Homework Assignment # 1 (Due February 2, 2010)

Chapter 1
1) Consider a gas mixture in a 2.00-dm3 flask at 27.0C. For each of the following mixtures,
calculate the partial pressure of each gas, the total pressure, and the composition of the mixture
in mole percent.
a) 1.00 g H2 and 1.00 g O2
b) 1.00 g N2 and 1.00 g O2
c) 1.00 g CH4 and 1.00 g NH3
a)
1.00 2.016 mol 8.314 J mol1 K 1 300 K
5 5
= 6.24
6.19 10
x10Pa
Pa
3
3
V
2.00 10 m
nO RT 1.00 32.00 mol 8.314 J mol1 K 1 300 K
PO2 = 2
=
= 3.90 104 Pa
V
2.00 103 m3
Ptotal = 6.57 105 Pa
mol H 2
1.00 2.016
= 100
= 94.1%
mol % H 2 = 100
mol H 2 + mol O 2
1.00 2.016 + 1.00 32.00
PH 2 =

nH 2 RT

mol % O 2 = 100

mol O 2
1.00 32.00
= 100
= 5.9%
mol H 2 + mol O 2
1.00 2.016 + 1.00 32.00

b)
1.00 28.02 mol 8.314 J mol 1 K 1 300 K
PN2 =
=
= 4.45 104 Pa
3
3
V
2.00 10 m
nO RT 1.00 32.00 mol 8.314 J mol1 K 1 300 K
PO2 = 2
=
= 3.90 104 Pa
V
2.00 103 m3
Ptotal = 8.35 104 Pa
mol N 2
1.00 28.02
= 100
= 53.3%
mol % N 2 = 100
mol N 2 + mol O 2
1.00 28.02 + 1.00 32.00
nN2 RT

mol % O 2 = 100

mol O 2
1.00 32.00
= 100
= 46.7%
mol N 2 + mol O 2
1.00 28.02 + 1.00 32.00

c)
PNH3
PCH 4
Ptotal

1.00 17.03 mol 8.314 J mol1 K 1 300 K

=
=
= 7.32 104 Pa
3
3
2.00 10 m
V
nCH 4 RT 1.00 16.04 mol 8.314 J mol1 K 1 300 K
=
=
= 7.77 104 Pa
2.00 103 m3
V
= 1.51 105 Pa
nNH3 RT

mol % NH 3 = 100
mol % O 2 = 100

mol NH 3
1.00 17.03
= 100
= 48.5%
mol NH 3 + mol CH 4
1.00 17.03 + 1.00 16.04

mol CH 4
1.00 16.04
= 100
= 51.5%
mol NH 3 + mol CH 4
1.00 17.03 + 1.00 16.04

2) Consider a 20.0-L sample of moist air at 60C and 1 atm in which the partial pressure of water
vapor is 0.120 atm. Assume that dry air has the composition 78.0 mole percent N2, 21.0 mole
percent O2, and 1.00 mole percent Ar.
a) What are the mole percentages of each of the gases in the sample?
PH O
b) The percent relative humidity is defined as % RH = *2 where PH 2O is the partial pressure of
PH 2O
water in the sample and PH2O = 0.197 atm is the equilibrium vapor pressure of water at 60C. The
gas is compressed at 60C until the relative humidity is 100%. What volume does the mixture
now occupy?
c) What fraction of the water will be condensed if the total pressure of the mixture is
isothermally increased to 200 atm?
a)

mol % N 2 = 100
mol % O2 = 100
mol % Ar = 100

PN 2
Ptotal
PO2
Ptotal

= 100

0.78 0.88 atm

= 68.6%
1 atm

= 100

0.21 0.88 atm

= 18.5%
1 atm

PAr
0.01 0.88 atm
= 100
= 0.9%
1 atm
Ptotal

mol % H 2 O = 100

PH 2O
Ptotal

= 100

0.12 atm
= 12.0%
1 atm

b)

PH 2OV =

nH 2O RT

PH 2OV = PH 2OV where the primed quantities refer to 100% RH

V =

PH 2OV
PH2O

0.12 atm 20.0 L

= 12.2 L
0.197 atm

c)
If all the water remained in the gas phase, the partial pressure of water at a total pressure of 200
atm would be
PH 2O = Ptotal mol fraction H 2 O = 200 atm 0.12 = 24.0 atm

However, the partial pressure of water cannot be greater than 0.197 atm, and the excess will
condense. The fraction that condenses is given by
24.0 atm 0.197 atm
fraction condensed =
= 0.992
24.0 atm

3) The total pressure of a mixture of oxygen and hydrogen is 1.00 atm. The mixture is ignited
and the water is removed. The remaining gas is pure hydrogen and exerts a pressure of 0.400
atm when measured at the same values of T and V as the original mixture. What was the
composition of the original mixture in mole percent?
2H2(g) + O2(g) 2H2O(l)
nOo 2
0
initial moles nHo 2
at equilibrium nHo 2 2

nOo 2

If the O2 is completely consumed, nOo 2 = 0 or = nOo 2 . The number of moles of H2 remaining

is nHo 2 2 = nHo 2 2nOo 2 .
Let P1 be the initial total pressure and P2 be the total pressure after all the O2 is consumed.
RT
RT
P1 = nHo 2 + nOo 2
and P2 = nHo 2 2nOo 2
V
V
Dividing the second equation by the first

nHo
nOo
P2
= o 2 o 2 o 2 o = xH 2 2 xO2 = 1 xO2 2 xO2 = 1 3xO2
P1 nH 2 + nO2
nH 2 + nO2
P 1 0.400 atm
1
xO2 = 1 2 = 1
= 0.20;
3
1.00 atm1
P1 3

xH 2 = 0.80

4) The barometric pressure falls off with height above sea level in the Earth's atmosphere as

M i gz

Pi = Pi 0 e RT where Pi is the partial pressure at the height z, Pi 0 is the partial pressure of

component i at sea level, g is the acceleration of gravity, R is the gas constant, and T is the
absolute temperature. Consider an atmosphere that has the composition
x N 2 = 0.600 and xCO2 = 0.400 and that T = 300 K. Near sea level, the total pressure is 1.00 bar.
Calculate the mole fractions of the two components at a height of 50.0 km. Why is the
composition different from its value at sea level? Mi is the molecular mass of the gas.

PN2 = PN02 e

M i gz
RT

28.04 103 kg 9.81 m s 2 50 103 m

= 0.600 1.0125 105 Pa exp

8.314 J mol1 K 1 300 K

= 242 Pa
0
PCO2 = PCO
e
2

xCO2

M i gz
RT

44.04 103 kg 9.81 m s 2 50 103 m

= 0.400 1.0125 105 Pa exp

8.314 J mol1 K 1 300 K

= 6.93 Pa
PCO2
6.93
=
=
= 0.028
PCO2 + PN2 6.93 + 242

xN2 = 1 xCO2 = 0.972

The mole fraction of CO2 at the high altitude is much reduced relative to its value at sea level
because it has a larger molecular mass than N2.

5) Calculate the pressure exerted by benzene for a molar volume 1.42 L at 790 K using the
RT
a
1
nRT
n2a
1
. The

Vm b
T Vm (Vm + b ) V nb
T V (V + nb )
Redlich-Kwong parameters a and b for benzene are 452.0 bar dm6 mol2 K1/2 and 0.08271 dm3
mol1, respectively. Is the attractive or repulsive portion of the potential dominant under these
conditions?
RT
a
1

P=
Vm b
T Vm (Vm + b )

Redlich-Kwong equation of state: P =

8.314102 bar dm3 mol1K 1 790 K

1.42 dm3 mol1 0.08271dm3mol1
1

452.0 bar dm 6 mol2 K 2

1

1
3
3
1.42 dm mol 1.42 dm mol1 + 0.08271dm3mol1
790 K

P = 41.6 bar
RT 8.3145102 L bar mol1K 1 790 K
=
= 46.3 bar
Pideal =
V
1.42 L
Because P < Pideal, the attractive part of the potential dominates.

Chapter 2
1) 3.00 moles of a gas are compressed isothermally from 60.0 L to 20.0 L using a constant

external pressure of 5.00 atm. Calculate q, w, U, and H.

w = Pexternal V

3
4
= 5 1.013 105 Pa ( 60
10-33 L 60x10
2.03 x 10
20 10-3L)
L )== +2.03
(20x10
104JJ

U = 0 and H = 0 because T = 0
4 4
q = w = 2.03
10
J J
-2.03
x10

2) An automobile tire contains air at 320 103 Pa at 20C. The stem valve is removed and the air

is allowed to expand adiabatically against the constant external pressure of 100 103 Pa until P =
Pexternal. For air, CV,m = 5/2 R. Calculate the final temperature of the gas in the tire. 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

P
Pi
f
The factor n cancels out. Rearranging the equation

RPext
CV ,m +
Pf

Tf
Ti

CV ,m
=
CV ,m

RPext
T f = CV ,m +
Ti
Pi

RP
+ ext
Pi
RP
+ ext
Pf

8.314 J mol-1 K 1 105 Pa

2.5 8.314 J mol K +
3.20 105 Pa
=
8.314 J mol-1 K 1 105 Pa
2.5 8.314 J mol-1 K 1 +
105 Pa
T f = 0.804Ti T f = 235 K
-1

-1

3) An ideal gas described by Ti = 300 K, Pi = 1.00 bar and Vi = 10.0 L is heated at constant
volume until P = 10.0 bar. It then undergoes a reversible isothermal expansion until P = 1.00
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
1.00 bar 10.0 L
i i
=
= 0.401 mol
RTi 8.314510-2 L bar mol-1 K -1 300 K
The process can be described by
step 1: Pi,Vi,Ti P1 = 10.0 bar,Vi, T1
step 2: P1,Vi, T1 Pi,V2 T1
step 3: Pi, V2, T1 Pi,Vi,Ti.
n=

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.
P
10.0 bar
T1 = Ti 1 = 300 K
= 3000 K
Pi
1.00 bar
Vf
P
w = nRT1 ln
= nRT1 ln i
Vi
Pf
= 0.401 mol 8.314 J mol -1 K -1 3000 K ln

10.0 bar
= 23.0103J
1.00 bar

In step 3,

PV
1 i = PV
i 2 ; V2 =

PV
1 i
= 10Vi = 100 L
Pi

105 Pa
10-3 m3
= 9.00103 J
(10 L 100 L )
bar
L
= 0 23.0 103J + 9.00 103J = 14.0 103 J

w = Pexternal V = 1.00 bar

wcycle

If the cycle were traversed in the opposite direction, the magnitude of each work term would be
unchanged, but all signs would change.

4) A pellet of Zn of mass 10.0 g is dropped into a flask containing dilute H2SO4 at a pressure P =
1.00 bar and temperature T = 298 K. What is the reaction that occurs? Calculate w for the
process.
Zn(s) + H2SO4(aq) Zn2+(aq) + SO42-(aq) +H2(g)
The volume of H2 produced is given by
V =

10.0 g
65.39 g ( mol Zn )

-1

1mol H 2 8.314 J mol -1 K -1 298 K

= 3.79 10-3 m 3
1mol Zn
1105 Pa

w = Pexternal V
V volume of H 2 produced.
w = 1105 Pa 3.7910-3 m 3 = 379 J

5) One mole of an ideal gas with CV,m = 3/2R initially at 298 K and 1.00 105 Pa undergoes a

reversible adiabatic compression. At the end of the process, the pressure is 1.00 106 Pa.
Calculate the final temperature of the gas. Calculate q, w, U and H for this process.
1

Vf
=
Ti Vi

Tf

Tf
=
Ti

5
3
5
3

Pi

Pf

P
Tf
;= = i
Pf
Ti

T f Pi
=
;
Ti Pf

1.00105 Pa
0.4
=
= ( 0.100 ) = 2.51

6
Ti 1.0010 Pa
T f = 2.51298 K = 749 K
q = 0 because the process is adiabatic.
38.314 J mol -1 K -1
w = U = nCV ,m T = 1 mol
( 749 K 298 K ) = 5.62 103 J
2
H = U + ( PV ) = U + R T = 5.62 103 J + 8.314 J mol-1 K -1 ( 749 K 298 K )
Tf

H = 9.37 103 J