Ch. 17 - Chemical ThermodynamicsSee all chapters
All Chapters
Ch.1 - Intro to General Chemistry
Ch.2 - Atoms & Elements
Ch.3 - Chemical Reactions
BONUS: Lab Techniques and Procedures
BONUS: Mathematical Operations and Functions
Ch.4 - Chemical Quantities & Aqueous Reactions
Ch.5 - Gases
Ch.6 - Thermochemistry
Ch.7 - Quantum Mechanics
Ch.8 - Periodic Properties of the Elements
Ch.9 - Bonding & Molecular Structure
Ch.10 - Molecular Shapes & Valence Bond Theory
Ch.11 - Liquids, Solids & Intermolecular Forces
Ch.12 - Solutions
Ch.13 - Chemical Kinetics
Ch.14 - Chemical Equilibrium
Ch.15 - Acid and Base Equilibrium
Ch.16 - Aqueous Equilibrium
Ch. 17 - Chemical Thermodynamics
Ch.18 - Electrochemistry
Ch.19 - Nuclear Chemistry
Ch.20 - Organic Chemistry
Ch.22 - Chemistry of the Nonmetals
Ch.23 - Transition Metals and Coordination Compounds
Sections
Spontaneous Reaction
First Law of Thermodynamics
Entropy
Gibbs Free Energy
Additional Sections
Second Law of Thermodynamics
Boltzman Equation

Entropy is the disorder or chaos associated with a system’s inability to convert thermal energy into mechanical work. 

Entropy and Spontaneity

Concept #1: The 2nd and 3rd Laws of Thermodynamics

The 2nd Law of Thermodynamics states systems (chemical reactions) spontaneously move to state of disorder. 

Concept #2: Entropy & Phase Changes

During a phase change as our molecules grow farther apart then entropy will increase. 

During a phase change as our molecules grow closer together then entropy will decrease.

Example #1: Which should have the highest molar entropy at 25oC?

Example #2: Which substance has greater molar entropy. 

Entropy and Phases

When comparing the entropy of different compounds then we must follow a set of guidelines in the following order. 

Example #3: Arrange the following substances in the order of increasing entropy at 25oC. 

Example #4: Containers A and B have two different gases that are allowed to enter Container C. Based on the image of Container C, what is the sign of entropy, ΔS°.

Practice: An ideal gas is allowed to expand at constant temperature. What are the signs of ∆H, ∆S & ∆G.

Whenever a phase change occurs, first determine if bonds are broken or formed to figure out the signs of enthalpy and entropy. Afterwards, determine if the reaction is spontaneous to determine the sign of Gibbs Free energy. 

Example #5: Consider the spontaneous fusion of ice at room temperature. For this process what are the signs for ΔH, ΔS and ΔG?

Practice: Consider the freezing of liquid water at 30°C. For this process what are the signs for ∆H, ∆S, and ∆G?

If bonds are broken then the entropy of a reaction increases, but if bonds are formed then the entropy of a reaction decreases. 

Practice: Predict the sign of ∆S in the system for each of the following processes:

a) Ag+ (aq) + Br - (aq) → AgBr (s)

b) CI2 (g) → 2 CI - (g)

c) CaCO3 (s) → CaO (s) + CO2 (g)

d) Pb (s) at 50°C → Pb (s) at 70°C

Practice: For each of the following reactions state the signs of ∆H (enthalpy) and ∆S (entropy):

a) Fusion of ice.

b) Sublimation of CO2

c) Vaporization of aqueous water.

d) Deposition of chlorine gas.

e) Condensation of water vapor. 


 Entropy and Calculations

The 2nd Law of Thermodynamics states that the entropy of the universe is always increasing and so it must always be greater than zero. 

Concept #3: The Universe & Entropy

The entropy of the universe takes the look at the entropy of our system (the chemical reaction) and of the universe. 

Concept #4: Total Entropy & Spontaneity

If the entropy is greater than zero then we classify the process as spontaneous. 

Concept #5: The Entropy of a Reaction

The entropy, enthalpy and Gibbs Free energy of a reaction is equal to products minus reactants. 

Example #6: The oxidation of iron metal is given by the following reaction: 

Practice: Diethyl ether (C4H10O2, MW = 90.1 g/mol) has a boiling point of 35.6oC and heat of vaporization of 26.7 kJ/mol. What is the change in entropy (in kJ/K) when 3.2 g of diethyl ether at 35.6oC vaporizes at its boiling point?

Concept #6: Trouton's Rule & Boltzmann's Equation