Chem@HC

Secondary 4 Chemistry Olympiad

Name: ______________________ Class: Sec 4_____ Date: ________

Equilibrium
The Reaction Quotient

A general chemical equation will look like:

y1Y1 + y 2 Y2 + + y m Ym z1Z1 + z2 Z2 + + zn Zn ,

where the y i’s and the z j ’s refer to stoichiometric coefficients, while the Yi ’s and Z j ’s refer to
chemical species.

For any species Y , and at any point in the reaction, we define its activity, denoted a(Y), to
be:
−3
• the numerical value of its molar concentration (in mol dm ), if Y is a solute in a
liquid solvent (usually water);
• the numerical value of its partial pressure (in bar), if Y is a gas;
• unity, if Y is a solid or liquid.

For the general chemical reaction above, we define the reaction quotient Q as:

a(Z1 )  a(Z2 )
z1 z2 zn
a(Zn )
Q= .
a( Y1 )  a(Y2 )
y 1 y 2 y
m
a(Ym )

The heuristic is as such:

1. Raise the activities of the species to the power of their stoichiometric coefficients.
2. Multiply the factors involving the products together, likewise for the reactants.
3. Divide the product term by the reactant term.

At first glance, the expression looks daunting and scary, but it is in fact very easy to
understand. A few examples will clarify this.

Let us look at the gaseous equilibrium between the chlorides of phosphorus:

PCl5 (g) PCl3 (g) + Cl2 (g)

Since the species involved in this reaction are all gaseous, the activities refer to the
numerical value of their partial pressures, so:

Q=
( pPCl3
/ bar )( pCl / bar )
2

( pPCl5
/ bar )

Another example comes from aqueous chemistry. This time, it is the redox equilibrium
between manganate(VII) and iron(II) in acidic medium:

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 − 2+ + 2+ 3+
MnO4 (aq) + 5 Fe (aq) + 8 H (aq) Mn (aq) + 5 Fe (aq) + 4H2O(l )

The reaction quotient expression for this is:

2+ 3+ 5
[Mn ][Fe ] −8
Q=
24
− 2+ 5 + 8
/ mol dm
[MnO4 ][Fe ] [H ]

Water does not appear in the reaction quotient because it is a liquid, and its activity is unity.

If we have both gaseous and aqueous species in an equilibrium, say:

+ −
CO2 (g) + H2O(l ) H (aq) + HCO3 (aq) ,

then the reaction quotient is:

+ −
[H ][HCO3 ] −6 −1
Q=
2
/ mol dm bar
pCO 2

Again, water does not appear in the reaction quotient because its activity is unity.

In the three examples we have encountered above, there is a division by the units of the
factors involved. This is because Q is, by definition, dimensionless. However, when no
confusion arises, it is the usual practice to drop the units behind, just so long we are
working with the correct units.

For the remainder of this set of material, the units will not be emphasized again unless
necessary.

Question 1:

Write expressions for the reaction quotient Q for the following equilibria:

(a) C(s) + O2 (g) CO2 (g)

3+ −
(b) Fe(OH)3 (s) Fe (aq) + 3 OH (aq)
(c) CaCO3 (s) CaO(s) + CO2 (g)
(d) SO3 (g) SO2 (g) + 21 O2 (g)
+ −
(e) H (aq) + HS (aq) H2S(g)

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The Equilibrium Constant

As a reaction progresses in the forward direction, the amounts of products increase while the
amounts of reactants decrease. By the definition of Q , we see that Q will increase in value.
Conversely, Q will decrease in value as the reaction progresses in the reverse direction.
When Q remains constant with time, equilibrium is reached.

For a fixed reaction at a fixed temperature, the value of Q at equilibrium takes on a fixed
value, independent of the initial composition. At equilibrium, we denote this fixed value of
Q by K , and it is named the equilibrium constant.

That is, the formula for K looks exactly the same as that for Q , but the value of K only
applies to concentrations and partial pressures at equilibrium. Thermodynamics says that:

• when Q  K , the reaction is not at equilibrium, and it will proceed in the reverse
direction to reduce the value of Q to bring it closer to K ;
• when Q  K, the reaction is not at equilibrium, and it will proceed in the forward
direction to increase the value of Q , bringing it closer to K ;
• when Q = K , the reaction is at equilibrium, and there will be no net reaction.

Qualitatively, this is described by Le Chatelier’s principle, which states that “if a dynamic
equilibrium is disturbed by changing the conditions, the position of equilibrium moves to
counteract the change.” Hence, the addition of more reactant to a system at equilibrium will
cause the concentration of the reactant to increase, causing the position of equilibrium to
shift to the products side and thus the concentration of products will increase. Similarly, the
reverse occurs when more product is added. Can you explain Le Chatelier’s principle for
changes in pressure and concentration by applying the concepts of Q and K ?

The value of K is temperature-dependent. Its variation with temperature provides the

mathematical basis for Le Chatelier’s principle. While a formula relating temperature and the
equilibrium constant will not be given here, we note some general rules:

• For exothermic reactions, K decreases as T increases.

• For endothermic reactions, K increases as T increases.

This agrees with Le Chatelier’s principle.

Due to historical legacy, there is often a distinction between reaction quotients and
equilibrium constants described in terms of concentrations and in terms of partial pressures.

• If the formula for Q and K are expressed solely using concentrations of solutes, a
subscript ‘c ’ is often used, as in Qc and K c .
• If the formula for Q and K are expressed solely using partial pressures of gaseous
species, a subscript ‘p ’ is often used, as in Q p and K p.

While this set of notes will largely not make such a distinction, students should be familiar
with the notation.

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Question 2:

Silver(I) carbonate, Ag2CO3, undergoes the following decomposition equilibrium:

Ag2CO3 (s) Ag2O(s) + CO2 (g)

−3
At 298 K, the value of the equilibrium constant K is 3.2  10 . However, at 5000 K, the value
of K is 1.5. Is the decomposition exothermic or endothermic?

Question 3:

At 800 K, the following reaction has equilibrium constant K = 0.29:

H2 (g) + CO2 (g) H2O(g) + CO(g)

If 0.80 mol of hydrogen gas and 0.60 mol of carbon dioxide react at 800 K under a constant
pressure of 1.00 bar, what is the amount of carbon dioxide at equilibrium?

Strong Acids and Bases

Water undergoes an auto-dissociation equilibrium:

+ −
H2O(l ) H (aq) + OH (aq)
+ −
This equilibrium has an equilibrium constant Kw = [H ][OH ], which is known as the auto-
−14
dissociation constant of water. At 25 C, it has a value of 1.00  10 .
+ −
In pure water at 25 C, stoichiometry tells us that [H ] = [OH ] at equilibrium. Therefore,
+ 2 −14 + −7 −3
[H ] = 1.00  10  [H ] = 1.00  10 mol dm .

The pH of an aqueous solution is defined as:

+
pH = − log10 [H ].

From this definition, the pH of pure water at 25 C is 7.00. However, because K w varies with
temperature, the pH of pure water will not be 7.00 at a temperature different from 25 C.
−3
Let us consider a solution of 0.100 mol dm hydrochloric acid. As a strong acid, it
completely dissociates in water to give hydrogen ions and chloride ions. Then, the pH of the
solution will simply be − log10 (0.100) = 1.00. While the auto-dissociation of water also
provides hydrogen ions to the solution, its contribution is negligible, since it is less than
−7 −3
1.00  10 mol dm (why?).
−3
For comparison, consider a solution of 0.100 mol dm potassium hydroxide. This dissociates
in water to give potassium and hydroxide ions. Then, from K w, we can compute the hydrogen
ion concentration, and hence the pH of the solution:
−14
+ Kw 1.00  10 −13 −3
[H ] = −
= = 1.00  10 mol dm  pH = 13.0
[OH ] 0.100

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Again, although the auto-dissociation of water contributes some hydroxide ions to the
solution, it is negligible compared to the contribution from the potassium hydroxide.

Question 4:

Calculate the pH of the following solutions:

−3
(a) 0.250 mol dm aqueous sodium hydroxide
−3
(b) 0.0400 mol dm aqueous barium hydroxide
−3
(c) 0.800 mol dm perchloric acid, HClO4 (a strong acid)
−3
(d) 0.150 mol dm sulfuric acid (assume both dissociations are complete)

When equal volumes of the solutions in (a) and (c) are mixed, what is the pH of the resultant
solution? (Assume that volumes are additive.)

Weak Acids and Bases

Unlike strong acids, weak acids do not undergo complete dissociation in water. Only a
fraction of the aqueous weak acid molecules will dissociate to give hydrogen ions. In a
typical weak acid solution, the fraction of dissociated molecules is less than 5%.

For a generic weak acid HA, the reversible dissociation is given below:
+ −
HA(aq) H (aq) + A (aq)

The equilibrium constant for the dissociation is called the acid dissociation constant of HA,
and is denoted by K a. The table below lists some K a values for common weak acids.

Acid Ka (at 298.15 K) pK a (at 298.15 K)

−3
Phosphoric acid, H3PO4 (first dissociation) 7.11 10 2.15
−5
Ethanoic acid, CH3CO2H 1.74  10 4.76
−4
Lactic acid, CH3CH(OH)CO2H 1.38  10 3.86
−5
Benzoic acid, C6H5CO2H 6.28  10 4.20
−8
Chloric(I) acid, HOCl 3.01 10 7.52

The rightmost column lists the pK a values, where pKa = − log10 Ka.

Let us consider a solution of a weak acid HA, with concentration cHA and acid dissociation
constant K a. If K a is sufficiently small, and cHA is sufficiently large, then it can be shown that:
+
[H ]  KacHA .

Note that:

• cHA refers to the analytical concentration of the weak acid; and

+
• [H ] refers to the species concentration of the hydrogen ion (at equilibrium).

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The analytical concentration of a solute refers to its “initial” concentration as it is prepared,
ignoring all dissociations and equilibrium processes. The species concentration, on the
other hand, is the concentration taking into account the equilibria in water.

From here on, the square bracket notation will strictly refer to species concentrations, while
the c notation will denote analytical concentrations.

In a weak base, only a fraction of the molecules will be protonated in aqueous solutions.
The protonation equilibrium is:
+ −
B(aq) + H2O(l ) BH (aq) + OH (aq)

The associated equilibrium constant is denoted K b. Analogous to the weak acids, we have
the following formula for weak bases, assuming K b is sufficiently small, and cB is sufficiently
large:
−
[OH ]  KbcB .
+
If the pH of the solution is desired, then we can use K w to compute [H ] in a weak base
solution, much like the case of strong bases.

Question 5:

Show that, if K a is sufficiently small and cHA is sufficiently large, then

+
[H ]  KacHA .
−3
Use this equation to estimate the pH of 0.250 mol dm ethanoic acid (pKa = 4.76). Is the
approximation valid?

Repeat the approximation for the pH of the following solutions. If the approximation is not
valid, provide a more accurate computation of the pH.
−3 −3
(a) 5.00  10 mol dm solution of phenol (pKa = 10.0)
−3 −3
(b) 5.00  10 mol dm solution of lactic acid (pKa = 3.86)
−3
(c) 0.200 mol dm solution of picric acid (Ka = 0.43)
−3 −3
What is the pH of the resultant solution when equal volumes of 5.00  10 mol dm
−3 −3
hydrochloric acid and 5.00  10 mol dm lactic acid are mixed?

Question 6:

A conjugate acid-base pair is a pair of species, one acid and one base, that differ by one
−
proton. For example, HA and A form a conjugate acid-base pair. A weak base B and its
+
protonated form BH also form a conjugate acid-base pair.

(a) Show that, for a conjugate acid-base pair, we have Kw = KaKb.

(b) Explain why most chemical tables only tabulate K a values and not K b values.

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(c) Given that the pK a value of ethanoic acid given is 4.76, calculate the pH of an aqueous
−3
solution of 0.800 mol dm sodium ethanoate.

Solubility Equilibrium

A saturated solution of a salt in water is one where no more of the compound can dissolve.
The molar solubility of a salt in water is the (analytical) concentration of a saturated
solution of the salt.

When excess undissolved salt is present in a saturated solution, the following equilibrium is
set up:
y+ x−
Mx A y (s) x M (aq) + y A (aq)

The associated equilibrium constant is called the solubility product, and is denoted K sp. For
y+ x x− y
the salt Mx A y above, we have Ksp = [M ] [ A ] . The ionic product refers to the reaction
quotient of the solubility equilibrium. It is usually denoted as IP or Qsp .

• If Qsp  K sp, then the solution is not saturated, and more salt (if present) can continue
to dissolve.
• If Qsp = K sp, then the solution is saturated.
• If Qsp  K sp, then the solution is supersaturated, and the salt will start to precipitate
out of the solution, until equilibrium is reached (i.e. saturation).

Question 7:

Calculate the molar solubility of the following salts at 298 K:

−5
(a) Lead(II) chloride (Ksp = 1.72  10 )
−9
(b) Barium iodate(V), Ba(IO3 )2 (Ksp = 1.57  10 )
−9
(c) Zinc(II) oxalate, ZnC2O4 (Ksp = 7.63  10 )

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