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Solution:
n(C p T
1
nMv 2
2
H melting )
1
n 207.2 10 3 v 2
2
363(m / s )
QBurning
P W /t
QBurning / t
Pincreasin g
mg
Solution
h
t
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 )
(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 )
Adiabatic
T
P
( ) R / CP
T0
P0
solution
T0 (
P0 0 R / CP
)
P0
T0
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 CH 4 )
191.76 103
10 3
1
0.30483 103 252 103
(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
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
C p ,i X i
C p , p ,i ni
8.87(cal / mol
C)
C p ,r ,i ni )dT
2800000 10 3
189570 9.25 11.48(1600 800)
1
(
4.1868
)
11.48
0.0224
1644(m 3 / 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
C P ,CO2
C P ,O2
CP, N 2
2CO2
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
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
T
(b)
1250
Q298
282838 0.2
1250
Q298
282838 0.2
1250
298
1250
298
(33.28 5.58 10 3 T
(33.28 5.58 10 3 T
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)
(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
n pC p , P dT
298)
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
H 2O
0.04CH 2O
0.92C N2
43.6308KJ
53.8( J / K )
810( K )
H CO
CO2
HH2
H 2O
43.6308KJ
CP , r ,i ni
0.36CCO2
0.04CH 2 O 1.016C N 2
0.024CO2
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
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
CP ,r ,i ni
59.373 103
53.8
1401.6( K )
T
T
0.04CH 2O
0.96C N2
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
43.6308 10
54.2
1103( K )
n( N 2 )
0.92
H 2O
0.008
43.6308KJ
0.92C N2
54.2( J / K )
805( K )
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)
Cu2O H 2
H
Cu
H 2O
,exothermic reaction
H l ,1000
932
1000
298
932
CP , S dT
CP , L dT
H LS
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 )
Solution: Q
Water
/ min
1000
63.54 min
1(80 20)V
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:
TH
TL
TH
(90
90
QH
W
t
6.25(m 2 )
25)
273
104
St
60
746(W )
Solution:
TH TL
QH
TH
0.75P
PL
3
4
TH
TL
TL
PL
273 20
0.25 746
35 20
643(W )
Solution:
PL
M
TH
TL
TL
PL
273
0.25 746 334m
20
60m 457( g )
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)
a furnace ? do the
(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 )
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
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 )
(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
540 273 8
10
540 40
1.626 10 (W )
no
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
2.13
solution:
(a)2 Al
N2
(b) H
152940(cal / mol)
2 AlN
(c ) S
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 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:
H
G
S
T S
G
T
5850 ( 108.9)
268
22.23J /( mol K )
C P,bath
100cal / K
418J / mol
C P ,alloy
C P ,bath
Q2
C P,alloy (T T ' ) ,
Q1
Q2
C P,alloy (T T ' )
water at
H
Tm
6030
273
Tm S = H
22.09 J /( mol.K )
(b) At 0 C, G =0
C P,water
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)
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 .
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
10-7 atm 1
10-6 C-1
(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
1.57 10 6 m 3 / mol
dP
dT
1
V fus
dP
1
V fus
fus
T
H
T
fus
dT
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
H vap
28kcal / mol
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
H vap
90Tb
in joules per
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
Vl
vapor
pressure,
Gv
18 g / mol
1g / cm 3
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
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
of
solid
Zn
varies
with
as:
ln P(atm)
15755
T
15246
T
1.255 ln(T )
21.79 .
Calculate: (a)
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
15246
1.255 ln(T ) 21.79
T
15755
0.755 ln(T ) 19.25
T
509
0.5 ln(T ) 2.54
T
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
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
At Tb =1180K,
H vap
126755 10.43T
ln P
d (ln P)
H vap
H fus
R
1
d( )
T
H fus
H fus
15755 0.755T
R(15755 0.755T )
(e)
d ( H fus )
CP
d ( H fus )
0.755
dT
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%
H vap
P2
P1
R
5000 1
(
8.314 T2
458.6 K
1
T2
1
)
300
1
T2
1L
P2V2
n2 RT2 ,
2 10130 10 3
8.314 458.6
P2V2
RT2
n2
mol(vapor)%
5.3 10 3 mol
5.3%
43522
T
23.716
1.222 ln T ( K )
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
348 103 J
348kJ
C
i d
t
e
i a
m o
that
graphite
and
diamond
are
DATA
Diamond
1.897
2.38
Graphite
5.74
Solution: (a)
C graphite
H of ,diamond
C diamond
S of ,diamond
H T S
5.74 2.38
S of , graphite
3.36 J /( mol.K )
2898.28J / mol
12 10
3.51
G V diamand P
99 10130
34.29 J / mol
(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)
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
S900
3.36J / mol.K
S 298
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
H (g)
2000
o
H 298
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
RT ln
PH 2
1/ 2
PH ( g )
125684
8.314 2000
1
0.0005atm
7.56
4921J / m
Co( s)
59850 19.6T ,
1
O2 ( g )
2
where
CoO( S )
G o is
(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
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%
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
H f forAg 2 O
Assume
[cal/(mol.K)]
Ag2O
29.1
49.0
that O2Cp = 0 for
the
Ag
10.2
Solution: (a)
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
Go
RT ln J
ie 30514 66.044T
0
RT ln PO 2
RTlnPO2 = 0
30514-66.044T = 0
T = 462K
ie.
2Cu ( s)
1
O2 ( g )
2
Cu 2 O( s)
2Cu ( s)
1
O2 ( g )
2
Cu 2 O( s) ,
(5.4, p145)
Solution: (a) When the equilibrium is reached,
Go
RT ln J
1
G o RT ln PO2
2
ln PO 2
T = 500 C = 773K
ln PO 2
PO 2
36.69
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?
PH 2
1
Ka 2
K a 2 PH 22
1atm, H
is a constant,
[H ]
PH1 /22
[ H ]'
( PH' 2 )1 / 2
( PH' 2 )
( PH' 2 )1 / 2
0.1
7.34
0.0136
1.6 10 6 mol
nRT
4.05 10
4.05 10 2 / 18.8
0.00215m 3
2.15L
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
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
(b)
RT ln K a
Go
J
RT ln J
15%
5%
RT ln K a
RT ln J
RT ln
66.6kJ
J
Ka
Ka
Solution:
N2 =2N, H2 = 2H
N
K a ,2N PN 22
[N ]
PN1 /22
For N2 dissolving :
[H ]
K a ,2H PH 22 ,
[ N ]'
( PN' 2 )1 / 2
[ H ]'
( PH' 2 )1 / 2
( PN' 2 )1 / 2 [ N ]
PN1 /22
35 (0.5)1 / 2
the
2SiO( g )
Gibbs
is
free
Go
energy
change
(J)
equilibrium pressure of SiO gas at 1100K; (b) For the reaction above,
calculate
Ho and
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
DATA: At 2263K,f
Vapor
(5.9,p146)
pressure
pure
uranium
is:
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 )
100000
100000
25.35
18.89
T
2263
0.6 10 8 (atm)
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
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
CaCO3
CaO CO2
Pressure (atm)
0.10
0.01
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
1
0.1
Ho 1
(
R T
1
)
1030
1168K
MgO
CO
174000 48.7T
G of
G
28000 20.2T
o
f
Go
G
G of ,CO
RT ln K
G of , MgO
CO( g ) Mg ( g )
146000 68.9T
(146000 68.7T )
PCO
PMg
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)
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
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
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
0, ie 2675201 168T
T
1592 K
H 2 (g)
Mg ( g ) 2HCl( g )
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 )
5.27 10 7
x 1.6 10 3 (atm )
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 )
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
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
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:
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
x Zn d (ln
x Zn d (ln x Zn )
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
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
AT 900K,
3Fe C( graphite)
Go
Fe3C
3463 J
determined
for
the
activity
of
mercury
in
liquid
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 )
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
log
Pb
0.32 1 x Pb
Sn
with
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
xMgCl2 )) .
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
Solution:
(a) ZnS 2O2
ZnSO4
(b)two
(c) because F=(3-1)-3+1=0 so yes
Fe ( s)
G
1
O2 FeO ( s)
2
259000 62.55T
For Mn
Mn( s)
G
1
O2 MnO( s)
2
384700 72.8T
21
Solution:
(a)
Ag
Cu
solution
(b)F=C-P=(2-1)-1=0 (c)
Cu
Ag
phase in the
decreases
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
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%
what temperature does the first solid formed and what is the
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%