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IONIC EQUILIBRIUM INVOLVING WEAK ELECTROLYTES

SECTION I
KCl HCl + H2O HCl 1. 2. 1a. 2a. 3. 3a. H2A + H2O HA- + H2O H2A HAH2A H2O + HOAc
3 +

K+ + ClH3O+ + Cl-

H+ + Cl-

H3O+ + HAH3O + A= H+ + HAH+ + A= 2H+ + A= H3O+ + OAc

4.

[ H O ][ OAc ] K=
[ H 2 O][ HOAc]
K[H2O] =

5.

[H

3O

[ HOAc]

][ OAc ]

K[H2O] = Ka 6.

[H Ka =
Ka =

3O

[ HOAc]
+

][ OAc ]

7.

[ H ][ OAc ]
[ HOAc]

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Example 1 Calculate the Ka for HOAc if .1 M solution of HOAc is 1.34% ionizable. Solution HOAc Since HOAc is 1.34% ionizable Concentration of [H+] which is equal to the concentration of [OAc-] = The concentration of HOAc = .1 H+ + OAc-

1.34 .1 = 1.34 10-3 m.l. 100

1.34 .1 = .099 100


3
-5

Ka = Example 2

[1.34 10 ][1.34 10 ] = 1.8 10


3

.099

Kb for NH4OH is 1.8 10-5. Calculate the concentration of NH4+ and the OH- and the % ionization if . 5 molar NH4OH solution. Solution NH4OH NH4+ + OH-

The concentration of NH4+ = the concentration of OH-. Let x be the concentration of NH4+. Then x is the concentration of OH- and the concentration of NH4OH is .5 - x.

[ NH ][ OH ] Kb =
4 +

[ NH 4 OH]
x. x .5 x

1.8 10-5 =

x is very small compared to .5. It can be deleted from the denominator: 1.8 10-5 =
x2 .5

.9 10-5 = x2 9 10-6= x2
9 10 6 = x

3 10-3 = x = NH4+ = OH% ionization =

concentration of NH 4 + or concentration of OH concentration of original base

100

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% ionization =

3 10 3 .5

100 = .6%

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SECTION II
1. Calculate the concentration of each ion in the following solutions. (a) (b) (c) .05 M HCl 1.2 M NaOH .1 M NaOAc

2.

Calculate the H+ and the % ionization in a .1 M HCN (Ka HCN 4 10-10).

3.

.1 M NH4OH solution is 1.34% ionizable. Calculate the Kb for NH4OH.

4.

Calculate the H+ and the % ionization in a 1 M HOAc (Ka 1.8 10-5).

ANSWERS FOR SECTION II: 1. (a) (b) (c) 2. [H+] = .05 [Cl-] = .05 [Na+] = 1.2 [OH-] = 1.2 [Na+] = .1 M [OAc-] = .1

[H+] = 6.3 10-6 % ionization = 6.3 10-3%

3. 4.

1.85 10-5 [H+] = 4.24 10-3 % ionization = .424%

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SECTION III
(Common Ion) PbCl2 HCl Pb+2 + 2ClH+ + Cl-

If HCl is added, the solubility of PbCl2 will be reduced. HOAc Example 1 Calculate the [H+] in a .1 M HOAc which contains .1 M NaOAc (Ka HOAc 1.8 10-5). HOAc Solution HOAc is a weak electrolyte. The Ka expression is given by Equation 7 of Section 1.
+ H OAc [ HOAc ]

H+ + OAc-

H+ + OAc-

Ki =

Assume the concentration of H+ = x. The concentration of OAc- from OHAc = x. NaOAc is a strong electrolyte; thus the concentration of the OAc- = .1, and the total concentration of OAc- is .1 + x. 1.8 10-5 =

[ x] [ . 1 + x]
.1

The value of x compared to .1 is very small. It can be neglected. Hence: 1.8 10-5 =
+

[ x] [ . 1]
.1

H = x = 1.8 10-5 Reaction 1: Reaction 2: HOAc NaOAc H+ + OH H+ + OAcNa+ + OAcH2O

66

Example 2 Calculate the [OH-] in a .2 M NH3 solution which also contains .5 M NH4Cl. Kb NH3 is 1.8 10-5.

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Solution NH4OH is a weak electrolyte. NH3 + H2O


4 +

NH4 + + OH

[ NH ] [ OH ] Kb =
[ NH 3 ]
NH4Cl NH4+ + ClAssume the concentration of OH- = x. Concentration of NH4+ from NH4OH is also x. But in addition to NH4+ from NH4OH, we have NH4 from NH4Cl which is .5 M. The total NH4+ = .5 + x.
+

Substitute the values obtained from the ionization expression for NH4OH 1.8 10-5 =

[ . 5 + x] [ x] [ . 2]
[ . 5] [ x]
.2

x is very small compared to .5; thus it can be neglected. 1.8 10-5 =

.36 10-5 = .5x .72 10-5 = x 7.2 10-6 = x x = 7.2 10-6

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Section IV
1. Calculate the concentration of [H+] in a .1 M HCN solution which also contains .2 M NaCN (Ka HCN 4 10-10).

2.

Calculate the [H+] in a .2 M HOAc solution which also contains .2 M NaOAc (Ka HOAc 1.8 10-5).

3.

How many m/l of hydrogen ions are contained in a .1 M HOAc solution which contains .2 Mole of NaOAc? (Ka HOAc 1.8 10-5 ).

ANSWERS TO SECTION IV: 1. 2. 3. [H+] = 2 10-10 mole/liter [H+] = 1.8 10-5 mole/liter [H+] = 9 10-6 mole/liter

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Section V
(Ionization of Water)
Reaction 3: Reaction 4: Eq. 8 H2O + H2O H2O
+

H3O+ + OH-

H+ + OH-

[ H ] [ OH ] Ke =
[ H 2 O]
Ke[H2O] = [H+][OH-]

Eq. 9

Kw = [H+][OH-] Kw is the ion product constant for water. Kw is a constant at 25C and has a value of 1 10-14.

Eq. 10 [H+][OH-] = 1 10-14 It follows that in an aqueous solution at 25C. Eq. 11 pH + pOH = 14 In pure water the [H+] = [OH-] = 1 10-7. For example, calculate the [OH-] in a .01 molar HCl. Solution [H+][OH-] = 1 10-14 [1 10-2][OH-] = 1 10-14 OH- =

1 10 14 1 10 2

= 1 10-12

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Section VI
(pH)
Eq. 12 pH = -log[H+] Eq. 13 pOH = -log[OH-] Example 1 Calculate the pH of a solution in which [H+] is 1 10-3 m/l. Solution Substitute the value given in Equation 12. pH = -log[H+] = -log[1 10-3] = -[log 1 + log 10-3] = -[-3 log 10] = -[-3] = 3 Example 2 Calculate the pH of .0055 molar HCl. Solution HCl is completely ionzied; thus the H+ is .0055 or 5.5 10-3. Substitute the value in Equation 12. pH = -log[5.5 10-3 = [log 5.5 + log 10-3] = -[.74 - 3] = -[-2.26] = 2.26 If the pOH is required, remember that: pH + pOH = 14 pOH = 14 - 2.26 pOH = 11.74

71

Example 3 Calculate the pH of .1 M HOAc. Ka 1.8 10-5. Solution HOAc is a weak electrolyte. Ki expression is given by Equation 7. Ka =

[ H ] [ OAc ]
+

[ HOAc]

H+ = x OAc- = x 1.8 10-5 =


x. x .1

1.8 10-6 = x2 1.34 10-3 = x therefore, therefore, H+ = 1.34 10-3 pH = -log[1.34 10-3] = -[.11 - 3] = -[-2.89] = 2.89 IMPORTANT POINTS TO REMEMBER 1. 2. 3. The pH of a neutral solution is 7; at this point the [H+] = [OH-] = 1 10-7 m/l. If the pH of solution is less than 7, then the solution is acidic and the [H +] is larger than 1 10-7. If the pH of a solution is more than 7, then the solution is basic and the [H+] is less than 1 10-7.

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Section VIII
1. Calculate the pH of .1 M HCl.

2.

Calculate the pH of .1 M HOAc (Ka HOAc 1.8 10-5)

3.

Calculate the pH, pOH of .0005 M HCl.

4.

Calculate the pH of .05 M HCN (Ka 4 10-10)

5.

Calculate the pOH of .5 M HOA (Ka HOAc 1.8 10-5)

ANSWERS TO SECTION VIII: 1. 2. 3. pH = 1 pH = 2.89 pH = 3.3 pH = 10.7 4. 5. pH = 5.35 pOH = 11.48

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Section IX
(Hydrolysis)
Reaction 5: Reaction 6: Reaction 7: NH4Cl + H2O NaOAc + H2O NH4+ + HOH NH4OH + HCl NaOH + HOAc NH4OH + H+

Eq. 14 Ka =

[ NH 4 OH ] [ H + ] [ NH 4 + ] [ HOH]

Ka[HOH] = Kh

Eq. 15 Kh =

[ NH 4 OH ] [ H + ]

[ NH ]
4 +

Eq. 16 Kh = Eq. 9

Kw Kb

[H+][OH-] = Kw

From the hydrolysis of the NH4+ NH4+ + HOH

NH4OH + H+

Eq. 17 Therefore, Kh =

[ NH 4 OH ] [ H + ]

[ NH ]
4 +

Substitute the value of [H+] from Eq. 9 into Eq. 17 and obtain Eq. 18.

Eq. 18 Kh =

[ NH 4 OH ] [ Kw]

[ NH ] [ OH ]
4 + +

but

[ NH ] [ OH ]
4

[ NH 4 OH ]

1 k1

i.e.

Kw = Kh Kb

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Example 1 Calculate the pH of a solution which is .1 M NaOAc. (Ka HOAc 1.8 10-5) Solution OAc- + HOH HOAc + OH-

The hydrolysis of OAc- indicates an increase in the OH-; hence, the solution should be basic. Assume the concentration of HOAc = x. Then the concentration of OH- = x.

[ HOAc] OH Kw = Kh = Ka OAc

1 10 14 18 . 10
5

x. x .1

10 10 16 18 . 10 5

= x2

5.5 10-11 = x2 55 10-12 = x 7.5 10-6 = x pOH = -log[OH-] = -log[7.5 10-6] = [.88 - 6] = 5.12 therefore, pH = 14 - 5.12 = 8.88

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Example 2 Calculate the pH of a .1 M NaCN solution. Ka HCN 4 10-10. Solution CN- + HOH HCN + OH-

From the reaction between CN- and water, it can be seen that there is an increase in the OH-, and therefore the solution will be basic. Let x be the concentration of HCN; then the concentration of OH - is x. That is, [HCN] = [OH-] = x. Eq. 19

[ HCN ] OH Kw = Kh = Ka CN

10 10 15 4 10
10

x. x .1

2.5 10-6 = x2 1.58 10-3 = x pOH = -log[1.58 10-3] = [.2 - 3] = 2.8 pH = 14 - 2.8 = 11.2

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Section X
1. Calculate the [OH-], [H+], and the pH in .2 M (NaCN). (Ka HCN = 4 10-10)

2.

Calculate the [H+] and the pOH in .2 M NH4Cl. (Kb NH4OH = 1.8 10-5)

3.

Calculate the [H+] and the pH of .5 M NaOAc. (Ka HOAc 1.8 10-5)

ANSWERS FOR SECTION X: 1. [OH-] = 2.24 10-3 [H+] = 4.46 10-12 pH = 11.35 2. [H+] = 1.05 10-5 pOH = 9.02 3. [H+] = 6 10-10 pH = 9.22

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