Chapter 13 Chemical Equilibrium

13.1 The Equilibrium Conditions

For a chemical reaction, chemical equilibrium is the state where the concentrations of all
reactants and products remain constant with time.

Characteristics of Chemical Equilibrium:

1.) The system is at chemical equilibrium
2.) The forward and reverse reactions are so slow that the system moves to
equilibrium at a rate that can not be detected.

13.2 The Equilibrium Constant

For a chemical reaction jA + kB-------- lC + mD

By using the law of mass action, the equilibrium constant K is expressed as:

K = [C]l[D]m/([A]j[B]k)

Where the square brackets indicate the concentrations of the chemical species at
equilibrium.

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Examples 13.1-13.2 (p583) Writing Equilibrium Expressions and Calculating the values
of K

Conclusions about the Equilibrium Expression:

1.) The equilibrium expression for a reaction is the reciprocal of that for the reaction
written in reverse.
2.) When the balanced equation for a reaction is multiplied by a factor, n, the
equilibrium expression for the new reaction is the original expression raised to the
nth power. Thus Knew= (Koriginal)n.
3.) K values are customarily written without units.

Example 13.3 (p585-586) Equilibrium positions

13.3 Equilibrium Expressions Involving Pressures

According to ideal gas equation, PV=nRT. Thus gas concentration C= n/V=P/(RT)

For a chemical reaction involves gases, such as N2(g) + 3H2(g) ----- 2NH3(g)

Equilibrium constant K= [NH3]2/([N2] [H2]3) =KC= CNH32/(CN2CH23)

KP= PNH32/(PN2PH23)

Where CNH3, CN2, and CH23 are the equilibrium concentration, respectively; PNH3, PN2, and PH2
are the equilibrium partial pressure, respectively.

Relationship Between KC and KP

jA + kB-------- lC + mD

Kc =K= Ccl CDm/(CAjCBk) = PClPDm/(PAjPBk) *(RT)(j+k)-(l+m) = Kp (RT)(j+k)-(l+m)

Thus KP = K (RT)(l+m)-(j+k)

Example 13.5 (P588) Calculating K from KP

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13.4 Heterogeneous Equilibria

Homogeneous equilibria: All the reactants and products are gases

Heterogeneous Equilibria: the reactants and products have more than one phase.

If pure solids or pure liquids are involved in a chemical reaction, their concentrations are
not included in the equilibrium expression.

For example CaCO3(s) ----- CaO (g) + CO2 (g)

K’ = CCO2 CCaO/CCaCO3 = K CCaO/CCaCO3

Thus K = CCO2

Example 13.6 (p590) Equilibrium Expressions for Heterogeneous Equilibria

13.5 Applications of the Equilibrium Constants

1.) To determine the direction of reaction (forward or reverse)

2.) Calculate equilibrium pressures and concentrations

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 1.) Reaction Quotient Q

For reaction N2(g) + 3H2(g) ----- 2NH3(g)

Q = [NH3]02/([N2]0 [H2]03)

Where the subscript zeros indicate initial concentrations

By comparing Q and K, there are 3 possible cases

1.) Q=K, the system is at equilibrium; no shift will occur.

2.) Q > K, a shift to left (products to reactants) will occur until equilibrium is
achieved.
3.) Q < K, a shift to right (reactants to products) will occur until equilibrium is
achieved.

Example 13.7 (p593-594) Using the reaction quotient

2.) Calculate Equilibrium Pressures and Concentrations

By giving the equilibrium constant K or Kp, one can find the equilibrium pressures or
concentrations using the equilibrium expression.

Examples 13.8-13.11 (p594-599) Calculating equilibrium pressures and concentrations

13.6 Solving Equilibrium Problems

Procedures for Solving Equilibrium Problems

1.) Write the balanced equation for the reaction

2.) Write the equilibrium expression using the law of mass action
3.) List the initial concentrations
4.) Calculate the Q and determine the direction of the shift to equilibrium
5.) Define the change needed to achieve equilibrium and define the equilibrium
concentration by applying the change to the initial concentrations
6.) Substitute the equilibrium concentration into the equilibrium expression and solve
the unknown.

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 7.) Check your calculated equilibrium concentrations by making sure they give the
correct value of K.

Example 13.2 (p601-602) Calculating equilibrium pressures

13.7 Le Chatelier’s Preinciples

La Chatelier’s principle: If a change is imposed on a system at equilibrium, the position

of the equilibrium will shift in a direction that tends to reduce the change.

Factors affect the equilibrium of reaction

1.) Effect of a change in concentration
2.) Effect of a change in pressure
3.) Effect of a change in temperature

Kc is related to ∆G0 for a reaction

∆G0 = -RT lnK

Examples 13.13-15 (p606-610)Using La Chatelier’s Principle