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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

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.

value.

(temperature, pressure, amount, and established.

identity of system).

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.

is the sum of the molecular energies

7

Two important concepts in

thermodynamics are work and energy.

X2

Work w = F(x)dx

X1

x

components in all three directions, then

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.

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.

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

14

2.2 HEAT (q)

m2, T2 m1, T1

T2 T1 Tf = final temperature

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.

dqP = mcPdT

CP = heat capacity at constant pressure.

CP = mcP

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

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

U = qV

22

2.5 HEAT CAPACITIES

process):

dq P H

CP = =

dT T P

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

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

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.

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

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:

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

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

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

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

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

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, -.

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.

melting w 0

vacuum.

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

and Second Laws of Thermodynamics

Able to calculate properties in

Thermochemistry

59

THE SECOND LAW OF THERMODYNAMICS

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:

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.

that has the property Suniv 0 for any process.

61

Rephrase:

There are 2 principal physical statements of

the Second Law of Thermodynamics:

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

work, it must exchange heat with two bodies at

different temperatures, absorbing heat from the hot

body and discarding heat to the cold body.

engine cannot function continuously.

This is the essential idea of one form of the second law of

thermodynamics.

http://stirlingengineforum.com/viewtopic.php?t=1694 63

2.8 HEAT ENGINES: Convert q w

qH

system

-w

-qC

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

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

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

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.

its own, is referred to as a nonspontaneous or

unnatural process.

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.

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

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.

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.

Cp = 1.00 cal/g K

90

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

0 C, 1 atm

(b)

(c)

(d)

91

(a)

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

(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

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

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

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

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

e

e e

d 2

d d d

e

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:

(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

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

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

127

mass T UC

(g) (K) (kJ/g)

wire 0.0121 - -6.28

b) Naphthalene (NA) 0.6018 2.035 ??

wire 0.0142 - -6.28

(b) UC and HC for C10H8(s)

C6H5COOH = benzoic acid = BA 128

(a) BA

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

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

g mol

= 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

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

Exercise

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.

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

2) 2NO(g) + O2(g) 2NO2(g) 114

3) 3NO2(g) + H2O(l) 2HNO3(l) + NO(g) 72

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

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)

8

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)

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

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

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

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

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:

i

152

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

CP,m 34.23 29.355 75.291 39.87

Sm,298 205.79 205.138 69.91 248.22

(b) S298

(c) H370

(d) S370

153

(a)

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 )

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)

= 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.

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.

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)

1

2

Srxn = 456.69 J

mol .K

mol

160

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