CHM432

FUNDAMENTAL PHYSICAL CHEMISTRY

March 2020 – July 2020

CHAPTER 2
THERMODYNAMICS

PROF. MADYA DR. NORAINI HAMZA

 Why do we study
Thermodynamics?

• to study the transformations of the heat

and spontaneity of the reactions

2
 A system is the
region of the
universe under study.
SYSTEM

Surroundings is
THERMODYNAMICS everything outside
the system.

The possible
exchanges of work,
heat, or matter
between the BOUNDARY SURROUNDING
system and the
surroundings take
place across this
boundary

3
Figure 6.1 A chemical system and its surroundings.

the surroundings

the system

4
 THERMODYNAMIC
SYSTEM

heat, work,
and matter Open Closed matter may
not cross the
may cross the boundary.
boundary.

Isolated Adiabatic

matter and heat may not cross

energy may not
the boundary.
cross the It means no heat
boundary. enters or leave the
system.

5
 Two forms of Energy Transfer

E = q + W

Heat, q Work, W
• energy transferred
between a system
• energy
and surroundings as transferred
a result of a when an
difference in object is
temperature.
moved by a
force
6
heat flowing out from a system heat flowing into a system

E = Efinal – Einitial = Eproduct - Ereactant

7
 A system losing energy as work only.

Work done on a system

Zn(s) + 2H+(aq) + 2Cl-(aq)

Energy, E

E<0 work done on

surroundings

H2(g) + Zn2+(aq) + 2Cl-(aq)

Work done by a system

8
Pressure-Volume Work (PV Work)

Type of work in which a

volume changes against
an external pressure

9
 Pressure-Volume
work.

𝑊 = −𝑃∆𝑉

10
 Table 6.1 The Sign Conventions* for q, W and E

q + W = E

+ + +

+ - depends on sizes o f q and W

- + depends on sizes o f q and W

- - -
* For q: + means system gains heat; - means system loses heat.
* For W: + means work done on system; - means work done by system.

11
A property do A property dependent
depend on the only on the current
path of the state of the system, not
system takes in on the path of the
undergoing the system took to reach
energy change. that state.

Path State

Functions
Example;
Example :
q, heat
E (energy)
(𝑞 = 𝑚𝑐∆𝑇)
P (pressure)
W, work V (volume)
(𝑊 = 𝐹𝑑 ) T (temperature)
H (heat of reaction)

12
First Law Second Law Third Law
(conservation (entropy) (absolute zero
of energy) • spontaneous temperature)
• work • Spontaneity
• Heat • Gibbs absolute
• enthalpy entropy
 State that the total internal
energy change of the system is
Heat energy transferred the sum of the heat and work
during the process.

E = q + W Work done by the

system

Energy change
Energy is
conserved
14
The Law of Energy Conservation
 Energy can be converted from one form to
another.

 It cannot be created or destroyed

 The total energy of the universe is constant

Euniverse = Esystem + Esurroundings = 0

15
 Ice cube melt in your hands
ice (s) ice (𝑙)
energy

hand

 Spontaneous reaction

16
 Internal Internal energy is the total
energy of a system which is the
Energy sum of all the kinetic and
potential energies of its
component parts.

Kinetic Potential
energy energy

Heat and/or work gained by the system is lost by

the surrounding and vice versa

(q + W)sys = −(q + W)surr

17
 The ‘Signs’ of the Values of
Heat, q, and Work, W.
Heat transfer in Heat transfer out
(endothermic), +q (exothermic), -q

Heat or work
Heat or work lost by the
gained by a system
(q>0; w>0) SYSTEM system (q<0 ; w<0)
decreases E
increases E
E = q + W

W transfer in
W transfer out
(+W)
(-W)

18
 Signs of the terms in the equation
q
 Positive if energy is transferred to the system by heat
 Negative if energy is transferred out of the system by heat
W
 Positive if work is done on the system
 Negative if work is done by the system

 Positive if the temperature increases ( T system , T surr 
= ENDOTHERMIC, q > 0)
 Negative if the temperature decreases ( T system  , T surr 
= EXOTHERMIC, q < 0)

19
 a) E = + 90 kJ
Its mean that 90kJ is the magnitude of the
changes. Sign + shows that Efinal > Einitial and
indicates that the system has gained energy
from its surrounding.

 b) E = - 90 kJ
Sign – shows that Efinal < Einitial and indicates that
the system has released energy to the
surrounding.

20
Exercise
A system receives 575 J of heat and delivers 425 J
of work. Calculate the change in the internal
energy, ΔE, of the system.

A. -150 J
B. 150 J
C. -l000 J
D. 1000 J
E. 575 J

21
 Determining the Change in
Internal Energy of a System

When gasoline burns in a car engine, the heat

released causes the products CO2 and H2O to
expand, which pushes the pistons outward.
Excess heat is removed by the car’s cooling
system. If the expanding gases do 451 J of work
on the pistons and the system loses 325 J to the
surroundings as heat, calculate the change in
energy (E) in Joule.

22
 Euniverse = Esystem +Esurroundings

Units of Energy

Joule (J) 1 J = 1 kg*m2/s2

Calorie (cal) 1 cal = 4.18J

British Thermal Unit 1 Btu = 1055 J

23
 Pressure-Volume Work

When the volume remains

constant ( V = 0)
No work is done on the gas

When the gas is compressed When the gas is allowed to expand

∆V is negative ∆V is positive
The work done on the gas is The work done on the gas is
positive (+W) negative (-W)
24
 Enthalpy and
Constant Pressure Processes
 If a process takes place at
constant pressure, then
pressure-volume work results
if the volume of the system
changes. So 𝑊 = −𝑃∆𝑉

 We can re-write the first law

under these conditions as;
∆𝐸 = 𝑞𝑝 − 𝑃𝑒𝑥𝑡 ∆𝑉

25
 which can be rearranged to

𝑞𝑝 = ∆𝐸 + 𝑃𝑒𝑥𝑡 ∆𝑉

 Enthalpy is defined as the internal energy plus

the product of the product and volume.

𝐻 = 𝐸 + 𝑃𝑉

∆𝐻 = ∆𝐸 + 𝑃∆𝑉

26
 The change in enthalpy (H) is the change in
internal energy plus the product of the constant
pressure and the change in volume:

H = E + PV

 combine;
E = q + W where W = −PV
E = q + w = q + (−PV)
= q − PV

 most chemical reaction occur at constant P

27
 At constant pressure; denote q as qp

so qp = E + PV

 therefore ; qp = E + PV = H
where H = enthalpy

 Thus, the change in enthalpy equals the heat gained or

lost at constant pressure.

 H is more relevant than E and easier to find: to find

H, measure qp

28
 Expansion of Ideal Gas

the system is the system is

thermally insulated. thermally insulated.
In this process, the ideal The gas continues to
surroundings do Surroundings
gas in the system expand and do work
work to the gas at Tl, continue to do work to
absorbs qin amount heat on surroundings,
and causes a loss of the gas, which causes
from a heat source at a which causes the
heat, qout. the temperature to rise
high temperature Th, system to cool to a
expands and does work on lower temperature, Tl. back to Th .
surroundings.
29
 Expansion of Ideal Gas

Reversible Isothermal Expansion

 Isothermal = Temperature of the system is

constant, so T = constant (∆T = 0).

 For expansion of the gas ,heat can be absorbed to

do the work. (isothermal expansion only)

30
Reversible Adiabatic Expansion
 Since no heat is absorbed,
the energy to do work from
internal energy of the
system.

 during an adiabatic
expansion process in which
the volume increases, the
internal energy must
necessarily decrease.

31
 When internal energy of the system decreasing,
it resulting in cooling of the gas.

 So temperature changes of the system becomes

negative (T< 0) .

 It shows final temperature is lower than initial

temperature.

 Then temperature of the system decreasing.

32
 Limitation of the
First Law of Thermodynamics

Tell nothing about the direction of a spontaneous

direction of a spontaneous change

33
 Second Law of
Thermodynamics
 State that change in the entropy of the
universe, Suniv, is the sum of the changes in
entropy of the system, Ssys and of the
surrounding, Ssurr.

Suniv = Ssys + Ssurr

34
a measure of randomness or disorder

35
 Suniv = Ssys + Ssurr = 0
Reversible
(equilibrium)

Suniv = Ssys + Ssurr < 0 Process

Irreversible Irreversible
(non- (spontaneous)
spontaneous)

Suniv = Ssys + Ssurr > 0

36
 Gases expand spontaneously to fill a
volume.

Ice melt spontaneously at temperature

above its melting point even though it is
an endothermic process.

Salts such as NH4NO3 and KCl readily

dissolves in water even though Hsoln >0

37
Figure 20.2 Spontaneous expansion of a gas

stopcock
closed

1 atm evacuated

stopcock
opened

0.5 atm 0.5 atm

38
 Entropy, S
 Spontaneity is associated with an increase in
randomness or disorder of a system.

 The disorder is expressed by a thermodynamic

quantity called entropy , given the symbol S.

 Note : The more disordered a system, the larger its

entropy.

39
Freedom of Particle Motion
Phase change: solid→ liquid→ gas

 solid: particle motion is restricted

 Liquid : particle have more freedom to move around each

other

 Gas : much greater freedom of particle motion

S gas > S liquid > S solid

40
 The Concept of Entropy (S)

Entropy refers to the state of order.

A change in order is a change in the number of ways of
arranging the particles, and it is a key factor in determining
the direction of a spontaneous process.
more order less order
solid liquid gas

more order less order

crystal + liquid ions in solution

more order less order

crystal + crystal gases + ions in solution

41
 The change in entropy of a system,

Ssys = Sfinal –Sinitial

depend only on the initial and final states of the system

and not on the particular pathway by which the system
changes.

 Note :
A positive, S > 0 indicates an increase in
randomness or disorder.
A negative,S < 0 indicates a decrease in
randomness or disorder.

42
 Dry ice sublimes to gaseous carbon dioxide
CO2(s) → CO2(g)

Ssys = Sfinal –Sinitial

= Sgaseous – S solid
= positive

43
 Predict the sign of entropy change, S for each of
the following reactions.

1. H2O(l)  H2O(g)
2. Ag+(aq) + Cl-(aq)  AgCl(s)
3. 4Fe(s) + 3O2(g)  2FeO3(s)
4. CO2(s)  CO2(g)
5. CaO(s) + CO2(g)  CaCO3(s)

44
Calculating Entropy Changes, ∆𝐒
For the isothermal expansion or compression of an
ideal gas from an initial volume V1 to a final volume V2.

𝑉2
∆S = 𝑛R ln (ideal gas, constant T)
𝑉1

Where : 𝑛 = mol of gas = PV/RT

R = 0.0821 L atm mol-1 K-1
R = 8.314 J mol-1 K-1

45
A sample of gas is enclosed in a cyclinder equipped
with a piston. This system is maintained at a
constant temperature of 25C. The gas occupies an
initial volume of 15.0L at a pressure of 1.5 atm. It is
compressed to a final volume of 9.5L. Assume the
gas behaves ideally.

a)What is the entropy change for the compression

of the gas?
( -3.5 J/K)
b)Is the sign of S consistent with your
expectations?

46
Predicting Relative 𝐒 value of a
°

System
Entropy of a substance is affected by:
 Temperature

 Physical state

 Dissolution

 Atomic

 Molecular complexity

47
Temperature Changes
 S increase as the temperature rises
 So S increase for a substance as it is heated, q > 0

48
Physical State and Phase Changes
 S increase for a substance as it changes from solid
to a liquid to a gas

 Note that the increase in entropy form liquid to

gas is much larger than from solid to liquid.

 So H vaporization always > H fusion

49
Figure 20.5 The increase in entropy from solid to liquid to gas.

50
Dissolving a Solid or Liquid
 The entropy of a dissolved solid or liquid is
usually greater than the entropy of the pure
solute

 Eg:
S NaCl (s) = 72.1
S NaCl (aq) = 115.1

 Entropy of the ion is greater in the solution than

in the crystal.

51
 Figure 20.6
The large entropy change accompanying the dissolution of a salt.

S=72.1
pure solid

MIX

pure liquid

solution

S=115.1

52
Figure 20.7
The small increase in entropy when ethanol dissolves in water.

Ethanol Water Solution of

ethanol
S =127 and water
S =132

53
Dissolving a Gas
 The entropy of a solution of a gas in a liquid or
solid is always less than the entropy of a gas.

54
Figure 20.8
The large decrease in entropy when a gas dissolves in a liquid.

O2 gas
S(g)O2 =205

O2 gas in H2O
S(aq)O2 =110.9

55
Atomic Size or Molecular Complexity

 Entropy increase down the group in periodic

table.
 Eg : element in group 1

Li Na K
Atomic radius(pm ) 152 186 227
Molar mass(g/mol) 6.94 22.99 39.10
S(s) 29.1 51.4 64.7

56
Atomic Size or Molecular Complexity

 For allotropes:
graphite ; S = 5.69 J/mol.K
diamond ; S = 2.44 J/mol.K

 Diamond : covalent bonds extend in three

dimensions, allowing the atoms little movement

 Graphite: covalent bonds extend only within a

sheet

57
Figure 20.9 Entropy and vibrational motion.

NO

N 2O4
NO2

58
Sample Problem 20.1: Predicting Relative Entropy Values

PROBLEM: Choose the member with the higher entropy in each of the following
pairs, and justify your choice [assume constant temperature, except
in part (e)]:
(a) 1mol of SO2(g) or 1mol of SO3(g)
(b) 1mol of CO2(s) or 1mol of CO2(g)
(c) 3mol of oxygen gas (O2) or 2mol of ozone gas (O3)
(d) 1mol of KBr(s) or 1mol of KBr(aq)
(e) Seawater in midwinter at 20C or in midsummer at 230C
(f) 1mol of CF4(g) or 1mol of CCl4(g)

SOLUTION:
(a) 1mol of SO3(g) - more atoms (d) 1mol of KBr(aq) - solution > solid
(b) 1mol of CO2(g) - gas > solid (e) 230C - higher temperature
(c) 3mol of O2(g) - larger #mols (f) CCl4 - larger mass

59
 Choose the substance with greater entropy in each
pair and explain your choice:

 1 mol of NaCl(s) or 1 mol of HCl(g) at 25C

 2 mol of HCl(g) or 1 mol of HCl(g) at 25C
 1 mol of HCl(g) or 1 mol of Ar(g) at 25C
 1 mol of N2(s) at 24 K or 1 mol of N2(g) at 298 K.

60
Third Law of Thermodynamics
 the entropy of a perfect crystal of an element at
the absolute zero of temperature is zero.

 At the absolute zero of temperature, there is zero

thermal energy or heat.

 means that the average atom does not move at all.

61
 Figure 20.4 Random motion in a crystal

The third law of

thermodynamics.

A perfect crystal has

zero entropy at a
temperature of
absolute zero.

Ssystem = 0 at 0 K

62
 As the temperature of such a perfect crystal is
raised, the atoms or molecules in the crystal gain
energy in the form of vibrational motion about
their lattice positions.

 The entropy of the lattice therefore increases with

temperature because vibrational motion causes
the atoms or molecules to be less ordered.

63
 Standard Molar Entropies, 𝐒 °

 The molar entropy value of substances in their

standard states

 The standard state for any substance is defined as

the pure substance at 1 atm pressure.

64
 Standard Molar Entropies
of selected substances at 298 K
Substance S (J 𝐦𝐨𝐥−𝟏 𝐊 −𝟏 )

Gases:
H2(g) 130.6
H2O(g) 188.8
N2(g) 191.5
NH3(g) 192.5
C6H6(g) 269.2
Liquid:
H2O(l) 69.9
C6H6(l)
172.8
Solids:
Fe(s) 27.2
Ca(OH)2(s) 83.4

65
 The standard molar entropies of gases are
greater than those of liquids and solids.

 The standard molar entropy increases with

increasing molecular complexity.

 unlike enthalpies of formation, the standard molar

entropies of elements are not zero.

66
• gas is dissolved in a liquid, volume become smaller.

• Condensing a gas

• Freezing a liquid

• A reaction lead to a decrease in number of gaseous

molecule.

67
 gas expand – volume increase and increase in the disorder of the
system
 The number mole of gas increase

 gasses are formed from either solids or liquids

 The temperature of a substance is increased- dissolving a liquid or

solid

 The chain has more freedom of motion than the ring

◦ Entropy increases with chain length
◦ Entropy increases with the of atom in the molecule
◦ For similar compound, Entropy increases with molar mass

68
 The entropy change, S in a chemical reaction is
given by the sum of the entropies of the products
less the sum of the entropies of the reactants:

Srxn = nS(product) - mS(reactant)

the coefficients n and m are the coefficients in the

chemical equation.

69
 Calculate S for the synthesis of ammonia from
N2(g) and H2(g).

N2(g) + 3H2(g)  2NH3(g)

S = 2S(NH3) – [S(N2) + 3S(H2)]

= 2(192.5) – [191.5 + 3(130.6)
= -198.3 J/K

 So the value for S is negative.

70
Gibbs Free Energy, G
The Gibbs free energy, G, of a state is defined as :

𝑮 = 𝑯 − 𝑻𝑺

Where ; T (temp. in K),

H is enthalpy,
S is entropy.

71
For a process occurring at constant temperature,
the changes in free energy of the system, G ,is
given by the expression

∆𝑮 = ∆𝑯 − 𝑻∆𝑺

72
 The sign of G provides us with valuable
information about the spontaneity of processes
that occur at constant temperature and pressure.

 If G is negative, the reaction is spontaneous in

the forward direction.

 If G is zero, the reaction is at equilibrium.

 If G is positive, the reaction in the forward

direction is non spontaneous;
work must be supplied from the surroundings to
make it occur. However, the reverse reaction will
be spontaneous.

73
 Free energy is a state function, like enthalpy.

G = nGf(products) - mGf (reactants)

74
 If : G < 0 – a mixture of reactants and
products, each present under standard
conditions , would spontaneously react in the
forward direction to produce more product.

 If : G > 0 reverse direction is spontaneous to

form more reactant.

 If : G = 0 The process at equilibrium

75
 Determine the standard free-energy change for the
following reaction at 298 K:
N2(g) + 2H2(g)  2NH3(g)

The standard free energies,Gf for the three substances

as follow:
N2(g) = 0.0 ; H2(g) = 0.0 ; NH3(g) = -16.66 kJ/mol.

 So ,G = -33.32 kJ

 G is negative tell us that a mixture of H2 , N2 and NH3

at 25C, each present at a pressure of 1 atm, would react
spontaneously to form more ammonia.

76
The Effects of Temperature on
Reaction Spontaneity
Overall spontaneity of many reactions depends on
the temperature

∆𝑮° = ∆𝑯° − 𝑻∆𝑺°

77
 Temperature-Independent Cases
(Opposite Sign)
 Reaction is spontaneous at all temperature .
H < 0 , S > 0
∆𝑮 = ∆𝑯 − 𝑻∆𝑺
So - TS is negative
thus G is always negative

78
 Temperature-Independent Cases
(Opposite Sign)
 Reaction is nonspontaneous at all temperature .
H > 0 , S < 0

∆𝑮 = ∆𝑯 − 𝑻∆𝑺
so - TS is positif
thus G is always positive

79
 Temperature-Dependent Cases
(Same Sign)
 Reaction is spontaneous at higher temperature
H > 0 , S > 0
∆𝑮 = ∆𝑯 − 𝑻∆𝑺
so - TS is < 0
thus G is always negative

 But non spontaneous at lower T

80
 Temperature-Dependent Cases
(Same Sign)
 Reaction is spontaneous at lower temperature
H < 0 , S < 0
∆𝑮 = ∆𝑯 − 𝑻∆𝑺
with negative H, the reaction will occur
spontaneously (G is negative) only if the -
TS term is smaller than the H term and
this happen at lower temperature

 But non spontaneous at higher T

81
 Reaction Spontaneity & Signs of
∆𝐇, ∆𝐒 𝐚𝐧𝐝 ∆𝐆
H S -T S G description
- + - - Spontaneous at all
temp.
+ - + + Non spontaneous at
all temp

+ + - - Spontaneous at
higher temp
+ Non spontaneous at
lower temp
- - + - Spontaneous at
lower temp
+ Non spontaneous at
higher temp

82
Calculate G at 500C, assuming that H and
S do not change with temperature.

Given H = −92.38 kJ and S = −198.3 J/K

83
 Answer :
T = 500 + 273 = 773 K
So G= H - TS
= -92.38 kJ – ( 773 K ) ( -198.3 / 103 kJ / K )
= 61 kJ

Since G is positive, the reaction is non spontaneous at

temperature 500C

84
 Determining the Effect of
Temperature on ∆𝐆
 A key step in the production of sulfuric acid is the
oxidation of SO2(g) to SO3(g)
2SO2(g) + O2(g)→ 2SO3(g)

At 298K, G = -141.6 kJ;

H = -198.4 kJ; and
S = -187.9 J/K

85
Use the data to decide if this reaction is spontaneous
at 25C, and predict how G will change with
increasing T.

solution:

G < 0, so the reaction is spontaneous at 298K

at higher T, the term -TS >0 become more positive.

therefore G will become less negative, and the

reaction less spontaneous with increasing T

86
 Predict whether the following reaction is
spontaneous at higher temperature , lower
temperature or at all temperature.

2H2O2(l) → 2H2O(l) + O2(g); H = -196 kJ

Solution;
H < 0 ; S > 0 , so -TS is negative then G is
always negative
Therefore the reaction is spontaneous at all
temperature

87
 Determining when a reaction
becomes spontaneous
 Switches positive G (non spontaneous) to negative
G (spontaneous)
 Setting G equal to zero
G = H - TS = 0
therefore, H = TS
T = H / S
 can estimate melting/boiling point

88
Consider the reaction below;
Cu2O(s) + C(s)→ 2Cu(s) + CO(g)
This reaction does not occur at low temperature. (non
spontaneous at lower T)
Given S = +165 J/K , H =+ 58.1 kJ at 25C

Find the temperature above which the reaction is

spontaneous.

89
Solution:
At 25C
G = 58.1 kJ – (298K x 165 X 103 kJ)
= 8.9 kJ
Because G is positive, the reaction will not
proceed on its own at 25C.
At the crossover temperature, G =0
T = 58.1 kJ / 165 J/K = 352 K
Therefore the reaction occur spontaneously at
temperature 352K or 79C.

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 Free Energy & Equilibrium Constant
 For any chemical process, the general relationship
between the free-energy change under standard
conditions, G and the free-energy change under
any other conditions, G, is given by the following
expression.

∆𝑮 = ∆𝑮° + 𝑹𝑻 𝐥𝐧 𝑸

Where R = ideal gas constant = 8.314 J/mol K

T = temperature ( K)
Q = reaction quotient

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Calculate G at 298K for the following reaction if
the reaction mixture consists of 1.0 atm N2 , 3.0
atm H2 and 1.0 atm NH3. G 298 is -33.32 kJ.

N2(g) + 3H2(g)  2NH3(g)

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When a system is at equilibrium,
G = 0.
Thus at equilibrium (when G = 0 and Q = K ),

G = G + RT lnQ
0 = G + RT lnK

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 We can calculate the value of K if we know the
value of G.

∆𝑮° = −𝑹𝑻 𝐥𝐧 𝑲

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 Free Energy, Equilibrium and
Reaction Direction
• If Q/K < 1, then ln Q/K < 0; the reaction proceeds to the right (G < 0)

• If Q/K > 1, then ln Q/K > 0; the reaction proceeds to the left (G > 0)

•If Q/K = 1, then ln Q/K = 0; the reaction is at equilibrium (G = 0)

G = RT ln Q/K = RT lnQ - RT lnK

Under standard conditions (1M concentrations, 1atm for gases), Q = 1

and ln Q = 0 so

G0 = - RT lnK

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Table 20.2 The Relationship Between G0 and K at 250C

G0(kJ) K Significance

200 9x10-36 Essentially no forward reaction;

100 3x10-18 reverse reaction goes to completion

FORWARD REACTION
50 2x10-9

REVERSE REACTION
10 2x10-2
1 7x10-1
Forward and reverse reactions
0 1 proceed to same extent
-1 1.5
-10 5x101
-50 6x108
-100 3x1017 Forward reaction goes to
completion; essentially no reverse
-200 1x1035 reaction

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 Calculate the equilibrium constant,K for the
following reaction at 25C. Given G = -33.32 kJ

N2(g) + 3H2(g) ⇄ 2NH3(g)

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