4.3.3

Free Energy

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Free Energy

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

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Thermodynamic favorability

  • 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 thermodynamically favorable.
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Standard Gibbs free energy change

  • The standard Gibbs free energy change is represented with the symbol ΔG°.
  • With ΔG°, all substances are pure, gases are at a pressure of 1 bar, and solutions are at a concentration of 1M.
  • The symbol "°" is used to represent reactions occuring under standard conditions.
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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.
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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.
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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.
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Free Energy Calculations

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

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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 = ΔHoΔSo\frac{\Delta H^o}{\Delta S^o}
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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.
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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

1Structure - Models of the Particulate of Matter

2Structure - Models of Bonding & Structure

3Structure - Classification of Matter

3.1The Periodic Table: Classification of Elements

3.2Periodic Trends

3.3Group 1 Alkali Metals

3.4Halogens

3.5Noble gases, group 18

3.6Functional Groups: Classification of Organic

3.7Functional Group Chemistry

3.8Alkanes

3.9Alcohols

3.10Halogenoalkanes

4Reactivity - What Drives Chemical Reaction?

5Reactivity - How Much, How Fast & How Far?

6Reactivity - The Mechanisms of Chemical Change

7Measurement, Data Processing & Analysis

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