Physical Chemistry II Chem 402 Spring 2012

Chapter 2 (2, 22, 18, 19, 33, 35)

P2.2) The temperature of 2.50 moles of an ideal gas increases from 13.5°C to 55.1°C as the gas
is compressed adiabatically. Calculate q, w, U , and H for this process assuming that CV,m =
3/2R.
q = 0 because the process is adiabatic.

3×8.314 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  nRT  1.30 103 J  2.50 mol×8.314 J mol-1K -1   55.1 C  13.5 C 
H  2.16 103 J

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 P–V 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 bar×10.0 L
n i i
  0.481 mol
RTi 8.3145×10-2 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 K×ln  21.4×103 J
1.10 bar
In step 3,
 PV 9.80
1 i  PV V2   Vi  89.1 L
1 i
PV i 2;
Pi 1.10
105 Pa 10-3 m3
w   Pexternal V  1.00 bar× × 9.80 L  89.1 L  ×  8.70×103 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.

P2.22) One mole of carbon dioxide, for which CP,m = 37.1 J K-1 mol-1 at 298 K, is expanded
reversibly and adiabatically from a volume of 2.85 L and temperature of 300. K to a final volume
of 16.5 L. calculate the final temperature, q, w,H, and U. Assume that CP,m is constant over
the temperature interval.

q = 0 because the process is adiabatic

1CP CV 1 37.1  37.18.314  
 Vf   16.5 L 
T f  Ti    300. K     181 K
 Vi   2.85 Li 
U  CV T f  Ti    37.1  8.314  J K 1 mol1  181 K  300. K 
U  w  3.44 103 J mol1
H   CV  R  T f  Ti   4.43 103 J mol1

P2.33) An automobile tire contains air at 275.  103 Pa at 27.5°C. The stem valve is removed
and the air is allowed to expand adiabatically against the constant external pressure of one bar
until P = Pexternal. For air, CV,m = 5/2R. Calculate the final temperature. Assume ideal gas
behavior.
because q  0, U  w
nCV , m T f  Ti    Pext V f  Vi 
 nRT f nRTi 
nCV , m T f  Ti    Pext   
 Pf Pi 

The factor n cancels out. Rearranging the equation

 RP   RP 
 CV ,m  ext  T f   CV ,m  ext  Ti
 Pf   Pi 
RP
CV ,m  ext
Pi
Tf   Ti
RPext
CV ,m 
Pf
8.314 J mol-1K 1 105 Pa
2.5  8.314 J mol-1K -1 
 2.75 105 Pa  300.65 K
8.314 J mol-1K 1 105 Pa
2.5  8.314 J mol K 
-1 -1

1.00 105 Pa
T f  246 K

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  1
Tf  Vf   Tf   Pi   Tf   P  Tf P  
      ;    i  ;  i 
Ti  Vi    Ti  Pf
 Ti   Pf   Ti   Pf  
5
1
3
 5.50bar  5
Tf    3  285 K  144 K
 1.00 bar 

b)

U  nCV ,m T f  Ti    Pexternal V f  Vi 
  Tf T 
nCV ,m T f  Ti    nRPexternal   i 
P P
 f i 

 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    1.5×8.314 J mol K + 
Pi 5.50 bar
T f  Ti    285 K   
 RPexternal   -1 -1 8.314 J mol K ×1.00 bar 
-1 -1

 CV ,m  P   1.5×8.314 J mol K + 1.00 bar 

 f   
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.