Gibbs (Free) Energy

PRESENTORS FOR TODAY

Sobida, Fhiona Tolentino, Zara, Sherilyn

Gail J. Dianne C. M.
 Learning Objectives
To get an overview of Gibbs energy and its
general uses in chemistry.
Understand how Gibbs energy pertains to
reactions properties
Understand how Gibbs energy pertains to
equilibria properties
Understand how Gibbs energy pertains to
electrochemical properties
 Gibbs Free Energy
Gibbs free energy, denoted G, combines enthalpy and
entropy into a single value. The change in free energy, ΔG,
is equal to the sum of the enthalpy plus the product of the
temperature and entropy of the system. ΔG can predict
the direction of the chemical reaction under two
conditions:
1. constant temperature and
2. constant pressure.
If ΔG is positive, then the reaction is nonspontaneous (i.e.,
an the input of external energy is necessary for the
reaction to occur) and if it is negative, then it is
spontaneous (occurs without external energy input).
Gibbs energy was developed in the 1870’s by Josiah Willard
Gibbs. He originally termed this energy as the “available
energy” in a system. His paper published in 1873, “Graphical
Methods in the Thermodynamics of Fluids,” outlined how his
equation could predict the behavior of systems when they are
combined. This quantity is the energy associated with a
chemical reaction that can be used to do work, and is the sum
of its enthalpy (H) and the product of the temperature and the
entropy (S) of the system. This quantity is defined as follows:
G=H−TS
or more completely as
G=U+PV−TS
where
 G=H−TS

G=U+PV−TS

U is internal energy (SI unit: joule)

P is pressure (SI unit: pascal)
V is volume (SI unit: m^3)
T is temperature (SI unit: kelvin)
S is entropy (SI unit: joule/kelvin)
H is the enthalpy (SI unit: joule)
 Gibbs Free Energy, G
another thermodynamic property that is used to predict
whether the reaction or process will be spontaneous or non-
spontaneous.
Gibbs free energy is defined as: G = H - TS

G (symbol)
H (enthalphy)
T (temperature)
S (Entropy)
The change in free energy (ΔG) of a system for a constant-
temperature process is
ΔG = ΔH - TΔS

The formula for Gibbs Free Energy is:

ΔG = ΔH - TΔS
ΔG represents the change in Gibbs Free Energy

ΔH represents the change in enthalpy (heat content)

T represents the temperature in Kelvin

ΔS represents the change in entropy (degree of disorder)

Conditions for spontaneity and equilibrium at constant
temperature and pressure in terms of ΔG:

The reaction is spontaneous in the forward

ΔG < 0

direction.

The reaction is nonspontaneous. The

ΔG > 0 reaction is spontaneous in the opposite
direction.

The system is at equilibrium. There is no

ΔG = 0 net change.
These equations help us understand the energetics and
spontaneity of chemical reactions and physical processes
based on the signs of ΔH and ΔS.
 How to Determine if a Reaction is Exothermic or
Endothermic

If ΔH is negative (i.e., the reaction releases heat),

then the first term in the equation becomes more
EXOTHERMIC negative, making ΔG more negative. In this case,
the reaction is exothermic.

If ΔH is positive (i.e., the reaction absorbs heat),

then the first term in the equation becomes less
ENDOTHERMIC negative, making ΔG less negative. In this case,
the reaction is endothermic.

The sign of ΔH determines whether a reaction is exothermic or endothermic, and the

sign of ΔG determines whether a reaction is spontaneous or not.
 What is an increase or decrease in the
disorder of the system?
An increase or decrease in the disorder of the
system depends on the change in entropy (ΔS).
Positive and negative values of the change in entropy
of the system represent an increase and decrease in
the disorder of the system, respectively.
Example:
33.7 J/K is a positive value, so ΔS is greater than zero
(ΔS>0).
-56.9 J/K is a negative value, so ΔS is less than zero
(ΔS<0).
SAMPLE PROBLEM
Calculate the Gibbs free energy change (ΔG). The reaction occurs at
310K, the change in heat (ΔH) = 39,896 cal, and the change in entropy
(ΔS) = 120 cal/K.
Given:
ΔH= 39,896 cal Solution:
ΔS= 120 cal/K Substituting the given values, we get:
T=310K

ΔG=? ΔG = ΔH - TΔS

ΔG= 39,896 cal - (310K) (120 cal/K)
Formula: ΔG= 39,896 cal - 37,200 cal
ΔG = ΔH - TΔS

ΔG = 2,696 cal The reaction is non-

spontaneous at 310 K.
Activity
1.Calculate the Gibbs free energy for the
reaction of conversion of ATP into ADP at 293
Kelvin the change in enthalpy is 19.07 Kcal and
the change in entropy is 90 cal per Kelvin.
Quiz
1. Who developed the Gibbs free energy?
2. It represents the change in gibbs free energy
3. It represents the change in enthalpy (heat content)
4. What is the thermodynamic quantity that combines enthalpy
and entropy?
5. What is the formula for Gibbs free energy?
Chemical Equilibrium
Learning Objectives

Explain what is meant by chemical

equilibrium
To know the two types of chemical
equilibrium
Understand how the different factors affect
the chemical equilibrium
Know the importance of chemical
equilibrium
 Chemical Equilibrium
Chemical equilibrium is the state of a system in which the
rate of the forward reaction is equal to the rate of the
reverse reaction.

When the rate of the forward reaction is equal to the rate

of the reverse reaction, the state of chemical equilibrium is
achieved by the system. When there is no further change in
the concentrations of the reactants and the products due
to the equal rates of the forward and reverse reactions, the
system is said to be in a state of dynamic equilibrium.
 Why Is Chemical Equilibrium Called
Dynamic Equilibrium?
The stage at which the rate of
the forward reaction is equal
to the rate of the backward reaction is called an equilibrium
stage. At this point, the number of reactant molecules
converting into products and product molecules into
reactants is the same. The same equilibrium can be carried
out with the same reactants anywhere with similar
conditions with continuous interchanging of molecules, and
hence chemical equilibrium is dynamic.
 Types of Chemical Equilibrium
Homogeneous Equilibrium
In this type, the reactants and the products of chemical equilibrium are all
in the same phase. Homogenous equilibrium can be further divided into
two types:
Reactions in which the number of molecules of the products is equal to
the number of molecules of the reactants. For example,
⇌
H2 (g) + I2 (g) 2HI (g)
⇌
N2 (g) + O2 (g) 2NO (g)
Reactions in which the number of molecules of the products is not equal
to the total number of reactant molecules. For example,
2SO2 (g) + O2 (g)⇌ 2SO3 (g)
COCl2 (g)⇌ CO (g) + Cl2 (g)
 Types of Chemical Equilibrium
Heterogeneous Chemical Equilibrium
In this type, the reactants and the products of chemical equilibrium are
present in different phases. A few examples of heterogeneous equilibrium
are given below:
⇌
CO2 (g) + C (s) 2CO (g)
⇌
CaCO3 (s) CaO (s) + CO2 (g)
Thus, the different types of chemical equilibrium are based on the phase of
the reactants and products.
Factors Affecting Chemical Equilibrium
Change in Concentration
The concentration of the reactants or products added is
relieved by the reaction, which consumes the substance that
is added.
The concentration of reactants or products removed is
relieved by the reaction, which is in the direction that
replenishes the substance which is removed.
When the concentration of the reactant or product is
changed, there is a change in the composition of the
mixture in chemical equilibrium
Change in Pressure
Change in pressure happens due to the change in the
volume. If there is a change in pressure, it can affect the
gaseous reaction as the total number of gaseous
reactants and products are now different. According to
Le Chatelier’s principle, in heterogeneous chemical
equilibrium, the change of pressure in both liquids and
solids can be ignored because the volume is independent
of pressure.
Change in Temperature
The effect of temperature on chemical equilibrium depends upon the sign
of ΔH of the reaction and follows Le-Chatelier’s Principle.
As temperature increases, the equilibrium constant of an exothermic
reaction decreases.
In an endothermic reaction, the equilibrium constant increases with an
increase in temperature.
Along with the equilibrium constant, the rate of reaction is also affected
by the change in temperature. As per Le Chatelier’s principle, the
equilibrium shifts towards the reactant side when the temperature
increases in the case of exothermic reactions; for endothermic reactions,
the equilibrium shifts towards the product side with an increase in
temperature.
 Effect of a Catalyst
A catalyst does not affect the chemical equilibrium, it only
speeds up a reaction. In fact, the catalyst equally speeds up
the forward as well as the reverse reaction. This results in the
reaction reaching its equilibrium faster.
The same amount of reactants and products will be present
at equilibrium in a catalysed or non-catalysed reaction. The
presence of a catalyst only facilitates the reaction to
proceed through a lower-energy transition state of reactants
to products.
 Importance of Chemical Equilibrium
It is useful in many industrial processes, like
Preparation of ammonia by Haber’s process: In this
process, nitrogen combines with hydrogen to form
ammonia; the yield of ammonia is more at low
temperature, high pressure and in the presence of iron as a
catalyst.
Preparation of sulphuric acid by contact process: In this
process, the fundamental reaction is the oxidation of
sulphur dioxide into sulphur trioxide. This involves chemical
equilibrium.
Sample Problem
The reaction between gaseous sulfur dioxide and oxygen is a key
step in the industrial synthesis of sulfuric acid:
2SO2(g)+O2(g)↽−−⇀2SO3(g)

A mixture of SO2 and O2 was maintained at 800 K until the

system reached equilibrium. The equilibrium mixture contained
5.0×10−2MSO35.0×10^−2 M SO3,
3.5×10−3MO23.5×10^−3 M O2, and
3.0×10−3MSO23.0×10^−3 M SO2.
Calculate K and Kp at this temperature.
Given: balanced equilibrium equation and composition of
equilibrium mixture
Asked for: equilibrium constant
Solution
Substituting the appropriate equilibrium concentrations into the
equilibrium constant expression,
To solve for Kp, we use the relationship between K and Kp, where
Δn=2−3=−1:
Activity
Hydrogen gas and iodine react to form hydrogen iodide via
the reaction

H2(g)+I2(g)↽−−⇀2HI(g)H2(g)+I2(g)↽−−⇀2HI(g)

A mixture of H2H2 and I2I2 was maintained at 740 K until the

system reached equilibrium. The equilibrium mixture contained
1.37×10^−2 M HI
6.47×10^−3 M H2 and
5.94×10^−4M I2
Calculate K and Kp for this reaction.
Quiz
1.Chemical equilibrium is also called?
2-3.Give the two types of chemical equilibrium
4.What is the effect of a catalyst on a chemical equilibrium?
5.The Factors Affecting Equilibrium is according to principle
of?
6-9.Give the four Factors Affecting Equilibrium
10.The Importance of Chemical equilibrium is useful in?