CH 16

Study guide

CH 16 Study Guide 2

CH 16.2 · Thermodynamics: Entropy and Gibbs Free Energy

by @mingun09

This document outlines the fundamental concepts of Enthropy, Entropy Change (ΔS), and Gibbs Free Energy Change (ΔG). It covers how to calculate these values and determine reaction spontaneity under various conditions. Students should be prepared to apply the Gibbs Free Energy equation and interpret the signs of ΔH, ΔS, and ΔG to predict spontaneity, especially concerning temperature dependence.

Enthropy

Enthropy measures the degree of randomness of particles within a system.

Concept

Enthropy

A measure of the degree of randomness or disorder of particles within a system.

Key Processes Increasing Entropy (MCQ!!)

Many common processes lead to an increase in entropy, often involving an increase in the number of particles or a change to a more disordered state.

Concept

Decomposition

Entropy increases because a single compound breaks down into more moles of particles, often involving a state change from solid to gas/liquid, which increases disorder.

Concept

Dissolving

Entropy increases due to a state change where a solid disperses into a liquid, leading to a more disordered arrangement of particles.

Concept

Melting

Entropy increases as a substance transitions from a highly ordered solid state to a less ordered liquid state, allowing particles more freedom of movement.

Concept

Combustion

Entropy increases significantly as solid or liquid reactants typically produce gaseous products, increasing the number of moles of gas and overall disorder.

Concept

Boiling/Vaporization

Entropy increases substantially when a liquid changes to a gas, as gas particles have much greater freedom of movement and occupy a larger volume.

Concept

Sublimation

Entropy increases dramatically when a solid directly changes to a gas, bypassing the liquid phase and resulting in a large increase in disorder.

Entropy Change (ΔS)

Entropy Change (ΔS) quantifies the difference in system entropy during a process.

Concept

Entropy Change (ΔS)

The difference in the entropy of a system during a reaction or state change, indicating whether disorder increased or decreased.

Formula

ΔS = ΣS_products - ΣS_reactants

Entropy change equals the sum of the standard entropies of the products minus the sum of the standard entropies of the reactants.

The sign of ΔS indicates the direction of entropy change:

If ΔS > 0, entropy has increased* (more disorder).

If ΔS < 0, entropy has decreased* (less disorder).

Gibbs Free Energy Change (ΔG)

Gibbs Free Energy Change (ΔG) determines reaction spontaneity based on enthalpy, temperature, and entropy.

Concept

Gibbs Free Energy Change (ΔG)

A thermodynamic potential that measures the maximum reversible work that may be performed by a thermodynamic system at a constant temperature (T) and pressure. It determines if a reaction is spontaneous.

Formula

ΔG = ΔH - TΔS

Gibbs Free Energy Change equals Enthalpy Change minus Temperature times Entropy Change.

Spontaneity Condition

A reaction is considered spontaneous in the forward direction if ΔG < 0. If ΔG > 0, the reaction is non-spontaneous. If ΔG = 0, the system is at equilibrium.

Spontaneity based on ΔH and ΔS

ΔH > 0 (Endothermic)ΔH < 0 (Exothermic)
ΔS > 0 (Entropy Increased)ΔG < 0 at high temp (spontaneous)ΔG < 0 (reaction is always spontaneous)
ΔS < 0 (Entropy Decreased)ΔG > 0 (reaction is never spontaneous)ΔG < 0 at low temp (spontaneous)

Spontaneity of NH4Cl Decomposition

  1. 1

    Given Values

    Reaction: NH4Cl(s) → NH3(g) + HCl(g)

    Temperature (T): 298.15 K

    Enthalpy Change (ΔH°): 176 kJ/mol

    Entropy Change (ΔS°): 0.285 kJ/(mol • K)

  2. 2

    Calculate ΔG°

    ΔG° = ΔH° - TΔS°

    ΔG° = 176 kJ/mol - (298.15 K * 0.285 kJ/(mol • K))

    ΔG° = 176 kJ/mol - 84.97275 kJ/mol

  3. 3

    Determine Spontaneity

    Since ΔG° is positive, the reaction is not spontaneous at this temperature.

Answer

ΔG° = 91.0 kJ/mol. The reaction is not spontaneous in the forward direction at 298.15 K.

Temperature for Br2 Vaporization Spontaneity

  1. 1

    Given Values

    Reaction: Br2(l) → Br2(g)

    Enthalpy Change (ΔH°): 31.0 kJ/mol

    Entropy Change (ΔS°): 93.0 J/(mol • K) (convert to kJ: 0.0930 kJ/(mol • K))

  2. 2

    Set up Inequality for Spontaneity

    For spontaneity, ΔG < 0. So, ΔH - TΔS < 0.

    31.0 kJ/mol - T * 0.0930 kJ/(mol • K) < 0

  3. 3

    Solve for T

    31.0 kJ/mol < T * 0.0930 kJ/(mol • K)

    T > (31.0 kJ/mol) / (0.0930 kJ/(mol • K))

Answer

The process Br2(l) → Br2(g) is spontaneous when T > 333K.

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