CHAPTER 2

THERMODYNAMICS
to study the transformations of the heat and
spontaneity of the reactions

2
 From Greek word:
◦ thermos = heat
◦ dynamis = power

 Thermodynamics is the study of the

relationships between heat, work and energy

 Describe processes that involve changes in

temperature, transformation of energy,
relationship between heat (q) and work (w)
 A system is the
region of the
universe under study.
SYSTEM

Surroundings is
THERMODYNAMIC 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

4
A chemical system and its surroundings.

the surroundings

the system

5
 THERMODYNAMIC
SYSTEM

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

6
 Two forms of energy transfer

E = q + w

Heat , q Work ,w
energy transferred
between a system and energy transferred
surroundings as a result when an object is
of a difference in moved by a force
temperature.

7
heat flowing out from a system heat flowing into a system

E = Efinal – Einitial = Eproduct - Ereactant

8
 A system losing energy as work only.

Work done on a system

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

Energy, E
work done on
E<0 surroundings

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

Work done by a system

9
Type of work in which a
volume changes against
an external pressure

10
Pressure-volume
work.

11
 The Sign Conventions* for q, w and E

q + w = E

+ + +

+ - depends on sizes of q and w

- + depends on sizes of q and w

- - -
* For q: + means system gains heat; - means system loses heat.

* For w: + means word done on system; - means work done by system.

12
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
(q=mcT) E (energy)
P (pressure)
w, work V (volume)
(w = F x d ) T (temperature)
H (heat of reaction)

13
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
15
 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

16
 Ice cube melt in your hands
ice (s) ice (l)
energy

hand

 Spontaneous reaction

17
 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

18
 Heat transfer in Heat transfer out
(endothermic), +q (exothermic), -q

Heat or work Heat or work lost

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

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

19
 Q>0 W>0

System
Q<0 W<0

surroundings

Sign convention
Q = +ve if heat is absorbed by system (endothermic)
Q = -ve if heat is released by system (exothermic)
W= - ve if work is done by system to the surroundings
W = + ve if work is done on the system by the surroundings
 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
E
 Positive if the temperature of system increased ( T system , T
surr  = ENDOTHERMIC, q > 0)
 Negative if the temperature of system decreased ( Tsystem  , T
surr  = EXOTHERMIC, q < 0)

21
 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.

22
Eg:

 A system absorbs 50 kJ of heat as it goes from state 1 to

state 2. At the same time the surroundings does 60 kJ of
work on the system.

Calculate the change in internal energy of the system.

Q = +50 kJ W = +60 kJ
U =Q+W
= 50 + (+60)
= 110 kJ
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.

24
q = -325 J
w = -451 J

E = q + w
= -325 + (-451)
= -776 J
= -0.776 kJ

25
 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

26
 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)
27
 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

28
 which can be rearranged to

 enthalpy is defined as the internal energy plus the

product of the product and volume

H=E+PV

H=E+PV

29
 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 and w = -PV

E = q + w = q + (-PV)
= q - PV

 most chemical reaction occur at constant P

30
 At constant pressure; denote q = qp

so qp = E + PV ( PV = nRT)

R = 8.314 Jmol-1K-1
 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

31
 The decomposition of calcium carbonate in limestone is used
industrially to make lime, CaO for manufacturing cement. The
reaction is endothermic and has standard enthalpy change , H =
+571 kJmol-1.
CaCO3(s)  CaO(s) + CO2(g)

i) Calculate the value of the E (in kJmol-1).

ii) Calculate the difference between H and E.

32
33
 What is the change in internal energy (in J) of a
system that absorbs 0.615 kJ of heat from its
surroundings and has 0.247 kcal of work done on
it.(1 cal = 4.18 J) ( Ans : +1647 J)

 A system conducts 255 cal of heat to the

surroundings while delivering 428 cal of work.
What is the change in internal energy of the
system (in cal) . (Ans : -683 cal)

34
 the system is the system is
thermally insulated. thermally insulated.
The gas continues to Surroundings
In this process, the ideal
expand and do work continue to do work to
gas in the system surroundings do
on surroundings, the gas, which causes
absorbs qin amount heat work to the gas at Tl,
which causes the the temperature to rise
from a heat source at a and causes a loss of
high temperature Th, system to cool to a heat, qout. back to Th.
expands and does work on lower temperature, Tl.
surroundings. 35
 Isothermal = Temperature of the system is
constant, so T = constant.

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

do the work. (isothermal expansion only)

36
 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.

37
 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.

38
Tell nothing about the direction of a spontaneous
direction of a spontaneous change

39
 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

40
a measure of randomness or disorder

41
 Suniv = Ssys + Ssurr = 0
Reversible
(equilibrium)

Suniv = Ssys + Ssurr < 0 Process

Reversible Irreversible
(non- (spontaneous)
spontaneous)

Suniv = Ssys + Ssurr > 0

42
 Entropy Change in the Universe

The entropy of universe is composed of the system and the

surroundings.
Therefore,
Suniverse = Ssystem + Ssurroundings
Spontaneous /irreversible process: Suniv > 0
Equilibrium /reversible process: Suniv = 0
Non Spontaneous /reversible process: Suniv < 0

43
 Irreversible processes cannot be undone by exactly
reversing the change to the system.
 All Spontaneous processes are irreversible.
 All Real processes are irreversible.
 Spontaneous process – reaction that take place
without continuous supply of energy from outside
the system. (do not require a source of energy to
make them happen)

 All Spontaneous processes are irreversible.

(System and all parts of its surrounding cannot be
exactly restored to their respective initial state after
the process has occurred)

 The goal of thermodynamics is to be able to predict

if a reaction will take place when a given set of
reactant is brought together
Processes that are
spontaneous in one
direction are non-
spontaneous in the reverse
direction.
 Processes that are spontaneous at one temperature may be
non-spontaneous at other temperatures.
 Above 0C it is spontaneous for ice to melt.
 Below 0C the reverse process is spontaneous.
 Spontaneous Processes

• A waterfall runs downhill

• A lump of sugar dissolves in a cup of coffee
• Heat flows from a hotter object to a colder object
• Iron exposed to oxygen and water forms rust

spontaneous

nonspontaneous

48
 Spontaneous reactions

Does a decrease in enthalpy mean a reaction proceeds

spontaneously?

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H0 = -890.4 kJ/mol

H+ (aq) + OH-(aq) H2O (l) H0 = -56.2 kJ/mol

LARGE numbers of exothermic reactions are

spontaneous.

49
 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

50
 Spontaneous expansion of a gas

stopcock
closed

1 atm evacuated

stopcock
opened

0.5 atm 0.5 atm

51
 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.

52
 Entropy
Entropy (S) is a measure of the randomness or disorder
of a system.

order S disorder S

S = Sfinal - Sinitial
For any substance, the solid state is more ordered than the
liquid state and the liquid state is more ordered than gas state
Entropy mol-1
Ssolid < Sliquid << Sgas H2O(s) 41.0 J K-1
H2O(l) 62.3 J K-1
H2O(g) 188.3 J K-1
H2O (s) H2O (l) S > 0

53
 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

54
Processes that lead to an increase in entropy (S > 0)

55
Example: Br2(l) Br2(g) Example: I2(s) I2(g)

S > 0 S > 0

56
 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

57
 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.

58
 In general, entropy increases
when
◦ Gases are formed from
liquids and solids.
◦ Liquids or solutions are
formed from solids.
◦ The number of gas
molecules increases.
◦ The number of moles
increases.
 Entropy, S
- a measure of disorder

Ssolid  Sliquid  Sgas

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

Ssys = Sfinal – Sinitial

= Sgaseous – S solid
= positive

64
 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)

65
1. Disorder increase ,positive
2. Disorder decrease ,negative
3. Disorder decrease ,negative
4. Disorder increase, positive
5. Disorder decrease, negative

66
 For the isothermal expansion or compression of an
ideal gas from an initial volume V1 to a final volume
V2.

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

Where : n = mol of gas = PV / RT

R = 0.0821 L atmmol-1K-1
R = 8.314 Jmol-1K-1

67
Entropy of a substance is affected by:
 Temperature
 Physical state
 Dissolution
 Atomic
 Molecular complexity

68
 S increase as the temperature rises
 So S increase for a substance as it is heated, q > 0

69
 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

70
The increase in entropy from solid to liquid to gas.

71
 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.

72
The large entropy change accompanying the dissolution of a salt.

S=72.1
pure solid

MIX

pure liquid
solution

S=115.1

73
The small increase in entropy when ethanol dissolves in water.

Ethanol Water Solution of

ethanol
S =127 and water
S =132

74
 The entropy of a solution of a gas in a liquid or
solid is always less than the entropy of a gas.

75
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

76
 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

77
 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

78
79
The number of different vibrational motions increases with
the number of atom in the molecule

NO

NO2
N 2O4

Entropy increases with chain length

A ring compound has lower entropy than the chain compound with
the same molar mass eg; cyclopentane and pentene.
It because ring structure restricts freedom of motion

80
 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

81
 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.

82
◦ gaseous HCl has the higher entropy because gases
are more disordered than solids.

◦ The sample containing 2 mol of HCl has twice

compared the entropy of the sample containing 1
mol 1 mol.

◦ The HCl sample has the higher entropy because the

HCl molecule is capable of storing energy in more
ways than is Ar. HCl molecule can rotate and
vibrate; Ar atoms can not.

◦ The gaseous N2 sample has the higher entropy

because gases are more disordered than solids

83
 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.

84
 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

85
 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.

Azira Irma 86
 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.

Azira Irma 87
Substance S,J/mol K

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

88
 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.

89
• 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.

90
 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

91
 Entropy Changes in the System
When gases are produced (or consumed)
• If a reaction produces more gas molecules than it
consumes, S0 > 0.
• If the total number of gas molecules diminishes, S0 < 0.
• If there is no net change in the total number of gas
molecules, then S0 may be positive or negative BUT S0
will be a small number.
What is the sign of the entropy change for the following
reaction? 2Zn (s) + O2 (g) 2ZnO (s)

The total number of gas molecules goes down, S is negative.

92
 Entropy Changes in the Surroundings

Exothermic Process Endothermic Process

Ssurr > 0 Ssurr < 0

93
 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.

94
 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/mol.K

 So the value for S is negative.

95
Example:
Calculate the standard entropy change for the following
reaction at 250C? 2CO (g) + O2 (g) 2CO2 (g)

S0(CO) = 197.9 J/K•mol S0(CO2) = 213.6 J/K•mol

S0(O2) = 205.0 J/K•mol

S0rxn = 2 x S0(CO2) – [2 x S0(CO) + S0 (O2)]

S0rxn = 427.2 – [395.8 + 205.0] = -173.6 J/K•mol

96
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.

97
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

98
 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.

99
 Free energy is a state function, like enthalpy.

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

10
0
 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

10
1
 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.
= 2(-16.66) – ( 0 + 0) = - 33.32 kJ/mol

 So ,G = -33.32 kJ/mol

 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.
102
Overall spontaneity of many reactions depends on
the temperature

G = H - TS

10
3
 Reaction is spontaneous at all temperature .
H < 0 , S > 0

G = H - TS

so - TS is negative
thus G is always negative

10
4
 Reaction is nonspontaneous at all temperature .
H > 0 , S < 0

G = H - TS

so - TS is positif
thus G is always positive

10
5
 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

10
6
 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

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7
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
108
Calculate G at 500C, assuming that H and
S do not change with temperature. Given H =
-92.38 kJ/mol and S = -198.3 J/mol K

10
9
 Answer :
T = 500 + 273 = 773 K
So G= H - TS
= -92.38 kJ/mol – ( 773 K ) ( -198.3 / 103 kJ /mol K )
= 61 kJ/mol

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

temperature 500C

11
0
 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

11
1
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

11
2
 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

11
3
 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

11
4
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.

11
5
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.

11
6
 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 lnQ

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

T = temperature ( K)
Q = reaction quotient
11
7
 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)

11
8
Q = PNH32 / PN2 PH23
= (1.0 )2 / (1.0) (3.0)3
= 3.7 x 10-2
Therefore, for 1 mol N2 reacting with 3 mol H2 is
G = G + RT lnQ
= -33.32 kJ. + (8.314 x 298  1000) ln (3.7 x 10-2)
= -33.32 kJ + ( -8.17 kJ)
= -41.49 kJ

11
9
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

12
0
 We can calculate the value of K if we know the
value of G.

G = - RT lnK

Kp = Kc (RT)n

12
1
 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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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
Forward reaction goes to
-100 3x1017
completion; essentially no reverse
-200 1x1035 reaction
12
3
 Calculate the equilibrium constant,K for the
following reaction at 25C. Given G = -33.32 kJ

N2(g) + 3H2(g) ⇄ 2NH3(g)

12
4
 G0 = - RT lnK

ln K = -G/RT
= - (-33 320 J) / (8.314 x 298)
=13.45

So K = e 13.45
= 6.9 x 105

125