Chemistry 09-107: Honors Chemistry Carnegie Mellon University

Lecture Notes H-1: Chemical Equilibrium

Proton transfer reactions
Weak affinity for electrons
Half-Reaction Eo(V)
….. …..
Al3+ + 3e- Al -1.66
Mn2+ + 2e- Mn -1.18
2H2O + 2e- H2 (g) + 2 OH- -0.83
Zn2+ + 2e- Zn -0.76
Cr2+ + 2e- Cr -0.74
Fe2+ + 2e- Fe -0.44
Cr3+ + 3e- Cr -0.41
Cd2+ + 2e- Cd -0.40
… …
Cu2+ + e- Cu+ 0.16
…. …
Strong affinity for electrons

Weak affinity for protons

Hydrofluoric acid HF + H2O ⇌ H3O+ + F- Ka = 6.6x10-4 pKa = 3.18

Nitrous acid HNO2 + H2O ⇌ H3O+ + NO2- Ka = 4.6x10-4 pKa = 3.34
Acetyl Salicylic acid C9H8O4 + H2O ⇌ H3O+ + C9H7O4- Ka = 3x10-4 pKa = 3.52
Formic acid HCOOH + H2O ⇌ H3O+ + HCOO- Ka = 1.77x10-4 pKa = 3.75
Acetic acid HAc + H2O ⇌ H3O+ + Ac- Ka = 1.76x10-5 pKa = 4.75
Hydrocyanic acid HCN + H2O ⇌ H3O+ + CN- Ka = 6.17x10-10 pKa = 9.21

Strong affinity for protons

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Chemistry 09-107: Honors Chemistry Carnegie Mellon University

Nature of chemical equilibrium

Progress of reaction coordinate

Chemical equilibrium is dynamic

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 Chemistry 09-107: Honors Chemistry Carnegie Mellon University

LeChatelier’s Principle

Change in concentration

Change in volume (Gasses: change in pressure Solutions: dilution/evaporation)

Change in temperature

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Chemistry 09-107: Honors Chemistry Carnegie Mellon University

Practice problems on LeChatlier's Principle

Consider the reaction:

2 H2S (g) + O2 (g) ↔ 2 S(s) + 2 H2O (g) ΔH = -221.19 kJ/mol

If O2 (g) is added to the reaction vessel, what happens to the amount of S(s)?

a) It increases b) It decreases c) Nothing

If the volume of the vessel is cut in half, what happens to the ratio of PH2O/PH2S?

a) It increases b) It decreases c) Nothing

If the temperature is increased, what happens to the ratio of PH2O/PH2S?

a) It increases b) It decreases c) Nothing

Consider a mixture of NO2 (g) and N2O4 (g) in a sealed vessel. The following reaction is in equilibrium:
2 NO2 (g) ↔ N2O4 (g)
The colors are brown colorless

What happens to the color when NO2 is added to the vessel?

a) deeper brown b) lighter brown c) nothing

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 Chemistry 09-107: Honors Chemistry Carnegie Mellon University
Consider the gaseous equilibrium: H2 (g) + I2 (g) ↔ 2 HI (g)

The sketches below show the pressures, P, of these three gases as a function of time during an experiment. Only
one is real, i.e. is consistent with Le Chatelier’s principle. Which one is it?

The law of mass action, and LeChatlier's principle

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Chemistry 09-107: Honors Chemistry Carnegie Mellon University
Consider the reaction: A2 + B2 ↔ 2AB
The reactants are mixed together and the following is a plot of the reactant and product concentrations with
time:

What is the value of the equilibrium constant?

(A) 1/2 (B) 1 (C) 2 (D) 4

Consider the systems shown to the right:

Assume the following reaction is at equilibrium:

CH4(g) + H2O(g) ↔ CO(g) + 3 H2(g)

A relatively large amount of Ne is introduced into the system,

keeping the temperature constant.

a) Introduction of the Ne forces the equilibrium to the left.

b) Introduction of the Ne forces the equilibrium to the right.
c) Introduction of the Ne has no effect on the position of the equilibrium.
d) Can’t tell from the available information.

For system 2:
CH4(g) + H2O(g) ↔ CO(g) + 3 H2(g)

a) Introduction of the Ne forces the equilibrium to the left.

b) Introduction of the Ne forces the equilibrium to the right.
c) Introduction of the Ne has no effect on the position of the equilibrium.
d) Can’t tell from the available information.

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 Chemistry 09-107: Honors Chemistry Carnegie Mellon University

Heterogenous Equilibrium (a reaction involving more than one phase)

C(s) + CO2(g) ↔ 2CO(g)

Consider the equilibrium expression for the following reaction:

CaCO3(s) ↔ CaO(s) + CO2(g)

Which of the following is true:

a) The ratio of CaO(s) to CaCO3(s) will be the same in all samples of this solid.

b) The vapor pressure of CO2(g) above a mixture of CaCO3(s)/CaO(s) is independent of the

relative amount of these two solids.

c) You need both CaO(s) to CaCO3(s) to produce CO2(g).

Consider the reaction:

2 H2S (g) + O2 (g) ↔ 2 S(s) + 2 H2O (g) ΔH = -221.19 kJ/mol

If the temperature is increased, what happens to the equilibrium constant K?

a) It increases b) It decreases c) Nothing

If S(s) is added to the reaction, what happens to PH2O?

a) It increases b) It decreases c) Nothing

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