General Chemistry 2

Unit 5 Chemical among different possible 1. Liquids are more

ways that system can contain disordered than solids. Solids
Thermodynamics: energy have regular structure than
liquids
● Thermodynamics – the S= k ln W 2. Gas particles are in
S – entropy constant random motion, so
branch of science that
K – ideal gas are more disordered than
deals with the
constant/Avogadro’s liquids
relationship between
W – number of 3. Entropy increases, for any
heat and other forms of
equivalent ways of process that increases the
energy. Defined by three
describing the state number of particles
laws which describe the
of the system.
restrictions on how the
different forms of energy Standard State
• Microstates – the possible
are interconnected. Entropies of Reaction
ways of distributing the
● First Law of molecules.
• The change in entropy of
Thermodynamics –
the system depends on the
states that energy Factors that initial state and final state of
cannot be created nor
destroyed; it can only Affect Entropy the system, not on the path
taken to attain the final
change forms. Does not
• Phase Changes – depends state.
reveal the spontaneity
on the freedom of motion of ΔS= S ( Final)−S (Initial)
and direction of chemical
the particles • When the value of ΔS is
reactions.
• Temperature Changes – as positive, the final state is
● Spontaneous Process - a temperature changes, the more disordered than the
process that occurs in a kinetic energy of molecules initial state
system without the increases; thus increasing the • If ΔS is negative, it means
application of any entropy there is a decrease in
outside force and once • Atomic size – heavier entropy of the system and
this process takes place, atoms have greater entropy the final state is more
no action from the • Molecular Complexity – ordered than the initial state
surrounding is needed to entropy increases as
make it continue. molecules become more Sample Problem:
Case Example: A rusting complex Calculate the standard
iron chain. Spontaneous •Nature of Solute • Nature entropy of the reaction:
and takes place slowly 4 of Process 2H2(g) + O2(g)→ 2H20(l)
Fe (S) + 3O2(G)→ 2Fe2 Solution: ΔS°= S°(product) -
O3(S). The reverse is S° (reactant)
Generalizations on
non-spontaneous ΔS° H20(l) − (S°H2(g)+
Entropy of reactions S°O2(g))
• Entropy – a measure of
how spread out or dispersed
the energy of a system is
 General Chemistry 2

∆S= 2×69.61 J/k•mol − proportional to the inverse

[(2×130.68 J/k•mol) + of the enthalpy of the Gibbs Free Energy – the
(205.14 J/k• mol)] system. energy free to do work at
ΔS°= −326.68 J/K•mol constant temperature and
pressure denoted as G.
Second Law of Sample Problem: What is
G= H-TS
the entropy change if you
Thermodynamics boil your water at 100˚C?
Where H is the enthalpy of
the system, T as the
temperature in Kelvin, and S
● Second Law - The as the entropy of the system.
entropy of the universe
increases in a • was substituted by
spontaneous process. Sample Problem: Calculate
the inverse of enthalpy over
the standard entropy of the
temperature
reaction:
• The equation was derived
from the entropy equation.

A process that leads to

increase in randomness or • Multiplying all sides by T
disorder of the system will reveals:
be spontaneous. Solution:

• The change in free energy

of a system for a constant-
temperature process is
• Standard Entropy of The reaction of this problem expressed as:
Reaction – the difference in is therefore spontaneous at
standard entropies between 1 atm and 25˚C.
products and reactants. • Standard Free Energy
Third Law of Changes. ∆G°= H°-T∆S°
• Standard Free Energy of
Thermodynamics: Formation - the free-energy
change that occurs when 1
Solutions: The entropy of a perfect mole of the compound is
crystalline substance is zero synthesized from its
at the absolute zero of the elements in their standard
temperature. if the crystal is states.
impure or if it has defects,
• Entropy Changes in the
then its entropy is greater
Surroundings – the entropy
than zero even at 0 K.
of the surroundings is
 General Chemistry 2

Sample Problem: Calculate products divided by the

the standard entropy of the product of the concentration
reaction: of the reactants each raised
to the power equal to the
coefficient from the balanced
• If a chemical reaction has equation is equal to a
either its reactants or
constant
products not in their Sample Problem: Calculate
standard states, the Gibbs the standard entropy of the For the hypothetical
Free energy is expressed as: reaction: equation:
∆G= ∆G°+ RT ln Q
𝑎𝐴(𝑔) + 𝑏𝐵(𝑔) ↔️
• If the reaction is at
𝑐𝐶(𝑔)𝑑𝐷(𝑔)
equilibrium, then the
equation becomes: ∆ G= -RT The Equilibrium Constant
ln k 𝐾𝑒𝑞 is expressed as

or if the products and

reactants are gasses:
Sample Problem: For the
given reaction. Calculate ∆G
at 298.15 K. Unit 6 CHEMICAL
EQUILIBRIUM The values of 𝐾𝑒𝑞 and 𝐾𝑃
Given: ∆H = - 114.1 kJ ∆S = - Equilibrium – established for the same reaction at the
146.5 J/K to - 0.01465 kJ/K when the rate of forward same temperature is:

Solution: ∆G = ∆H - T∆S = - reaction

114.1 kJ – (298.15 K)(-0.1465 becomes equal to the rate of
kJ/K) = - 114.1 kJ – (-43.68 backward reaction
kJ) = -70.4 kJ Example: Consider the
Reversible Reactions – following reaction. Express
reactions that proceed in its Equilibrium Constant.
Sample Problem: Calculate both forward or backward
the equilibrium constant at directions
298.15K of the reaction:

If 𝐾𝑒𝑞 > 1, the farther the

Law of Chemical Equilibrium
forward reaction will have
– states that the product of
proceeded toward
the concentration of the
 General Chemistry 2

completion when equilibrium 3. Increasing pressure always 2. Increasing the volume -

is reached. drives the reaction in the Equilibrium shifts to the
direction that will reduce the right.
If 𝐾𝑒𝑞 < 1, only a small
number of molecules of gas.
amount of product/s is/are 3. Adding 𝑁2𝑂4 - Equilibrium
Changes in pressure have
present when equilibrium is shifts to the right.
significant effects only on
reached.
systems with gaseous 4. Decreasing the
If 𝐾𝑒𝑞 = 1, the product of components. temperature - Equilibrium
concentration of reactants shifts to the left.
4. Catalysts will not have a
and of products are nearly
net effect on the equilibrium. 5. Adding He – Equilibrium is
the same.
It may increase the rate of not affected.
Le Chatelier’s Principle – if reactions but will do so to
the same extent for both Reaction Quotient (Q) –
an external stress is applied
directions of reversible value obtained by
to a system at equilibrium,
reactions. substituting initial
the system adjusts in such a
concentration into the
way that the stress is
5. Adding an inert gas has no equilibrium expression
partially offset as the system
effect on the system.
reaches a new equilibrium Compared to the value of
position. 𝐾𝑒𝑞 to find the direction the
reaction proceeds to reach
1. Adding or removing a Sample Problem: Given the
equilibrium
reactant or product, the following reversible reaction:
reaction shifts to the 𝑁2𝑂4(𝑔) ↔️2𝑁𝑂2(𝑔) Δ𝐻 = • If 𝑄 < 𝐾𝑒𝑞, reaction will
direction that will remove 58.0 𝑘𝐽 move from left to right
the substance which
Predict the equilibrium shift • If 𝑄 = 𝐾𝑒𝑞, the system is in
increased in amount or
when each of the following equilibrium
replace the substance which
changes is carried out:
decreased in amount. • If 𝑄 > 𝐾𝑒𝑞, reaction will
1. Removing 𝑁𝑂2 move from right to left.
2. Increasing the volume

3. Adding 𝑁2𝑂4 Sample Problem: Given the

reaction: 𝑃𝐶𝑙5(𝑔) PCl3 (𝑔)
4. Decreasing the
2. Increasing the + 𝐶𝑙2(𝑔) 𝐾𝑒𝑞 = 0.0415
temperature
temperature will increase The mixture of 0.1000M of
the rate of endothermic 5. Adding He
𝑃𝐶𝑙5(𝑔), 0.0200M of 𝐶𝑙2(𝑔) ,
reaction more than the Solution: and 0.0400 M of 𝑃𝐶𝑙3(𝑔) is
exothermic reaction. placed in a 1.00L container.
1. Removing 𝑁𝑂2 -
Predict the direction of the
Equilibrium shifts to the
reaction.
right.
 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.