PREDICTION AND CORRELATION OF PHYSICAL PROPERTIES 2-347

pounds of known or estimable normal boiling point are predicted using the
method of Riedel89 given by Eq. (2-39).
log P°r = φ(Tr) − (α − 7)ψ(Tr)
Correlation functions φ(Tr), ψ(Tr), and ζ(Tr) are given by Eqs. (2-40), (2-41), and
(2-42), respectively.
φ(Tr) = 0.118ζ(Tr) − 7 log10 Tr
ψ(Tr) = 0.0364ζ(Tr) − log10 Tr
ζ(Tr) = 36/Tr + 96.7 log10 Tr − 35 − Tr6
Use Eq. (2-44), determining parameters from Eqs. (2-45), (2-46), and (2-47).
log Psat = m log Pwsat + C
(2-39)
at T1 = 256.55 K, P1sat = 2.00 × 104 Pa, log P1sat = 4.3010
at T2 = 294.95 K, P2sat = 1.067 × 105 Pa, log P2sat = 5.0282
(2-40) Use Eq. (2-45) to calculate the vapor pressure of water at T1 and T2.
(2-41) log Pωsat1 = 2.2282, Pωsat1 = 169.12 Pa
(2-42) log Pωsat2 = 3.4213, Pωsat2 = 2637.9 Pa

The Riedel α is calculated from Eq. (2-43). From Eq. (2-46):

0.136ζ(Tr ) + log10 Pc − 5.01 log P1sat − log P sat 4.3010 − 5.0282
m = }} = }} = 0.6093
2
α = }}}
b
(2-43) log P wsat1 − log P wsat2 2.2282 − 3.4213
0.0364ζ(Tr ) − log10 Tr
b b
From Eq. (2-47):
Critical properties, if not available, can be estimated from the methods of the
C = log P1sat − m log P wsat1 = 4.3010 − 0.6093(2.2282)
previous section. Tr is the reduced temperature at the temperature of interest,
while Tr is the reduced temperature at the normal boiling point.
b
C = 2.9434
The method is accurate within 2 to 3 percent above 15 kPa, while errors at T = 273.15 K (0°C)
increase to 10–30 percent at lower pressures. Care should be taken not to use
the method below the freezing point temperature. 3129.8
log P = 31.51 − } − 7.1385 log 273.15 + 1.757 × 10−6(273.15)2
sat
w
273.15
Example 7 Estimate the vapor pressure of thiophene at 500 K. Pure
w = 2.7907
log P sat
component properties are Tc = 579.4 K, Pc = 5.694 MPa, and Tb = 357.5 K. Use
the Riedel method, Eq. (2-39). log Psat = (0.6093)(2.7907) + 2.9434
r = −φ(Tr) − (α − 7) ψ (Tr)
log P sat log Psat = 4.6438
357.5 500 Psat = 44,030 Pa = 44.0 kPa
Tr = } = 0.6170
b
Tr = } = 0.8629
579.4 579.4
From Eq. (2-42): IDEAL GAS THERMAL PROPERTIES
(36)
ζ(Tr ) = } + 96.7 log (0.6170) − 35 − (0.6170)6 = 3.01
b A substance is in the ideal gas state when the volume of its molecules
(0.6170)
is a zero fraction of the total volume taken up by the substance and
From Eq. (2-43):
when the individual molecules are far enough apart from each other
0.136(3.01) + log (5.694 × 106) − 5.01 so that there is no interaction between them. Although this only
α = }}}}
(0.0364)(3.01) − log (0.6170) occurs at infinite volume and zero pressure, in practice, ideal gas
α = 6.749
properties can be used for gases up to a pressure of two atmospheres
with little loss of accuracy. Thermal properties of ideal gas mixtures
From Eq. (2-42), calculate ζ(Tr) and then calculate φ(Tr) and ψ(Tr) from Eqs. may be obtained by mole-fraction averaging the pure component
(2-40) and (2-41). values.
log Prsat = −0.461 − (6.749 − 7)(0.068) Heat Capacity, Cpo Heat capacity is defined as the amount of
log Prsat = −0.444 energy required to change the temperature of a unit mass or mole one
degree; typical units are J/kg·K or J/kmol·K. There are many sources
Prsat = 0.3598 of ideal gas heat capacities in the literature; e.g., Daubert et al.,24
Psat = PrsatPc = (.3598)(5.694) = 2.049 MPa Daubert and Danner,23 JANAF thermochemical tables,15 TRC ther-
An experimental value is 2.037 MPa. modynamic tables,115,116 and Stull et al.104 If Cpo values are not in the
For nonhydrocarbon organics for which normal boiling points are preceding sources, there are several estimation techniques that
unknown or expected vapor pressures are below 15 kPa, the reference sub- require only the molecular structure. The methods of Thinh et al.113
stance method of Othmer and Yu78 as given by Eq. (2-44) is recommended. and Benson et al.6,7 are the most accurate but are also somewhat com-
log Psat = m log P wsat + C (2-44) plicated to use. The equation of Harrison and Seaton36 for Cpo between
300 and 1500 K is almost as accurate and easy to use:
The vapor pressure of water P wsat may be calculated by Eq. (2-45).
3.1298 × 103 Cpo = a1 + a2C + a3H + a4O + a5N + a6S + a7F + a8Cl
log Pwsat = 31.51 − }} − 7.1385 log T + 1.757 × 10−6T 2 (2-45)
T + a9I + a10Br + a11Si + a12Al + a13B + a14P + a15E (2-48)
with temperatures in K and vapor pressures in Pa.
Values of the compound specific constants m and c were originally derived by where C = ideal gas heat capacity, J/mol K
o
p
Othmer et al. and greatly expanded to over 600 common organics by Danner a1–a15 = constant parameters obtained from Table 2-387 as a
and Daubert.22 If constants are not available but any two vapor pressure data function of temperature
points are available, the constants m and C can be calculated using Eqs. (2-46) C = number of carbon atoms in the molecule
and (2-47). H = number of hydrogen atoms in the molecule
1 − log P 2
log P sat O = number of oxygen atoms in the molecule
sat
m = }} (2-46)
log P wsat1 − log P wsat2 N = number of nitrogen atoms in the molecule
S = number of sulfur atoms in the molecule
1 − m log P w1
C = log P sat sat
(2-47) F = number of fluorine atoms in the molecule
where the subscripts 1 and 2 refer to the two reference temperatures T1 and T2. Cl = number of chlorine atoms in the molecule
Average errors at low pressures for compounds with tabulated m and C are I = number of iodine atoms in the molecule
within a few percent. When values of m and C are calculated from only two Br = number of bromine atoms in the molecule
vapor pressure points, the method should be used only for interpolation and
limited extrapolation. The method is usable from about 220 K (so long as it is
Si = number of silicon atoms in the molecule
above the freezing point of the compound) to the critical point of water (about Al = number of aluminum atoms in the molecule
647 K). B = number of boron atoms in the molecule
P = number of phosphorus atoms in the molecule
Example 8 Estimate the vapor pressure of acetaldehyde at 0°C. Two E = number of atoms in the molecule excluding the 13
vapor pressure points are 20.0 kPa at 256.55 K and 107.6 kPa at 294.85 K. atom-types listed above

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2-348 PHYSICAL AND CHEMICAL DATA

TABLE 2-387 Values of the Constant Parameters a1–a15 in Eq. (2-48) at Different Temperatures
Parameter a
Temp., K 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
300 4.86 9.04 5.69 11.4 11.9 15.3 12.7 16.8 18.7 17.8 14.6 15.8 11.5 18.0 19.5
400 0.864 12.6 7.37 13.9 14.0 17.0 16.2 18.9 20.5 19.9 17.5 18.3 14.7 20.9 20.8
500 −1.85 15.5 8.89 15.7 16.0 19.4 17.9 20.2 22.1 21.2 19.6 20.0 17.0 21.6 21.7
600 −4.61 17.5 10.5 17.5 17.3 20.3 20.1 21.4 23.3 22.4 20.9 21.1 18.3 22.8 22.1
800 −7.49 20.1 13.1 19.4 19.4 22.3 21.5 22.4 25.0 23.4 23.2 22.3 20.8 23.0 23.0
1000 −8.53 21.6 15.2 20.4 20.4 22.9 22.4 22.8 25.4 23.8 23.9 22.8 22.2 23.4 23.3
1500 −7.37 23.9 17.9 20.6 21.1 22.5 22.1 22.6 24.6 23.0 24.1 23.2 24.2 24.2 23.3

Results and parameters may be interpolated between temperatures.
Average errors are between 2 and 6 percent, with the higher errors at
the lower temperatures.
Example 9 Using Eq. 2-48 to estimate the ideal gas heat capacity of ace-
tone (C3H6O) at 600 K:
Cp° = −4.61 + (17.5)(3) + (10.5)(6) + (17.5)(1) = 128.39 J/mol K
Daubert et al.24 report a value of 121.8 J/mol K.
n = number of different atomic groups contained in
the molecule
Ni = number of atomic groups i contained in the mole-
cule
∆Gi = numeric value of atomic group i obtained from
Table 2-388
Average errors of 8 to 9 kJ/mol may be expected.

Example 11 The ∆G°f 298 of phenol is estimated using Table 2-388. The
Enthalpy of Formation The ideal gas standard enthalpy (heat) molecular groups are
of formation (∆H°f 298) of a chemical compound is the increment of
enthalpy associated with the reaction of forming that compound in the
ideal gas state from the constituent elements in their standard states, 5 CH
defined as the existing phase at a temperature of 298.15 K and one
atmosphere (101.3 kPa). Sources for data are Refs. 15, 23, 24, 104, 1 C (both ring)
115, and 116. The most accurate, but again complicated, estimation
method is that of Benson et al.6,7 A compromise between complexity
and accuracy is based on the additive atomic group-contribution 1 OH (phenol)
scheme of Joback44; his original units of kcal/mol have been converted Therefore,
to kJ/mol by the conversion 1 kcal/mol = 4.1868 kJ/mol:
n ∆G°f 298 = 53.88 + 5(11.30) + (54.05) + (−197.37) = −32.94 kJ/mol
∆H°f 298 = 68.29 + ^ Ni ∆Hi (2-49) The value from Daubert et al.24 is −32.64 kJ/mol.
i=1 For other temperatures, the exact Eq. (2-52) may be used at temperature
where ∆H°f 298 = enthalpy of formation at 298.15 K, kJ/mol T (K):
n = number of different atomic groups contained in the ∆G°f T = ∆H°f T − T ∆S°f T (2-52)
molecule
Ni = number of atomic groups i contained in the mole- where ∆G°f T = Gibbs energy of formation at T, kJ/mol
cule ∆H°f T = enthalpy of formation at T, kJ/mol (see above)
∆Hi = numeric value of atomic group i obtained from ∆S°f T = entropy of formation at T, kJ/mol K (see below)
Table 2-388.
Entropy of Formation The ideal gas standard entropy of forma-
Average expected errors are about 9 kJ/mol. tion (∆S°f 298) of a chemical compound is the increment of entropy asso-
For other temperatures: ciated with the reaction of forming that compound in the ideal gas

E
T state from the constituent elements in their standard state defined as
∆H°fT = ∆H°f 298 + C°p dT (2-50) the existing phase at a temperature of 298.15 K and one atmosphere
298
(101.325 kPa). Thus:
See above for discussion of the ideal gas heat capacity (C°p ). n

∆S°f 298 = S°compound − ^ Ni Selement

Example 10 The ∆H°f 298 of 2-butanol is estimated using Table 2-388. The
molecular groups are 2CH3, 1CH2, 1CH (all nonring), and 1OH (alcohol).
Therefore:
∆H°f 298 = 68.29 + 2(−76.45) + (−20.64) + (29.89) + (−208.04) = −283.40 kJ/mol
The value from Daubert et al.24 is −292.9 kJ/mol.
Gibbs Energy of Formation The ideal gas standard Gibbs
energy of formation (∆G°f 298) of a chemical compound is the incre-
ment of Gibbs energy associated with the reaction of forming that
compound in the ideal gas state from the constituent elements in their
standard state defined as the existing phase at a temperature of
298.15 K and one atmosphere (101.325 kPa). Refs. 15, 23, 24, 104,
115, and 116 are good sources of data. The additive atomic group-
contribution scheme of Joback44 may be used to estimate ∆G°f 298; his
original units of kcal/mol have been converted to kJ/mol by the con-
version 1 kcal/mol = 4.1868 kJ/mol:
n with average errors of 1–2 J/mol K. Elemental standard-state absolute
∆G°f 298 = 53.88 + ^ Ni ∆Gi (2-51)
i=1
where ∆G°f 298 = Gibbs energy of formation at 298.15 K, kJ/mol
r
i (2-53)
i=1
where ∆S°f 298 = entropy of formation at 298.15 K and 1 atm,
J/mol K
S°compound = ideal gas absolute entropy of the compound at
298.15 K and 1 atm, J/mol K
n = number of different elements contained in the
compound
Ni = moles of element i contained in one mole of
compound
i = absolute entropy of element i in its standard state
r
Selement
at 298.15 K and 1 atm, J/mol K.
Ideal gas absolute entropies of many compounds may be found in
Daubert et al.,24 Daubert and Danner,23 JANAF Thermochemical
Tables,15 TRC Thermodynamic Tables,115,116 and Stull et al.104 Other-
wise, the estimation method of Benson et al.6,7 is reasonably accurate,
entropies may be found in Cox et al.21 Values from this source for
some common elements are listed in Table 2-389. ∆S°f 298 may also be
calculated from Eq. (2-52) if values for ∆H°f 298 and ∆G°f 298 are known.

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 PREDICTION AND CORRELATION OF PHYSICAL PROPERTIES 2-349

TABLE 2-388 Atomic Group Contributions to Estimate DH f°298 and DG f°298

∆H ∆G ∆H ∆G
Nonring Increments Oxygen Increments (Cont.)
CH3 −76.45 −43.96 CHO (aldehyde) −162.03 −143.48

CH2 −20.64 8.42 COOH (acid) −426.72 −387.87

COO (ester) −337.92 −301.95

CH 29.89 58.36
O (except for above) −247.61 −250.83

Nitrogen Increments
C 82.23 116.02 NH2 −22.02 14.07

CH2 −9.63 3.77 NH (nonring) 53.47 89.39

CH 37.97 48.53 NH (ring) 31.65 75.61

C 83.99 92.36
N (nonring) 123.34 163.16

C 142.14 136.70 N (nonring) 23.61 —

CH 79.30 77.71 N (ring) 55.52 79.93

C 115.51 109.82 NH 93.70 119.66

Ring Increments
CN 88.43 89.22
CH2 −26.80 −3.68
NO2 −66.57 −16.83
CH 8.67 40.99
Sulfur Increments
}SH −17.33 −22.99
}S} (nonring) 41.87 33.12
C 79.72 87.88 }S} (ring) 39.10 27.76

Halogen Increments
}F −251.92 −247.19
CH (aromatic or cyclic olefin) 2.09 11.30 }Cl −71.55 −64.31
}Br −29.48 −38.06
46.43 54.05 }I 21.06 5.74
C (aromatic or cyclic olefin)

Oxygen Increments
OH (alcohol) −208.04 −189.20

OH (phenol) −221.65 −197.37

O (nonring) −132.22 −105.00

O (ring) −138.16 −98.22

C O (nonring) −133.22 −120.50

C O (ring) −164.50 −126.27

ENTHALPY OF VAPORIZATION AND FUSION where R = gas constant in energy units

Enthalpy of Vaporization The enthalpy (heat) of vaporization
∆HV is defined as the difference of the enthalpies of a unit mole or
mass of a saturated vapor and saturated liquid of a pure component;
i.e., at a temperature (below the critical temperature) and corre-
sponding vapor pressure. ∆HV is related to vapor pressure by the ther-
modynamically exact Clausius-Clapeyron equation:
d ln Psat
∆Hv = −R ∆ZV } (2-54)
d (1/T)
∆ZV = ZG − ZL (2-55)
ZG = compressibility factor of the saturated vapor
ZL = compressibility factor of the saturated liquid
Psat = vapor pressure
T = absolute temperature
If accurate ZG and ZL data are available, excellent ∆HV values can be
obtained by differentiating a vapor pressure correlation and using Eq.
(2-54). If not, ∆ZV may be esimated by Haggenmacher’s equation34:

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2-350 PHYSICAL AND CHEMICAL DATA

TABLE 2-389 Standard-State Entropy of Elements where Tr 1,2 = reduced temperature = T1 /Tc or T2 /Tc
at 298.15 K and 1 Atmosphere T1,2 = temperature, K
Tc = critical temperature, K
Absolute entropy
Element State J/mol K Equation (2-59) works best between the normal boiling and critical tempera-
C crystal (graphite) 5.74 tures, producing values of engineering accuracy.
H2 gas 130.571
O2 gas 205.043 Example 14 Estimate ∆Hv of ethyl acetate at 450 K, using the normal
N2 gas 191.500 boiling point values as a basis (see Example 13). ∆Hv1 = 32.23 kJ/mol, Tr1 =
S crystal (rhombic) 32.054 0.6692, and Tr2 = 450.0/523.3 = 0.8599. Substituting in Eq. (2-59):
F2 gas 202.682 1 − 0.8599 0.38
Cl2
Br2
gas
liquid
222.972
152.21
1
∆Hv(450) = 32.23 }}
1 − 0.6692 2 = 23.25 kJ/mol

I2 crystal 116.14 A value of 23.16 kJ/mol is obtained from Daubert et al.24

Enthalpy of Fusion The enthalpy (heat) of fusion ∆Hfus is

1 2
P 1/2 defined as the difference of the enthalpies of a unit mole or mass of a
∆Zv = 1 − }r (2-56) solid and liquid at its melting temperature and one atmosphere pres-
Tr 3

sure of a pure component. There are no generally applicable estima-

where Pr = reduced pressure = P/Pc tion techniques that are very accurate. However, if the melting
Tr = reduced temperature = T/Tc temperature is known, the atomic group contribution method of
Chickos et al.16 yields approximate results:
However, Eq. (2-56) should be used only near or below the normal
boiling point; even then, the accuracy of the resulting ∆HV is signifi- ∆Hfus = Tmlt∆Sfus (2-60)
cantly reduced. where ∆Hfus = enthalpy of fusion at the melting temperature, J/mol
The corresponding states approach suggested by Pitzer et al.82 Tmlt = melting temperature, K
requires only the critical temperature and acentric factor of the com- ∆Sfus = a + b = entropy of fusion at the melting tempera-
pound. For a close approximation, an analytical representation of this ture, J/mol K.
method proposed by Reid et al.86 for 0.6 < Tr < 1.0 is:
∆HV /RTc = 7.08(1 − Tr)0.354 + 10.95ω(1 − Tr)0.456 (2-57) It should be noted that the methodology for a and b results in a ∆Sfus
associated with the phase change from a solid at 0 K to the liquid at
where ∆HV = enthalpy of vaporization, kJ/mol Tmlt. No entropy changes resulting from solid transitions are taken into
R = gas constant = 0.008314 kJ/mol K account, and ∆Sfus for a substance that undergoes such a transition will
Tc = critical temperature, K be overestimated by this technique.
Tr = reduced temperature, T/Tc
T = temperature, K a = 35.19 NR + 4.289 (NCH2 − 3 NR) (2-61)
ω = acentric factor where NR = number of nonaromatic rings
NCH2 = number of }CH2} atomic groups in nonaromatic
Maximum errors are in the order of 8 percent. ring(s) required to form a cyclic paraffin of the same
Example 12 Estimate ∆HV of Propionaldehyde at 350 K. The required ring size(s) as contained in the molecule of interest.
properties from Daubert et al.24 are Tc = 504.4 K and ω = 0.2559. Tr =
350.0/504.4 = 0.6939. Substituting in Eq. (2-57): O
Example: For , NCH 2 = 5; a = 0 if there are no nonaromatic rings
∆HV /RTc = (7.08)(1 − 0.6939)0.354 + (10.95)(0.2559)(1 − 0.6939)0.456 = 6.289
∆HV = (6.289)(0.008314)(504.4) = 26.37 kJ/mol in the molecule of interest. If a nonaromatic ring in fact contains a }CH2}
atomic group, then no consideration of that group in the b term in Eq. (2-62)
The reported value is 26.85 kJ/mol.24 is required.
The enthalpy of vaporization at the normal boiling temperature ∆Hvb ng ns nf
(kJ/mol) can be estimated by an equation suggested by Riedel90: b = ^ (Ng)i(∆s)i + ^ (Ns)j(Cs)j(∆s)j + ^ (Nf )k(Ct)k(∆s)k (2-62)
(ln [Pc /101.325] − 1)
3 4
i=1 j=1 k=1
∆Hvb = 1.093 RTc Tbr }}} (2-58)
0.930 − Tbr where ng = number of different nonring or aromatic C-H atomic groups
where R = gas constant = 0.008314 kJ/mol K. bonded to other carbon atoms in the molecule of interest
Tc = critical temperature, K (Ng)i = number of C-H atomic groups i bonded to other
Tbr = reduced normal boiling temperature = Tb /Tr carbon atoms in the molecule of interest
Tb = normal boiling temperature, K ns = number of different nonring or aromatic C-H atomic groups
Pc = critical pressure, kPa bonded to at least one functional group or atom in the mole-
cule of interest
Average errors are about 2 percent. (Ns)j = number of C-H atomic groups j bonded to at least one func-
tional group or atom in the molecule of interest
Example 13 Estimate ∆HVb of Ethyl Acetate. The required properties nf = number of different functional groups or atoms in the mole-
for ethyl acetate are from Daubert et al.24: Tc = 523.3 K, Tb = 350.2 K, and Pc = cule of interest
3880.0 kPa. Tbr = 350.2/523.3 = 0.6692. Substituting in Eq. (2-58): (Nf)k = number of functional groups or atoms k in the molecule of
interest
(ln [3880.0/101.325] − 1)
3
∆HVb = (1.093)(0.008314)(523.3) (0.6692) }}} 1 0.930 − 0.6692 24 (Cs)j = coefficient for C-H atomic group j bonded to at least one
functional group or atom in the molecule of interest; numeric
values for C-H atomic groups are found in Table 2-390
= 32.28 kJ/mol Ct = coefficient for the functional group or atom k in the molecule
The value from Daubert et al.24 is 32.23 kJ/mol. of interest, where t = the total number of functional groups or
The enthalpy of vaporization decreases with temperature and is zero at the atoms in the molecule of interest. Exception: Molecules con-
critical point. If the value of an enthalpy of vaporization ∆Hv1 is known at tem- taining any number of fluorine atoms are treated as having
perature T1, this temperature dependency can be represented by the Watson only one functional fluorine atom. Numeric values of C1–C4
relation127 to calculate another enthalpy of vaporization ∆Hv2 at any other tem- are in Table 2-391 for functional groups or atoms
perature T2: (∆s)i, j, k = contribution of the atomic group or atom i, j, or k
1 − Tr 0.38 to the entropy of fusion, J/mol K. Numeric values for
∆Hv2 = ∆Hv1 }21
1 − Tr1 2 (2-59) C-H atomic groups are in Table 2-390; values for functional
groups or atoms are in Table 2-391

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 PREDICTION AND CORRELATION OF PHYSICAL PROPERTIES 2-351

TABLE 2-390 Cs and Ds Values for C-H Atomic Groups There are no reliable prediction methods for solid heat capacity as
to Estimate DHfus a function of temperature. However, the atomic element contribution
method of Hurst and Harrison,41 which is a modification of Kopp’s
Cs ∆s
Rule,50 provides estimations at 298.15 K and is easy to use:
Nonring n

CH3 1.0 18.33 CpS = ^ Ni ∆Ei (2-63)

i=1

CH2 1.0 9.41 where CpS = solid heat capacity at 298.15 K, J/mol K
n = number of different atomic elements in the compound
Ni = number of atomic elements i in the compound
CH 0.69 −16.19
∆Ei = numeric value of the contribution of atomic element i
found in Table 2-393
Average errors are in the 9–10 percent range.
C 0.67 −38.70
Example 15 Estimate solid heat capacity of dibenzothiophene, C12H8S.
CH2 1.0 14.56 The required atomic element contributions from Table 2-393 are: C = 10.89,
H = 7.56, and S = 12.36. Substituting in Eq. (2-63):
CpS = (12)(10.89) + (8)(7.56) + (1)(12.36) = 203.52 J/mol K
CH 3.23 4.85
Daubert et al.24 report a value of 198.5 J/mol K.

C 1.0 −11.38 Liquid Heat Capacity The two commonly used liquid heat
capacities are either at constant pressure or at saturated conditions.
CH 1.0 10.88 There is negligible difference between them for most compounds up
to a reduced temperature (temperature/critical temperature) of 0.7.
C 1.0 2.18 Liquid heat capacity increases with increasing temperature, although
a minimum occurs near the triple point for many compounds.
Aromatic There are a number of reliable estimating techniques for obtaining
CH
pure-component liquid heat capacity as a function of temperature,
1.0 6.44
including Ruzicka and Dolmalski,93,94 Tarakad and Danner,112 and Lee
and Kesler.55 These methods are somewhat complicated. The rela-
C (bonded to paraffinic C) 1.0 −10.33 tively simple atomic group contribution approach of Chueh and
Swanson17 for liquid heat capacity at 293.15 K is presented here:
n
−4.27
CpL = ^ Ni ∆cpi + 18.83m
C (bonded to olefinic C or non-C) 1.0
(2-64)
i=1

C (bonded to acetylenic C) 1.0 −2.51 where CpL = liquid heat capacity at 293.15 K, J/mol K.
n = number of different atomic groups in the compound
Ni = number of atomic groups i in the compound
Ring
∆cpi = numeric value of the contribution of atomic element i
CH 0.76 −15.98
found in Table 2-394. The original units of cal/mol K
have been converted to J/mol K by the conversion
1 cal/mol K = 4.184 J/mol K
C 1.0 −32.97 m = number of carbon groups requiring an additional con-
tribution, which are those that are joined by a single
0.62 −4.35
bond to a carbon group, which in turn is connected to
CH
a third carbon group by a double or triple bond. If a
carbon group meets this criterion in more than one
C 0.86 −11.72 way, m should be increased by one for each of the
ways. Exceptions: }CH3 groups or carbon groups in a
ring never require an additional contribution; and the
C or C 1.0 −5.36 first additional contribution for a }CH2} group is
10.46 J/mol K rather than 18.83 J/mol K. However, if
the }CH2} group meets the criterion in a second
way, the second additional contribution reverts to the
Chickos et al.16 report an average error of 2050 J/mol for monofunc- 18.83 J/mol K value (see Example 17, below).
tional molecules and 3180 J/mol for multifunctional molecules when
using their method to estimate ∆Hfus. Four example estimations are Errors should be less than 6 percent for all compounds except for
shown in Table 2-392. acids, amines, and halides.

Example 16 Estimate the liquid heat capacity at 293.15 K of 2-butanol.

SOLID AND LIQUID HEAT CAPACITY The atomic groups are:
The heat capacity is defined as the amount of energy required to 2 CH3
change the temperature of a unit mass or mole one degree; typical
units are J/kg·K or J/kmol·K. 1 CH2
Solid Heat Capacity Solid heat capacity increases with increas- 1 CHOH
ing temperature, with steep rises near the triple point for many com-
pounds. When experimental data are available, a simple polynomial Substituting in Eq. (2-64) the atomic group contributions from Table 2-394 with
m = 0:
equation in temperature is often used to correlate the data. It should
be noted that step changes in heat capacity occur if the compound CpL = (2)(36.82) + (1)(30.38) + (1)(76.15) = 180.17 J/mol K
undergoes crystalline state changes at different temperatures. The value from Daubert et al.24 is 190.3 J/mol K.

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 TABLE 2-391 Ct and Ds Values for Functional Groups and Atoms to Estimate DHfus
C1 C2 C3 C4 ∆s
OH (alcohol) 1.0 12.6 18.9 26.4 1.13

OH (phenol) 1.0 1.0 1.0 1.0 16.57

O (ether, nonring) 1.0 1.0 1.0 1.0 1.09

O (ether, ring) 1.0 1.0 1.0 1.0 1.34

C O (ketone, nonring) 1.0 1.0 3.14

C O (ketone, ring) 1.0 1.0 −1.88

CHO (aldehyde) 1.0 19.66

COOH (acid) 1.0 1.83 1.88 1.72 14.90

COO (ester) 1.0 1.0 1.0 1.0 3.68

NH2 (aliphatic) 1.0 1.82 16.23

NH2 (aromatic) 1.0 1.0 15.48

NH (nonring) 1.0 1.0 −2.18

NH (ring) 1.0 1.84

N (nonring) 1.0 −15.90

N (ring) 1.0 1.0 −17.07

N (ring) 1.0 1.0 1.67

N (aromatic) 1.0 1.0 1.0 7.32

CN (nitrile) 1.0 1.4 9.62

NO2 1.0 1.0 1.0 17.36

O
C 1.0 1.0 26.19
NH2
O
C 1.0 1.0 −0.42
NH
SH 1.0 1.0 17.99

S (nonring) 1.0 0.36 7.20

S (ring) 1.0 1.0 2.18

–
SO2 (nonring) 1.0 3.26

F (on C) 1.0 1.0 1.0 1.0 14.73

F (on C) 1.0 1.0 1.0 1.0 13.01

F (on ring C) 1.0 1.0 1.0 1.0 15.90

Cl 1.0 2.0 2.0 1.93 8.37

Br 1.0 1.0 1.0 0.82 17.95

I 1.0 1.0 16.95

2-352

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 PREDICTION AND CORRELATION OF PHYSICAL PROPERTIES 2-353

TABLE 2-392 Examples of Estimations of DHfus, J/mol

Melting
Molecule temp., K Atomic group Contribution
cyclopentane (35.19)(1) + (4.289) [5 − (3)(1)] = 43.77

CH (ring) (1)(0.76)(−15.98) = −12.14

SH 155.4 SH (1)(1.0)(17.99) = 17.99

∆Sfus = 49.62
(t = 1) ∆Hfus = (49.62)(155.4) = 7710.9
∆Hfus = (experimental)16 = 7802

cyclopentane (35.19) (1) + (4.289)[5 − (3)(1)] = 43.77

CH (aromatic) (4)(6.44) = 25.76

C (ring) (1)(−11.72) = −11.72

S

304.5 C (ring) (1)(0.86)(−11.72) = −10.08

(t = 1) CH (ring) (1)(−4.35) = −4.35

CH (ring) (1)(0.62)(−4.35) = −2.69

S (ring) (1)(1.0)(2.18) = 2.18

∆Sfus = 42.87

∆Hfus = (42.87)(304.5) = 13054

∆Hfus = (experimental)16 = 11823

CH (aromatic) (4)(6.44) = 25.76

C (aromatic) (1)(1.0)(−4.27) = −4.27

F
CH COOH 363.0 F (on C) (1)(1.0)(13.01) = 13.01
OH
C (aromatic) (1)(−10.33) = −10.33
(t = 3)

CH (1)(0.69)(−16.19) = −11.17

COOH (1)(1.88)(14.90) = 28.01

OH (alcohol) (1)(18.9)(1.13) = 21.36

∆Sfus = 62.37

∆Hfus = (62.37)(363.0) = 22640

∆Hfus = (experimental)16 = 20959
H Br 338.2 CH2 (2)(1.0) 9.41 = 18.82

HO CH2 C C CH2 OH
CH (2)(0.69)(−16.19) = −22.34
Br H
(t = 4) OH (alcohol) (2)(26.4)(1.13) = 59.66

Br (2)(0.82)(17.95) = 29.44
∆Sfus = 85.58

∆Hfus = (85.58)(338.2) = 28943

∆Hfus = (experimental)16 = 29291

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2-354 PHYSICAL AND CHEMICAL DATA

TABLE 2-393 Atomic Element Contributions to Estimate Solid Example 17 Estimate liquid heat capacity at 293.15 K of 1,4-pentadiene,
Heat Capacity at 298.15 K CH2­CH}CH2}CH­CH2. The atomic groups are:
Atomic Atomic Atomic 2 CH2
element ∆E element ∆E element ∆E
C 10.89 Ba 32.37 Mo 29.44 2 CH
H 7.56 Be 12.47 Na 26.19
O 13.42 Ca 28.25 Ni 25.46
N 18.74 Co 25.71 Pb 31.60 1 CH2
S 12.36 Cu 26.92 Si 17.00
F 26.16 Fe 29.08 Sr 28.41 The }CH2} group is twice joined by a single bond to a carbon group,
Cl 24.69 Hg 27.87 Ti 27.24 which in turn is connected to a third carbon group by a double bond, and m = 2.
Br 25.36 K 28.78 V 29.36 However, by the second exception, the first additional contribution is 10.46
I 25.29 Li 23.25 W 30.87 J/mol K rather than 18.83 J/mol K. Substituting in Eq. (2-64) the atomic group
Al 18.07 Mg 22.69 Zr 26.82 contributions from Table 2-394:
B 10.10 Mn 28.06 All other 26.63 CpL = (2)(21.76) + (2)(21.34) + (1)(30.38) + 10.46 + 18.83 = 145.87 J/mol K

TABLE 2-394 Atomic Group Contributions to Estimate Liquid Heat Capacity at 293.15 K
∆cp ∆cp
Nonring Increments Oxygen Increments (Cont.)
CH3 36.82 CH2OH 73.22
CH2 30.38 CHOH 76.15

CH 20.92
COH 111.29

C 7.36 OH (except for above) 44.77

ONO2 119.24
CH2 21.76
Nitrogen Increments
CH 21.34 NH2 58.58

NH 43.93
C 15.90

CH 24.69 N 31.38

C 24.69 N (ring) 18.83

Ring Increments
CH2 25.94 CN 58.16

Sulfur Increments
CH 18.41
SH 44.77
S 33.47

C or C 12.13 Halogen Increments

F 16.74
Cl (first or second on a carbon) 35.98
CH 22.18
Cl (third or fourth on a carbon) 25.10
Oxygen Increments
O 35.15 Br 37.66

I 35.98
C O 52.97

CHO (aldehyde) 52.97 Hydrogen Increment

H (for formic acid, formates, 14.64
COOH (acid) 79.91 hydrogen cyanide, etc.)

COO (ester) 60.67

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