CFR 13: Chemical Equilibria and Physiological Consequences

Chemical Equilibria and Physiological Consequences

Learning Outcomes

  • Define chemical equilibrium.
  • Write equilibrium constant expressions (K) for reactions involving solids, liquids, and gases for both forward and reverse reactions.
  • Understand the implications of K values:
  • K << 1 indicates reactants are favored.
  • K >> 1 indicates products are favored.
  • Given a balanced chemical equation, determine the value of K using equilibrium concentrations of reactants and products.
  • Given initial concentrations of reactants, find equilibrium concentrations using K.
  • State Le Chatelier’s principle and apply it in various scenarios affecting equilibrium:
  • Changes in concentrations,
  • Temperature adjustments,
  • Pressure or volume changes,
  • Addition of catalysts.
  • Relate to the bicarbonate blood buffer system in terms of response to hypoventilation or hyperventilation and blood acidity.
  • Discuss hemoglobin and oxygen equilibria related to altitude sickness.

Equilibrium Concepts

  • Reversible Reactions: Reactions that can proceed in both directions.
  • Dynamic Equilibrium: State achieved when the rates of the forward and reverse reactions are equal, despite ongoing reactions.
  • Physical Equilibrium: Example: Liquid water and vapor reaching equilibrium in a closed system.

Chemical Equilibrium

  • Occurs when forward and reverse reaction rates are equal, leading to constant concentrations of reactants and products:
  • Example: N2O4 (g) ⇌ 2NO2 (g)
  • Concentrations remain steady irrespective of changes in the system until disturbed.

Equilibrium Constant Expressions (K)

  • General Formula:
    [ K_{eq} = \frac{[products]}{[reactants]}]
  • For a chemical reaction:
  • aA + bB ⇌ gG + hH
    --> [ K_{eq} = \frac{[G]^g[H]^h}{[A]^a[B]^b} ]
  • Values of K are specific to temperature and reaction type.

Special Considerations for Equilibrium Constants

  • Inclusion of Phases:
  • Gases: Include partial pressures in Kp expressions.
  • Solids/Pure Liquids: Concentrations can be omitted from equilibrium expressions as they remain constant.

Analyzing K Values

  • K >> 1: Reaction favors formation of products.
  • Example: 2 H2(g) + O2(g) → 2 H2O(g)
  • K << 1: Reaction favors formation of reactants.
  • Example: CH3CO2H(aq) + H2O(l) ⇌ CH3COO⁻(aq) + H3O⁺(aq)

Solving Equilibrium Problems

  • Two main approaches:
  1. Determine K from equilibrium concentrations.
  2. Calculate equilibrium concentrations from initial concentrations using K.
Example Problems
  • Finding K:
  • Given equilibrium concentrations from a balanced chemical equation, calculate K.
  • Example: Given H2(g) + I2(g) ⇌ 2 HI(g) and concentrations, find K.
  • Using K to find equilibrium concentrations:
  • Example: For PCl3(g) + Cl2(g) ⇌ PCl5(g), with initial moles in a vessel, calculate Kc.

Le Chatelier’s Principle

  • If a stress is applied to a system at equilibrium, the system adjusts to counteract that stress:
  • Concentration Changes:
    • Increasing reactants shifts toward products;
    • Decreasing reactants shifts toward reactants.
  • Temperature Changes: Treat heat as a reactant/product:
    • For exothermic reactions, increase in temperature shifts toward reactants.
  • Pressure/Volume Changes:
    • Increasing pressure shifts towards the side with fewer gas moles.

Bicarbonate Blood Buffer System

  • CO2 + H2O ⇌ H+ + H2CO3 + HCO3⁻
  • Changes in pH during exercise affect this equilibrium.
  • Hypoventilation vs. hyperventilation effects on this system.

Altitude Sickness and Hemoglobin

  • At higher altitudes, lower O2 pressure results in hypoxia:
  • Hb + 4O2 ⇌ Hb(O2)4
  • The equilibrium shifts to respond to reduced available O2.

Haber Process for Ammonia Production

  • To optimize NH3 yield:
  1. Continuously remove NH3 as it forms.
  2. Keep reactant concentrations high.
  3. Increase pressure to shift equilibrium right.
  4. Lower temperature where possible favors the exothermic reaction.

Conclusion

  • Understanding chemical equilibria and Le Chatelier’s principle is crucial for predicting system responses to external changes, particularly in physiological systems like blood buffering and respiratory health.