SPONTANEOUS CHANGE, ENTROPY, AND FREE ENERGY

Spontaneous process - is a process where it is naturally occurring on its own without outside
assistance.
Nonspontaneous process - Nonspontaneous process occurs as it is driven by the continual input of
energy from the external source. When a process is spontaneous in one direction given a particular
condition, the reverse direction of this process is nonspontaneous. Consider the isolated system
below.
E.G.: Whereas, the rolling up a boulder on a hill is nonspontaneous since external force is needed in
order for the boulder to be returned to its original position on the hill.
Thermodynamics - is a scientific discipline that deals with the interconversion of heat and other forms
of energy.

Temperature and Entropy:

Increase in temperature generally leads to an increase in entropy.

higher temperature implies higher kinetic energy of particles, promoting more chaotic and random
motion, contributing to higher entropy.
Quantity and Entropy:

A substance with a higher quantity tends to have higher entropy.

Higher quantity often leads to more chaos or disorder, contributing to an increase in entropy.
States of Matter and Entropy:

Gas has the highest entropy among the states of matter.

Gas particles possess the highest kinetic energy, allowing for the most freely moving and chaotic
motion, leading to the highest degree of disorder or randomness.
Entropy Change Examples:

Melting of Ice:

∆S: Positive (+)

Explanation: As ice melts, it transitions from a more ordered state (solid) to a less ordered state
(liquid), increasing entropy.
Evaporation of Water:

∆S: Positive (+)

Explanation: During evaporation, water molecules transition from a more ordered liquid state to a
more chaotic gaseous state, leading to an increase in entropy.
Compression of Gas:

∆S: Negative (-)

Explanation: Compression reduces the volume of gas, causing particles to be less dispersed and
leading to a decrease in entropy.
Expansion of Gas:

∆S: Positive (+)

Explanation: Gas expanding into a larger volume increases the dispersion of particles, resulting in a
higher degree of disorder and an increase in entropy.
Solidification of a Molten Metal:

∆S: Negative (-)

Explanation: The transition from a disordered molten state to an ordered solid state reduces the
randomness, leading to a decrease in entropy.

2nd law of Thermodynamics

Second Law of Thermodynamics:

States that for any spontaneous process, the total entropy of the system and its surroundings
combined increases.
Total Entropy Change (∆Suniv):

Represents the change in entropy of the entire universe due to a process.

Unit: Joule/Kelvin (J/K).
Equation 1 - ∆Suniv = ∆Ssys + ∆Ssurr:

Describes the total entropy change of the universe.

∆Ssys: Represents the change in entropy of the system. It is the difference between the summation of
the standard molar entropy of the products and the reactants.
∆Ssurr: Represents the change in entropy of the surroundings. It is calculated as the quotient of
∆HOrxn (the difference in the summation of enthalpy formation of the products and the reactants)
divided by the temperature.
Units:

∆Suniv has units of Joule/Kelvin (J/K).

∆Ssys and ∆Ssurr also have units of Joule/Kelvin (J/K).
Temperature (T):

The temperature (T) in the denominator of the expression for ∆Ssurr is crucial.
It ensures that the units of ∆Ssurr match those of ∆Suniv and ∆Ssys, maintaining consistency in the
equation.

A positive ∆Suniv indicates that the process is spontaneous and nonspontaneous if the said quantity is
negative. With this condition, we could predict the spontaneity of unfamiliar processes occurring
around us.

Equation 1: ∆Suniv = ∆Ssys + ∆Ssurr

Equation 2: ∆SOrxn = [ ∑ xSO (product) - ∑ zSO (reactant) ]

Equation 3:
(∆Ssurr) = -∆HOrxn
T

Equation 4: ∆HOrxn = [ ∑ xHO (product) - ∑ zHO (reactant) ]

- Answer: B. Energy cannot be created nor destroyed, but randomness and disorder increase for all
spontaneous processes.

2. What does a positive entropy of the system imply?

- Answer: C. Increases.

3. Which of the following quantities can be used to predict spontaneity of processes?

- Answer: D. ΔS°univ.

4. Which of the following qualities is NOT gauged through entropy?

- Answer: C. Orderliness.

5. Which of the following processes is nonspontaneous?

- Answer: C. Combustion of propane upon exposure to oxygen gas and heat.

6. Which of the following can be used to describe the spontaneity of processes?

 - Answer: D. Both B and C (Entropy and Gibbs free energy).

7. What is Gibbs free energy?

A. An energy that is used to do useful work.
B. A quantity that could identify the reversibility of processes thermodynamically.
C. A thermodynamic quantity that is used to determine the spontaneity of processes.
- Answer: D. All of the above.

8. Using Gibbs-Helmholtz equation to identify the direction of processes, which of the following
parameters is/are involved?
- Answer: D. All of the above.

9. Which of the following quantities is NOT involved in determining the spontaneity of chemical
processes?
- Answer: C. Pressure.

10. Which of the qualities is TRUE when Gibbs free energy is zero?
- Answer: C. Spontaneous.

11. What is the property of a reaction that has reached chemical equilibrium?
- Answer: D. The rate of the forward reaction is equal to the rate of the reverse reaction.

12. Which of the following statements BEST describes Le Chatelier's principle?

- Answer: D. When a system at equilibrium is disturbed, the system will adjust itself to the change.

13. What is the reaction that releases heat energy known as?
- Answer: B. Exothermic.

14. Which of the following Le Chatelier's principle is applicable to?

- Answer: B. Homogeneous reaction.

15. In what state of substance changes in pressure have an effect?

- Answer: B. Gaseous.

Critical Thinking:

a. Could we use entropy of the system or the standard entropy of the reaction to predict the
spontaneity of the process? Justify your answer.
- Answer: Yes, entropy of the system or the standard entropy of the reaction (ΔS°rxn) can be used to
predict spontaneity. If ΔS°rxn is positive, the process is spontaneous.

b. Differentiate reversible and irreversible processes and spontaneity as the direction of chemical
reactions.
- Answer: Reversible processes can return to their original state, while irreversible processes cannot.
Spontaneity is the direction of a chemical reaction that proceeds without external influence.
c. How does Le Chatelier's principle apply to changes in pressure, temperature, and concentration on
a system at equilibrium?
- Answer: Le Chatelier's principle states that a system at equilibrium will adjust itself to counteract
changes in pressure, temperature, or concentration. Increasing pressure favors the side with fewer
moles of gas, and temperature and concentration changes lead to shifts that oppose the change.