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Salt hydrolysis

The ions of salts can have an influence on the pH of a


solution.
Ions that come from a strong acid or base do not
influence the pH.
WHY?

Since strong acids and bases are


100% ionized in water, the ions are
unable to reform the molecular acid
or the base in water.

HCl + H2O  H3O+ + Cl- “one way arrow”

NaOH + H2O  Na+ + OH- + H2O “one way arrow”


NaCl is the salt that comes from a strong acid and a
2
strong base.
What would the pH of a sodium chloride solution (@ 25oC)?
pH = 7
What gives rise to this pH?

Auto hydrolysis of water

H2O + H2O ↔ H3O+ + OH-

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Salts that contain ions that come from a weak acid or base
HNO2 : weak acid
A salt containing the anion of the weak acid and the cation
from a strong base.
KNO2
Add water: KNO2(s) + H2O  K+ + NO2- + H2O

Hydrolysis: NO2- + H2O ↔ HNO2 + OH-

A basic solution
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Salt hydrolysis

• When salts composed of ions of a strong electrolyte (acid


or base) and ions of a weak electrolyte are dissolved,
complete salt dissociation occurs because ions of a strong
electrolyte can exist only in ionized form

• Ions originating from a weak electrolyte react with water


producing their conjugated particle

• Examples: CH3COONa, KCN, NH4Cl, NH4NO3


 Write equation when these salts dissolved in water,
originating ions, which then reacted with water
producing its conjugate acid/base :
 NaOCN
 K2S
 Ba(CH3COO)2
 Sodium nicotinate, NaNic
 Sodium citrate, Na3Cit
 Ca-lactate, Ca(Lac)2
 anilinium chloride (C6H5NH3Cl)
 (CH3)2NH2Br
Salts of weak acids and strong bases
CH3COONa  CH3COO- + Na+ [CH3COO-]
KA = +
[H ][CH3COOH]

[CH3COOH] [OH-]
CH3 COO- + H 2O CH3COOH + OH- KH =
[CH3COO-]
[H+][OH-] = Kw

KH·KA = KW  KH = KW/KA

c-x x x
CH3COO- + H2O CH3COOH + OH- [CH3COOH] = [OH-]
c = concentration of salt at the beginning
c-x = concentration of anion of a weak acid at equilibrium
x = concentration of products at equilibrium

KW =10-14 [OH-]2
c-x = c =
KA c
KW · c (salt)
[OH-]2 = pOH = 7 – 1/2[pKA – log(c)]
KA

pH = 14 - pOH

pH = 7 + ½ [pKA + log(c)]

c-x x x
CH3COO- + H2O CH3COOH + OH- pOH = ….
pH = …..

x2
Kh = x=…
c-x
Salts of weak bases and strong acids

[NH4+] [OH-]
NH4Cl  NH4 + + Cl- KB =
[NH3]

[NH3] [H3O+]
NH4 + H2O
+ NH3 + H3 O+ KH =
[NH4+]
[H+][OH-] = Kv

KH·KB = KW  KH = KW/KB

NH4+ + H2O NH3 + H3O+ [H3O+] = [NH3]


c-x x x
c = concentration of salt at the beginning
KW [H3O+]2
=
c-x = c KB c
c-x = concentration of a cation of a weak base at equilibrium

x = concentration of products at equilibrium


[H3O+]2 = KW· c(salt)
KB

pH = 7 - ½[pKB + log(c)]
Salts of weak acids and weak bases
Anions and cations of weak acids and bases, that produce salt –
having concentration c, react with water e.g. NH4CN

CN- + H2O = HCN + OH-


NH4+ + H2O = NH3 + H3O+

NH4+ + CN- HCN + NH3


c-x c-x x x c-x = c
KH = [HCN][NH3]/[CN-][NH4+]
= [HCN]2/[CN-]2 [H3O+]2 = KW · KA

KH · KA ·KB = KW  KH = KW/KA KB KB

KA = [H3O+][CN-]/[HCN]  (1/KH)1/2
[H3O+]2 = KA2 KH = KW · KA/KB

pH = 7 + ½[pKA - pKB]
Examples of acid-base problems
Class exercise (weak acid)
Ka (CH3COOH) = 1.7 × 10–5 and [H+] = 3.4 × 10–4. Then
initial concentrations of CH3COOH is
(a) 3.4 × 10–4 (b) 6.8 × 10–3
(c) 3.4 × 10–3 (d) 6.8 × 10–2
Solution:
CH3COOH H+ + CH3COO-
C(1–) C C

C2
Ka=  C2
1- 
Solution
[H+]=3.4×10-4 = C

1.7  10–5 = 3.4 × 10–4  

1.7×10-5
  =5×10-2
3.4×10-4
3.4×10-4
C  = 0.68×10-2 = 6.8×10-3
5×10-2

Hence, the answer is (b).


Class exercise
(pH of mixture)

pH of a solution produced when an aqueous solution


of pH 6 is mixed with an equal volume of an aqueous
solution of pH 3, will be
(a) 4.5 (b) 4.3 (c) 4.0 (d) 3.3

Solution:
pH = 6 [H+]=10-6 M 10-6 +10-3
+
[H ]Total =
2
pH = 3 [H+] = 10-3 M
Solution

1.001×10-3
= =5.005×10-4
2

 pH = –log [H+]Total

= 4 – log 5.005
= 3.3

Hence, the answer is (d).


Class exercise (diprotic acid)
Which one of the following is true for
any diprotic acid, H2X?
(a) Ka2 > Ka1 (b) Ka1 > Ka2
(c) Ka1 = Ka2 1
(d) Ka =2
Ka1
Solution:
H2X being a diprotic acid,
H2X H+ + HX- Ka1
HX- H+ + X-2 Ka2
Due to the ‘common ion effect’ dissociation of HX–
will be less.
therefore, Ka1 > Ka2
Class exercise
(pH of mixture of strong and weak acid )
0.001 M HCl is mixed with 0.01 M HCOOH at 25° C. If Ka
HCOOH = 1.7 × 10–4, find the pH of the resulting solution.
Solution:
HCl  H+ + Cl-
0.001 0.001 0.001

HCOOH H+ + HCOO-

Initial mole 10–2


At eqm. 10–2(1– ) 10–2 +10-2

 H+ 
  Total 
= 102   103 
Solution
H+  HCOO- 
  Total  
Ka=
HCOOH

10-2  +10-3   102   103 
Ka 
-2
10 1-  
 
1.7 × 10–4 = 10–3  [ 10–2 2 << 10–3 ]

H+ = C =10-2 ×.17=1.7×10-3
 = 1.7 × 10–1
 H+ 
  Total  
= 1.7×10-3 +10-3 =2.7×10-3

 pH = 3 – log 2.7 = 2.57


Illustrative example
(salt hydrolysis)

When 0.20 M acetic acid is neutralised with 0.20 M


NaOH in 0.50 litre of water, the resulting solution is
slightly alkaline, calculate the pH of the resulting
solution (Ka for acetic acid = 1.8 x 10-5)
Solution:
CH3 COOH  NaOH 
 CH3COONa  H2 O
moles 0.2  0.5 0.2  0.5 0.2  0.5

 
CH3 COO  H2 O CH3COOH  OH

0.1(1  h) 0.1h 0.1h


Solution
Kw 0.1h2
Kh    0.1h2
Ka 1h
 h  1

1014
h  0.745  104
1.8  105  0.1

OH   0.1h pOH  5.128


 
pH  8.872
Illustrative example
(salt hydrolysis)
Calcium lactate is a salt of a weak organic acid and
represented as Ca(Lac)2. A saturated solution of Ca
(Lac)2 contains 0.13 mol of this salt in 0.50 litre solution.
The pOH of this solution is 5.60. Assuming a complete
dissociation of the salt, calculate Ka of lactic acid.
Solution:
 Ca2  2 Lac 1
Ca(Lac)2 
0.13 mol 2  0.13 mol.

Lac    0.26  0.52 M


  0.5
Solution
Lac   H2 O LacH  OH
0.52(1  h) 0.52h 0.52h

OH   0.52h  2.51  106


 
h  4.83  106 Kw
Kh   0.52h2  h  1
Ka

1014
Ka   8.24  104
 
2
6
0.52  4.83  10
Class exercise (salt hydrolysis )
What is the percentage hydrolysis
of N NaCN solution when the
80
Ka HCN = 1.3 × 10–9, Kw = 1 × 10–14?
(a) 2.48 (b) 5.26 (c) 9.6 (d) 8.2

Solution: + -
NaCN  Na + CN
CN- + H2O HCN + OH-
1 h h
1-h
80 80 80
Solution
2
 h 
Kw  80  h2
 Kh = =   
Ka 1
1-h 80
80

80×10-5
 h= = 6.15×10-4
1.3

10-14 h2
  = 2.48 × 10–2
1.3×10-19 80
 Percentage hydrolysis = 2.48 × 10–2 × 102 = 2.48
Class exercise (pH of acid and base mixture )
Calculate the pH of a solution obtained by mixing
100 mL of 0.1 M HCl with 9.9 ml of 1 M NaOH
Solution:
HCl + NaOH  NaCl + H2O
100×0.1×10-3 9.9×1×10-3
100×10-4 99×10-4

Acid remaining = 1 × 10–4 moles


-4
+ 1×10
H  =
  ×103 =9.09×10-4
109.9
pH = –log[H+] = 4 – log 9.09
= 3.04
Class exercise (salt hydrolysis )
Calculate the percentage hydrolysis of 3 × 10–3 M
aqueous solution of NaOCN (Ka HOCN = 3.33 × 10–4 M).
Solution:
NaOCN  Na+ + OCN-

OCN- + H2O HOCN + OH-


3×10-3 1-h 3×10-3 h 3×10-3 h

Kw 3×10-3 h2
Kh = =  3×10-3 h2
Ka 1- h
Solution

10-14
h= = 1×10-8 =10-4
3.33×10-4 ×3×10-3

Percentage hydrolysis = 10-4 ×102 = 0.01


Exercises
1) Give the formula of the conjugate base:
a) HPO4-2 b) NH4+ c) HS-1
2) Give the formula of the conjugate acid:
a) O-2 b) SO4-2 c) H2O
3) Which are Bronsted-Lowry acids and which are
Bronsted-Lowry bases?
a) Na+ b) NH3 c) CN-1 d) BF3
4) Classify the following as Arrhenius, Bronsted-Lowry, or
Lewis acid-base reactions. A reaction may fit all, two,
one, or none of the categories:
a) Ag+ + 2NH3  Ag(NH3)2
b) H2SO4 + NH3  HSO4-1 + NH4+
c) 2HCl  H2 + Cl2
d) AlCl3 + Cl-1  AlCl4-1
5) A 0.040 M solution of a weak acid (HA) has a pH of 4.70.
What are the Ka and pKa?
6) A 0.25 mol sample of a weak acid HA is dissolved in water to
make 500 mL of the solution. The pH of the solution is
measured to be 3.30, what is the Ka of the weak acid?
7) For a diprotic weak acid H2A, Ka1 = 10-4 and Ka2 = 10-8.
Calculate [H2A], [HA-1], [A-2], [H+], pH and pOH in a 1.00 M
solution of H2A.
8) Phenol (C6H5OH) is a weak acid with a Ka = 1.0 x 10-10. What is
the pH of 0.100 M sodium phenolate (C6H5ONa), the sodium
salt of phenol?
9) What is the pH of a 0.40 M anilinium chloride (C6H5NH3Cl)
solution? Kb of aniline (C6H5NH2) is 4 x 10-10.
10) Calculate the pH of a 6.0% (mass/volume) acetic acid (molar
mass = 60.0 g/mol) solution in water if the pKa of acetic acid
is 4.74.
11) Explain with equations and calculations, when
necessary, whether an aqueous solution of each of
these salts is acidic, basic, or neutral:
a) KBr
b) NH4I
c) KCN
12) Explain with equations and calculations, when
necessary, whether an aqueous solution of each of
these salts is acidic, basic, or neutral:
a) SrBr2
b) Ba(CH3COO)2
c) (CH3)2NH2Br
13) Calculate the pH of a buffer solution that has 0.50 M HA
and 1.0 M KA. (Ka of HA is 2 x 10-5).
14) Calculate the pH of a solution that consists of 0.50 M
NH3 and 0.50 M NH4Cl. The pKb of ammonia is 4.74
15) What is the ratio of [HA/A-] of a buffer solution that has
a pH = 2.70 if the pKa of HA is 3.00?
16) A solution containing 0.10 M HA (a weak acid) and 0.20
M NaA (the salt of the weak acid) has a pH = 3.30. What
is the pH after 25 mmol of HCl is added to 500 mL of this
solution?
17) A solution containing 0.40 M B (a weak base) and 0.20
M BH+ (the salt of the weak base) has a pH = 10.30.
What is the pH after 25 mmol of HCl is added to 250 mL
of this solution?
Thank you