1

2.1 P-V Work

2.2 Heat
2.3 The First Law of Thermodynamics
2.4 Enthalpy
2.5 Heat Capacities
2.6 Calculation of First Law Quantities
2.7 The 2nd law of thermodynamics
2.8 Heat engines
2.9 Entropy
2.10 Calculation of entropy changes
2.11 Thermochemistry

 Able to perform calculations using

First and Second Laws of
Thermodynamics
Able to calculate properties in
Thermochemistry

Work

X2

w F(x)dx
X1

2.1 P-V WORK

Pext

Pint

Mechanical
equilibrium

System

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

 Action = reaction

Fx F PA
w Fx
dw Fdx PAdx PdV
2

wrev PdV
1

Closed system
reversible
process
6

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

2.2 HEAT (q)

m2, T2
T2 T1

m1, T1
Tf = final temperature

m2 c2 (T2 Tf) = m1 c1 (Tf T1) q

q = amount of heat flows from body 2 to body 1.
c1, c2 = specific heat capacity. (constant, evaluated
experimentally, functions of T and P)
Unit for heat: J or cal
1 cal = 4.184 J
8

 Heat capacity: Heat required to raise the

temp of system by one K(or oC)

3 types of heat capacities:

heat capacity (C): unit J/K,

specific heat capacity(c): unit J/Kg,
molar heat capacity(cm): unit J/Kmol.

For heat flowing at constant pressure:

dqP = mcPdT
CP = heat capacity at constant pressure.
CP = mcP
dqP = CPdT CP = dqP/dT

ENERGY: capacity to do work

Mechanical Energy
Kinetic energy, K = mv2
Potential energy, V = mgh

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)

10

 E=K+V+U
E = Total energy of system.
System at rest, K = 0 and no external field,
V = 0, E = U

11

2.3 FIRST LAW OF THERMODYNAMICS

U = q + w
Heat
absorbed
by system

closed system

+q

+w

Work done
on the
system

SYSTEM

Heat
released
from system

-q

-w

Work done
by system
surrounding
12

P
1

(a)
2

w PdV
1

wa wb wc

(b)

(c)

= area under the curve

w is not a state function
13

dU U

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.
Energy is conserved any energy that is lost
by the system must be gained by the
surroundings, and vice versa.
14

2.4 ENTHALPY, H
H = U + PV
H is state function.

Heat absorbed (q) at P & V

H H 2 H 1 U 2 P2V2 U 1 P1V1
U P2V2 P1V1

For constant-pressure process, P2 = P1

H U P V

H q P

For constant-volume process (V=0):

U qV

15

2.5 HEAT CAPACITIES

Heat capacity at constant pressure (isobaric
process):
dq P H

CP

dT

Heat capacity at constant volume (isochoric

process):
dqV U

CV

dT

Generally Cp>Cv except if the fluid contracts upon heating

(H2O)

16

 Molar heat capacity:

C P ,m
CV ,m

CP

n
CV

J
unit
molK

For ideal gas:

C P CV nR
C P ,m CV ,m R
17

2.6 CALCULATION OF FIRST LAW

QUANTITIES
Isothermal dT = 0
Reversible
process in
perfect gas,
closed system

Constant-volume or
isochoric dV = 0
Constant-pressure
or isobaric dP = 0
Adiabatic dq = 0

U
PV nRT ,

Perfect gas obeys:

V

0
T

18

 Perfect-gas change of state U and H depend on

T only.
U
H
CV
,CP

T V
T

CV

dU
dH
, CP
dT
dT

T2

U CV T dT
T1

T2

H C P T dT
T1

2
2
on path.
q and w depend
T
w PdV nR dV
V
1
1

19

2.6.1 Isothermal Process (reversible)

dT = 0 U = 0 H = 0
U = 0 = q + w q = -w
2

w PdV
1

nRT
P
V

nRT
w
dV
V
1

V2

w nRT ln
V1

20

P1V1 P2V2

T1
T2

because T1 = T2

V2 P1

V1 P2
P1

w nRT ln
P2
21

Calculate q, w, U and H for reversible

isothermal expansion at 300K of 5.00 mol
perfect gas from 500 to 1500 cm3.
n = 5.00 mol T = 300 K
V1 = 500 cm3 V2 = 1500 cm3

22

 V2
w nRT ln
V1

8.314 J
5.00mol

molK

1500cm 3

300 K ln
3
500cm

w 13.7kJ
q w 13.7 kJ
U 0 H
23

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)
24

2.6.3 Constant-Pressure Process (reversible, no

phase change)
2

wrev PdV PV
1

T2

q P C P T dT H
T1

dq P
CP
dT

q P n C P ,m T dT H
T1

If CP,m doesnt vary with temperature,

qP = nCP,m (T2-T1),
U = qP + w

25

Calculate q, w, U and H if 2.00g He(g) with

CV,m = 3/2 R undergoes:
(a) Reversible constant-pressure expansion from
20.0 dm3 to 40.0 dm3 at 0.80 bar.
(b) Reversible constant-volume heating from
0.600 bar to 0.900 bar at V = 15.0 dm3.

26

(a)

2.00 g
n
0.500molHe
4 g / mol
V1 20.0dm 20000cm
3

0.9869atm
P1 0.800bar
0.789atm
1bar

P2 P1 0.789atm
V2 40.0dm 40000cm
3

T1 = ?

T2 = ?
27

P1V1

0.789atm 20000cm 3
T1

3
nR
cm
0.500mol 82.06 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
28

C P ,m CV ,m R
C P ,m 2.5 R
const. pressure : H q P
H q P nC P ,m T
0.500mol 2.5 R 384.6 K
4.00kJ

U q w
w U q
2.40 4.00
1.60kJ
29

(b)

P1 0.600bar 0.5921atm
V1 15.0dm 3 15000cm 3 V2

0.5921atm 15000cm 3
T1
3
cm
0.500mol 82.06 atm molK

T1 216.5 K
T2 324.7 K

T 108.2 K

const vol U qV nCV ,m T

3
U qV 0.50mol R 108.2 K
2
674.7 J
30

w U q 0 J
H nC P ,m T

0.50mol 2.5R 108.2 K

1.13kJ

H q

31

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
reversible heated from 27 127C with P held
fixed at 1.00 atm.

32

C P ,m

CP

nC P ,m C P n a bT
n
2

dq P C P dT C P dT n a bT dT

b 2

2
q n aT2 T1 T2 T1
2

6.15cal
400 300 K

molK

q 2.00mol
1 0.00310cal
2
2

400

300

2
2
molK

q 1447cal
H q P 1447cal

33

w PdV PV nRT
1

w 2.00mol 1.987 cal

100 K
molK

w 397cal
U q w
1447cal 397cal
1050cal

34

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

35

 T2
CV ,m ln
T1

V2
R ln

V1

T2
V1
ln

ln
T1
V2

T2 V1

T1 V2
If V2 V1, T2 T1

V1
R ln

V2

R / CV ,m

R / CV ,m

36

 For ideal gas:

P1V1 P2V2

T1
T2

T2 P2V2

T1
P1V1

For adiabatic process:

T2 V1

T1 V2

CV , m

R
gas:
For adiabatic process in ideal
CV , m
T2 P2V2 V1

T1
P1V1 V2

37

T2 P2V2 V1

T1 P1V1 V2

P1 V1

1 R / CV ,m

R / CV ,m

P2 V2

1 R / CV ,m

CV ,m R C P ,m
R
1

CV ,m
CV ,m
CV ,m

P1V1 P2V2

U w
38

P1

P2
P2

isotherm

adiabat
V1

V2

Isothermal expansion: V2 V1, P2 P1, T2 = T1

Adiabatic expansion: V2 V1, P2 P1, T2 T1
P2(adiabatic) P2(isothermal)

39

1 mol He with CV,m = 3/2 R expands reversibly

from 24.6 L to 49.2 L at 300 K. Calculate final
pressure and temperature if the expansion is:
(a) Isothermal
(b) adiabatic
(c) Sketch on a PV diagram

40

(a) Isothermal T2 = T1 = 300 K

nRT2
P2
V2

cm atm
300 K
1.00mol 82.06
molK

49200cm 3
0.500atm
3

41

(b) Adiabatic process P1V1 = P2V2

C P ,m
CV ,m

CV ,m R
CV , m

2.5 R

1.667
1.5 R

nRT1 1.00mol R 300 K

P1

V1
24600cm 3
P1 1.00atm

V1
P2
V2

24.6 L
P1

49.2

1.667

1.00atm
42

P2V2
T2

nR

0.315atm 49200cm 3

1.00mol

P
(atm)

cm atm

82.06
molK
3

189 K

isotherm

0.5

adiabat
24.6

49.2

V/L
43

2.6.5 Reversible phase change at constant T & P

2

w PdV PV
1

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

44

H2O: Hfus = 79.7 cal/g

C P 1.00 cal

gK

Hvap= 539.4 cal/g

H2O(l)

ice 0.917 g

(0 C)

H 2O ( l )

(0 C)

H 2O ( l )

cm 3
g
1.000
cm 3
0.958 g 3
cm

(100 C)

Calculate q, w, U, H for each case.

45

(a)

Melting of ice:
H2O(s)

H2O(l)

at 0 C, 1 atm

q P 79.7 cal 18.015 g 1436cal H

g

1
1
w PdV PV Pm

2 1
1
2

1atm 18.015 g

1
1.00 g

cm 3

1
0.917 g

cm 3

1.987 cal

molK
3

cm
atm
82.06
molK

0.039cal

U q w 1436cal 0.039cal 1436.039cal 1436

46

(b) Reversible constant heating of 1 mol liquid

water from 0 to 100 C at 1 atm.
H2O(l), 0C H2O(l), 100C, 1 atm
2

q P C P dT C P T H
1

18.015 g 100C 1801cal

q P 1.00 cal
gK

w PV

1
1

1atm 18.015 g

g
g
0.958 cm 3 1.00 cm 3
0.019cal
U q w 1801 0.019cal 1801cal

1.987 cal

molK
82.06 cm 3 atm

molK

47

(c)The vapourisation of 1 mol of water at 100 C

and 1 atm. H2O(l), 100C H2O(v), 100C
q P H 18.015 g 539.4 cal 9717cal
g

3
cm
1mol 82.06 atm molK 373.15K
V2 vol.H 2 O(v)
1atm
V2 30620cm 3

18.015 g

V1 vol.H 2 O(l )

0.958 g

19cm 3

cm

1.987cal
w PV 1atm 30620 19cm

3
82.06cm atm
w 741cal
3

U q w 9717cal 741cal 8976cal

48

Deduce whether q, w, U, H = +, 0, -.
(a) Reversible melting of benzene solid at 1 atm
and normal melting point.

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

49

(b) Reversible melting of ice at 1 atm, 0 C.

Same as (a) except the system contracts on
melting w 0
(c) Adiabatic expansion of perfect gas into a
vacuum.
q = 0, w = 0, U = 0, P=0 (free expansion)
H = U + (PV) = 0
50

(d) Reversible heating of perfect gas at constant

P.
q 0 (heating)
dqP = CPdT, CP 0;
dU = CVdT,

T0

U 0 since CV 0

PV = nRT,
V 0;
w = -PV 0
H = U + (PV) 0.

51

2.7 THE SECOND LAW OF THERMODYNAMICS

(a) Kelvin-Planck statement:
It is impossible for a system to undergo a
cyclic process whose sole effects are the flow
of heat into the system from a heat reservoir
and the performance of an equivalent amount
of work by the system on the surroundings.
Heat reservoir

Cyclic machine (syst)

Work output = q
52

(b)

Clausius statement:

It is impossible for a system to undergo a

cyclic process whose sole effects are the flow
of heat into the system from a cold reservoir
and the flow of an equal amount of heat out of
the system into a hot reservoir.

53

Rephrase:
There are 2 principal physical statements of
the Second Law of Thermodynamics:
1. It is impossible for a system in a cyclic process
to turn heat completely into work. (KelvinPlanck).
2. Heat cannot flow spontaneously from a cooler
to hotter object if nothing else happens.
(Clausius).
54

2.8 HEAT ENGINES:

Convert q w

qH

system

-w
-qC
Efficiency = e =

w
e
qH

work out per cycle

energy input per cycle

55

 For cyclic process, the first law gives U = 0

q + w = qH + qC + w
-w = qH + qC

qH qC
qC
e
1
qH
qH
qC negative
qH positive
e 1
56

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
It is not possible to make a
heat engine whose only effect
is to absorb heat from a hightemperature region and turn
all that heat into work

qH
Heat engine

Cold reservoir at C

-w
qC
57

erev

wrev

qH ,rev

(I) All reversible heat engines operating between

the same two temperature, have the same
efficiency.
erev = f(H, C).
(II) This reversible efficiency is the maximum
possible for any heat engine that operates
between these temperatures.

eirrev erev

58

CARNOT CYCLE
P

isotherm
2
adiabat

adiabat
4

isotherm

dU dq dw dq PdV
dV
dU dq nRT
V
dV
CvdT dq nRT
V

3
V

59

1. Heat flows into cylinder at temperature

TH The fluid expands isothermally and
does work on the piston.
2. The fluid continues to expand,
adiabatically.
3. Work is done by the piston on the fluid,
which undergoes an isothermal
compression.
4. The fluid returns to its initial condition
by an adiabatic compression.

60

divide by T:

dT dq
dV
Cv

nR
T
T
V
Integrate both sides:

dT
dq
dV
Cv

nR
T T
V
1

61

(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
T T3
T
T1
T1

dT
Cv
0
T
T1
dT
Cv
0
T

62

(3)

dV
nR
0, (V1 V2 )
V

dT
dq
dV
Cv T T nR V
0

(1)

(2)

(3)

dq

0
T
63

(2)

0 4

dq
dq
dq
dq
dq

0
T 1 T 2 T 3 T 4 T
2

dq 1
1
T T 1 dq T 3 dq 0

dq qH qC
T TH TC 0

Carnot cycle

64

qC
TC

qH
TH
erev

qC
TC
1
1
qH
TH

Upper limit to the

efficiency of real
heat engines

65

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.

66

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
67

A Carnot heat engine receive 500kJ OF heat per cycle form

a high temperature source of 652 degree C and reject a low
Temperature sink at 30 degree C.
a)
b)

Determine the thermal efficiency of this Carnot engine

Determine the amount of heat rejected to the sink per
cycle

a=0.672
b= 164kJ
68

 Able to perform calculations using

First and Second Laws of
Thermodynamics
Able to calculate properties in
Thermochemistry

69

70

2.9 ENTROPY (S)

An infinitesimal change in entropy ds,

dqrev
dS
T

Closed system,
reversible process
2

dqrev
S S 2 S1
T
1

Measurable change

S of a substance is the energy transferred

as heat to it reversibly divided by the
temperature at which the transfer takes
71
place.

 S is an extensive state function.

Sm = S/n molar entropy.
Unit J mol-1 K-1 or cal mol-1 K-1
2.10 CALCULATIONS OF ENTROPY CHANGES.
1. Cyclic process

dqrev
T 0 S

2. Reversible adiabatic process

dqrev 0, S 0
72

3. Reversible phase change at constant T, P.

At constant T gives:
2

dqrev 1
qrev
S
dqrev
T
T
T
1
Since P is constant,

qrev qP H
H
S
T
73

4. Reversible Isothermal Process

T = constant,
2

S dqrev / T
1

S qrev / T

74

5. Reversible change of state of perfect gas.

dU dqrev dwrev dqrev dU dwrev

dqrev

dV
Cv dT nRT
V

dqrev
dT
dV
dS
Cv
nR
T
T
V
T2
V2
dT
dV
nR ln

S Cv
nR
Cv ln
T
V
T1
V1
75

Find S for the conversion of 1.00 mol ice at 0

C and 1.00 atm to 1.00 mol H2O vapour at 100
C and 0.500 atm.
Hfus = 79.7 cal/g

Hvap = 539.4 cal/g

Cp = 1.00 cal/g K

76

H2O(s)

H2O
(a)(l), 0 C, 1 atm

0 C, 1 atm

(b)

H2O(l), 100 C, 1 atm

(c)

H2O(v), 100 C, 1 atm

(d)

H2O(v), 100 C, 0.5 atm

77

(a)

qrev 18.015 g 79.7cal / g

S a

T
273.15 K

5.26cal / K

78

(b)
H2O(l), 0 C, 1 atm H2O(l), 100 C, 1 atm

T2

S b C p ln
T1
1.00cal 373.15 K
ln
18.015 g

gK 273.15 K
5.62cal / K
79

(c)
H2O(l), 100 C, 1 atm H2O(v), 100 C, 1 atm

qrev
S c
T

18.015 g 539.4cal / g

373.15 K
26.04cal / K
80

(d)
H2O(v), 100 C, 1 atm H2O(v), 100 C, 0.5 atm
Isothermal expansion

T2 0
V2
P1
nR ln
nR ln

S Cv ln
T1
V1
P2

cal 1atm
S d 1.00mol 1.987
ln

molK 0.5atm

1.38cal / K

Stotal S a Sb S c S d 38.30cal / K
81

6. Irreversible change of state of perfect gas.

S is a state function, Srev=Sirrev
7. Constant-pressure heating.

T2
dqrev
dH
CpdT

Cp ln
T
T
T
T1
1
1
1
2

8. General change of state (P1,T1)(P2,T2)

2

Cp
S S 2 S 1
dT VdP
T
1
1
2

Cp
Sa
dT , Sb VdP
T
1
1
Const. P = P1

Const. T = T1

P
1

a)

P1

b)
P2

T1

T2

82

9. Irreversible phase change.

H2O(l), -10C, 1 atm
supercooled H2O

irrev
H2O(s), -10C, 1 atm
(c) rev

(a) rev
H2O(l), 0C, 1 atm

(b)
rev

H2O(s), 0C, 1 atm

Sirrev S a Sb S c
83

Find S for conversion of 10.0 g supercooled

H2O at -10C, 1 atm to ice at -10C, 1 atm.
Cpice=0.50cal/g K

Cpsupercooled H2O=1.01 cal/g K

Hfus = 79.7 cal/g

84

(a)

T2
S a C p ln
T1

cal 273.15 K
ln
10 g 1.01

gK 263.15 K

cal
0.38
K

85

(b)

H2O(l), 0C H2O(s), 0 C

H fus
qrev H freezing
S b

T
T
T

79.7cal / g 10 g
cal
S b
2.92
273.15 K
K

86

(c)

H2O(s), 0C H2O(s), -10 C

T2
0.50cal 263.15
10 g
ln
S C p ln

gK 273.15
T1

cal
0.19
K

Total S S a Sb S c
cal
2.73
K

87

10. Mixing of different inert perfect gas at

constant T and P.
a

b
b

a
a
Pa, Va
P, T
1. Rev isothermal
expansion

irrev
a

Va = V, Vb = V

b
b

Pb, Vb
P, T

P, na, nb,
V= Va, Vb, T
2. Rev isothermal
mixing
88

 V
V
nb R ln

S1 na R ln
Va
Vb
0
S irrev S1 S 2
V na nb 1

Va
na
xa

Xi ;mole fractions of gas i

V
1
ln
ln 1 ln xa ln xa
ln
Va
xa
S mix na R ln xa nb R ln xb Perf. gas, const T, P
89

Calculate S for the mixing of 10.0 g He at

120.0 C and 1.50 bar with 10.0 g O2 at the same
T, P.

90

S mix na R ln xa nb R ln xb

na
xa

na nb

10.0 gHe

4.0 gHe / mol

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
91

S mix

8.314 J
2.50mol
ln 0.889
molK
8.314 J
0.313mol
ln 0.111
molK

8.17 J

K
92

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.

93

q and w cannot be calculated because the path was

not specified
2

U nCV ,m dT n a bT dT

nb 2
2
naT2 T1
T2 T1
2
25.0 J
4.00mol
500 300 K
molK

4.00mol 0.0300 J
2
2
2

500

300
K

2
2
molK

U 29.6kJ

94

H U (PV )
U nRT
8.314 J
29.6 10 J 4.00mol
200 K
molK
36.3kJ
3

95

 V2
Cv

S dT nR ln
T
V1
1
Cv nCV ,m
a

n b
T
T
T

V2
a

S n b dT nR ln
T

V1
1
2

T2

na ln
T1

nRT2


P2

nbT2 T1 nR ln
nRT1


P1

96

 25.0 J 500 K
4.00mol
ln

molK 300 K
0.0300 J
500 300 K
4.00mol
2
molK
8.314 J 500 K 2.00atm
4.00mol
ln

molK 300 K 3.00atm

S 78.6 J

K
97

Reversible Process

dSuniv dS syst dS surr

dqrev dqrev

0
Tsyst
Tsurr

Suniv 0

98

Irreversible Process
P

Thr

Reversible isothermal
3
Reversible
Reversible
adiabatic
adiabatic
1

2
Irreversible adiabatic

23 rev. adiabatic S = 0 S2 = S3
41 rev. adiabatic S = 0 S4 = S1
34:

dqrev
1
q34
3 T Thr 3 dqrev Thr
99

0 dS syst S 2 S1 S3 S 2 S 4 S3 S1 S 4

dS

syst

q34
S 2 S1
Thr

dU 0 dq dw q

3 4

w = -q34

q34 0 so that it doesnt

q34
S 2 S1
0 violate the 2nd law

Thr

Ssyst 0

100

Suniv = Ssyst + Ssurr

Suniv = 0

reversible process

Suniv 0irreversible process

Suniv 0 any process

101

Isolated Process
S
Thermo. equilibrium

time

Real processes: mixing, chemical reaction, flow of

heat from hot to cold bodies will continue to occur
until S reach maximum value.
102

Irreversible Mixing
d

Unmixed

Nonequilibrium state
e
e
d

d
d

Equilibrium state

2
d
103

S = k lnp + a
p = probability
k = Boltzman constant
a = constant
p2

S S2 S1 k ln
p1
8.314 J

R
molK
k

N A 6.022 10 23 / mol

1.38 10

23

K
104

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:
(a) an isothermal reversible expansion.
(b) an isothermal irreversible expansion against
Pext = 0.
(c) an adiabatic reversible expansion.

105

(a)

S syst nR ln

Vf
Vi

8.314 J
14 g


ln 2
28.02 g / mol Kmol
2.9 J
K

S surr ,rev nR ln
S surr 2.9 J

Vf
Vi

Stot 0
106

(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
(c) qrev = 0 Ssyst = 0
Ssurr = 0 = Stot

107

2.11 THERMOCHEMISTRY
2.11.1 Standard Enthalpy of Reaction, Hrxn
aA + bB cC + dD
Hrxn,T cH f ,T C dH f ,T D aH f ,T A bH f ,T B
Hrxn

iHf,i

H f ,i = standard enthalpy of formation for

substance i from its elements in their

reference form (at T, 1 bar)
108

2.11.2 Adiabatic Bomb Calorimeter

Ua = 0

R+K
25C

P+K
25C + T

(a)

(c)

(b)

8
29
r,

P+K
25C

R = reactants, P = products, K = wall + H2O

109

110

U a q w 0

V constant

U a U b U c 0
U b C K P T

U c U b C K P T U r , 298
CK+P = heat capacity of system
H U PV
ng
Hrxn Urxn
RT
mol

ng = change in mol for gases

111

a)
b)

Benzoic acid (BA)

wire
Naphthalene (NA)
wire

mass

UC

(g)

(K)

(kJ/g)

1.270
2.035
-

-26.434
-6.28
??
-6.28

0.5742
0.0121
0.6018
0.0142

Calculate CK+P, UC, HC for C10H8(s)

C10H8(s) = naphthalene =NA
C6H5COOH = benzoic acid = BA
112

(a) BA
Ur xn UC,BA mBA UC,wire m wire
26.434 kJ

15.254kJ

0.5742 g 6.28 kJ
g

0.0121g

Urxn CK P T
CK P

Urxn
15.254kJ

12.01kJ
K
T
1.270K
113

(b)

NA

Urxn UC,NA mNA UC m wire

Urxn UC,NA 0.6018g 6.28 kJ 0.0142g
g

Urxn CK P T
12.01 kJ 2.035 K
K
24.44kJ

24.44kJ U C , NA 0.6018 g 0.089kJ

U C , NA 40.46 kJ

U m ,C , NA 40.46 kJ 128.17 g
g
mol

5186 kJ
U C
mol

114

 Combustion reaction:
C10H8(s) + 12O2(g) 10CO2(g) + 4H2O(l)

n g
mol

10 12 2

H C U C

n g
mol

5186 kJ
5191 kJ

RT

298K
2 8.314 J
mol
Kmol

mol
115

2.11.3 Hesss Law: Combine heats of several

reactions to obtain H of desired reaction.
2C(graphite) + 3H2(g) C2H6(g)

Hf,298 = ?

Given:
(1) C2H6(g) + 7/2O2(g) 2CO2(g) + 3H2O(l)

H298 kJ/mol

-1560

(2) C(graphite) + O2(g) CO2(g)

-393.5

(3) H2(g) + 1/2O2(g) H2O(l)

-286

116

(1) -1:
2CO2(g) + 3H2O(l) C2H6(g) + 7/2O2(g)

1560

(2) 2: 2C(graphite) + 2O2(g) 2CO2(g)

-787

(3) 3: 3H2(g) + 3/2O2(g) 3H2O(l)

2C(graphite) + 3H2(g) C2H6(g)

-858
85

H298 = -85 kJ/mol = Hf,298

Exothermic reaction
117

HkJ/mol
1) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(l)

1170

2) 2NO(g) + O2(g) 2NO2(g)

114

3) 3NO2(g) + H2O(l) 2HNO3(l) + NO(g)

72

Calculate H298 for:

NH3(g) + 2O2(g) HNO3(l) + H2O(l)

118

 :
NH3(g) + 5/4O2(g) NO(g) + 6/4H2O(l)
(2) :
3/2NO(g) + 3/4O2(g) 3/2NO2(g)

292.5
-85.5

(3) :
3/2NO2(g) + 1/2H2O(l) HNO3(l) + 1/2NO(g) -36

NH3(g) + 8/4O2(g) HNO3(g) + 4/4H2O(l)

-414
119

2.11.4 Temperature dependence of reaction heats

H i H m ,i
i

dH m,i
dH
i
dT
dT
i
H m,i

C P , m ,i
P

dH
i C P ,m ,i C P
dT
120

dH C P dT
T2

T2

dH C

T1

dT

T1

T2

H T2 H T1 C P dT
T1

C P ,m a bT cT

or
C P ,m d eT fT

2
121

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
122

T2

T2

T1

T1

H T2 H T1 C P dT C P dT
H T2 H T1 C P T2 T1
C P i C P ,m,i

H2(g) + O2(g) H2O(g)

1
C P C P ,m H 2 O, g C P ,m H 2 , g C P ,m O2 , g
2
1

33.58 28.84 29.37

2

9.94 J
K .mol

123

H f ,373

241.82 kJ
242.6 kJ

9.94 J

75 K

mol Kmol

mol

124

Calculate Hf,1000 for HCl(g).

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
CP,m unit = cal/mol K
Hf,298, HCl(g) = -22.06 K cal/mol

125

H2(g) + Cl2(g) HCl(g)

1
1

C P, m , H 2 C P, m , Cl2
2
2

C P C P, m , HCl

6.34 1110 4 T 0.26 105 T 2

1
6.52 7.8 10 4 T 0.12 105 T 2
2

1
8.82 0.6 10 4 T 0.68 105 T 2
2

C P 1.33 6.8 10 4 T 0.54 10 5 T 2

126

T2

H T2 H T1 C P dT

1.33 6.8 10 4 T 0.54 10 5 T 2 dT

T1

6.8 10 4 2
1
2
5 1
1.33T2 T1
T2 T1 0.54 10

2
T2 T1

T2 1000 K , T1 298 K

H T2 H T1 497 cal
H f ,1000 H f , 298

mol
497 cal

22.06 kcal

mol

mol

497 cal

mol

22557 cal

mol
127

Standard Entropy
solid/liquid elements

S m , 0 lim S m ,T 0
T 0

Third Law of Thermodynamics:

lim S 0
T 0

T fus

S m ,T2

C P ,m ( s )
T

dT

H m , fus

(melting)

T fus
T2

T fus

C P ,m (l )
T

(solid)

dT

(liquid)
128

T2

C P
S T2 S T1
dT
T
T1
Standard entropy change for a reaction:

S T i S m ,T ,i

i = stoichiometric coefficient

129

2H2S(g) + 3O2(g)

2H2O(l) + 2SO2(g)

Hf,298

-20.63

285.830

296.83

CP,m

34.23

29.355

75.291

39.87

Sm,298

205.79

205.138

Calculate H298, H

370

69.91

248.22

, S298, S370

130

H T i H f ,T ,i
i

H 298 2H f , 298, H 2O 2H f , 298, SO2

2H f , 298, H 2 S 2H f , 298,O2
2 285.83 2 296.83
2 20.63 3 0

1124 kJ

mol
131

S 298 i S m , 298,i
2 69.91 2 248.22 2 205.79 3 205.138
390.73 J

mol.K
370

S 370 S 298

298

C p, m
T

T2
o
dT C p, m ln
T1

132

C P 2C P, m H 2O, l 2C P, m SO2 , g 2C P, m H 2 S , g 3C P, m (O2 , g )

2 75.291 2 39.87 2 34.23 3 29.355

73.797 J

mol.K

T2
o
S 370 S 298 C p, m ln
T1
o

370
S 370 390.73 73.797 ln
374.76
298
o

133

370
o

H 370 H 298

o
C p, m dT C p, m (T2 T1 )

298

H o370 H 298 C op, m (370 298)

1124 x103 73.797(370 298)
1119 kJ / mol

134

2.11.5 Standard Gibbs Energy for Reaction, Grxn

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.

Grxn Hrxn TSrxn

135

Urea, CO(NH2)2 has the following properties:

Hf,298 = -333.51 kJ/mol; Sf,298 = 104.60 J/mol K
Calculate Grxn,298.
C(graphite) + O2(g) + N2(g) + 2H2(g) CO(NH2)2

S 298

Srxn

Grxn

iSf ,i S

f ,urea

S f ,c

1
S f ,O 2 S f ,N2 2S f ,H2
2

1
104.60 5.740 205.138 191.61 2130.684
2
456.69 J
mol.K
Hrxn TSrxn

333.51 298K 0.45669 197.35 kJ

mol

136