Summary: Ionic Equilibria

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aA + bB cC + dD

K =
[C]
c
[D]
d
[A]
a
[B]
b
Weak acids Weak Bases
HA + H
2
O A
-
+ H
3
O
+
B + H
2
O BH
+
+ OH
-

K
a
=
[A
][H
3
O
+
]
[HA]

K
b
=
[BH
+
][OH
]
[B]
Self-ionisation of water
2H
2
O H
3
O
+
+ OH
-
K
w
= [H
3
O
+
][OH
-
]

For conjugate acid-base pair,
K
w
= K
a
K
b

Indicators
HInd + H
2
O Ind
-
+ H
3
O
+

K
Ind
= [H
3
O
+
]
[Ind
]
[HInd]
Colour change is detected
when [Ind
-
]/[Hind] = 1/10
or 10
Sparingly soluble salts
E.g. MX
2
MX
2
(s) M
2+
(aq) + 2X
-
(aq)
K
sp
= [M
2+
][X
-
]
2

Buffers
Equilibrium Law & Ionic Equilibria
2
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As applied to:
H
+
concentration pH = -log
10
[H
+
]
K
a
pK
a
= -log
10
K
a

K
b
pK
b
= -log
10
K
b

K
w
pK
w
= -log
10
K
w

3
Bronsted-Lowry definition
Acid proton donor
must have a hydrogen atom that can be lost
Base proton acceptor
must have a lone pair of electrons which can form a
coordinate bond with a hydrogen ion
Weak acids / bases dissociate partially in
solution
An acid always works in tandem with a base
one to donate proton, the other to accept.
4
Conjugate acid-base pairs

This equation may be simplified as:
HA A
-
+ H
+
HA + H
2
O A
-
+ H
3
O
+

acid base conjugate
base
conjugate
acid
5
Conjugate acid-base pairs
B + H
2
O BH
+
+ OH
-

base acid conjugate
acid
conjugate
base
6
Acid Dissociation Constant

In dilute aqueous solutions, amount of H
2
O that
reacts with HA is insignificant compared to the total
amount of water present.
[H
2
O] remains relatively constant, and is left out of
the K
a
expression.
HA + H
2
O A
-
+ H
3
O
+

7

K
a
=
[A
][H
3
O
+
]
[HA]
To calculate pH of weak acid, HA

where [HA]
i
is the initial concentration of HA, before
x of it dissociates to form A
-
and H
3
O
+
ions
HA A
-
+ H
3
O
+

Initial conc / mol dm
-3
[HA]
i
0 0
Change in conc
/ mol dm
-3

-x +x
+x

Eqm conc / mol dm
-3

[HA]
i
- x x x
8
To calculate pH of weak acid
Assuming degree of acid dissociation is small such
that [HA]
i
>> x, and [HA]
i
x [HA]
i

K
a
=
[A
][H
3
O
+
]
[HA]
=
x
2
[HA]
i
x
~
x
2
[HA]
i
x = [H
+
] = K
a
{[HA]
i
x} ~ K
a
[HA]
i

pH= lg K
a
[HA]

pH ~ lg K
a
[HA]
i
or
9
equals to [HA]
at equilibrium
Base Dissociation Constant

K
b
is derived similarly.
B + H
2
O BH
+
+ OH
-

10

K
b
=
[BH
+
][OH
]
[B]
To calculate pH of weak base, B

where [B]
i
is the initial concentration of B, before x
of it dissociates to form BH
+
and OH
ions
B + H
2
O BH
+
+
OH
-

Initial conc
/ mol dm
-3
[B]
i
- 0 0
Change in conc
/ mol dm
-3

-x - +x
+x

Eqm conc
/ mol dm
-3

[B]
i
- x - x x
11
To calculate pOH of weak base
Assuming degree of base dissociation is small such
that [B]
i
>> x, and [B]
i
x [B]
i

K
b
=
[BH
+
][OH
]
[B]
=
x
2
[B]
i
x
~
x
2
[B]
i
x = [OH
] = K
b
{[B]
i
x} ~ K
b
[B]
i

pOH = lg K
b
[B]

pOH ~ lg K
b
[B]
i
or
12
equals to [B]
at equilibrium
Ionic Product of Water, K
w

2H
2
O H
3
O
+
+ OH
-
K
w
= [H
3
O
+
][OH
-
]
pK
w
= pH + pOH
13
Temperature dependence of K
w

pH + pOH = 14 is only applicable at 25 C!
pH of pure water decreases with temperature as
[H
+
] increases. Is water becoming more acidic?
Temperature
/ C
K
w
/ x 10
-14

mol
2
dm
-6
pK
w
[H
+
]
/ 10
-7

mol dm
-3
[OH
-
]
/ 10
-7

mol dm
-3

pH
0 0.114 14.9 0.338 0.338 7.47
25 1.01 14.0 1.00 1.00 7.00
50 5.48 13.3 2.34 2.34 6.63
14
Relationship between K
w
, K
a
and K
b

Consider a weak acid HA,

Its conjugate base, A
-
, undergoes salt hydrolysis as
follows:
A
-
+ H
2
O HA + OH
-

K
a
=
[A
][H
3
O
+
]
[HA]

K
b
=
[HA][OH
]
[A
]
HA + H
2
O A
-
+ H
3
O
+

acid conjugate
base
15
Relationship between K
w
, K
a
and K
b

16

K
a
K
b
=
[A
][H
3
O
+
]
[HA]

[HA][OH
]
[A
]
K
a
K
b
= [H
3
O
+
][OH
] = K
w
pH Titration Curves
Source: catalog.flatworldknowledge.com
17
Choice of Indicator
pH transition range of chosen indicator should fall
within the region where a sharp change in pH is
observed on the titration curve.
E.g. Source: www.chemguide.co.uk
18
Buffers
Acidic buffer: weak acid HA + conjugate base A
-
HA H
+
+ A
-

MA M
+
+ A
-

Alkaline buffer: weak base B + conjugate acid BH
+
B + H
2
O BH
+
+ OH
-
BH
+
Cl
-
BH
+
+Cl
-

i.e. salt of weak acid HA
i.e. salt of strong
mineral acid, e.g. HCl
19
How do buffers work?
Consider an acidic buffer, an equimolar mixture of
CH
3
CO
2
H and CH
3
CO
2
-
Na
+
,

20
CH
3
CO
2
H CH
3
CO
2
-
OH
-
CH
3
CO
2
-
H
+
CH
3
CO
2
H
CH
3
CO
2
H + OH
-
CH
3
CO
2
-
+ H
2
O

CH
3
CO
2
-
+ H
+
CH
3
CO
2
H

CH
3
CO
2
H CH
3
CO
2
-
CH
3
CO
2
H
CH
3
CO
2
-
CH
3
CO
2
H
CH
3
CO
2
-
+H
+
+OH
-
pH of buffer
decreases only slightly

pH of buffer
increases only
slightly

21
To calculate pH of an acidic buffer

where [HA]
i
and [A
-
]
i
are initial concentrations of HA
and A
-
respectively, before x of HA dissociates to
form ions.
HA + H
2
O A
-
+ H
3
O
+

Initial conc
/ mol dm
-3
[HA]
i
- [A
-
]
i
0
Change in conc
/ mol dm
-3

-x - +x
+x

Eqm conc
/ mol dm
-3

[HA]
i
- x - [A
-
]
i
+ x x
22

K
a
=
[A
][H
3
O
+
]
[HA]
= [H
3
O
+
]
[A
]
[HA]
lgK
a
= lg[H
+
] + lg
[A
]
[HA]
lg[H
+
] = lgK
a
+ lg
[A
]
[HA]
pH= pK
a
+ lg
[A
]
[HA]
23
Henderson-Hasselbalch
Equation
Assuming [HA]
i
x [HA]
i
and [A
-
]
i
+ x [A
-
]
i

pH= pK
a
+ lg
{[A
]
i
+ x}
{[HA]
i
x}
(where x = [H
+
])
24

pH~ pK
a
+ lg
[A
]
i
[HA]
i

pH= pK
a
+lg
[A
]
[HA]
Similarly, expressions to calculate pOH of
alkaline buffers may be derived.

pOH= pK
b
+ lg
[BH
+
]
[B]

pOH ~ pK
b
+ lg
[BH
+
]
i
[B]
i
25
An indicator is a weak acid whose conjugate
base is of a different colour.
or a weak base whose conjugate acid is of a
different colour.

26
HIn + H
2
O In
-
+ H
3
O
+

acid
Colour A
conjugate
base
Colour B

The end-point is the sudden colour change
seen in a titration.
A colour change is typically detected when
27

K
Ind
= [H
3
O
+
]
[Ind
]
[HInd]

[Ind
]
[HInd]
=
1
10
or
10
1
Difference between end point and
equivalence point
The equivalence point of the titration is reached
when moles of acid exactly react with moles of
base.
If indicator is chosen correctly, the end point will be
very close to the equivalence point.
28
Solubility Product, K
sp
Consider a sparingly soluble salt, MX
2
MX
2
(s) M
2+
(aq) + 2X
-
(aq)
Since MX
2
is a solid, its concentration is taken to be
its density, and is a constant.
Thus K
sp
does not contain [MX
2
(s)] in its expression.

K
sp
= [M
2+
][X
-
]
2
29
To predict occurrence of precipitation
Calculate ionic product (IP), and compare with K
sp
.
IP = K
sp
saturated solution
On the brink of precipitation
Precipitate forms immediately if seed crystal is added.
IP < K
sp
unsaturated solution
No precipitation
IP > K
sp
over-saturated solution
Precipitate forms.
30
Solubility Product, K
sp

Ionic Product (IP)

IP expression is exactly the same as K
sp
expression
Only used with ionic
concentrations in a
saturated solution
Applicable to all types of
solutions (unsaturated or
saturated) of any
concentration
At constant temperature,
K
sp
value is constant
IP value keeps changing
with ionic concentration,
even at constant
temperature
31
Common Ion Effect
Consider a sparingly soluble salt, MX
2
,
MX
2
(s) M
2+
(aq) + 2X
-
(aq)
When a common ion (i.e. M
2+
or X
-
) is added to a
solution of MX
2
, by Le Chateliers Principle,
equilibrium shifts left to decrease concentration of
common ion.
More MX(s) is precipitated.
Solubility of MX(s) is reduced.
32
Summary

Summary: Ionic Equilibria

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