CH116P | Physical Chemistry 1 Lecture

PROBLEM SET 1: Volumetric Properties of Pure Fluids

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Exercise Set 1
1. How many phase-rule variables must be specified to fix the thermodynamic state of each of
the following systems?
a. water in equilibrium with its vapor
b. liquid water in equilibrium with a mixture of water vapor and nitrogen
c. a three-phase system of a saturated aqueous salt solution at its boiling point with excess
salt crystals present

2. How many phase-rule variables must be specified to fix the thermodynamic state of each of
the following systems?
a. A sealed flask containing liquid ethanol-water mixture in equilibrium with its vapor
b. A sealed flask containing a liquid ethanol-water mixture in equilibrium with its vapor and
nitrogen
c. A sealed flask containing ethanol, toluene, and water as two liquid phases plus vapor

3. A renowned laboratory reports quadruple-point coordinates of 10.2 bar and 24.1 C for four-
phase equilibrium of allotropic solid forms of the exotic chemical -miasmone. Evaluate the
claim.

Exercise Set 2
1. For liquid acetone at 20 C and 1 bar:

 = 1.487  10 −3 C −1  = 62  10 −6 bar −1 V = 1.287 cm3  g −1

For acetone, find:
 P 
a. the value   at 20C and 1 bar
 T V
b. the pressure after heating at constant volume from 20 C/1 bar to 30 C
c. the volume change when T and P go from 20 C/1 bar to 0C/10 bar
2. The Tait equation for liquids is written for an isotherm as:

 AP 
V = V0 1 − 
 B+P
where V is molar or specific volume, V0 is the hypothetical molar or specific volume at zero
pressure, and A and B are positive constants. Find an expression for the isothermal
compressibility consistent with this equation.

Exercise Set 3
1. Reported values of the virial coefficients of isopropanol vapor at 200 C are as given below.
Calculate V and Z for isopropanol vapor at 200 C and 10 bar.
B = -388 cm3/mol C = -26,000 cm6/mol2
a) using ideal-gas EOS
b) using the virial equations (both forms)
c) vdW EOS
d)

Exercise Set 4
1. Calculate V and Z for isopropanol vapor at 200 C and 10 bar.
a) using RK EOS
b) using SRK EOS
c) using PR EOS

2. Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find the molar volume of (a)
saturated-vapor and (b) saturated-liquid n-butane at these conditions as given by the RK EOS.

Exercise Set 5
1. Determine the molar volume of n-butane at 510 K and 25 bar based on each of the following:
a) the ideal-gas state
b) the generalized compressibility-factor correlation
c) Pitzer correlations for the second virial coefficient
d) Pitzer correlations for the third virial coefficient