How Far? The Extent Of Chemical Change

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Notes de leçon

Dynamic Equilibrium

  • In a reversible reaction, products can react to reform the original reactants; shown by the ⇌ symbol.
  • Dynamic equilibrium is reached in a closed system when the rate of the forward reaction equals the rate of the backward reaction.
  • At equilibrium, the concentrations of reactants and products remain constant, but they are not necessarily equal.
  • Macroscopic properties such as colour and density remain constant because they depend on concentration.
  • Equilibrium can be reached starting from either reactants or products.
  • For reactions involving gases, equilibrium can only be reached in a closed system; reactions entirely in solution can reach equilibrium in open flasks.
  • Physical equilibria also exist, e.g. C₂H₅OH(l) ⇌ C₂H₅OH(g) in a sealed bottle.

A reversible reaction at equilibrium

A reversible reaction at equilibrium

The Equilibrium Law and Kc Expression

  • For the general reaction aA + bB ⇌ cC + dD, the equilibrium constant expression is: Kc = [C]c[D]d / [A]a[B]b.
  • Square brackets represent equilibrium concentrations in mol dm⁻³; round brackets are incorrect and lose marks.
  • Solids are ignored in equilibrium constant expressions (e.g. Ag(s) is omitted).
  • The equilibrium constant, Kc, is specific to a given equation and depends on temperature.
  • For the reverse reaction, K' = 1/Kc (the reciprocal).
  • If an equation is multiplied by a factor n, the equilibrium constant is raised to the power n.
  • Example: N₂(g) + 3H₂(g) ⇌ 2NH₃(g) gives Kc = [NH₃]² / ([N₂][H₂]³).

Interpreting the Magnitude of K

  • If K << 1, the reaction hardly proceeds; equilibrium lies far to the left and the mixture contains mostly reactants.
  • If K < 1, the reaction favours the reactants; equilibrium lies to the left.
  • If K = 1, there are significant amounts of both reactants and products; equilibrium is balanced.
  • If K > 1, the reaction favours the products; equilibrium lies to the right.
  • If K >> 1, the reaction goes almost to completion; equilibrium lies far to the right with mostly products present.
  • Stronger acids have a higher K value because they dissociate more, shifting equilibrium towards products.

Le Chatelier's Principle

  • Le Chatelier's principle: if a change is made to a system at dynamic equilibrium, the position of equilibrium moves to minimise the change.
  • The position of equilibrium refers to the relative amounts of products and reactants in the mixture.
  • Changes that can affect equilibrium include temperature, pressure, and concentration.
  • A catalyst increases the rate of both forward and reverse reactions equally; it has no effect on the position of equilibrium or the value of Kc.
  • Concentration changes: increasing a reactant shifts equilibrium right; decreasing a reactant shifts it left; increasing a product shifts it left; decreasing a product shifts it right.
  • Changes in concentration do not change the value of Kc, provided temperature remains constant.

Equilibrium and the Haber process

Equilibrium and the Haber process

Effects of Pressure and Temperature on Equilibrium

  • Pressure changes only affect reactions involving gases; if the number of gas molecules is the same on both sides, pressure has no effect.
  • Increasing pressure shifts equilibrium towards the side with fewer gas molecules to reduce the pressure.
  • Decreasing pressure shifts equilibrium towards the side with more gas molecules to increase the pressure.
  • Changes in pressure do not change the value of Kc.
  • Increasing temperature shifts equilibrium in the endothermic direction (absorbs energy).
  • Decreasing temperature shifts equilibrium in the exothermic direction (releases energy).
  • Temperature changes do change the value of Kc: for an endothermic reaction, Kc increases with increasing temperature; for an exothermic reaction, Kc decreases with increasing temperature.

The Reaction Quotient, Q (HL)

  • The reaction quotient, Q, uses the same expression as Kc but with concentrations that may not be at equilibrium.
  • If Q = Kc, the reaction is at equilibrium and no net reaction occurs.
  • If Q < Kc, the reaction proceeds to the right, favouring products.
  • If Q > Kc, the reaction proceeds to the left, favouring reactants.
  • Q is not a fixed value; it can be measured at any time, whereas Kc is constant at a given temperature.
  • Comparing Q and Kc allows prediction of the direction in which a reaction will shift to reach equilibrium.

Equilibrium Calculations (HL)

  • Concentration is calculated using: concentration (mol dm⁻³) = amount (mol) / volume (dm³).
  • ICE tables (Initial, Change, Equilibrium) are used when initial and equilibrium concentrations of all species are not given.
  • Use the stoichiometric ratios from the balanced equation to determine changes in moles or concentration.
  • For reactions with the same number of concentration terms in numerator and denominator, volume cancels and Kc can be calculated directly from moles.
  • When Kc < 10⁻³, the reaction lies far to the left; assume the equilibrium concentration of reactant ≈ initial concentration.
  • In such cases, state the approximation and justify it because Kc is small.
  • Always give the final answer to the appropriate number of significant figures.

Equilibrium Constant and Gibbs Energy (HL)

  • The equilibrium constant is related to Gibbs energy change by: ΔG° = –RT lnK.
  • R = 8.31 J K⁻¹ mol⁻¹; T is in Kelvin; ΔG° is usually in kJ mol⁻¹ (convert to J mol⁻¹ for calculations).
  • If K > 1, ΔG° < 0 (negative); products are favoured and the reaction is feasible/spontaneous.
  • If K = 1, ΔG° = 0; neither side is favoured.
  • If K < 1, ΔG° > 0 (positive); reactants are favoured.
  • As ΔG° becomes more negative, the forward reaction is favoured more and K increases.
  • The equation can be rearranged to: ln K = –ΔG° / RT, allowing calculation of K from ΔG°.

Diapos

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  1. 1.Which statement correctly describes the concentrations of reactants and products in a system at dynamic equilibrium?

    Easy
    • AThe concentrations of reactants and products are constant.
    • BThe concentrations of reactants and products are equal.
    • CThe concentration of reactants is always greater than that of products.
    • DThe concentrations of reactants and products are zero.
  2. 2.For the reaction N2(g) + 3H2(g) ⇌ 2NH3(g), which is the correct equilibrium constant expression?

    Easy
    • AKc = [NH3]2 / ([N2][H2]3)
    • BKc = ([N2][H2]3) / [NH3]2
    • CKc = [NH3]2 / ([N2] + [H2]3)
    • DKc = [NH3] / ([N2][H2])
  3. 3.For the reaction 2SO2(g) + O2(g) ⇌ 2SO3(g), the equilibrium constant Kc is 0.282 at temperature T. If the reaction quotient Q is calculated to be 0.5, in which direction will the reaction proceed?

    Medium
    • ATo the left, towards reactants.
    • BTo the right, towards products.
    • CThe reaction is already at equilibrium.
    • DThe direction cannot be determined without more information.
  4. 4.For the reaction 2NH3(g) + CO2(g) ⇌ CO(NH2)2(g) + H2O(g), ΔH < 0. What is the effect of increasing the temperature on the equilibrium constant Kc?

    Medium
    • AKc decreases.
    • BKc increases.
    • CKc remains the same.
    • DKc becomes zero.
  5. 5.For the reaction H2(g) + I2(g) ⇌ 2HI(g) with ΔH < 0, what happens to the value of Kc when the temperature is increased from 761 K?

    Medium
    • AKc decreases.
    • BKc increases.
    • CKc remains unchanged.
    • DKc becomes zero.
  6. 6.For the reaction H2(g) + I2(g) ⇌ 2HI(g), the equilibrium constant Kc is 48.52. What is the value of Kc for the reaction ½H2(g) + ½I2(g) ⇌ HI(g) at the same temperature?

    Medium
    • A6.97
    • B48.52
    • C97.04
    • D24.26
  7. 7.What is the effect of adding a catalyst to a reaction at equilibrium?

    Easy
    • AIt increases the rate of both forward and reverse reactions equally, so the position of equilibrium remains unchanged.
    • BIt shifts the equilibrium to the right, increasing the yield of products.
    • CIt shifts the equilibrium to the left, increasing the yield of reactants.
    • DIt increases the value of the equilibrium constant Kc.
  8. 8.For the reaction 2SO3(g) ⇌ 2SO2(g) + O2(g) with ΔH = +196 kJ mol⁻¹, what is the effect on the yield of SO2 if the concentration of SO3 is increased?

    Medium
    • AThe yield of SO2 increases.
    • BThe yield of SO2 decreases.
    • CThe yield of SO2 remains the same.
    • DThe equilibrium shifts to the left.

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