Jeffrey Mack

California State University,

Sacramento
Chapter 19

Principles of
Chemical Reactivity:
Entropy and Free
Energy
Chemical Kinetics provides us
with information about the rate
of reaction and how the
reaction proceeds.
Chemical Thermodynamics
provides us with information
about equilibrium and whether
or not a reaction is
Spontaneous.
Entropy & Free Energy
Chemical Thermodynamics provides us with information
about equilibrium and whether or not a reaction is
Spontaneous.
Spontaneous changes occur only in the direction
that leads to equilibrium.
Systems never change spontaneously in a direction
that takes them farther from equilibrium.
Example: Heat Transfer
Heat (thermal energy) always flows spontaneously from a
hot object to a cold object.
The process occurs until thermal equilibrium is achieved,
that is when both objects are at the same temperature.
Entropy & Free Energy
Additional Examples:
Solvation of a Soluble salt: NH
4
NO
3
(s) dissolves
spontaneously even the process is endothermic (AH
> 0)
Expansion of a gas and Diffusion. Gasses mix to
form homogeneous mixtures spontaneously.
Certain Phase Changes: Ice melts spontaneously
above 0
o
C. Water evaporates even though the
enthalpy of vaporization is endothermic.
Certain Chemical Reactions: Na(s) reacts
vigorously when dropped in water. Iron rusts when
exposed to the atmosphere.
Spontaneous Process
But many spontaneous reactions or processes
are endothermic or even have H > 0.
NH
4
NO
3
(s) + heat NH
4
NO
3
(aq)
H = 0
Spontaneous Process
A Review of Concepts of Thermodynamics
First law of thermodynamics: The law of conservation
of energy; energy cannot be created or destroyed.
State Function: Quantity in which its determination is
path independent.
AU = q + w: The change in internal energy of a system
is a function of heat and work done on or by the system.
AH: Heat transferred at constant pressure.
Exothermic Process: AH < 0
Endothermic Process: AH > 0
Thermodynamics
Enthalpy alone does not predict spontaneity:
Some processes are energetically favored (A
r
H < 0)
but not spontaneous.
Equilibrium alone cannot determine spontaneity:
Some processes are favored based on Equilibrium (K
>> 1) yet they are non-spontaneous.

There must be another factor that plays a role in
determination of spontaneity!
Thermodynamics
Diamond is
thermodynamically favored to
convert to graphite, but not
kinetically favored.

Paper burns once the
reaction is initiates. The
process is product-favored
& kinetically favored.
Thermodynamics & Kinetics
Reactants
Products
K
i
n
e
t
i
c
s

Thermodynamics
Thermodynamics & Kinetics
Factors that Affect Spontaneity
(Thermodynamic favorability):
1. Enthalpy: Comparison of bond energy (AH)
2. Entropy: Randomness vs. Order of a system
(AS)
In general, enthalpy is more important
than entropy.
Thermodynamics & Kinetics
In a spontaneous processes the
energy of the final state is more
dispersed.
The system moves to a higher state
of disorder.
The thermodynamic quantity
associated with disorder and
energy dispersal is called
ENTROPY, S.
The 2
nd
law of thermodynamics
states that a spontaneous process
results in an increase in the entropy
of the universe. AS > 0
Reaction of K
and water
Dispersal of Energy: Entropy
Observation of a spontaneous process shows
that it is associated with a dispersal of energy.
Energy Dispersal

Dispersal of Energy: Entropy
The change in entropy for a spontaneous process is
given by:


Where q
rev
is the heat gained or lost by the system
during the process and T is the absolute temperature.
A reversible process can be returned to its original
state. (chemical equilibrium), an irreversible process
cannot.
Example: The breaking of a coffee mug into many
pieces is an irreversible process.
rev
q
S
T
=
Dispersal of Energy: Entropy
To begin, particle 1 has 2 units of energy and 2-4
have none.
Dispersal of Energy: Entropy
Particle 1 can transfer one unit of energy to particle 2,
then the other to 3 or 4.
Dispersal of Energy: Entropy
Particle 2 can initially have two units of energy.
Dispersal of Energy: Entropy
Particle 2 transfer one unit to particles 4 or 3. (2 to 1
has already been counted.)
Dispersal of Energy: Entropy
Particle 4 can initially have two units of energy.
Dispersal of Energy: Entropy
Particle 4 transfer one unit to particle 3. (4 to 1 & 4 to
2 have already been counted.)
Dispersal of Energy: Entropy
Particle 3 can start with two units of energy. Energy
transfers between particle 3 were previously counted.
Dispersal of Energy: Entropy
Each unique combination that results in a dispersion of energy
is called a microstate. There are 10 microstates in this
system. The greater the number of microstates, the greater the
entropy of the system.
Dispersal of Energy: Entropy
Dispersal of Energy: Entropy
As the size of the
container increases, the
number of microstates
accessible to the system
increases. Therefore the
entropy of the system
increases.
Dispersal of Energy: Entropy
The entropy of liquid
water is greater than
the entropy of solid
water (ice) at 0 C.
Energy is more
dispersed in liquid
water than in solid
water due to the lack
of an ordered network
as in the solid state.
Dispersal of Energy: Entropy
S
o
(J/Kmol)
H
2
O(liq) 69.95
H
2
O(gas) 188.8
Energy dispersal
S (solids) < S (liquids) < S (gases)
Entropy & States of Matter
S(Br
2
liq) < S(Br
2
gas) S(H
2
O sol) < S(H
2
O liq)
Entropy & States of Matter
Entropy and Microstates:
As the number of microstates increases, so
does the entropy of the system.

S = klnW

k = Boltzmans constant (1.381 10
23
J/K)

W = the number of microstates
Dispersal of Energy: Entropy
Entropy and Microstates:
The change in entropy associated with a
process is a function of the number of final and
initial microstates of the system.




If W
final
> W
inital
, AS > 0
If W
final
< W
inital
, AS < 0
final initial
final final
final
initial
S S S
S k lnW k lnW
W
S k ln
W
= =
=

=


Entropy, Entropy Change, & Energy
Dispersal: A Summary
When a solute dissolves in a solvent the process is
spontaneous owing to the increase in entropy.
Matter (and energy) are more dispersed. The number
of microstates is increased.
Dispersal of Energy: Entropy
The entropy of a substance increases with
temperature.
Molecular motions of
heptane, C
7
H
16
Molecular motions of
heptane at different temps.
Entropy Measurements & Values
An Increase in molecular
complexity generally leads
to increase in S.
Entropy Measurements & Values
Entropies of ionic solids depend on
coulombic attractions.
S (J/Kmol)
MgO 26.9
NaF 51.5
Mg
2+
& O
2-
Na
+
& F
-

Entropy Measurements & Values
Defined by Ludwig Boltzmann, the third law states that a
perfect crystal at 0 K has zero entropy; that is, S =0.
The entropy of an element or compound under any other
temperature and pressure is the entropy gained by converting
the substance from 0 K to those conditions.
To determine the value of S, it is necessary to measure the
energy transferred as heat under reversible conditions for the
conversion from 0 K to the defined conditions and then to use
Equation 19.1

Because it is necessary to add energy as heat to raise the
temperature, all substances have positive entropy values at
temperatures above 0 K.
rev
q
S
T
=
Standard Molar Entropies
The standard molar entropy, S, of a substance is the entropy
gained by converting 1 mol of it from a perfect crystal at 0 K to
standard state conditions (1 bar, 1m for a solution) at the specified
temperature.
Standard Molar Entropies
rev
boil
q 40,700 J/ mol J
S 109
T 373.15 K mol K
= = = +

For a phase change,

where q = heat transferred in the
phase change

rev
q
S
T
=
2 2
For H O (liq) H O(g)
J
H q 40,700
mol
= = +

Entropy Changes for Phase
Changes
S increases
slightly with T
S increases a large
amount with phase
changes
Entropy & Temperature
Standard molar entropy values can be used to
calculate the change in entropy that occurs in various
processes under standard conditions.
The standard entropy change for a reaction (A
r
S)
can be found in the same manner as A
r
H were:


Where n & m are the stoichiometric balancing
coefficients.
This calculation is valid only under reversible
conditions.
S n S (products) m S (reactants) A =

Determining Entropy Changes in
Physical & Chemical Processes
Problem:
Consider the reaction of hydrogen and oxygen to form liquid
water.
What is the standard molar entropy for the reaction?








Determining Entropy Changes in
Physical & Chemical Processes
Problem:
Consider the reaction of hydrogen and oxygen to form liquid
water.
What is the standard molar entropy for the reaction?








r
S n S (products) m S (reactants) A =

Determining Entropy Changes in
Physical & Chemical Processes
Problem:
Consider the reaction of hydrogen and oxygen to form liquid
water.
What is the standard molar entropy for the reaction?








r
2 2 2
r
S n S (products) m S (reactants)
2H (g) O (g) 2H O(l)
J J J J
S 2 69.95 2 130.7 205.1 326.6
K K K K
A =
+
| |
A = + =
|
\ .

Determining Entropy Changes in
Physical & Chemical Processes
Problem:
Consider the reaction of hydrogen and oxygen to form liquid
water.
What is the standard molar entropy for the reaction?





The enthalpy change is negative (net decrease in dispersion)
due to the change in number of moles: 3 reduced to 2


2 2 2
o
r
2H (g) O (g) 2H O(l)
J J J J
S 2 69.6 2 130.7 205.3 326.9
K K K K
+

= + =


Determining Entropy Changes in
Physical & Chemical Processes
The second law of thermodynamics states:..

AS
universe
= S
system
+ S
surroundings


Any change in entropy for the system plus the entropy
change for the surroundings must equal the overall
change in entropy for the universe.
A process is considered to be spontaneous under
standard conditions if AS(universe) is greater than
zero.
2
nd
Law of Thermodynamics
The solution process for
NH
4
NO
3
(s) in water is an
entropy driven process.
S
universe
=
S
system
+
S
surroundings
2
nd
Law of Thermodynamics
Calculating AS
Surroundings
:







2
nd
Law of Thermodynamics
Calculating AS
Surroundings
:







system surroundings
system surroundings
q q
S S
T T
A = A =
2
nd
Law of Thermodynamics
Calculating AS
Surroundings
:







system surroundings
system surroundings
q q
S S
T T
A = A =
system surroundings system surroundings
q q 0 q q + = =
2
nd
Law of Thermodynamics
Calculating AS
Surroundings
:




at constant pressure, q
system
= A
r
H
system



system surroundings
system surroundings
q q
S S
T T
A = A =
system surroundings system surroundings
q q 0 q q + = =
2
nd
Law of Thermodynamics
Calculating AS
Surroundings
:




at constant pressure, q
system
= A
r
H
system



system surroundings
system surroundings
q q
S S
T T
A = A =
system surroundings system surroundings
q q 0 q q + = =
2
nd
Law of Thermodynamics
surroundings r system
r system
surroundings
Therefore : q H
H
and S
T
= A
A
A =
Problem:
Calculate the entropy change for the surroundings for
the reaction: 2H
2
(g) + O
2
(g) 2H
2
O(l)

2
nd
Law of Thermodynamics
Problem:
Calculate the entropy change for the surroundings for
the reaction: 2H
2
(g) + O
2
(g) 2H
2
O(l)


The enthalpy change for the reaction is calculated
using standard molar enthalpies of formation:

2
nd
Law of Thermodynamics
r system
surroundings
H
S
T
A
A =
Problem:
Calculate the entropy change for the surroundings for
the reaction: 2H
2
(g) + O
2
(g) 2H
2
O(l)


The enthalpy change for the reaction is calculated
using standard molar enthalpies of formation:

2
nd
Law of Thermodynamics
r system
surroundings
H
S
T
A
A =
3
surroundings
10 K
571.7kJ
1kJ
J
S 1917
K
298.15K

A = = +
Problem:
Calculate the entropy change for the surroundings for
the reaction: 2H
2
(g) + O
2
(g) 2H
2
O(l)
As calculated previously:

AS
universe
= 327 J/K + 1917 J/K =1590. J/K

surroundings
J
S 1917
K
A = +
system
J
S 327
K
A =
2
nd
Law of Thermodynamics
Problem:
Calculate the entropy change for the surroundings for
the reaction: 2H
2
(g) + O
2
(g) 2H
2
O(l)

AS
universe
= 327 J/K + 1917 J/K = 1590. J/K

The entropy of the universe increases ( > 0) therefore
the process is spontaneous at standard state
conditions.
The process is spontaneous due to the entropy
change in the surroundings, not the system.
2
nd
Law of Thermodynamics
Spontaneous or Not?
The method used so far to determine whether a
process is spontaneous required evaluation of two
quantities, AS(system) and AS(surroundings).
J. Willard Gibbs asserted that that the
maximum non-PV work available to the
system must be a function of Enthalpy
and Entropy:
G = H TS

G = Gibbs Free energy of the system, H = system
enthalpy and S = the entropy of the system.
J. Willard Gibbs
1839-1903
Gibbs Free Energy, G
Since it is impossible to measure individual values of
enthalpy, we often express free energy in terms of the
changes of thermodynamic quantities.
A(G = H TS)
At constant temperature:


AG = Gibbs Free energy change of the system,
AH = enthalpy change and AS = the entropy
change at SS conditions.
G H T S A = A A
Gibbs Free Energy, G


If the reaction is exothermic (AH < 0)
And the change in entropy is positive (AH > 0)
at a given temperature, then AS < 0.
We then can assert that if AG < 0 that the
reaction is spontaneous as well as product
favored!
Spontaneity is a function of energy and
dispersion!
G H T S A = A A
Gibbs Free Energy, G



AH AS AG Reaction
+
Product Favored
+ +
Reactant Favored
?
Temperature
dependant
+ + ?
Temperature
dependant
Gibbs Free Energy, G
G H T S A = A A
Since A
r
G is related to AS
universe
, it follows
that:
If A
r
G < 0: The process is spontaneous in the
direction written under standard conditions.
If A
r
G = 0: The process is at equilibrium under
standard conditions and K=1
If A
r
G > 0: The process is non-spontaneous in
the direction written under standard conditions.
Conclusion: A reaction proceeds spontaneously
toward the minimum in free energy, which
corresponds to equilibrium.
A
r
G
o
& Equilibrium
Product Favored Reactions, G negative, K > 1
Q < K: Heading to
equilibrium AG < 0
Q = K: At
equilibrium AG = 0
Q > K: Heading
away from
equilibrium AG > 0
G, G, Q, & K
Product-favored
2 NO
2
N
2
O
4


r
G = 4.8 kJ
State with both reactants
and products present is
more stable than
complete conversion.
K > 1, more products
than reactants.
G, G, Q, & K
Reactant Favored Reactions, G positive, K < 1
Q < K: Heading to
equilibrium AG < 0
Q = K: At
equilibrium AG = 0
Q > K: Heading
away from
equilibrium AG > 0
G, G, Q, & K
Reactant-favored
N
2
O
4
2 NO
2


r
G = +4.8 kJ
State with both
reactants and products
present is more stable
than complete
conversion.
K < 1, more reactants
than products
G, G, Q, & K
A
r
G represents the free energy change for a
process at standard state conditions. (Equilibrium)
What if this is not the case?
Under nonstandard conditions:


Where R is the
gas law constant
and Q =


r r
G G RTln(Q) A = A +
[ ] [ ]
[ ] [ ]
c d
a b
C D
Q
A B
for aA + bB cC dD
=
+
G, G, Q, & K
At equilibrium, we know that A
r
G = 0 and Q = K

Therefore:





So knowing one quantity yields the other.

r r
r
r
G G RTln(Q)
0 G RTln(K)
G RTln(K)
A = A +
= A +
A =
G, G, Q, & K
Problem:
A
r
G for the formation of ammonia at SS conditions is 16.37
kJ/mol. What is the value of Kp at this temperature and
pressure? (1 mol, 20 C and 1 atm)







G, G, Q, & K
Problem:
A
r
G for the formation of ammonia at SS conditions is 16.37
kJ/mol. What is the value of Kp at this temperature and
pressure? (1 mol, 20 C and 1 atm)







2 2 3
r p
3 1
H (g) N (g) NH (g)
2 2
G RTln(K )
+
A =
G, G, Q, & K
Problem:
A
r
G for the formation of ammonia at SS conditions is 16.37
kJ/mol. What is the value of Kp at this temperature and
pressure? (1 mol, 20 C and 1 atm)







r p
r
3
r
p
G RTln(K )
G
ln(K)
RT
kJ 10 J
16.37
G
mol 1 kJ
K exp exp 740.
J
RT
8.314 298 K
mol K
A =
A
=
| |

|
A
| |
= = =
| |
\ .
|

\ .
G, G, Q, & K
Problem:
A
r
G for the formation of ammonia at SS conditions is 16.37
kJ/mol. What is the value of Kp at this temperature and
pressure? (1 mol, 20 C and 1 atm)







r p
r
3
r
p
G RTln(K )
G
ln(K)
RT
kJ 10 J
16.37
G
mol 1 kJ
K exp exp 740.
J
RT
8.314 298 K
mol K
A =
A
=
| |

|
A
| |
= = =
| |
\ .
|

\ .
K >> 1, product
favored as
predicted by AG
G, G, Q, & K
The relation of
r
G,
r
G, Q, K, reaction spontaneity,
and product- or reactant favorability.
Summary
C (graphite) + 2H
2
(g) CH
4
(g)
A
r
H
(kJ/mol)
0 0 74.9
S (J/K) +56 +130.7 + 186.3
Calculating & Using Free Energy
Standard Free Energy of Formation
r f f
r
H n H (products) m H (reactants)
S n S (products) m S (reactants)
A = A A
A =


C (graphite) + 2H
2
(g) CH
4
(g)
A
r
H
(kJ/mol)
0 0 74.9
S (J/K) +56 +130.7 + 186.3
Calculating & Using Free Energy
Standard Free Energy of Formation
r r
J
H 74.9 kJ S 80.7
K
A = A =
Calculating & Using Free Energy
Standard Free Energy of Formation
C (graphite) + 2H
2
(g) CH
4
(g)
A
r
H
o

(kJ/mol)
0 0 74.9
S
o
(J/K) +56 +130.7 + 186.3
r r
r r r
r
3
r
J
H 74.9 kJ S 80.7
K
G H T S
J 1 kJ
G 74.9 kJ 298 K 80.7
K 10 J
kJ
G 50.9
mol
A = A =
A = A A
| | | |
A =
| |
\ . \ .
A =
A
r
G is negative at 298 K, so the reaction is
predicted to be spontaneous under standard
conditions at this temperature. It is also predicted to
be product-favored at equilibrium.
Calculating & Using Free Energy
Standard Free Energy of Formation


Under reversible conditions, both enthalpy and
entropy are state functions. It follows that the
Gibbs free energy must also be.
Therefore we can write that:
G H T S A = A A
r f f
G n G (products) m G (reactants) A = A A

Gibbs Free Energy, G
Note that
f
G for an element = 0
Free Energies of Formation
Using the A
f
G found in appendix L of your text,
calculate A
r
G for the following reaction:
4NH
3
(g) + 7O
2
(g) 4NO
2
(g) + 6H
2
O(g)






Free Energies of Formation
Using the A
f
G found in appendix L of your text,
calculate A
r
G for the following reaction:
4NH
3
(g) + 7O
2
(g) 4NO
2
(g) + 6H
2
O(g)






r f f
G n G (products) m G (reactants) A = A A

Free Energies of Formation
Using the A
f
G found in appendix L of your text,
calculate A
r
G for the following reaction:
4NH
3
(g) + 7O
2
(g) 4NO
2
(g) + 6H
2
O(g)






r f f
G n G (products) m G (reactants) A = A A

Free Energies of Formation
( ) ( ) ( ) | |
r f 2 f 2 f 2
G 4 G NO (g) 6 G H O(g) 4 G NO (g) 0 A = A + A A +
Using the A
f
G found in appendix L of your text,
calculate A
r
G for the following reaction:
4NH
3
(g) + 7O
2
(g) 4NO
2
(g) + 6H
2
O(g)







A
r
G = 1101.14 kJ/mol (product-favored
( ) ( ) ( ) | |
r f 2 f 2 f 2
r
G 4 G NO (g) 6 G H O(g) 4 G NO (g) 0
G 4 mol (51.23 kJ/ mol) 6 mol ( 228.59 kJ/ mol)
4 mol ( 16.37 kJ/ mol)
A = A + A A +
A = +

r f f
G n G (products) m G (reactants) A = A A

Free Energies of Formation
Is the dissolution of ammonium nitrate product-
favored?
If so, is it enthalpy- or entropy-driven?
NH
4
NO
3
(s) + heat NH
4
NO
3
(aq)
Calculating
r
G
By definition:
G = H TS
Indicating that free energy is a function of
temperature.
A
r
G will therefore change with temperature.
A consequence of this temperature
dependence is that, in certain instances,
reactions can be product-favored at
equilibrium at one temperature and reactant-
favored at another.
Free Energy & Temperature
When a reaction has
A
r
H < 0
&
A
r
S > 0
at all temperatures
A
r
G is negative.
(Product favored)
Free Energy & Temperature
When a reaction has
A
r
H > 0
&
A
r
S > 0
at high temperatures
A
r
G is negative.
(Product favored)
When a reaction has
A
r
H < 0
&
A
r
S < 0
at low temperatures
A
r
G is negative.
(Product favored)
Free Energy & Temperature
Free Energy & Temperature
At what temperature will a reaction that is non-spontaneous
turn over to a reaction that is? (A
r
G changes from + to )









Free Energy & Temperature
At what temperature will a reaction that is non-spontaneous
turn over to a reaction that is? (A
r
G changes from + to )
Example: The reaction,


Has the following thermodynamic values.

r
H

= +470.5 kJ

r
S = +560.3 J/K

r
G = +301.3 kJ
Reaction is reactant-favored at 298 K

2 3 2
2Fe O (s) 3C(s) 4Fe(s) 3CO (g) + +
Free Energy & Temperature
2 3 2
2Fe O (s) 3C(s) 4Fe(s) 3CO (g) + +
Free Energy & Temperature
At what temperature will a reaction that is non-spontaneous
turn over to a reaction that is? (A
r
G changes from + to )
Example: The reaction,


When A
r
G s 0, the reaction begins to become spontaneous.

2 3 2
2Fe O (s) 3C(s) 4Fe(s) 3CO (g) + +
2 3 2
2Fe O (s) 3C(s) 4Fe(s) 3CO (g) + +
At what temperature will a reaction that is non-spontaneous
turn over to a reaction that is? (A
r
G changes from + to )
Example: The reaction,


When A
r
G s 0, the reaction begins to become spontaneous.

2 3 2
2Fe O (s) 3C(s) 4Fe(s) 3CO (g) + +
r r r
r
r
G H T S 0
H
T
S
A = A A =
A
=
A
Free Energy & Temperature
At what temperature will a reaction that is non-spontaneous
turn over to a reaction that is? (A
r
G changes from + to )
Example: The reaction,




r
H

= +467.9 kJ

r
S = +560.3 J/K

3
r
r
10 J
467.9 kJ
H
1 kJ
T 839.7 K
J
S
560.3
K
+
A
= = =
A
+
Free Energy & Temperature
2 3 2
2Fe O (s) 3C(s) 4Fe(s) 3CO (g) + +