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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 2
Able to perform calculations using First
and Second Laws of Thermodynamics
Able to calculate properties in
Thermochemistry

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

Independent of path taken to Dependent on path taken to establish


establish property or value. property or value.

Can integrate using final and initial Need multiple integrals and limits of
values. integration in order to integrate.

Multiple steps result in same value. Multiple steps result in different


value.

Based on established state of system Based on how state of system was


(temperature, pressure, amount, and established.
identity of system).

Normally represented by an Normally represented by a lowercase


uppercase letter.1 letter.1
1The last comparison made is a generalization that does not necessarily hold for all aspects and
calculations involved in chemistry. 6
The First Law of Thermodynamics
The first law states that the total energy of system plus
surroundings remains constant (is conserved).
A key state function in thermodynamics is the internal energy U,
whose existence is postulated by the first law of
thermodynamics.

The internal energy of a thermodynamic system


is the sum of the molecular energies

7
Two important concepts in
thermodynamics are work and energy.

X2
Work w = F(x)dx
X1

where F is the component of the force in the direction of


x

the displacement. If the infinitesimal displacement has


components in all three directions, then

dw = F(x) dx + F(y) dy + F(z) dz

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.

The force exerted by the woman equals the weight of the


object, which is F = mg (30.0 kg) (9.81 m/s2) = 294 N.
the work she does on the object is:
w = F x = 294 N *2.00 m = 588 J.

The earth exerts an equal and opposite force on the object


compared with the lifter, so the earth does -588 J of work on the
object. This work is negative because the force and the
displacement are in opposite directions. The total work done on the
object by all forces is zero.
9
2.1 P-V WORK
l
Pext Pint Mechanical
System equilibrium
x b

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

Class work: solve for Fig. b


14
2.2 HEAT (q)

m2, T2 m1, T1

T2 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
15
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,
specific 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 16


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)
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

Heat Work done


absorbed +q +w on the
by system 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

For constant-volume process (V=0):

U = qV
22
2.5 HEAT CAPACITIES

Heat capacity at constant pressure (isobaric


process):
dq P H
CP = =
dT T P

Heat capacity at constant volume (isochoric


process):
dqV U
CV = =
dT T V
Generally Cp>Cv except if the fluid contracts upon heating
(H2O) 23
Molar heat capacity:

CP
C P ,m =
n J
unit =
CV molK
CV ,m =
n

For ideal gas:

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

q and w depend on path.


T
2 2
w = PdV = nR dV
1
1
V
26
2.6.1 Isothermal Process (reversible)
dT = 0 U = 0 H = 0
U = 0 = q + w q = -w
2
nRT
w = PdV P=
1
V
2
nRT
w = dV
1
V

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.

n = 5.00 mol T = 300 K


V1 = 500 cm3 V2 = 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

If CP,m doesnt vary with temperature,


qP = nCP,m (T2-T1),
U = qP + w 32
Calculate U, H, q, and w 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.

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

For adiabatic process:


R
T2 V1 CV , m
=
T1 V2
For adiabatic process in ideal gas:
R
T2 P2V2 V1 CV , m
= =
T1 P1V1 V2
44
R / CV ,m
T2 P2V2 V1
= =
T1 P1V1 V2

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

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


Adiabatic expansion: V2 V1, P2 P1, T2 T1
P2(adiabatic) P2(isothermal)
46
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

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

24.6 49.2 V/L


50
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 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

U = q w = 1436cal 0.039cal = 1436.039cal 1436


53
(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

q P = 1.00 cal 18.015 g 100C = 1801cal


gK
w = PV
cal
1 .987
= 1atm 18.015 g
1 1 molK

0.958 g 1.00 g 82.06 cm 3
atm
cm 3
cm
3 molK
= 0.019cal
U = q w = 1801 0.019cal 1801cal 54
(c)The vapourisation of 1 mol of water at 100 C
and 1 atm. H2O(l), 100C H2O(v), 100C
qP = H = 18.015 g 539.4 cal = 9717cal
g

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, -.

(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 56
(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

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

Able to perform calculations using First


and Second Laws of Thermodynamics
Able to calculate properties in
Thermochemistry
59
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.
q
Heat reservoir Cyclic machine (syst)

Work output = q

60
(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.

(c) Third statement:

dqrev/T is the differential of a state function S


that has the property Suniv 0 for any process.
61
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. (Kelvin-
Planck).
2. Heat cannot flow spontaneously from a cooler
to hotter object if nothing else happens.
(Clausius).

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

For a heat engine to produce continuous mechanical


work, it must exchange heat with two bodies at
different temperatures, absorbing heat from the hot
body and discarding heat to the cold body.

Without a cold body for the discard of heat, the


engine cannot function continuously.
This is the essential idea of one form of the second law of
thermodynamics.

French engineer, Sadi Carnot, 1824


http://stirlingengineforum.com/viewtopic.php?t=1694 63
2.8 HEAT ENGINES: Convert q w

qH
system
-w
-qC

Efficiency = e = work out per cycle


energy input per cycle
w
e=
qH
64
For cyclic process, the first law gives U = 0
q + w = q H + qC + w
-w = qH + 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

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
III. erev is independent of the nature of the
working substance
67
CARNOT CYCLE
P 1 isotherm
2

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

Integrate both sides:

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

qC TC Upper limit to the


erev = 1 = 1 efficiency of real
qH TH heat engines

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.

The reverse process which does not proceed on


its own, is referred to as a nonspontaneous or
unnatural process.

In general, the tendency of a process to occur


naturally is called the spontaneity.

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.

On a warm day, ice melts by itself. The evaporation


of water is another example of a spontaneous
endothermic process. Thus arose the need of
inventing another driving force that affects the
spontaneity. This was known as the entropy change,
S
80
Entropy change

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

2.10 CALCULATIONS OF ENTROPY CHANGES.


1. Cyclic process
dqrev
T = 0 = S
2. Reversible adiabatic process

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.

dU = dqrev dwrev dqrev = dU dwrev


dV
dqrev = Cv dT nRT
V
dqrev dT dV
dS = = Cv nR
T T V
dT dV T2 V2
S = Cv nR = Cv ln nR ln
T V T1 V1
Discuss the influence of T2 > T1 and V2 > V1
89
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

90
H2O(s) (a) H2O(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


91
(a)

qrev 18.015 g 79.7cal / g


S a = =
T 273.15K

= 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

(a) rev (c) rev

(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.

Cpice=0.50cal/g K Cpsupercooled H2O=1.01 cal/g K

Hfus = 79.7 cal/g

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

qrev H freezing H fus


Sb = = =
T T T
Sb =
79.7cal / g 10 g
= 2.92
cal
273.15K K

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

Pa, Va Pb, Vb P, na, nb,


P, T P, T V= Va, Vb, T
1. Rev isothermal 2. Rev isothermal
expansion mixing
Va = V, Vb = V
103
V V
S1 = na R ln nb R ln
Va Vb
0
Sirrev = S1 S 2
Xi ;mole fractions of
V na nb 1 gas i
= =
Va na xa
V 1
ln = ln = ln 1 ln xa = ln xa
Va xa
S mix = na R ln xa nb R ln xb
Perf. gas, const T, P
104
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.

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

dSuniv = dS syst dS surr


dqrev dqrev
= =0
Tsyst Tsurr

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

Real processes: mixing, chemical reaction, flow


of heat from hot to cold bodies will continue to
occur until S reach maximum value.
117
Irreversible Mixing

d d e e d d e e
d d e e 1
d d e e

Unmixed Nonequilibrium state

e
e e
d 2
d d d
e

Equilibrium state 118


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 1023 / mol

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:

(a) an isothermal reversible expansion.


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

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

(c) qrev = 0 Ssyst = 0


Ssurr = 0 = Stot

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

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


126
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


127
mass T UC
(g) (K) (kJ/g)

a) Benzoic acid (BA) 0.5742 1.270 -26.434


wire 0.0121 - -6.28
b) Naphthalene (NA) 0.6018 2.035 ??
wire 0.0142 - -6.28

Calculate (a) CK+P


(b) UC and HC for C10H8(s)

Note: C10H8(s) = naphthalene =NA


C6H5COOH = benzoic acid = BA 128
(a) BA

Ur xn = UC,BA mBA UC,wire mwire

= 26.434 kJ 0.5742 g 6.28 kJ 0.0121g


g g
= 15.254kJ

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

Urxn = UC,NA 0.6018g 6.28kJ 0.0142g


g
U rxn = CK P T

U rxn = 12.01kJ
K
2.035K = 24.44kJ
24.44kJ = U C , NA 0.6018 g 0.089kJ
U C , NA = 40.46 kJ
g

U m,C , NA = 40.46 kJ 128.17 g


g mol

= 5186 kJ U C
mol 130
Combustion reaction:

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

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,T = cHf ,T C dHf ,T D aHf ,T A bHf ,T B

Hrxn = iHf,i

Hf ,i = standard enthalpy of formation for


substance i from its elements in their
reference form (at T, 1 bar)
132
ENTHALPY OF A REACTION
The enthalpy of a system is defined as the sum of the internal
energy and the product of its pressure and volume.
That is, H = U + PV
Just like internal energy, enthalpy is also a state function and it
is not possible to measure its absolute value. However a
change in enthalpy (H) accompanying a process can be
measured accurately and is given by the expression
H = Hproducts Hreactants
H = U + P * V

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

4 NH2CH2COOH(s) + 9 O2(g) 8 CO2(g) + 10 H2O (l) + 2 N2 (g)

(Answer: -973.49 kJ/mol.)

Exercise

Use Appendix data to find H298 for the combustion of


one mole of sucrose, C12H22O11(s), to CO2(g) and H2O(l).
(Answer: -5644.5 kJ/mol.)
134
135
2.11.3 Hesss Law: Combine heats of several
reactions to obtain H of desired reaction.

2C(graphite) + 3H2(g) C2H6(g) Hf,298 = ?

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

(2) 2: 2C(graphite) + 2O2(g) 2CO2(g) -787

(3) 3: 3H2(g) + 3/2O2(g) 3H2O(l) -858

2C(graphite) + 3H2(g) C2H6(g) 85

H298 = -85 kJ/mol = Hf,298

Exothermic reaction
137
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)

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

NH3(g) + 8/4O2(g) HNO3(g) + 4/4H2O(l) -414

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

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

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)

H298 = -565.968 kJ/mol

CP,29 -13.37 J/mol-K


8

H1200 = -578.03 kJ/mol


145
Addendum to Exercise 16
The CP,ms of the gases O2, CO, and CO2 in the range 298 to 1500 K
can each be represented by CP,m = a + bT + cT2 + dT3 with these
coefficients: 2CO + O 2CO
(g) 2(g) 2(g)

C = -39.87 + 0.11744 T + -9.8296*10-5 T2 + 2.8049*10-8 T3


P,m

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

From exercise 16, H298 = -565.968 kJ/mol

H 1200 563.85 kJ/mol Compare this result with exercise 16


146
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

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

= 1.33 6.8 10 4 T 0.54 10 5 T 2 dT

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

Third Law of Thermodynamics:


lim S = 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:

S T = i S m,T ,i i = stoichiometric coefficient


i

152
2H2S(g) + 3O2(g) 2H2O(l) + 2SO2(g)

Hf,298 -20.63 0 285.830 296.83


CP,m 34.23 29.355 75.291 39.87
Sm,298 205.79 205.138 69.91 248.22

Calculate (a) H298


(b) S298
(c) H370
(d) S370
153
(a)

H T = i H f ,T ,i
i

H 298 = 2H f , 298, H 2O 2H f , 298,SO2 2H f , 298, H 2S 2H f , 298,O2

= 2 285.83 2 296.83 2 20.63 30

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 )

CP = 275.291 239.87 234.23 329.355 = 73.797 J


mol.K

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)

= 1124 x103 73.797(370 298)


= 1119kJ / mol
157
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


158
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

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)

= 104.60 5.740 205.138 191.61 2130.684


1
2

Srxn = 456.69 J
mol .K

Grxn = Hrxn TSrxn

= 333.51 298K 0.45669 = 197.35 kJ


mol
160