Physical Chemistry Third Edition

(C. Jardin) #1

4.4 Gibbs Energy Calculations 181


B 3 b^2. Find the value of∆Afor the isothermal
expansion of 1.000 mol of argon at 298.15 K from
a volume of 10.000 L to a volume of 25.000 L.
Compare with the result assuming argon to be an
ideal gas.

4.34Assume that argon obeys the truncated pressure virial
equation of state


PVmRT+A 2 P

withA 2 − 15 .8cm^3 mol−^1.
a.Find the value ofGm−G◦mfor argon gas at 298.15 K
and 1.000 atm.
b. Repeat the calculation for 298.15 K and 20.00 atm.

4.35 a.Find an expression for∆Afor the isothermal expansion
of a gas obeying the van der Waals equation of state
from volumeV 1 to volumeV 2.
b.Find the value of∆Afor the isothermal expansion of
1.000 mol of argon gas at 298.15 K from a volume of
10.000 L to a volume of 25.000 L. Compare with the
result assuming argon to be an ideal gas, and with the
result of Problem 4.33.


4.36 Calculate∆Gfor each of the following processes. If∆G
cannot be calculated, write “no numerical calculation
possible.”
a.1.000 mol of ice is melted at 0.00◦C and 1.000 atm.
b. 1.000 mol of water is heated at a constant pressure of
1.000 atm from 20.00◦C to 80.00◦C.
c.2.500 mol of an ideal gas is compressed isothermally at
a temperature of 400.0 K from 1.000 bar to
5.35 bar.
d.1.000 mol of solid water (ice) is pressurized
isothermally from 1.000 atm to 50.00 atm.


4.37 a.Calculate∆H◦,∆S◦,∆H◦−T∆S◦, and∆G◦for the
reaction at 298.15 K:
CH 4 (g)+2O 2 (g)−→CO 2 (g)+2H 2 O(g).
b.Calculate∆H◦,∆S◦, and∆G◦for the same reaction
at 498.15 K. Assume that the heat capacities are
constant.
c.If 2.000 mol of methane is burned at constant pressure
and a temperature of 498.15 K and 80.0% of the heat
produced is put into a steam engine with an efficiency
that is 75.0% as great as that of a Carnot engine
operating between 200.0◦C and 100.0◦C, find the


amount of work in joules that can be done on the
surroundings.
4.38 If∆Gcan be defined for the process, calculate∆Gfor
each of the following processes:
a. 1.000 mol of water is vaporized at 100.0◦C and
1.000 atm.
b. 1.000 mol of an ideal gas is heated at a constant
pressure of 1.000 atm from 20.00◦C to 80.00◦C.
c.1.000 mol of diamond is converted isothermally into
graphite at 298.15 K and 1.000 bar.
4.39Assume that a gas can be described adequately by either of
the following equations of state:

PVm
RT

 1 +

B 2
Vm
or

PVmRT+A 2 P

where it can be shown thatA 2 B 2.
a.Find a formula for∆Gfor an isothermal pressure
change of such a gas.
b.Find a formula for∆Afor an isothermal volume
change of a such a gas.
c.Find∆Gfor the isothermal expansion at 50.0◦Cof
2.000 mol of CO 2 from a pressure of 5.000 atm to a
pressure of 1.000 atm. For CO 2 at 50.0◦C,
B 2 − 1. 03 × 10 −^4 m^3 mol−^1.
4.40Assume that a gas can equally well be described by the two
equations of state:

PVm
RT
 1 +

B 2
Vm

and

PVmRT+A 2 P

where it can be shown thatA 2 B 2.
a. Find an expression for∆Gand∆Afor isothermally
changing the volume of 1.000 mol of the gas from a
molar volumeVm1to a molar volumeVm2.
b. Find the value of∆Gand∆Afor compressing
1.000 mol of argon from 25.00 L to 5.00 L at a constant
temperature of 298.15 K. The value of B 2 for argon at
this temperature is− 15 .8cm^3 mol−^1.
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