Physical Chemistry II Chem 402 Spring 2011

Chapter 2 (2, 8, 18, 19, 21, 35, 40, 41)

P2.2: The temperature of 2.50 moles of an ideal gas increases from 13.5C to 55.1C as the gas is
compressed adiabatically. Calculate q, w, U , and H for this process assuming that CV,m = (3/2)R.

q = 0 because the process is adiabatic. (This value of Cv is appropriate for a monatomic IG. Do you know
WHY?)

38.314 J mol-1K -1
w U nCV ,m T 2.50 mol 55.1 C 13.5 C 1.30 103 J
2
H U PV
U nRT 1.30 103 J 2.50 mol8.314 J mol-1K -1 55.1 C 13.5 C
H 2.16 103 [J]

P2.8: Calculate w for the adiabatic expansion of 1 mol of an ideal gas at an initial pressure of 2.25 bar
from an initial temperature of 475 K to a final temperature of 322 K. Write an expression for the work
done in the isothermal reversible expansion of the gas at 322 K from an initial pressure of 2.25 bar. What
value of the final pressure would give the same value of w as the first part of this problem? Assume that
CP,m = (5/2)R. (This value of Cp is appropriate for a monatomic IG. Do you know WHY?)

3
wad U n CP , m R T 8.314 J mol-1K -1 322 475 K 1.91103 [J]
2

dV V P
wreversible PdV nRT nRT ln f nRT ln i
V Vi Pf
Pi wreversible
ln
Pf nRT
Pi 1.91103 J
ln 0.7127
Pf 1 mol8.314 J mol-1K -1 322 K
Pf 0.472 Pi 1.10 [bar]
P2.18: An ideal gas undergoes an expansion from the initial state described by Pi, Vi, T to a final state
described by Pf, Vf, T in (a) a process at the constant external pressure Pf and (b) in a reversible process.
Derive expressions for the largest mass that can be lifted through a height h in the surroundings in these
processes.

Pf V f Vi
a ) w mgh Pf V f Vi ; m
gh
Vf nRT V f
b) w mgh nRT ln ; m ln
Vi gh Vi

P2.19: An ideal gas described by Ti = 300. K, Pi = 1.10 bar, and Vi = 10.0 L is heated at constant volume
until P = 9.80 bar. It then undergoes a reversible isothermal expansion until P = 1.10 bar. It is then
restored to its original state by the extraction of heat at constant pressure. Depict this closed-cycle process
in a PV diagram. Calculate w for each step and for the total process. What values for w would you
calculate if the cycle were traversed in the opposite direction?
 PV 1.10 bar10.0 L
n i i
0.481 [mol]
RTi 8.314510-2 L bar mol-1K -1 275 K

The process can be described by

step 1: Pi,Vi,Ti P1 = 9.80 bar,Vi, T1
step 2: P1,Vi, T1 Pi,V2 T1
step 3: Pi, V2, T1 Pi,Vi,Ti.
In step 1, Pi,Vi,Ti P1,Vi, T1, w = 0 because V is constant.
In step 2, P1,Vi, T1 Pi, V2, T1
Before calculating the work in step 2, we first calculate T1.
P1 9.80 bar
T1 Ti 275 K 2450 K
Pi 1.10 bar

Vf Pi
w nRT1 ln nRT1 ln
Vi Pf
9.80 bar
0.481 mol 8.314 J mol-1K -1 2450 Kln 21.4103 [J]
1.10 bar
In step 3,

PV 9.80
1 i PV
i 2 ; V2 Vi 89.1 [L]
1 i
PV
Pi 1.10
105 Pa 10-3 m3
w Pexternal V 1.00 bar 9.80 L 89.1 L 8.70103 [J]
bar L

wcycle 0 21.4 103 J 8.70 103 J 12.7 103 [J]

If the cycle were traversed in the opposite direction, the magnitude of each work term would be
unchanged, but all signs would change.
P2.21: The heat capacity of solid lead oxide is given by
T
CP , m 44.35 1.47 103 in units of [J K 1 mol1 ]
K
Calculate the change in enthalpy of 3.25 mol of PbO(s) if it is cooled from 750. to 300. K at constant
pressure.

Tf

H n C p ,m dT
Ti
300
T T
44.35 1.47 10
3
3.25 d
750
K K
44.35 300 K 750 K
300 K

= 3.25 1.47 103 T 2


2 K
750 K

64.9 103 J 1.13 103 J

66.0 103 [J]

P2.35: Consider the adiabatic expansion of 0.500 mol of an ideal monatomic gas with CV,m = 3/2R. The
initial state is described by P = 5.50 bar and T = 285. K.
a. Calculate the final temperature if the gas undergoes a reversible adiabatic expansion to a final pressure
of P = 1.00 bar.
b. Calculate the final temperature if the same gas undergoes an adiabatic expansion against an external
pressure of P = 1.00 bar to a final pressure P = 1.00 bar.
Explain the difference in your results for parts (a) and (b).
a)
1 1 1 1
Tf V TP T Pf
i i f i
Ti V f
PT
i f
T
f Pi
1 1
Tf Tf T P
* f f
Ti Ti Ti Pi
1 1
Tf P P
f i
Ti Pi P
f
5
1
3
5.50 bar 5
Tf 3 285 K 144 [K]
1.00 bar

b)

U nCV ,m T f Ti Pexternal V f Vi

T T
nCV ,m T f Ti nRPexternal f i
Pf Pi

nRPexternal nRPexternal
T f nCV ,m Ti nCV ,m

Pf Pi
RPexternal -1 -1 8.314 J mol K 1.00 bar
-1 -1

CV , m 1.58.314 J mol K +
Pi 5.50 bar
T f Ti 285 K
C RPexternal -1 -1 8.314 J mol K 1.00 bar
-1 -1

V ,m Pf 1.58.314 J mol K + 1.00 bar

T f 192 [K]
More work is done on the surroundings in the reversible expansion, and therefore U and the temperature
decrease more than for the irreversible expansion.

P2.40: The formalism of the Youngs modulus is sometimes used to calculate the reversible work
involved in extending or compressing an elastic material. Assume a force F is applied to an elastic rod of
cross sectional area A0 and length L0. As a result of this force the rod changes in length by L. The
Youngs modulus E is defined as
tensile stress F
FL0
E
A0

tensile strain L
L0 A0 L
a) Relate k in Hookes Law to the Youngs modulus expression given above.
b) Using your result in part a show that the magnitude of the reversible work involved in changing the
2
1 L
length L0 of an elastic cylinder of cross sectional area A0 by L is w EA0 L0 .
2 L0

FL0 EA0 L
E F k L
A0 L L0
L 2
1 1 L
wtwist
0
Fdx Ld L k L2 EA0 L0
2 2

L0

P2.41) The Youngs modulus (see P2.40) of muscle fiber is approximately 3.12107 Pa. A muscle fiber
2.00 cm in length and 0.100 cm in diameter is suspended with a mass M hanging at its end. Calculate the
mass required to extend the length of the fiber by 10%.
EA0 L
F k L gm
L0
2
0.0010 m
3.12 10 Pa 0.10 0.0200 m
7

EA L 2 0.25 [kg]
m 0
L0 g 0.0200 m 9.81 m s 2