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IONIC EQUILIBRIA
7.1 Acids and Bases
Learning Outcomes
E.g:
(a) HCl(s) + H2O H3O+(aq) + Cl-(aq)
E.g:
(a) NH3(s) + H2O(l) NH4+(aq) + OH-(aq)
Video 1
Brnsted-Lowry definition
NH3(aq) + HCl(aq) NH4+(aq) + Cl-(aq)
HCl
Is it an acid or base?
Acid
Who accepted the proton?
H2O
Is it an acid or base?
Base
Now let us look at NH3 and see why it is a
base.
..
:O:H -
..
base
F H F H
acid base
H .. :O: :O:
O: + C
H C ..
O
..
..
H O: O:
.. H
..
acid ..
base
Carbonic
acid
Example :
i. NH3(aq) + H+(aq) NH4+(aq)
(base) (acid)
BASE
Produce OH- when dissociates in water
H+ acceptor
Electron donor
Conjugate Acids and Bases
The acid-base reaction is reversible.
HA + B A- + HB+
acid base conjugate conjugate
base acid
100%
Example:
ionisation
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
100%
ionisation H O+(aq) + NO3-(aq)
HNO (aq) + H O(l)
3 2 3
Strong base
strong bases dissociate completely in an aqueous
solution to produce high concentration of OH-.
- 100% ionisation
- or 100% dissociated or =1
100%
ionisation
e.g: NaOH(aq) Na+(aq) + OH-(aq)
Weak Acid and Weak Base
Weak acid
weak acids dissociate only slightly in an aqueous
solution to produce a low concentration of H3O+.
- % dissociation less than 100% or <<1.
e.g:
CH3COOH(ak) + H2O(l) CH3COO-(aq) + H3O+(aq)
Weak base
weak bases dissociate only slightly in an
aqueous solution to produce a low
concentration of OH-.
- % dissociation less than 100% or <<1.
e.g:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
Strong Acid Weak Acid
Strong base
Weak base
Notes:
Strong acid & strong base are strong electrolyte
(=1).
Weak acid & weak base are weak electrolyte (<<1).
Electrolyte substance that can conduct electricity
in the liquid state or aqueous solution.
The pH Scale
pH concept
The pH Scale
pH = log H3O+
@ pH = - log [H+]
- If [H+] , pH .
pOH is the negative logarithm (log) of the
hydroxide ion ( OH- )concentration
pOH = log OH
If [OH-] , pOH , pH
In pure water,
H3O+ = OH = 1 x 10-7M
pH = log H3O+
= log (1 x 10-7 )
= 7
Water and The pH Scale
Kw
The Water Ionization Constant, Kw
K = H3O+ (aq)OH(aq)
H2O(l) 2
K H2O 2 = H3O+OH
or
Kw = H3O+ OH-
Kw is the ionization constant for water at 25C
In pure water,
H3O+ = OH at 25C.
H3O+ = OH
= 10-7 M
Kw = H3O+ OH
= (1 x 10-7) (1 x 10-7)
Kw = 1 x 10-14 M2
14 = pH + pOH
If,
pH < 7 solution is acidic
pH = 7 solution is neutral
pH > 7 solution is basic
pH scale
0 7 14
acidic neutral basic
[H+]>[OH-] [H+]=[OH-] [H+]<[OH-]
CHAPTER 7
IONIC EQUILIBRIA
7.1 Acids and Bases
At the end of this lesson, students should
be able to:
(e) Calculate the pH values of a strong acid and
base.
HCl H+ + Cl
0.5 M 0.5M
NaOH Na+ + OH
0.1 M 0.1M
1.0 10-14
1.0 10 -14
[H ] 4.0 10 M
-12
[OH - ] 2.5 10 -3
pH = - log [H+]
= - log (4.0 x 10-12 M)
= 11.4
Solution : (Method 2)
[OH-] = 2.5 x 10-3 M
pOH = - log [OH-]
= - log (2.5 x 10-3 M)
= 2.6
pOH = log OH
= log 0.0361
= 1.442
pH = 14 pOH
= 14 1.442
= 12.558
2. A solution of 5 x 10-3 M H2SO4
pH = log H+
= log (1 x 10-2)
= 2
Extension
Example
Calculate the pH of 0.15 mol dm-3 of HCl solution.
Solution :
HCl(aq) H+(aq) + Cl-(aq)
[ ]initial 0.15 M 0 0
[ ]final 0 0.15 M 0.15 M
pH = - log [H+]
= - log (0.15 M)
= 0.82
Exercise
1. What is the pH of a 0.040 M solution of HClO4
?
2. What is the pH of 0.05 M NaOH ?
3. An aqueous solution of HNO3 has a pH of 2.34.
What is the concentration of the acid ?
Answers:
(7.8 x 10-3, 12.45)
Exercise
1. Calculate pH for the following solutions:
a) 2.0 x 10-3 M HCl d) 0.025 M KOH
b) 5.0 x 10-4 M HNO3 e) 0.02 M H2SO4
c) 5.4 x 10-3 M NaOH f) 0.005 M Mg(OH)2
3. 3.16 10-4
4. 0.25 g
Weak Acid and Weak Base
Initial conc C 0 0 0
Change -x 0 +x +x
Eq. conc. cx 0 x x
The ionization expression is given by:
Ka = H3O+ A
HA
Ka = (x)(x)
(cx)
By assuming only a small amount of acid
dissociates, i.e. Ka <<< 1
HA = cx ~ c
Ka = x2
c
x2 = Ka.c
x = Ka . c
= H3O+
The approximation ( cx ~ c ) is only valid
if the % is equal or less than 5 % @ Ka
10-4
Example
= 1.34 % ( < 5 % )
pH = - log H3O+
= - log 1.34 x 10-3
= 2.87
If the degree of dissociation, is given,
Change -c +c +c
Eq.
Concen. c(1-) c c
Ka = H3O+ A
HA
= (c)(c)
c(1)
= c2
1
- Assuming is very small, i.e. <<< 1, so 1
~ 1, the equation above becomes:
Ka = c2 or
= Ka / c
WEAK BASE
B(aq) + H2O(l) BH+(aq) + OH (aq)
= (x)(x)
(cx)
Assuming, that only a small amount of acid
dissociates, i.e. Kb <<< 1, therefore:
B = cx ~ c
Kb = x2
c
x = Kb.c = OH
If the degree of dissociation, is given, the same
equation can be derived as the weak acid.
Kb = BH+OH
B
= (c)(c)
c(1 )
= c 2
1
Assuming is very small, i.e. <<< 1,
so 1- 1, the equation above becomes,
Kb = c2
= Kb / c
Example 1 :
Calculate the pH of a 0.20 M solution of HCN. Ka
for HCN is 4.9 x 10-10.
Solution :
HCN(aq) + H2O(l) H3O+(aq) + CN-(aq)
[ ]initial 0.20 M 0 0
[ ]change -x +x +x
[ ]equilibrium 0.20-x x x
[H3O ] [CN - ]
At equilibrium, K
a
[HCN]
(x) (x)
Ka = = 4.9 x 10-10 M
(0.20 - x)
Assume that the amount of acid dissociated,
x is small compared with the initial concentration of
acid, c; that is c-x c, therefore
x2 = 4.9 x 10-10 M
(0.20)
x2 = (4.9 x 10-10 M) (0.20 M)
x = 9.9 x 10-6 M
Therefore,
[H+] = 9.9 x 10-6 M
pH = -log [H+]
= 5.00
Example 2 :
The base-dissociation constant for ammonia, NH3(aq)
is 1.8 x 10-5 M. Calculate the concentration of OH-
ion, pH and % dissociation at equilibrium if the
initial concentration of NH3 is 0.15 M.
Solution :
NH3(aq) + H2O(l) NH4+(aq) + OH-
(aq)
[ ]initial 0.15 M 0 0
[ ]change -x +x +x
[ ]equilibrium 0.15-x x x
[NH ] [OH-]
K
At equilibrium, 4
b [NH ]
3
Kb =
(x) (x) = 1.8 x 10-5 M
(0.15 - x)
Assume that x is too small compared to the initial
concentration of base, c; that is c-x c, therefore
x2 = 1.8 x 10-5 M
(0.15)
x2 = (1.8 x 10-5 M) (0.15 M)
x = 1.64 x 10-3 M
Therefore, [OH-] = 1.64 x 10-3 M
pOH = -log [OH-]
= 2.79
pH + pOH = 14
pH = 14 2.79
= 11. 21
1.64 x 10-3 x 100
% dissociation =
0.15
= 1.09 %
1.1 %
) = 0.011
Degree of dissociation (
Exercise :
1. The Ka for formic acid is 1.8 x 10-4. What is the
pH of a 0.010 M solution of formic acid?
( 2.87)
2. Calculate the percentage of HF molecules
ionized in
(a) a 0.10 M HF solution (7.9 %)
(b) a 0.010 M HF solution (23 % )
given the Ka of HF is 6.8 x 10 -4
Exercise :
1. A 0.20 M solution of weak acid HX is 9.4%
dissociated. Using this information, calculate
H3O+ , X- and HX concentrations at equilibrium.
Determine also pH and Ka for HX acid.
(1.88 x 10-2 M, 0.1812 M, 1.726, 1.95 x 10-3)
Ka = NH3 H3O+
NH4+
Kb = NH4+ OH
NH3
Therefore, the product of Ka x Kb is
NH3 H+ x NH4+ OH = H+ OH = Kw
NH4+ NH3
product of the acid dissociation constant for an
acid and the base dissociation constant for its
conjugate base is the ion product constant for
water,
Ka x Kb = Kw
= 14
Acid-dissociation constant (Ka) and base-dissociation
constant (Kb)
The value of Ka or Kb can be used to distinguish
the relative acidity strength of weak acid and weak
base.
Acid pKa
CH3COOH 4.74
HCOOH 3.76
Relative acidity, HCOOH > CH3COOH
Base pKb
C6H5NH2 9.37
NH3 4.74
Relative basicity, NH3 > C6H5NH2
CHAPTER 7
IONIC EQUILIBRIA
7.1 Acids and Bases
At the end of this lesson, students should be able to:
(h) Explain salt hydrolysis using hydrolysis
equations and classify the salts formed from
the reaction between:
introduction
Given a general equation:
M(OH) + HX M+ X + H2O
base acid salt
i) Partial hydrolysis
Occurs in a salt solution which comes from a
weak acid and a strong base or a strong acid
and a weak base. In these salt solutions, either
the cations or anions from the salt are
hydrolysed.
Example:
EXAMPLE
introduction
A buffer solution has two requirements,
CH3COO-
CH3COOH CH3COOH CH3COO- + H2O
CH3COO-
CH COOH
CH3COO- 3
Ka = CH3COOH3O+
CH3COOH
H3O+ = CH3COOH x Ka
CH3COO
H3O+ = w.acid x Ka
conjugate base
Taking -log at both sides of the equation
= 4.13
Example
= 4.76
b) After adding 1.0 cm3 H2SO4 (0.1 M)
= 4.75
c) Moles of NaOH added = 0.1 x 1.0 = 1.0 x 10-4 mol
1000
= 4.76
b) Basic Buffer Solution
Example
Kb = NH4+ OH
NH3
OH = NH3 x Kb
NH4+
Taking the log of both sides of the equation
pH = 14 pOH
Example:
Calculate the pH of the solution prepared by mixing
500 mL 0.1 M hydrazinium chloride,N2H5Cl with 500
mL 0.2 M hydrazine, N2H4. (Kb = 1.7 x 10-7)
Solution:
N2H5Cl = 0.05
(0. 50 + 0.50)
= 0.05 M
No of moles of N2H4 = 500 x 0.2
1000
= 0.1 moles
N2H4 = 0.1
(0.50 + 0.50)
= 0.1 M
Using the equation,
pH = 14 - pOH
= 14 - 6.469
= 7.531
Example
A buffer solution is prepared by mixing 400 mL
of 1.50 M NH4Cl solution with 600 mL of 0.10 M
NH3.
i. Calculate the pH of a the buffer solution.
ii. Calculate the pH of the buffer solution after the
addition of
(a) 0.15 M NaOH (b) 0.011 M H
(Assume that the volume of the solution does
not change when HCl and NaOH is added)
Kb for NH3 = 1.8 x 10-5 M
Solution
i. V = 400 ml + 600 ml
= 1000 ml
=1L
MV 1.50 x 400
mol NH4Cl = 1000 = 1000 = 0.6 mol
pH = 14 5.74 = 8.26
ii. (a) pH when 0.15 M NaOH is added
Buffer action :
NH4+(aq) + OH-(aq) NH3(aq) + H2O(l)
[ ]initial 0.60 M 0.15 M 0.06 M
[ ]change -0.15 M -0.15 M +0.15 M
[ ]final 0.45 M 0 0.21 M
[conjugate acid]
pOH = pKb + log [weak base]
-5 (0.45)
= -log(1.8 x 10 )+ log (0.21)
= 5.08
pH = 14 5.08
= 8.92
ii.(b) pH when 0.011 M HCl is added
Buffer action : NH3(aq) + H+(aq) NH4+(aq)
[ ]initial 0.06 M 0.011 M 0.6 M
[ ]change -0.011 M -0.011 M +0.011 M
[ ]final 0.049 M 0 0.611 M
[conjugate acid]
pOH = pKb + log [weak base]
pH = 14 5.84
= 8.16
Exercise :
1. How many moles of NH4Cl must be added to 2.0 L
of 0.10 M NH4 to form a buffer whose pH is 9.00 ? (
Assume that the addition of NH4Cl does not change
the volume of the solution ) Kb = 1.8 x 10-5 (0.36
mol)
2. Calculate the concentration of sodium benzoate
that must be present in a 0.20 M solution of benzoic
acid ( C6H5CO2H) to produce a pH of 4.00.
(0.13 M)
3. Calculate the pH of a buffer composed of 0.12 M
benzoic acid and 0.20 M sodium benzoate. Ka = 6.3
x 10-5. ( 4.43 )
4. What is the pH of a buffer that is 0.12 M in lactic
acid ( HC3H5O3) and 0.10 M in sodium lactate?
Ka =1.4 x 10-4 (3.77)
Exercise
Answer.
a)8.24
b)8.235
Exercise
Calculate the pH of a buffer solution consisting
of 0.10 M CH3COOH and 0.25 M CH3COONa.
( Ka for CH3COOH = 1.8 10-5 mol dm-3 )
Calculate the pH when
i ) 10 cm3 of 1.0 M HCl
ii ) 10 cm3 of 1.0 M NaOH
is added to 1.0 dm3 of the buffer solution above.
pH = 5.14
pH = 5.08
pH = 5.20
7.2 ACID-BASE
TITRATIONS
At the end of this lesson, students
should be able to:
(a) Describe the titration process and
distinguish the end point and
equivalence point.
ACID-BASE TITRATIONS
titrant
analyte
Titrant is the solution added from the burette.
The equivalent point is the point at which the
amount of acid and base present exactly
neutralizes one another.
For reactions that have the same stoichiometric
value of acid and base the number of moles of
OH- ions and number of moles of H+ ions are
equal.
E.g: HCl + NaOH NaCl + H2O
(1 mol of acid react with 1 mol of base)
Indicator is a substance that is generally
added to the solution in the receiving vessel an
which undergoes some sort of colour change
when reaction is over.
The end point of titration is the point when the
indicator changes colour.
Titration Endpoint
Types
Strong acid Weak acid
of
+ +
Strong base Titration Strong base
Weak acid
+
Weak base
Acid-Base Titration
Titrations involving only strong acids or bases
are straightforward (equivalence pH = 7) .
Titrations involving weak acids or bases are
complicated by hydrolysis of salt formed.
Weak AcidStrong Base pH at equivalence
point will always be >7
Strong AcidWeak Base pH at equivalence
point will always be <7
The Acid-Base Titration Curve
Titrant is a standardized solution with known
concentration added from the burette
Video 1
Curve for a strong acid-strong base
titration
Suitable
indicators for
strong acid-
strong base
titration
Video 2
2. WEAK ACID-STRONG BASE
TITRATIONS
Neutralization reaction between acetic acid ( weak acid )
and sodium hydroxide (strong base )
CH3COOH(aq) + NaOH(aq) CH3COONa (aq) + H2O(l)
Dissociation of salt:
CH3COONa CH3COO-(aq)+ Na+(aq)
Video 4
Titration of 40.00mL of 0.1000M HF
with 0.1000M NaOH
Curve for a
weak acid-
strong
base
titration
pH = 8.80 at
equivalence point
pKa of HF (hydrolysis of F-)
= 4.89
methyl red
[HF] = [F-]
3. Strong Acid-Weak Base
Titrations
Titration of HCl, a strong acid with NH3, a weak
base
HCl (aq) + NH3 (aq) NH4Cl (aq)
Dissociation of salt
NH4Cl (aq) NH4+(aq) + Cl-(aq)
Video 5
pH profile and titration curve of a strong
acid-weak base titration
Titration of 40.00mL of 0.1000M
NH3 with 0.1000M HCl
pKa of NH4+
= 9.25
Suitable
indicators :
litmus and
methyl red pH = 5.27 at
equivalence
point (hydrolisis
of NH4+)
The Titration
Curve
The Titration Curve
Types of End Point Equivalence
Titrations (pH Range) Point
Strong Acid
-Strong Base 3 10 7
Weak Acid
-Strong Base 7 11 >7
Strong Acid
-weak Base 37 <7
7.2 ACID-BASE
TITRATIONS
At the end of this lesson students should
be able to:
Video 2
Weak Base as Indicator
[H+] is high
- colour of conjugate base (In+) predominates
[OH] is high
- colour of base (InOH) predominates.
Choosing The Suitable Indicator
13_07
Picture of
BaSO4
dissolving
Saturated and Unsaturated
Kc = [ Ag+ ] [Cl- ]
AgCl
The concentration of the solid is constant
and therefore be included with the constant
Kc so that :
Ksp = [M2+][X]2
Example:
Write the expression for the solubility product
of silver chromate, Ag2CrO4
Solution:
First write the balance equation for the
solubility equilibrium,
Ag2CrO4(s) 2Ag+(aq) + CrO42-(aq)
What do Ksp
values tell us..?
The smaller the
Ksp, the less
soluble the salt!
Calculating Solubility Product, Ksp
Example 1 :
s = 5.29 x 10-5
K sp Ag Br
5.7 x 10 3.3 x 10
-7 2 -13
Problem solving 2
The solubility of Ag2CO3 is 1.26 x 10-4 at 25oC.
Calculate the Ksp for silver carbonate.
Ag2CO3(s) 2 Ag+ + CO32-
Initial 0 0 s use s
Change +2s +s to indicate
Equil 2s s solubility
K sp 1.33 x 10 6.63 x 10 1.16 x 10
-4 2 -5 -12
Problem solving 4
Problems working from Ksp values.
Given: Ksp for MgF2 is 6.4 x 109 @ 25 oC
Find: solubility in mol/L and in g/L
MgF2(s) Mg2+ + 2F
s 2s
Ksp = [Mg2+][F]2
Ksp = [s][2s]2 = 4s3
6.4 x 109 = 4s3
s = 1.2 x 10-3 mol L-1
Problem solving 4(cont.)
Ksp= [x][2x]2 = 4s3
6.4 x 109 = 4s3
-9
1.2 x 10-3 Mg2 MgF2
6.4 x 10
s3
4
-3
now for g/L :
1.2 x 10 mol MgF2 62.3 g
L mol
g MgF2
7.3 x 102
L
Exercises:
The solubility of calcium sulfate (CaSO4) is found
experimentally to be 0.67 g/L. Calculate the value
of Ksp for calcium sulfate.
2.42 x 10-5 (mol L-1)2
The solubility of lead chromate (PbCrO4) is
4.5 x 105 g/L. Calculate the solubility product of
this compound. 1.94 x 10-14 (mol L-1)2
Solubility of compound
Ksp of compound
(b) Steps of calculating solubility
from Ksp data
Ksp of compound
Solubility of compound
NOTE : s use s to indicate solubility.
Solubility is per mole of salt, not the molarity of
each dissolved ion!
Two ions per formula : s2
Three ions per formula : (2s)2s = 4s3
7.3 Solubility equilibria
Learning outcomes
Q = Ksp Equilibrium
Q > Ksp reaction proceeds from left to right
Example 1 :
Therefore:
Q > Ksp
Add I-
via NaI
AgI(s) AgI(s)
13_07
2
= s = 9.92 10 -5
M indeed 9.92 x 10-5 << 0.025
0.025
Example 4 :
Ksp for AgCl is 1.7 x 10-10 mol2 dm-6. Calculate the
molar solubility of AgCl in
i. Water
ii. In a solution of 0.1 mol dm-3 KCl.
Solution :
i. Let s be the molar solubility of AgCl in water.
1.7 x 10-10 = s2
= (y) (y+0.1)
Assume y << 0.1, so, (y+0.1) 0.1