The equilibrium constant (Kc) for this system is 24.0 at 200°C. Suppose that initially only cis-stilbene is present at a concentration of 0.850 mol/L. How do we calculate the concentrations of cis- and trans-stilbene at equilibrium?
Strategy Let x be the equilibrium concentration of trans-stilbene in mol/L 12 Calculating Equilibrium Concentrations Sample application 3: Solution: cis-stilbene ⇄ trans-stilbene Initial (M): 0.850 zero Change (M): -x +x Equilibrium (M): 0.850 –x +x
Equilibrium concentrations are:
[cis-stilbene] = 0.850 – 0.816 = 0.034 M [trans-stilbene] = 0.816 M 13 Calculating Equilibrium Concentrations
Sample application 4:
A mixture of 0.500 mol H2 and 0.500 mol I2 was placed in a 1.00-L stainless-steel flask at 430°C. The equilibrium constant Kc for the reaction: H2(g) + I2(g) ⇄ 2HI(g) is 54.3 at this temperature. Calculate the concentrations of H2, I2, and HI at equilibrium.
Answers: [H2] = 0.107 M [I2] = 0.107 M [HI] = 0.786 M 14 Factors affecting the equilibrium
Le Châtelier’s principle, states that if an external stress is applied to a system
at equilibrium, the system adjusts in such a way that the stress is partially offset as the system reaches a new equilibrium position.
1. Changes in Concentration:
15 Factors affecting the equilibrium
2. Changes in Volume and Pressure:
(Pressure is inversely proportional to volume)
2A(g) ⇄ B(g)
Stress Equilibrium shifting
Volume increases side with most gas moles (left)
Volume decreases side with fewest gas moles (right)
Pressure increases side with fewest gas moles (right)
Pressure decreases side with most gas moles (left) 16
Factors affecting the equilibrium
Sample application 5:
Consider the following equilibrium systems:
(a) 2PbS(s) + 3O2(g) ⇄ 2PbO(s) + 2SO2(g)
(b) PCl5(g) ⇄ PCl3(g) + Cl2(g)
(c) H2(g) + CO2(g) ⇄ H2O(g) + CO(g)
Predict the direction of the net reaction in each case as a result of increasing the pressure (decreasing the volume) on the system at constant temperature. 17 Factors affecting the equilibrium
Sample application 5: Solution: (a) (a) Consider only the gaseous molecules. In the balanced equation, there are 3 moles of gaseous reactants and 2 moles of gaseous products. Therefore, the net reaction will shift toward the products (to the right) when the pressure is increased.
(b) The number of moles of products is 2 and that of reactants is 1; therefore,
the net reaction will shift to the left, toward the reactant.
(c) The number of moles of products is equal to the number of moles of
reactants, so a change in pressure has no effect on the equilibrium.
18 Factors affecting the equilibrium
3. Changes in Temperature:
✓ Exothermic reaction: ΔH <0
A + B ⇄ C + D + heat If Temperature increases shifts left to decrease heat K decreases. If Temperature decreases shifts right to increase heat K increases
✓ Endothermic reaction: ΔH >0
A + B + heat ⇄ C + D If Temperature decreases shifts left to increase heat K decreases. If Temperature increases shifts right to decrease heat K increases
19 Factors affecting the equilibrium
4. Adding catalyst:
A catalyst speeds up the reaction by lowers the
activation energy of the forward reaction and the reverse reaction to the same extent.
Thus, • Catalyst has no effect on K. • Catalyst has no shifting effect on the equilibrium system.
20 Summary of Le chatelier’s Principle
21 Factors affecting the equilibrium
Sample application 6:
22 Factors affecting the equilibrium
Sample application 6: Solution:
a) The reaction is endothermic (ΔH>0). Then, the heating process causes shifting of equilibrium to the right to remove the excess of heat (K increases). N2F4(g) + heat ⇄ 2NF2(g) ΔH >0
b) Some N2F4 is removed at constant temperature and volume. Then, the
equilibrium is shifted to the left side to produce more N2F4 until the equilibrium is established (K constant)
23 Factors affecting the equilibrium
Sample application 9: Solution:
c) Since the pressure is decreased at same temperature. Then, the system
causes shifting of equilibrium to the right to increase the pressure in presence of more gas moles until the equilibrium is reestablished (K constant).
d) Catalyst is added to the reacting mixture to speed up both reactions sides at
the same time. Thus, it does not affect on the equilibrium shifting (K constant).
