Chemical Equilibrium

The Concept of Equilibrium

Equilibrium State
Requirement Variety
Physical equilibrium H2O (l) H2O (g)

Chemical equilibrium N2O4 (g) 2NO2 (g)

Depicting Equilibrium
In a system at equilibrium, both the forward and reverse reactions are being carried out; as a result, we write its equation with a double arrow
N2O4 (g) 2 NO2 (g)

N2O4(g)

2NO2(g)

Start with NO2

Start with N2O4

Start with NO2 & N2O4

Equilibrium is a state in which there are no observable changes as time goes by. Chemical equilibrium is achieved when: the rates of the forward and reverse reactions are equal and they are not zero.

the concentrations of the reactants and products remain constant

The Equilibrium Constant

The Equilibrium Constant

Forward reaction:
N2O4 (g) 2 NO2 (g)

Rate law:
Rate = kf [N2O4]

The Equilibrium Constant

Reverse reaction:
2 NO2 (g) N2O4 (g)

Rate law:
Rate = kr [NO2]2

The Equilibrium Constant

Therefore, at equilibrium Ratef = Rater kf [N2O4] = kr [NO2]2 Rewriting this, it becomes

kf kr

[NO2]2 = [N2O4]

The Equilibrium Constant

The ratio of the rate constants is a constant at that temperature, and the expression becomes

kf Keq = kr

[NO2]2 = [N2O4]

The Equilibrium Constant

To generalize this expression, consider the reaction

aA + bB

cC + dD

The equilibrium expression for this reaction would be

[C]c[D]d Kc = [A]a[B]b

Homogenous equilibrium applies to reactions in which all reacting species are in the same phase. N2O4 (g) Kc = [NO2 ]2 2NO2 (g)

[N2O4] Kc Kp

Kp =
In most cases

2 PNO 2

P N2O4

aA (g) + bB (g)

cC (g) + dD (g)

Kp = Kc(RT)Dn Dn = moles of gaseous products moles of gaseous reactants = (c + d) (a + b)

Heterogenous equilibrium applies to reactions in which reactants and products are in different phases.

CaCO3 (s)
[CaO][CO2] Kc = [CaCO ] 3

CaO (s) + CO2 (g)

[CaCO3] = constant [CaO] = constant Kp = PCO2

[CaCO3] Kc = [CO2] = Kc x [CaO]

The concentration of solids and pure liquids are not included in the expression for the equilibrium constant.

CaCO3 (s)

CaO (s) + CO2 (g)

PCO 2 = Kp
PCO 2 does not depend on the amount of CaCO3 or CaO

What Does the Value of K Mean?

If K >> 1, the reaction is product-favored; product predominates at equilibrium.

What Does the Value of K Mean?

If K >> 1, the reaction is product-favored; product predominates at equilibrium.

If K << 1, the reaction is reactant-favored; reactant predominates at equilibrium.

The equilibrium concentrations for the reaction between carbon monoxide and molecular chlorine to form COCl2 (g) at 740C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M. Calculate the equilibrium constants Kc and Kp.

A closed system initially containing 1.000 x 103 M H2 and 2.000 x 103 M I2 At 448C is allowed to reach equilibrium. Analysis of the equilibrium mixture shows that the concentration of HI is 1.87 x 103 M. Calculate Kc at 448C for the reaction taking place, which is
At 12800C the equilibrium constant (Kc) for the reaction

Br2 (g)

2Br (g)

Is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063 M and [Br] = 0.012 M, calculate the concentrations of these species at equilibrium.

The Reaction Quotient (Q)

To calculate Q, one substitutes the initial concentrations on reactants and products into the equilibrium expression. Q gives the same ratio the equilibrium expression gives, but for a system that is not at equilibrium.

If Q = K, the system is at equilibrium.

If Q > K, there is too much product and the equilibrium shifts to the left.

If Q < K, there is too much reactant, and the equilibrium shifts to the right.