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Free Energy

Free energy is a simple way to determine if a reaction is feasible. Free energy includes both entropy and enthalpy.

Feasibility

Feasibility

  • For a reaction to happen, the total entropy of everything involved must increase.
    • This includes its molar entropies, but also the entropy change of the air when it is heated.
    • Instead of calculating the entropies of everything, we can define the Gibbs free energy change as ΔG = ΔH - TΔS.
    • There’s some complex maths, but it boils down to: If ΔG is negative, the overall entropy increases and a reaction will happen.
    • The reaction is said to be feasible.
Temperature dependance

Temperature dependance

  • If a reaction has a negative ΔH and a positive ΔS it will always be feasible.
    • But some reactions are endothermic, or lose entropy.
    • These reactions show a temperature dependence of feasibility.
    • We shall explore this on the next few slides.
Endothermic reactions

Endothermic reactions

  • If a reaction has a positive ΔH, it will only be feasible if the ΔS term is positive and larger than it. You can see a graph above of ΔG vs T for positive ΔH, and positive ΔS.
Reactions with a negative entropy change

Reactions with a negative entropy change

  • Entropy always increases. For a reaction to happen if the standard molar entropies of the reactants decreases, it must heat it's surroundings and cause the entropy of the surroundings to increase.
    • So the reaction must be exothermic.
    • Above is a graph of ΔG vs T for negative ΔH and ΔS.

Free Energy Calculations

You can calculate the temperature at which a reaction becomes feasible.

Feasibility

Feasibility

  • For a reaction to happen, ΔG must be negative.
  • We can calculate the temperature at which a reaction switches from unfeasible to feasible by setting ΔG equal to zero.
  • To find this temperature, we must rearrange the equation for Gibbs free energy:
    • ΔG = ΔH - TΔS becomes 0 = ΔH - TΔS
    • So, T = ΔHΔS\frac{\Delta H}{\Delta S}
Example - bismuth extraction

Example - bismuth extraction

  • A step in the extraction of bismuth from it's ore is the reduction of bismuth hydroxide (Bi(OH)3) by hydrogen according to the equation:
    • 2(Bi(OH)3) + 3H2 → 2Bi + 6H2O
  • If the entropy change is: +400JK-1mol-1 and the enthalpy change is 50kJmol-1, what temperature does it become feasible at?
    • See next slide for solution.
Solution

Solution

  • First, make sure your entropy change and enthalpy change both use Joules.
    • 50kJmol-1 = 50,000Jmol-1
  • Insert this value into the rearranged Gibbs free energy equation to find the temperature at which this reaction is feasible:
    • T = 50,000 ÷ 400 = 125K
    • So, the reaction is feasible at temperatures above 125K.
Jump to other topics
1

Physical Chemistry

1.1

Atoms, Molecules & Stoichiometry

1.2

Atomic Structure

1.3

Chemical Bonding

1.4

States of Matter

1.5

Chemical Energetics

1.6

Electrochemistry

1.7

Equilibria

1.8

Partition Coefficient

1.9

Reaction Kinetics

2

Inorganic Chemistry

3

Organic Chemistry & Analysis

3.1

Introduction to Organic Chemistry

3.2

Hydrocarbons

3.3

Halogen Derivatives

3.4

Hydroxy Compounds

3.5

Carbonyl Compounds

3.6

Carboxylic Acids & Derivatives

3.7

Nitrogen Compounds

3.8

Polymerisation

3.9

Analytical Techniques

3.10

Organic Synthesis

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