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Nomenclature

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

that for real liquids cv can

be approximated by cp is

not correct. To get accurate

cv values, use equations

of state.

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

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.

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)

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-

www.cepmagazine.org

cv

July 2002

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

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

Temperature, K

300

350

400

450

Temperature, K

300

350

400

450

Saturated Water

Temperature, K

300

350

400

450

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

Lee and Kesler (8)

Wu and Stiel (9)

Wu and Stiel (9)

Keenan (10)

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).

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

www.cepmagazine.org

65

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