Spontaneous

Process and
Chemical
Equilibrium
 1st Law - Energy of the universe is constant.
“Energy can be converted from one form to another
but cannot be created nor destroyed.”
2nd Law – Entropy of universe increases.
“The entropy of the universe increases in a
Three laws of spontaneous process and remains unchanged in an
thermodynamics equilibrium process.”
3rd Law – At absolute zero, the entropy of a perfect
crystal is 0.
“The entropy of a perfect crystalline substance is
zero at the absolute zero of temperature (T = 0 K=
-273.15 oC).”
 A spontaneous process is a physical or
chemical change that occurs by itself.
These processes occur without requiring
an outside force and continue until
Spontaneous equilibrium is reached.
Examples:
Process Heat flows from a hotter object to a
colder one.
An iron object rusts in moist air.
Sugar dissolves in a cup of coffee.
 Entropy, S
Entropy, sometimes referred as the measure of randomness
and disorder, is a thermodynamic quantity that is a measure of
how spread out or dispersed the energy of a system is among
the different possible ways that system can contain energy. It is
a quantity that is generally used to describe the course of a
process, that is, whether it is a spontaneous process and has a
probability of occurring in a defined direction, or a
non-spontaneous process and will not proceed in the defined
direction, but in the reverse direction.

The SI unit of entropy is joules per Kelvin (J/K) and, like enthalpy,
is a state function.
 Ssolid < Sliquid < Sgas
The spreading out of more concentrated molecules and the spreading out of more
concentrated energy are changes from more order to more random. The changes
that occur are the ones that lead to an increasing randomness of the universe.
Entropy and the Second Law
of Thermodynamics
The Second Law of Thermodynamics deals
with entropy. It tells whether a process or
chemical reaction can occur. The
connection between entropy and the
spontaneity of a reaction is expressed by
the second law of thermodynamics.
“The entropy of the universe increases in a
spontaneous process and remains
unchanged in an equilibrium process.”
 Factors Relationship to entropy
Phase Entropy is greatest in gaseous state
Factors
affecting the Number of particles Directly proportional
entropy
Temperature Directly proportional

Pressure Inversely proportional

 Because the universe is made up of the system and the
surroundings, the entropy change in the universe ( ΔSuniv) for any
process is the sum of the entropy changes in the system (ΔSsys) and
in the surroundings ( ΔSsur).

ΔSuniv = ΔSsys +
ΔSsur
ΔSuniv > 0 Process is spontaneous
ΔSuniv =0 Process tends not to occur; equilibrium is
attained.
ΔSuniv < 0 Reverse process occurs spontaneously.
General rules for predicting
entropy change of the system:

1. If the reaction produces more gas molecules

than it consumes, ΔS° is positive.
2. If the total number of gas molecules
diminishes, ΔS° is negative.
3. If there is no net change in the total number
of gas molecules, ΔS° may be positive or
negative, but will be relatively small
numerically.
Predict whether the entropy change of the
system in each of the following is positive
or negative (increases or decreases) .

N2(g, 10 atm) 🡪 N2 (g, 1atm)

6CO2(g) + 6H2O(g) 🡪 C6H12O6(g) + 6O2(g).
NH4Cl (s) 🡪 NH3(g) + HCl (g)
 Calculating Entropy Changes in the System, ΔSsys

ΔSsys = ΣnS (products) − ΣmS (reactants)

*Where m and n are the stoichiometric coefficients in the reaction.

* Remember, the greater the value of ΔSsys then the greater is the increase in the
randomness of the system.

The standard entropy values of compounds have been measured in J/K mol. To calculate the
Δssys, the values may be found in the Thermodynamic Data Table. Thermodynamic tables have
absolute entropy of substances at 25°C and 1atm.
Sample
From the standard entropy values in the Thermodynamic Data table,
calculate ΔSsys for the following reaction.

H2(g) + I2(s) 🡪 2HI(g)

130.6 116.7 206.3 -- From the table, S°(J/K·mol)
Calculating the Entropy Changes in the
Surroundings, ΔSsurr
For constant-pressure process the heat change is equal to the enthalpy
change of the system ΔHsys(aka Δho),. Then the change in entropy of the
surroundings ΔSsurr is proportional to the ΔHsys.

ΔSsurr 🡪 − ΔHsys

The minus sign is used because, if the process is exothermic, ΔHsys is

negative and the ΔSsurr is a positive quantity, indicating an increase in
entropy.
The change in entropy for a given amount of heat absorbed also depends on
the temperature.

Therefore, ΔSsurr = −ΔHsys

T
*Where T is temperature in kelvin
Sample problem
Calculate the ΔSsurr if the heat of reaction of the system ΔH=-80kJ/mol
and occurred at room temperature.
Sample problem (Predicting the spontaneity of a
process based on entropy)
You are told that a special chamber allows O2 to combine with N2 to
form NO2 (nitrogen dioxide) using reaction.

½N2(g) + O2(g) 🡪 NO2(g) ΔH=34kJ/mol

S° J/K mol: 191.5 205.0 240.5

Predict wheter the reaction is a spontaneous process.

1. Determine whether entropy increases or decreases on the following system
and state the reason.
a. Deposition (gas to solid)
b. O2(g) 🡪 2O(g)
2.
Mg + ½ O2 🡪 MgO ΔH= -60.12KJ/mol
S° J/K mol: 32.7 205.0 26.9
a. Solve ΔSsys
b. Solve Δssurr
c. Solve Δsuni
d. Predict wheter the reaction is a spontaneous process at room temperature.
Activity

1. Determine whether entropy increases or decreases on the following system and

state the reason. (5 points each)
a. H2(g, 10atm) 🡪 H2(g, 5atm)
b. 2H2(g) + O2 (g) 🡪 2H2O (l)

2. N2(g) + 3H2(g) 🡪 2NH3(g) ΔHsys = - 92.6 KJ/mol

S°(J/K· mol): 192 131 193
a. Solve ΔSsys
b. Solve Δssurr
c. Solve Δsuni
d. Predict wheter the reaction is a spontaneous process at room temperature.
Gibbs Free Energy, G
Another thermodynamic function is used in order to express the spontaneity of a
reaction more directly. This is called Gibbs free energy, G. The use of G predicts
changes that are focused on the system.
Gibbs free energy is defined as: ΔG = ΔH – TΔSsys

• All the quantities in the equation pertain to the system; the temperature T is the
temperature of the system.
• G has units of energy; both H and TS are in energy units.
• H, S and G are all state functions.
If the entropy of the universe increases, then, the ΔG of the system will decrease.
The direction of spontaneous change is negative ΔG for system. The ΔG tells us if
a change can occur for a chemical reaction.
If ΔSuniv is (+) for universe then ΔG for system is ( - ). The ΔG for the system is a
convenient way to predict a change.
ΔSuniv ΔG ΔSuniv Reaction

+ - Increase Spontaneous, will go

0 0 Stay the same No change at equilibrium

- + decrease Not spontaneous, will not go, the

reverse will
In this context, free energy is the energy available to do work. If a particular
reaction is accompanied by a release of usable energy (ΔG is negative), the
reaction is spontaneous. * Unless stated otherwise, the ΔH, ΔS and ΔG refer to the
system at 25oC.

Summary of conditions for spontaneity and equilibrium at constant temperature

and pressure in terms of ΔG

ΔG < 0 The reaction is spontaneous in the forward direction.

ΔG > 0 The reaction is nonspontaneous. Reverse direction.

ΔG = 0 The system is at equilibrium. There is no net change.

Ozone (O3) in the atmosphere can react with nitric oxide (NO):

O3(g) + NO(g) —> NO2(g) + O2(g)

Calculate the G for this reaction at 25oC. (H = -199 kJ/mol, S = -4.1 J/K·mol)
Sample problem
The old camera flash bulb used Mg metal sealed in a bulb with oxygen. The
reaction is:
Mg + ½ O2 🡪 MgO ΔH= -601.2KJ/mol
S° J/K mol: 32.7 205.0 26.9

Calculate the free energy and determine if the process is spontaneous.

Chemical equilibrium
Many chemical reactions do not proceed to
just one direction or proceed essentially to
completion. These are called reversible
reactions. In reversible reactions, the reactants
are not completely converted into products and
some of the products may be converted back
into reactants. When the reactants start to
form the products, the products would then
start to reform the reactants. The two opposing
processes happen at different rates, but a
certain point in the reaction will be reached
where the rates of the forward and backward
reactions are the same. This is the state of
chemical equilibrium.
In a state of chemical equilibrium, since the rate of product formation is equal to
the rate of the reformation of the reactants, then the concentrations of the
reactants and products remain constant.
The relationship between the concentrations of the reactants and products may be
expressed using the law of mass action expression/equilibrium constant
expression. For the general equilibrium reaction:

aA + bB 🡪🡪 cC + dD
the law of mass action expression is written as

c d
Keq = [C] [D]
[A]a[B]b
Example
For the reaction: N2O4(g) 🡪🡪 2NO2(g), the law of mass action expression is written
as
Keq = [NO2]2
[N2O4]

For equilibrium reactions where the reactants and products are in different phases
(heterogeneous equilibria), pure solids and pure liquids are excluded in writing
equilibrium constant expressions. For example, consider the reaction.
PbCl2(s) 🡪🡪 Pb2+(aq) + 2Cl-(aq)

Kc = [Pb2+][Cl-]2
Other samples:

2NO(g) + Cl2(g) 🡪🡪 2NOCl(g) Kc= [NOCl]2 .

[NO]2[Cl2]

CO2(g) + H2(g) 🡪🡪 CO(g) + H2O(l) K c= [CO] .

[CO2 ][H2]
Consider the reaction for the production of phosgene (COCl2), a toxic gas used in
the manufacture of certain polymers and insecticides, at 100°C:
CO(g) + Cl2(g) 🡪🡪 COCl2(g)

Kc = [COCl2] .
= 4.56 X 109
[CO][Cl2]

The large value of 4.56 × 109 suggests that the concentration of COCl2 must be very
large as compared to the individual concentrations of CO and Cl2. The value
suggests that at equilibrium, the reactions mixture contains more of the product
COCl2 than the reactants CO and Cl2. This is experimentally verified. In other
words, the equilibrium lies to the right or towards the product side based from the
chemical equation given.
Sample
Gaseous hydrogen iodide is placed in a closed container at 425°C,
where it partially decomposes to hydrogen and iodine:
2HI(g) 🡪🡪 H2(g) +I2(g)
At equilibrium, it is found that [HI] = 3.53 × 10–3 M, [H2] = 4.79 × 10–4 M
and [I2] =4.79 × 10–4 M. What is the value of Kc at this temperature?
The Reaction Quotient, Q
It is the value obtained when product and reactant concentrations or partial
pressures at any point of the reaction is plugged in the equilibrium constant
expression. It is calculated in the same way as K. Thus for a general equilibrium
reaction
aA + bB 🡪🡪 cC + dD

The reaction quotient can be expressed as:

Keq = [C]c[D]d
[A]a[B]b
Example
The Kc value for the reaction N2(g) 🡪🡪 H2(g) + 2NH3(g) at 472°C is
0.105. Suppose a mixture of 2.00 mol of H2, 1.00 mol of N2 and 2.00
mol of NH3 is placed on a sealed 1.00-L container.
LE CHATELIER’S PRINCIPLE.
States that if a stress (changes in reaction conditions) is
applied to a system in equilibrium, then the systems
adjusts in order to reduce the effect of the stress applied.
The stress that may affect a system at chemical
equilibrium include changes in the concentration of either
products or reactants, changes in temperature and
changes in pressure for gaseous equilibria.
A(g) + 2B(g) 🡪🡪 C(g) + D(g)