CHEMICAL EQUILIBRIA

Part 1
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
• the concentrations of the reactants and products remain
constant

Physical equilibrium

H2O (l) H2O (g)

NO2
Chemical equilibrium
N2O4 (g) 2NO2 (g)

2
Basic Concepts
• Chemical equilibrium exists when two opposing
reactions occur simultaneously at the same rate.
• A chemical equilibrium is a reversible reaction that the
forward reaction rate is equal to the reverse reaction
rate.
• Chemical equilibria are dynamic equilibria.
• Molecules are continually reacting, even though the
overall composition of the reaction mixture does not
change.
Equilibrium is Dynamic
Reactants convert to products
aA+bB cC+dD
BUT, products can also react to make reactants.

Equilibrium occurs when [A], [B], [C] and [D] stop changing - a dynamic equilibrium:

▪ Species do not stop forming OR being destroyed

▪ Rate of formation = rate of removal
▪ Concentrations are constant.
 N2O4 (g) 2NO2 (g)

equilibrium equilibrium

equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4

5
 The Equilibrium Constant
For a general reaction: kf ratef = kf [A][B]2
A + 2B AB2 rater = kr [AB2]
kr

Equilibrium
ratef = rater

kf [A][B]2 = kr [AB2] Products raised to

stoichiometric
powers…

kf [AB2]
= Kc =
kr [A][B]2
…divided by reactants raised to
their stoichiometric powers
Equilibria Involving Pure Liquids and Solids
[Solid] is constant throughout a reaction.
density g/L
• pure solid concentration =
mol. wt g / mol

• [S8] = dS8 / mol. wt S8

• d and mol. wt. are constants, so [S8] is constant.
• This constant factor is “absorbed” into Kc.

Pure liquids are omitted for the same reason.

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

8
Examples
Provide the equilibrium constant expression of the
following:

N2(g) + O2(g) 2 NO(g)

I2(g) + H2(g) 2 HI(g)

1
8
S8(s) + O2(g) SO2(g)

SiH4(g) + 2 O2(g) SiO2(s) + 2 H2O(g)

2 NaOH(aq) + H2SO4(aq) Na2SO4(aq) + 2 H2O(l)

Equilibrium Constants in Terms of Pressure
For a gas-phase reaction:
aA+bB cC+dD

“p” for pressure PCc PDd

based Kp = PAa PBb

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)
Examples
1. Consider: 2 A (aq) B (aq)
At equilibrium [A] = 2.0 M & [B] = 4.0 M. What is Kc?
Answer: 1.0

2. Calculate Kp from Kc for the reaction:

N2(g) + 3 H2(g) 2 NH3(g) Kc = 5.8 x 105 at 25°C.
Answer: Kp = 9.7 x 102 atm-2
3. One liter of equilibrium mixture from the following system at
a high temperature was found to contain 0.172 mole of
phosphorus trichloride, 0.086 mole of chlorine, and 0.028 mole
of phosphorus pentachloride. Calculate Kc for the reaction.
PCl5(g) PCl3(g)+ Cl2(g) Answer: Kc = 0.53
… In other cases stoichiometry is used to find some concentrations.
4. H2(g) and I2(g) were added to a heated container. [H2]initial =
0.0100 mol/L and [I2]initial = 0.00800 mol/L. At equilibrium [I2] =
0.00560 mol/L. Determine Kc.
H2(g) + I2(g) 2 HI(g) Kc = 0.541
5. The decomposition of PCl5 was studied at another temperature. One mole of
PCl5 was introduced into an evacuated 1.00 liter container. The system was
allowed to reach equilibrium at the new temperature. At equilibrium 0.60 mole
of PCl3 was present in the container. Calculate the equilibrium constant at this
temperature.
PCl5(g) PCl3(g)+ Cl2(g) Kc = 0.90
Meaning of the Equilibrium Constant
When:
Kc >> 1 Reaction is strongly product favored.
• very little reactant remains
• often written as a forward reaction only.
• assume reaction goes to completion.
Kc << 1 Reaction is strongly reactant favored.
• very little product forms
• usually written as “no reaction” or NR
Kc ≈ 1 Reactants & products present at equilibrium.
• use equilibrium methods discussed here.
 [C]c[D]d
K= aA + bB cC + dD
[A]a[B]b

Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants

16
 Kc for a Reaction that Combines Reactions
If a reaction can be written as a series of steps:

step 1 [NO]2
N2(g) + O2(g) 2NO(g) Kc =
[N2][O2]

step 2 [NO2]2
2 NO(g) + O2(g) 2 NO2(g) Kc =
[NO]2[O2]

overall [NO2]2
N2(g) + 2 O2(g) 2 NO2(g) Kc =
[N2][O2]2

The overall Kc is the product of the steps:

2 2 [NO ] 2
Kc(step1) x Kc(step2) = [NO] [NO2 ] 2
=
[N2][O2] [NO]2[O2] [N2][O2]2
Kc for a Reaction

If a reaction can be written as:

[NO]2
N2(g) + O2(g) 2NO(g) Kc =
[N2][O2]
When
1
2NO(g) N2(g) + O2(g) Kc ‘ =
Kc
12
4NO(g) 2N2(g) + 2O2(g) Kc “ =
(Kc)2
Manipulating K in Chemical Equations
 Predicting the Direction of a Reaction
The reaction quotient, Q can be used to predict the
direction of a reaction:
• Q will help us predict how the equilibrium will respond to an
applied stress.
• To make this prediction we compare Q with Kc.

For the reaction: aA + bB cC + dD

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

Q looks identical to Kc, BUT… the concentrations are not equilibrium values.
(Kc = Q whenever a system is at equilibrium)
 Predicting the Direction of a Reaction
Reactants Products

[Products]0 [Products]equilib
Qc =[Reactants] Kc= [Reactants]
0 equilib

Kc is a constant (only changes if T changes). So:

If Q < Kc, Q must increase to reach equilibrium.
• make more product (and less reactant).
• move forward.

If Q > Kc, Q must decrease to reach equilibrium.

• make less product (and more reactant).
• move back.
Predicting the Direction of a Reaction
Example:
2 SO2(g) + O2(g) 2 SO3(g) Kc = 245 at 1000 K
Predict the direction of the reaction if SO2 (0.085 M), O2
(0.100 M) and SO3 (0.250 M) are mixed in a reactor at
1000 K.

[ SO3]2 (0.250)2
Q = [SO ]2[O ] = (0.085)2(0.100) = 86.5
2 2

Q < Kc, Q must increase to reach equilibrium.

• Need more product (less reactant).
• Forward direction
End of Part 1 Discussion in
Chemical Equilibria