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4.2Unit 4. Rates, Equilibria and Further Organic Chemistry

Entropy — IAL Edexcel Linear (Chemistry) Revision Notes & Topical Questions

5 min read 13 parts Lesson 2 of 56 1 quiz

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4.2 Entropy — disorder, entropy changes, total entropy and feasibility — IAL EDEXCEL LINEAR (CHEMISTRY) notes: Explain entropy in terms of arrangements of particles and energy, calculate system, surroundings and total entropy changes, and use them to judge feasibility and kinetic…

  • Entropy, S
  • Melting increases entropy
  • Boiling increases entropy greatly
  • Condensing and freezing decrease entropy
  • Second law
  • Entropy (S)

Part 1 of 11Why entropy is needed

Enthalpy change alone cannot explain why endothermic reactions occur, because the products end in a higher-energy state.
Entropy, S
  • Entropy, S a measure of the number of possible arrangements of the particles and their energy in a system;
    • in effect, how disordered the system is.
An increase in entropy makes a system energetically more favourable, because its energy is more spread out.
Units
  • J K−1 mol−1.

Part 2 of 11Arrangements of particles and energy

1
Distribution of molecules
  • Five molecules that can be in either of two jars have W = 25 = 32 arrangements; 100 molecules have 2100.
  • The number of arrangements rises rapidly with the number of particles.
  • S = k ln W, where k is the Boltzmann constant.
2
Distribution of energy
  • Energy exists in packets called quanta, shared among particles.
  • More quanta or more particles give more ways of arranging the energy, so entropy increases with temperature.
3
Diffusion and spreading of heat both increase entropy.
4
A perfect crystal at 0 K has S = 0; elements have non-zero standard entropies, unlike ΔfH.

Part 3 of 11Entropy and changes of state

1Melting increases entropy
  • Melting increases entropy particles in a regular lattice become a more random arrangement and can slide past one another.
2Boiling increases entropy greatly
  • Boiling increases entropy greatly gas particles move freely and are far apart.
3Condensing and freezing decrease entropy
  • Condensing and freezing decrease entropy particles become more ordered, so there are fewer ways to arrange the energy.
4
Order of entropy: solid < liquid < gas.
5
Entropy rises when temperature is raised because particles become more disordered.
6
Complex molecules have higher entropy than simple ones.

Part 4 of 11Reactions and dissolving

1
Producing a gas increases entropy.
  • CaCO3(s) → CaO(s) + CO2(g) forms a gas from a solid.
  • (NH4)2CO3 reacting with ethanoic acid forms a solution and CO2, so entropy rises although the reaction is endothermic.
2
Dissolving ammonium nitrate is endothermic (ΔsolH = +25.7 kJ mol−1) but the ions are free to move, so entropy increases.
  • For ionic solids, breaking the lattice raises disorder while solvent bonding lowers it, so the sign of ΔH is hard to predict.
3
Two solids reacting, e.g. Ba(OH)2·8H2O with NH4Cl, form NH3 gas and a liquid, so entropy rises even though the reaction is endothermic.
4
When two solids react, the entropy change depends on the physical states of the products.

Part 5 of 11Entropy change of the system

1
ΔSsystem = ΣS⦵(products) − ΣS⦵(reactants).
2
Multiply each S⦵ by its balancing number and use data-book values, which are never zero for elements.
3
Entropy changes are much smaller than enthalpy changes, so they are quoted in J K−1 mol−1.
4
An increase in the number of moles of gas almost always gives a positive ΔSsystem.
ChangeSign of ΔS systemReason
Solid to liquid to gasPositiveParticles more free to move
More moles of gas formedPositiveMore possible arrangements
Dissolving a solidUsually positiveIons spread through solvent
Gas to solidNegativeParticles become ordered
Increase in temperaturePositiveMore energy quanta to distribute

Part 6 of 11Entropy change of the surroundings

Entropy change of the surroundings
ΔSsurroundings = −ΔH ÷ T, with T in kelvin and ΔH converted from kJ mol−1 to J mol−1 (× 1000).
An exothermic reaction passes energy to the surroundings, so ΔSsurroundings is positive.
The same amount of energy transferred to cooler surroundings gives a larger entropy change than to hotter ones.

Part 7 of 11Total entropy and feasibility

ΔStotal = ΔSsystem + ΔSsurroundings.
Second law
  • Second law in any spontaneous change the total entropy increases, so a reaction is feasible if ΔStotal > 0.
ΔStotal is positive when:
  • both ΔSsystem and ΔSsurroundings are positive,
  • ΔSsurroundings is positive and ΔSsystem is negative, but ΔSsurroundings is larger,
  • ΔSsurroundings is negative and ΔSsystem is positive, but ΔSsystem is larger.
Na + Cl2 → NaCl has negative ΔSsystem but a large exothermic ΔSsurroundings, so it is feasible.
Ethanoic acid with ammonium carbonate is endothermic, but a gas forms, so ΔSsystem outweighs ΔSsurroundings.
ΔHΔS systemFeasible?
NegativePositiveAt all temperatures
PositiveNegativeNever
NegativeNegativeOnly at low temperature
PositivePositiveOnly at high temperature

Part 8 of 11Gibbs energy and the temperature of feasibility

1
ΔG = ΔH − TΔSsystem, with ΔS in kJ K−1 mol−1; a reaction is feasible when ΔG ≤ 0.
2
Exothermic with positive ΔS is feasible at all temperatures; endothermic with negative ΔS is never feasible.
3
Endothermic with positive ΔS becomes feasible at high temperature, e.g. metal extraction in the blast furnace at about 1500 °C.
  • The minimum temperature is where ΔG = 0: T = ΔH ÷ ΔSsystem.
4
ΔStotal = R ln K links entropy to the equilibrium constant: a large positive value gives a large K.

Part 9 of 11Thermodynamic and kinetic stability

Thermodynamic and kinetic stability
Thermodynamic feasibility says whether a reaction can happen, not how fast.
A reaction with a high activation energy is kinetically stable and may not occur at room temperature.
  • Methane and oxygen do not react until ignited.
  • H2O2 → H2O + ½O2 is feasible but needs MnO2, which gives a lower Ea route.
  • Diamond to graphite is feasible but extremely slow.
ΔH and ΔS vary slightly with temperature, and non-standard conditions change the values.

Part 10 of 11More from the specification

  • Substance
    • A material with only one type of particle.

Part 11 of 11More on this topic

More on this topic
Temperature has the largest effect.
  • A much larger fraction of molecules exceeds the activation energy, shown as the area beyond Ea on a Maxwell-Boltzmann curve.
Higher pressure favours the side with fewer gas molecules.
Higher temperature favours the endothermic direction.

Key terms

TermMeaning
Entropy (S)A measure of the number of ways particles and their energy can be arranged, in J K−1 mol−1.
Standard molar entropyThe entropy of one mole of a substance under standard conditions.
Entropy change of surroundingsΔS surroundings = −ΔH/T.
Total entropy changeΔS total = ΔS system + ΔS surroundings.
Feasible reactionA reaction with a positive total entropy change (ΔG ≤ 0).
Gibbs energy changeΔG = ΔH − TΔS system; feasible when ΔG ≤ 0.
Kinetic stabilityA feasible reaction that does not occur at a noticeable rate because of a high activation energy.

Avoid these mistakes

1
Giving ΔS in kJ — use J K−1 mol−1 and convert ΔH to J mol−1 before ΔS surroundings = −ΔH/T.
2
Using the wrong sign in ΔS surroundings — it is −ΔH/T.
3
Assuming elements have zero standard entropy — only ΔfH of elements is zero.
4
Assuming a feasible reaction is fast — a high activation energy can make it very slow.
5
Saying a decrease in system entropy means no reaction — the surroundings may compensate.

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