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1

ACID-BASE CHEMISTRY
2
EXAMPLES OF ACIDS AND BASES
PRESENT IN NATURAL WATERS
Most important base: HCO
3
-
Other bases: B(OH)
4
-
, PO
4
3-
, NH
3
0
, AsO
4
3-
,
SO
4
2-
, CO
3
2-
, etc.
Most important acid: CO
2
(aq) or H
2
CO
3
0

Other acids: H
4
SiO
4
0
, NH
4
+
, B(OH)
3
0
,
H
2
SO
4
0
, CH
3
COOH
0
(acetic), H
2
C
2
O
4
0
(oxalic), etc.

3
Most acid-base reactions in aqueous
solutions are very fast (almost
instantaneous); thermodynamic equilibrium
is attained and thermodynamic principles
yield correct answers.
Acid-base reactions involve proton, but a
bare proton (H
+
) does not exist in aqueous
solution; it is hydrated, e.g., hydronium ion
(H
3
O
+
) or more likely (H
9
O
4
+
).

4
BRONSTED DEFINITION
Acid: A substance that can donate a proton
to any other substance.

Base: A substance that can accept a proton
from any other substance.
5
ACIDS AND BASES ARE ALWAYS
PAIRED IN REACTIONS
H
2
CO
3
0
+ H
2
O H
3
O
+
+ HCO
3
-

NH
4
+
+ H
2
O H
3
O
+
+ NH
3
0
CH
3
COOH
0
+ H
2
O H
3
O
+
+ CH
3
COO
-

H
2
O + H
2
O H
3
O
+
+ OH
-

6
SOME DEFINITIONS
Amphoteric - A substance that can act as
either an acid or a base, e.g., H
2
O, HCO
3
-

Polyprotic acid or base - An acid or base
that can donate or accept, respectively,
more than one proton, e.g., H
3
PO
4
0
,
H
2
CO
3
0
, H
4
EDTA
7
SIMPLE METAL IONS ARE
ALSO ACIDS
All metal ions are hydrated in aqueous solution.
The attached waters can lose protons, and are
therefore acids. The positive charge of metal
ion determines the strength of the acid.
Zn(H
2
O)
6
2+
+ H
2
O H
3
O
+
+ Zn(H
2
O)
5
(OH)
+

Cu(H
2
O)
4
2+
+ 3H
2
O 3H
3
O
+
+ Cu(H
2
O)(OH)
3
-

8
CONJUGATE ACID-BASE
PAIRS
HCl
0
, Cl
-

H
2
CO
3
0
, HCO
3
-

HSO
4
-
, SO
4
2-

CH
3
COOH
0
, CH
3
COO
-

Zn(H
2
O)
6
2+
, Zn(H
2
O)
5
(OH)
+
9
LEWIS DEFINITION
Acid: Any substance that can accept an
electron pair.
Base: Any substance that can donate an
electron pair.
10
STRENGTH OF AN ACID OR
BASE
Strength: The tendency to donate or accept a
proton, i.e., how readily does the substance donate
or accept a proton?
Weak acid has weak proton-donating tendency; a
strong acid has a strong proton-donating tendency.
Similarly for bases,
Cannot define strength in absolute sense. Strength
depends on both the acid and base involved in an
acid-base reaction.
Strength measured relative to some reference, in
our case, the solvent water.
11
STRENGTH MEASURED
QUANTITATIVELY BY THE
IONIZATION CONSTANT
HA
0
+ H
2
O H
3
O
+
+ A
-

or
HA
0
H
+
+ A
-

] [
] ][ [
0
HA
A H
K
A
+
=
The larger K
A
, the stronger the acid; the
smaller K
A
, the weaker the acid
12
DEFINITION OF pK
A
AND pH
pK
A
= - log K
A

Thus, the larger pK
A
, the weaker the acid; the
smaller pK
A
, the stronger the acid.
Similarly,
pH = - log [H
+
]
pOH = - log [OH
-
]
pX = - log X
13
STRENGTH OF A BASE
A
-
+ H
2
O HA
0
+ OH
-

] ][ [
] ][ [
2
0
O H A
OH HA
K
B

=
pK
B
= - log K
B

The larger pK
B
, the weaker the base; the
smaller pK
B
, the stronger the base.
14
SELF-IONIZATION OF WATER
AND NEUTRAL pH
H
2
O H
+
+ OH
-

Neutrality is defined by the condition: [H
+
] = [OH
-
]
K
w
= [H
+
]
2

log K
w
= 2 log [H
+
]
-log K
w
= -2 log [H
+
]
14 = 2 pH
pH
neutral
= 7
14
2
10
] [
] ][ [

+
= =
O H
OH H
K
w
At 25
o
C and
1 bar
15
CONJUGATE ACIDS-BASES
H
+
+ A
-
HA
0
1/K
A

H
2
O H
+
+ OH
-
K
w

A
-
+ H
2
O HA
0
+ OH
-
K
B

K
B
= K
w
/K
A

The stronger an acid, the weaker the conjugate
base, and vice versa.



16
ACTIVITY SCALES
INFINITE DILUTION SCALE

A
= a
A
/c
A
Based on the fact that solutions approach
ideality as the total concentration of all ions
in solutions approaches zero. In other
words:

A
1
as
(c
A
+ Ec
i
) 0

17
ACTIVITY SCALES
IONIC MEDIUM SCALE
Applied to solutions with a dominant
concentration of a relatively inert electrolyte
to maintain a constant ionic medium.

A
1 as c
A
0, but Ec
i
is constant
If Ec
i
~ 10 c
A
, then
A
~

1
Seawater is a good example, with approximately
constant composition of dominantly NaCl
18
pH CONVENTIONS
Infinite dilution scale:
p
a
H = - log {H
+
} = - log [H
+
] - log
H
+
Ionic medium:
pH = - log [H
+
]
NBS (NIST) scale:
defines pH relative to a series of standard
buffers
19
OPERATIONAL ACIDITY
CONSTANTS
1) Infinite dilution scale


2) Ionic medium scale
(concentration quotient
or conditional constant)

3) Mixed constant
} {
} }{ {
0
HA
A H
K
A
+
=
] [
] }[ {
0
HA
A H
K
A
+
=
] [
] ][ [
0
HA
A H
K
A
c
+
=
20
IONIC STRENGTH
A quantity required to calculate activity
coefficients.
Attempts to account for effects of both
concentration and charge of ion on activity
coefficients.

=
=
n
i
i i
Z c I
1
2
2 / 1
21
ACTIVITY COEFFICIENT
EXPRESSIONS
I AZ
i i
2
log =
I B
I AZ
i
i
1
log
2
+

=
I
I AZ
i
i
+

=
1
log
2

|
|
.
|

\
|

+
= I
I
I
AZ
i i
2 . 0
1
log
2

1) Debye-Hckel Limiting Law


Valid at I < 0.005 M
2) Full Debye-Hckel Equation
Valid at I < 0.1 M
3) Gntelberg Equation
Valid at I < 0.1 M
Useful for mixed electrolytes
4) Davies Equation
Valid at I < 0.5 M
A = 0.5; B = 0.33 at 25
o
C and 1 bar
22
NUMERICAL EQUILIBRIUM
CALCULATIONS
Monoprotic acid
What are the pH and the concentrations of all
aqueous species in a 5 x 10
-4
M solution of
aqueous boric acid (B(OH)
3
)?
Steps to solution
1) Write down all species likely to be present
in solution: H
+
, OH
-
, B(OH)
3
0
, B(OH)
4
-
.

23
2) Write the reactions and find the equilibrium
constants relating concentrations of all
species:
H
2
O H
+
+ OH
-

10
2
0
3
4
10 7
] ][ ) ( [
] ) ( ][ [

+
= = x
O H OH B
OH B H
K
A
14
2
10
] [
] ][ [

+
= =
O H
OH H
K
w
(i)
(ii)
B(OH)
3
0
+ H
2
O B(OH)
4
-
+ H
+

24
3) Write down all mass balance relationships:
5 x 10
-4
M = EB
= [B(OH)
4
-
] + [B(OH)
3
0
] (iii)

4) Write down a single charge-balance
(electroneutrality) expressions:
[H
+
] = [B(OH)
4
-
] + [OH
-
] (iv)

5) Solve n equations in n unknowns.
25
EXACT NUMERICAL SOLUTION
Eliminate [OH
-
] in (i) and (iv)
[H
+
][OH
-
] = K
w
[OH
-
] = K
w
/[H
+
]
[H
+
] = [B(OH)
4
-
] + K
w
/[H
+
]
[H
+
] - [B(OH)
4
-
] = K
w
/[H
+
]
] [
] ) ( [ ] [
4
+
+
=

H
OH B H
K
w
(v)
26
Solve (iii) for [B(OH)
3
0
]
[B(OH)
3
0
] = EB - [B(OH)
4
-
]
A
K
OH B B
OH B H
=
E

+
] ) ( [
] ) ( ][ [
4
4
[H
+
][B(OH)
4
-
] = K
A
(EB - [B(OH)
4
-
]) (vi)

Now solve (v) for [B(OH)
4
-
]
- [B(OH)
4
-
] = K
w
/[H
+
] - [H
+
]
[B(OH)
4
-
] = [H
+
] - K
w
/[H
+
]
Substitute this into (vi)

27
[H
+
]([H
+
] - K
w
/[H
+
]) = K
A
(EB - [H
+
] + K
w
/[H
+
])
[H
+
]
2
- K
w
= K
A
EB - K
A
[H
+
] + K
A
K
w
/[H
+
]
[H
+
]
3
- K
w
[H
+
] = K
A
EB[H
+
] - K
A
[H
+
]
2
+ K
A
K
w

[H
+
]
3
+ K
A
[H
+
]
2
- (K
A
EB + K
w
)[H
+
] - K
A
K
w
= 0
[H
+
]
3
+ (7x10
-10
)[H
+
]
2
- (3.6x10
-13
)[H
+
] - (7x10
-24
) = 0

We can solve this by trial and error, computer or
graphical methods. From trial and error we obtain
[H
+
] = 6.1x10
-7
M or pH = 6.21
28
[OH
-
] = K
w
/[H
+
]
[OH
-
] = 10
-14
/10
-6.21
[OH
-
] = 10
-7.79
M

[B(OH)
4
-
] = [H
+
] - K
w
/[H
+
]
[B(OH)
4
-
] = 6.1x10
-7
- 1.62x10
-8

[B(OH)
4
-
] = 5.94x10
-7
M

[B(OH)
3
0
] = EB - [B(OH)
4
-
]
[B(OH)
3
0
] = 5x10
-4
- 5.94x10
-7
M = 4.99x10
-4
M


29
APPROXIMATE SOLUTION
Look for terms in additive equations that are
negligibly small (multiplicative terms, even if
very small, cannot be neglected.
Because we are dealing with an acid, we can
assume that [H
+
] >> [OH
-
] so that the mass
balance becomes:
[H
+
] = [B(OH)
4
-
]
and then
[B(OH)
3
0
] = EB - [H
+
]
30
10
2
0
3
4
10 7
] ][ ) ( [
] ) ( ][ [

+
= = x
O H OH B
OH B H
K
A
] [
] [
2
+
+
E
=
H B
H
K
A
(ii)
[H
+
]
2
= K
A
EB-K
A
[H
+
]
[H
+
]
2
+ K
A
[H
+
] - K
A
EB = 0
This is a quadratic equation of the form:
ax
2
+ bx + c = 0
and can be solved using the quadratic equation
a
ac b b
x
2
4
2

=
31
In our case this becomes:
2
4
] [
2
B K K K
H
A A A
E
=
+
Only the positive root has any physical meaning.
[H
+
] = 5.92 x 10
-7

We could have made this problem even simpler.
Because boric as is a quite weak acid (i.e., very
K
A
value, very little of it will be ionized, thus
[B(OH)
3
0
] >> [B(OH)
4
-
]
EB ~ [B(OH)
3
0
] = 5 x 10
-4
M
32
10
2
0
3
4
10 7
] ][ ) ( [
] ) ( ][ [

+
= = x
O H OH B
OH B H
K
A
10
0
3
2
10 7
] ) ( [
] [

+
= = x
OH B
H
K
A
10
4
2
10 7
10 5
] [

+
= = x
x
H
K
A
[H
+
]
2
= 3.5 x 10
-15

[H
+
] = 5.92 x 10
-7
M

It is wise to check your assumptions by back substituting
into original equations. If the error is s 5%, the approxi-
mation is probably justified because K
A
values are at least
this uncertain!
33
CALULATE THE pH OF A STRONG
ACID
Compute the pH and equilibrium concentrations of all
species in a 2 x 10
-4
M solution of HCl.
1) Species: H
+
, Cl
-
, HCl
0
, OH
-

2) Mass action laws:
14
2
10
] [
] ][ [

+
= =
O H
OH H
K
w
3
0
10
] [
] ][ [
~ =
+
HCl
Cl H
K
A
3) Mass balance: [HCl
0
] + [Cl
-
] = 2 x 10
-4
M
4) Charge balance: [H
+
] = [Cl
-
] + [OH
-
]
34
Assumptions: HCl is a very strong acid so
[H
+
] >> [OH
-
] and [Cl
-
] >> [HCl
0
]
Now the only source of H
+
and Cl
-
are the dissociation of
HCl, so
[H
+
] = [Cl
-
]
(this is also apparent from the charge balance)
Thus, pH = - log (2 x 10
-4
) = 3.70, and [Cl
-
] = 2 x 10
-4
M.
[OH
-
] = K
w
/[H
+
] = 10
-14
/2 x 10
-4
= 5 x 10
-11
M

3
0
10
] [
] ][ [
~ =
+
HCl
Cl H
K
A
M x
x
HCl
11
3
2 4
0
10 4
10
) 10 2 (
] [

= =
35
CALCULATE THE pH OF A WEAK
MONOPROTIC BASE
Compute the pH and equilibrium concentrations of
all species in a 10
-4.5
M solution of sodium acetate.
1) Species: H
+
, Na
+
, Ac
-
, HAc
0
, OH
-
2) Mass action laws:
70 . 4
0
10
] [
] ][ [

+
= =
HAc
Ac H
K
A
14
2
10
] [
] ][ [

+
= =
O H
OH H
K
w
3) Mass balances: [HAc
0
] + [Ac
-
] = 10
-4.5
M = C
[Na
+
] = 10
-4.5
M = C
4) Electroneutrality: [Na
+
] + [H
+
] = [Ac
-
] + [OH
-
]
Combine 3) and 4) to get proton condition:
[HAc
0
] + [H
+
] = [OH
-
]
36
We cannot make any approximations relative to the
concentrations of [H
+
] and [OH
-
] because acetate is a
weak base and total acetate concentration is low.
However, because base is weak: [Ac
-
] >> [HAc
0
] so
[Ac
-
] ~ 10
-4.5
M = C
Substitute for [OH
-
] in proton condition
[HAc
0
] + [H
+
] = K
w
/[H
+
]
[HAc
0
] = K
w
/[H
+
] - [H
+
]
Now substitute into ionization constant expression
70 . 4
0
10
] [
] ][ [

+
= =
HAc
Ac H
K
A
] [
] [
] [
+
+
+

=
H
H
K
C H
K
w
A
37
[H
+
]C = K
A
K
w
/[H
+
] - K
A
[H
+
]
[H
+
]
2
C = K
A
K
w
- K
A
[H
+
]
2

[H
+
]
2
C + [H
+
]
2
K
A
= K
A
K
w

[H
+
]
2
(C + K
A
) = K
A
K
w

[H
+
]
2
= K
A
K
w
/(C + K
A
)
[H
+
] = (K
A
K
w
/(C + K
A
))
0.5

[H
+
] = (10
-4.7
10
-14
/(10
-4.5
+ 10
-4.70
)
[H
+
] = 6.2 x 10
-8
M
pH = 7.2
pOH = pK
w
- pH = 14.0 - 7.2 = 6.8
[OH
-
] = 1.61 x 10
-7



38
Rearranging the proton condition we get:
[HAc
0
] = [OH
-
] - [H
+
] = 1.6 x 10
-7
- 6.2 x 10
-8

= 9.8 x 10
-8


Check of assumption:
[Ac
-
] = C - [HAc
0
] = 10
-4.50
- 9.8 x 10
-8

so [Ac
-
] ~ 10
-4.50
and the assumption made is valid.
39
CALCULATE THE pH OF AN
AMPHOLYTE
Calculate the pH of a 10
-3.7
M solution of sodium
hydrogen phthalate (NaHP).
1) Species: H
2
P
0
, HP
-
, P
2-
, H
+
, OH
-
, Na
+

2) Mass action expressions:
COOH
COONa
] [
] ][ [
10
0
2
95 . 2
1 ,
P H
HP H
K
A
+

= =
] [
] ][ [
10
2
41 . 5
2 ,

+

= =
HP
P H
K
A
14
2
10
] [
] ][ [

+
= =
O H
OH H
K
w
3) Mass balance expressions:
P
T
= 10
-3.7
M = [H
2
P
0
] + [HP
-
] + [P
2-
]
40
P
T
= 10
-3.7
M = [Na
+
]
4) Charge balance:
[H
+
] + [Na
+
] = [OH
-
] + [HP
-
] + 2[P
2-
]
Now, substitute 3) into 4) to get proton condition:
[H
+
] + [H
2
P
0
] + [HP
-
] + [P
2-
] = [OH
-
] + [HP
-
] + 2[P
2-
]
[H
+
] + [H
2
P
0
] = [OH
-
] + [P
2-
]
Because both pK values are less than 7, assume:
[OH
-
] << [H
+
]
[H
+
] + [H
2
P
0
] = [P
2-
]
[H
+
] + P
T
= 2[P
2-
] + [HP
-
]

41
] [
] [
] [ 2
] [
2 ,
+

+
+ = + HP
H
HP K
P H
A
T
] [ 1
] [
2
] [
2 ,
+
+
|
|
.
|

\
|
+ = + HP
H
K
P H
A
T
|
|
.
|

\
|
+
+
=
+
+

1
] [
2
] [
] [
2 ,
H
K
P H
HP
A
T
] [ ] [ ] [
2 0
2

+ + = P HP P H P
T
] [
] [
] [
] ][ [
2 ,
1 ,
+

+
+ + =
H
K HP
HP
K
H HP
P
A
A
T
] [
] [
1
] [
2 ,
1 ,

+
+
|
|
.
|

\
|
+ + = HP
H
K
K
H
P
A
A
T
42
|
|
|
|
.
|

\
|
+
+
|
|
.
|

\
|
+ + =
+
+
+
+
1
] [
2
] [
] [
1
] [
2 ,
2 ,
1 ,
H
K
P H
H
K
K
H
P
A
T
A
A
T
( )
T
A
A
T
T A
P H
H
K
K
H
P
H
P K
+
|
|
.
|

\
|
+ + = +
+
+
+
+
] [
] [
1
] [
] [
2
2 ,
1 ,
2 ,
] [
] [
] [
] [
] [
2
2 ,
1 ,
2 ,
1 ,
2
2 ,
+
+
+
+
+
+ + + + + = +
H
K P
P
K
H P
K H
K
H
P
H
P K
A T
T
A
T
A
A
T
T A
2 ,
1 ,
2
2 ,
2
1 ,
3
2 ,
] [
] [ ] [
] [
2
A T
A
T
A
A
T A
K P
K
H P
H K H
K
H
P K + + + + =
+
+ +
+
43
1 , 2 ,
2
1 , 2 ,
2
1 ,
3
1 , 2 ,
] [
] [ ] [ ] [ 2
A A T T
A A A T A A
K K P H P
H K K H K H P K K
+ +
+ + =
+
+ + +
0 ] [ ] )[ ( ] [
1 , 2 , 1 , 2 ,
2
1 ,
3
= + + +
+ + +
T A A A A T A
P K K H K K H P K H
[H
+
] = 2.4 x 10
-5
pH = 4.62
44
CALCULATION OF THE pH OF A
POLYPROTIC ACID
Compute the pH and concentrations of all species in
equilibrium in a 10
-3
M H
3
PO
4
solution.
1) Species: H
+
, OH
-
, H
3
PO
4
0
, H
2
PO
4
-
, HPO
4
-
, PO
4
3-

2) Mass action expressions:
14
2
10
] [
] ][ [

+
= =
O H
OH H
K
w
] [
] ][ [
10
0
4 3
4 2
1 . 2
1 ,
PO H
PO H H
K
A
+

= =
] [
] ][ [
10
4 2
2
4
0 . 7
2 ,

+

= =
PO H
HPO H
K
A
] [
] ][ [
10
2
4
3
4
2 . 12
3 ,

+

= =
HPO
PO H
K
A
45
3) Mass balance:
P
T
= [H
3
PO
4
0
] + [H
2
PO
4
-
] + [HPO
4
2-
] + [PO
4
3-
]
4) Charge balance:
[H
+
] = [OH
-
] + [H
2
PO
4
-
] + 2[HPO
4
2-
] + 3[PO
4
3-
]
Assumptions: Because phosphoric acid is an acid,
assume that [H
+
] >> [OH
-
]. Also, because K
A,2
and
K
A,3
are quite small, then [HPO
4
2-
] and [PO
4
3-
] are
negligible compared to [H
3
PO
4
0
] and [H
2
PO
4
-
]. The
mass balance then becomes:
P
T
= [H
3
PO
4
0
] + [H
2
PO
4
-
]
46
And the charge balance expression becomes:
[H
+
] = [H
2
PO
4
-
]
which can be substituted into the expression for K
A,1
.
] [
] [
10
2
1 . 2
1 ,
+
+

= =
H P
H
K
T
A
K
A,1
P
T
-K
A,1
[H
+
] = [H
+
]
2

[H
+
]
2
+ K
A,1
[H
+
] - K
A,1
P
T
= 0

2
4
] [
2
T A A A
P K K K
H

=
+
47
[H
+
] = 8.986 x 10
-4
M
pH = 3.05
pOH = pK
w
- pH = 14 - 3.05 = 10.95
[OH
-
] = 1.122 x 10
-11
M
[H
3
PO
4
0
] = P
T
- [H
2
PO
4
-
] = 10
-3
- 8.986 x 10
-4

[H
3
PO
4
0
] = 1.014 x 10
-4
M

] [
] ][ [
10
4 2
2
4
0 . 7
2 ,

+

= =
PO H
HPO H
K
A
M K
H
K PO H
HPO
A
A 0 . 7
2 ,
2 , 4 2 2
4
10
] [
] [
] [

+

= = =
48
] [
] ][ [
10
2
4
3
4
2 . 12
3 ,

+

= =
HPO
PO H
K
A
0 . 7
3
4
05 . 3
2 . 12
3 ,
10
] [ 10
10

= =
PO
K
A
[PO
4
3-
] = 10
-16.15
M = 7.079 x 10
-17
M

A check of all the assumptions shows that they are all
valid.
49
CALCULATION OF pH OF A
VOLATILE BASE
Compute the pH and concentrations of all species of
a solution exposed to an atmosphere of p
NH3
= 10
-4
atm.
1) Species: NH
3
0
, NH
4
+
, OH
-
, H
+
2) Mass action expressions:
14
2
10
] [
] ][ [

+
= =
O H
OH H
K
w
3
] [
10
0
3
75 . 1
NH
H
p
NH
K = =
] ][ [
] ][ [
10
2
0
3
4
5 . 4
O H NH
OH NH
K
B
+

= =
50
3) Charge balance: [NH
4
+
] + [H
+
] = [OH
-
]
Assumptions: NH
3
is a moderate base, so we can
assume that [OH
-
] >> [H
+
] so the charge balance
becomes
[NH
4
+
] = [OH
-
]
also
[NH
3
0
] = p
NH3
K
H
= 10
-4
(10
1.75
) = 10
-2.25
M

25 . 2
2
0
3
4
5 . 4
10
] [
] [
] ][ [
10

= = =
OH
NH
OH NH
K
B
[OH
-
]
2
= 10
-6.75
[OH
-
] = 10
-3.375
M = 4.22 x 10
-4
M
51
pH = pK
w
- pOH = 14 - 3.375 = 10.625
so the assumption that [OH
-
] >> [H
+
] is valid.
The concentrations are then:
[OH
-
] = 4.22 x 10
-4
M
[NH
4
+
] = 4.22 x 10
-4
M
[H
+
] = 2.37 x 10
-11
M
[NH
3
0
] = 5.62 x 10
-3
M

52
GRAPHICAL APPROACH TO
EQUILIBRIUM CALCULATIONS
Consider the monoprotic acid HA:
] [
] ][ [
10
0
5 . 5
HA
A H
K
A
+

= =
C
T
= 10
-3
= [HA
0
] + [A
-
]; so [A
-
] = C
T
- [HA
0
]
K
A
[HA
0
] = [H
+
][A
-
]
K
A
[HA
0
] = [H
+
](C
T
- [HA
0
])
K
A
[HA
0
] = [H
+
]C
T
- [H
+
][HA
0
]
K
A
[HA
0
] + [H
+
][HA
0
] = [H
+
]C
T

] [
] [
] [
0
+
+
+
=
H K
H C
HA
A
T
53
C
T
K
A
- K
A
[A
-
] = [H
+
][A
-
]
C
T
K
A
= [A
-
]([H
+
] + K
A
)

] [
] ][ [

=
A C
A H
K
T
A
A
A T
K H
K C
A
+
=
+

] [
] [
1) At pH < pK
A
, [H
+
] >> K
A
so [H
+
] + K
A
~ [H
+
]
[HA
0
] = C
T
([H
+
]/[H
+
]) = C
T

log [HA
0
] = log C
T

[A
-
] = C
T
K
A
/[H
+
]
log [A
-
] = log C
T
- pK
A
+ pH



54
2) pH = pK
A
; [H
+
] = K
A
so [H
+
] + K
A
= 2[H
+
]
[HA
0
] = C
T
[H
+
]/(2[H
+
]) = C
T
/2
log [HA
0
] = log C
T
- log 2 = log C
T
- 0.301
[A
-
] = C
T
[H
+
]/(2[H
+
]) = C
T
/2
log [A
-
] = log C
T
- log 2 = log C
T
- 0.301
3) pH > pK
A
; [H
+
] << K
A
so K
A
+ [H
+
] ~ K
A

[HA
0
] = C
T
[H
+
]/K
A

log [HA
0
] = log C
T
+ pK
A
- pH
[A
-
] = C
T
K
A
/K
A
= C
T

log [A
-
] = C
T


55
pH
0 2 4 6 8 10 12 14
l
o
g

[
i
]
-10
-8
-6
-4
-2
HA
0
A
-
OH
-
H
+
10
-3
M NaAc
10
-3
M HA
Speciation diagram for HA with pK
A
= 5.5 and C
T
= 10
-3

56
To compute the composition of a 10
-3
M solution
of HA, we start with the charge balance:
[H
+
] = [A
-
] + [OH
-
]
[H
+
] >> [OH
-
]
[H
+
] ~ [A
-
]
To compute composition of 10
-3
M NaA solution,
start with proton condition:
[HA
0
] + [H
+
] = [OH
-
]
[OH
-
] >> [H
+
]
[HA
0
] ~ [OH
-
]
57
SPECIATION DIAGRAM FOR A
DIPROTIC SYSTEM
Consider H
2
S with pK
1
= 7.0, pK
2
= 13.0
S
T
= 10
-3
M = [H
2
S
0
] + [HS
-
] + [S
2-
]
2
2 1 1
0
2
] [ ] [
1
] [
+ +
+ +
=
H
K K
H
K
S
S H
T
] [
1
] [
] [
2
1
+
+

+ +
=
H
K
K
H
S
HS
T
1
] [ ] [
] [
2 2 1
2
2
+ +
=
+ +

K
H
K K
H
S
S
T
58
1) pH < pK
1
< pK
2
; [H
+
] > K
1
> K
2

T
T
S
H
K K
H
K
S
S H ~
+ +
=
+ + 2
2 1 1
0
2
] [ ] [
1
] [
log [H
2
S
0
] = log S
T

1
2
1
] [
] [
1
] [
] [
K
H
S
H
K
K
H
S
HS
T T
+
+
+

~
+ +
=
log [HS
-
] = log (S
T
K
1
) + pH
2 1
2
2 2 1
2
2
] [
1
] [ ] [
] [
K K
H
S
K
H
K K
H
S
S
T T
+ + +

~
+ +
=
log [S
2-
] = log (S
T
K
2
K
1
)
+ 2pH
59
2) pH = pK
1
< pK
2
; [H
+
] = K
1
> K
2

2
] [ ] [
1
] [
2
2 1 1
0
2
T T
S
H
K K
H
K
S
S H ~
+ +
=
+ +
log [H
2
S
0
] = log S
T
- 0.301
2
] [
1
] [
] [
2
1
T T
S
H
K
K
H
S
HS ~
+ +
=
+
+

log [HS
-
] = log S
T
- 0.301
2 2 2 1
2
2
] [ 2
1
] [ ] [
] [
K
H
S
K
H
K K
H
S
S
T T
+ + +

~
+ +
=
log [S
2-
] = log (S
T
K
2
/2)
+ pH
60
3) pK
1
< pH < pK
2
; K
1
> [H
+
] > K
2
] [ ] [ ] [
1
] [
1
2
2 1 1
0
2
+ + +
~
+ +
=
H
K
S
H
K K
H
K
S
S H
T T
log [H
2
S
0
] = log (S
T
K
1
)
- pH

T
T
S
H
K
K
H
S
HS ~
+ +
=
+
+

] [
1
] [
] [
2
1
log [HS
-
] = log S
T

2 2 2 1
2
2
] [
1
] [ ] [
] [
K
H
S
K
H
K K
H
S
S
T T
+ + +

~
+ +
=
log [S
2-
] = log (S
T
K
2
)
+ pH
61
4) pK
1
< pK
2
= pH; K
1
> [H
+
] = K
2
] [
2
] [ ] [
1
] [
1
2
2 1 1
0
2
+ + +
~
+ +
=
H
K
S
H
K K
H
K
S
S H
T T
log [H
2
S
0
] = log (S
T
K
1
/2)
- pH

2
] [
1
] [
] [
2
1
T T
S
H
K
K
H
S
HS ~
+ +
=
+
+

log [HS
-
] = log S
T
- 0.301
2
1
] [ ] [
] [
2 2 1
2
2
T T
S
K
H
K K
H
S
S ~
+ +
=
+ +

log [S
2-
] = log S
T
- 0.301
62
5) pK
1
< pK
2
< pH; K
1
> K
2
> [H
+
]
2
2 1
2
2 1 1
0
2
] [ ] [ ] [
1
] [
+ + +
~
+ +
=
H
K K
S
H
K K
H
K
S
S H
T T
log [H
2
S
0
] = log (S
T
K
1
K
2
)
- 2pH

] [
] [
1
] [
] [
2
2
1
+
+
+

~
+ +
=
H
K
S
H
K
K
H
S
HS
T T
log [HS
-
] = log (S
T
K
2
) - pH
T
T
S
K
H
K K
H
S
S ~
+ +
=
+ +

1
] [ ] [
] [
2 2 1
2
2
log [S
2-
] = log S
T

63
pH
0 2 4 6 8 10 12 14
l
o
g

[
i
]
-12
-10
-8
-6
-4
-2
H
2
S
0
HS
-
S
2-
H
+
OH
-
Speciation diagram for H
2
S with C
T
= 10
-3
at 25C
64
IONIZATION FRACTIONS
Monoprotic acid: HB
o
B
= o
1
[B]/C = K
A
/(K
A
+ [H
+
])
o
HB
= o
0
[HB]/C = [H
+
]/(K
A
+ [H
+
])
o
1
+ o
0
= 1
Diprotic acid: H
2
A
2
2 1 1
2
0
] [ ] [
1
1 ] [
+ +
+ +
=
H
K K
H
K
C
A H
o
65
] [
1
] [
1 ] [
2
1
1
+
+

+ +
=
H
K
K
H C
HA
o
1
] [ ] [
1 ] [
2 2 1
2
2
2
+ +
=
+ +

K
H
K K
H C
A
o
1
2 1 0
= + + o o o
66 Figure 3.10a-c from Stumm and Morgan
67
TITRATION OF ACID OR BASE
Titration curve: plot of pH vs. quantity of base
added
At any point on a titration curve, electroneutrality
must be maintained, e.g., titration of HA with
NaOH: [Na
+
] + [H
+
] = [A
-
] + [OH
-
]
but [Na
+
] = C
B
, so C
B
= [A
-
] + [OH
-
] - [H
+
]
By combining this equation and a log C vs. pH
diagram (speciation diagram), we can contruct a
titration curve.
Equivalent fraction:
C
Na
C
C
f
B
] [
+
=
68
What about dilution during titration?
If we initially have v
0
mL of acid, the concentration
of acid at any point becomes:
0
0
0
v v
v
C C
+
=
This can be substituted into the previous expression.
Equivalence point: the point where you have added
just enough base to just neutralize the acid, i.e., f =
C
B
/C = 1, or C
B
= C. Starting with [A
-
] = Co
1
and
C
B
= [A
-
] + [OH
-
] - [H
+
] we obtain:
C
B
= Co
1
+ [OH
-
] - [H
+
]
C
H OH
C
C
f
B
] [ ] [
1
+

+ = = o
69
At the equivalence point we have:
H
2
O + A
-
OH
-
+ HA
0

and the only HA
0
is that due to dissociation of A
-
, so
[OH
-
] ~ [HA
0
]
Now lets titrate the conjugate base of the weak acid
HA (i.e., KA) with a strong acid (e.g., HCl).
Again we must have electroneutrality so:
[K
+
] + [H
+
] = [A
-
] + [OH
-
] + [Cl
-
]
C + [H
+
] = [A
-
] + [OH
-
] + C
A

C
A
= C - [A
-
] + [H
+
] - [OH
-
]
C
A
= [HA
0
] + [H
+
] - [OH
-
]
C
A
= Co
0
+ [H
+
]
70
Define the equivalent fraction of the titrant here as:
C
OH H
C
C
g
A
] [ ] [
0
+

+ = o
At the endpoint, g = 1, so C
A
= C. Note that, g = 1 - f.
At this equivalence point [H
+
] = [A
-
] because the
only A
-
is due to the reaction:
HA
0
H
+
+ A
-

Buffer: HA and A
-
present in near equal quantities acts
as a buffer in that it slows down the change in pH as
an acid or base is added:
HA
0
H
+
+ A
-

HA
0
+ OH
-
A
-
+ H
2
O

71
EXAMPLES OF BUFFERS
Any conjugate acid/base pair can work as a
buffer, e.g.:
HCO
3
-
/CO
3
2-
; B(OH)
3
0
/B(OH)
4
-
; H
2
PO
4
-
/HPO
4
2-

Buffers are most effective at pH ~ pK
A
because
then [HA
0
] ~ [A
-
], and acid and base are
present in approximately equal quantities.
72
CALCULATION OF A TITRATION
CURVE
Titrate 0.1 M solution of a weak acid (pK
a
= 5) with
0.1 M NaOH.
1) f = 0 (zero base added or start of titration):
HA
0
H
+
+ A
-
Assume [HA
0
] ~ 0.1 M >> [A
-
], [H
+
] ~ [A
-
]

5
2
0
10
1 . 0
] [
] [
] ][ [

+ +
= = =
H
HA
A H
K
a
[H
+
]
2
= 10
-6

pH = 3.0

73
2) f = 0.1 (10% titration)
[A
-
]/[HA
0
] = 10/90
In the region between endpoints, pH depends only on
the [A
-
]/[HA
0
] ratio, not on absolute
concentrations.
90
10 ] [
10
] [
] ][ [
5
0
+

+
= = =
H
HA
A H
K
a
[H
+
] = 9 x 10
-5
pH = 4.05
3) f = 0.5 (50% titration)
] [
50
50 ] [
10
] [
] ][ [
5
0
+
+

+
= = = H
H
HA
A H
pH = 5.0
74
4) f = 0.8 (80% titration)
20
80 ] [
10
5
+

= =
H
K
A
[H
+
] = 2.5 x 10
-6

pH = 5.60
5) f = 1.0 (endpoint of titration)
Here all original HA has been converted to A
-
.
Taking dilution into account, [A
-
] ~ 0.05 M. The
only HA
0
present is that due to the reaction:
A
-
+ H
2
O HA
0
+ OH
-
also, [HA
0
] = [OH
-
] and
pK
B
= 14.0 - pK
A
= 14.0 - 5.0 = 9.0
75
pOH = 5.15; pH = 14.0 -5.15 = 8.85
6) f = 1.20 (120% titration)
The pH is calculated from excess OH
-
concentration alone
(OH
-
is a stronger base than A
-
). Assume we started with
100 mL of 0.1 M HA. At f = 1.0, we also would have
added 100 mL of 0.1 M NaOH. At f = 1.2, we would
have added an additional 20 mL of 0.1 M NaOH. The
total volume would then be 220 mL.
05 . 0
] [
] [
] ][ [
10
2 0
0 . 9

= = =
OH
A
HA OH
K
B
5 . 5 11
10 23 . 2 10 5 ] [

= = x x OH
M OH 0091 . 0 1 . 0
220
20
] [ = =

pOH = 2.04; pH = 14.0 - 2.04 = 11.96


76
f
0.0 0.2 0.4 0.6 0.8 1.0 1.2
p
H
4
6
8
10
12
CURVE FOR TITRATION OF WEAK ACID WITH STONG BASE
pK
a
= 5
77
Buffer capacity: number of moles of a strong base
needed to raise the pH of 1 L of buffer by 1 pH
unit.
] [
] [
log
0
HA
A
pK pH
A

+ =
[A
-
]/[HA
0
] pH ([A
-
]/[HA
0
]) pH
ApH = pH - pH
1/99 3.00 2/98 3.31 0.31
10/90 4.05 11/89 4.09 0.04
20/80 4.40 21/79 4.42 0.02
50/50 5.00 49/51 4.98 -0.02
80/20 5.60 79/21 5.58 -0.02
90/10 5.95 89/11 5.91 -0.04
99/1 7.00 98/2 6.69 -0.31
99.9/0.1 8.00 98.9/1.1 6.95 -1.05
DEMONSTRATION OF BUFFER CAPACITY
78
EXAMPLE BUFFER CALCULATION
In what ratio would o-phthalic acid and sodium
hydrogen phthalate have to be mixed to get a pH
of 3.2 (pK
A,1
= 2.92)?
92 . 2
0
2
10
] [
] ][ [

+
= =
P H
HP H
K
A
] [
] [
log
0
2
1 ,
P H
HP
pK pH
A

+ =
3.2 = 2.92 + log R
0.28 = log R
R = 1.91
We can make this solution by mixing 0.1 moles of
H
2
P and 0.191 moles of NaHP in 1 L of water.
79
Titration of a strong acid with strong base at various
concentrations of acid and base.
80
Titration of a strong base with strong acid.
81
Titration of weak acids with strong base.
82
Buffer regions in titration curves.
83
Titration of a weak acid with strong base in presence of indicators.
84
Titration of a weak base with strong acid.
85
What can titrations tell us?
Concentration of acid or base present (analysis)
pK of acid or base present (thermodynamics)

Titration of mixtures of acids or bases:
If the pKs are sufficiently different, the stronger
acid (base) will be titrated first, then weaker acid
(base). We will be able to see two or more breaks
in titration curve, i.e., equivalence points, if ApK ~
4 or more. Same rule applies for polyprotic acids.
86
Titration of a mixture of weak acids with a strong base.
pK
A
= 3.88 pK
A
= 4.86
87
Titration of a mixture of weak and strong acids with a strong base.
pK
A
~ -3
pK
A
~ 4.86
88
BUFFER INTENSITY
Buffer intensity - A measure of the buffer intensity
(buffer capacity) would be the inverse of the slope
of the titration curve at any point.
pH
C
pH
C
A B
d
d
d
d
= |
For a monoprotic system, recalling that:
C
B
= Co
1
+ [OH
-
] - [H
+
]
pH
H
pH
OH
pH
C
pH
C
B
d
] d[
d
] d[
d
d
d
d
1
+
+ =
o
|
89
] [ 3025 . 2
] [
] d[
] d[ 3025 . 2
] ln[ d ) 3025 . 2 / 1 (
] d[
d
] d[
+
+
+
+
+
+ +
= =

H
H
H
H
H
H
pH
H
] [ 3025 . 2
] ln[ d ) 3025 . 2 / 1 (
] d[
d
] d[


= = OH
OH
OH
pH
OH
2
1 1
]) [ (
] [
3025 . 2
] d[
d
d
] d[
d
d
+
+
+
+
+
= =
H K
H K
C
H pH
H
C
pH
C
A
A
o o
]) [ (
1
+
+
=
H K
K
A
A
o
]) [ (
] [
0
+
+
+
=
H K
H
A
o
C
A HA
C
pH
C
] ][ [ 3025 . 2
3025 . 2
d
d
0
1 0
1

= = o o
o
90
) ] [ ] ([ 3025 . 2
0 1
o o | C OH H + + =
+
|
|
.
|

\
|
+
+ + =

+
] [ ] [
] ][ [
] [ ] [ 3025 . 2
0
0
A HA
A HA
OH H |
The maximum buffer intensity occurs at the inflection
point of the titration curve, or where:
0
) d(
d
2
1
2
=
pH
o
This condition occurs where o
1
= o
0
, [HA
0
] = [A
-
] or pH
= pK
A
. A solution is well buffered at three points: when
[H
+
] is dominant, when [OH
-
] is dominant and where pH
= pK
A
.
91 Figure 3.10a-c from Stumm and Morgan
92
Figure 3.10d from Stumm and Morgan
93
BUFFER INTENSITY FOR
MIXTURES OF ACIDS
( ) + + + + =
+
B HB B A HA A
C C OH H o o o o | ] [ ] [ 3025 . 2
|
|
.
|

\
|
+
+
+
+
+ + =

] [ ] [
] ][ [
] [ ] [
] ][ [
] [ ] [ 3025 . 2
0
0
0
0
B HB
B HB
A HA
A HA
OH H |
BUFFER INTENSITY FOR
POLYPROTIC ACIDS
|
|
.
|

\
|
+
+
+
+
+ + ~

] [ ] [
] ][ [
] [ ] [
] ][ [
] [ ] [ 3025 . 2
2
2
0
2
0
2
C HC
C HC
HC C H
HC C H
OH H |
The above is valid as long as K
1
/K
2
> 100.
94
GRAPHICAL DETERMINATION OF
BUFFER INTENSITY
At pH < pK
A
, [HA
0
] + [A
-
] ~ [HA
0
] so:
| ~ 2.3([H
+
] + [OH
-
] + [A
-
])
At pH > pK
A
, [HA
0
] + [A
-
] ~ [A
-
] so:
| ~ 2.3([H
+
] + [OH
-
] + [HA
0
])
Thus, buffer intensity can be calculated from a speciation
diagram by summing all concentrations represented by
a line of slope 1 and multiplying by 2.3025.
|
|
.
|

\
|
+
+ + =

+
] [ ] [
] ][ [
] [ ] [ 3025 . 2
0
0
A HA
A HA
OH H |
95
Base neutralizing capacity = [BNC] = the equivalent
sum of all acids that can be titrated with a strong base to
an equivalence point. For a monoprotic acid HA:
[BNC] = [HA
0
] + [H
+
] - [OH
-
]
[BNC] is the excess of protons above a reference, i.e., pure
NaA (f = 1), for which the proton condition is [HA
0
] +
[H
+
] = [OH
-
]. Addition of NaA does not affect [BNC]!
Acid neutralizing capacity = [ANC] = the equivalent
sumof all bases that can be titrated with a strong acid to
an equivalence point. For a monoprotic base:
[ANC] = [A
-
] + [OH
-
] - [H
+
]
[ANC] is the deficiency of protons over a reference level,
i.e., pure HA (f = 0) for which [A
-
] + [OH
-
] = [H
+
].
Addition of HA does not affect [ANC]!
96
EXAMPLE PROBLEM
Calculate [ANC] of the following solutions:
a) [NH
4
+
] + [NH
3
0
] = 5 x 10
-3
M; pH = 9.3
b) [NH
4
+
] + [NH
3
0
] = 10
-2
M; pH = 9.0
Which has the greater [ANC]? pK
A
= 9.3.
[ANC] = [NH
3
0
] + [OH
-
] - [H
+
]
[ANC] = Co
1
+ [OH
-
] - [H
+
]
For a):
5 . 0
10 10
10
] [
3 . 9 3 . 9
3 . 9
1
=
+
=
+
=

+
H K
K
A
A
o
[ANC] = 0.5(5 x 10
-3
M) + 10
-4.7
- 10
-9.3
[ANC] ~ 2.5 x 10
-3
M
97
EXAMPLE PROBLEM CONTINUED
For b):
33 . 0
10 10
10
] [
0 . 9 3 . 9
3 . 9
1
=
+
=
+
=

+
H K
K
A
A
o
[ANC] = 0.33(10
-2
M) + 10
-5.0
- 10
-9.0
[ANC] ~ 3.3 x 10
-3
M
Thus, solution b) has the higher acid neutralizing
capacity, even though it has the lower pH, i.e., is
more acidic than a). [ANC] should not be
confused with pH!
98
[ANC] AND [BNC] OF MULTIPROTIC
ACID/BASE SYSTEMS
For multiprotic acids we can define various reference levels
(f = 0, 1, 2 ).
Example: Sulfide-containing solution. [ANC] with
reference to the equivalence point f = 0, g = 2, i.e., a
solution of pure H
2
S is:
[ANC]
f =0
= [HS
-
] + 2[S
2-
] + [OH
-
] - [H
+
]
[ANC]
f =0
= S
T
(o
1
+ 2o
2
) + [OH
-
] - [H
+
]
Example: Phosphoric acid system with reference to f = 2,
i.e., a solution of pure Na
2
HPO
4.
[BNC]
f =2
= 2[H
3
PO
4
0
] + [H
2
PO
4
-
] + [H
+
] - [PO
4
3-
] - [OH
-
]
[BNC]
f =2
= P
T
(2o
0
+ o
1
- o
3
) + [H
+
] - [OH
-
]
99
GENERALIZED EQUATIONS FOR
[ANC] AND [BNC]
[BNC]
f =n
= C{no
0
+ (n-1)o
1
+ (n-2)o
2
+ (n-3)o
3

+ } + [H
+
] - [OH
-
]
[ANC]
f =n
= C{-no
0
+ (1-n)o
1
+ (2-n)o
2
+ (3-n)o
3

+ } - [H
+
] + [OH
-
]
o
x
= refers to the ionization fraction of the species
that has lost x protons from the most protonated
species.

100
MIXED ACID-BASE SYSTEM
A mixed acid-base system would be, for example, a natural
water containing bicarbonate, borate and ammonium. If we
employ H
2
CO
3
0
as the reference, then [ANC]
f =0
represents
the equivalent sum of all bases stronger than H
2
CO
3
0
minus
the equivalent sum of all acids stronger than H
2
CO
3
0
.
[ANC]
f =0
= [HCO
3
-
] + 2[CO
3
2-
] + [NH
3
0
] + [B(OH)
4
-
]
+ [OH
-
] - [H
+
]

101
RELATIONSHIP BETWEEN [ANC]
AND BUFFER INTENSITY
In carbonate systems, [ANC]
f =0
is called
alkalinity and [BNC]
f =2
is called acidity.
}
=
=
=
=
x f
n f
n f
pH ANC d ] [ |