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2.

Acids-Base titration

7.0 IONIC EQUILIBRIA


OVERVIEW

1. Acids and bases

Arrhenius theory

a)

Define acid and base

Lewis theory

b)

d)

Define and identify conjugate acids and


conjugate base according to Bronsted-Lowry
theory
strong acid and base
Define
weak acid and base
Define pH, pOH

e)

Relate pH and pOH to Kw at 250C

f)

Calculate pH value of strong acid and base

g)

Relate strength of a weak acid and weak base


to the Ka and Kb (pKa,pKb,pKw,pH,pOH)

h)

Perform calculation (pH, Ka, Kb, [ ], )

i)

Exp salt hydrolysis and write its equation


strong acid and strong base

c)

a)

Describe titration process

b)

Distinguish between the end point and


equivalence point

c)

Sketch and interpret the variation of pH againts


titre value for titration between

Bronsted-Lowry theory

a)

j)

Define buffer solution

k)

Describe how buffer solution controls pH

l)

Derive Henderson-Hasselbalch equation

strong acid-strong base

ii)

strong acid-weak base

iii)

weak acid-strong base

Identify suitable indicator for acid-base titration

3. Solubility equilibria
a)

strong acid and weak base


weak acid and strong base

i)

Define
i)

solubility

ii)

molar solubility

iii)

solubility product ,Ksp

b)

Calculate Ksp

c)

Predict the possibility of precipitation of slightly


soluble ionic compounds by comparing the value
of ion-product, Q to Ksp

d)

Define and explain the common ion effect

e)

Perform calculation related to common ion effect

Learning outcomes: (1 hour)


At the end of this lesson , students should be able to:
Define acid and base according to Arrhenius, BronstedLowry and Lewis theories.
Define and identify conjugate acid and conjugate base
according to Bronsted- Lowry theory.
Define strong acid and base, weak acid and base.

What is the pH of the gastric juice in your stomach?

The pH of the gastric juice is about 1.5, which


corresponds to HCl 0.03 M
a concentration strong enough to dissolve
zinc metal!

IONIC EQUILIBRIUM
7.1 Theory of Acids and Bases

We generally classify acids


and bases as either strong or
weak, according to the extent of
their dissociation into ions in
water.
The concentration of
[H+] or [OH-]

GENERAL PROPERTIES OF ACIDS and BASES


ACIDS

BASES

Have a sour taste

Have a bitter taste

Change color of litmus


from blue to red

Change color of litmus


from red to blue

Aqueous acid solutions


conduct electricity

Aqueous base solutions


conduct electricity

React with active metals


such as Al and Zn to
produce H2 gas
React with carbonates
and bicarbonates such
as Na2CO3, CaCO3 and
NaHCO3 to produce CO2 gas

Feel slippery

WHAT IS ACID ?

WHAT IS BASE ?

Acidbase definition:
Arrhenius
Svante August Arrhenius (1859-1927). Swedish chemist.

BrnstedLowry
Johannes Nicolaus Brnsted (1879-1947). Danish chemist.
Thomas Martin Lowry (1874-1936), English chemist.

Lewis theories
Gilbert Newton Lewis (1875-1946). American chemist.

ARRHENIUS ACIDBASE DEFINITION


Acid: Substance that has H in its formula and
dissociates in water to yield H3O+
EXAMPLE:
HNO3(aq)
CH3COOH(aq)

+
+

H2O(l)
H2O(l)

H3O+(aq)

CH3COO(aq)

NO3(aq)
+

H3O+(aq)

Base: Substance that has OH in its formula


and dissociates in water to yield OH
EXAMPLE:
NaOH(aq)

Na+(aq)

OH(aq)

BRNSTEDLOWRY ACIDBASE
DEFINITION
Acid: Any species that donates H+ (proton donor)
EXAMPLE:
CH3COOH(aq)
acid

H2O(l)
base

CH3COO(aq)
conjugate
base

+ H3O+(aq)
conjugate
acid

Base: Any species that accepts H+ (proton acceptor)


EXAMPLE:
NH3(aq) +
base

H2O(l)
acid

NH4+(aq) + OH(aq)
conjugate
conjugate
acid
base

The definition focus on products and reactants


(acidbase reaction)

BASE-CONJUGATE ACID PAIR

CH3COOH(aq) + CN(aq)
acid
base

CH3COO(aq) + HCN(aq)
conjugate
conjugate
base
acid

Acid: proton donor


Base: proton acceptor

Every acid has a conjugate base


Every base has a conjugate acid

LEWIS ACIDBASE DEFINITION


Acid: Any species that accepts an electron pair
EXAMPLE: BF3 , AlCl3 , SO2 , CO2 , Na+

Base: Any species that donates an electron pair


EXAMPLE: NH3, CH3Cl, CH3OCH3, H2O, O2

A +
acid

:B

AB

base
new covalent bond

LEWIS ACIDS WITH


ELECTRON DEFICIENT ATOMS
Contains a central atom that is electron deficient
incomplete octet
EXAMPLE:

acid

H
N

B
F

H
H

N
H

base

Table 6.1 : Examples of Lewis acids and bases


Lewis acid

Lewis base

(a) Positive ions


e.g : H+ , Fe2+ , Al3+

(a) Negative ions


e.g : OH- , CN- , Cl-

(b) Molecules with an incomplete


octet of electrons.
e.g : BF3 , BeCl2 , BCl3

(b) Molecules with lone pair of


electrons.
e.g : H2O , NH3 , ROH

EXAMPLE
Identify the conjugate acidbase pairs:
a) HCOOH(aq) + H2O(l)
b) H2O(l) + F(aq)
c) H2PO4(aq) + CO32(aq)
d) H2O(l) + SO32(aq)

HCOO(aq) + H3O+(aq)
OH(aq)

HF(aq)

HCO3(aq) + HPO42(aq)
OH(aq) +

HSO3(aq)

Ans: EXAMPLE
A = acid

B = base

cA = conjugate acid

cB = conjugate base

a) HCOOH(aq) + H2O(l)

b) H2O(l) + F(aq)

HCOO(aq) + H3O+(aq)

OH(aq)

HF(aq)

Ans: EXAMPLE
A = acid

B = base

cA = conjugate acid

cB = conjugate base

c) H2PO4(aq) + CO32(aq)

d) H2O(l) + SO32(aq)

HCO3(aq) + HPO42(aq)

OH(aq) +

HSO3(aq)

STRONG ACID
Dissociate completely (100 %, = 1.0) into ions
in water
HA(l) + H2O(l) H3O+(aq) + A(aq)

Ka extremely large
EXAMPLE:
HNO3(aq)

H2O(l)

H3O+(aq)

Hydrohalic acids: HCl, HBr and HI


Oxoacids: HNO3, H2SO4 and HClO4

NO3(aq)

WEAK ACID
Dissociate very slightly ( < 1.0) into ions in water
HA(aq) + H2O(l)

H3O+(aq) + A(aq)

Ka very small
EXAMPLE:
HCN(aq) + H2O(l)

H3O+(aq) + CN(aq)

Hydrohalic acids: HF
Oxoacids: HClO, HNO2 and H3PO4
Organic acids: CH3COOH and C6H5COOH
Other: HCN and H2S

STRONG BASE
Dissociate completely (100 %) into ions in water
Kb extremely large

Soluble compounds containing O2 or OH


EXAMPLE:

M2O or MOH:
M: Group (1) metal (Li, Na, K, Rb, Cs)
MO or M(OH)2:
M: Group (2) metal (Ca, Sr, Ba)
NaOH(aq)

Na+(aq)

OH(aq)

WEAK BASE
Dissociate very slightly into ions in water
Kb very small
EXAMPLE:

..

Molecules with an N atom that has a lone


pair electrons:
NH3
NH3(g) + H2O(l)

NH4+(aq) + OH(aq)

EXAMPLE
Classify each of the following compounds as
a strong acid, weak acid, strong base, or
weak base, or species with negligible acidity.
a)
b)
c)
d)
e)
f)
g)
h)

(CH3)2CHCOOH
KOH
(CH3)2CHNH2
HNO2
H2SO4
HPO42
CH4
CH3NH3+

Ans: EXAMPLE
a)

(CH3)2CHCOOH

b)

KOH

c)

(CH3)2CHNH2

d)

HNO2

e)

H2SO4

f)

HPO42

g)

CH4

h)

CH3NH3+

Define pH and pOH

Relate pH and 0pOH to the ionic product of


water, Kw at 25 C

Calculate the pH values of a strong acid


and base.

7.1.4: pH and pOH


pH is defined as the negative logarithm (log) of
the hydronium,H3O+ concentration.
[H3O+] in a solution is measured using
pH scale method.

pH = - log [H+]
If [H+] , pH .
pOH is defined as the negative logarithm (log) of
the hydroxide ion.
concentration of OH- is measured using pOH.

pOH = - log [OH-]


If [OH-] , pH , pOH

pH SCALE
pH = log [H3O+]
pOH = log [OH]
The higher [H3O+], the lower pH
The higher the [OH], the lower pOH

pH MEASUREMENT
Acidbase indicator
pH paper (& color chart)
pH meter
pH of a neutral solution = 7.0
pH of an acidic solution < 7.0
pH of an basic solution > 7.0

AUTOIONIZATION OF WATER
Water dissociates into ions very slightly
H2O(l) + H2O(l)

H3O+(aq) + OH(aq)

KW = [ H3O+ ] [ OH ]
= 1.0 x 1014 (at 25oC)
KW : ion product constant for water
In pure water at 25oC;
[H3O+] = [OH] = 1.0 x 107 M

Relationship between Kw, pH and pOH at 25oC,


[H+] [OH-] = Kw
-log both side,
-log ([H+] [OH-]) = -log Kw
-log [H+] + ( log [OH-]) = - log (1.0 x 10-14)
pH ++ pOH
pH
pOH == pK
14w

[H3O+] and [OH]


A change in [H3O]+ causes an inverse change
in [OH]
Higher [H3O+]

lower [OH]

Higher [OH]

lower [H3O+]

[H+] [OH-] = Kw
Both ions are present in all aqueous systems
In acidic solution,

[H3O+] > [OH]

In basic solution,

[H3O+] < [OH]

In neutral solution, [H3O+] = [OH]

CALCULATING [H3O+] AND [OH]


IN AQUEOUS SOLUTION

KW = [ H3O+ ] [ OH ]

[ H3 O + ] =

KW
[ OH]

= 1.0 x 1014 (at 25oC)

[ OH ] =

KW
[H3O+ ]

pH / pOH STRONG ACIDS AND BASES


Strong acids and bases are considered to
be 100% dissociated in an aqueous
solution
EXAMPLE: Strong acid
HCl(aq) +
before:

H2O(l)

0.020 M

0
after:
(100% dissociated)

pH = log [H3O+]
= log [0.020]
= 1.70

H3O+(aq)
0
0.020 M

Cl(aq)
0
0.020 M

pH / pOH STRONG ACIDS AND BASES


EXAMPLE: Strong base
Ba(OH)2(aq)
before:
after:

Ba2+(aq)
0

0.00035 M
0

2OH(aq)
0

0.00035 M

0.00070 M

(100% dissociated)
[ H3O+ ] =

KW
[OH ]

1.0 x 1014
0.00070

= 1.43 x 1011 M

pH = log [H3O+]
= log (1.43 x 1011) = 10.85

EXAMPLE
a)

What is the pH of a 0.040 M solution of


HClO4 ?

b)

An aqueous solution of HNO3 has a pH of


2.34. What is the concentration of the acid ?

c) What is the pH of A 0.0011 M solution of Ca(OH)2?

Ans: EXAMPLE

Ans:
Ans:EXAMPLE
EXAMPLE

Ans: EXAMPLE

Ans: EXAMPLE

Relate the strength of a weak acid and weak base to


the respective dissociation constant, Ka and Kb.

Perform calculations involving pH, dissociation


constant, initial concentration and the degree of
dissociation,

**** Calculations are limited to problems with quadratic


equation: ax2+bx+c=0. Apply approximation
method if Ka or Kb 10-5

ACIDDISSOCIATION CONSTANT (Ka)


Dissociation of weak acid in water:
HA(aq) + H2O(l)
Ka

H3O+(aq) + A(aq)
[ H3 O + ] [ A ]
[ HA ]

EXAMPLE:
HCN(aq) + H2O(l)
Ka =

H3O+(aq) + CN(aq)

[ H3O+ ] [ CN ]
[ HCN ]

H+(aq) = H3O+(aq)
EXAMPLE:
HCN(aq) + H2O(l)
Ka =

H3O+(aq) + CN(aq)

[ H3O+ ] [ CN ]
[ HCN ]

or
HCN(aq)

H+(aq) + CN(aq)
Ka =

[ H+ ] [ CN ]
[ HCN ]

stronger acid

higher [H3O+]

larger Ka

smaller Ka

lower % HA dissociated

weaker acid

For strong acids and bases (dissociate 100%):


Ka or Kb values have not been measured

EXAMPLE
Nitrous acid, HNO2, is a weak acid that formed in the
stomach when nitrite food preservatives encounter
stomach acid. There has been some concern that
this acid may for carcinogenic products by reaction
with proteins.
Write the chemical equation for the equilibrium
ionization of HNO2 in water and the appropriate
Ka expression.

Ans: EXAMPLE

BASEDISSOCIATION CONSTANT (Kb)


Dissociation of weak base in water:
B(aq) + H2O(l)

BH+(aq) + OH(aq)
[ BH+ ] [ OH ]

Kb =

[ B]

EXAMPLE:
NH3(aq) + H2O(l)
Kb =

NH4+(aq) + OH(aq)

[ NH4+ ] [ OH ]
[ NH3 ]

When a proton (H+) is accepted by a weak


base contains a N atom, the H+ binds to a lone
pair of electrons on a N atom of the base
EXAMPLE: (for the reaction with water)
NH3(aq) + H2O(l)

N2H4(aq) + H2O(l)
(CH3)2NH(aq) + H2O(l)

NH4+(aq) + OH(aq)

N2H5+(aq) + OH(aq)
0(CH3)2NH2+(aq)

+ OH(aq)

EXAMPLE
Hydrazine is a weak base. It is a poisonous substance
thats sometimes formed when chlorine bleach is
added to an aqueous solution of ammonia.
Write the equation for the reaction of hydrazine
(N2H4) with water and write the expression for
its Kb.

Ans: EXAMPLE

pH Calculation for Weak Acid


Consider a general weak acid, HA.
The ionisation equation in water is given by:
H3O+(aq) + A-(aq)

HA(aq) + H2O(l)

Given,c = initial concentration


x=concentration of H3O+ iondissociated
HA(aq)

H3O+(aq)

Initial Conc. (M)


Change (M)
Equilibrium Conc.(M)

At equilibrium,

[ H 3O + ] [ A ]
[ HA]

A-(aq)

Ka for a weak acid in water.


Ka = ( x ) ( x)
( c-x )

Assuming, that only a small amount of acid


dissociates, i.e. Ka <<< 1, therefore:
[HA] =

cx ~ c

Ka =

x2
c
x2 = Ka.c
x

= (Ka . C)
= [H3O+]

pH Calculation for Weak Acid


If the degree of dissociation, is given,
A-(aq) + H3O+(aq)

HA(aq) + H2O(l)

Given,c = initial concentration


=Degree of dissociation
Initial Conc. (M)
Change (M)
Equilibrium conc.(M)

At equilibrium,

HA(aq)

A-(aq)

H3O+(aq)

-c

+c

+c

c - c
= c( 1- )

Ka = [A-] [H3O+]
[ HA ]

[ H 3O + ] [ A ]
Ka =
[ HA]

(c ) (c )
c(1 )
c 2
(1 )

For a weak electrolyte, is very small.


Thus, only a small amount of acid dissociates,
Hence,

Ka <<< 1, therefore: 1 - 1
Ka = c 2

= (Ka

/ c) 1/2

[H+] = c = c (Ka / c) 1/2


= (Ka. c) 1/2

pH Calculation for Weak Base


Consider a general weak base, B.
The ionisation equation in water is given by:
B(aq) + H2O(l)

HB+(aq) + OH-(aq)

Given,c = initial concentration


x=concentration of OH- iondissociated
B(aq)

HB+(aq)

OH-(aq)

Initial Conc. (M)

Change (M)

-x

+x

+x

Equilibrium conc.(M)

c- x

At equilibrium,

Kb = [BH+] [OH]
[B]

Kb for a weak base in water.


Kb = [HB+] [OH]
[B]

At equilibrium,

= ( x ) ( x)
( c-x )

Assuming, that only a small amount of base


dissociates, i.e. Kb <<< 1, therefore:
[B] =

Kb =

cx ~ c
x2

c
x2 = Kb.c

= Kb . c
= [OH-]

pH Calculation for Weak Base


If the degree of dissociation, is given,
B(aq) + H2O(l)

HB+(aq) + OH-(aq)

Given,c = initial concentration


=Degree of dissociation
Initial Concentration (M)
Change (M)
Equilibrium
concentration(M)
At equilibrium,

B(aq)

HB+(aq)

OH-(aq)

-c

+c

+c

c( 1- )

Kb = [HB+] [OH]
[B]

At equilibrium, Kb = [HB+] [OH]


[B]

(c ) (c )
c(1 )
c 2
(1 )

For a weak electrolyte, is very small.


Thus, only a small amount of acid dissociates,
Hence, Kb <<< 1, therefore: 1 - 1

Kb = c 2

= (Kb

/ c) 1/2

[H+] = c = c (Kb / c) 1/2


= (Kb. c) 1/2

SOLVING PROBLEMS INVOLVING


WEAK ACID / WEAK BASE EQUILIBRIA
Two general types of problems:
Given equilibrium concentration,
find Ka (or Kb)
Given Ka (or Kb) and some concentration
information, find the other equilibrium
concentrations
Use ICE table !

Assumptions:
[H3O+] from autoionization of H2O is
negligible
A weak acid has a small Ka, So:
[HA]initial [HA]dissoc [HA]initial

[HA]initial x = [HA]initial (x very small)

Apply 5 % test to check the


assumption is justified

Approximation
method or quadratic
method??

Apply the
approximation
method if Ka or
Kb 10-5

HOW??

Example if Ka or Kb is
1.8 x 10-5 M then use
approximation method if
6.8 x 10-4 M use quadratic

HOW??

Or your can check the % value, if


% less than 5% than you can
choose approximation method. The
formula is :
= Ka or Kb x 100
c

B.Weak Base
Example 1 :

Kb

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.
[ ] initial

use approximation
method because
Ka is 1.8 x 10-5

CHECK!
=

Ka or Kb x 100
c
= 1.8 x 10-5 x 100
0.15
= 1.09 % less than 5%
(use approximation method )

Exercise :
1. Calculate the percentage of HF molecules ionized in
(a) a 0.10 M HF solution the Ka of HF is 6.8 x 10 -4
use quadratic
because Ka of HF is
6.8 x 10 -4 greater
than 10-5

(7.9 %)
CHECK!

Ka or Kb x 100
c
= 6.8 x 10 -4 x 100
0.10
= 8.24% more than 5%
(use quadratic)

EXAMPLE 1
What is the pH of a 0.5 M HF solution (at 25oC)?
Ka of HF = 7.1 x 104

Ans: EXAMPLE 1

Ans: EXAMPLE 1

EXAMPLE 2
Calculate:
a) The basedissociation constant, Kb,
for the fluoride ion (F)
Ka of HF = 6.8 x 104
b) The aciddissociation constant, Ka,
for the ammonium ion (NH4+)
Kb of NH3 = 1.8 x 105

Ans: EXAMPLE 2

Ans: EXAMPLE 2

RELATIONSHIP BETWEEN Ka and Kb


Dissociation of NH3 in water:
NH3(aq) + H2O(l)
base

Kb =

NH4+(aq)

+ OH(aq)

Conjugate acid

[ NH4+ ][ OH ]
[ NH3]

Dissociation of NH4+ in water:


NH4+(aq) + H2O(l)
Ka =

NH3(aq)
[ NH3 ] [ H3O+ ]
[ NH4+]

+ H3O+(aq)

Ka , Kb , Kw , pKa , pKb AND pKW


NH3(aq) + H2O(l)

NH4+(aq)

+ OH(aq)

NH4+(aq) + H2O(l)

NH3(aq)

+ H3O+(aq)

base

Conjugate acid

acid

Conjugate base

2H2O(l)
Kb x Ka =

[ NH4+ ] [OH-]
[ NH3]

H3O+(aq) + OH(aq)
x

[ NH3 ] [H3O+ ]
[ NH4+]

Ka x Kb = Kw
pKa + pKb = pKw

= [ H3O+ ][OH]

Ka AND pKa
pKa = log Ka

High Ka low pKa


higher acidity

Kb AND pKb
pKb = log Kb
Kb

pKb
4.74
8.77
9.42

14.82

High Kb low pKb


higher basicity

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.
Ka (pKa ) = [H+] , thus pH (more acidic)
Kb (pKb ) = [OH-] , thus pH (more basic)
Example :
Acid

pKa

Base

pKb

CH3COOH

4.74

C6H5NH2

9.37

HCOOH

3.76

NH3

4.74

Relative acidity,
HCOOH > CH3COOH

Relative basicity,
NH3 > C6H5NH2

EXERCISE 1
a) Lactic acid, HC3H5O2, is responsible for the
taste of sour milk. At 25oC it Ka = 1.4 x 104.
What is the Kb of its conjugate base, the
lactate ion, C3H5O2?
b) Methylamine, CH3NH2, resembles ammonia in
odor and basicity. Its Kb = 4.4 x 104.
Calculate the Ka of its conjugate acid
ANS:
a) 7.1 x 1011
b) 2.3 x 1011

EXERCISE
EXERCISE224
Propanoic acid (C2H5COOH)(monoprotic)
is an organic acid whose salts are used to
retard mold growth in foods.
What is the [H3O+] of 0.10 M C2H5COOH ?
Note: Ka = 1.3 x 10-5.

ANS:
[H3O+] = 1.1 x 10-3 M

7.1

EXAMPLE
20
EXERCISE
3

7.1

The average pH of normal arterial blood is 7.40.


At normal body temperature (37oC),
Kw = 2.4 x 1014. Calculate [H+] and [OH] for blood
at this temperature.

ANS:
a) [H+] = 4.0 x 108 M
b) [OH] = 6.0 x 107 M

EXERCISE 4
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, 1.73, 1.76 x 10-3)

2. Calculate the formate ion concentration and pH of a


solution that is 0.050 M in formic acid.
(HCHO2 : Ka = 1.8 x 10-4).
(CHO2- = 9.0 x10-5 , pH = 1.00 )

Explain salt hydrolysis and write hydrolysis equation


for the salt formed from the reaction between:
i. Strong acid and strong base
ii. Strong acid and weak base
iii. Weak acid and strong base

Define buffer solution

SALT HYDROLYSIS
Salt hydrolysis: reaction of an anion or cation of a
salt (or both) with water.
General equation of neutralization :
HX

+ MOH
(acid)
(base)

MX

+ H 2O
(salt)
(water)

MX salt dissociation equation:


MX

M+

X-

Cation Hydrolysis : M+(aq) + H2O(l)

MOH(aq) + H+(aq)

Anion Hydrolysis : X-(aq) + H2O(l)

HX(aq) + OH-(aq)

EXAMPLE:
CH3COONa(s)

H2O

Na+(aq) + CH3COO(aq)

Species exist:
Na+ and CH3COO
H3O+ and OH from autoionization of H2O
(negligible)
Salt hydrolysis:
Na+ + H2O What happen ?
CH3COO + H2O What happen?
What is the effect to the acidity of the solution?

SALT HYDROLYSIS : FROM STRONG ACID AND


STRONG BASE
Salt consisting:
Anion from strong acid ( Cl, NO3, Br, ClO4 )
Cation from strong base ( Na+, K+, Li+, Ca2+ )
May From NaOH solution

EXAMPLE: NaCl solution


NaCl(s)

H2O

May From HCl solution

Na+(aq) + Cl(aq)

Neither Na+ nor Cl ionize in water

SALT HYDROLYSIS : FROM WEAK ACID AND


STRONG BASE
Salt consisting:
Anion from weak acid ( e.g: CH3COO, F, NO2 )
Cation from strong base ( Na+, K+, Li+, Ca2+ )
EXAMPLE: CH3COONa solution
CH3COONa(s)

H2O

May From NaOH


solution
From CH3COOH
solution

Na+(aq) + CH3COO(aq)

Na+ does not ionize in water


Therefore, the hydrolysis salt equation:
CH3COO(aq) + H2O(l)

CH3COOH(aq) + OH(aq)

SALT HYDROLYSIS : FROM STRONG ACID AND


WEAK BASE
Salt consisting:
Anion from strong acid ( Cl, NO3, Br, ClO4 )
Cation from weak base ( e.g: NH4+, CH3NH3+ )
From NH3 solution

EXAMPLE: NH4Cl solution


NH4Cl(s)

H2O

NH4+(aq) + Cl(aq)

Cl does not ionize in water


Therefore, the hydrolysis salt equation:

From HCl solution

Dissolution and dissociation of salts in water can be


written as:
NaCl(s)

H2O

Na+(aq) + Cl(aq)
or

NaCl(aq)

Na+(aq) + Cl(aq)

EXAMPLE
Write the hydrolysis salt equation:
a)
b)
c)
d)
e)
f)
g)
h)
i)

NH4I
CaCl2
KCN
LiClO4
CH3NH3+ NO3
NaOCl
KCl
NH4NO3
NaNO2

Ans: EXAMPLE

EXAMPLE
Ans: EXAMPLE
35

7.1

EXAMPLE
Ans: EXAMPLE
35

7.1

BUFFER SOLUTION
How does blood maintain a constant
pH in contact with countless cellular
acidbase reaction ?
The normal of pH of blood is 7.4
Severe illness or death can results
from sustained variation just a few
tenths of a pH unit
from this
normal value

There must be as system in our body


to maintain the pH of blood or any
aqueous solution !

BUFFER SOLUTION
is a solution which has the ability to maintain its pH
when a small amount of strong acid or strong base
is added to the solution.
It must contains:
Acidic component
can react with added [OH]
Basic component
can react with added [H3O+]
Most common buffer components:
base - Conjugate acid pair (of weak base) OR
acid - Conjugate base pair (of weak acid)

Buffer solution contains only either


weak acid or base.
If the system contains strong acid or base,
the system CANNOT act as a buffer solution.

BUFFERRED Vs UNBUFFERED SOLUTION

Addition of 1 M HCl

Solution of dilute HCl

The system is not buffer solution due


to the large different of pH value.

Addition of 1 M HCl

Solution of mixture of
1 M CH3COOH and
1 M CH COONa

Addition of 1 M NaOH

Addition of 1 M NaOH

The system is buffer solution due to


the small different of pH value.

EXAMPLE
Which of the following are buffer systems?
(a) KF / HF
(b) KBr / HBr
(c) Na2CO3 / NaHCO3

Ans: EXAMPLE

Decribe qualitatively how a buffer solution


controls its pH
Derive the Henderson-Hasselbalch equation.
Calculate the pH of buffer solutions.

BUFFER SOLUTION
Two types of buffer solutions :
i. Acidic buffer solution (pH<7)
ii. Basic buffer solution (pH>7)
EXAMPLE:

A weak acid and its conjugate base


Mixture of CH3COOH / CH3COONa
Acidic component
Basic component

CH3COOH
CH3COO

A weak base and its conjugate acid


Mixture of NH3 / NH4Cl
Acidic component
NH4+
Basic component
NH3

HOW A BUFFER CONTROL its pH:


Example: CH3COOH / CH3COONa
CH3COOH (aq)
CH3COONa (aq)

CH3COO- (aq) + H+ (aq)


CH3COO- (aq) + Na+ (aq)
base (OH-)

acid (H+)

H+(added) + CH3COO-

CH3COOH

OH-(added) + CH3COOH

CH3COOCH3COOH

CH3COO- + H2O

CH3COOCH COOH
CH3COO- 3

A buffer system contains ethanoic acid,CH3COOH


and ethanoat ion, CH3COO- from CH3COONa

Addition of H3O+ :
H3O+(aq) + CH3COO(aq)

CH3COOH(aq) + H2O(l)

Amount of H3O+ added = Amount of CH3COO consumed


= Amount of CH3COOH produced
(H+)

CH3COO- (aq) + H+

CH3COOH (aq)

CH3COOCH3COOH
CH3COOH
CH3COO-

[CH3COO-] decrease and [CH3COOH] increase


As a result, there will be only a small change in pH

Addition of OH :
OH(aq) + CH3COOH(aq)

CH3COO(aq) + H2O(l)

Amount of OH added = Amount of CH3COOH consumed


= Amount of CH3COO produced
(HO-)

CH3COOH (aq) + HO-

CH3COO- (aq)

CH3COOCH3COOH
CH3COOH
CH3COO-

[CH3COO-] increase and [CH3COOH] decrease


As a result, there will be only a small change in pH

EXAMPLE 1 38
EXERCISE

7.1

Show how NH3NH4Cl solution is a


buffer solution.
(Hint: Identify a component in the solution
that neutralizes acids and a component
that neutralizes bases)

Ans: EXAMPLE 1

HENDERSONHASSELBALCH EQUATION
For weak acid:
HA(aq) +

Ka =

A(aq) + H3O+(aq)

H2O(l)

[A] [ H3O+]

rearrange

[HA]

[ H3O+] = Ka x [ HA]
[A]

log [H3O+] = log Ka log

pH

pKa

log

[ HA]
[A]

[ Conjugate base]
[weak acid]

HENDERSONHASSELBALCH EQUATION
For weak base:
NH3(aq) +

Kb =

H2O(l)
rearrange

[NH4+][OH-]
[NH3]

log [OH-]

pOH

NH4+(aq) + OH-(aq)

[OH-] = Kb x [ NH3]
[NH4+]

= log Kb log

pKb

+ log

[NH3]
[NH4+]

[ Conjugate acid]
[weak base]

EXAMPLE241
EXAMPLE

7.1

a)

Calculate the pH of a solution containing


0.20 M CH3COOH and 0.30 M CH3COONa.

b)

What would the pH of a 0.20 M of


CH3COOH solution be if no salt were
present?
Ka of CH3COOH = 1.8 x 105.

Ans:
EXAMPLE
EXAMPLE
41 2

7.1

EXAMPLE
41 2
Ans:
EXAMPLE

7.1

EXAMPLE
41 2
Ans:
EXAMPLE

7.1

EXAMPLE349
EXAMPLE

7.1

To study the influence of an alkaline medium


of a reaction, a buffer solution was prepared by
dissolving 0.12 mol of NH3 and 0.095 mol of
NH4Cl in water. What is the pH of the buffer?
Kb of NH3 = 1.8 x 105

Ans:
EXAMPLE
EXAMPLE
49 3

7.1

Ans:
EXAMPLE
EXAMPLE
49 3

7.1

Example :

EXERCISE 1

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

Ans: EXERCISE 1

Ans: EXERCISE 1

Ans: EXERCISE 1

Ans: EXERCISE 1

7.2 :
ACID-BASE
TITRATION

Describe the titration process and distinguish the


end point and equivalence point.

Sketch and interpret the variation pH against titre value for


titration between :
i. strong acid- strong base
ii. strong acid-weak base
iii. weak acid-strong base

Identify suitable indicators for acid-base titrations.

KEYWORDS
titration
end point

equivalence point

titration curve

indicators

ACIDBASE TITRATION
A solution of accurately known concentration
is added gradually to another solution of
unknown concentration until the chemical
reaction (neutralization) between the two solution
is complete.

ACIDBASE TITRATION
Burette:
Concentration of solution inside:
known (EXAMPLE: NaOH(aq))
Indicator:
(EXAMPLE:
phenolphthalein)

Before titration
begin

After titration
(at the end point)
Conical flask:
Concentration of solution inside:
unknown (EXAMPLE: CH3COOH(aq))

INDICATOR
A weak organic acid that has different color
than it conjugate base
Color changes occurring over a specific and
relatively narrow pH range

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.

pH RANGE
Range over which the indicator changes from
the acid color to the base color
EXAMPLE:
pH range
Phenolphthalein

8.3 ~ 10.0

Methyl orange

3.1 ~ 4.4

Methyl red

4.2 ~ 6.3

Some Common AcidBase Indicators

Colors and Approximation pH Range of


Some Common AcidBase Indicators

acidic

in
between

Most indicators have a range of about 2 pH units

basic

EQUIVALENT and ENDPOINT

The equivalent point is the point at which the


amount of acid and base present exactly
neutralizes one another. (number of moles of OHions and number of moles of H+ ions are equal)
The end point of titration is the point when the
indicator changes colour.

TITRATION CURVE
3 types of acid-base titration :
Strong Acid Strong Base
Weak Acid Strong Base
Strong Acid Weak Base

TITRATION CURVE: Strong Acid and Strong Base


(example: HCl and NaOH
pH

pH range
Phenolphthalein 8.3 ~ 10.0
Methyl red

4.2 ~ 6.3

Volume of NaOH
added (mL)

Either methyl red or phenolphthalein is a suitable


indicator because each changes color on the
steep portion of the curve

WEAK ACIDSTRONG BASE CURVES


Three different with strong acidstrong base:
Initial pH is higher
Weak acid dissociates slightly
Gradual rising portion buffer region
Mixture of acid and salt
HA/A buffer system produced
pH at equivalence point > 7.00
Salts of weak acid and strong base
(Example: CH3COONa+) is basic in water

TITRATION CURVE: Weak Acid and Strong Base


(example CH3COOH and NaOH)

pH range
Phenolphthalein 8.3 ~ 10.0
pH

Methyl red

4.2 ~ 6.3

Phenolphthalein is a suitable indicator because it


changes color on the steep portion of the curve, but
methyl red is not its color changes over a large
volume range

STRONG ACIDWEAK BASE CURVES


EXAMPLE: NH3(aq) in conical flask
HCl(aq) in burette
Initial solution = weak base pH > 7.00
Gradual rising portion buffer region
Mixture of base (NH3) and salt (NH4+)
pH at equivalence point < 7.00
Salt (NH4+Cl) is acidic in water
pH decrease slowly as excess H3O+ is
added

TITRATION CURVE: Strong Acid and Weak Base


(example: HCl and NH3 )

pH range

pH

Phenolphthalein 8.3 ~ 10.0


Methyl red

4.2 ~ 6.3

Methyl red is a suitable indicator because it changes


color on the steep portion of the curve, but
phenolphathalein is not its color changes over a large
volume range

EXAMPLE
Sketch titration curves for the following
acidbase titrations:
a) HCl versus NaOH
b) HCl versus CH3NH2
c) CH3COOH versus NaOH
In each case, the base is added to the acid
in a conical flask. Your graph should show
pH on the yaxis and volume of base added
on the xaxis.

Ans: EXAMPLE
a) Titration curve: HCl versus NaOH
pH

7.00

equivalence
point

Volume of
NaOH added

Ans: EXAMPLE
b) Titration curve: HCl versus CH3NH2
pH
buffer region

< 7.00

equivalence
point

Volume of
NaOH added

Ans: EXAMPLE
Titration curve: CH3COOH versus NaOH
pH

equivalence
point

> 7.00

buffer region

Volume of
NaOH added

EXERCISE
EXERCISE130

7.1

1. What is the colour of the solution when 3 drops of the


below indicators are added separately to water (pH = 7) ?
Indicator

pH range

Phenolphthalein

8.2 10.0

Methyl orange

3.2 4.2

Bromothymol
blue

6.0 7.6

phenol red

6.8 8.4

colour change

Define solubility, molar solubility and solubility


product, Ksp.

Calculate Ksp from concentration of ion and vice


versa
Predict the possibility of precipitation of slightly
soluble ionic compounds the values of ion-product,
Q to Ksp.

Define and explain the common ion effect.


Perform calculations related to common ion effect.

KEYWORDS
solubility
molar solubility
solubility product (Ksp)
precipitation
Q

common ion effect

Solubility and Molar Solubility


Solubility: is the maximum amount of solute( g or mole
or kg) that can be dissolved in a given quantity of
solvent to form a saturated solution at a given
temperature. For example;
Solubility (g/L)
Grams of solute dissolved in 1 L of a saturated
solution
Molar solubility (mol/L):
Moles of solute dissolved in 1 L of a saturated
solution
+

Sugar (solute)
In max. amount

A cup Bitter tea


(solvent)

Very sweet tea


(saturated solution)

SOLUBILITY OF SLIGHTLY
SOLUBLE IONIC COMPOUNDS
Assumption: The small amount of a slightly
soluble ionic compound that dissolves in water
also dissociates completely into ions
EXAMPLE:
Slightly soluble PbCl2(aq)
100% dissociates into ions
Pb2+
(aq)

PbCl2(s)

2Cl
(aq)

PbCl2(s)

Pb2+(aq) + 2Cl(aq)

Equilibrium exist between solid solute and


aqueous ions:
EXAMPLE:
PbCl2(s)

Pb2+(aq) + 2Cl(aq)

Ag2S(s)

2Ag+(aq) + S2(aq)

SOLUBILITYPRODUCT CONSTANT, Ksp


EXAMPLE: Saturated solution of AgCl in water
AgCl(s)

Ag+(aq) + Cl(aq)
Ksp =

[Ag+] [Cl]

Ksp : The product of ion concentrations in saturated


solution, each raised to the power of its
stoichiometric in the equilibrium equation.

An equilibrium constant related to the


equilibrium between solid salt and its ions
in solution
Its provide a quantitative measure of the
solubility of a slightly soluble salt

Soluble ionic compounds (100 % soluble and dissociate


in water) such as NaCl have no Ksp value

EXAMPLE
Write the ionproduct (Ksp) expression for each
of the following:
a)
b)
c)
d)
e)
f)

Silver carbonate
Barium fluoride
Copper(II) sulfide
Iron(III) hydroxide
Barium phosphate
Tin(II) sulfide

Ans: EXAMPLE

Ans: EXAMPLE

Ans: EXAMPLE

USING Ksp TO COMPARE SOLUBILITIES


Ksp

Solubility

EXAMPLE:
MgCO3(s)

Mg2+(aq) + CO32(aq)

Ksp = 3.5 x 108

PbSO4(s)

Pb2+(aq) + SO42(aq)

Ksp = 1.6 x 108

MgCO3 is more soluble than PbSO4


You must compare Ksp of compounds
whose formula have same total number
of ions

CALCULATION INVOLVING Ksp


Two types:
Determining Ksp from
solubility or molar solubility
Determining solubility or
molar solubility from Ksp

EXAMPLE 1
Silver bromide, AgBr, is the lightsensitive
compound used in nearly all photographic film.
The molar solubility of AgBr is 7.1 x 107 M.
at 25oC. Calculate Ksp for AgBr at this
temperature.

ANS:
5.0 x 1013

Ans: EXAMPLE 1

EXAMPLE 2
The solubility of silver carbonate is
0.032 mol L1 at 20oC. Calculate the Ksp
of silver carbonate.

ANS:
1.3 x 104

Ans: EXAMPLE 2

EXAMPLE 3
The solubility of calcium sulfate is found
experimentally to be 0.67 g/L.
Calculate the value of Ksp for calcium sulfate.
(Molar mass of CaSO4 = 136.2 g/mol)

ANS:
2.4 x 105

Ans: EXAMPLE 3

Ans: EXAMPLE 3

When Ksp is given,

EXAMPLE 1
What is the molar solubility of AgCl in
pure water at 25oC?
Ksp of AgCl = 1.8 x 1010

ANS:
1.3 x 105 mol L1

Ans: EXAMPLE 1

EXAMPLE 2
Calculate the molar solubility of PbCl2.
Ksp = 1.6 x 105

ANS:
1.6 x 102 M

Ans: EXAMPLE 2

EXERCISE
EXERCISE130

7.1

1. The solubility of magnesium hydroxide, Mg(OH)2 is


1.7 x 10-4 mol dm-3. Calculate the solubility product of
this compound.

2. The solubility of calcium sulfate, CaSO4 is found


experimentally to be 0.67 g L-1. Calculate the Ksp value
for CaSO4. (Molar mass of CaSO4 = 136.2 g mol-1)

3. 1.00 liter of a saturated solution of silver chromate,


Ag2CrO4 at 25oC contains 0.0435 gram of dissolved
Ag2CrO4. Calculate its molar solubility and its solubility
product constant.

Prediction of precipitation, Qsp Vs. Ksp


Q = Ksp
- the solution is saturated
- equilibrium exist between undisolve
solid salt and its dissolved ions
Q < Ksp
More solid can
- the solution is unsaturated
dissolve !
- no precipitation of MA
- more salt should be dissolved to increase
the ion concentrations until Q = Ksp
Q > Ksp
- the solution is supersaturated
- MA(s) will precipitate out until the product
of the ionic concentrations is equal to Ksp.

EXAMPLE 1
Will a precipitate of CaSO4 form in a solution
if the Ca2+ concentration is 0.0025 M and the
SO42 concentration is 0.030 M ?
(Ksp of CaSO4 = 2.4 x 105)

ANS:
Precipitate will form until Qsp = Ksp

Ans: EXAMPLE 1

EXAMPLE 2
What possible precipitate might form by
mixing 50.0 mL of 1.0 x 104 M NaCl with
50.0 mL of 1.0 x 106 M AgNO3? Will it form?
(Ksp of AgCl = 1.8 x 1010)

ANS:
Qsp = 2.5 x 1011
AgCl precipitate will not form

Ans: EXAMPLE 2

Ans: EXAMPLE 2

Ans: EXAMPLE 2

Ans: EXAMPLE 2

COMMON ION EFFECT


Shift of equilibrium caused by addition or the
the presence of a compound having an ion in
common with the dissolved substance
EXAMPLE:
PbCrO4(s)

Add CrO42
Pb2+(aq) + CrO42(aq)

EFFECT OF COMMON ION


ON SOLUBILITY
Presence of a common ion decreases solubility
of slightly soluble ionic compound
EXAMPLE: Addition of Na2CrO4 (soluble salt) to
saturated solution of PbCrO4
Add CrO42PbCrO4(s)
Ksp = [Pb2+][CrO42]

Pb2+(aq) + CrO42(aq)
= 2.3 x 10-13

Effect of the addition of common ion CrO42 :


Some CrO42 combine with
Pb2+ to form solid PbCrO4
Solubility of PbCrO4
[CrO42]

Add CrO42
PbCrO4
Pb2+
CrO42
PbCrO4

Pb2+
CrO42
PbCrO4

The same results if:


PbCrO4 dissolves in Na2CrO4 solution
Soluble lead (II)salt such as Pb(NO3)2 is added

EXAMPLE 1
What is the molar solubility of AgBr in
(a) pure water
(b) 0.0010 M NaBr ?.
Ksp of AgBr = 7.7 x 1013

ANS:
a) 8.8 x 107 M
b) 7.7 x 1010 M

Ans: EXAMPLE 1

Ans: EXAMPLE 1

EXAMPLE 2
Calculate the solubility of silver chloride
(in g/L) in
a)
b)

pure water
a 6.5 x 103 M silver nitrate solution
Ksp of AgCl = 1.6 x 1010

ANS:
a) 1.8 x 103 g/L
b) 3.6 x 106 g/L

Ans: EXAMPLE 2

Ans: EXAMPLE 2

Ans: EXAMPLE 2

Ans: EXAMPLE 2

EXAMPLE130
EXERCISE
EXERCISE

7.1

1. It was found experimentally that the solubility of


calcium sulphate is 0.67 g L-1. Calculate the Ksp for
calcium sulphate. ( 2.4 x 10-4 )

2. The solubility of silver sulphate is 1.5 x 10-2 mol L-1.


Calculate the solubility product of the salt. ( 1.4 x 10-5 )

3. Will precipitate form if 200 mL of 0.0040 M BaCl 2 are


added to 600 mL of 0.0080 M K2SO4 ? Ksp BaSO4 = 1.1 x
10-10) ( Q> Ksp therefore BaSO4 will precipitate)

Kidney Stone

Are pains shooting through your body that are


so severe that they cause you to curl up in pain?
Does your lower back feel like being
stabbed over and over again with
a hot knife?
Are your pains so severe that make
you feel nauseous or even cause
you to vomit?

Kidney stones consist largely calcium oxalate,


CaC2O4 (Ksp = 2.3 x 109)

The normal physiological concentration of calcium


ions in blood plasma is about 5 mM
Oxalate ion (C2O42), derived from oxalic acid present
in many vegetables such as rhubarb and spinach,
reach with calcium ions to form insoluble calcium
oxalate, which can gradually build up in the kidneys
Ca2+(aq) + C2O42(aq) CaC2O4(s)

Proper adjustment of a patients diet can help


to reduce precipitate formation
CaC2O4(s)

Ca2+(aq) + C2O42(aq)