i) present.
The values of h
vi
are given in 9.2 in Table 3.
Example: Estimate the enthalpy of vapourisation of methanol at 298 K according to the method of
Constantinou and Gani
There is one CH
3
group, i.e. 4.116
There is one OH group, i.e. 24.529
Using equation 40:
537 . 35 529 . 24 116 . 4 892 . 6 h
K 298 , vap
= + + = kJ/mol
The NIST website gives the value as 37.466 kJ/mol.
The error is thus 5 %
The enthalpy of vapourisation decreases with temperature and is zero at the critical point. If the value
of the enthalpy of vapourisation is know at one point, the method of Watson can be used to describe
the enthalpy of vapourisation at any other temperature:
Watson
38 . 0
2 , r
1 , r
1 , vap 2 , vap
T 1
T 1
h h
|
|
\
|
= (41)
Example: Estimate the enthalpy of vapourisation for ethyl acetate at 450.0 K using the normal boiling
point as reference and using the method of Watson
h
vap,1
= 32.23 kJ/mol at T
1
= 350.2, T
r,1
= 0.6692
T
r,2
= 450.0/523.3 = 0.8599
Therefore according to equation 41:
mol / kJ 25 . 23
6692 . 0 1
8599 . 0 1
23 . 32 h
38 . 0
2 , vap
= |
\
|
=
The experimental value is 23.16 kJ/mol (Perry).
The error is thus 0.4 %
Chemical Engineering 317: Additional Notes Properties of Compounds Page 20 of 34
Perry also published correlations for the heats of vapourisation for over 230 compounds. The heat of
vapourisation is listed as a function of temperature:
Perry
( )
( )
2
r 4 r 3 2
T C T C C
r 1 f
T 1 C h
+ +
= (42)
Where C
1
through C
4
are component specific parameters, listed in table 2-193 page 2-156 to 2-160
(7
th
Edition)
Example: Estimate the enthalpy of vapourisation for ethyl acetate at 450 K using the method of Perry
For ethyl acetate:
C
1
= 4.933E7
C
2
= 0.3847
C
3
= C
4
= 0
T
r
= 450.0 / 523.3 = 0.8599
( ) kJ/mol 2 . 23 kmol / J 7 E 32 . 2 8599 . 0 1 7 E 933 . 4 h
3847 . 0
f
= = =
The experimental value is 23.16 kJ/mol !
Enthalpy (heat) of fusion (liquid to solid)
The enthalpy of fusion h
fus
is defined as the difference of the enthalpies of a unit mole or mass of a
solid and liquid at its melting temperature and one atmosphere of pressure. Basically, the enthalpy of
fusion is the amount of energy required to melt a solid at its melting temperature and one atmosphere
of pressure. Similarly, the enthalpy of fusion is the amount of energy released when a liquid solidifies
at its melting temperature and one atmosphere of pressure. Perry list the enthalpy of fusion for a
number of compounds.
Correlations regarding the enthalpy of fusion are not as accurate as those for the enthalpy of
vapourisation and generally rely on group contribution methods. These group contribution methods
are complicated and beyond the scope of this course. (For additional reading see page 2-250 and the
tables on pages 2-252 and 2-253 in Perry, 7
th
Edition).
4.3 Enthalpy (heat) of formation
The enthalpy of formation is the energy required to form the compound at a specific temperature
(usually at 298 K) from its elements. The enthalpy of formation is often used in chemical reaction
thermodynamics, hence its importance here. The enthalpy of formation of a number of compounds is
listed in sources such as Physical Chemistry Textbooks and in Properties of Gases and Liquids by
Reid and Prausnitz. However, on occasion the values are not available and need to be estimated.
Constantinou and Gani proposed a group contribution method to calculate the enthalpy of formation at
298 K:
Constantinou and Gani
+ =
fi K 298 , f
h n 835 . 10 h (kJ/mol) (43)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 21 of 34
Example: Estimate the standard (298 K) enthalpy of formation for ethanol using the method of
Constantinou and Gani
There is one CH
3
group, i.e. -45.947
There is one CH
2
group, i.e -20.763
There is one OH group, i.e. -181.422
Using equation 43:
30 . 237 422 . 181 763 . 20 947 . 45 835 . 10 h
K 298 , f
= = kJ/mol
Atkins gives the value as -235.10 kJ/mol.
The error is thus 1 %.
Note: This value is the standards energy of formation in the VAPOUR phase.
If you want to calculate the standard energy of formation in the liquid phase,
you need to take the heat of vaporisation at 298 K into account.
The heat of formation can also be estimated from the heats of combustion (if available). This method
is quite useful, especially for organic compounds containing N, S, O etc.
Example: Estimate the heat of formation for liquid ethanol using heat of combustion of ethanol
The formation reaction is as follows:
2 C (graphite) + 1/2 O
2
(g) + 3 H
2
(g) C
2
H
6
O (liq)
Consider the combustion reactions of C, H
2
, and CH
3
NO
2
:
C(graphite) + O
2
(g) CO
2
(g) h
c
= - 393.5 kJ/mol R1
H
2
(g) + 1/2 O
2
(g) H
2
O (liq) h
c
= - 285.8 kJ/mol R2
C
2
H
6
O (liq) + 3 O
2
(g) 2 CO
2
(g) + 3 H
2
O (liq)
h
c
= -1366.8 kJ/mol R3
Consider 2 * R1 + 3 * R2 R3:
Chemical reaction same as the formation reaction
h
f
= 2 * (-393.5) + 3 * (-285.8) (-1366.8) = -277.6 kJ/mol
The literature value is 277.6 kJ/mol
Remember, this is for LIQUID ethanol, because that is the way the reactions
are set up!
Similarly, Hesss Law together with information on other chemical reactions can be used to determine
the heat of formation. This was discussed in Engineering Chemistry 123.
5 PHYSICAL PROPERTIES
Most of the properties discussed above concern themselves with the thermodynamic and critical
properties of substances. These are the properties most commonly used in thermodynamics.
Substances do, however, also have a number of physical properties which are important in
engineering calculations, for example viscosity, thermal conductivity, diffusivity and surface tension.
The amount of data available regarding these properties varies and often, in the absence of reliable
experimental data, these properties need to be estimated. Estimation of these properties is beyond the
scope of this course yet similar methods as those used for the above discussed properties are used.
For further information consult sources such as Perrys Chemical Engineers Handbook and Properties
of Gases and Liquids.
6 WEB SOURCES
With the coming of the electronic age, a large amount of data is available electronically. However, due
to the abundance of data and ease of publication, one needs to exercise caution with unknown
sources. The American National Institute of Standards and Technology (NIST) has a website with very
reliable data. Thermodynamic and physical data for a number of pure components is available with
Chemical Engineering 317: Additional Notes Properties of Compounds Page 22 of 34
excellent accuracy and can be used with confidence. The website is accessible through the university
network at:
http://webbook.nist.gov/chemistry/fluid/
7 NOMENCLATURE
a Coefficient of heat capacity equation
a
n
Parameter in the Harrison and Seaton equation with n = 1 through 15
A Constant in the Antoine equation / Constant in the Reid and Prausnitz
vapour pressure correlation
b Coefficient of heat capacity equation
B Constant in the Antoine equation / Constant in the Reid and Prausnitz
vapour pressure correlation
c Intercept of the vapour pressure correlation / Coefficient of heat capacity
equation
C Constant in the Antoine equation / Constant in the Reid and Prausnitz
vapour pressure correlation
C
n
Constants in vapour pressure / enthalpy of vapourisation correlation in
Perry with n = 1 through 5
C
p
Heat capacity at constant pressure
C
v
Heat capacity at constant volume
d Coefficient of heat capacity equation
D Constant in the Reid and Prausnitz vapour pressure correlation
h Enthalpy
h
vi
Contribution of group i to the enthalpy of vapourisation in the method
according to Constantinou and Gani.
h
fi
Contribution of group i to the standard enthalpy of fusion in the method
according to Constantinou and Gani.
m Gradient of the vapour pressure correlation
MW Molecular Mass
n Number of groups (i) in a group contribution method
n
i
The number of atoms of type i in a molecule (used in the Harrison and
Seaton equation)
N Number of carbon atoms in a linear hydrocarbon
R Gas constant
P Pressure
T Temperature
v Specific volume
x Temperature function used in the vapour pressure correlation
Z Compressibility
Acentric factor
Group contribution parameter for critical constants according to the
method of Lydersen / Fedors
h
c
Standard (298K, 1 atm) enthalpy of combustion
h
f
Standard (298K, 1 atm) enthalpy of fusion
h
vap
Enthalpy of vapourisation
Superscripts
ig Refers to the property of an ideal gas
sat Refers to the property at saturated conditions
Subscripts
1 Refers to the property at condition 1
2 Refers to the property at condition 2
298K Refers to the property at 298 K
b Refers to the property at the normal boiling point
bi Refers to the contribution of the group i to the normal boiling point
(Constantinou and Gani method)
c Refers to the property at the critical point
Chemical Engineering 317: Additional Notes Properties of Compounds Page 23 of 34
ci Refers to the contribution of the group i to the critical
temperature/pressure (Constantinou and Ganis method)
i Contribution of group i
m Refers to the property at the melting point
p Refers to the contribution of the group to the critical pressure (Lydersen
method)
r Refers to the reduced property
t Refers to the contribution of the group to the critical temperature
(Lydersen method)
v Refers to the contribution of the group to the critical volume (Fedors
method)
8 REFERENCES
The following general references are good sources of physical properties and their estimation:
[1] Perry, R.H.; Green, D.W. (Ed) (1997) Perrys Chemical Engineering Handbook, 7
th
Edition
(International Edition), McGraw-Hill
[2] Reid, R.C.; Prausnitz, J.M.; Poling, B.E. (1987) Properties of Gases and Liquids, 4
th
Edition,
McGraw-Hill
[3] Lide, D.R. (Ed.) (1997) CRC Handbook of Chemistry and Physics, 77
th
Edition, CRC Press
Other References
[1] Constantinou, L.; Gani, R. (1994) New Group Contribution Method for Estimating Properties of
Pure Compounds, AIChE Journal 40 (10) 1697 1710.
[2] Rika, V.Jr.; Domalski, E.S.(1993) Estimation of the Heat Capacities of Organic Liquids as a
Function of Temperature Using Group Additivity. I. Hydrocarbon Compounds, Journal of
Physical and Chemical Reference Data 22 (3) 597 618.
[3] Rika, V.Jr.; Domalski, E.S.(1993) Estimation of the Heat Capacities of Organic Liquids as a
Function of Temperature Using Group Additivity. I. Compounds of Carbon, Hydrogen,
Halogens, Nitrogen, Oxygen, and Sulphur, Journal of Physical and Chemical Reference Data
22 (3) 619 655.
Chemical Engineering 317: Additional Notes Properties of Compounds Page 24 of 34
9 APPENDICES
9.1 Group contribution parameters for the Lydersens method
Table 1: Group contribution paramters for the Lydersen method to calculate T
c
and P
c
(From Perrys Chemical Engineers Handbook, page 2-343, Table 2-385)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 25 of 34
9.2 Group contribution parameters for the Constantinou and Ganis method
Table 2: First order group contribution parameters for the estimation of critical properties and
normal boiling points for the method of Constantinou and Gani
(From AIChE Journal, volume 40, no 10, 1994, pages 1699 and 1700, Table 1)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 26 of 34
Table 2 continued
Table 3: First order group contribution parameters for the estimation of thermodynamic
properties and normal boiling points for the method of Constantinou and Gani
(From AIChE Journal, volume 40, no 10, 1994, page 1700, Table 2)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 27 of 34
9.3 Group increments for the Fedors method
Table 4: Group contribution parameters for the Fedors method to calculate v
c
(From Perrys Chemical Engineers Handbook, 7
th
Edition page 2-344, Table 2-386)
9.4 Constants for the Antoine equation
Table 5: Constants for the Antoine equation to estimate the vapour pressure of some
compounds
(From Basic Principles and Calculations in Chemical Engineering, 6
th
Edition, page 669, Table G1)
NOTE: P in mmHg and T in K
Chemical Engineering 317: Additional Notes Properties of Compounds Page 28 of 34
9.5 Parameters for method of Harrison and Seaton
Table 6: Parameters for the method of Harrison and Seaton to calculate ideal gas heat capacity
(From Perrys Chemical Engineerss Handbook, page 2-348, Table 2-387)
Note: Results and parameters may be interpolated between temperatures
Chemical Engineering 317: Additional Notes Properties of Compounds Page 29 of 34
9.6 Group contribution parameters for Rihani and Doraiswamys method
Table 7: Group contribution parameters for aliphatic hydrocarbon groups for estimation of
vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 18, Table 1)
Table 8: Group contribution parameters for aromatic hydrocarbon groups for estimation of
vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 18, Table 2)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 30 of 34
Table 9: Group contribution parameters for contributions due to ring formation for estimation
of vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 19, Table 3)
Table 10: Group contribution parameters for oxygen containing groups for estimation of
vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1 page 1965, Table 4)
Table 11: Group contribution parameters for nitrogen containing groups for estimation of
vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 19, Table 5)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 31 of 34
Table 12: Group contribution parameters for sulphur containing groups for estimation of
vapour heat capacities according to the method of Rihani and Doraiswamy
(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 19, Table 6)
9.7 Group contribution parameters for Shaws method
Table 13: Group contribution parameters for estimation of liquid heat capacity at 25
o
C
according to the method of Shaw
(From Journal of Chemical and Engineering Data, volume 14 no 4, page 464, Table 2)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 32 of 34
9.8 Group contribution parameters for Rika and Domalskis method
Table 14: Group contribution parameters for linear hydrocarbon groups for estimation of liquid
heat capacities according to the method of Rika and Domalski
(From Journal of Physical and Chemical Reference Data, volume 22 no 3, page 604, Table 5)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 33 of 34
Table 15: Group contribution parameters for halogen, nitrogen, oxygen and sulphur containing
groups for estimation of liquid heat capacities according to the method of Rika and
Domalski
(From Journal of Physical and Chemical Reference Data, volume 22 no 3, page 632 and 633, Table 8)
Chemical Engineering 317: Additional Notes Properties of Compounds Page 34 of 34
Table 15 continued