General Chemistry 2
Unit 5 Chemical among different possible
Thermodynamics:
● Thermodynamics – the
branch of science that
deals with the
relationship between
heat and other forms of
energy. Defined by three
laws which describe the
restrictions on how the
different forms of energy
are interconnected.
● First Law of
Thermodynamics –
states that energy
cannot be created nor
destroyed; it can only
change forms. Does not
reveal the spontaneity
and direction of chemical
reactions.
● Spontaneous Process - a
process that occurs in a
system without the
application of any
outside force and once
this process takes place,
no action from the
surrounding is needed to
make it continue.
Case Example: A rusting
iron chain. Spontaneous
and takes place slowly 4
Fe (S) + 3O2(G)→ 2Fe2
O3(S). The reverse is
non-spontaneous
• Entropy – a measure of
how spread out or dispersed
the energy of a system is
1. Liquids are more
ways that system can contain
energy
S= k ln W
S – entropy
K – ideal gas
constant/Avogadro’s
W – number of
equivalent ways of
describing the state
of the system.
• Microstates – the possible
ways of distributing the
molecules.
Factors that
Affect Entropy
• Phase Changes – depends
on the freedom of motion of
the particles
• Temperature Changes – as
temperature changes, the
kinetic energy of molecules
increases; thus increasing the
entropy
• Atomic size – heavier
atoms have greater entropy
• Molecular Complexity –
entropy increases as
molecules become more
complex
•Nature of Solute • Nature
of Process
Generalizations on
Entropy of reactions
disordered than solids. Solids
have regular structure than
liquids
2. Gas particles are in
constant random motion, so
are more disordered than
liquids
3. Entropy increases, for any
process that increases the
number of particles
Standard State
Entropies of Reaction
• The change in entropy of
the system depends on the
initial state and final state of
the system, not on the path
taken to attain the final
state.
ΔS= S ( Final)−S (Initial)
• When the value of ΔS is
positive, the final state is
more disordered than the
initial state
• If ΔS is negative, it means
there is a decrease in
entropy of the system and
the final state is more
ordered than the initial state
Sample Problem:
Calculate the standard
entropy of the reaction:
2H2(g) + O2(g)→ 2H20(l)
Solution: ΔS°= S°(product) -
S° (reactant)
ΔS° H20(l) − (S°H2(g)+
S°O2(g))
 General Chemistry 2
∆S= 2×69.61 J/k•mol −
[(2×130.68 J/k•mol) +
(205.14 J/k• mol)]
ΔS°= −326.68 J/K•mol
Second Law of
Thermodynamics
● Second Law - The
entropy of the universe
increases in a
spontaneous process.
A process that leads to
increase in randomness or
disorder of the system will
be spontaneous.
• Standard Entropy of
Reaction – the difference in
standard entropies between
products and reactants.
Solutions:
• Entropy Changes in the
Surroundings – the entropy
of the surroundings is
proportional to the inverse
of the enthalpy of the
system.
Sample Problem: What is
the entropy change if you
boil your water at 100˚C?
Sample Problem: Calculate
the standard entropy of the
reaction:
Solution:
The reaction of this problem
is therefore spontaneous at
1 atm and 25˚C.
Third Law of
Thermodynamics:
The entropy of a perfect
crystalline substance is zero
at the absolute zero of the
temperature. if the crystal is
impure or if it has defects,
then its entropy is greater
than zero even at 0 K.
Gibbs Free Energy – the
energy free to do work at
constant temperature and
pressure denoted as G.
G= H-TS
Where H is the enthalpy of
the system, T as the
temperature in Kelvin, and S
as the entropy of the system.
• was substituted by
the inverse of enthalpy over
temperature
• The equation was derived
from the entropy equation.
• Multiplying all sides by T
reveals:
• The change in free energy
of a system for a constant-
temperature process is
expressed as:
• Standard Free Energy
Changes. ∆G°= H°-T∆S°
• Standard Free Energy of
Formation - the free-energy
change that occurs when 1
mole of the compound is
synthesized from its
elements in their standard
states.
 General Chemistry 2
• If a chemical reaction has
either its reactants or
products not in their
standard states, the Gibbs
Free energy is expressed as:
∆G= ∆G°+ RT ln Q
• If the reaction is at
equilibrium, then the
equation becomes: ∆ G= -RT
ln k
Sample Problem: For the
given reaction. Calculate ∆G
at 298.15 K.
Given: ∆H = - 114.1 kJ ∆S = -
146.5 J/K to - 0.01465 kJ/K
Solution: ∆G = ∆H - T∆S = -
114.1 kJ – (298.15 K)(-0.1465
kJ/K) = - 114.1 kJ – (-43.68
kJ) = -70.4 kJ
Sample Problem: Calculate
the equilibrium constant at
298.15K of the reaction:
Sample Problem: Calculate
the standard entropy of the
reaction:
Sample Problem: Calculate
the standard entropy of the
reaction:
Unit 6 CHEMICAL
EQUILIBRIUM
Equilibrium – established
when the rate of forward
reaction
becomes equal to the rate of
backward reaction
Reversible Reactions –
reactions that proceed in
both forward or backward
directions
Law of Chemical Equilibrium
– states that the product of
the concentration of the
products divided by the
product of the concentration
of the reactants each raised
to the power equal to the
coefficient from the balanced
equation is equal to a
constant
For the hypothetical
equation:
𝑎𝐴(𝑔) + 𝑏𝐵(𝑔) ↔️
𝑐𝐶(𝑔)𝑑𝐷(𝑔)
The Equilibrium Constant
𝐾𝑒𝑞 is expressed as
or if the products and
reactants are gasses:
The values of 𝐾𝑒𝑞 and 𝐾𝑃
for the same reaction at the
same temperature is:
Example: Consider the
following reaction. Express
its Equilibrium Constant.
If 𝐾𝑒𝑞 > 1, the farther the
forward reaction will have
proceeded toward
 General Chemistry 2
completion when equilibrium
is reached.
If 𝐾𝑒𝑞 < 1, only a small
amount of product/s is/are
present when equilibrium is
reached.
If 𝐾𝑒𝑞 = 1, the product of
concentration of reactants
and of products are nearly
the same.
Le Chatelier’s Principle – if
an external stress is applied
to a system at equilibrium,
the system adjusts in such a
way that the stress is
partially offset as the system
reaches a new equilibrium
position.
1. Adding or removing a
reactant or product, the
reaction shifts to the
direction that will remove
the substance which
increased in amount or
replace the substance which
decreased in amount.
2. Increasing the
temperature will increase
the rate of endothermic
reaction more than the
exothermic reaction.
3. Increasing pressure always
drives the reaction in the
direction that will reduce the
number of molecules of gas.
Changes in pressure have
significant effects only on
systems with gaseous
components.
4. Catalysts will not have a
net effect on the equilibrium.
It may increase the rate of
reactions but will do so to
the same extent for both
directions of reversible
reactions.
5. Adding an inert gas has no
effect on the system.
Sample Problem: Given the
following reversible reaction:
𝑁2𝑂4(𝑔) ↔️2𝑁𝑂2(𝑔) Δ𝐻 =
58.0 𝑘𝐽
Predict the equilibrium shift
when each of the following
changes is carried out:
1. Removing 𝑁𝑂2
2. Increasing the volume
3. Adding 𝑁2𝑂4
4. Decreasing the
temperature
5. Adding He
Solution:
1. Removing 𝑁𝑂2 -
Equilibrium shifts to the
right.
2. Increasing the volume -
Equilibrium shifts to the
right.
3. Adding 𝑁2𝑂4 - Equilibrium
shifts to the right.
4. Decreasing the
temperature - Equilibrium
shifts to the left.
5. Adding He – Equilibrium is
not affected.
Reaction Quotient (Q) –
value obtained by
substituting initial
concentration into the
equilibrium expression
Compared to the value of
𝐾𝑒𝑞 to find the direction the
reaction proceeds to reach
equilibrium
• If 𝑄 < 𝐾𝑒𝑞, reaction will
move from left to right
• If 𝑄 = 𝐾𝑒𝑞, the system is in
equilibrium
• If 𝑄 > 𝐾𝑒𝑞, reaction will
move from right to left.
Sample Problem: Given the
reaction: 𝑃𝐶𝑙5(𝑔) PCl3 (𝑔)
+ 𝐶𝑙2(𝑔) 𝐾𝑒𝑞 = 0.0415
The mixture of 0.1000M of
𝑃𝐶𝑙5(𝑔), 0.0200M of 𝐶𝑙2(𝑔) ,
and 0.0400 M of 𝑃𝐶𝑙3(𝑔) is
placed in a 1.00L container.
Predict the direction of the
reaction.
 General Chemistry 2

Solution:

The reaction will then

proceed to the right to reach
equilibrium.

Sample Problem: Given the

reaction:

𝐶𝐻4(𝑔) + 2𝐻2𝑆(𝑔) ↔️
𝐶𝑆2(𝑔) + 4𝐻2(𝑔)

𝐾𝑒𝑞 𝑎𝑡 960℃ = 0.036

In one experiment, 1.00

mole of 𝐶𝐻4(𝑔) , 1.00 mole
of 𝐶𝑆2(𝑔) , 2.00 mole of 𝐻 2𝑆
(𝑔) and 2.00 mole of 𝐻2(𝑔)
are mixed in a 250-ml beaker
at 960˚C.

Solution: Find the molarity of

the reactants and products.