-

(Acids and Bases)

-

H+ ()
HCl(aq)
H+(aq) + Cl-(aq)
OH NaOH(aq)
Na+ (aq) + OH- (aq)

Bronsted Acids and Bases

Bronsted acid proton hydronium ion
acids H+ H3O+
Bronsted base proton hydronium ion
base ; OH- + H3O+ 2H2O

- (Conjugate acidbase pair)

Acid

H+ + conjugate base
( proton )

CH3COOH (aq) + H2O(l)

acid1
base2
Base

CH3COO- (aq) + H3O+(aq)

base1
acid2
(conjugate base)

conjugate acid + OH-

NH3(aq) + H2O(l)
base1
acid2

NH4+(aq) + OH-(aq)
acid1
base2
(conjugate acid)

 - (The acid-base properties of water)

H+(aq) + OH-(aq)
1
H2O (l)
H3O+(aq) + OH-(aq)
2
H2O (l) + H2O (l)
acid1 base2
acid2
base1
(Autoionization)
Kw (ion product constant) = [H+][OH-] ( 1)
25 oC ; [H+] = [OH-] = 1.0 10-7 M
Kc[H2O] = Kw = [H+][OH-]

Kw = (1.0 10-7)(1.0 10-7) = 1.0 10-14

pH (acidity)
pH = -log[H+]
[H+] = 1.0 10-7 M
pH = -log(1.0 107)
= 7 ( )
[H+] > 1.0 10-7 M pH 7 ( )
[H+] < 1.0 10-7 M pH 7 ( )

pH ;

pOH
pOH = -log[OH-]
pH + pOH

14

 pH
1 H+ 3.2 10-4 M
1 H+ 1.0 10-3 M
pH 1
;

1 ;

[H+]1 = 3.2 10-4 M

pH = -log [H+]
= -log(3.2 10-4)
= 3.49
[H+]2 = 1.0 10-3 M
pH = -log(1.0 10-3)
= 3.00

 pH
2 KOH 2.9 10-4 M pOH pH
pOH [OH-]
[OH-]
pOH =
=
=
pH + pOH =
pH =
=
=

-log[OH-]
-log(2.9 10-4)
3.54
14
14 pOH
14 3.54
10.46

 (Strength of Acids and Bases)

(strength)
1 Strength of Acids and Bases
Strength (ionization)

Acid
HClO4
HI
HBr
HCl
H2SO4
HNO3
H 3O +
HSO4HF
HNO2
HCOOH
CH3COOH
NH4+
HCN
H 2O
NH3

Conjugate base
ClO4IBrClSO42NO3H 2O
SO42FNO2HCOOCH3COONH3
CNOHNH2-

Strong acid weak conjugate base

HNO2 strong acid CH3COOH
NO2- weak base CH3COO-

 (Typical Acid-Base Reactions)

1. Strong acids and strong bases
( 100% )
HCl + NaOH net ionic equation ; H+ + OH- H2O
spectator ions : Na+ Cl-
H2O H+ OHHCl + NaOH H2O + Cl- + Na+

2. Weak acids and Strong bases

100 % NaOH Na+ + OHCH3COOH(aq) + OH-(aq) CH3COO-(aq) + H2O
CH3COO- (CH3COOH)

CH3COO-(aq) + H2O(l) CH3COOH(aq) + OH-(aq)

3. Strong acids and Weak bases

100%

HCl H+ + ClH+(aq) + NH3(aq) NH4+(aq)

NH4+ (NH3)

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

4. Weak acids and weak bases

( < 100%)
CH3COOH(aq) + NH3(aq)

CH3COO-(aq) + NH4+(aq)

CH3COOH(aq) + OH-(aq)
CH3COO-(aq) + H2O(l)
NH3(aq) + H3O+(aq)
NH4+(aq) + H2O(l)
* OH- H3O+ (neutral)
/

 (Acid Base Equilibrium)

(Weak acids and acid ionization constants)
HA

HA(aq)
H+(aq) + A-(aq)

(acid ionization constant, Ka)
+
[H ][A ]
Ka =
[HA]
- Ka strength [H+]
Ka

 2 Ionization constant (Ka)

Acid
HF
HNO2
HCOOH
Ascorbic acid
CH3COOH
HCN
Phenol

Ka
7.1 10-4
4.5 10-4
1.7 10-4
8.0 10-5
1.8 10-5
4.9 10-10
1.3 10-10

Conjugate base
FNO2HCOOC6H7O6CH3COOCNC6H5O-

Kb
1.4 10-11
2.2 10-11
5.9 10-11
1.3 10-10
5.6 10-10
2.0 10-5
7.7 10-5

Ka law of mass action

chemical equilibrium

 3 HCOOH ion pH
HCOOH 0.1 M (Ka = 1.7 10-4 )
H+ + HCOO0
0
+x
+x
x
x
+ ][HCOO - ]
[H
Ka =
[HCOOH]
2
x
-4
1.7 10 =
(0.1- x )

HCOOH
(M)
0.1
(M) -x
(M)
(0.1-x)

: (0.1 x) 0.1

1.7 10-4
x2
x

x
=
0.1
= 1.7 10-4 (0.1)
= 4.1 10-3 M

[HCOOH] = 0.1 x
= 0.1 0.0041 = 0.096 M
[H+] = 0.0041 M
[HCOO-] = 0.0041 M
[H+] 4.1 10-3 M

pH
pH = -log[H+]
= -log(4.1 10-3) = 2.39


[H+]
Ka
M

[H+] = K a . M

[H+] = (1.7 10 -4 )(0.1)

= 4.1 10-3 M
pH = -log(4.1 10-3)
= 2.39

 pH 0.05 M HNO2 (Ka = 4.5 10-4 )

HNO2(aq)
H+(aq) + NO2- (aq)
(M)
0.05
0
0
(M)
-x
+x
+x
(M)
(0.05-x)
x
x
+
[H ][NO 2 ]
Ka =
[HNO
]
2 2
x
-4
4.5 10 =
(0.05 - x )

: (0.05 x ) 20.05
x
4.5 10-4 =
0.05
x = 4.8 10-3 M = [H+]

pH

= -log[H+]
= -log(4.8 10-3)
= 2.32

[H+]

[H+]
pH

Ka . M
-4

= (4.5 10 )(0.05)
= 4.8 10-3 M
= -log(4.8 10-3)
= 2.32

 5 pH HA 2.85 0.1 M Ka
[H+] pH = -log[H+] = 2.85
log[H+] = -2.85
[H+] = 10-2.85
= 1.41 10-3 M

[H+] =

1.41 10-3 =

Ka . M

K a . (0.1)

1.99 10-6 = Ka (0.1)

Ka

-6

1.99 10
=
0.1 -5
= 2.0 10


(Weak bases and base ionization constants)

NH4+(aq) + OH- (aq)

NH3(aq) + H2O (l)
[OH-] > [H+]
pH > 7
+
4

[NH ][OH ]
K[H2O] = Kb =
[NH 3 ]

 3 Kb 25 oC

C2H5NH2
CH3NH2
NH3
C6H5NH2

Kb
5.6 10-4
4.4 10-4
1.8 10-5
3.8 10-10

Conjugate acid
C2H5NH3+
CH3NH3+
NH4+
C6H5NH3+

Ka
1.8 10-11
2.3 10-11
5.6 10-11
2.6 10-5

 6 pH 0.4 M (Kb = 1.8 10-5)

NH3(aq) + H2O (l)
NH4+(aq) + OH- (aq)
(M)
0.4
0
0
(M) -x
+x
+x
(M)
(0.4 x)
x
x
+
[NH 4 ][OH ]
Kb =
[NH 3 ]
2
x
-5
1.8 10 =
(0.4 - x )
: (0.4 x) 0.4 2
x
1.8 10-5 =
0.4
x = 2.7 10-3 M

x [OH-]
pOH [OH-]
pOH = -log [OH-]
= -log (2.7 10-3)
= 2.57

pH

= 14 pOH
= 14 2.57
= 11.43

[OH-] =
=

Kb . M
-5

(1.810 )(0.4)

2.7 10-3 M

pOH = -log [OH-]

= -log (2.7 10-3)
= 2.57

pH

= 14 pOH
= 14 2.57
= 11.43

 Ka acid Kb conjugate base

CH3COOH(aq)
H+(aq) + CH3COO-(aq)
acid
conjugate base
+
[H ][CH 3 COO ]
Ka =
[CH 3 COOH]
CH3COO-(aq) + H2O(l)

---(1)

CH3COOH(aq) +OH-(aq) ---(2)

-

Kb = [CH 3 COOH][OH ]
[CH 3 COO ]
(1) + (2) ; H2O(l)
H+(aq) + OH-(aq)
+
[H ][CH 3 COO ] [CH 3 COOH][OH - ]

Ka.Kb =
[CH 3 COOH]
[CH 3 COO ]
Ka.Kb = [H+] [OH-] = Kw = 1.0 10-14

 (Diprotic and polyprotic acids)

1

1

pH

 4 Ionization constants (Ka) diprotic acids polyprotic acids

25oC Kb conjugate bases
Acids
H2SO4
HSO4H2C2O4
HC2O4H2SO3
HSO3H2CO3
HCO3H3PO4
H2PO4HPO42-

Ka
Very large
1.3 10-2
6 10-2
6 10-5
6 10-5
1 10-2
4 10-7
4 10-11
7 10-3
6 10-8
4 10-13

Conjugate bases
HSO4SO42HC2O4C2O42HSO3SO32HCO3CO32H2PO4HPO42PO43-

Kb
Very small
7.7 10-13
1 10-13
1 10 10
7 10-13
1 10-7
2 10-8
2 10-4
1 10-12
1 10-7
2 10-2

Strong acid Ka conjugate base Kb

 7 H2CO3
0.10 M (Ka1 = 4.2 10-7 , Ka2 = 4.80 10-11)
H2CO3 diprotic 2 steps
step 1
(M)
(M)
(M)

H+(aq) + HCO3-(aq)
0
0
+x
+x
x
x

H2CO3 (aq)
0.10
-x
(0.1 x)
+

= [H ] [HCO ]
[H 2 CO 3 ]
2
-7
x
4.2 10 =
(0.1 - x )
Ka1

 : (0.1 x) 0.1 ;
4.2 10-7
x

x
=
0.1
= 2.05 10-4 M

[H+] = 2.05 10-4 M

[HCO3-] = 2.05 10-4 M
[H2CO3] = 0.1 (2.05 10-4)
= 9.98 10-2 M

step 2
(M)
(M)
(M)

CO32-(aq) + H+(aq)
0
2.05 10-4
+y
+y
y
(2.05 10-4+ y)

HCO3- (aq)
2.05 10-4
-y
(2.05 10-4 y)
23

Ka2 = [CO ][H ]

[HCO 3 -4]
4.80 10-11 = (2.05 10 + y) y
-4
(2.05 10 - y)
; (2.05 10-4+ y) (2.05 10-4 y) 2.05 10-4
-4
(2.05 10 ) y
4.80 10-11 = (2.05 10 -4 )
y

= 4.80 10-11 M

[CO32-]
[H+]
[HCO3-]

= 4.80 10-11 M
= (2.05 10-4) + (4.80 10-11)
= 2.05 10-4 M
= (2.05 10-4) (4.80 10-11)
= 2.05 10-4 M

- 2 diprotic [H+]
1 [H+] 1
- pH 1 2
pH = -log [H+]
= -log (2.05 10-4)
= 3.69
- polyprotic steps

 - (Acid-base properties of salts)

1. Salts neutral solutions ( + )
HNO3 + NaOH NaNO3 + H2O
NaNO3 Na+ + NO3
2. Salts basic solutions ( + )
CH3COOH + NaOH CH3COONa
CH3COONa (s) CH3COO- (aq) + Na+ (aq)
CH3COO- (aq) + H2O (l) CH3COOH(aq) + OH- (aq)
Kb = [CH 3 COOH][OH ]
[CH 3 COO ]

3. Salts acidic solutions ( + )

NH4Cl (s) NH4+(aq) + Cl- (aq)
NH3 (aq) + H3O+ (aq)
NH4+(aq) + H2O (l)
+
[NH 3 ][H ]
Ka =
+
[NH 4 ]
4. Salts cation anion hydrolyzed
- + hydrolyzed
- pH Ka Kb
- Ka > Kb cation hydrolyzed H+ ( )
Kb > Ka anion hydrolyzed OH- ( )
Ka Kb

 8 pH 0.15 M CH3COONa
( ) Ka CH3COOH 1.8 10-5
CH3COONa(s) CH3COO-(aq) + Na+(aq)
CH3COOH (aq) + OH-(aq)
CH3COO-(aq) + H2O(l)
(M)
0.15
0
0
(M) -x
+x
+x
(M)
(0.15 x)
x
x
K
[CH
COOH][OH
]
Kb =
w =
3
Ka
[CH 3 COO ]
2
x
-10
5.6 10 =
(0.15 - x )

 ; (0.15x) 0.15
2
5.6 10-10 = x
0.15

x = 9.2 10-6 M
( [OH-] )
[OH-] = 9.2 10-6 M
pOH = -log [OH-]
= -log (9.2 10-6) = 5.04
pH = 14 pOH
= 14 5.04 = 8.96

[OH-]

=
=

Kw
( )(M)
Ka
1.0 10

-14

1.8 10

-5

0.15

= 9.2 10-6 M
pOH = -log [OH-]
= -log (9.2 10-6) = 5.04
pH

= 14 pOH
= 14 5.04 = 8.96

 9 pH 0.2 M NH4Cl ( )
Kb NH3 1.8 10-5
NH4Cl(s) NH4+(aq) + Cl-(aq)
NH3(aq) + H3O+(aq)
NH4+(aq) + H2O(l)
(M)
0.2
0
0
(M)
-x
+x
+x
(M)
(0.2 x)
x
x
+
Ka = [NH 3 ][H ]
+
[NH 4 ]
Kw
Ka =
Kb
2
x
=
(0.2 - x )

 ; (0.2x) 0.2
2

5.6 10-10 =

x
0.2

x = 1.05 10-5 M
( [H+] )

[H+]
pH

=
=
=
=

1.05 10-5 M
-log [H+]
-log (1.05 10-5)
4.98

[H+]

=
=

Kw
( )(M)
Kb

1.0 10

-14

1.8 10

-5

0.2

= 1.05 10-5 M
pH

= -log (1.05 10-5)

= 4.98

 (The Common Ion Effect)

- 1
CH3COONa CH3COOH CH3COOCH3COONa CH3COO-(aq) + Na+(aq) ---(1)
strong electrolyte 100 %
CH3COOH (aq)
CH3COO- (aq) + H+(aq) ---(2)
< 100%
2 CH3COO- CH3COO- common ion
- CH3COO- (1) H+ (2)
CH3COOH ( H+ )
- pH CH3COOH
( )
-
Common ion effect

-
- (Acid -Base Titration)


pH

( Equivalent point)

 (End point )


pH= 7
HCl 0.10 mol dm3- 50 cm3 NaOH
0.10 mol dm3-


NaOH 0.10 mol dm3-
CH3COOH 0.10 mol dm3- 50 cm3
pH 7


NH3 0.10 mol dm3- 50
cm3 HCl 0.10 mol dm3- pH
7




H3PO4 0.10 mol dm3- 25 cm3 NaOH
0.10 mol dm3-

-
. -
2
1.
1
a() + b()

 2

= (g)

= [][] (mol dm3-) x (dm3-)

1000

 3
= a

b
4

aM1V1 = bM2V2


a = H+ 1
b = OH- 1
M1 , M2 =
(mol dm3-)
V1 ,V2 =
cm3

. -
-

Back Titration

6.

- pH
pH
pH
pH

pH
2

 pH
pH

 (Buffer Solutions)

2
1.
2.
pH (H+) (OH-)

pH
pH

CH3COONa / CH3COOH CH3COO- / CH3COOH

H+ ( ) CH3COO- H+

CH3COO-(aq) + H+(aq) CH3COOH (aq)
OH- ( ) CH3COOH OH
CH3COOH(aq) +OH-(aq) CH3COO-(aq) + H2O (aq)
[H+] [OH-]
pH

 10

buffer system

a) KH2PO4 / H3PO4

KH2PO4 H3PO4
H3PO4

b) NaClO4 / HClO4

NaClO4 HClO4
HClO4

c) NH4Cl / NH3

NH4Cl NH3
NH3

d) NaCl / HCl

NaCl HCl
HCl

 pH
HA
HA(aq) H+(aq) + A-(aq)
+

Ka

[H+]

-log[H+] =
-log[H+] =

[H ][A ]
[HA]
K a [HA]
[A ]
[HA]
-logKa - log [A ]
-logKa + log [A ]
[HA]

pH

pKa + log [A ]
[HA]

[A-] conjugate base

[A-] ionized [HA]
[HA]


NH3 NH4+ NH4Cl common ion NH4+
+
4

[NH ]
pOH = -logKb + log
[NH 3 ]
+
pOH = pKb + log [NH 4 ]
[NH 3 ]
pH = 14 - pOH

pH
NH3

 11

a)

pH (Ka CH3COOH 1.8 10-5 )

a) 1.0 M CH3COOH / 1.0 M CH3COONa
b) 0.10 M HCl buffer 1 L
c) 0.10 M NaOH buffer 1 L
CH3COONa CH3COO-(aq) + Na+(aq)
CH3COO-(aq) + H+(aq)
CH3COOH
+
[CH 3 COO ][H ]
Ka =
[CH 3 COOH]
K
[CH
COOH]
+
a
3
[H ] =
[CH 3 COO ]
-5
[H+] = (1.8 10 ) (1.0) = 1.8 10-5 M
(1.0)

pH

=
=
=

pH

pH

=
=

-log [H+]
-log (1.8 10-5)
4.74
-

pKa + log [CH 3 COO ]

[CH 3 COOH]
-log(1.8 10-5) + log 1.0
1.0
4.74

b) 0.1 M HCl [H+] = 0.1 M

CH3COO-(aq) + H+(aq) CH3COOH(aq)
0.1 M
0.1 M
0.1 M
: CH3COOH = 0.1 M CH3COO- = 0.1 M
CH3COO-(aq) + H+(aq)
CH3COOH(aq)
;
CH3COOH(aq) 1.0 + 0.1 = 1.1 M
CH3COO-(aq) 1.0 0.1 = 0.9 M
+
[CH 3 COO ][H ]
=
Ka
[CH 3 COOH]
+
0.9
[H
]
-5
1.8 10 =
1.1
[H+] = 2.2 10-5 M

pH

pH
pH

= -log[H+]
= -log(2.2 10-5)
= 4.66
-

pKa + log[CH 3 COO ]

[CH 3 COOH]
= -log(1.8 10-5) + log 0.9
1.1
= 4.66
=

c) 0.1 M NaOH [OH-] = 0.1 M

CH3COOH(aq) + OH-(aq) CH3COO-(aq)
0.1 M
0.1 M
0.1 M
: CH3COO- = 0.1 M CH3COOH = 0.1 M

CH3COOH(aq) 1.0 - 0.1 = 0.9 M
CH3COO-(aq) 1.0 + 0.1 = 1.1 M
+
[CH 3 COO ][H ]
Ka =
[CH 3 COOH]
+
-5
1.8 10 = 1.1 [H ]
0.9
[H+] = 1.5 10-5 M

pH = -log[H+]
= -log(1.5 10-5)
= 4.83
pH
pH

[CH 3 COO ]
= pKa + log
[CH 3 COOH]
1.1
-5
= -log(1.8 10 ) + log
0.9
= 4.83

 12

a)

pH (Kb NH3 1.8 10-5)

a) 1.0 M NH3 / 2.0 M NH4Cl
b) 0.10 M HCl buffer 1 L
c) 0.10 M NaOH buffer 1 L
NH4+(aq) + OH-(aq)
---(1)
NH3(aq) + H2O(l)
---(2)
NH4Cl(s) NH4+(aq) + Cl-(aq)
+
[NH 4 ][OH ]
Kb =
[NH 3 ]
K b [NH 3 ]
[OH ] =
+
[NH 4 ]
-5
(1.8

10
)
(1.0)
=
= 9 10-6 M
(2.0)

pOH =
=
=
pH =
=
=

-log [OH- ]
-log (9 10-6)
5.04
14 pOH
14 5.04
8.96
+
4

pOH = -logKb + log [NH ]

[NH 3 ]
= -log (1.8 10-5) + log (2.0)
(1.0)
= 5.04
pH = 14 5.04
= 8.96

b) 0.1 M HCl [H+] = 0.1 M

NH3 + H3O+ NH4+ + H2O
0.1 M 0.1 M
0.1 M

- [NH4+] 0.1 M [NH4+] = 2.0 + 0.1 = 2.1 M
- NH3 0.1 M H+ 0.1 M [NH3]
[NH3] = 1.0 - 0.1 = 0.9 M
+
[NH
][OH
]
4
Kb =
[NH 3 ]
K
[NH
]
b
3
[OH ] =
+
[NH 4 ]
-5
= (1.8 10 ) (0.9) = 7.7 10-6 M
(2.1)

pOH =
=
=
pH =
=
=
pOH =

pH

=
=
=
=

-log[OH- ]
-log(7.7 10-6)
5.11
14 pOH
14 5.11
8.89
+
-logKb + log [NH 4 ]
[NH 3 ]
-log (110-5) + log(2.1)
(0.9)
5.11
14 5.11
8.89

c) 0.1 M NaOH [OH-] = 0.1 M

[OH-]
NH3(aq) + H2O(l)
NH4+(aq) + OH-(aq)
0.1 M
0.1 M
0.1 M

- [NH3] 0.1 M [NH3] = 1.0 + 0.1 = 1.1 M
- [NH4+] 0.1 M [NH4+] = 2.0 0.1 = 1.9 M
+
[NH 4 ][OH ]
Kb =
[NH 3 ]
[OH-] = K b [NH 3 ]
+
[NH 4 ] -5
= (1.8 10 ) (1.1) = 1.04 10-5 M
(1.9)

pOH =
=
=
pH =
=
=

-log[OH- ]
-log(1.04 10-5)
4.98
14 pOH
14 4.98
9.02
+
4

pOH = -log Kb + log [NH ]

[NH 3 ]
= -log(1.8 10-5) + log (1.9)
(1.1)
= 4.98
pH

= 14 4.98
= 9.02

 1

HCN
=..........................................................
=.........................................................
H2SO4
=.........................................................
HNO3
=.........................................................
Ca(OH)2
CH3COONH4 =.........................................................
KBr
=.........................................................
HF
=.........................................................
=.........................................................
ZnI2
=.........................................................
Li2SO4
=.........................................................
CH3COOH
=.........................................................
Ca(NO3)2
NaHSO4
=.........................................................

 2
HF + NO3HNO3 + FNO3- ...................... HNO3 HF ................. F 3 H2S HCN OH 4 H3C3N CO32- Br-

 5 Ca2+ OH- 0.030 M

Ca(OH)2
6 Ca(OH)2 0.1 mol/dm3 100
cm3 OH- 400 cm3 OH
7 HB 0.2 mol/dm3 0.05
mol/dm3
8 3.4% 1
mol/dm3 H+

 9 (CH3COOH) 1.3%
0.1 mol/dm3

10 H3O+
0.5 mol/dm3 Ka
1.8 x 10-5 mol/dm3
11 0.02 mol/dm3
OH- Kb NH3 1.8 x 10-5
12 NaCN
OH- NaCN 0.01 mol/dm3 Kb
CN- 2.5 x 10-5 mol/dm3

 13 H3O+ 1.0 x 10-7 mol/dm3

H3O+
1.0 x 10-4 mol/dm3 OH-
14 HCl 3.65 5
dm3 H3O OH- (H=1,
Cl=35.5)

 15 2.0 x 10-7
mol/dm3 pH
16 1.0 x 10-6
mol/dm3 pH
17 HCl 2.0 mol/dm3 KOH
2.0 mol/dm3 pH
18 3.0 x 10-2
mol/dm3 pH pOH

 19 pKI = 7.1
A pH 6.5, 5.2 9.1

20 HIn HIn 0.2 molar 10%

pH