THERMODYNAMICS: 2ND LAW

Thermodynamics
• Is the study of the relationship between all forces of energy.
• Study of energy and its transformation.

Thermodynamic System
• System – the region which is inside the flask
• Surrounding – the region which is outside the flask
• Boundary – the imaginary line which separates the system and surrounding

Types of thermodynamic System

•Open System
•Close System
•Isolated System

Open System
- The system in which heat transfer as well as mass transfer takes place with the
surrounding.

Closed System
- The system in which only heat energy is exchange with the surroundings.
Isolated System
- No heat transfer takes place.

Intensive Properties
• These are the parameters that size does not matter or size independent.
Ex. Temperature, pressure, density

Extensive properties
• Thermodynamic property that depends on the size of the matter.
Ex. Mass, volume, total energy

First Law of Thermodynamics

• It follows the Law of Conversation of Energy
o Heat energy cannot be created nor destroyed and can only be transferred to
one form to another.
• Relationship of internal energy, work and heat.

Formula: ΔU = Q + W
ΔU = change the internal energy
Q = energy transferred as heat
W = work done on or by the system
Unit = joules (J)

Remember:
1. Q = positive (+) – heat is absorbed (endothermic process)
2. Q = negative (-) – heat is released (exothermic process)
3. W = positive (+) – if work done on the system
4. W = negative (-) – if work done by system

ENTHALPY CHANGE (HEAT OF REACTION)

Enthalpy Change (Heat of Reaction)
To quantity the heat flow out and into the system is called Enthalpy. It is impossible to
measure the enthalpy of the substance, but actually it is the change in enthalpy being
measured.
 Enthalpy change is the energy exchange between a chemical reaction and its
surroundings
and constant pressure.
ΔH=H (products) – H (reactants)

• For endothermic reaction - ΔH is positive + energy flows into the system

• For exothermic reaction - ΔH is negative - energy flows out of the system

What is spontaneous process?

• Spontaneous reactions or processes happen automatically and do not require external
energy
• spontaneous processes have a great tendency to proceed in one direction
• the reverse is nonspontaneous

Examples
• Water runs downhill
• Sugar dissolves in water which does not trip reappear in its original form.
• Heat always flows from hot object to cold one and never the other way around.

Spontaneity
• A water runs downhill
• A lump of sugar dissolves in a Cup of coffee
• smell diffusing in a room
• heat flows from a hotter object to colder object
• are you an exposed to oxygen and water form rust
• a ball rolling downhill
 • processes that are spontaneous is one direction are non spontaneous in the
reverse direction.

How to determine whether a process is spontaneous or not?

spontaneous process
• -ΔH exit thermic reactions (release heat)
nonspontaneous process
• +ΔH endothermic reactions (absorbs heat)

= not on me ΔH is the popcorn consider in predicting a spontaneous process. we need to

consider another thermodynamic quantity Entropy (S).

What is entropy?
• A thermodynamic quantity called entropy is needed to predict the spontaneity
of a process. Entropy is a measure of how dispersed where is spread out the
energy of a system. The greater the dispersal or disorder the higher its
entropy.
• In solids the particles are highly ordered than those in liquids while liquid
particles are more highly ordered than those in gases
Second law of thermodynamics
• This law states that the entropy of the universe increases in a spontaneous process and
remains unchanged in an equilibrium process.
• The second law does specify that only certain processes will take place spontaneously.
• Example heat flows from a hot object to a cooler one.
• A simple statement of the second law might be: a spontaneous process occurs only if
there is an increase in entropy of a system in its surroundings.
• The universe is comprised of surrounding and a system; therefore the entropy change of
the universe (ΔSuniverse) for any process in the sum of entropy change in the
surroundings and in the system.
ΔSuniverse = ΔSsystem + ΔSsurronding
• In a spontaneous process, the entropy change of the universe must be greater than
zero.
ΔSuniverse = ΔSsystem + ΔSsurronding

𝒒 𝒔𝒖𝒓𝒓
ΔSuniverse = ΔSsystem +
𝑻

𝚫𝐡
ΔSuniverse = ΔSsystem +
𝑻

Entropy in the system

ΔS°rxn = ΣnS°products - ΣnS°reactants
 GIBBS FREE ENERGY
Gibbs free energy, denoted G, combines enthalpy and entropy into a single value. Gibbs
free energy of a system is defined as the enthalpy of the system minus the product of
the temperature times the entropy of the system. ΔG can predict the direction of the
chemical reaction under two conditions:
1. constant temperature and
2. constant pressure.

Using ΔG we can determine the condition of spontaneity and equilibrium at constant

temperature and pressure as follows:

When ∆G < 0, the reaction will proceed spontaneously in forward direction to form more
products and the reaction will release energy; the reaction is exergonic.

When ΔG > 0, the reaction will not proceed spontaneously in forward direction but will
proceed spontaneously in the opposite direction. It absorbs energy from the
surroundings; the reaction is endergonic.

ΔG = ΔH – TΔS

where:
ΔG = change in free energy
ΔH = change in enthalpy
T = Temperature
ΔS = change in entropy
• If ΔG is positive, then the reaction is nonspontaneous (external is necessary for the
reaction to occur)

• If ΔG is negative, then it is spontaneous (occurs without external energy)

Examples: