IONIC EQUILIBRIA

1. Concepts of Acid/Base 1.1 Arrhenius Theory 1.1.1 Definition + 1. An acid is a substance which dissolves in water to give hydrogen ions, H (aq). 2. A base is a substance which dissolves in water to give hydroxide ions, OH (aq). + 3. An acid-base reaction (i.e. neutralization) is the combination of H (aq) and OH (aq) to form H2O(l). + Neutralization : H (aq) + OH (aq) H2O(l) Summary : H
+ (aq)

and OH (aq) are responsible for acidic and basic properties respectively.

1.1.2 Drawbacks of Arrhenius Theory 1. It confines to aqueous solution only. However, many acids are capable of giving hydrogen ions in solvents other than water. e.g. nitric acid in ethanol ionizes to give hydrogen ions 2. Some compounds are not classified as acids because they do not contain the element hydrogen explicitly, although they are capable of releasing hydrogen ions after reacting with water. 2+ e.g. SO2(g) + H2O(l) 2H (aq) + SO3 (aq) 3. Some substances are not classified as bases because they do not contain hydroxide explicitly, although they are capable of releasing hydroxide ions by reacting with water. + e.g. NH3(g) + H2O(l) NH4 (aq) + OH (aq) 1.2 Bronsted-Lowry Theory 1.2.1 Introduction + This theory emphasizes on the role of hydrogen ion, H (i.e. proton). Definition : + 1. An acid is a molecule or ion that can donate a proton, H (i.e. a proton donor). + 2. A base is a molecule or ion that can accept a proton, H (i.e. a proton acceptor). 3. An acid-base reaction is the transfer of proton from an acid to a base (i.e. a proton-transfer reaction). + Neutralization : H (aq) + OH (aq) H2O(l) + NH3(aq) + HCl(aq) NH4Cl(aq) or NH4 (aq) + Cl (aq) Implications : 1. An acid must possess the element hydrogen for donation. 2. A base can either be a negative ion or a neutral molecule with a lone pair of electrons to form dative covalent bond with proton. Reason : Since proton has no electrons, bonding between the base and proton must be dative covalent in nature, with the base providing both electrons a base must have a lone pair of electrons available for donation

H N H H + H+ H N H H H

3. Bronsted-Lowry definition includes all substances that fit the Arrhenius definition. In addition, it includes + a. as acids, ions such as HSO4 and NH4 that can donate proton in solution, even though they cannot exist alone; and 2b. as bases, all substances that can accept proton such as CO3 or CN , even though they do not contain hydroxide explicitly.

Chemistry/Ionic Equilibria

1.2.2 Conjugate Acid-Base Pair Consider the ionization of ethanoic acid in water : + CH3COO (aq) + H3O (aq) CH3COOH(aq) + H2O(l) After CH3COOH(aq) has lost its proton, it becomes CH3COO (aq). From reverse reaction, CH3COO (aq) is capable of accepting a proton to form back the acid CH3COO (aq) is itself a CH3COO (aq) is called the CH3COOH(aq) + H2O(l) acid CH3COO (aq) + H3O conjugate base
+ (aq) -

of CH3COOH(aq)

Similarly, consider the ionization of ammonia in water : + NH4 (aq) + OH (aq) NH3(aq) + H2O(l) After NH3(aq) has accepted a proton, it becomes NH4 (aq). + From reverse reaction, NH4 (aq) is capable of donating its proton to form back the base NH4 NH4
+ (aq) + (aq) +

is itself an is called the NH4 (aq) + OH (aq) conjugate acid

+ -

of NH3(aq)

NH3(aq) + H2O(l) base

Conclusion : 1. After an acid loses a proton, it becomes a base and is called the conjugate base of the given acid. 2. After a base accepts a proton, it becomes an acid and is called the conjugate acid of the given base. These pairs of species are known as conjugate acid-base pairs; they convert into each other by the transfer of , i.e. gain/loss of a . Remark : 1. An acid-base reaction must involve both acid and base. Q Both donor and acceptor of proton must be present for transfer of proton to take place. 2. An acid only shows its properties in the presence of a base. Similarly, a base only shows its properties in the presence of an acid. + H. Q For an acid to function, a base must be present to + H. For a base to function, an acid must be present to 3. In an acid-base reaction, since the given acid (acid1) will be converted into its conjugate base (base1) and the given base (base2) will be converted into its conjugate acid (acid2), the process can be represented as : As there are acids and bases on both sides of the equation, the process can go either way and is represented by an . The forward reaction is the transfer of a proton from acid1 to base2, acid + base 1 2 and the reverse reaction is the transfer of the proton from acid2 to base1.

conjugate acid-base pair2 base1 + acid2

Essentially, the process can be taken as base1 and base2 competing to accept proton an acid-base reaction is in fact the competition to gain/lose proton between bases alternatively, an acid-base reaction can also be taken as the competition to gain/lose proton between acids

conjugate acid-base pair1

Chemistry/Ionic Equilibria

Example :

HCl(aq) acid

H2O(l) base

Cl (aq) conjugate base of HCl

H3O (aq) conjugate acid of H2O

Exercise : 1. Identify the conjugate acid-base pairs in the following neutralization reactions. + + H2O(l) H3O (aq) + CH3COO (aq) a. CH3COOH(aq)

b. NH4

+ (aq)

H2O(l)

H 3O

+ (aq)

NH3(aq)

c.

H2O(l)

CO3

2(aq)

HCO3 (aq) +

OH (aq)

2. Write an equation to show that HPO4 Solution :

2(aq)

can act as a Bronsted base in water.

(94, I)

3. Outline the Bronsted-Lowry theory of acids and bases with respect to the following reaction : + H2O(l) + HCl(aq) H3O (aq) + Cl (aq) Solution : H2O(l) + HCl(aq) H 3O
+ (aq)

(89, II)

Cl (aq)

2 conjugate acid-base pairs : 4. Which of the following is a conjugate acid-base pair ? A. NH4+(aq) and NH3(aq) B. H2SO4(aq) and SO42-(aq) C. H3O+(aq) and OH-(aq) D. HCl(aq) and NaOH(aq)

&

(1 mark, 06, I, 3c) 1.2.3 Amphoteric Substances Some substances can both act as an acid to donate a proton, or act as a base to accept a proton. Such behaviour is known as amphoteric. Example : 1. water
H H OH H 2 O H 3 O +
+ +

2. HSO4 (aq). As an acid As a base

H H SO4 2 HSO 4 H 2 SO 4

: :

HSO4 (aq) + OH (aq) HSO4 (aq) + H3O

+ (aq)

SO4

2(aq)

+ H2O(l)

H2SO4(aq) + H2O(l)

For an amphoteric substance, whether it behaves as an acid or a base depends on the other substance present. If a stronger acid is present, the amphoteric species is forced to act as acid/base to accept/donate a proton. If a stronger base is present, the amphoteric species is forced to act as acid/base to accept/donate a proton. Example : Give the equation for the reaction between HCO3 (aq) and (a) NaOH(aq) (b) HCl(aq)

Chemistry/Ionic Equilibria

1.2.4 Acid Strength & Base Strength The strength of an acid is a measure of its tendency to donate a proton. The strength of a base is a measure of its tendency to accept a proton. Both are related to the extent of equilibrium. Example : HCl(aq) + H2O(l) Cl (aq) + H3O
+ (aq)

complete ionization/dissociation

This equilibrium lies very far to the right most HCl(aq) dissociate HCl(aq) has a very high tendency to lose proton HCl(aq) is a strong acid Example : HCN(aq) + H2O(l) H 3O
+ (aq)

+ CN (aq)

incomplete ionization/dissociation

This equilibrium lies very far to the left few HCN(aq) dissociate HCN(aq) has a low tendency to lose proton HCN(aq) is a weak acid The strength of a base can be defined accordingly. Example : Strong base : equilibrium favours the gain of proton CN (aq) + H2O(l) Weak base :
-

HCN(aq) + OH (aq)

equilibrium far to right

equilibrium not favoured by gain of proton NH3(aq) + H2O(l) NH4

+ (aq)

+ OH (aq)

equilibrium far to left

1.2.5 Fact :

Strength within Conjugate Acid-Base Pair The conjugate base of a strong acid is a weak base.

Reason : For a strong acid, its tendency to lose proton must be high/low the ability for its conjugate base to accept a proton to form back the strong acid must be high/low, its conjugate base must be strong/weak Example : HCl(aq) + H2O(l) Cl (aq) + H3O
+ (aq)

HCl(aq) is a strong acid the above equilibrium lies far to left/right + Cl has little/strong tendency to accept H to form back HCl Cl is a strong/weak base Exercise : Convince yourself with the following statement. The conjugate base of a weak acid is a strong base. The conjugate acid of a strong base is a weak acid. The conjugate acid of a weak base is a strong acid.

Example : Example : Example :

HCN vs CN
-

CN vs HCN Cl and HCl

-

Remark : Strength is a relative term. It takes two acids or two bases to tell which is stronger and which is weaker.

Chemistry/Ionic Equilibria

1.3 Hydrogen Ion + Fact : In aqueous solution, isolated hydrogen ion H (aq) never exists. Reason : Hydrogen ion is just a bare proton with extremely high/low charge density (due to exceptionally H seeks out positive/negative centre immediately and will bond to + H is therefore hydrated with molecules of water
+

) in water

Remark : + 1. The most predominant hydrated species is believed to be hydroxonium ion (or hydronium ion) H3O (aq), with + bond with H . Other higher hydrated ions like the lone pair on H2O forming a + + [H(H2O)2] (aq) and [H(H2O)3] (aq) etc. are also believed to exist.

+ O H H
+ (aq)

+ H+
or H3O
+ (aq)

O H

H H
+

2. For convenience, it is understood that H

refers to hydrated H in aqueous solution.

Chemistry/Ionic Equilibria

2. Dissociation of Water 2.1 Ionic Product of Water The ionization of water can be represented by the following equilibrium : H2O(l) H
+ (aq)

+ OH (aq)

H = +57.3 kJ mol

-1

with equilibrium constant, K, at a given temperature as :

K=

[ H + ]eqm [OH ]eqm [ H 2 O ]eqm

As the degree of ionization is extremely small [H2O]eqm is virtually constant the equation can be rewritten as + Kw = K [H2O] = [H ]eqm [OH ]eqm At 25 C (298 K), Kw = 1.0 x 10
o -14

where Kw is called the ionic product of water

mol dm .

-6

Remarks : o + -7 -3 1. In pure water at 25 C, [H ] = [OH ] = 1 x 10 mol dm . 8 This corresponds to approximately 1 in every 5 x 10 molecules of water being split up into ions at 298 K, confirming that the degree of ionization is extremely small. 2. This equilibrium always holds in solution, no matter the solution is acidic or alkaline. + In acidic solution, [H ] increases and [OH ] decreases accordingly. Similarly, in alkaline solutions, [OH ] + o + -14 2 -6 increases and [H ] decreases accordingly. In any case, at 25 C, [H ] [OH ] = 1.0 x 10 mol dm . 3. Kw is like any equilibrium constant, its value only changes with .

Chemistry/Ionic Equilibria

2.2 Kw and Temperature Values of KW vs T are given below : KW / mol dm -14 0.11 x 10 -14 0.30 x 10 -14 0.68 x 10 -14 1.00 x 10 -14 5.47 x 10 -14 51.3 x 10 Trend : Reason :
2 -6

Temperature / K 273 283 293 298 323 373

As temperature increases, Kw increases/decreases. H2O(l) H

+ (aq)

+ OH (aq)

H = +57.3 kJ mol

-1

Either : Q H is positive, by ln K = As T 1 / T H / RT ln K / K Or :

H +C RT

By Le Chateliers Principle, As temperature increases, equilibrium position shifts to endothermic/exothermic reaction shifts to the left/right more/less water ionized K

Exercise : + 3 1. What is the concentration of H (aq) and OH (aq) if 0.01 mole of solid NaOH is dissolved in a 1.0 dm of pure water o at 25 C ? [OH ] [H ]
+ -

= =
+ (aq)

2. What are the concentrations of H In pure water, [H ] [OH ] = [H ] =

+ + -

and OH (aq) in pure water at 373 K ?

Chemistry/Ionic Equilibria

3. pH and its Measurement 3.1 The p Notation Definition : p value of a number is the negative of the logarithm (base 10) of that number. Reason of using p notation : + -something [H ] & [OH ] are usually very small, 10 inconvenience to handle p values can avoid the use of negative indices in small numerical values. 3.2 pH pH = -log [H ] For a neutral solution at 25 C, [H ] = [OH ] = 1 x 10 mol dm -7 pH = pOH = -log (1 x 10 ) = - (-7) = 7
+ o + -7 -3 + -

pOH = -log [OH ]

no unit

If the pH/pOH of the solution is given, its [H ]/[OH ] can be found easily. + pOH = -log [OH ] pH = -log [H ] + log [OH ] = -pOH log [H ] = -pH + -pH -pOH [OH ] = 10 [H ] = 10 Example : For a solution has pH = 3.25, [H ] = Remarks : o 1. At 25 C,
+ -14 +

mol dm

-3

[H ] [OH ] = 1 x 10
+ -

log ([H ] [OH ]) = log (1 x 10 ) log [H ] + log [OH ] = -14 -log [H ] - log [OH ] = 14 pH + pOH = 14 2. A change of 1 unit in pH/pOH represents a change in [H ]/[OH ] by a factor of Exercise : 1. What is the pH of 0.02 M HCl ? 2. What is the pH of 10 M H2SO4 ? 3. What is the pH of 3 M HX which is only 50% dissociated ? 4. If a solution contains a concentration of H
+ (aq) -3 + + + + -

-14

[H ] = [H ] = [H ] =
-9 -3 + +

equal to 8.69 x 10 mol dm , what is the pH of the solution ? pH =

5. If the pH of a solution is 2.73, what is the concentration of H

+ (aq)

ions ? [H ] =
+

Chemistry/Ionic Equilibria

6. Account for the fact that at 373K, the pH of pure water is less than 7.0. Solution : From Le Chateliers Principle, As T , equilibrium position shifts to exothermic/endothermic reaction more/less water is ionized + o [H ] /, higher than that at 25 C + -7 -3 [H ] >/< 1 x 10 mol dm pH more/less than 7
-14

(94, II)

7. At 37 C, Kw = 2.42 x 10 Solution : At pH = 6.808,

mol dm . The pH of a solution is 6.808. Is the solution acidic ?

-6

[H ] = [OH ] =
+ -

Since [H ] >/=/< [OH ], solution is acidic/neutral/alkaline. 8. Explain why the mean [H3O ] between pH 4 and pH 5 corresponds to pH 4.26 rather than pH 4.50. Solution : + At pH = 4, [H ] = Mean [H ] = pH = Remarks : 1. Since Kw changes with temperature, o a. pH = 7 does not imply that the solution is neutral. pH = 7 only implies a neutral solution at 25 C. b. pH of any neutral solution (e.g. pure water) also changes with temperature and is not necessarily 7. o A neutral solution has pH = 7 only at 25 C. + + + 2. A solution is neutral when [H ] = [OH ]; is acidic when [H ] > [OH ] and is alkaline when [H ] < [OH ].
+ +

At pH = 5, [H ] =

Chemistry/Ionic Equilibria

3.3 Measurement of pH pH of a solution can be measured accurately by a

or roughly by

or

3.3.1 pH Meters The theory and instrumentation of pH meter are not required.

Set up : A pH meter is an electrochemical cell consisting of 2 electrodes : 1. a reference electrode with constant electrode potential (e.g. calomel electrode, a platinum wire dipping into mercury in a solution of mercury(I) chloride). 2. a glass electrode sensitive to hydrogen ion concentration. Principle : The voltage or e.m.f. of the cell depends on the H
+ (aq)

concentration.

Remark : 1. The pH meter has to be calibrated before use. It usually takes at least 2 pH values for the calibration. Procedure : 1. Rinse the glass electrode with distilled water. 2. Dip the glass electrode into a buffer solution of known pH value. 3. Adjust the pH meter so that its reading agrees with the pH of the buffer solution, i.e. calibration. 4. Rinse the electrode with distilled water again. 5. Dip the glass electrode into another buffer solution of known pH value. 6. Calibrate the pH meter again. 7. The whole scale of pH should be calibrated. 8. Once the calibration is finished, dip the glass electrode into the solution whose pH to be determined and the pH can be read from display. 2. The glass electrode is very delicate and sensitive. It should be kept clean and never be dried.

Chemistry/Ionic Equilibria

10

4. pH Calculations with Strong Acids or Bases A strong acid or base is one that ionizes or dissociates completely in water. Example : HCl(aq) H (aq) + Cl (aq) + NaOH(aq) Na (aq) + OH (aq)
+ (aq) + -

In strong acid or base, in principle there are two sources of H 1. from the complete ionization of the strong acid/base 2. from the self-ionization of water Example 1 : What is the pH of 1.00 M HCl(aq) ? HCl(aq) H 1.0
+ (aq)

or OH (aq) in solution :

+ Cl (aq) 1.0

H2O(l) (y + 1) y = 1. 0 x 10 y = 1.0 x 10
+ -14 -14

H (aq) + (y + 1.00)

OH (aq) y

Using ionic product of water,

[H ] = 1.00 + 1.0 x 10 pH = 0

-14

= 1.00

Finding : Reason :

This is essential the same as if there is no contribution from the self-ionization of water. [H ] arising from self-ionization of water is negligible compared to the contribution from strong acid.
+

Example 2 : What is the pH of 0.10 M HCl(aq) ? + -3 [H ] = 0.1 mol dm pH = 1 Finding : A dilution of 10 times will change pH by 1 in strong acid/base.

Example 3 : -8 What is the pH of 1.0 x 10 HCl(aq) ? Finding : Reason : Direct pH calculation will give pH = acidic/alkaline reasonable/unreasonable

At such a low concentration of acid, self-ionization of water is negligible/not negligible. HCl(aq)

-8

H (aq) + Cl (aq) -8 -8 1 x 10 1 x 10
-14

H2O(l)

H (aq) + -8 (y + 1.0 x 10 )

OH (aq) y

y (y + 1.0 x 10 ) = 1.0 x 10
-8

y = 9.51 x 10 or -1.05 x 10 (rejected) [H ] = 9.51 x 10 + 1.0 x 10 = 1.051 x 10 mol dm pH = 6.98

+ -8 -8 -7 -3

-7

slightly acidic, makes sense

Chemistry/Ionic Equilibria

11

Exercise : -4 o 1. Calculate the pH and pOH of 3.2 x 10 M solution of Ba(OH)2 at 25 C. (You may assume that Ba(OH)2 is a strong electrolyte that completely dissociates in water.) [OH ] = pOH = pH = 2. Calculate the molarity of an aqueous solution of NaOH having a pH of 10.5 at 25 C. [H ] = [OH ] = [NaOH] = 3. The degree of dissociation of Ca(OH)2 in a 0.1 M solution is 0.05 at 25 C. (a) Calculate the hydroxide ion concentration. [OH ] = (b) Calculate the pH of the solution. [H ] = pH = Summary : + 1. The contribution of H (aq) or OH (aq) from self-ionization of water can usually be neglected, except at very low concentration of strong acid/base. 2. A dilution of 10 times changes pH by 1 unit in strong acid/base.
+ o + o -

Chemistry/Ionic Equilibria

12

5. pH Calculations of Weak Acid/Base 5.1 Weak Acid + + The dissociation of weak acid HA(aq) in solution to form H (aq) (or more formally H3O (aq)) and its conjugate base (A (aq)) can be represented by an equilibrium : HA(aq) H
+ (aq)

+ A (aq)

or

HA(aq) + H2O(l)

H 3O

+ (aq)

+ A (aq)

with equilibrium constant KC [ H + ]eqm [ A ]eqm KC = [ HA]eqm

or

KC =

[ H + ]eqm [ A ]eqm [ H 2 O ]eqm [ HA]eqm

Since [H2O] is a constant, we can define acid dissociation constant Ka for any weak acid as [ H + ]eqm [ A ]eqm [ H 3O + ]eqm [ A ]eqm [ H + ]eqm [conjugate base]eqm = = Ka = [ HA]eqm [ HA]eqm [undissociated acid]eqm

Unit of Ka : Example : + What is the concentration of H (aq), OH (aq), CH3COOH(aq), CH3COO (aq) and pH of 0.1 M ethanoic acid (Ka = 1.75 x -5 -3 10 mol dm ) ? What is the degree of dissociation ? CH3COOH(aq) 0.1 0.1 - y CH3COO (aq) 0 y
-

Initial At eqm.

H 0 y

+ (aq)

Ka =

[ H + ][CH 3COO ] y2 = = 1.75 x10 5 [CH 3COOH ] 0 .1 y

Solve with assumption, Assume y << 0.1, (0.1 - y) 0.1
-3 -3

Solve with quadratic equation, y = 1.31 x 10

+ -3

[H ] = 1.31 x 10 mol dm pH = 2.88

y2 1.75 x10 5 0 .1 2 -6 -3 y = 1.75 x 10 or y = 1.32 x 10 pH = 2.88 Check of assumption (5% check) : 1.32 x10 3 x100% = 1.32% < 5% valid 0.1

[OH ] =

= 7.63 x 10 mol dm 1.31x10 3 + -3 -3 [CH3COO ] = [H ] = 1.31 x 10 mol dm -3 -3 [CH3COOH] = 0.1 - 1.31 x 10 = 0.0987 mol dm

1.0 x10 14

-12

-3

Degree of dissociation =

no. of moles dissociated concentration dissociated 1.31x10 3 = = = 0.0131 original total no. of moles original total concentration 0.1

Remarks : 1. The use of assumption can always simplify the problem. However, the assumption must be checked (usually error < 5% is acceptable). + 2. The contribution of H from self-ionization of water is assumed to be negligible. This is a valid assumption here. + + Q [H ] from self-ionization of water << [H ] from weak acid

Chemistry/Ionic Equilibria

13

Exercise : If now water is added to the above mixture to make the concentration of the ethanoic acid 0.01 M. Calculate the + H (aq), OH (aq), pH and degree of dissociation. How can you account for the change in degree of dissociation (compared to 0.1 M solution) in terms of Le Chateliers Principle ? Solution : Concentration Initial At eqm.
+ (aq) -

CH3COOH(aq) 0.01

CH3COO (aq) 0

Ka = [H ] = [OH ] = [CH3COO ] = [CH3COOH] = Degree of dissociation = If the equilibrium is rewritten as CH3COOH(aq) + H2O(l) Addition of water shifts equilibrium position to left/right CH3COO (aq) + H3O (aq) more/less acid molecules dissociate degree of ionization /
+ +

Remarks : 1. In weak acid, a dilution of 10 times does not change pH by 1 (contrast to strong acid). 2. Dilution in weak acid increases the degree of dissociation, this can be explained by Le Chateliers Principle. Exercise : o The pH of 0.001 M solution of aminoethanoic acid (NH2CH2COOH) is 6.38 at 25 C. Calculate the value of Ka at this temperature. Solution : Concentration Initial At eqm.

Ka =

Chemistry/Ionic Equilibria

14

Exercise : The degree of dissociation of a monobasic acid in 0.1 M solution at a certain temperature is 0.014. Calculate the pH and the dissociation constant of the acid at this temperature. Solution : Concentration Initial At eqm.

pH =

Ka = 5.2 Weak Base + The dissociation of weak base B(aq) in solution to form OH (aq) and its conjugate acid (HB (aq)) can be represented by an equilibrium : B(aq) + H2O(l) HB
+ (aq)

+ OH (aq)

with equilibrium constant K C =

[OH ] eqm [ HB + ] eqm [ H 2 O] eqm [ B ] eqm

Since [H2O] is a constant, we can define base dissociation constant Kb for any weak base as

Kb =

[OH ] eqm [ HB + ] eqm [ B] eqm

[OH ] eqm [conjugate acid] eqm [base]eqm

Unit of Kb : Exercise : The pH of a 0.50 M solution of ammonia at 298 K is 11.48. Calculate the base dissociation constant at 298 K for the reaction : + NH3(aq) + H2O(l) NH4 (aq) + OH (aq) -14 2 -6 (89, I) (At 298 K, Kw = 1.0 x 10 mol dm ) Solution :
+

[H ]eqm = [OH ]eqm = Concentration Initial At eqm. NH3 + H 2O NH4

+ -

OH

Kb =

Chemistry/Ionic Equilibria

15

Exercise : 3 When excess solid Mg(OH)2 is shaken with 1.00 dm of 1.00 M NH4Cl solution, the resulting saturated solution has a pH of 9.0 at 298 K. (i) Calculate the concentration of the OH ion. -5 -3 + (ii) Given that Kb for ammonia is 1.80 x 10 mol dm at 298 K, calculate the concentrations of NH3 and the NH4 ion. (87, II) Solution : (i) + [H ] = [OH ] = (ii) Concentration Initial At eqm. NH3 + H 2O NH4
+ -

OH

Kb =

[NH3] = [NH4 ] =
+

Chemistry/Ionic Equilibria

16

5.3 Magnitude of Ka and Kb Acid : HA(aq) + H2O(l) B(aq) + H2O(l) H 3O

+ (aq) + A (aq) -

Ka = Kb =

[ H 3 O + ] eqm [ A ] eqm [ HA] eqm [OH ] eqm [ HB + ] eqm [ B ] eqm

stronger/weaker acid/base stronger/weaker acid/base

Base

OH (aq) + HB

+ (aq)

Larger Ka/Kb Smaller Ka/Kb Larger pKa/pKb Smaller pKa/pKb

forward reaction is more/less complete forward reaction is more/less complete larger/smaller Ka/Kb larger/smaller Ka/Kb

stronger/weaker acid stronger/weaker acid

5.4 Relationship between Ka and Kb For an acid (HA), the basic properties of its conjugate base (A ) can also be expressed by an equilibrium : [OH ] eqm [ HA] eqm K b ( A ) = HA(aq) + OH (aq) A (aq) + H2O(l) [ A ]eqm This Kb of A is related to Ka of HA. K b ( A ) [OH ] eqm [ HA] eqm 1 x = + Kw [ A ] eqm [ H ] eqm [OH ] eqm
-

[ HA] eqm K b ( A ) 1 = = + Kw K a ( HA) [ A ] eqm [ H ] eqm

K b ( A ) =

Kw K a ( HA) K a ( HB + ) = Kw K b ( B)
(Verify it yourself)

Similarly Ka of HB is related to Kb of HB. Thus for a conjugate acid-base pair,

Ka Kb = Kw log Ka + log Kb = log Kw -log Ka -log Kb = -log Kw pKa + pKb = pKw o pKa + pKb = 14 at 25 C

Chemistry/Ionic Equilibria

17

Exercise : -5 Calculate the pH of a 0.10 M aqueous solution of sodium ethanoate. The Ka value for ethanoic acid is 1.80 x 10 -3 -14 2 -6 mol dm , and Kw for water at 298 K is 1.00 x 10 mol dm . Kb for CH3COO = Concentration Initial At eqm. CH3COO
-

H 2O

CH3COOH 0

OH 0

Kb = [OH ] = [H ] = pH =
+ -

Chemistry/Ionic Equilibria

18

Example : A solution is prepared by dissolving potassium hydrogencarbonate in water at 298 K. Write chemical equations for four equilibrium reactions, each involving the hydrogencarbonate ion, that occur in the solution and calculate the value of the equilibrium constant for each reaction. -7 -3 -11 -3 Given that at 298 K : K1 = 4.3 x 10 mol dm ; K2 = 4.8 x 10 mol dm for H2CO3 -14 2 -6 (93, I) Kw = 1.0 x 10 mol dm for H2O Solution : HCO3 is amphoteric. Species in solution : With H3O
+ + +

H H CO3 2 HCO3 H 2 CO3

HCO3 (aq) + H3O K=

+ (aq)

With OH

HCO3 (aq) + OH (aq) K=

With H2O

HCO3 (aq) + H2O(l) K=

With H2O

HCO3 (aq) + H2O(l) K=

Is a solution of potassium hydrogencarbonate acidic or alkaline ? Ka(HCO3 ) = Since Ka >/< Kb, the solution is acidic/alkaline.
-

Kb(HCO3 )

Chemistry/Ionic Equilibria

19

5.5 Calculations Involving Polybasic Weak Acid For a polybasic weak acid, each ionization step is governed by an equilibrium with a specific Ka. H3PO4(aq) H2PO4 (aq) HPO4
2(aq) -

H2PO4 (aq) + H HPO4 PO4

3(aq) + 2(aq)

+ (aq) + (aq)

Ka1 = Ka2 = Ka3 =

+H
+

+H

(aq)

After each removal of H , the resulting species has one more negative charge + further removal of H will be progressively more/less difficult due to increased/decreased electrostatic attraction Ka1 >/< Ka2 >/< Ka3 Together with the ionic product of water, in a solution of phosphoric acid, there are a total of 4 equilibria, all these relationships have to be satisfied. Example : Calculate the concentration of all ionic species present in 0.05 M phosphorus acid. + + Although three ionization processes produce H , as Ka1 > Ka2 > Ka3, it is reasonable to assume that all H come solely from the first ionization. The assumption will be checked. + H3PO4 H + H2PO4 Concentration 0.05 0 0 Initial 0.05 - x x x At eqm. Ka1 =

x2 -3 = 7.1 x 10 0.05 x

Assume 0.05 x 0.05

x2 -3 = 7.1 x 10 0.05

x = 0.0188

Assumption is not valid. Solve by quadratic equation, x = 0.0156 + -3 [H ] = [H2PO4 ] = 0.0156 mol dm This [H ] can be used to calculate [HPO4 ] and [PO4 ]. Since Ka1 > Ka2, we may assume that the amount of H2PO4 and H after dissociation is essentially the same as the one just calculated. 2+ H2PO4 H + HPO4 Concentration 0.0156 0.0156 0 Initial 0.0156 - y 0.0156 + y y At eqm. Ka2 =
+ + 23-

y (0.0156 + y ) -8 = 6.3 x 10 0.0156 y

-8

Assume 0.0156 y 0.0156 y = 6.3 x 10 2-8 -3 [HPO4 ] = 6.3 x 10 mol dm 2+ Notice that [HPO4 ] << [H ], assumption is valid.

Chemistry/Ionic Equilibria

20

Again as Ka2 > Ka3, we may assume that the amount of HPO4 and H after dissociation is essentially the same as the one just calculated. + 23H HPO4 + PO4 Concentration -8 6.3 x 10 0.0156 0 Initial -8 6.3 x 10 - z 0.0156 + z z At eqm. Ka3 =

2-

z (0.0156 + z ) 6.3x10 8 z

= 4.2 x 10
-8

-13

Assume z << 6.3 x 10 , [PO4 ] = 1.70 x 19

33-18

-3

z (0.0156) 6.3x10
8

= 4.2 x 10

-13

z = 1.70 x 10

-18

mol dm
+

Notice that [PO4 ] << [H ], assumption is valid. Lastly [OH ] =

-

Kw [H + ]

1x10 14 -13 -3 = 6.41 x 10 mol dm 0.0156

Example : The dissociation constant of H2PO4 (aq) in water is 6.2 x 10 mol dm at 298 K, where K a = Calculate the pH at 298 K of (a) an aqueous solution of 0.10 M NaH2PO4(aq). (b) an aqueous solution of 0.05 M NaH2PO4(aq) and 0.05 M Na2HPO4(aq). 3(The concentrations of H3PO4 and PO4 are assumed to be negligible in these solutions.) Solution : The equation for equilibrium : (a) H2PO4 Concentration 0.10 Initial 0.10 - x At eqm. H2PO4
-8 -3

[ HPO4 2 ][ H + ] [ H 2 PO4 ]

HPO4 + H

2-

HPO4 0 x

2-

H 0 x

Ka =
+

[ HPO4 2 ][ H + ] [ H 2 PO4 ]
-5

x2 x2 = 6.2 x10 8 0.10 x 0.10

x = 7.874 x 10 pH = 4.10
2-

-5

[H ] = 7.874 x 10 M (b) Concentration Initial At eqm.

-

H2PO4 0.05 0.05 - x

HPO4 0.05 0.05 + x

H 0 x

Ka =
+

[ HPO4 2 ][ H + ] [ H 2 PO4 ]
-8

(0.05 + x) x 0.05 x = x = 6.2 x10 8 0.05 x 0.05

pH = 7.21

[H ] = 6.2 x 10 M

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21

Exercise : The following reversible reaction occurs in an aqueous solution of ammonium ethanoate : + CH3COOH(aq) + NH3(aq) (I) CH3COO (aq) + NH4 (aq) (i) Write an expression for the dissociation constant, Ka, of ammonium ion. (ii) Calculate the equilibrium constant of reaction (I) at 298 K. (iii) For a 0.10 M solution of ammonium ethanoate at 298 K, calculate (1) the concentration of ammonia, and (2) the pH of the solution. -5 -3 -10 (At 298 K, the dissociation constants of ethanoic acid and ammonium ion are 1.76 x 10 mol dm and 5.59 x 10 -3 (95, II) mol dm respectively.) Solution :

Exercise : The pH of a 0.02 M ethanedioic acid solution (H2C2O4) is 1.8. Calculate the concentration of each species present o (90, II) in the solution at 25 C. o -2 -3 -5 -3 [Dissociation constants of ethanedioic acid at 25 C are : K1 = 6.5 x 10 mol dm , K2 = 6.1 x 10 mol dm ] Solution :

Chemistry/Ionic Equilibria

22

6. 6.1 1. 2. 3. 4. 5. 6. 7. 8. 9.

Calculations on Acid-Base Equilibria Procedure Identify the conjugate acid/base pair. Write appropriate equilibrium equation using the acid/base given and water. Use the appropriate K value, Ka for acid; Kb for base. Find initial concentrations of species before equilibrium is established. Define the change required to achieve equilibrium; hence calculate the equilibrium concentrations. Relate equilibrium concentrations to the appropriate K. Solve the equation, making reasonable assumption if necessary. Check any assumption to make sure it is valid. Convert to quantities required in question.

In general, acid/base calculations are of three general types. A. Only acid is present initially. B. Only base is present initially. C. Both acid-base pair are present initially. 6.2 Acid Only (Initially) -5 -3 Calculate the pH of a solution of 0.10 M CH3(CH2)2COOH, whose Ka = 1.5 x 10 mol dm . Step 1 Step 2 Step 3 Step 4 Step 5 Step 6 Step 7 Conjugate acid/base pair CH3(CH2)2COOH/CH3(CH2)2COO Equilibrium equation Since acid is present initially, its reaction with water will be + CH3(CH2)2COO + H3O CH3(CH2)2COOH + H2O [ H O + ][CH 3 (CH 2 ) 2 COO ] Write K expression Ka = 3 [CH 3 (CH 2 ) 2 COOH ] + CH3(CH2)2COO + H3O Find initial conc. CH3(CH2)2COOH + H2O init. conc. 0.10 0 0 Define eqm. conc. eqm. conc. 0.10 - x x x [ H 3 O + ][CH 3 (CH 2 ) 2 COO ] x2 Relate to K Ka = = = 1.5 x10 5 [CH 3 (CH 2 ) 2 COOH ] 0.10 x Solve eqn. Assume x << 0.10, i.e. 0.10 - x 0.10 x2 -3 = 1.5 x10 5 x = 1.225 x 10 0.10 -3 Since 1.225 x 10 << 0.10, assumption is valid. + -3 [H ] = x = 1.225 x 10 M + -3 pH = -log [H ] = -log (1.225 x 10 ) = 2.91
-

Step 8 Step 9

Check assumpt. Calculate pH

In short, the steps will be : CH3(CH2)2COO + H3O CH3(CH2)2COOH + H2O init. conc. 0.10 0 0 eqm. conc. 0.10 - x x x [ H O + ][CH 3 (CH 2 ) 2 COO ] x2 Ka = 3 = = 1.5 x10 5 [CH 3 (CH 2 ) 2 COOH ] 0.10 x
+

Assume x << 0.10, i.e. 0.10 - x 0.10 x2 -3 = 1.5 x10 5 x = 1.225 x 10 0.10 -3 Since 1.225 x 10 << 0.10, assumption is valid. + -3 + -3 [H ] = x = 1.225 x 10 M pH = -log [H ] = -log (1.225 x 10 ) = 2.91

Chemistry/Ionic Equilibria

23

6.3 Base Only (Initially) + 3 Calculate the pH of a solution by dissolving 0.10 mole CH3(CH2)2COO Na in 1 dm , Ka of CH3(CH2)2COOH = -5 -3 1.5 x 10 mol dm . Step 1 Step 2 Conjugate acid/base pair Equilibrium equation CH3(CH2)2COOH/CH3(CH2)2COO Since the salt ionized completely, CH3(CH2)2COO is present initially, its reaction with water will be CH3(CH2)2COO + H2O CH3(CH2)2COOH + OH [OH ][CH 3 (CH 2 ) 2 COOH ] Kb = [CH 3 (CH 2 ) 2 COO ] CH3(CH2)2COO + H2O CH3(CH2)2COOH + OH init. conc. 0.10 0 0 eqm. conc. 0.10 - x x x [OH ][CH 3 (CH 2 ) 2 COOH ] K x2 Kb = = = w = 6.667 x10 10 0.10 x K a [CH 3 (CH 2 ) 2 COO ] Assume x << 0.10, i.e. 0.10 - x 0.10 x2 -6 = 6.667 x10 10 x = 8.165 x 10 0.10 -6 Since 8.165 x 10 << 0.10, assumption is valid. -6 [OH ] = x = 8.165 x 10 M -6 pOH = -log [OH ] = -log (8.165 x 10 ) = 5.09 pH = 14 - pOH = 8.91
-

Step 3 Step 4 Step 5 Step 6 Step 7

Write K expression Find initial conc. Define eqm. conc. Relate to K Solve eqn.

Step 8 Step 9

Check assumpt. Calculate pH

In short, the steps will be : CH3(CH2)2COO + H2O CH3(CH2)2COOH + OH init. conc. 0.10 0 0 eqm. conc. 0.10 - x x x [OH ][CH 3 (CH 2 ) 2 COOH ] K x2 Kb = = = w = 6.667 x10 10 0.10 x K a [CH 3 (CH 2 ) 2 COO ] Assume x << 0.10, i.e. 0.10 - x 0.10 x2 -6 = 6.667 x10 10 x = 8.165 x 10 0.10 -6 Since 8.165 x 10 << 0.10, assumption is valid. -6 [OH ] = x = 8.165 x 10 M -6 pOH = -log [OH ] = -log (8.165 x 10 ) = 5.09 pH = 14 - pOH = 8.91

Chemistry/Ionic Equilibria

24

6.4 Both Conjugate Acid-Base Pair (Initially) 3 3 Calculate the pH of a solution made up by 500 cm of 0.10 M of CH3(CH2)2COOH and 500 cm of 0.10 M + CH3(CH2)2COO Na . We may use acid dissociation or base dissociation, as long as the dissociation constant is appropriate. (1) Use acid dissociation, use Ka, calculate H and get pH. + CH3(CH2)2COO + H3O CH3(CH2)2COOH + H2O init. conc. 0.05 0.05 0 eqm. conc. 0.05 - x 0.05 + x x [ H O + ][CH 3 (CH 2 ) 2 COO ] x(0.05 + x) Ka = 3 = = 1.5 x10 5 [CH 3 (CH 2 ) 2 COOH ] 0.05 x Assume x << 0.05, i.e. 0.05 x 0.05 x(0.05) -5 = 1.5 x10 5 x = 1.5 x 10 0.05 -5 Since 1.5 x 10 << 0.05, assumption is valid. + -5 [H ] = x = 1.5 x 10 M + -5 pH = -log [H ] = -log (1.5 x 10 ) = 4.82 (2) Use base dissociation, use Kb, calculate OH and get pOH. CH3(CH2)2COOH + OH CH3(CH2)2COO + H2O init. conc. 0.05 0.05 0 eqm. conc. 0.05 - x 0.05 + x x [OH ][CH 3 (CH 2 ) 2 COOH ] x(0.05 + x) K w Kb = = = = 6.667 x10 10 Ka 0.05 x [CH 3 (CH 2 ) 2 COO ] Assume x << 0.05, i.e. 0.05 x 0.05 0.05 x -10 = 6.667 x10 10 x = 6.667 x 10 0.05 -10 Since 6.667 x 10 << 0.10, assumption is valid. -10 [OH ] = x = 6.667 x 10 M -10 pOH = -log [OH ] = -log (6.667 x 10 ) = 9.18 pH = 14 - pOH = 4.82 6.5 Reminders in Acid-Base Equilibrium Calculations + 1. The ionic product of water [H ] [OH ] = Kw always holds. 2. All equilibria hold, i.e. all equilibrium expressions must be satisfied. E.g. : For a tribasic acid, there are three dissociation as represented by three equilibria. All three equilibrium expressions are satisfied by the concentrations of the species involved. 3. Calculations must be done using equilibrium concentrations. 4. In a solution, there is only one concentration for each species, which equals to the sum from all contributions for that species. Equilibrium calculations are based on that concentration. + E.g. : In dibasic acids, H comes from ionization of water, first dissociation and second dissociation of acid. + However, there is only one [H ], which equals to sum of all of the above processes. All equilibria + involving H will make use of this concentration. 5. Acid-base equilibria proceed very fast and can be assumed to have established immediately (i.e. time required for attainment of equilibrium is negligible).
+

Chemistry/Ionic Equilibria

25

7. Buffers 7.1 Introduction Definition : Buffers are solutions that resist change in pH when small amounts of acid, base or water are added to it. Importance of Buffers For many chemical reactions (especially those in living organisms with enzymes), they can only proceed within a narrow range of pH. Example : Normal human blood has a pH range of 7.3 - 7.5 and a variation of 0.4 unit could prove fatal. Types of Buffers It can be divided into 2 classes : 1. Acidic buffer : made by a solution of weak acid and its salt (which is a weak base) + (e.g. CH3COOH & CH3COO Na ) 2. Alkaline buffer : made by a solution of weak base and its salt (which is a weak acid) + (e.g. NH3 & NH4 Cl ) Principle of Buffers In a buffer there are appreciable amounts of weak acid and weak base. In acidic buffer, they are the weak acid (CH3COOH) and its conjugate base (CH3COO ). + In alkaline buffer, they are the weak base (NH3) and its conjugate acid (NH4 ). When a strong acid is added, it will react and thus be removed by the weak base in solution. The weak base is converted to its conjugate weak acid. When a strong base is added, it will react and thus be removed by the weak acid in solution. The weak acid is converted to its conjugate weak base.

Example : CH3COOH/CH3COO buffer Addition of HCl : CH3COO + HCl CH3COOH + Cl [weak acid] , [weak base]

Addition of NaOH : + CH3COOH + NaOH CH3COO + Na + H2O [weak acid] , [weak base]

The addition of strong acid/base will change the relative amount of weak acid and weak base in buffer. The pH change is then governed by the equilibrium of the conjugate acid/base pair.

Chemistry/Ionic Equilibria

26

7.2 Buffer Calculations It is just a modification of the case where both conjugate acid/base pair are present initially. The added strong acid/base can be assumed to be removed completely and immediately upon addition, thus changing the initial concentrations of the conjugate acid/base pair. Example : 3 3 + For a solution made up by 500 cm of 0.10 M of CH3(CH2)2COOH and 500 cm of 0.10 M CH3(CH2)2COO Na , (1) Calculate the pH of the solution after addition of 0.001 mole of gas HCl. The added strong acid can be assumed to be completely removed by the weak base present, thus changing [CH3(CH2)2COOH]init. and [CH3(CH2)2COO ]init. accordingly. HCl + CH3(CH2)2COO CH3(CH2)2COOH + Cl CH3(CH2)2COO + H3O CH3(CH2)2COOH + H2O init. conc. 0.05 + 0.001 0.05 - 0.001 0 = 0.051 = 0.049 eqm. conc. 0.051 - x 0.049 + x x + [ H O ][CH 3 (CH 2 ) 2 COO ] x(0.049 + x) Ka = 3 = = 1.5 x10 5 [CH 3 (CH 2 ) 2 COOH ] 0.051 x
+

Assume x << 0.049, i.e. 0.051 - x 0.051; 0.049 + x 0.049 x(0.049) -5 = 1.5 x10 5 x = 1.561 x 10 0.051 -5 Since 1.561 x 10 << 0.049, assumption is valid. + -5 [H ] = x = 1.561 x 10 M + -5 makes sense as this is lower than before pH = -log [H ] = -log (1.561 x 10 ) = 4.81 (2) Calculate the pH of the solution after addition of 0.001 mole of solid NaOH. The added strong base can be assumed to be completely removed by the weak acid present, thus changing [CH3(CH3)2COOH]init. and [CH3(CH2)2COO ]init. accordingly. + NaOH + CH3(CH2)2COOH CH3(CH2)2COO + Na + H2O CH3(CH2)2COOH + H2O init. conc. 0.05 - 0.001 = 0.049 eqm. conc. 0.049 - x + [ H O ][CH 3 (CH 2 ) 2 COO ] Ka = 3 = [CH 3 (CH 2 ) 2 COOH ] CH3(CH2)2COO + H3O 0.05 + 0.001 0 = 0.051 0.051 + x x x(0.051 + x) = 1.5 x10 5 0.049 x
+

Assume x << 0.049, i.e. 0.051 + x 0.051; 0.049 - x 0.049 x(0.051) -5 = 1.5 x10 5 x = 1.441 x 10 0.049 -5 Since 1.441 x 10 << 0.049, assumption is valid. + -5 [H ] = x = 1.441 x 10 M + -5 makes sense as this is higher than before pH = -log [H ] = -log (1.441 x 10 ) = 4.84 Remarks : 1. The added strong acid/base will change the concentrations of the weak acid & base to by the same amount. If strong acid is added, [weak acid] and [weak base] by the same amount. If strong base is added, [weak acid] and [weak base] by the same amount. 2. Always check if the answer makes sense; the addition of strong acid should lower the pH whereas the addition of strong base should raise the pH.

Chemistry/Ionic Equilibria

27

Exercise : Kb for NH3 = 1.8 x 10 mol dm . (1) Calculate the pH of a 0.20 M solution of NH3. 3 (2) Calculate the pH of a 1 dm solution with 0.40 mole NH4Cl. 3 3 (3) Calculate the pH of a solution by mixing 600 cm of solution in (1) and 400 cm of solution in (2). (4) Calculate the new pH of the solution in (3) when 0.01 mole of solid NaOH is added to it. 3 (5) Calculate the new pH of the solution in (3) when 0.0005 cm of 18M HCl is added to it. (You may neglect the increase in volume after addition.) Solution : (1) Concentration Initial At eqm.

-5

-3

NH3 0.20 0.20 x

H 2O

NH4 0 x

OH 0 x

Kb =

[ NH 4 + ][OH ] x2 = = 1.8 x10 5 [ NH 3 ] 0.20 x

x = 1.897 x 10
-3

Assume 0.20 >> x, i.e. 0.20 - x 0.20,

x2 = 1.8 x10 5 0.20 -3 Since 1.897 x 10 << 0.20, assumption is valid. -3 [OH ] = 1.897 x 10 M pOH = 2.72
(2) Concentration Initial At eqm.
+

pH = 14 - 2.72 = 11.28
+

NH4 0.40 0.40 - x

H 2O

NH3 0 x

H 3O 0 x

Ka =

[ NH 3 ][ H + ] [ NH 4 + ]

K x2 1x10 14 = w = = 5.556 x10 10 0.40 x K b 1.8 x10 5

x = 1.491 x 10 pH = 4.83
+ -5

Assume 0.40 >> x, i.e. 0.40 - x 0.40,

x2 = 5.556 x10 5 0.40 -5 Since 1.491 x 10 << 0.40, assumption is valid. + -5 [H ] = 1.491 x 10 M

(3) Concentration Initial At eqm.

NH3 0.2x0.6/1 = 0.12 0.12 - x

H 2O

NH4 0.4x0.4/1 = 0.16 0.16 + x

OH 0 x

Kb =

[ NH 4 + ][OH ] (0.16 + x) x = = 1.8 x10 5 [ NH 3 ] 0.12 x 0.16 x = 1.8 x10 5 0.12

x = 1.35 x 10
-5

Assume 0.12 >> x, i.e. 0.12 - x 0.12 and 0.16 + x 0.16, Since 1.35 x 10 << 0.12, assumption is valid. -3 pOH = 4.87 [OH ] = 1.35 x 10 M
-5

pH = 14 - 4.87 = 9.13

Chemistry/Ionic Equilibria

28

(4) Concentration Initial At eqm.

NH3 0.12 + 0.01 = 0.13 0.13 - x

H 2O

NH4 0.16 - 0.01 = 0.15 0.15 + x

OH 0 x

Kb =

[ NH 4 + ][OH ] (0.15 + x) x = = 1.8 x10 5 [ NH 3 ] 0.13 x 0.15 x = 1.8 x10 5 0.13

x = 1.56 x 10
-5

Assume 0.13 >> x, i.e. 0.13 - x 0.13 and 0.15 + x 0.15, Since 1.56 x 10 << 0.12, assumption is valid. -3 pOH = 4.81 [OH ] = 1.56 x 10 M (5) No. of moles of HCl = 18 x 0.0005 = 9 x 10 + NH3 Concentration -3 0.12 - 9x10 = 0.111 Initial 0.111 - x At eqm.
-3 -5

pH = 14 - 4.81 = 9.19
-

H 2O

NH4 -3 0.16 + 9x10 = 0.169 0.169 + x

OH 0 x

Kb =

[ NH 4 + ][OH ] (0.169 + x) x = = 1.8 x10 5 [ NH 3 ] 0.111 x

Assume 0.111 >> x, i.e. 0.111 - x 0.111 and 0.169 + x 0.169, 0.169 x -5 = 1.8 x10 5 x = 1.182 x 10 0.111 -5 Since 1.182 x 10 << 0.111, assumption is valid. -5 pOH = 4.93 [OH ] = 1.182 x 10 M

pH = 14 - 4.93 = 9.07

Chemistry/Ionic Equilibria

29

7.3 Short Cut in Buffer Calculations 7.3.1 Acidic Buffer Take an acidic buffer as example. HA + H2O H 3O + A
+ -

Ka =

[ H + ] eqm [ A ] eqm [ HA] eqm [ HA] eqm [ A ] eqm )

[H ] depends on ratio (
+

[ H + ] eqm = K a (

[ HA] eqm [ A ] eqm

log[ H + ] eqm = log(

K a [ HA] eqm [ A ] eqm

) ) )

log[ H + ] eqm = log K a + log(

[ HA] eqm [ A ] eqm

log[ H + ] eqm = log K a log( pH = pK a + log

Henderson-Hasselbalch equation

[ HA] eqm [ A ] eqm

[ A ] eqm [ HA] eqm [base] eqm [acid ] eqm

pH = pK a + log
-

Usually, as seen from above examples, [A ]eqm [A ]init. and [HA]eqm [HA]init.. [ A ]init . . This is very often a valid assumption. Thus pH pK a + log [ HA]init . After addition of strong acid/base, the ratio the solution is resistant to pH change From pH = pK a + log(

[ A ] init . changes but usually only by a little. [ HA] init .

[base] eqm [acid ] eqm

) , there are several results.

1. The pH of the buffer depends only on the ratio of the concentrations of acid and base, not on their actual values. 2. When [acid]eqm = [base]eqm, pH = pKa. Thus pKa equal to the pH of a solution made from a solution of the acid which has been half neutralized by a strong base. 3. Addition of water does not change the pH of the buffer. Addition of water changes [acid] and [base] to the same extent, so the ratio

[base] is not changed. [acid ]

4. Once the weak acid/weak base in the buffer is completely used up, the buffering action will be gone. Example : In a solution with CH3COOH/CH3COO , when enough strong base (e.g. NaOH) is added which reacts all CH3COOH, or when enough strong acid (e.g. HCl) is added which reacts all CH3COO , then the solution is no longer a buffer and its resistance to pH change is gone.

Chemistry/Ionic Equilibria

30

5. For a buffer with larger values of [acid] and [base], when strong acid/base is added, change in

[base] will [acid ] be smaller and thus the buffer is more resistant to change its pH. The buffer is said to have higher buffering capacity. Example : For two buffers (1) [acid] = 0.1 M, [base] = 0.1 M (2) [acid] = 0.01 M, [base] = 0.01 M [base] = 1 for both buffers and thus pH = pKa. [acid ] 3 Addition of 0.001 mole of NaOH to 1 dm of each buffer separately, [base] 0.1 + 0.001 0.101 for (1), = = 1.020 , = pH = pKa + log(1.020) [acid ] 0.1 0.001 0.099 [base] 0.01 + 0.001 0.011 for (2), = = 1.222 , = pH = pKa + log(1.222 ) [acid ] 0.01 0.001 0.009 pH change in (2) will be larger than that in (1), buffer (1) is said to have a higher buffering capacity.

Remarks : 1. There is a similar expression for pKb, pOH & [acid]eqm and [base]eqm. [ HB + ] eqm [OH ] eqm + Ka = HB + OH B + H 2O [ B] eqm

[OH ] eqm = K b (

[ B] eqm [ HB ] eqm
+

[OH ] depends on ratio (

[ B] eqm [ HB + ] eqm

log[OH ] eqm = log(

K b [ B] eqm [ HB + ] eqm

) [ B] eqm

log[OH ] eqm = log K b + log(

[ HB + ] eqm

log[OH ] eqm = log K b log( pOH = pK b + log

Henderson-Hasselbalch equation

[ HB + ] eqm [ B] eqm

[ HB + ] eqm [ B] eqm [acid ] eqm [base] eqm

Make sure to use Ka

pOH = pK b + log [base] eqm [acid ] eqm

2. The expression pH = pK a + log(

) is also applicable to alkaline buffer.

(usually Kb is given and it has to be converted to Ka first). Example : Consider an alkaline buffer NH3/NH4 . We may treat the problem either as + + NH3 + H3O NH4 + H2O acid base [base] eqm pH = pK a + log [acid ] eqm
+

or NH3 + H2O base NH4 + OH acid [acid ] eqm

+ -

pOH = pK b + log

[base] eqm [ NH 4 + ] eqm [ NH 3 ] eqm

pH = pK a ( NH 4 + ) + log

[ NH 3 ] eqm [ NH 4 + ] eqm

pOH = pK b ( NH 3 ) + log

Chemistry/Ionic Equilibria

31

Example : 3 3 A solution X is formed by mixing 0.50 dm of 0.30 M methanoic acid with 0.50 dm of 0.15 M sodium hydroxide. -4 -3 (i) Given that Ka for methanoic acid is 1.75 x 10 mol dm at 298 K, calculate the pH of solution X. (ii) What special property does solution X have ? What is it commonly known as ? (87, II) Solution : The substances present are methanoic acid (weak acid) and sodium methanoate (its conjugate base). (i) + HCOO + H HCOOH 0 After mixing 0.5 x0.3 0.5 x 0.15 0.5 x 0.15 = 0.075 = 0.075 1 1 At eqm. 0.075 - x 0.075 + x x

Ka =

x (0.075 + x) 0.075x = x = 1.75x104 0.075 x 0.075

[H ] = 1.75 x 10 M

-4

pH = 3.76

(ii) The solution has the ability to resist a change in pH when small amounts of either acid or base are added. The solution is generally known as a buffer solution. Example : The following solutions can act as a buffer : (I) a solution with [CH3COOH] = 0.100 M and [CH3COO ] = 0.075 M (II) a solution with [CH3COOH] = 1.000 M and [CH3COO ] = 0.750 M (i) Calculate the approximate pH value of (I) and (II). -5 -3 [Ka = 1.85 x 10 mol dm for CH3COOH] (ii) Which of the above solutions is the better buffer ? Explain your answer. (iii) Can a solution of ethanoic acid alone act as a buffer ? Explain your answer. Solution : (i) CH3COOH
+

(89, II)

CH3COO + H

pH = pK a + log(
For I,

[base] eqm [acid ] eqm

) = pK a + log(

[CH 3 COO ] eqm [CH 3 COOH ] eqm

)
[CH3COOH]eqm 1.000 M [CH3COO ]eqm 0.750 M pH = 4.61
-

[CH3COOH]eqm 0.100 M [CH3COO ]eqm 0.075 M pH = 4.61

For II,

(ii) Solution (II) is a better buffer than (I) because it has larger [CH3COOH] and [CH3COO ] and thus has a larger buffering capacity. (iii) An ethanoic acid solution alone cannot be a buffer because it contains little CH3COO ions (from the ionization + of ethanoic acid). Thus when a strong acid is added, the solution cannot effectively remove H ions and the pH of the solution will change by a large amount.
-

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Example : (i) At 298 K, the pH of 0.050 M CH3CH2COOH is 3.10. Calculate the Ka of CH3CH2COOH at 298 K. (ii) Calculate the pH at 298 K of a solution which is 0.050 M with respect to CH3CH2COOH and to CH3CH2COONa. -4 (iii) 5.0 x 10 mol of solid NaOH were added separately to 3 (1) 100 cm of 0.050 M CH3CH2COOH, and 3 (2) 100 cm of the solution in (ii) above. Assuming that the change in volume upon the addition of NaOH is negligible, calculate the pH at 298 K of the solution in each case. Comment on the difference in the pH change of the two solutions. (96, II) Solution : (i) Initial At eqm. CH3CH2COOH 0.050 -3.1 0.050 10 CH3CH2COO 0 -3.1 10
-

H 0 -3.1 10

Ka =

10 3.1 x10 3.1 0.050 10 3.1

= 1.28 x10 5 mol dm 3

[CH 3 CH 2 COO ] eqm [CH 3 CH 2 COOH ] eqm
-

(ii)

pH = pK a + log(

[base] eqm [acid ] eqm

) = pK a + log(

[CH3CH2COOH]eqm 0.050 M, [CH3CH2COO ]eqm 0.050 M 0.050 pH = log(1.28 x10 5 ) + log( ) = 4.89 0.050 (iii) pH = pK a + log( For solution (1),

[CH 3 CH 2 COO ] eqm [CH 3 CH 2 COOH ] eqm

) 0.050 x(100 ) 5 x10 4 1000 = 0.045M 100 1000

[CH 3 CH 2 COOH ] eqm [CH 3 CH 2 COO ] eqm

pH = 3.93

5 x10 4 = 0.005M 100 1000 0.050 x(100

For solution (2),

[CH 3 CH 2 COOH ] eqm [CH 3 CH 2 COO ] eqm

pH = 4.98

) 5 x10 4 1000 = 0.045M 100 1000 0.050 x(100 ) + 5 x10 4 1000 = 0.055M 100 1000

0.05 M CH3CH2COOH is not a buffer and thus pH changes significantly (0.83 unit) while the solution in (ii) is a buffer and thus pH changes little (0.09 unit).

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Exercise : + 3 1. Calculate the volume of 0.1 M HCOO Na (aq) that must be added to 1 dm of 0.1 M methanoic acid solution to give a buffer solution of pH = 3.50. The pKa for methanoic acid is 3.75. Solution : 3 + Let V dm be the volume of HCOO Na required. [base] eqm [ HCOO ] eqm pH = pK a + log( ) = pK a + ( ) [acid ] eqm [ HCOOH ] eqm

[ HCOOH ] =

0.1x1 0.1xV ; [ HCOO ] = V +1 V +1 0.1V ( ) V +1 3.5 = 3.75 + log ( 0 .1 ) V +1

3

logV = 0.25
3

V = 0.562 dm

2. 1 dm of a solution is obtained by mixing 500 cm of 0.200 M HCl and 500 cm of 0.700 M NaCN. Given that -10 -3 (88, II) the dissociation constant of HCN is 4.0 x 10 mol dm , calculate the pH of this solution. Solution :

pH = pK a + log( [ HCN ] eqm

[base] eqm [acid ] eqm

) = pK a + log(

[CN ] eqm [ HCN ] eqm

0.200 x(500

1 500 0.7 x( ) 0.200 x(500 ) 1000 1000 = 0.25M [CN ] eqm 1 0.25 10 pH = log(4.0 x10 ) + log( ) pH = 9.80 0.10

) 1000 = 0.10 M

3. Given : -5 -3 Ka for CH3(CH2)2COOH = 1.5 x 10 mol dm at 298 K. Calculate the pH of (i) an aqueous solution of 0.1 M CH3(CH2)2COOH ; (ii) an aqueous solution of 0.05 M CH3(CH2)2COONa and 0.05 M CH3(CH2)2COOH ; and 3 -3 (iii) 1.0 dm of the solution in (ii) after the addition of 1.0 x 10 mol of solid NaOH. Solution : (i) Initial At eqm. CH3(CH2)2COOH 0.1 0.1 - x CH3(CH2)2COO 0 x

-

(94, II)

H 0 X

Ka =

x2 x2 = 1.5 x10 5 0.1 x 0.1

x = 1.225 x 10
+

-3 -3

[H ] = 1.225 x 10 M

pH = 2.91

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34

(ii)

pH = pK a + log(

[base] eqm [acid ] eqm

) = pK a + log(

[CH 3 CH 2 COO ] eqm [CH 3 CH 2 COOH ] eqm

[CH3(CH2)2COOH]eqm 0.05 M [CH3(CH2)2COO ]eqm 0.05 M 0.05 pH = log(1.5 x10 5 ) + log( ) 0.05
-3

pH = 4.82

(iii) [CH3(CH2)2COOH]eqm 0.05 - 1.0 x 10 = 0.049 M -3 [CH3(CH2)2COO ]eqm 0.05 + 1.0 x 10 = 0.051 M 0.051 pH = log(1.5 x10 5 ) + log( ) pH = 4.84 0.049 Exercise : -5 -3 + A weak base MOH has an ionization constant Kb = 2.0 x 10 mol dm , where Kb = [M ][OH ]/[MOH]. 3 Solution S is made up of 0.10 mol of MOH in 1.0 dm , and a second solution T has 0.10 mol of MOH and 0.50 mol 3 of MCl in 1.0 dm . (i) Calculate the pH of solutions S and T. (ii) 0.01 mol of a strong acid HX is added separately to the solutions S and T. The new pH value for solution S is 10.26; calculate that for solution T. What conclusion can you draw from this result ? -14 2 -6 (Kw = 1.0 x 10 mol dm ) (91, II) Solution :

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35

8. Indicators 8.1 Introduction Acid-base indicators are usually coloured organic compounds. They are either weak acids or weak bases, whose colour depend on pH of the solution. Example : H3O (aq) + In (aq) HIn(aq) + H2O(l) colour A colour B Colour A has to be distinct from colour B.
+ -

With Henderson-Hasselbalch equation pH = pK a + log(

[base] eqm [acid ] eqm

or

) , and treating indicators as weak acids gives [ In ] eqm [ HIn] eqm ) = pH pK a

pH = pK a + log(

[ In ] eqm [ HIn] eqm

log(

The colour of an indicator depends on the relative amount of the two coloured species, i.e. terms depends on the pH of the solution.

[ In ] , which in [ HIn]

8.2 Working Range of Indicator The pH range in which an indicator functions (i.e. changes colour) is known as its working range. Working range of an indicator depends on its Ka. Example : Phenolphthalein (HPh) has a pKa = 9. HPn(aq) + H2O(l) colourless At pH < 7, H 3O
+ (aq)

+ Pn (aq) red

log(

[ Pn ] ) < 2 [ HPn]

[ Pn ] 1 < [HPn] > 100 [Pn ] [ HPn] 100 colour will be that of HPn, i.e. colourless [ Pn ] 1 = [HPn] = 10 [Pn ] [ HPn] 10 colour of Pn (red) becomes detectable [ Pn ] =1 [HPn] = [Pn ] [ HPn] equal amount of HPn and Pn , red colour darkens [ Pn ] = 10 10 [HPn] = [Pn ] [ HPn] red colour fully developed

At pH = 8,

log(

[ Pn ] ) = 1 [ HPn]

At pH = 9,

log(

[ Pn ] )=0 [ HPn]

At pH = 10,

log(

[ Pn ] ) =1 [ HPn]

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Experimental working range of some indicators Indicator Thymol blue (1 ) Methyl orange Methyl red nd Thymol blue (2 ) Phenolphthalein
st

pKa 1.7 3.7 5.1 8.9 9.3

pH range 1.2 - 2.8 3.2 - 4.2 4.2 - 6.3 8.0 - 9.6 8.2 - 10.0

Colour change Acidic Colour Alkaline Colour Red Yellow Red Yellow Red Yellow Yellow Blue Colourless Red

Remarks : 1. Most indicators have a detectable colour change over a range of about 2 pH units. This is a consequence of the sensitivity of our eyes to colour changes. Thus the working range of an indicator is usually pKa 1. 2. Some pH ranges are not exactly pKa 1. This is because the completion of colour change for different indicator is different. We have assumed above that completion occurs when there is a ten-fold ratio between the two colour forms. This ratio may be different for different indicator. 3. Thymol blue has two working ranges. This is because it is a dibasic acid, with three different coloured forms. + + 2H3O (aq) + HIn (aq) HIn (aq) + H2O(l) H3O (aq) + In (aq) H2In(aq) + H2O(l) red yellow yellow blue Exercise : 1. Account for the fact that at 298 K, in a solution of pH 7.0, the indicator methyl orange shows its alkaline colour (yellow), while phenolphthalein shows its acidic colour (colourless). (94, II) Solution :

2. An acid-base indicator, HIn, is a weak acid with dissociation constant Ka. + H3O (aq) + In (aq) HIn(aq) + H2O(l) yellow blue [ In ( aq ) ] (i) Show that pH = pK a + log [ HIn( aq ) ] (ii) Given that Ka of HIn is 1.0 x 10 mol dm , deduce the colour of a solution containing the indicator (I) at pH 3.9. (II) at pH 10.0. Solution :
-4 -3

(00, II)

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37

9. Acid-Base Titrations Equivalence Point : Point in titration at which equivalent amounts of acid and alkali have reacted completely according to the stoichiometric equation. End-Point : Point in titration at which there is a marked colour change in its indicator used. Remark : It is customary to put acid in the burette for the titration. This is because bases like NaOH can attack glass joint in stop-cock in burette, thus blocking the jet. The titration curves for the four possible combinations are shown below.

STRONG ACID vs STRONG BASE

STRONG ACID vs WEAK BASE

WEAK ACID vs STRONG BASE

WEAK ACID vs WEAK BASE

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38

If base is used in the burette, the titration curve will just be the opposite of the above ones.

For a suitable indicator, its working range must lie in the steep region when the pH changes significantly.

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39

In summary : Strong Acid vs Strong Base HCl vs NaOH 7 4-10 All indicators Strong Acid vs Weak Base HCl vs NH3 <7 3-7 methyl orange and methyl red Weak Acid vs Strong Base CH3COOH vs NaOH >7 7-11 phenolphthalein Weak Acid vs Weak Base CH3COOH vs NH3 depends on acid and base used depends on acid and base used no indicator

Example pH at equivalence point pH change near equivalence point Suitable indicators

Example : 3 Calculate the pH at the equivalence point when 25 cm of 0.1 M CH3COOH is neutralized by 0.1 M NaOH. Ka of -5 -3 CH3COOH is 1.75 x 10 mol dm . CH3COOH + NaOH CH3COO Na + H2O 3 At equivalence point, 25 cm of NaOH has to be added. 3 Total volume at equivalence point = 50 cm . + + At equivalence point, CH3COO Na ionizes completely to give CH3COO and Na . conjugate acid by the following equilibrium and is thus basic. + H 2O CH3COOH CH3COO Initial 0.05 0 At eqm. 0.05 - x x
+

CH3COO is related to its + OH 0 x

-

[CH 3 COO ] -6 [OH ] = 5.34 x 10 M

Kb =

[CH 3 COOH ][OH ]

K x2 x2 1.0 x10 14 = w = 0.05 x 0.05 K a 1.75 x10 5 pOH = 5.27 pH = 8.73

x = 5.34 x 10 M

-6

Exercise : 3 Calculate the pH at the equivalence point when 25 cm of 0.05 M NH3 is neutralized by 0.1 M HCl. Kb of NH3 is -5 -3 1.80 x 10 mol dm . Solution :

Chemistry/Ionic Equilibria

40

5.6.1.3 By conductivity measurements Changing ions concentrations of a solution changes electrical conductivity of the solution, so acid-alkali (carbonate) titrations can be followed by conductivity measurements.

Example : Referring to the graph, At A : Conductivity is high due to presence of large number of mobile OH- and Na+ ions from NaOH. A to E : HCl added ionizes in water, giving H+ and Cl-. HCl(aq) H+(aq) + Cl-(aq) + H added combines with OH- to form H2O, which undergoes essentially no ionization. H+(aq) + OH-(aq) H2O(l) Although the no. of ions is not changed in solution (the OH- lost is replaced by Cladded), since Cl- is less mobile than OH-, conductivity decreases. At E : The end point. Conductivity is at a minimum when neutralization is complete. The conductivity at the end point is not zero as the solution contains Na+ and Cl- ions which conduct electricity. E to B : Conductivity increases due to the addition of excess mobile H+ and Cl- ions from HCl.

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41

Example : Conductivity measurement is one of the principle ways of detecting the end-points of weak acid-weak base titrations. By plotting conductivity against volume of weak acid added, account for the change in conductivity in terms of the dissociation of the weak acid and weak base. Explain how this plot can be used to determine the endpoint in such a titration. (88, II) Conductivity is directly proportional to the concentration of mobile ions in solution.

Initially, the conductivity is low as weak base only dissociates slightly. Addition of weak acid neutralizes the weak base, the resulting salt ionizes completely and conductivity increases. At equivalence point, the base is completely neutralized by the acid added. Only salt is present and it ionizes completely giving the highest conductivity. This is recorded as the end-point of the titration. After that, addition of further acid which ionizes slightly will barely change the conductivity. Exercise : Temperature change and conductivity measurement can also be used to determine end-points in titrations. Draw on the following graphs, when sodium hydroxide is added to (1) a strong acid, e.g. HCl, and (2) a weak acid, e.g. CH3COOH.

temperature

conductivity

NaOH added

NaOH added

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The titration of sodium carbonate with hydrochloric acid consists of two stages. Stage 1 Na2CO3(aq) + HCl(aq) NaHCO3(aq) + NaCl(aq) phenolphthalein as indicator pH at this equivalence point 8.5 Stage 2 NaHCO3(aq) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g) pH at this equivalence point 4.0

methyl orange as indicator

Example : 3 3 25.0 cm of a solution containing sodium carbonate and sodium hydrogencarbonate required 27.5 cm of 0.80 M 3 hydrochloric acid to decolorize phenolphthalein. On addition of methyl orange, a further 32.5 cm of the acid were required to turn the indicator to its neutral colour. Determine the concentration of sodium carbonate and sodium hydrogencarbonate in the solution. The titration of sodium carbonate consists of two stages : Stage 1 Na2CO3(aq) + HCl(aq) NaHCO3(aq) + NaCl(aq) Stage 2 NaHCO3(aq) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g) Stage 1 : 2No. of moles of HCl needed to convert CO3 to HCO3 = No. of moles of Na2CO3 = Concentration of Na2CO3 = Stage 2 : No. of moles of HCl needed to neutralize all HCO3 = No. of moles of HCl used to neutralize HCO3 coming from Na2CO3 = No. of moles of HCl used to neutralize HCO3 coming from NaHCO3 = No. of moles of NaHCO3 in solution = Concentration of NaHCO3 =
-

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43

10. Solubility Product 10.1 Introduction Consider a saturated solution of silver chloride that is in contact with solid silver chloride. solution. undissolved silver chloride solid present, the solution is a

Since there is

Macroscopically, the amount of solid silver chloride present changes/does not change with respect to time. The state. system seemingly has attained a completely However, microscopically, a exactly the same as the rate of equilibrium has in fact been established, with the rate of .

The solubility equilibrium can be represented as

AgCl(s)

dissolution precipitation

Ag+(aq) + Cl-(aq)

As for any heterogeneous reactions, the concentration of a solid is a constant; it does not appear in the equilibrium expression. + Therefore, equilibrium constant for the dissociation of AgCl is Ksp = [Ag ]eqm [Cl ]eqm, where Ksp is called the solubility product constant or simply the solubility product. Example : Write the solubility products and their units for the following compounds. 1. MgF2 2. Ag2CO3 3. Ca3(PO4)2 Ksp = Ksp = Ksp = Unit : Unit : Unit :

Remarks : 1. The value of Ksp is related to the solubility of an ionic compound. A smaller Ksp implies a less/more soluble compound in water. 2. Such equilibrium only holds when both components are present, i.e. there is undissolved solid present in a saturated solution. produced from dissolution. 3. There is/is no fixed unit for Ksp. It depends on the 10.2 Solubility and Solubility Product -3 -3 Solubility of a solute is either expressed in g dm or mol dm . Solubility and solubility product can be interconverted fairly easily. Example: -3 The solubility of calcium sulphate is found to be 0.67 g dm . Calculate the value of Ksp for calcium sulphate. CaSO4(s) [Ca ] = [SO4 ] = Ksp = Exercise : -15 -3 The solubility of bismuth sulphide (Bi2S3) is 1.0 x 10 g dm . Calculate the solubility product of this compound.
2+ 2-

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44

Example: -3 -20 3 -9 Calculate the solubility of copper(II) hydroxide, Cu(OH)2 in g dm . [Ksp(Cu(OH)2 = 2.2 x 10 mol dm .] Cu(OH)2(s) At eqm. Ksp = 2.2 x 10
x=
-20

Cu

2+ (aq)

2OH (aq)

x =

Solubility of Cu(OH)2 = Exercise : -3 -3 -10 2 -6 Calculate the solubility of silver chloride in g dm and mol dm . [Ksp(AgCl) = 1.7 x 10 mol dm .]

10.3 Ionic Product When a ionic solid is added to an aqueous solution, there can be three possibilities : (1) the solution is unsaturated (2) the solution is saturated (3) the solution is supersaturated For concentrations that do not correspond to equilibrium conditions, reaction quotient rather than solubility product can be calculated. In solubility situation, we called the reaction quotient (Q) ionic product. For AgCl + solution, ionic product = [Ag ]0 [Cl ]0 Remarks: Note that Q has the same form as Ksp except that the concentrations of ions are not equilibrium concentrations. Ionic product is useful to predict whether a precipitate will form. The possible relationships between Q and Ksp are Unsaturated/Saturated/Supersaturated solution (no precipitation) Ionic product < Ksp Ionic product = Ksp Unsaturated/Saturated/Supersaturated solution (no precipitation yet) Unsaturated/Saturated/Supersaturated solution; Ionic product > Ksp AgCl will precipitate out until the ionic product = Example : 3 3 Exactly 200 cm of 0.0040 M BaCl2 are mixed with exactly 600 cm of 0.0080 M K2SO4. Will a precipitate form ? -10 2 -6 [Ksp(BaSO4) = 1.1 x 10 mol dm ] [Ba ] = [SO4 ] = [Ba ] [SO4 ] = The solution is unsaturated/saturated/supersaturated. out of the solution until Some of the BaSO4 will
2+ 222+

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10.4 The Common Ion Effect and Solubility Suppose there is a saturated solution of AgCl(aq). + Ag (aq) + Cl (aq) AgCl(s) If AgNO3(aq) is added, since AgNO3 is essentially completely ionized,
H2 AgNO3(s) O Ag
+ (aq)

+ NO3 (aq) dissolution, [Ag ] = contribution from AgCl + contribution from AgNO3.
+

Since both species gives Ag

(aq) upon +

Such action has increased [Ag ], making the ionic product greater than Ksp, and some AgCl has to precipitate out, until the ionic product decreases to Ksp. This precipitation effect is known as the common ion effect. The phenomenon can also be explained by Le Chateliers principle : + + system responses by increasing/decreasing [Ag ] An increase in [Ag ] shifting equilibrium position to the left/right more/less AgCl(s) is precipitated out Common Ion Effect is the effect of adding a common ion which causes a decrease in the solubility of the salt in the solution. Remarks : + + Notice that since [Ag ] came from two sources, [Cl ] no longer equals to [Ag ]. + In terms of the equilibrium law, the relationship Ksp = [Ag ] [Cl ] still holds. Example -3 -3 Calculate the solubility of silver chloride (in mol dm ) in a 6.5 x 10 M silver nitrate solution. -10 2 -6 [Ksp(AgCl) = 1.7 x 10 mol dm .] AgCl(s) At eqm. Ksp = =
x=

Ag

+ (aq)

Cl (aq) x

Solubility of AgCl = Exercise : Mercury(I) chloride, Hg2Cl2(s), is sparingly soluble in water, and gives Hg22+(aq) and Cl-(aq) ions. The solubility product Ksp of Hg2Cl2(s) is 2.4 x10-18 mol3 dm-9 at 298 K. Calculate, at 298K, the solubility of Hg2Cl2(s) (I) in pure water, and (4 marks, 08) (II) in 0.10 mol dm-3 KCl(aq)

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