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The problems of the first law

1.1 a lead bullet is fired at a frigid surface. At what speed must it


travel to melt on impact, if its initial temperature is 25 and
heating of the rigid surface of the rigid surface is neglected? The
melting point of lead is 327. The molar heat of fusion of the lead
is 4.8kJ/mol. The molar heat capacity CP of lead may be taken as
29.3J/(mol K)

Solution:

Qabsorb Qincrease Qmelt


1 2
mv
2
Qabsorb W

n(C p T

1
nMv 2
2

n[29.3 (327 25) 4.8 103 ]


V

H melting )

1
n 207.2 10 3 v 2
2

363(m / s )

1.2 what is the average power production in watts of a person who


burns 2500 kcal of food in a day? Estimate the average additional
powder production of 75Kg man who is climbing a mountain at the
rate of 20 m/min

QBurning

2500 10 3 4.1868 10467000( J )


10467000
121( J / S )
24 60 60
20
75 9.8
245( J / S )
60

P W /t

QBurning / t

Pincreasin g

mg

Solution

h
t

1.3 One cubic decimeter (1 dm3) of water is broken into droplets


having a diameter of one micrometer (1 um) at 20.
(a) what is the total area of the droplets?
(b)Calculate the minimum work required to produce the droplets.
Assume that the droplets are rest (have zero velocity)
Water have a surface tension of 72.75 dyn/cm at 20 (NOTES: the
term surface energy (ene/cm2) is also used for surface tension
dyn/cm)
Solution

Stotal

nS Single

(1 10 1 )3

(0.5 10 6 ) 2

4
(0.5 10 6 )3
3
72.75 10 5 2 (3 103 6 10 2 )

6 103 (m 2 )

436.6( J )

1.4 Gaseous helium is to be used to quench a hot piece of metal. The


helium is in storage in an insulated tank with a volume of 50 L and a
temperature of 25, the pressure is 10 atm. Assume that helium is
an ideal gas.

(a) when the valve is opened and the gas escapes into the quench
chamber (pressure=1 atm), what will be the temperature of the
first gas to hit the specimen?
(b)As the helium flows, the pressure in the tank drops. What will be
the temperature of the helium entering the quench chamber when
the pressure in the tank has fallen to 1 atm?
Solution:

(a)
Adiabatic
T
P
( ) R / CP
T0
P0
298 (

1 0.4
)
10

118( K )

(b)
T
T

W
nC p
T0

1 (500 5) 101325 10 3
10 50 101325 10 3
2.5R
R 298
T 298 118 180( K )

118( K )

1.5 An evacuated (P=0), insulted tank is surrounded by a very large


volume (assume infinite volume) of an ideal gas at a temperature T0.
The valve on the tank is oened and the surrounding gas is allowed
to flow suickly into t(e tank until the pressure insi`e the tank is
equals the pressure outside. Assume that no heat flow takes place.
What is the0final tempeture kf te gaS in the tank? The heat cap!city
mf the gas, Cp and Cv each ay be(assumed to be c/nsuant over th
temperature rang!spanNed by the dperiment. You answer may be
meft in terms of Cp and SvMhint: one way to approach the xroblem
is to define the system as the gas ends up in the tank.
hint: one way to approach the xroblem is to define the system as the
gas ends up in the tank.

Adiabatic
T
P
( ) R / CP
T0
P0

solution

T0 (

P0 0 R / CP
)
P0

T0

1.6 Calculate the heat of reaction of methane with oxygen at 298K,


assuming that the products of reaction are CO2 and CH4 (gas)[This
heat of reaction is also called the low calorific power of methane]
convert the answer into unites of Btu/1000 SCF of methane. SCF
means standard cubic feet, taken at 298 and 1atm
NOTE: this value is a good approximation for the low calorific
powder of natural gas
0
H 298
[ Kcal / g mol ]

FOR

DATA:

CO2 ( g )

17.89
94.05

H 2 O( g )

57.80

CH 4 ( g )

solution

CH 4
H 298

2O2

CO2

( H CO2

2 H 2O
2 H H 2O

H 298 191.76( Kcal / g mol)

H CH 4 )

( 94.05 2 57.80 17.89)

191.76 103
10 3

1
0.30483 103 252 103

26.9( Btu / 1000SCF )

1.7 Methane is delivered at 298 K to a glass factory, which operates


a melting furnace at 1600 K. The fuel is mixed with a quantity of air,
also at 298 K, which is 10% in excess of the amount theoretically
needed for complete combustion (air is approximately 21% O2 and
79% N2)
(a) Assuming complete combustion, what is the composition of the
flue gas (the gas following combustion)?
(b)What is the temperature of the gas, assuming no heat loss?

(c) The furnace processes 2000kg of glass hourly, and its heat losses
to the surroundings average 400000 kJ/h. calculate the fuel
consumption at STP (in m3/h) assuming that for gas
H1600-H298=1200KJ/KG
(d)A heat exchanger is installed to transfer some of the sensible heat
of the flue gas to the combustion air. Calculate the decrease in
fuel consumption if the combustion air is heated to 800K
DATA STP means T=298K, P=1atm
for
CH 4
CO 2
H 2O
N2
O2

C P (cal / mol

C)

16
13.7
11.9
8.2
8.2
(a)
CH 4

2O2

CO2

2H 2O

1
79
3 2 1.1
2 (1.1 1)
21
H 2 O% 2CO2 % 17.43%

CO2 %

Solution

N2 %

72.12%

O2 %

0.87%

8.71%

(b)
C p, p
T

C p ,i X i
T0

298

0.01[13.7 8.71 11.9 17.43 8.2 (72.12 0.87)] 9.25(cal / mol


191.76 1000
9.25 11.48

2104( K )

C)

(C )
P 1200 2000 400000

2800000( KJ / h)

2800000 10 3
191.76 1000 9.25 11.48(1600 298)
1
(
4.1868
)
11.48
0.0224

VConsumin g

3214(m 3 / h)

(d )
C p ,r
H

H 298

100
] / 11.48
21

[16 8.2 2.2

C p ,i X i

C p , p ,i ni

8.87(cal / mol

C)

C p ,r ,i ni )dT

191.76 1000 [(9.25 11.48) 8.87 11.48)](800 298) 189570(cal / g mol )


VConsumin g

2800000 10 3
189570 9.25 11.48(1600 800)
1
(
4.1868
)
11.48
0.0224

1644(m 3 / h)

1.8 In an investigation of the thermodynamic properties of


a-manganese, the following heat contents were determined:
H700-H298=12113 J/(g atom)

H1000-H298=22803 J/(g atom)

Find a suitable equation for HT-H298 and also for CP as a function of


temperature in the form (a+bT) Assume that no structure
transformation takes place in the given tempeture rang.
H

C P dT

a bTdT

[aT

b 2 T
T ] 298
2

b
(700 2 298 2 ) 12113
2
b
a(1000 298)
(1000 2 298 2 ) 22803
2
a 35.62
a(700 298)

Solution

b
CP

0.011
35.62 0.011T

T
H 298

35.62(T

298) 0.0055(T 2

298 2 )

1.9 A fuel gas containing 40% CO, 10% CO2, and the rest N2 (by
volume) is burnt completely with air in a furnace. The incoming and
ongoing temperatures of the gases in the furnace are 773K and
1250K,respectively. Calculate (a) the maximum flame temperature
and (b) heat supplied to the furnace per cu. ft of exhaust gas

H f , 298,CO
H

0
f , 298, CO2

110458 J / mol
393296 J / mol

C P ,CO

28.45 3.97 10 3 T 0.42 105 T 2 ( J / molK )

C P ,CO2

44.35 9.20 10 3 T 8.37 105 T 2 ( J / molK )

C P ,O2

19.92 4.10 10 3 T 1.67 105 T 2 ( J / molK )

CP, N 2

29.03 4.184 10 3 T ( J / molK )


2CO

2CO2

O2

when 1mole fuel need 1mole air ( N 2 / O2

4)

then
reation
20%

CO

5%

CO2
N2

65%

O2

10%

production
CO2

27.8%
72.2%

N2

H i , 298

0
f , 298, r

ni

0
f , 298, p

393296

ni

110458

282838( J / mol )

(a)
C p,r

0.2C P , CO

C p , p , i ni

28.77

4.38 10 T

C p,r

0.67 10 T

0.278C P , CO2

C p , p , i ni

5.58 10 3 T

33.28
H

T
298

0.65C P , N 2

( J / molK )

( J / molK )
C p , r , i ni ) dT

C p , p , i ni

5.58 10 3 T

(33.28

0.1C P , O2

0.722C P , N 2

0.19 105 T
(

H i , 298ni

282838 0.2

0.05C P , CO2

0.19 105 T

0.9dT

28.77

4.38 10 3 T

0.67 105 T

2.19 10 3 T 2

dT

733

28283.8

Solution

(1.18T
T

H i , 298ni

282838 0.2

T
298

( 28.77T

0.321T 2

0.499T

) T298

0.67 105 T

) 733
298

C p , r ,i ni )dT

C p , p ,i ni

(33.28 5.58 10 3 T

0.19 105 T 2 ) 0.9dT

28.77 4.38 10 3 T

0.67 105 T 2 dT

1250

28283.8 2 (28.77T
(1.18T

0.321T 2

2.19 10 3 T 2

0.499T 1 ) T298

0.67 105 T 1 ) 1250


298

T
(b)
1250
Q298

282838 0.2

1250
Q298

282838 0.2

1250
298
1250
298

(33.28 5.58 10 3 T

0.19 105 T 2 ) 0.9dT

(33.28 5.58 10 3 T

0.19 105 T 2 ) 0.9dT

1.10 (a) for the reaction CO

1
O2
2

CO2 ,what

is the enthalpy of

reaction ( H 0 ) at 298 K ?
(b) a fuel gas, with composition 50% CO, 50% N2 is burned using
the stoichiometric amount of air. What is the composition of the flue
gas?
(c) If the fuel gas and the air enter there burner at 298 K, what is the
highest temperature the flame may attain (adiabatic flame
temperature)?
DATA :standard heats of formation
CO
CO2

Hf

at 298 K

110000( J / mol)
393000( J / mol)

Heat capacities [J/(mol K)] to be used for this problem N2=33,


O2=33, CO=34, CO2=57
0

(a) H 0

H f , 298, r ni

110000 393000

H f , 298, P ni

283000( J / mol )

0.5
22.2%, N 2 % 66.6%, O2 % 11.1%
1 0.25 / 0.2
22.2
product CO2 %
25%, N 2 % 75%,
100 11.1
(C )C p , P
Ci , p , P X i 33 0.666 33 0.222 34 0.111 33( J / mol K )
(b) fuel CO %

Solution

Cr , P
H

Ci , r , P X i
H0

57 0.25 33 0.75 39( J / mol K )

n pC p , P dT

283000 0.222 (0.889 39)(T


T 2110( K )

298)

1.11 a particular blast furnace gas has the following composition by


(volume): N2=60%, H2=4, CO=12%, CO2=24%
(a) if the gas at 298K is burned with the stochiometric amount of dry
air at 298 K, what is the composition of the flue gas? What is the
adiabatic flame temperature?
(b) repeat the calculation for 30% excess combustion air at 298K

(C)what is the adiabatic flame temperature when the blast furnace


gas is preheated to 700K (the dry air is at 298K)
(d) suppose the combustion air is not dry ( has partial pressure of
water 15 mm Hg and a total pressure of 760 mm Hg) how will thE
dlaMe temperature be affected?
Air :
n(O2 )

0.104

n( N 2 )

0.416

DaTA(k J?mol)
FOR

H f (kJ / mol )

CO
CO2

110.523

??

FOR
CO

393.513

CO2

CP [ J / m o l K ]
33
57
50

H 2O ( g )

34

N 2 , O2

Solution
1
O2
2

(a)CO

1
O2
2

H2

CO2
H 2O

Fuel :
n(CO )

0.12

n(CO2 )

0.24

n( H 2 )

0.04

n( N 2 )

0.6

H CO

CP ,r ,i ni
T
T

H H2

CO2

0.36CCO2

43.6308 10
53.8
1108.98( K )

Flue :

Air :
n(O2 )

0.08

n( N 2 )

0.32

n(CO2 )

0.36

n ( H 2O )

0.04

n( N 2 )

0.92

0.12 (393.51 110.523) 0.04 (241.8 0)

H 2O

0.04CH 2O

0.92C N2

0.36 57 0.04 50 0.92 34

43.6308KJ
53.8( J / K )

810( K )

(b)repeat the calculation for 30% excess0combustion air at 298K


H

H CO

CO2

HH2

H 2O

0.12 (393.51 110.523) 0.04 (241.8 0)

43.6308KJ
CP , r ,i ni

0.36CCO2

0.04CH 2 O 1.016C N 2

0.024CO2

0.36 57 0.04 50 1.016 34 0.024 34


57.88( J / K )
T
T

43.6308 103
57.88
1051.8( K )

753.8( K )

Fuel :
n(CO )

0.12

n(CO2 )

0.24

n( H 2 )

0.04

n( N 2 )

0.6

Flue :

Air :
n(O2 )

0.104

n( N 2 )

0.416

n(CO2 ) 0.36
n( H 2O) 0.04

Maret 8, 2013

n( N 2 ) 1.016
n(O2 ) 0.024

(C)what is the adiabatic flame temperature when the blasp furnace


gas is preheated to 700K (the dry air is at 298K)
Fuel :
n(CO )

0.12

n(CO2 )

0.24

n( H 2 )

0.04

n( N 2 )

0.6

H CO

H H2

CO2

Flue :

Air :
n(O2 )

0.08

n( N 2 )

0.32

H 2O

n(CO2 )

0.36

n ( H 2O )

0.04

n( N 2 )

0.92

H fuel 700 298

0.12 (393.51 110.523) 0.04 (241.8 0)


(700 298) (0.12 33 0.24 57 0.04 28 0.6 34)
59.373KJ
0.36CCO2

CP ,r ,i ni

59.373 103
53.8
1401.6( K )

T
T

0.04CH 2O

0.96C N2

0.36 57 0.04 50 0.92 34

53.8( J / K )

1103.6( K )

(d) suppose the combustion air is not dry ( has partial pressure of
water 15 mm Hg and a total pressure of 760 mm Hg) how will the
flame temperature be affected?
n(CO )

0.12

n(CO2 )

0.24

n( H 2 )

0.04

n( N 2 )

0.6

Flue :

Air :

Fuel :

H CO

n(O2 )

0.08

n(CO2 )

0.36

n( N 2 )

0.32

n( H 2 O )

0.048

n ( H 2O )

H H2

CO2

15
0.4
760 15

0.36CCO2

0.048CH 2O

0.36 57 0.048 50 0.92 34


T
T

43.6308 10
54.2
1103( K )

n( N 2 )

0.92

H 2O

0.12 (393.51 110.523) 0.04 (241.8 0)


CP ,r ,i ni

0.008

43.6308KJ

0.92C N2
54.2( J / K )

805( K )

1.12 A bath of molten copper is super cooled to 5 below its true

melting point. Nucleation of solid copper then takes place, and the
solidification proceeds under adiabatic conditions. What percentage
of the bath solidifies?
DATA: Heat of fusion for copper is 3100 cal/mol at 1803(the
melting point of copper)
CP,L=7.5(cal/mol), CP,S=5.41+(1.5*10-3T )(cal/mol)
Solution
H SL,1803

1803

1798

1798

1803

CP , S dT

CP , L dT

H LS,1798 0

H SL,1798 3100 5.41 5 1.5 10 3 (18032 17982 ) 0.5 7.5 5 3103(cal / mol)

1.13 Cuprous oxide (Cu2O) is being reduced by hydrogen in a


furnace at 1000K,
(a)write the chemical reaction for the reduced one mole of Cu2O
(b)how much heat is release or absorbed per mole reacted? Given the
quantity of heat and state whether heat is evolved (exothermic
reaction) or absorbed (endothermic reaction)
DATA: heat of formation of 1000K in cal/mol Cu2O=-41900
H2O=-59210
solution

Cu2O H 2
H

Cu

H 2O

59210 41900 17310(cal / mol)

,exothermic reaction

1.14(a) what is the enthalpy of pure, liquid aluminum at 1000K?


(b) an electric resistance furnace is used to melt pure aluminum at
the rate of 100kg/h. the furnace is fed with solid aluminum at 298K.
The liquid aluminum leaves the furnace at 1000K. what is the

minimum electric powder rating (kW) of furnace.


DATA : For aluminum : atomic weight=27g/mol, Cp,s=26(J/molK),
Cp,L=29(J/molK), Melting point=932K, Heat of fusion=10700J/mol
Solution

H l ,1000

932

1000

298

932

CP , S dT

CP , L dT

H LS

26 (932 298) 29 (1000 932) 10700 27184( J / mol )


27184
1
P
1000
279.7(W ) 0.28(kW )
27
3600

1.15 A waste material (dross from the melting of aluminum) is found


to contain 1 wt% metallic aluminum. The rest may be assumed to
aluminum oxide. The aluminum is finely divided and dispersed in
the aluminum oxide; that is the two material are thermally
connected.
If the waster material is stored at 298K. what is the maximum
temperature to which it may rise if all the metallic aluminum is
oxidized by air/ the entire mass may be assumed to rise to the same
temperature. Data : atomic weight Al=27g/mol, O=16g/mol,
Cp,s,Al=26(J/molK),

Cp,s,

Al2O3=104J/mol,

heat

formation

of

Al2O3=-1676000J/mol
Solution;

1
1676000
27 2
T 302( K )
T

16 1.5 27
27
102

99
104

600( K )

1.16 Metals exhibit some interesting properties when they are


rapidly solidified from the liquid state. An apparatus for the rapid
solidification of copper is cooled by water. In the apparatus, liquid
copper at its melting point (1356K) is sprayed on a cooling surface,

where it solidified and cools to 400K. The copper is supplied to the


apparatus at the rate of one kilogram per minute. Cooling water is
available at 20, and is not allowed to raise above 80. What is
the minimum flow rate of water in the apparatus, in cubic meters per
minute?
DATA; for water: Cp=4.184J/g k, Density=1g/cm3; for copper:
molecular weight=63.54g/mol
Cp=7cal/mol k, heat of fusion=3120 cal/mol
QCopper / min

Solution: Q

Water

/ min

[3120 7 (1356 400)]

1000
63.54 min

1(80 20)V

2.573 10 3 (m3 / min)

1.17 water flowing through an insulated pipe at the rate of 5L/min is


to be heated from 20 to 60 b an electrical resistance heater.
Calculate the minimum power rating of the resistance heater in watts.
Specify the system and basis for you calculation. DATA; For water
Cp=4.184J/g k, Density=1g/cm3
Solution: W 4.184 (60 20) 5 1000 13947(W )
60

1.18 The heat of evaporation of water at 100 and 1 atm is


2261J/mol
(a) what percentage of that energy is used as work done by the
vapor?
(b)if the density of water vapor at 100 and 1 atm is 0.597kg/m3
what is the internal energy change for the evaporation of water?

P V

Solution:

101325

3101
2261 18
U W Q

373
0.0224 3101( J / mol )
273
7.6%
3101 2261 18 37597( J / mol )

1.19 water is the minimum amount of steam (at 100 and 1 atm
pressure) required to melt a kilogram of ice (at 0)? Use data for
problem 1.20
Solution m(2261 4.18 100) 1000 334, m 125( g )
1.20 in certain parts of the world pressurized water from beneath the
surface of the earth is available as a source of thermal energy. To
make steam, the geothermal water at 180 is passed through a
flash evaporator that operates at 1atm pressure. Two streams come
out of the evaporator, liquid water and water vapor. How much water
vapor is formed per kilogram of geothermal water? Is the process
reversible? Assume that water is incompressible. The vapor pressure
of water at 180 is 1.0021 Mpa( about 10 atm) Data: CP,L=4.18J/(g
k),

CP,v=2.00J/(g k),

Solution:

HV=2261J/g, Hm=334 J/g

(2261 2 80 4.18 80) x


irreversible

4.18 80 (1000 x), x 138( g )

The problems of the second law


2.1 The solar energy flux is about 4J cm2/min. in no focusing
collector the surface temperature can reach a value of about 900.
If we operate a heat engine using the collector as the heat source and

a low temperature reservoir at 25, calculate the area of collector


needed if the heat engine is to produce 1 horse power. Assume the
engine operates at maximum efficiency.
Solution

TH

TL
TH

(90
90

QH

W
t

6.25(m 2 )

25)
273

104
St
60

746(W )

2.2 A refrigerator is operated by 0.25 hp motor. If the interior of the


box is to be maintained at -20 ganister a maximum exterior
temperature of 35, what the maximum heat leak (in watts) into the
box that can be tolerated if the motor runs continuously? Assume the
coefficient of performance is 75% of the value for a reversible
engine.
W

Solution:

TH TL
QH
TH

0.75P
PL

3
4

TH

TL
TL

PL

273 20
0.25 746
35 20

643(W )

2.3 suppose an electrical motor supplies the work to operate a Carnot


refrigerator. The interior of the refrigerator is at 0. Liquid water is

taken in at 0 and converted to ice at 0. To convert 1 g of ice to


1 g liquid. H=334J/g is required. If the temperature outside the
box is 20, what mass of ice can be produced in one minute by a
0.25 hp motor running continuously? Assume that the refrigerator is
perfectly insulated and that the efficiencies involved have their
largest possible value.
P

Solution:

PL
M

TH

TL
TL

PL

273
0.25 746 334m
20
60m 457( g )

2.4 under 1 atm pressure, helium boils at 4.126K. The heat of


vaporization is 84 J/mol what size motor (in hp) is needed to run a
refrigerator that must condense 2 mol of gaseous helium at 4.126k to
liquid at the same temperature in one minute? Assume that the
ambient temperature is 300K and that the coefficient of performance
of the refrigerator is 50% of the maximum possible.
W

Solution:

50%

0.5P' P

TH

TL
TL

TH

P' 393(W )

QL

TL
TL

PL

300 4.216 84 2
4.216
60

0.52(hp)

2.5 if a fossil fuel power plant operating between 540 and 50


provides the electrical power to run a heat pump that works between
25 and 5, what is the amount of heat pumped into the house per
unit amount of heat extracted from the power plant boiler.
(a) assume that the efficiencies are equal to the theoretical maximum
values

(b)assume the power plant efficiency is 70% of maximum and that


coefficient of performance of the heat pump is 10% of maximum
(c) if a furnace can use 80% of the energy in fossil foe to heat the
house would it be more economical in terms of overall fissile fuel
consumption to use a heat pump or

a furnace ? do the

calculations for cases a and b


solution:

(a) P1

TH ,1 TL ,1
PH ,1
TH ,1

P2

TH , 2 TL , 2
PH , 2
TH , 2

P1

P2

540 50
25 5
PH ,1
PH , 2
540 273
273 25
PH , 2 8.98 PH ,1

(b)
PH , 2

0.6286 PH ,1

(c)a is ok , b is not.
2.6 calculate U and S when 0.5 mole of liquid water at 273 K
is mixed with 0.5 mol of liquid water at 373 K and the system is
allowed to reach equilibrium in an adiabatic enclosure. Assume that
Cp is 77J /(mol K) from 273K to 373K

Solution:
U
S

0( J )
n1CP ln(

TE
)
T1

n2CP ln(

TE
)
T2

0.5CP ln(

323
)
373

0.5CP ln(

323
)
273

0.933( J / K )

2.7 A modern coal burning power plant operates with a steam out let
from the boiler at 540 and a condensate temperature of 30.
(a) what is the maximum electrical work that can be produced by the
plant per joule of heat provided to the boiler?
(b)How many metric tons (1000kg) of coal per hour is required if
the plant out put is to be 500MW (megawatts). Assume the
maximum efficiency for the plant. The heat of combustion of coal
is 29.0 MJ/k g
(c) Electricity is used to heat a home at 25 when the out door
temperature is 10 by passing a current through resistors. What
is the maximum amount of heat that can be added to the home per
kilowatt-hour of electrical energy supplied?
(a)

Solution: W

TH TL
QH
TH

540 30
1 0.89( J )
540 30

(c )
W

(b)
29.0m
m

TL
TH

TL

69371(kg)

500 3600

QH

TH TL
QH
TH
273 25
1 19.9( J )
25 10

69.3(ton )

2.8 an electrical resistor is immersed in water at the boiling


temperature of water (100) the electrical energy input into the
resistor is at the rate of one kilowatt
(a) calculate the rate of evaporation of the water in grams per second
if the water container is insulated that is no heat is allowed to

flow to or from the water except for that provided by the resistor
(b)at what rate could water could be evaporated if electrical energy
were supplied at the rate of 1 kw to a heat pump operating
between 25 and 100
data for water enthalpy of evaporation is 40000 J/mol at 100;
molecular weight is 18g/mol; density is 1g/cm3
m

solution: (a) 18 40000


(b)

1000, m

0.45( g )

m
100 273
40000 1000
,m
18
100 25

2.23( g )

2.9 some aluminum parts are being quenched (cooled rapidly ) from
480 to -20 by immersing them in a brine , which is maintained
at -20 by a refrigerator. The aluminum is being fed into the brine
at a rate of one kilogram per minute. The refrigerator operates in an
environment at 30; that is the refrigerator may reject heat at 30.
what is them minus power rating in kilowatts, of motor required to
operate the refrigerator?
Data for aluminum heat capacity is 28J/mol K; Molecular weight
27g/mol
Solution: P

PW

1000
28 (480 20)
27
TH TL
30 20
PL
PL
TL
273 20

102474(W ) 102.5(kW )

2.10 an electric power generating plant has a rated output of 100MW.


The boiler of the plant operates at 300. The condenser operates at
40

(a) at what rate (joules per hour) must heat be supplied to the boiler?
(b)The condenser is cooled by water, which may under go a
temperature rise of no more than 10. What volume of cooling
water in cubic meters per hour, is require to operate the plant?
(c) The boiler tempeture is to be raised to 540,but the condensed
temperature and electric output will remain the same. Will the
cooling water requirement be increased, decreased, or remain the
same?
Data heat capacity 4.184, density 1g/cm3
Solution:

(a) P H

TH
TH

300 273 8
10
300 40

2.2 108 (W )
QH

(c ) P H

TH
P
TH TL

TL

PH t

7.9 1011( J )

(b)
QL

4.3 1011( J )

V 106 10 4.184 QL
V

1.03 104 (m3 )

540 273 8
10
540 40

1.626 10 (W )
no

2.11 (a) Heat engines convert heat that is available at different


temperature to work. They have been several proposals to generate
electricity y using a heat engine that operate on the temperature
differences available at different depths in the oceans. Assume that
surface water is at 20, that water at a great depth is at 4, and that
both may be considered to be infinite in extent. How many joules of
electrical energy may be generated for each joule of energy absorbed
from surface water? (b) the hydroelectric generation of electricity
use the drop height of water as the energy source. in a particular

region the level of river drops from 100m above sea level to 70m
above the sea level . what fraction of the potential energy change
between those two levels may be converted into electrical energy?
how much electrical energy ,in kilowatt-hours, may be generated per
cubic meter of water that undergoes such a drop?
Solution:

20 4
1 0.055( J )
20 273

(a)W

TH TL
QH
TH

(b) P

mg h
3600 1.06 106 (kW / h)
1000

2.12 a sports facility has both an ice rink and a swimming pool. to
keep the ice frozen during the summer requires the removal form the
rink of 105 KJ of thermal energy per hour. It has been suggested that
this task be performed by a thermodynamic machine, which would
be use the swimming pool as the high temperature reservoir. The ice
in the rink is to be maintain at a temperature of 15, and the
swimming pool operates at 20 , (a) what is the theoretical
minimum power, in kilowatts, required to run the machine? (b) how
much heat , in joule per hour , would be supplied t the pool by this
machine?
Solution:

TH

(a) P

TL
TL

(b)QH

PL

20 15 5
10 / 3600 3.77(kW )
273 15

273 20 5
10
273 15

1.14 105 (kJ )

2.13
solution:

(a)2 Al

N2

(b) H

152940(cal / mol)

2 AlN

(c ) S

4.82 2 6.77 2 45.77

49.67(cal / molK )

(d ) H 152940(cal / mol )
S 4.82 2 6.77 2 45.77 8.314 ln 10

68.81(cal / molK )

2.14
m(

solution:

0
10

CP , ICE
dT
T

273 336
263 273
22574( J / K )

(2.1ln

40

Hm
Tm
4.184 ln

CP ,WATER
dT )
T

273 40
)12000
273

2.15
W

TH

TL

W2

70428( J )

TL

300 77
1000
77

QL

2896( J )

2.16
W
W

TH

TL

300 4.2
83.3 5866.7( J )
4.2

QL

TL

300 4.2
(83.3 1.5 8.314(300 4.2)) 3719.4( J )
300

TH TL
QH
TH

2.17
(a) T 0
U O
Q

(b) S
(c)Q

n
nR ln

pdV
P0
P

1 8.314 298 ln 10 5704( J )

1 8.314 ln 10 19.1( J / K )

(d ) yes

2.18
500 60

TH

TL
TL

335m

20 0
335m
273

m 1222( g )

Property Relations
1. At -5 C, the vapor pressure of ice is 3.012mmHg and that of
supercooled liquid water is 3.163mmHg. The latent heat of fusion of
ice is 5.85kJ/mol at -5 C. Calculate G and S per mole for the
transition of from water to ice at -5 C. (3.2, 94)

RT ln

PH 2O ,ice
PH 2O , water

3.012
3.163
8.314 268 ln 0.9523
108.9 J / mol
8.314 (273 5) ln

Solution:

5.85 103 J / mol

H
G
S

T S

G
T

5850 ( 108.9)
268

22.23J /( mol K )

2. (1) A container of liquid lead is to be used as a calorimeter to


determine the heat of mixing of two metals, A and B. It has been
determined by experiment that the heat capacity of the bath is
100cal/ C at 300 C. With the bath originally at 300 C, the following
experiments are performed;(2) A mechanical mixture of 1g of A and
1g of B is dropped into the calorimeter. A and B were originally at
25 C. When the two have dissolved, the temperature of the bath is
found to have increased 0.20 C. 2. Two grams of a 50:50(wt.%) A-B
alloy at 25 C is dropped similarly into the calorimeter. The
temperature decreases 0.40 C. (a) What is the heat of mixing of the
50 50 A-B alloy (per gram of alloy)? (b) To what temperature does it
apply ? (3.5, 94)
Solution:
(a)

C P,bath

100cal / K

418J / mol

C P,bath T / 2 100 0.2 / 2 10cal / g

This is the heat of mixing.

(b) The heat capacity of CP, alloy :

C P ,alloy

C P ,bath

2 (300 0.4 25)


100 0.4
0.072cal /( g K )
2 274.6

Assuming that the calorimeter can be applied to the maximum of


T C, the for mixing to form 1 gram of alloy:
Q1

C P,bath (300 T ' ) 10

C P,bath (300 T ' ) 10

Q2

C P,alloy (T T ' ) ,

Q1

Q2

C P,alloy (T T ' )

3. The equilibrium freezing point of water is 0 C. At that


temperature the latent heat of fusion of ice (the heat required to melt
the ice) is 606 3J/mol. (a) What is the entropy of fusion of ice at 0 C ?
(b) What is the change of Gibbs free energy for ice

water at

0 C?(c) What is the heat of fusion of ice at -5 C ? CP(ice) = 0.5 cal/(g.


C); CP(water) = 1.0 cal/(g. C). (d) Repeat parts a and b at -5 C. (3.6,
p94)
Solution: (a) At 0 C, G =0,
S

H
Tm

6030
273

Tm S = H

22.09 J /( mol.K )

(b) At 0 C, G =0

CP,ice 0.5cal /( g.K ) 0.5 4.18 18J /( mol.K ) 37.62 J /( mol.K )

C P,water

1.0cal /( g.K ) 1.0 4.18 18J /( mol.K

a reversible process can be designed as follows to do the


calculation:

2
Ice, 0 C

water, 0 C

ice, -5 C

water, -5 C
4

fu

H (1)

H ( 2)

273

C p ,ice dT

268
273
268

(C p ,ice

(37.62

268
273

C p , water dT

C P , water )dT

75.24) 5

5841 .9 J / mol

H ( 3)

6030

S ( 4)

S (1)

3 ( 3)

S ( 2)

C p ,ice

273
268

dT

T
273(C p ,ice

268

C p , water

268

273

C P , water )
T

(37.62 75.24) ln

dT

273
268

dT

S
22.09

21.39 J /( mol.K )

G ( 4)

H ( 4)

T S ( 4)

5841.9 268 21.39 109.38

4. (a) What is the specific volume of iron at 298K, in cubic peter per
mole? (b) Derive an equation for the change of entropy with pressure
at constant temperature for a solid, expressed in terms of physical
quantities usually available, such as the ones listed as data; (c) The
specific entropy of iron (entropy per mole )at 298K and a pressure of
100 atm is needed for a thermodynamic calculation. The tabulated
standard entropy(at 298 K and a pressure of 1 atm) is
o
S298
27.28J / K .mol .

What percentage error would result if one assumed

that the specific entropy at 298K and 100 atm were equal to the
value of

o
S 298

given above

DATA
for iron

Cp = 24 J K-1mol-1
Compressibility = 6

Linear coefficient of thermal expansion = 15

10-7 atm 1
10-6 C-1

Density = 7.87 g/cm3


Molecular weight = 55.85g/mol
Note: It may be possible to solve this problem with out using all the

data given. (3.7, 95)


Solution: (a)

(b)

55.85 g / mol
7.87 g / cm 3

mol weight
density

V iron

S
P
S
P

V
T

7.10cm 3 / mol

7.10 10 6 m 3 / mol

3V

for iron:
S
P

3V iron

l ,iron

3 7.10 10
3.2 10

S iron

10

15 10

(m 3 /( mol.K ))

3.2 10

10

(c)
S iron

3.2 10

10

3.2 10

10

320.9 10

error%

S iron
100%
o
S 298

(100 1) 1.013 10
99 1.013 10
5

3.21 10 3 ( J / mol.K )

1.12 10

Equilibrium
1. At 400 C, liquid zinc has a vapor pressure of 10-4 atm. Estimate
the boiling temperature zinc, knowing that its heat of evaporation
is approximately 28 kcal/mol. (4.2, P116)
Solution: (a)

18 g / mol
0.92 g / cm 3

V ice

V water

V fus

18 g / mol
1g / cm 3

19.57cm 3 / mol 19.57 10 6 m 3 / mol

18cm 3 / mol 18 10 6 m 3 / mol

1.57 10 6 m 3 / mol

According to the Clapeyron equation:

dP
dT

1
V fus

dP

1
V fus

fus

T
H
T

fus

dT

take definite integration of the above:

50 1.013 105
5

1.013 10

ln

T
273

H fus

dP

fus

fus

fus

1
dT
273 T
T

49 1.013 10 5

1.57 10

49 1.013 10 5
6009

0.013

272.8K

(b)

150
0.01 3

50 10 3 lb / in.2

50 10 3 6897 Pa

345 10 6 Pa

345 10 6 Pa

(c )
ln

T
273

fus

fus

345 10 6

1.57 10 6 345 10 6
6009
0.09

249.46K

1. At 400 C, liquid zinc has a vapor pressure of 10-4 atm. Estimate


the boiling temperature of zinc, knowing that its heat of
vaporation is approximately 28kcal/mol. (4.3,117)
Solution:

H vap

4.18 28 103 J / mol 117.04 J / mol

28kcal / mol

According to Claperon equation in vapor equilibrium:


d (ln P )
P2
P1

d (ln P )

H vap
R

1
d( )
T

H vap 1
(
R
T2

1
)
T1

H vap 1
(
R
T2

ln

P1
P2

ln

1
10 4

T2

1
)
T1

117.04 10 3 1
(
8.314
T2

1
)
673

1202K

The boiling point of zinc is 1202K.


2. Troutons rule is expressed as follows:

H vap

90Tb

in joules per

mole, where Tb is the boiling point (K). The boiling temperature


of mercury is 630K. Estimate the partial pressure of liquid Hg at
298K. Use Troutons rule to estimate the heat of vaporization of
mercury.
Solution:

H vap
P

90Tb
H vap

d (ln P)

1
298

6823
10.83
298

ln P

1
)
630

22.90 10.83

12.07

P=5.73 10-6 atm


3. Liquid water under an air pressure of 1 atm at 25 C has a large
vapor pressure that it would have in the absence of air pressure.
Calculate the increase in vapor pressure produced by the pressure
of the atmosphere on the water. Water has a density of 1g/cm3;
the vapor pressure ( in the absence of the air pressure) is
3167.2Pa. (4.5, p116)
Solution:

Vl

vapor
pressure,

Gv

18 g / mol
1g / cm 3

18cm 3 / mol 18 10 6 m 3 / mol

pressure
Gl

changes

with

the

total

external

RT ln

RT ln

Pe, 2
Pe,1
Pe, 2
Pe,1

Pe, 2
Pe,1

V l ( PT

Pe,1 )

18 10 6 (10130 3167.2)

1.000051

Pe, 2

P = 0.16Pa

3167.36Pa

the vapor pressure increase is 0.16Pa.


4. The boiling point of silver (P=1 atm) is 2450K. The enthalpy of
evaporation of liquid silver is 255,000 J/mol at its boiling point.
Assume, for the purpose of this problem, that the heat capacities
of liquid and vapor are the same. (a) Write an equation for the
vapor pressure of silver, in atmospheres, as a function of kelvin
temperature. (b). The equation should be suitable for use in a
tabulation, NOT in differential form. Put numerical values in the
equation based on the data given. (4.7, p117)
Solution:

P
1

d (ln P)

ln P

H vap 1
(
R
T

1
)
2450

ln P

255000 1
(
8.314 T

1
)
2450

30685
104.08
T

6. Zinc may exist as a solid, a liquid, or a vapor. The equilibrium


pressure-temperature relationship between solid zinc and zinc vapor
is giben by the vapor pressure equation for the solid. A similar
relation exists for liquid zinc. At the triple point all three phases,
solid, liquid, and vapor exist in equilibrium. That means that the
vapor pressure of the liquid and the solid are the same. The vapor
pressure

of

solid

Zn

varies

with

as:

ln P(atm)

15755
T

0.755 ln(T ) 19.25

and the vapor pressure of liquid

15246
T

Zn varies with T as: ln P(atm)

1.255 ln(T )

21.79 .

Calculate: (a)

The boiling point of Zn under 1 atm; (b) The triple-point temperature;


(c) the heat of evaporation of Zn at the normal (1 atm) boiling point;
(d) The heat of fusion of Zn at the triple-point temperature; (e)The
differences between the heat capacities of solid and liquid Zn. (4.8,
p118)
Solution :(a) At boiling point, P=1 atm, that is lnP=0
15246
1.255 ln(T ) 21.79
T

15246 1.255T ln(T ) 21.79T

To solve the equation, let y1 = 21.79T-15246, y2 = 1.255TlnT. Plot

y-T of the functions, and the intersection is the answer.

30000
28000
26000
24000
22000
20000
18000
16000
14000
12000
10000
8000
6000
4000
2000
0
-2000
-4000
-6000

y1
y2

400

600

800

1000

1200

1400

1600

1800

2000

2200

T, K

From the plot, the intersection is 1180 K. So at 1180K, zinc boils.


(b) At triple point, vapor pressure of solid Zn equals that of liquid
Zn;

15246
1.255 ln(T ) 21.79
T

509 0.5T ln(T ) 2.54T

15755
0.755 ln(T ) 19.25
T

509
0.5 ln(T ) 2.54
T

To solve the equation, assume two functions, y1=2.54T+509; y2 =


0.5TlnT. Plot y1-T and y2-T. The intersection is the answer.
y11
y22

8000
7500
7000
6500
6000
5500

5000
4500
4000
3500
3000
2500
2000
1500
1000
400

600

800

1000

1200

1400

1600

1800

2000

2200

T, K

The intersection is 695.3K, and this is the triple point temperature.


(c )
d (ln P)

15246 1.255
T
T2

21.79

1
( 15246 1.255T )( 2 )dT
T
1
( 15246 1.255T )d ( )
T

H vap
R

H vap

d (ln P)

1
d( )
T

15246 1.255T

R(15246 1.255T ) 126755 10.43T

At Tb =1180K,

H vap

126755 10.43T

114.4 103 J / mol 114.4kJ / mol

(d) For solids,


15755
0.755 ln(T ) 19.25
T
15755 0.755
d (ln P) ( 2
)dT
T
T
1
( 15755 0.755)( 2 )dT
T
1
( 15755 0.755)d ( )
T

ln P

d (ln P)

H vap

H fus
R

1
d( )
T

H fus

H fus

15755 0.755T

R(15755 0.755T )

At triple point, Ttr = 695.4K


H fus

(e)

d ( H fus )
CP

8.314 (15755 0.755T ) 126.6 103 J / mol 126.6kJ / mol


C P dT

d ( H fus )

0.755

dT

7. A particular material has a latent heat of vaporization of


5000J/mol. This heat of vaporization does not change with
temperature or pressure. One mole of the material exists in a
two-phase equilibrium (liquid-vapor) in a container of volume V=1L,
a temperature of 300K, and pressure of 1 atm. The container
(constant volume ) is heated until the pressure reaches 2 atm. (Note
that this is not a small

P.) The vapor phase can be treated as an

ideal monatomic gas and the molar volume of the liquid can be
neglected relative to that of the gas. Find the fraction of material in
the vapor phase in the initial and final states. (4.9, P118)
Solution: In the initial state,
P1V1

n1 RT ,

n1

mol(vapor)%

P1V1
RT1

T1

300K , P1

10130 10 3
8.314 300

4.06 10 3 mol

4.06%

In the final state, P2=2 atm, V2 = 1L


According to Clayperon equation:
RT ln
2
ln
1
T2

H vap

P2
P1

R
5000 1
(
8.314 T2

458.6 K

1
T2
1
)
300

1
T2

1atm 1.013 105 Pa, V1

1L

P2V2

n2 RT2 ,

2 10130 10 3
8.314 458.6

P2V2
RT2

n2

mol(vapor)%

5.3 10 3 mol

5.3%

8. The melting point of gold is 1336K, and vapor pressure of liquid


gold is given by:
ln P(atm)

43522
T

23.716

1.222 ln T ( K )

. (a) Calculate the heat of

vaporization of gold at its melting point; Answer parts b, c, and d


only if the data given in this problem statement are sufficient to
support the calculation. If there are not enough data, write solution
not possible. (b) What is the vapor pressure of solid gold at its
melting point? (c) What is the vapor pressure of solid gold at 1200K ?
(d) What is the v
Solution: (a)
d (ln P)

43522
T2

1.222
)dT
T

1
)dT
T2
1
( 43522 1.222)d ( )
T
( 43522 1.222)(

H vap

R( 43522 1.222T )

(a) At 1336K,

H vap

361841 10.19T

361841 10.19 1336

348 103 J

348kJ

(b)Solution not possible;


(c) Solution not possible.

9. (a) At 298K, what is the Gibbs free energy change for


the following reaction?
Cg

C
i d
t

e
i a

m o

(b) Is the diamond thermodynamically stable relative


to graphite at 298K?
(c ) What is the change of Gibbs free energy of
diamond when it is compressed isothermally from 1atm
to 1000 atm?
(d) Assuming

that

graphite

and

diamond

are

incompressible, calculate the pressure at which the


two exist at equilibrium at 298K.
(e) What is the Gibbs free energy of diamond relative
to graphite at 900K? to simplify the calculation,
assume that the heat capacities of the two materials
are equivalent.
Density of graphite is 2.25g/cm3

DATA

Density of diamond is 3.51g/cm3


H of ( 298) (kJ / mol)
H of ( 298) ( J / mol.K )

Diamond

1.897

2.38

Graphite

5.74

Solution: (a)

C graphite

H of ,diamond

C diamond

H of , graphite 1897kJ / mol

S of ,diamond

H T S

5.74 2.38

S of , graphite

1897 298 ( 3.36)

3.36 J /( mol.K )

2898.28J / mol

(b) No, diamond is not thermodynamically stable


relative to graphite at 298K.
(c )

12 10
3.51

G V diamand P

99 10130

34.29 J / mol

(c ) Assuming N atm , G = 0, reversible processes as


following can be designed to realize this,
4
graphite, 298K, N atm

diamond, 298K, N atm

(3)

1
2

diamond, 298K,1atm

graphite, 298K,1atm

G( 4 ) G(1) G( 2 ) G(3)
V graphite P 2898.28 V diamond (

P)

(V graphite V diamond )(1 N ) 10130 2898.28


N

12 10
2.25

0.194 N
N

Cp

12 10
3.51

2898.28

10130 2898.28

14939 (atm )

0,

H 900

T'
T

C p dT

0,

T'

Cp

dT

H 298 1897 J / mol

S900

3.36J / mol.K

S 298

H T S 1897 900 3.36

Chemical Equilibrium
1. Calculate the partial pressure of monatomic hydrogen in hydrogen
in hydrogen
gas at 2000K and 1atm.
1
H 2 (g)
2

For

1
C P,H 2
2

C P,H ( g )

o
H 2000

3
8.314
2

2000

o
H 298

217990 J

o
S 298

49.35 J / K

1
31
2

H (g)
3.035

CP (2000 298)

o
H 298

CP dT

298

o
H 298

1
H 2 (g)
2

For the reaction :


Cp

H (g)

217990 3.035 1702 212824 J


o
H 2000

2000

o
H 298

217990 3.035 1702


o
S 2000

2000

o
S 298

298

49.35 3.035 ln
0
G2000

RT ln

PH 2

PH ( g )

1
PH ( g )

125684

PH 2( g )
7.562

PH ( g )

RT ln

1/ 2

PH 2 ( g )
ln

0
0
H 2000
T S 2000

RT ln K

o
G2000

2000
298

ln

PH 2
PH 2

1, PH 2
PH

1/ 2

1/ 2

PH ( g )

212824 J
C P ln

o
S 298

C P dT

C P (2000 298)

o
H 298

C P dT

298

2000
298

43.57 J

212824 2000 43.57 125684 J

RT ln

PH 2

1/ 2

PH ( g )

125684
8.314 2000

1
0.0005atm

7.56

4921J / m

2. For the reaction :


Go

Co( s)

59850 19.6T ,

1
O2 ( g )
2

where

CoO( S )

G o is

in calories and T is in Kelvin.

(a) Calculate the oxygen equilibrium pressure (atm) over Co and


CoO at 1000 C. (b) What is the uncertainty in the value calculated in
Ho term is estimated to be 500 cal? (5.2,

part a if the error in


p144)
Solution:

(a)

At

1000 C,

=-59850+19.6T=-59850+19.6 (1000+273)
=-34899.2cal = -1458.79J/mol
At equilibrium:
Go
ln PO2
PO2

RT ln K

RT ln

1
PO2

1/ 2

1
RT ln PO2
2

145879 J

27.6
1.07 10

12

atm

(b) uncertainty in Ho = 500cal/mol = 2090J/mol


So uncertainty in Go = 500cal/mol = 2090J/mol
That means:
1
RT ln PO' 2
2
P'
1
RT ln O 2
2
PO 2
ln

PO' 2
PO 2

PO' 2
PO 2

1
RT ln PO 2
2

2090

2090

0.25
1.286

P
PO 2

28.6%

Similarly, uncertainty in Ho =- 500cal/mol =- 2090J/mol


Go = -2090J/mol

Go

1
1
RT ln PO' 2
RT ln PO 2
2
2
P'
ln O 2
0.25
PO 2
PO' 2
PO 2

0.779

2090

22.1%

PO 2

3. Calculate the temperature at which silver oxide (Ag 2O) begins to


decompose into silver and oxygen upon heating: (a) in pure oxygen
at P = 1 atm; (b) in air at Ptotal = 1 atm.
DATA

7300 cal / mol

H f forAg 2 O

Standard Entropy at 298K

Assume

[cal/(mol.K)]
Ag2O
29.1
49.0
that O2Cp = 0 for
the
Ag
10.2

Solution: (a)

Ag2O = 1/2O2 + 2Ag

Ho
So

7300cal / mol

H of , AgO
2 S Ag , 298

Ho

1
S O 2, 298
2

30514

S Ag 2O , 298

1
49 29.1 66.044 J / mol.K
2

2 10.2

Go

decomposition reaction.

T So

30514 T S o

30514 66.044T

when Ag2O begins to decompose,


G

Go

RT ln J

ie 30514 66.044T

(a) in pure oxygen at 1 atm,

0
RT ln PO 2

RTlnPO2 = 0
30514-66.044T = 0
T = 462K

(b)in air at Ptotal = =1 atm , PO2 =0.21

ie.

30514- 66.044T + RTln0.21 = 0


T = 386K

4. One step in the manufacture of specially purified nitrogen is the


removal of small amounts of residual oxygen by passing the gas
over copper gauze at approximately 500 C. The following reaction
takes place:

2Cu ( s)

1
O2 ( g )
2

Cu 2 O( s)

(a) Assuming that equilibrium is reached in this process, calculate


the amount of oxygen present in the purified nitrogen; (b) What
would be the effect of raising the temperature to 800 C? Or lowering
it to 300 C? What is the reason for using 500 C? (c) What would be
the effect of increasing the gas pressure?
For

2Cu ( s)

1
O2 ( g )
2

Cu 2 O( s) ,

Go (in calories ) is 39850+15.06T.

(5.4, p145)
Solution: (a) When the equilibrium is reached,
Go

RT ln J

1
G o RT ln PO2
2

4.18 ( 39850 15.06T )


1
RT
2

ln PO 2

T = 500 C = 773K
ln PO 2
PO 2

4.18 ( 39850 15.06 773)


1
8.314 773
2
1.14 10 26 atm

36.69

(b) at T=300 C=573K,


Although the equilibrium PO2 is very low, kinetically the reaction is
not favoured and reaction speed is very slow. So 300 C is not

suitable at
At T=800 C=1073K, lnPO2 =-22.2, PO2 =2.28 10-10 atm.
At 800 C, if the equilibrium is reached, nitrogen can be of high
purity level. However, at this high temperature , particles of Cu will
weld together to reduce effective work surface. So it is not suitable
to use this high temperature in purification either.
(c ) The equilibrium oxygen pressure remains the same when the
total pressure increases, which means a higher purity level of N2 .
5. The solubility of hydrogen(PH2 = 1 atm ) in liquid copper at
1200 C 7.34cm3(STP) per 100g of copper. Hydrogen in copper
exists in monatomic form. (a) Write the chemical equation for the
dissolution of H2 in copper; (b) What level of vacuum(atm) must be
drown over a copper melt at 1200 C to reduce its hydrogen content
to 0.1 cm3 (STP) per 100g?

(c) A 100g melt of copper at 1200 C

contains 0.5 cm3(STP) of H2. Argon is bubbled through the melt


slowly so that each bubble equilibrates with the melt. How much
argon must be bubbled through the melt to reduce the H2 content to
0.1 cm3(STP) per 100g ? Note: STP means standard temperature and
pressure(298K and 1 atm). (5.5, p145)
Solution: (a) H2(g) = 2H
(b)

PH 2
1

Ka 2

K a 2 PH 22
1atm, H

7.34cm 3 / 100 gCu

is a constant,

PH1 /22 [ H ]'


[H ]

[H ]
PH1 /22

[ H ]'
( PH' 2 )1 / 2

( PH' 2 )

0.00019atm 18.56 10130 18.8Pa

( PH' 2 )1 / 2

0.1
7.34

0.0136

(c ) The amount of H2 needed to be brought out by Ar is:


P V
RT

10130 (0.5 0.1) 10


8.314 298

1.6 10 6 mol

This amount of H2 is in equilibrium with the melt in the bubble, ie.


The partial pressure of H2 in the bubbles is 18.8Pa.
PH' 2Vbubble
PH' 2

nRT

4.05 10

4.05 10 2 / 18.8

0.00215m 3

2.15L

2.15L Ar is needed to be bubbled into the melt.

6. The following equilibrium data have been determined for the


reaction:

NiO(s) CO( g ) Ni(s) CO2 ( g )


T( C)
663
716
754
793
852

K 10-3
4.535
3.323
2.554
2.037
1.577

(a)
(b)
(c)
(d)Plot the data using appropriate axes and find Ho, K and Go at
1000K;
(e) Will an atmosphere of 15%CO2, 5%CO, and 80%N2 N2 oxidize

nickel at 1000K? (5.6, p145)


Solution: (a)

Ho 1
d( )
R
T

d ln K a

Plot ln K a ~ 1 / T
8.6

Kduishu
Linear Fit of Data1_Kduishu

8.4
8.2

lnKa

8.0
7.8

lnKa =2.01+6003(1/T)

7.6
7.4
7.2
0.88

0.90

0.92

0.94

0.96

0.98

1/T, 10

1.00

1.02

1.04

1.06

1.08

-3

.
d ln K a
dT

Ho
R

6003

Ho

R 6003

49909 J

At T=1000K, lnKa =8.01, Ka = 3010


o
G1000

(b)

RT ln K a
Go
J

8.314 1000 8.01 66600 J

RT ln J
15%
5%

RT ln K a

RT ln J

RT ln

66.6kJ

J
Ka

Ka

So the atmosphere will oxidize Ni.


7. At 1 atm pressure and 1750 C, 100 g of iron dissolve 35cm3 (STP)
of nitrogen. Under the same conditions, 100 g of iron dissolves 35
cm3 of hydrogen. Argon is insoluble in molten iron. How much gas
will 100 g of iron dissolve at 1750 C and 760 mm pressure under an
atmosphere that consists of: (a) 50% nitrogen and 50% hydrogen? (b)
50% argon and 50% hydrogen? (c) 33% nitrogen, 33 hydrogen, and
34 argon? (5.7, p145)

Solution:

N2 =2N, H2 = 2H
N

K a ,2N PN 22
[N ]
PN1 /22

For N2 dissolving :

[H ]

For H2 dissolving PH1 /22

K a ,2H PH 22 ,

[ N ]'
( PN' 2 )1 / 2

[ H ]'
( PH' 2 )1 / 2

aFor dissolving N2, PN2 = 1 atm, [N]=35cm3/100g melt,


[N
]

( PN' 2 )1 / 2 [ N ]
PN1 /22

35 (0.5)1 / 2

24.75cm 3 / 100 g melt

similarly: [H] =24.75cm3/100g melt


total gas : [H] [N] = 49.5 cm3/100g melt
(b)

[H] =24.75 cm3/100g melt

(c ) [H] [N] = [N](0.33)1/2 /1+[H](0.33)1/2 /1=20.10+20.10 =


40.2cm3/100g melt
8. Solid silicon in contact with solid silicon dioxide is to be heated to
a temperature of 1100 K in a vaccum furnace. The two solid phases
are not soluble in each other, but is known that silicon and silicon
dioxide can react to form gaseous silicon monoxide. For the
reaction:
Si(s) SiO2

the

2SiO( g )

Gibbs

is

free

Go

667000 25.0T ln T 510T

energy

change

(J)

(a) Calculate the

equilibrium pressure of SiO gas at 1100K; (b) For the reaction above,
calculate

Ho and

So at 1100K; (c) Using the Ellingham chart

(Figure 5.7), estimate the pressure of oxygen (O2) in equilibrium

with the materials in the furnace. (5.8, P146)


(a)

2
RT ln PSiO

RT ln K

Go

2RT ln PSiO

At 1100K,
Go =667000+25.0TlnT-510T
= 667000+25.0 1100ln1100-510 1100
=667000+192584-561000
=298584
-2RTlnPSiO =298584
lnPSiO =-16.32
PSiO = 8.1 10-8 (atm)
(b ) Go =667000+25.0TlnT-510T =-RTlnK
667000 25
ln T 510
RT
R
667000 25
667000
d ln K
)dT (
RT
R
RT 2
Ho
25
667000
T
R
R
H o 667000 25T

ln K

25
T )d (1 / T )
R

Ho
d (1 / T )
R

T = 1100K, Ho = 639500J
So

Ho

Go
T

667000 298584
1100

334.9 J / K

(c ) PO2 =10-30 atm


9. What is the pressure of uranium (gas) in equilibrium with uranium
dicarbide
Go

DATA: At 2263K,f
Vapor
(5.9,p146)

pressure

for UC2 is 82,000 cal/mol


of

pure

uranium

is:

ln P(atm, uranium ) 25.33

Solution:

82000cal / mol

G of

U(g)
RT ln K

G of ,UC 2
RT ln Pu ( g )
ln Pu ( g )

C( s )
RT ln(

100000
(T in K )
T

342760 J

UC2( s )
1
)
Pu ( g )

RT ln Pu ( g )

342760

1.2 10 8 (atm )

vapor pressure of uranium:


ln Pu ( g ) (atm, uranium ) 25.33
Pu ( g )

100000
100000
25.35
18.89
T
2263

0.6 10 8 (atm)

the vapor pressure is lower than the one determined by chemical


reaction. It is the one in equilibrium with dicarbide.

10. The direct reduction of iron oxide by hydrogen maybe


represented by the following equation:
Fe2 O3

3H 2

the

reaction?

2 Fe
H2

3
O2
2
1
O2
2

2Fe 3H 2 O

Fe 2 O3
H 2O

Is
Go
Go

What is the enthalpy change, in joules, for


it
810250

exothermic
254.0T

246000 54.8T

(5.10)

or

endothermic?

Solution:
2 Fe
H2

3
O2
2
1
O2
2

Fe2 O3
G3o

3 G2o

G1o

Fe 2 O3

(1)
(2)

H 2O

3H 2

G1o
G 2o

810250 254.0T
246000 54.8T

2Fe 3H 2 O

3 24600 54.8T

(3)

G3o

( 810250 254.0T )

72250 89.6T
H 3o

72250 J

The reaction is an endothermic one.


11.Calcium carbonate decomposes into calcium oxide and carbon
dioxide according to the reaction

CaCO3

CaO CO2

DATA for the pressure of carbon dioxide in equilibrium with CaO


and CaCO3:
Temperature (K)
1030
921

Pressure (atm)
0.10
0.01

(a) What is the heat effect ( H) of the decomposition of one mole of


CaCO3 ? Is the reaction endothermic or exothermic? (b) At what
temperature will the equilibrium
pressure of CO2 equal one atmosphere? (5.11, P146)
Solution: (a)

Ho
1
d
, K
R
T

d ln K

Ho
1
d
R
T

d ln PCO 2
ln
ln

PCO 2, 2
PCO 2,1
0.01
0 .1

Ho

PCO2

Ho 1
R T2

1
T1

Ho 1
1
R 921 1030
166528 J

the reaction is endothermic


(b)PCO2 =1atm
ln

1
0.1

Ho 1
(
R T

1
)
1030

1168K

At 1168K, the equilibrium pressure of CO2 equals one atmosphere.


12. In the carbothermic reduction of magnesium oxide, briquettes of
MgO and and carbon are heated at high temperature in a vacuum
furnace to form magnesium (gas) and carbon monoxide(gas).
(a) write the chemical reaction for the process; (b) What can
you say abou the relationship between the pressure of magnesium
gas and the pressure of carbon monoxide? (c) Calculate the
temperature at which the sum of the pressures of Mg(gas) and CO
reaches on atmosphere. With T in Kelvin, the free energies of
formation, in calories, of the relevant compounds are:

MgO
CO

174000 48.7T

G of
G

28000 20.2T

o
f

(a). The reaction is: MgO(s) C(s)


(b).

Go
G

G of ,CO
RT ln K

G of , MgO

CO( g ) Mg ( g )

146000 68.9T

RT ln( PCO( g ) PMg ( g ) )

(146000 68.7T )

PCO

PMg

(c ) Ptotal = 1 atm, PCO = 0.5 atm, PMg =0.5 atm


RT ln(0.5 0.5)

(146000 68.7T ) 4.18

T = 2037 K
13. Metallic silicon is to be heated to 1000 C. To prevent the
formation of silicon dioxide (SiO2), it is proposed that a hydrogen
atmosphere be used. Water vapor, which is present as an impurity in
the hydrogen, can oxidize the silicon. (a) Write the chemical
equation for the oxidation of silicon to dioxide by water vapor;
(b)Using the accompanying data, where Go is in joules, determine
the equilibrium constant fro the reaction at 1000 C (1273K); (c)
What is the maximum content of water in the hydrogen (ppm) that is
permitted if the oxidation at 1000 C is to be prevented ? (d) Check
the answer to part c on the Ellingham diagram (Figure 5.7)
DATA

H 2 (g)
Si

O2

1
O2 ( g )
2
SiO 2 ( s)

H 2 O( g )

Go
Go

246000 54.8T
902000 174T

5.13, P147
Solution: (a)

Si(s) 2H 2 O( g )

SiO2 (s) 2H 2 ( g )

(b)
H 2 (g)
Si

O2

1
O2 ( g )
2
SiO 2 ( s)

Si(s) 2H 2 O( g )

H 2 O( g )

(1)
(2)

G(o1)
G

o
( 2)

SiO2 (s) 2H 2 ( g ) (3)

246000 54.8T
902000 174T

G3o

G3o

2 G1o

G2o

902000 174T

( 246000 54.8T ) 2

410000 64.4T
G

RT ln K

o
3

At T
K

410000 64.4T
410000 64.4 1273
8.314 1273

1273K , ln K

31

2.9 1013

(c )
K

PH 2( g )

PH 2O ( g )

PH 2 ( g )
PH 2O ( g )
PH 2O ( g )
PH 2 ( g )

2.9 1013

5.38 10 6
1
5.38 10 6

0.186 10

0.186 ppm

14. Solid barium oxide(BaO) is to be prepared by the decomposition


of the mineral witherite (BaCO3) in a furnace open to the atmosphere
(P = 1 atm).
(a) Write the equation of the decomposition (witherite and BaO are
immiscible).
(b)Based on the accompanying data, what is the heat effect of the
decomposition of the witherite(J/mol). Specify whether heat is to
be added (endothermic) or evolved (exothermic).
(c) How high must the temperature be raised to raise the carbon
dioxide pressure above the mineral to one atmosphere? ( 5.14,
P147 )
DATA

Thermodynamic

Properties

[KCAL/(g.mol)]
G of ( 298)

H of ( 298)

CO2
-94
-94
BaO
-126
-133
BaCO3
-272
-291
(Assuming that CP,CO2+ CP, BaO = CP,BaCO3)

Solution: (a)

BaCO3 (s)

BaO(s) CO2 ( g )

(b) CP = 0
H of ,CO2( 298)

H of , BaO( 298)

94 133 ( 219)

H of , BaCO3( 298)

64kcal

267.52kJ

the reaction is endothermic


(c ) At 298K,
o
G298

G of ,CO2, 298

G of ,CaO, 298

94 126 272
o
G298
o
S 298

GTo

52kcal

G of ,CaCO3, 298
217.36kJ

o
o
H 298
T S 298
o
H 298

o
G298

T
H To

(267.52 217.36)
298

168 J / mol.K

T S To

when PCO2=1 atm,


GTo

0, ie 2675201 168T
T

1592 K

15. As the Elligham diagram indicated, Mg has a very stable oxide.


Therefore Mg metal can be obtained from the oxide ore by a
two-step process. First the oxide is converted to a chloride. In the
second step the chloride is converted to metal Mg by passing H 2 gas
over liquid MgCl2 at 1200 C. The reaction in this last step is:
MgCl 2 (l )

H 2 (g)

Mg ( g ) 2HCl( g )

(a) Calculate the equilibrium pressure of H2(g), Mg(g) and HCl(g) if


the total pressure is maintained constant at 1 atm.
(b)Calculate the maximum vapor pressure of H2O that can be

tolerated in the hydrogen without causing the oxidation of the Mg


vapor.
DATA
Go at 1200 C

Reaction
Mg(g)+Cl2(g)
H2 (g) + Cl2(g)
Mg(g) +1/2O2(g)
H2 (g) + 1/2O2(g)

= MgCl (l)
= 2HCl(g)
= MgO(s)
= H2O(g)

425484 J
207856 J
437185 J
165280J

515 p48
Solution: (a)

MgCl 2 (l )

H 2 (g)

Mg(g)+Cl2(g)

Mg ( g ) 2HCl( g )

(1)

G1o

MgCl (l)

(2)

Go2

2HCl(g)

(3)

Go3

425484 J
H2 (g) + Cl2(g)

207856 J
G1o

G3o

G2o

207856 425484

217628J

RT ln K

G1o

RT ln

2
PHCl
PMg ( g )
(g)

8.314 1473 ln

PH 2( g )

2
PHCl
PMg ( g )
(g)

PH 2 ( g )

217628
ln

2
PHCl
PMg ( g )
(g)

PH 2( g )

2
PHCl
PMg ( g )
(g)

5.27 10 7

PH 2( g )
PH 2 ( g )

17.78

PMg ( g )

PHCl

1, PHCl

2 PMg ( g )

let PMg(g) =x, PHCl = 2x, PH2 = 1-3x


1 3x
x(2 x) 2

5.27 10 7

x 1.6 10 3 (atm )

Mg(g) + H2O(g) = MgO(s)+ H2 (g)


Mg(g) +1/2O2(g)

Go4

(4)

= MgO(s)

(5)

Go5

(6)

Go6

437185 J
H2 (g) + 1/2O2(g)

= H2O(g)

165280J
G4o

271905
PH 2 ( g )
PH 2O ( g ) PMg ( g )

PH 2O ( g )

RT ln

PH 2( g )
PH 2O ( g ) PMg ( g )

271905J

8.314 1473 ln

PH 2 ( g )
PH 2O ( g ) PMg ( g )

22.2

1.6 10 3
PH 2O ( g ) 1.6 10
ln PH 2O ( g )

437185 ( 165280)

G6o

RT ln K

G4o

ln

G5o

22.2

22.2
2.28 10

10

(atm )

16. A common reaction for the gasification of coal is:


H 2 O( g ) C(s)

H 2 ( g ) CO( g )

(a) Write the equilibrium constant for this reaction and compute its
value at 1100K;

(b)If the total gas pressure is kept constant at 10 atm, calculate the
fraction of H2O that reacts;
(c) If the reaction temperature is increased, will the fraction of
water reacted increase or decrease? Explain your answer. Use
the data in Table 5.1. (5.16, 148)
Solution:

H 2 O( g ) C(s)

(a)

H 2 ( g ) CO( g )

PCO( g ) PH 2( g )

PHO 2( g )

Go

G f ,CO

G f , H 2O

111710 87.65 1100 ( 246740 54.81 1100)

RT ln K

Go

ln K

2.3

21676 J

9.97

(b)
let

PH 2( g )

x atm, PCO( g )

x atm, PH 2O ( g )

(10 2 x) atm

x
1 2x
4.14 atm
K

9.97

(c ) if the temperature is increased, the fraction of water reacted


will increase since the equilibria constant increases with increasing
temperature.

Solutions
1. The activity coefficient of zinc in liquid brass is given (in joules )
by
RT ln

the
Zn

following
2
38300 xCu

equation

for

temperature

1000-1500K:

, where xCu is the mole fraction of copper.

Calculate the partial pressure of zinc PZn over a solution of 60 mol %


copper and 40 mol % zinc at 1200K. The vapor pressure of pure zinc

is 1.17 atm at 1200K. (7.1, p196)


Solution:
ln

Zn

Zn

2
38300 xCu
RT
0.25

2
38300 0.6 Cu
8.314 1200

x Zn

0.25 0.4

0.1

P a Zn

0.1 1.17

0.117(atm )

a Zn

Zn

PZn

p
Zn

1.38

2. Using the equation give in Problem 7.1, for the activity


coefficient of zinc in liquid brass, derive an equation for the
activity coefficient of copper using the Gibbs-Duhem equation.
(7.2, 196)
Solution: According to Gibbs Duhem Equation:
x Zn d (ln a Zn )

xCu d (ln aCu )

x Zn d (ln

x Zn d (ln x Zn )

xCu d (ln aCu )

x Zn d (ln x Zn )xCu d (ln xCu )

dx Zn

x Zn d (ln

d (ln
ln
0

Zn )

Cu

d (ln

Zn

)xCu d (ln
x Zn
d (ln
xCu

Cu

xCu

1
xCu
1

ln

Cu

Zn

Cu

dxCu

xCu d (ln xCu )


dx Zn

d (1 x Zn )

x Zn
xCu

38300
2 xCu dxCun
RT

38300
2 x Zn dxCu
RT

xZ n
1

38300
2 x Zn dx Zn
RT

38300 2
x Zn
RT

3.
(a) At 900K, is Fe3C a stable compound relative to pure Fe and
graphite?( 7.3, 196)
(b)At 900K, what is the thermodynamic activity of carbon in
equilibrium with Fe and Fe3C ? Carbon as graphite is taken as
the standard state.
(c) In the Fe-C phase diagram, the carbon content of

-iron in

equilibrium with Fe3C is 0.0113 wt. %. What is the solubility of


graphite in -iron at 900K?
DATA

AT 900K,

3Fe C( graphite)

Go

Fe3C

3463 J

4. From vapor pressure measurements, the following values have


been

determined

for

the

activity

of

mercury

in

liquid

mercury-bismuth alloys at 593K. Calculate the activity of bismuth in


a 40 atom % alloy at this temperature
NH 0.94 0.89 0.85 0.75 0.65 0.53 0.43 0.33 0.20 0.06
9

aH 0.96 0.92 0.90 0.84 0.76 0.65 0.54 0.43 0.27 0.09
1

(7.4,196)
Solution:
NH 0.94 0.89 0.85 0.75 0.65 0.53 0.43 0.33 0.20 0.06
9

aH 0.96 0.92 0.90 0.84 0.76 0.65 0.54 0.43 0.27 0.09
1

g
Hg

1.01 1.04 1.06 1.12 1.17 1.21 1.24 1.31 1.34 1.46
3

Plot ln

Hg

~xHg

lnB
Linear Fit of Data1_lnB

0.40
0.35
0.30
0.25

ln

Hg

0.20
0.15
0.10

ln Hg=0.395-0.391xHg

0.05
0.00
0.0

0.2

0.4

0.6

0.8

1.0

xHg

d (ln
ln
0

ln

Bi

x Hg

x Bi
)

d (ln

d (ln

Bi

0.391

Bi

0.391(ln x Bi

Hg
x Bi
1

)
(

1
x Bi

x Hg
x Bi

( 0.391)dx Hg

1)dx Bi

x Hg )

when xBi = 0.4, xHg =0.6


ln

0.391(ln 0.4 0.6)

Bi

Bi

0.1

1.107

7.5 For a given binary system at constant T and P, the liquid molar
volume
V

100 x A

of

the

80 xB

2.5x A x B

solution

(cm3/mol)

is

given

by

(a) Compute the partial molar volumes of A and B and plot them,
together with the molar volume of the solution, as a function of
the composition of the solution;
(b)Compute the volume of mixing as a function of composition.
(7.5, 196)
Solution:

the

100 x A

80 x B

calculated
2.5x A x A

partial

variables

are

as

follows:

V
xA

VA

V
xB

VB

100 2.5 x B
T , P , xB

80 2.5 x A

82.5 2.5 x B

T , P , xB

105

100
partial volume of A
partial volume of B
molar volume of the solution

cm /mol

95

90

85

80
0.0

0.2

0.4

0.6

0.8

1.0

xB

(b)

VA

100,V B

VM

80

(100(1 x B ) 80 x B

(100 x B )

2.5 x A x B

4. For an ideal binary solution of A and B atoms, plot schematically


the chemical potential of both species as a function of the
composition of the solution. Indicate on the plot the molar Gibbs
free energy of pure A and B. (7.6,196)

5. At 473 C, the system Pb-Sn exhibits regular solution behavior,


and the activity coefficient of Pb is given by:

log

Pb

0.32 1 x Pb

Write the corresponding equation of the variation of

Sn

with

composition at 473 C. (7.7, p196)

6. MgCl2 and MgF2 are two salts that can form solutions. The Gibbs
free energy of fusion(J/mol) for both compounds is given by:

For MgCl2 :

G = 43905-43.644T,

Melting point

=987K
For MgF2:

G = 58702-38.217T,

Melting point

1536K
The free energy of mixing (J/mol) for liquid mixture MgCl 2 and
MgF2 is given by:
GMix

2RT ( xMgCl2 ln xMgCl2

xMgF2 ln xMgF2 ) xMgCl2 xMgF2 ( 2556 25( xMgF2

xMgCl2 )) .

Compute the maximum solubility of MgF2 in liquid MgCl2 at 900 C.


MgCl2 does not dissolve in solid MgF2. (7.8, 197)

7. The thermodynamic properties of Al-Mg solution at 1000K are


given in accompanying table. (a) If one mole of pure liquid
aluminum and one mole of pure liquid magnesium, each at 1000K,
are mixed adiabatically, what will be the final temperature of the
solution that is formed ? (b) What is the total change in entropy for
the process ?
DATA

Quantities of Mixing Liquid Alloys at 1000K

x Mg

GM (cal / mol)

0.1

-800

H M (cal / mol)

-300

S M (cal / mol)

0.5

C p [cal /( mol.K )]

7.1

0.2

-1250

-600

0.65

7.18

0.3

-1550

-750

0.8

7.26

0.4

-1700

-850

0.85

7.34

0.5

-1800

-900

0.9

7.42

0.6

-1700

-850

0.85

7.5

0.7

-1550

-750

0.8

7.58

0.8

-1250

-600

0.65

7.66

0.9

-800

gf-300

0.5

7.74

The problems of the phase rule


8.1 Zinc sulfide (ZnS) is reacted in pure oxygen to form zinc sulfate
(ZnSO4) (a) write the chemical reaction representing the process (b)
how many solid phases may exist in equilibrium if pressure and
temperature are arbitrarily fixed? (c) if the temperature is fixed, will
the pressure be determined if ZnS and ZnSO4 exist in equilibrium?

Solution:
(a) ZnS 2O2

ZnSO4

(b)two
(c) because F=(3-1)-3+1=0 so yes

8.2 an Fe-Mn solid solution containing 0.001 mole fraction Mn is in


equilibrium with an FeO-MnO solid solution and a gaseous
atmosphere containing oxygen at 1000K. How many degree of
freedom does the equilibrium have? What is the composition of the
equilibrium oxide solution, and what is the oxygen pressure in the
gas phase? Assume that both solid solutions are ideal?
Data: for Fe

Fe ( s)
G

1
O2 FeO ( s)
2
259000 62.55T

For Mn

Mn( s)
G

1
O2 MnO( s)
2
384700 72.8T

Solution: (a) F=(5-2-1-1)-2+1=0


1
RT ln PO2
2
(b) PO 1 exp( 2 G 0 ) 3.0 10 21
2
RT
2 G0
PO2 2 exp(
) 2.6 10 33
RT
P 0.999 PO2 1 0.001PO2 2 3.0 10
G0

21

The problems of the phase diagram


9.1 (a) if an alloy of 50 atom % copper and 50 atom % silver is
brought to equilibrium at 600 at one atmosphere pressure, what
phase or phase in the accompanying Ag-Cu phase diagram are
present?
(b) apply the phase rule to the situation in part A, how many degrees
of freedom does the system have?
(c) Assume that the system described in part a is brought a new
equilibrium at 700. Describe the physical changes you expect to

occur in the system


Fig

Solution:
(a)

Ag

Cu

solution

solution increases and

(b)F=C-P=(2-1)-1=0 (c)
Cu

Ag

phase in the

decreases

9.6 in the accompanying eutectic equilibrium phase diagram of


temperature versus mole fraction of B for the A-B system shown,
note that the pressure for the diagram is constant at 1 atm. Consider
an alloy containing 40 mol% of B.
Fig

In the table indicate which of the phase are present in the 40% alloy
and give the composition of each and the fraction present of each for
the temperature shown
Temperature

Phase

Composition

Fraction

1300

Liquid

60

61.5

38.5

99

Liquid

70

50.8

49.2

1000+

1000-

98

Liquid

63.7

98

36.3

9.8 The phase behavior of material A and B can be described using


the accompanying phase diagram. Assume that A and B form ideal
solutions in the liquid state and in the solid state.
fig
(a) if a solution containing 50 mole% B is cooled from 1300K, what
is the composition of the first solid to form? What is the
composition of the last liquid to solidify?
(b)For this 50 mole% B solution ,estimate the fraction solid and
liquid in equilibrium at 1000K.

Solution:
(a) 90% is the composition of the first solid to form;10% is the
composition of the last liquid drop.
(b) solid (60% is the composition) is about 77% ; liquid (15% is
the composition) is 23%

9.9an alloy composed of 80 atom% rhodium and 20 atom% rhenium

is being slowly cooled from 3500 during processing. Equilibrium


is maintained at each temperature. Use the accompanying Rh-Re
phase diagram to answer parts A-C
(a) at

what temperature does the first solid formed and what is the

composition of that solid?


(b)At what temperature does the last liquid solidify, and what is the
composition of the last liquid
(c) Which phase exist at 2000 and what is their composition?
Given the fraction of each phase. How many degrees of freedom
are therr in this equilibrium?

(a) 2900 , (12%) (b) 2300 , liq(95%) (c) 8.2%


(composition is 24% )+91.8%(85%)

9.10 the accompanying diagram represents the liquidus surface in


the ternary phase diagram for BaCl2-NaCl-KCl-CaCl2 assume for the
purpose of this problem that there is no solid solubility of the
compounds in one another.
(a) on the diagram trace the path of the liquid composition when a
material consisting of BaCl2 60%, NaCl 20%, KCl-CaCl220% is
cooled from 900. Assume that equilibrium is maintained at all
temperature.

(b)Sketch two blank ternary diagram and draw in the isothermal


section at 750 and 650
(c) What will be the fraction liquid when the liquid reaches the
ternary eutectic temperature but none has solidified as a ternary
eutectic? That is what will be the fraction of ternary eutectic in
the material when it is all solidified?
Solution:
(a)liq liq+ BaCl2 liq+ BaCl2+ NaCl liq+ BaCl2+ NaCl+
KCl-CaCl2BaCl2+ NaCl+ KCl-CaCl2
BaCl2

20%

NaCl

KCl, CaCl2
20%

BaC
l2

(b) 750
20
%

750

Soli
Na
d
Cl

Soli
d

750

Liq
uid
20
%

KCl, CaCl2

600
BaCl2

20%

Solid

Liquid
NaCl

KCl, CaCl2
20%

(c) 20%liquid; 30%BaCl2+ 20%NaCl+50% KCl-CaCl2

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