Entropy & Spontaneity
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Entropy and Dispersal of Energy
- Entropy, S, is a measure of the distribution of matter and/or energy in a system.
- It tells us how many possible ways the particles and their energy can be arranged.
- A more disordered system has higher entropy and is usually more energetically stable.
- The driving force behind reactions cannot be explained by enthalpy changes alone; entropy explains why endothermic reactions occur.
- Under the same conditions, entropy increases in the order: solid < liquid < gas.
Predicting Entropy Changes
- Entropy increases when a gas is formed or when a solid becomes a liquid or gas.
- Entropy decreases when a gas is used up or when a gas becomes a liquid or solid.
- Particles becoming more mobile or disordered leads to an increase in entropy.
- For example, in CaCO₃(s) → CaO(s) + CO₂(g), a gas is formed, so entropy increases.
- Melting ice: H₂O(s) → H₂O(l) increases entropy because molecules become more disordered.
Calculating Standard Entropy Changes
- The standard molar entropy, S⦵, refers to substances in their standard states at 298.15 K and 100 kPa.
- The entropy change of a reaction is calculated using: ΔS⦵ = ΣS⦵(products) – ΣS⦵(reactants).
- The units of ΔS⦵ are J K⁻¹ mol⁻¹.
- Coefficients from the balanced equation must be applied when calculating ΔS⦵.
- Standard entropy values are found in Section 13 of the IB Chemistry data booklet.
- A negative ΔS⦵ means the system becomes more ordered.
Gibbs Free Energy
- The feasibility of a reaction is determined by both enthalpy change and entropy change.
- These combine in the Gibbs equation: ΔG = ΔH – TΔS.
- ΔG is in kJ mol⁻¹, ΔH in kJ mol⁻¹, T in K, and ΔS must be converted to kJ K⁻¹ mol⁻¹ by dividing by 1000.
- ΔG can be calculated from ΔH and ΔS values or from standard Gibbs free energies of formation: ΔG⦵ = ΣΔG⦵f(products) – ΣΔG⦵f(reactants).
- A negative ΔG means the reaction is spontaneous under standard conditions.
Spontaneous Reactions
- For a reaction to be spontaneous, ΔG must be negative (ΔG ≤ 0).
- When ΔG is positive, the reaction is not spontaneous and unlikely to occur.
- Spontaneity depends on the signs of ΔH and ΔS and on temperature.
- Exothermic (ΔH < 0) with positive ΔS: always spontaneous regardless of temperature.
- Endothermic (ΔH > 0) with negative ΔS: never spontaneous regardless of temperature.
- Exothermic with negative ΔS: spontaneous only at low temperatures (TΔS < ΔH).
- Endothermic with positive ΔS: spontaneous only at high temperatures (TΔS > ΔH).
Temperature and Spontaneity
- The temperature at which a non-spontaneous reaction becomes feasible can be found by setting ΔG = 0.
- Rearranging the Gibbs equation gives T = ΔH⦵ / ΔS⦵.
- At this temperature, the reaction is at the boundary between spontaneous and non-spontaneous.
- For example, the reduction of Al₂O₃ with carbon becomes spontaneous at about 2299 K.
Gibbs Free Energy and Equilibrium
- When a reversible reaction reaches equilibrium, Gibbs free energy is at its lowest.
- As products increase, Gibbs free energy decreases until equilibrium is reached.
- At equilibrium, ΔG = 0 and the reaction is spontaneous in the direction that decreases free energy.
- The standard Gibbs free energy change is related to the equilibrium constant by ΔG⦵ = –RT ln K.
- R = 8.31 J K⁻¹ mol⁻¹, T in K, and ΔG⦵ in J mol⁻¹ when using this equation.
- If K > 1, products are favoured; if K < 1, reactants are favoured.
Reaction Quotient and Gibbs Free Energy
- The reaction quotient, Q, is calculated like the equilibrium constant but with non-equilibrium concentrations.
- The relationship between ΔG and Q is ΔG = ΔG⦵ + RT ln Q.
- At equilibrium, Q = K and ΔG = 0, so ΔG⦵ = –RT ln K.
- The size of Q indicates how far a reaction is from equilibrium and in which direction it proceeds.
- These equations are given in Section 1 of the IB Chemistry data booklet.
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1.Which statement best defines entropy?
Easy- AA measure of the distribution of matter and/or energy in a system
- BThe total heat content of a system at constant pressure
- CThe energy available to do useful work
- DThe minimum energy required for a reaction to occur
2.For a given substance, entropy increases when its solid form melts into a liquid.
EasyTrue or false?
3.Under the same conditions, in which order does entropy increase?
Easy- Asolid < liquid < gas
- Bgas < liquid < solid
- Cliquid < solid < gas
- Dsolid < gas < liquid
4.Which of the following changes results in a decrease in entropy?
Easy- AH2O(l) → H2O(g)
- BCl2(g) → Cl2(l)
- CCaCO3(s) → CaO(s) + CO2(g)
- DMelting ice to form liquid water
5.Which of the following changes are accompanied by an increase in entropy? (select all that apply)
Medium- AH2O(l) → H2O(g)
- BCl2(g) → Cl2(l)
- CCaCO3(s) → CaO(s) + CO2(g)
- DN2(g) + 3H2(g) ⇌ 2NH3(g)
- EH2O(s) → H2O(l)
6.Which equation links Gibbs free energy, enthalpy and entropy?
Medium- AΔG = ΔH − TΔS
- BΔG = ΔH + TΔS
- CΔG = ΔS − TΔH
- DΔG = TΔH − ΔS
7.A reaction has ΔH = +135 kJ mol−1 and ΔS = +344 J K−1 mol−1. What is the free energy change at 298 K?
Medium- A+32.5 kJ mol−1
- B−32.5 kJ mol−1
- C+237 kJ mol−1
- D−102 kJ mol−1
8.For the reaction CO(g) + H2O(g) → CO2(g) + H2(g), ΔH = −41.4 kJ mol−1 and ΔS = −135 J K−1 mol−1. What is ΔG at 700 K?
Medium- A+53.1 kJ mol−1
- B−53.1 kJ mol−1
- C+94.5 kJ mol−1
- D−94.5 kJ mol−1
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