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Heat Transfer

Nomenclature

Use the Correct


Constant-Volume
Specific Heat

K
p
T
v

Subscripts
eos = equation of state
p = at constant pressure
pub = published value
T = at constant temperature
v = at constant volume

The common assumption


that for real liquids cv can
be approximated by cp is
not correct. To get accurate
cv values, use equations
of state.

n a previous CEP article (1), a new estimation method


for liquid specific heat at constant pressure was presented. Here, the related liquid specific heat at constant volume is discussed.
Values of liquid specific heat at constant volume (cv) are
required for various process calculations, such as determining
emergency relief-venting requirements for process vessels.
Published values of liquid cv are usually not available; it is
widely assumed that cv is approximately equal to the specific
heat at constant pressure (cp). The assumption that the difference between liquid cp and cv is small is explicitly made in
many thermodynamics textbooks and application papers
(e.g., Refs. 26). However, this is incorrect, as a review of the
properties of common liquids shows that the two specific
heats in fact differ significantly.

Thermodynamic relationships
The difference between the two specific heats can be expressed (7) as:
cp cv = Tv2/K

sion coefficients of real liquids. (Ideal incompressible liquids


are defined by both 0 and K 0 in such a manner that
2/K 0 and hence cp cv 0.) It is assumed that since
and K are both small for liquids, then 2/K, and hence the difference cp cv, will also be small. However, for real liquids,
2/K does not generally approach zero, but retains a significant value. The arguments in the literature emphasize the fact
that takes on small values for liquids, while ignoring the
even smaller values taken on by K.

Examination of physical properties


The ranges of values of the terms in Eq. 1 have been determined for common compounds over temperatures ranging from 300 K to 450 K, as shown in Table 1. The calculations were carried out using the Lee-Kesler (8) and Wu and
Stiel (9) equations of state for the organic compounds and
the equation of state of Keenan, et al. (10) for water. Values
of cp and cv for the selected compounds are given in Table
2.
The computed values of cp cv have been verified by
comparing computed and published (11) values of K, as
shown in Table 3. The values calculated from the relevant
equations of state agree quite well with the published values.
Table 1. Ranges of values of the terms in Eq. 1.
Term

Units

cp cv
cp /cv
T
v

J/kg-K
Dimensionless
K
103 m3/kg
per 1,000 K
per 109 Pa

(1)

where T is the absolute temperature, v is the specific volume,


is the thermal expansion coefficient = (1/v)(v/T)p, and K
is the bulk compressibility = (1/v)(v/p)T.
The assumption that cp cv is small for liquids is frequently made in the published literature (26). The justifications
for this assumption given in these references include the
near-incompressibility and the small values of thermal expan-

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cv

July 2002

= liquid specific heat at constant


pressure, J/kg-K
= liquid specific heat at constant
volume, J/kg-K
= liquid bulk compressibility
= (1/v)(v/p)T, 1/109 Pa
= pressure, bar abs.
= absolute temperature, K
= liquid specific volume, 103 m3/kg

Greek letters
= liquid thermal expansion
coefficient = (1/v)(v/T)p, 1/1,000 K

John Garvin,
Madison Technical Software

64

cp

CEP

Range of
Values
02,300
11.92
300450
1.02.4
012
0.0871

Average
Value
700
1.35
375
1.4
2.3
6.6

Note: The values in the table have been calculated for the liquid
phase for acetone, benzene, ethyl acetate, diethyl ether and water.

Recommendations
Computed values of liquid cv and K from the Lee-Kesler (8),
Wu and Stiel (9), and Keenan (10) equations of state are generally consistent with and are verified by the published values of
K, the bulk compressibility.
In general, it is not valid to assume for real liquids that cv
is approximately equal to cp. With the single (and wellknown) exception of water in the vicinity of 4C (where the

thermal expansion coefficient reaches a zero value), cv values


are significantly less than cp values for the liquids examined.
For the selected compounds and temperature range, the ratio
of cp to cv lies between 1 and 2.
It is recommended that cv , if not available from the
published literature, be computed from applicable equaCEP
tions of state.

Literature Cited
Table 2. Computed values of liquid cp and cv for selected compounds.
Saturated Acetone
Pressure,
bar abs.

cp ,
kJ/kg-K

cv ,
kJ/kg-K

cp /cv

0.33
1.96
7.07
18.8

2.180
2.375
2.657
3.006

1.781
1.875
2.003
2.043

1.22
1.27
1.33
1.47

cp ,
kJ/kg-K

cv ,
kJ/kg-K

1.751
1.910
2.010
2.237

1.110
1.288
1.404
1.581

1.58
1.48
1.43
1.41

Pressure,
bar abs.

cp ,
kJ/kg-K

cv ,
kJ/kg-K

cp /cv

0.14
1.01
4.11
11.8

1.947
2.103
2.271
2.532

1.442
1.555
1.676
1.811

1.35
1.35
1.36
1.40

Pressure,
bar abs.

cp ,
kJ/kg-K

cv ,
kJ/kg-K

cp /cv

0.77
3.70
11.6
28.0

2.379
2.722
3.315
4.735

1.721
1.983
2.344
2.472

1.38
1.37
1.41
1.92

Pressure,
bar abs.

cp ,
kJ/kg-K

cv ,
kJ/kg-K

cp /cv

0.04
0.42
2.5
9.3

4.219
4.184
4.263
4.388

4.215
4.131
3.650
3.424

1.001
1.01
1.17
1.28

Temperature, K
300
350
400
450
Saturated Benzene
Temperature, K

Pressure,
bar abs.

300
350
400
450

0.14
0.91
3.52
9.69

cp /cv

Saturated Ethyl Acetate


Temperature, K
300
350
400
450

Saturated Diethyl Ether


Temperature, K
300
350
400
450
Saturated Water
Temperature, K
300
350
400
450

Table 3. Comparison of values of liquid bulk compressibilities derived


from equations of state and published values.
Compound Temperature, Pressure,
Kpub,
Keos,
Equation
C
bar abs. 109Pa1 109Pa1
of State
Acetone
Benzene
Ethyl Acetate
Ethyl Ether
Water

14
17
13
25
20

24
6
24
24
14

1.11
0.89
1.03
1.88
0.49

1.09
0.84
1.03
1.78
0.41

Wu and Stiel (9)


Lee and Kesler (8)
Wu and Stiel (9)
Wu and Stiel (9)
Keenan (10)

1. Garvin, J., Determine Liquid Specific Heat for


Organic Compounds, Chem. Eng. Progress, 98
(5), pp. 4850 (May 2002).
2. Howell, J. R., and R. O. Buckuis, Fundamentals of Engineering Thermodynamics, 2nd ed.,
McGraw-Hill, New York, NY (1992).
3. Cengel, Y. A., and M. A. Boles, Thermodynamics: an Engineering Approach, 3rd ed., McGraw-Hill, New York, NY (1998).
4. Rogers, G., and Y. Mayhew, Engineering
Thermodynamics, Work and Heat Transfer,
Longman, Harlow, U.K. (1992).
5. Sonntag, R. E., and G. J. Van Wylen, Introduction to Thermodynamics Classical and Statistical, 3rd ed., Wiley, New York, NY (1991).
6. Leung, J. C., Simplified Vent Sizing Equations
for Emergency Relief Requirements in Reactors
and Storage Vessels, AIChE Journal, 32 (10),
pp. 16221634 (1986).
7. Jones, J. B., and R. E. Dugan, Engineering
Thermodynamics, Prentice Hall, Englewood
Cliffs, NJ (1996).
8. Lee, B. I., and M. G. Kesler, A Generalized
Thermodynamic Correlation Based on Three-Parameter Corresponding States, AIChE Journal,
21 (3), pp. 510527 (May 1975).
9. Wu, G. Z. A., and L. I. Stiel, A Generalized
Equation of State for the Thermodynamic Properties of Polar Fluids, AIChE Journal, 31 (10),
pp. 16321644 (1985).
10. Keenan, J. H., et al., Steam Tables: Thermodynamic Properties of Water Including Vapor, Liquid
and Solid Phases, Wiley, New York, NY (1978).
11. Perry, R. H., and D. Green, Perrys Chemical
Engineers Handbook, 6th ed., McGraw-Hill,
New York, NY (1984).

JOHN GARVIN is president of Madison Technical


Software Inc., Westwood, MA (E-mail:
madison@iol.ie). He has over 25 years of experience
in the design and management of chemical and
biochemical projects and has worked as a design
engineer and project manager for a range of
engineering and technology companies in Ireland
and the U.S. For Madison Technical Sofware, he has
written and sold commercial chemical engineering
software on physical properties, heat transfer and
combustion for clients throughout the U.S., Western
Europe and East Asia. Currently, he is director of
process and project engineering for Callaghan
Engineering, Dublin, Ireland.

CEP

July 2002

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