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*Revision Materials and Past Papers* 2.1.1 Atomic structure and isotopes 2.1.2 Compounds, formulae and equations 2.1.3 Amount of substance 2.1.4 Acids 2.1.5 Redox 2.2.1 Electron structure 2.2.2 Bonding and structure 3.1.1 Periodicity 3.1.2 Group 2 3.1.3 The halogens 3.1.4 Qualitative analysis 3.2.1 Enthalpy 3.2.2 Reaction Rates 3.2.3 Chemical equilibrium 4.1 Basic concepts and hydrocarbons 4.1.2 Alkanes 4.1.3 Alkenes 4.2.1 Alcohols 4.2.2 Haloalkanes 4.2.3 Organic synthesis 4.2.4 Analytical techniques 5.1.1 How fast? 5.1.2 How far? 5.1.3 Acids, bases and buffers 5.2.1 Lattice enthalpy 5.2.2 Enthalpy and entropy 5.2.3 Redox and electrode potentials 5.3.1 Transition elements 5.3.2 Qualitative analysis 6.1.1 Aromatic compounds 6.1.2 Carbonyl compounds 6.1.3 Carboxylic acids and esters 6.2.1 Amines 6.2.2 Amino acids, amides and chirality 6.2.3 Polyesters and polyamides 6.2.4 Carbon–carbon bond formation 6.2.5 Organic synthesis 6.3.1 Chromatography and qualitative analysis 6.3.2 Spectroscopy Required Practicals

5.2.2 Enthalpy and entropy

Entropy Free energy

Gibbs Free Energy Change

Specification Reference 5.2.2 (d)–(f)

Quick Notes

  • Gibbs Free Energy Change (ΔG) determines whether a reaction is feasible (spontaneous).
  • Equation for Gibbs Free Energy: ΔG = ΔH − TΔS
      where:
    • ΔG = Gibbs Free Energy change (kJ mol⁻¹)
    • ΔH = Enthalpy change (kJ mol⁻¹)
    • T = Temperature (K)
    • ΔS = Entropy change (J K⁻¹ mol⁻¹)
      (converted to kJ K⁻¹ mol⁻¹ by dividing by 1000)
  • A reaction is feasible (can happen) when ΔG < 0 (negative).
    • Endothermic reactions (+ΔH) can still be feasible if entropy change is positive (+ΔS) and temperature is high.
    • Just because a reaction can happen and is feasible doesn’t mean that it will happen - a high activation energy barrier may prevent a feasible reaction from occurring.

Full Notes

Gibbs Free Energy and Reaction Feasibility

Both the enthalpy change (ΔH) and entropy change (ΔS) of a reaction have an impact on whether the reaction can happen. These can be linked, along with temperature (T), by something called Gibbs Free Energy Change (ΔG).

Gibbs Free Energy Change determines whether a reaction can happen spontaneously (is feasible) under standard conditions.

It can be calculated using:

AQA A-Level Chemistry calculating Gibbs Free Energy Change ΔG = ΔH − TΔS with term meanings.

A reaction is feasible if ΔG is negative (ΔG < 0).

Even if ΔG < 0, a reaction may not occur if activation energy is too high.

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Matt’s exam tip

Remember to check and convert units when using this equation! Entropy change (ΔS) is always given in J per K per mol, whereas Enthalpy change (ΔH) and Gibbs Free Energy Change (ΔG) are given in kJ per mol. Convert entropy to kJ K⁻¹ mol⁻¹ (divide by 1000).

Conditions for Reaction Feasibility

Condition Effect on Feasibility
ΔH negative, ΔS positive ΔG is always negative
Reaction is always feasible
ΔH positive, ΔS negative ΔG is always positive
Reaction is never feasible
ΔH negative, ΔS negative Reaction is feasible at low temperatures
ΔH positive, ΔS positive Reaction is feasible at high temperatures

Temperature at Which a Reaction Becomes Feasible

To find the minimum temperature (T) at which a reaction is feasible, we can set ΔG = 0:

(If ΔG has to be zero for a reaction to be feasible, then the temperature when ΔG is zero is the minimum that it can be!)

T = ΔH / ΔS
If T is high, the reaction is only feasible at high temperatures.
If T is low, the reaction is feasible at lower temperatures.

Worked Example

Example Calculation: A reaction has the following enthalpy and entropy changes. Find the minimum temperature, T, at which the reaction is feasible.
ΔH = +50 kJ mol⁻¹
ΔS = +100 J K⁻¹ mol⁻¹ (= +0.100 kJ K⁻¹ mol⁻¹)

Use ΔG = ΔH − TΔS and set ΔG = 0:

0 = ΔH − TΔS
T = ΔH / ΔS
T = 50 / 0.100
T = 500 K
The reaction becomes feasible at T ≥ 500 K.

Summary Table: Effect of Temperature on Feasibility

Condition Effect on Feasibility
ΔH < 0, ΔS > 0 Always feasible (ΔG < 0)
ΔH > 0, ΔS < 0 Never feasible (ΔG > 0)
ΔH < 0, ΔS < 0 Feasible at low temperatures
ΔH > 0, ΔS > 0 Feasible at high temperatures

Why Some Feasible Reactions Don’t Happen

Just because a reaction can happen (ΔG is negative) and is feasible doesn’t mean that it will happen - a high activation energy barrier may prevent a feasible reaction from occurring. The rate of reaction may be so slow that the reaction doesn’t happen fast enough to observe.

For example The conversion of diamond into graphite has a negative ΔG, meaning it is thermodynamically feasible. In theory, this process should happen spontaneously.

Diamond to graphite is thermodynamically feasible but kinetically slow.

However, in reality, the transformation does not occur noticeably because it has a very high activation energy (Ea). This large energy barrier prevents the reaction from proceeding at a measurable rate under standard conditions.

Summary