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3
State functions
A state function is a property whose value
does not depend on the path taken to
reach that specific value, e.g. temperature,
pressure, volume, internal energy, etc.
Path functions
Path functions are functions that depend
on the path taken to reach that specific
value, e.g. work, heat load, etc.
4
Two different paths from same initial and final states results in the state variables values
5
State Functions vs. Path Functions
State Function Path Function
Can integrate using final and initial Need multiple integrals and limits of
values. integration in order to integrate.
7
Two important concepts in
thermodynamics are work and energy.
X2
Work w = F(x)dx
X1
8
Example on Work from classical mechanics
A woman slowly lifts a 30.0-kg object to a height of 2.00 m
above its initial position. Find the work done on the object
by the woman, and the work done by the earth.
x = pistons position
l = length of system
If Pext, Vsyst until Pext = Pint
V = Al = A(b-x)
If piston moves by dx, dV = -Adx
10
Action = reaction
Fx = F = PA
w = Fx
dw = Fdx = PAdx = PdV
2
Closed system
wrev = PdV reversible
1 process
11
Reversible Process
System is infinitesimally close to equilibrium.
Infinitesimal change in conditions can reverse
the process to restore both system and
surroundings to their initial states.
2
wrev = PdV
1
Irreversible Process
2
wirrev = Pext dV
1 12
Line Integrals
P P P
1
1 1
2 2 2
V V V
(a) (b) (c)
2
w = PdV = area under the curve
w is not a state function
1
wa wb wc 13
EXAMPLE P-V work
Find the work wrev for processes (a) and (b) in previous
Figure if P1 = 7.00 atm, V1 = 800 cm3, P2 = 4.00 atm, and
V2 = 3200 cm3.
2
We have wrev = PdV
1
The line integral P dV equals the area under the P vs V curve. In Fig. a,
this area is rectangular and equals:
P2 (V2 V1) = 4 atm (3200 - 800)cm3 = 9600 atm cm3.
= 973 Nm = 973 J
m2, T2 m1, T1
T2 T1 Tf = final temperature
Internal Energy, U
Energy at the molecular level
U = translational + rotational + vibrational +
electronic energy + potential energy of
interactions between molecules
U extensive property (J)
Um = U/n molar internal energy
intensive property (J/mol)
17
E=K+V+U
E = Total energy of system.
System at rest, K = 0 and no external field,
V = 0, E = U
Chemical engineers often deal with systems of
flowing fluids; here, K 0.
18
2.3 FIRST LAW OF THERMODYNAMICS
U = q + w closed system
SYSTEM
Heat
released
-q -w Work done
by system
from system
surrounding 19
2
dU = U
1
2 U 1 = U
U a = U b = U c
U is a state function, value depends on the
state of the system, not on path of process.
In contrast to U, the quantities q and w are not
state functions.
The heat q and the work w depend on the path
used to go from state 1 to state 2.
Energy is conserved any energy that is lost
by the system must be gained by the
surroundings, and vice versa. 20
b c d
U2 T2
U1 T1
a
V
Uab = Uac = Uad (state function)
Uab = qab constant-volume process
qab qac qad (q is not a state function)
21
2.4 ENTHALPY, H
H = U + PV Heat absorbed (q) at P & V
H is state function.
H = H 2 H1 = U 2 P2V2 U1 P1V1
= U P2V2 P1V1
For constant-pressure process, P2 = P1
H = U PV H = q P
U = qV
22
2.5 HEAT CAPACITIES
CP
C P ,m =
n J
unit =
CV molK
CV ,m =
n
CP CV = nR
CP ,m CV ,m = R
24
2.6 CALCULATION OF FIRST LAW
QUANTITIES
Isothermal dT = 0
Reversible Constant-volume or
process in isochoric dV = 0
perfect gas,
closed system Constant-pressure
or isobaric dP = 0
Adiabatic dq = 0
U
Perfect gas obeys: PV = nRT , =0
V T
25
Perfect-gas change of state U and H depend on
T only.
U H
CV = , CP = CV =
dU
, CP =
dH
T V T P dT dT
T2
U = CV T dT
T1
T2
H = C P T dT
T1
V2
w = nRT ln
V1 27
P1V1 P2V2
= because T1 = T2
T1 T2
V2 P1
=
V1 P2
P1
w = nRT ln
P2
28
Calculate q, w, U and H for reversible
isothermal expansion at 300K of 5.00 mol
perfect gas from 500 to 1500 cm3.
29
V2
w = nRT ln
V1
8.314 J 1500cm
3
= 5.00mol 300 K ln 3
molK 500cm
w = 13.7kJ
q = w = 13.7kJ
U = 0 = H
30
2.6.2 Constant-Volume Process (reversible)
dV = 0 (No phase change)
U = q w = q PdV where PdV = 0
U = qV = CV dT
T2
U = qV = nCV ,m dT
T1
= nCV ,m T2 T1
(assuming CV,m doesnt change with temperature)
31
2.6.3 Constant-Pressure Process (reversible,
no phase change)
2
wrev = PdV = PV
1
T2
dq P
q P = C P T dT = H CP =
T1
dT
T
q P = n C P ,m T dT = H
T1
33
(a) 2.00 g
n= = 0.500molHe
4 g / mol
V1 = 20.0dm = 20000cm
3 3
0.9869atm
P1 = 0.800bar = 0.789atm
1bar
P2 = P1 = 0.789atm
V2 = 40.0dm 3 = 40000cm 3
T1 = ? T2 = ?
34
P1V1
0.789atm 20000cm 3
T1 = =
nR 0.500mol 82.06 cm 3 atm
molK
T1 = 384.6 K
T2 = 769.2 K
T = 384.6 K
U = nCV ,m T
3
= 0.500mol R 384.6 K
2
= 2.40kJ
35
C P ,m CV ,m = R
C P ,m = 2.5R
const. pressure : H = q P
H = q P = nC P ,m T
= 0.500mol 2.5R 384.6 K
= 4.00kJ
U = q w
w = U q
= 2.40 4.00
= 1.60kJ
36
(b) P1 = 0.600bar = 0.5921atm
V1 = 15.0dm 3 = 15000cm 3 = V2
0.5921atm 15000cm 3
T1 =
0.500mol 82.06 atm molK
cm 3
T1 = 216.5K
T = 108.2K
T2 = 324.7 K
const vol U = qV = nCV ,m T
3
U = qV = 0.50mol R 108.2 K
2
= 674.7 J
37
w = U q = 0 J
H = nC P ,m T
= 0.50mol 2.5R 108.2 K
= 1.13kJ
H q
38
CP,m for O2 at T 300 400 K is CP,m = a + bT
where a = 6.15 cal/mol K, b = 0.00310 cal/mol K2.
Calculate q, w, U, H when 2.00 mol O2 is
reversibly heated from 27 127C with P held
fixed at 1.00 atm.
39
nC P ,m = C P = na bT
CP
CP ,m =
n
2 2
dqP = C P dT = C P dT = na bT dT
1 1
2
q = n aT2 T1 T2 T1
b 2
2
6.15cal
400 300K
q = 2.00mol
molK
1 0.00310cal 2
2 molK 2
2 2
400 300 K
q = 1447cal
H = qP = 1447cal 40
2
w = PdV = PV = nRT
1
w = 2.00mol 1.987 cal
molK
100 K
w = 397cal
U = q w
= 1447cal 397cal
= 1050cal
41
2.6.4. Reversible Adiabatic Process
dq = 0
dU = dw dq
CV dT = PdV
nRT
CV dT = dV
V
RT
CV ,m dT = dV
V
2 2
CV ,m dV
1
T
dT = R
1
V 42
T2 V2 V1
CV ,m ln = R ln = R ln
T1 V1 V2
R / CV ,m
T2 V1
ln = ln
T1 V2
R / CV ,m
T2 V1
=
T1 V2
If V2 V1, T2 T1
43
For ideal gas: P1V1 P2V2
=
T1 T2
T2 P2V2
=
T1 P1V1
P1 V1 = P2 V2
1 R / CV ,m 1 R / CV ,m
R CV ,m R CP ,m
1 = = =
CV ,m CV ,m CV ,m
P1V1 = P2V2
U = w
45
P1 isotherm
P2
adiabat
P2
V1 V2 V
47
(a) Isothermal T2 = T1 = 300 K
nRT2
P2 =
V2
cm atm
3
1.00mol 82.06 300 K
= molK
49200cm 3
= 0.500atm
48
(b) Adiabatic process P1V1 = P2V2
C P ,m CV ,m R 2.5R
= = = = 1.667
CV ,m CV ,m 1.5R
nRT1 1.00mol R 300 K
P1 = = 3
V1 24600cm
P1 = 1.00atm
V1
1.667
24.6 L
P2 = P1 = 1.00atm
V2 49.2 L
49
T2 =
P2V2
=
0.315atm 49200cm 3 = 189 K
nR cm atm
3
1.00mol 82.06
molK
P 1
(atm)
0.5 isotherm
adiabat
H = q P = q
fusion/melting vaporization
Latent heat of fusion of H2O = 79.7 cal/g
To melt 18 g of ice;
q = 79.7 cal 18 g = 1436cal
g
H = q P = q = 1436cal 51
H2O: Hfus = 79.7 cal/g Hvap= 539.4 cal/g
C P = 1.00 cal
gK H2O(l)
ice = 0.917 g 3 (0 C)
cm
H O (l ) = 1.000 g (0 C)
2
cm 3
H O (l ) = 0.958 g 3 (100 C)
2
cm
Calculate q, w, U, H for each case.
52
(a) Melting of ice:
H2O(s) H2O(l) at 0 C, 1 atm
q P = 79.7 cal 18.015 g = 1436cal = H
g
2
1 1
w = PdV = PV = Pm
1 2 1
cal
1 .987
= 1atm 18.015 g
1 1 molK
g g 82.06 cm 3
atm
1.00
cm 3
0.917
cm 3 molK
= 0.039cal
V2 = vol.H 2O(v) =
1mol 82.06 atm molK 373.15K
cm 3
1atm
V2 = 30620cm 3
V1 = vol.H 2 O(l ) =
18.015 g = 19cm 3
0.958 g
3
cm
1.987cal
w = PV = 1atm 30620 19cm 3
82.06cm atm
3
w = 741cal
U = q w = 9717cal 741cal = 8976cal 55
Deduce whether q, w, U, H = +, 0, -.
Heat is required q 0
Constant pressure H = qP 0, w = -PV
Benzene expands on melting, w 0
vol is small w q
U = q + w q U 0 56
(b) Reversible melting of ice at 1 atm, 0 C.
57
(d) Reversible heating of perfect gas at constant
P.
q 0 (heating)
dqP = CPdT, CP 0; T0
dU = CVdT, U 0 since CV 0
PV = nRT, V 0; w = -PV 0
H = U + (PV) 0.
58
THE SECOND LAW OF
THERMODYNAMICS
Work output = q
60
(b) Clausius statement:
Note that the second law does not forbid the complete
conversion of heat to work in a noncyclic process
62
THE SECOND LAW OF THERMODYNAMICS
qH
system
-w
-qC
qH qC qC
e= = 1
qH qH
qC negative
qH positive
e 1
65
CARNOTS PRINCIPLE
No heat engine can be more efficient than a
reversible heat engine when both engines work
between the same pair of temperature H and
C.
Hot reservoir at H
qH
Heat engine -w
qC
Cold reservoir at C
66
wrev
erev =
qH ,rev
adiabat adiabat
4 3
isotherm
V
dU = dq dw = dq PdV
Carnot-cycle efficiency e rev
dV
dU = dq nRT
V
dV
CvdT = dq nRT
V 68
divide by T:
dT dq dV
Cv = nR
T T V
dT dq dV
T T
Cv = nR V
1 2 3
69
(1)
T2 T3 T4 T1
dT dT dT dT dT
Cv T = T Cv T T Cv T T Cv T T Cv T
1 2 3 4
T3 T1
dT dT
= Cv Cv
T1
T T3 T
T1
dT
= Cv =0
T1
T
dT
Cv =0
T 70
(3) dV
nR = 0, (V1 = V2 )
V
0
dT dq
0 dV
Cv T = T nR V
(1) (2) (3)
dq
=0
T
71
(2) 2 3 0 4 1 0
dq dq dq dq dq
T 1 T 2 T 3 T 4 T
= = 0
2 4
dq 1 1
T = T 1 dq T 3 dq = 0
Since processes 2 3 and 4 1 are adiabatic with dq 0,
the second and fourth integrals are zero.
Carnot cycle
dq qH qC
T TH TC
= = 0
72
qC TC
=
qH TH
73
A Carnot-cycle heat engine does 2.50 kJ of
work per cycle and has an efficiency of 45.0%.
Calculate w, qH and qC for one cycle.
74
w = 2.50kJ
w 2.50kJ
e= = 0.45 =
qH qH
qH = 5.56kJ
U = 0 = q w = qC qH w
qC 5.56kJ 2.50kJ = 0
qC = 3.06kJ
75
SPONTANEOUS PROCESSES
A process which proceeds of its own accord,
without any outside assistance, is termed a
spontaneous or natural process.
76
Examples of Spontaneous Processes
77
CRITERIA OF SPONTANEITY
(1)A spontaneous change is one-way or
unidirectional. For reverse change to occur, work
has to be done.
(2) For a spontaneous change to occur, time is no
factor. A spontaneous reaction may take place
rapidly or very slowly.
(3) If the system is not in equilibrium state
(unstable), a spontaneous change is inevitable.
The change will continue till the system attains
the state of equilibrium.
78
(4) Once a system is in equilibrium state, it does not
undergo any further spontaneous change in state if left
undisturbed. To take the system away from equilibrium,
some external work must be done on the system.
(5) A spontaneous change is accompanied by decrease of
internal energy or enthalpy (H).
It implies that only such process will occur which are
exothermic. But the melting of ice and evaporation of rain
water are endothermic processes which proceed
spontaneously. Clearly, there is some other factor in
addition to H which governs spontaneity. It is the second
law of thermodynamics which introduces this new factor
that is called entropy.
79
ENTROPY
For many years scientists believed that only
exothermic changes resulting in a lowering of internal
energy or enthalpy could occur spontaneously. But
melting of ice is an endothermic process and yet
occurs spontaneously.
81
82
83
84
2.9 ENTROPY (S)
An infinitessimal change in entropy ds,
dqrev
dS = Closed system, reversible process
T
2
dqrev
S = S 2 S1 = Measurable change
1
T
S of a substance is the energy
transferred as heat to it reversibly,
divided by the temperature at which the
transfer takes place. 85
S is an extensive state function.
Sm = S/n molar entropy.
Unit J mol-1 K-1 or cal mol-1 K-1
dqrev = 0, S = 0
86
3. Reversible phase change at constant T, P.
At constant T gives:
2
dqrev 1 qrev
S = = dqrev =
1
T T T
Since P is constant,
qrev = qP = H
H
S =
T
87
4. Reversible Isothermal Process
T = constant,
2
S = dqrev / T
1
S = qrev / T
88
5. Reversible change of state of perfect gas.
90
H2O(s) (a) H2O(l), 0 C, 1 atm
0 C, 1 atm
(b)
(c)
(d)
= 5.26cal / K
92
(b)
H2O(l), 0 C, 1 atm H2O(l), 100 C, 1 atm
T2
Sb = C p ln
T1
1.00cal 373.15K
= 18.015 g ln
gK 273.15K
= 5.62cal / K
93
(c)
H2O(l), 100 C, 1 atm H2O(v), 100 C, 1 atm
qrev
S c =
T
=
18.015 g 539.4cal / g
373.15K
= 26.04cal / K
94
(d)
H2O(v), 100 C, 1 atm H2O(v), 100 C, 0.5 atm
Isothermal expansion
T2 0 V2 P1
S = Cv ln nR ln = nR ln
T1 V1 P2
cal 1atm
S d = 1.00mol 1.987 ln
molK 0.5atm
= 1.38cal / K
Stotal = Sa Sb Sc Sd = 38.30cal / K
95
CLASSWORK
A. Classwork 1: S for a phase change
1. Find S for the melting of 5.0 g of ice (heat of fusion
= 79.7 cal/g) at 0 C and 1 atm. Find S for the
reverse process.
2. The heat of vaporization of water at 100 C is 40.66
kJ/mol. Find S when 5.00 g of water vapor
condenses to liquid at 100 C and 1 atm.
B. Classwork 2: S for heating at constant P
1. The specific heat capacity cP of water is nearly
constant at 1.00 cal/(g C) in the temperature range
25 C to 75 C at 1 atm. Find S when 100 g of water
is reversibly heated from 25C to 50C, and from 50
C to 75 C both at 1 atm. Report the answer in J/K
and compare the values. 96
9. Irreversible phase change.
irrev
H2O(l), -10C, 1 atm H2O(s), -10C, 1 atm
supercooled H2O
(b)
H2O(l), 0C, 1 atm rev H2O(s), 0C, 1 atm
Sirrev = Sa Sb Sc
97
6. Irreversible change of state of perfect gas.
S is a state function, Srev=Sirrev
7. Constant-pressure heating.
2
dqrev dH CpdT
2
T2
2
S = = = = Cp ln
1
T 1
T 1
T T1
8. General change of state (P1,T1)(P2,T2)
2 2
Cp
S = S 2 S 1 = dT VdP
P
1 a)
1
T 1
P1
b)
P2 2
2 2
Cp
Sa = dT , Sb = VdP T1 T
1
T 1
T2
Const. P = P1 Const. T = T1 98
Find S for conversion of 10.0 g supercooled
H2O at -10C, 1 atm to ice at -10C, 1 atm.
99
(a)
T2
S a = C p ln
T1
cal 273.15K
= 10 g 1.01 ln
gK 263.15K
cal
= 0.38
K
100
(b) H2O(l), 0C H2O(s), 0 C
101
(c) H2O(s), 0C H2O(s), -10 C
T2 0.50cal 263.15
S = C p ln = 10 g ln
T1 gK 273.15
cal
= 0.19
K
TotalS = Sa Sb Sc
cal
= 2.73
K
102
10. Mixing of different inert perfect gas at
constant T and P.
a b a
b b a
a irrev
b
b b
a a
a
a b b
105
S mix = na R ln xa nb R ln xb
10.0 gHe
xa =
na
= 4.0 gHe / mol
na nb 10.0 g 10.0 g
4.0 g / mol 32.01gO2 / mol
xa = 0.889, na = 2.50mol
xb = 0.111, nb = 0.313mol
106
8.314 J
S mix = 2.50mol ln 0.889
molK
8.314 J
0.313mol ln 0.111
molK
= 8.17 J
K
107
A certain perfect gas has Cv,m = a + bT where a
= 25.0 J/mol K and b = 0.0300 J/mol K2. Let
4.00 mol of this gas go from 300 K and 2.00
atm to 500 K and 3.00 atm. Calculate q, w, U,
H and S for this change of state.
108
q and w cannot be calculated because the path was
not specified
2 2
U = nCV ,m dT = na bT dT
1 1
= naT2 T1
nb 2
2
T2 T1
2
25.0 J
= 4.00mol 500 300K
molK
4.00mol 0.0300 J
2
molK
2
500 2
300 2
K 2
U = 29.6kJ
109
H = U (PV )
= U nRT
8.314 J
= 29.6 10 J 4.00mol
3
200 K
molK
= 36.3kJ
110
2
Cv V2
S = dT nR ln
1
T V1
Cv nCV ,m a
= = n b
T T T
a
2
V2
S = n b dT nR ln
1 V1
T
nRT2
T2 P2
= na ln nbT2 T1 nR ln
T nRT
1
1
P1 111
25.0 J 500 K
= 4.00mol ln
molK 300 K
0.0300 J
4.00mol 2
500 300K
molK
8.314 J 500 K 2.00atm
4.00mol ln
molK 300 K 3. 00 atm
S = 78.6 J
K
112
Reversible Process
Suniv = 0
113
Irreversible Process
Thr
P 4 Reversible isothermal
3
Reversible Reversible
adiabatic adiabatic
1 2
Irreversible adiabatic
V
23 rev. adiabatic S = 0 S2 = S3
41 rev. adiabatic S = 0 S4 = S1
34: 4 dq 1
4
q34
3 T = Thr 3 dqrev = Thr
rev
114
0 0
0 = dS syst = S2 S1 S3 S2 S4 S3 S1 S4
= S 2 S1 =
q34
dS syst
Thr
dU = 0 = dq dw = q 3 4 w
w = -q34 q34 0 so that it doesnt
violate the 2nd law
q34
S 2 S1 = 0
Thr
Ssyst 0
115
Suniv = Ssyst + Ssurr
Suniv =0 reversible process
Suniv 0 irreversible process
Suniv 0 any process
116
Isolated Process
Thermo. equilibrium
time
d d e e d d e e
d d e e 1
d d e e
e
e e
d 2
d d d
e
23
= 1.38 10 J
K
119
Calculate the change in the entropies of the
system and the surroundings and Stot when 14
g N2 gas at 298 K and 1.00 bar doubles its
volume in:
120
(a) Vf
S syst = nR ln
Vi
14 g 8.314 J
= ln 2
28.02 g / mol Kmol
= 2.9 J
K
Vf
S surr,rev = nR ln
Vi
S surr = 2.9 J
K
Stot = 0
121
(b) Ssyst = +2.9 J/K (S is a state function)
Surrounding:
w = 0, T = constant , U = 0 no energy
transfer between system surrounding
Ssurr = 0
Stot = +2.9 J/K
122
2.11 THERMOCHEMISTRY
Thermochemistry is the branch of physical chemistry which
deals with the thermal or heat changes caused by chemical
reactions.
We have studied that;
every substance has a definite amount of energy known as the
intrinsic energy or internal energy, U
The exact value U cannot be determined but the change in internal
energy, U, can be accurately measured experimentally.
aA + bB cC + dD
U = Uproducts Ureactants
If U = positive endothermic reaction
If U = negative exothermic reaction
The amount of heat released or absorbed in a chemical
reaction is termed the heat of reaction. 123
124
125
2.11.1 Adiabatic Bomb Calorimeter
Ua = 0 P+K
R+K
25C (a) 25C + T
(b)
(c)
P+K
25C
H = U PV
ng
Hrxn = Urxn RT
mol
Urxn = CK P T
Urxn 15.254kJ
CK P = = = 12.01kJ
T 1.270K K
129
(b) NA
Urxn = UC,NA mNA UC m wire
= 5186 kJ U C
mol 130
Combustion reaction:
n g
= 10 12 = 2
mol
n g
H C = U C RT
mol
= 5186 kJ
mol
28.314 J
Kmol
298K
= 5191 kJ
mol
131
2.11.2 Standard Enthalpy of Reaction, Hrxn
aA + bB cC + dD
Hrxn = iHf,i
A+BC+D
133
EXAMPLE: Calculation of H from fH data
Find H298 for the combustion of one mole of the simplest amino
acid, glycine, NH2CH2COOH, according to
Exercise
H298 kJ/mol
Given:
(1) C2H6(g) + 7/2O2(g) 2CO2(g) + 3H2O(l) -1560
(2) C(graphite) + O2(g) CO2(g) -393.5
(3) H2(g) + 1/2O2(g) H2O(l) -286
136
(1) -1:
2CO2(g) + 3H2O(l) C2H6(g) + 7/2O2(g) 1560
Exothermic reaction
137
HkJ/mol
138
(1) :
NH3(g) + 5/4O2(g) NO(g) + 6/4H2O(l) 292.5
(2) :
3/2NO(g) + 3/4O2(g) 3/2NO2(g) -85.5
(3) :
3/2NO2(g) + 1/2H2O(l) HNO3(l) + 1/2NO(g) -36
139
2.11.4 Temperature dependence of reaction heats
H = i H m ,i
i
dH dH m,i
= i
dT i dT
H m ,i
= C P ,m ,i
T P
dH
= i C P ,m ,i = C P
dT
140
dH = C P dT
T2 T2
dH = C
T1 T1
P dT
T2
H T2 H T1 = C P dT
T1
C P ,m = a bT cT 2
or
2
C P ,m = d eT fT
141
Hf,298(g) = -241.82 kJ/mol. Calculate Hf,373
H2O(g).
Given:
C P ,m H 2 O( g ) = 33.58 J
K .mol
C P ,m H 2 ( g ) = 28.84 J
K .mol
C P ,m O2 ( g ) = 29.37 J
K .mol
142
T2 T2
H T2 H T1 = C P dT = C P dT
T1 T1
H T2 = H T1 C P T2 T1
C P = i C P ,m,i
C P = C P ,m H 2 O, g C P ,m H 2 , g C P ,m O2 , g
1
2
1
= 33.58 28.84 29.37
2
= 9.94 J
K .mol 143
9.94 J
H f ,373 = 241.82 kJ
mol Kmol 75K
= 242.6 kJ
mol
144
Use Appendix data and the approximation that CP is
independent of T to estimate H1200 for the reaction:
2CO(g) + O2(g) 2CO2(g)
T2 2 3 4 1500
T T T
CP dT = -39.87 T 0.11744
T1
2
- 9.8296 *10-5
3
2.8049 *10-8
4 298
Given:
CP,m, H2(g) = 6.52 + 7.8 10-4 T + 0.12 105T-2
CP,m, Cl2(g) = 8.82 + 0.6 10-4 T 0.68 105 T-2
CP,m, HCl(g) = 6.34 + 11 10-4 T + 0.26 105 T-2
147
H2(g) + Cl2(g) HCl(g)
1 1
C P = C P,m , HCl C P, m , H 2 C P,m , Cl 2
2 2
= 6.34 11104 T 0.26 105 T 2
6.52 7.8 104 T 0.12 105T 2
1
2
8.82 0.6 104 T 0.68 105T 2
1
2
C P = 1.33 6.8 10 4 T 0.54 105 T 2
148
T2
H T2 H T1 = C P dT
T1
5 1 1
= 1.33T2 T1
6.8 10 4 2
T2 T1 0.54 10
2
2 T2 T1
T2 = 1000K , T1 = 298K
H T2 H T1 = 497 cal
mol
H f ,1000 = H f , 298 497 cal
mol
= 22.06 kcal 497 cal = 22557 cal
mol mol mol 149
STATEMENT OF THE THIRD LAW Entropy of varying phases
Higher entropy
Zero entropy
Lower entropy
150
Standard Entropy
solid/liquid elements
S m,0 = lim S m,T = 0
T 0
C P ,m ( s)
T fus
S m,T2 =
0
T
dT (solid)
H m , fus
(melting)
T fus
T2
C P ,m (l )
T fus
T
dT (liquid)
151
C P
T2
S T2 S T1 = dT
T1
T
Standard entropy change for a reaction:
152
2H2S(g) + 3O2(g) 2H2O(l) + 2SO2(g)
H T = i H f ,T ,i
i
H 298 = 1124 kJ
mol
154
(b)
S 298 = i S m, 298,i
= 269.91 2248.22 2205.79 3205.138
= 390.73 J
mol.K
370
C p, m
o o T2
S 370 S 298 = dT = C p, m ln
T T1
298
155
(c)
CP = 2CP,m H 2O, l 2CP,m SO2 , g 2CP,m H 2 S , g 3CP,m (O2 , g )
o o T2
S 370 = S 298 C p, m ln
T1
o 370
S 370 = 390.73 73.797 ln = 374.76
298
156
(d)
370
o
H 370 H 298 =
298
o
C p, m dT = C p, m (T2 T1)
o o
H 370 = H 298 C p,m (370 298)
Grxn = iGf,i
Gf,i = Standard Gibbs energy of formation of
a substance from its elements in their
reference form.
Gf = 0 for element in its reference form.
S298 = iSf,i
1
= S f ,urea S f ,c S f ,O2 S f , N 2 2S f , H 2
2
159
CO(NH2)2 - C(graphite) + O2(g) + N2(g) + 2H2(g)
Srxn = 456.69 J
mol .K