Physical Chemistry Third Edition

38 1 The Behavior of Gases and Liquids

e.The equilibrium state of a system is independent of the

history of the system.

f.The macroscopic state of a one-phase fluid system

containing one substance is specified by the value of

three state variables.

g.Two gaseous systems containing the same substance

and having the same values ofT,P, andncan have

different volumes.

h.Negative pressures can occur in metastable systems.

i.Negative pressures can occur in equilibrium systems.

j.Above the critical temperature and pressure, there is no

distinction between the liquid and gaseous phases.

1.50 a.Find the expression for the isothermal compressibility

of a gas obeying the truncated pressure virial equation

of state:

PVnRT+nA 2 P

whereA 2 depends onTbut not onPorn.

b.Find the value of the isothermal compressibility

of carbon dioxide at a temperature of 273.15 K and

a pressure of 2.000 atm using the expression from

part a.

c.Find the value of the isothermal compressibility of

carbon dioxide at a temperature of 273.15 K and a

pressure of 2.000 atm using the ideal gas law.

References

O. Redlich and J. N. S. Kwong,Chemi. Rev., 44 , 233 (1949).

G. Soave,Chem. Eng. Sci., 27 , 1197 (1972).

R. M. Gibbons and A. P. Laughton,J. Chem. Soc., Faraday Trans. 2, 80 , 1019 (1984).

J. O. Hirschfelder, C. F. Curtiss, and R. B. Bird,MolecularTheory of Gases and Liquids,

Wiley, New York, 1954, pp. 250ff.