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Ionic Equilibria

Ionic Equilibria

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Published by Kathy Cheng

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Published by: Kathy Cheng on Nov 30, 2011
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Chemistry/Ionic Equilibria 1
IONIC EQUILIBRIA
1. Concepts of Acid/Base1.1 Arrhenius Theory
1.1.1 Definition
 
1. An
acid 
is a substance which
dissolves in water to give hydrogen ions
, H
+(aq)
.2. A
base
is a substance which
dissolves in water to give hydroxide ions
, OH
-(aq)
.3. An
acid-base reaction
(i.e.
neutralization
) is the combination of H
+(aq)
and OH
-(aq)
to form H
2
O
(l)
.
Neutralization
: H
+(aq)
+ OH
-(aq)
 
H
2
O
(l)
 
Summary 
:
H
+(aq)
and
OH
-(aq)
are responsible for 
acidic
and
basic
properties respectively.
1.1.2 Drawbacks of Arrhenius Theory 
1. It confines to
aqueous solution only
. However, many acids are
capable of giving hydrogen ions
in
solventsother than water 
.
e.g.
nitric acid in ethanol ionizes to give hydrogen ions2. Some compounds are
not classified as acids
because they
do not contain the element hydrogen explicitly
,although they are
capable of releasing hydrogen ions
after 
reacting with water 
.
e.g.
SO
2(g)
+ H
2
O
(l)
2H
+(aq)
+ SO
32-(aq)
 3. Some substances are
not classified as bases
because they
do not contain hydroxide explicitly
, althoughthey are
capable of releasing hydroxide ions
 
by 
reacting with water 
.
e.g.
NH
3(g)
+ H
2
O
(l)
NH
4+(aq)
+ OH
-(aq)
 
1.2 Bronsted-Lowry Theory
1.2.1 Introduction
This theory emphasizes on the role of 
hydrogen ion, H
+
 
(i.e.
proton
).
Definition
:1. An
acid
 
is a molecule or ion that can
donate a proton
, H
+
(i.e. a
 proton donor 
).2. A
base
is a molecule or ion that can
accept a proton
, H
+
(i.e. a
 proton acceptor 
).3. An
acid-base reaction
is the
transfer of proton from an acid to a base
(i.e. a
 proton-transfer reaction
).
Neutralization
: H
+(aq)
+ OH
-(aq)
 
H
2
O
(l)
 NH
3(aq)
+ HCl
(aq)
 
NH
4
Cl
(aq)
or NH
4+(aq)
+ Cl
-(aq)
 
Implications :
1. An
acid
must
possess the element hydrogen
for donation.2. A base can either be
a negative ion or a neutral molecule with a lone pair of electrons
to form
dativecovalent bond
with
proton
.
Reason
:Since
proton has no electrons
, bonding between the base and proton must be
dative covalent 
in nature, withthe
base providing both electrons
 
a base must have a
lone pair of electrons available for donation
 
 NH HH+ H+ NHHHH+
 
3. Bronsted-Lowry definition
 
includes all substances
that fit the
 Arrhenius definition
. In addition, it includes
a.
as acids
, ions such as HSO
4-
and NH
4+
that can
donate proton in solution, even though they cannot exist alone
; and
b.
as bases
, all substances that
can accept proton
such as CO
32-
or CN
-
, even though they do not containhydroxide explicitly.
 
Chemistry/Ionic Equilibria 2
1.2.2 Conjugate Acid-Base Pair 
Consider the ionization of ethanoic acid in water :CH
3
COOH
(aq)
+ H
2
O
(l)
CH
3
COO
-(aq)
+ H
3
O
+(aq)
After CH
3
COOH
(aq)
has lost its proton, it becomes CH
3
COO
-(aq)
.From
reverse reaction
, CH
3
COO
-(aq)
is
capable of accepting a proton to form back the acid 
 
CH
3
COO
-(aq)
is itself a
CH
3
COO
-(aq)
is called the
of CH
3
COOH
(aq)
 
CH
3
COOH
(aq)
+ H
2
O
(l)
CH
3
COO
-(aq)
+ H
3
O
+(aq)
acid 
 
conjugate base
 Similarly, consider the ionization of ammonia in water :NH
3(aq)
+ H
2
O
(l)
NH
4+(aq)
+ OH
-(aq)
 After NH
3(aq)
has accepted a proton, it becomes NH
4+(aq)
.From
reverse reaction
, NH
4+(aq)
is
capable of donating its proton to form back the base
NH
4+(aq)
is itself an
NH
4+(aq)
is called the
of NH
3(aq)
 
NH
3(aq)
+ H
2
O
(l)
NH
4+(aq)
+ OH
-(aq)
 
base
 
conjugate acid 
 
Conclusion
:1. After 
an acid loses a proton
, it becomes a
base
and is called the
conjugate base of the given acid 
.2. After 
a base accepts a proton
, it becomes an
acid 
and is called the
conjugate acid of the given base
.These pairs of species are known as
conjugate acid-base pairs
;they convert into each other by the
transfer of 
, i.e.
gain/loss of a
.
Remark 
:1. An
acid-base reaction
must involve
both acid and base
.
Q
 
Both donor and acceptor of proton must be present 
for 
transfer of proton
to take place.2. An
acid
only shows its properties in the
presence of a base
. Similarly, a
base
only shows its properties in the
presence of an acid
.
Q
For an
acid to function
, a
base
must be present to
+
.For a
base to function
, an
acid 
must be present to
+
.3. In an acid-base reaction, since the
given acid 
(
acid
1
) will be converted into
its conjugate base
(
base
1
) and the
given base
(
base
2
) will be converted into
its conjugate acid 
(
acid
2
), the process can be represented as :As there are
acids and bases on both sides of the equation
, theprocess can
go either way
and is represented by an .The
forward reaction
is the
transfer of a proton from acid 
1
to base
,and the
reverse reaction
is the
transfer of the proton from acid 
tobase
1
.Essentially, the process can be taken as
base
1
and base
 competing to accept proton
 
an acid-base reaction is in fact the
competition to gain/lose proton between bases
 
alternatively, an acid-base reaction can also be taken as the
competition to gain/lose proton betweenacids
 
acid1+ base2base1+ acid2conjugateacid-base pair 2conjugateacid-base pair 1
 
Chemistry/Ionic Equilibria 3
Example
: HCl
(aq)
+ H
2
O
(l)
Cl
-(aq)
+ H
3
O
+(aq)
 acid base conjugate base conjugate acidof HCl of H
2
O
Exercise
:1. Identify the conjugate acid-base pairs in the following neutralization reactions.a. CH
3
COOH
(aq)
+ H
2
O
(l)
H
3
O
+(aq)
+ CH
3
COO
-(aq)
 b. NH
4+(aq)
+ H
2
O
(l)
H
3
O
+(aq)
+ NH
3(aq)
 c. H
2
O
(l)
+ CO
32-(aq)
HCO
3-(aq)
+ OH
-(aq)
 2. Write an equation to show that HPO
42-(aq)
can act as a Bronsted base in water. (94, I)
Solution
:3. Outline the Bronsted-Lowry theory of acids and bases with respect to the following reaction :H
2
O
(l)
+ HCl
(aq)
 
H
3
O
+(aq)
+ Cl
-(aq)
(89, II)
Solution
: H
2
O
(l)
+ HCl
(aq)
 
H
3
O
+(aq)
+ Cl
-(aq)
 2 conjugate acid-base pairs :&
4. Which of the following is a conjugate acid-base pair ? A.
 
NH
4+(aq)
and NH
3(aq)
 B.
 
H
2
SO
4(aq)
and SO
42-(aq)
 C.
 
H
3
O
+(aq)
and OH
-(aq)
 D.
 
HCl
(aq)
and NaOH
(aq)
 (1 mark, 06, I, 3c)
1.2.3 Amphoteric Substances
Some substances
can both act as an acid to donate a proton
,
or act as a base to accept a proton
. Such behaviour is known as
amphoteric 
.
Example
: 1. water 
+±±
       
++
O H O H OH 
 H 
32
 2. HSO
4-(aq)
.
42424
SO H  HSOSO
 H 
       
++
±±
 
 As an acid 
: HSO
4-(aq)
+ OH
-(aq)
SO
42-(aq)
+ H
2
O
(l)
 
 As a base
: HSO
4-(aq)
+ H
3
O
+(aq)
H
2
SO
4(aq)
+ H
2
O
(l)
 For an
amphoteric 
substance, whether it
behaves as an acid or a base
depends on the other substance present.If a
stronger acid 
is present, the
amphoteric species
is forced to
act as acid/base to accept/donate a proton
.If a
stronger base
is present, the
amphoteric species
is forced to
act as acid/base to accept/donate a proton
.
Example
:Give the equation for the reaction between HCO
3-(aq)
and(a) NaOH
(aq)
 (b) HCl
(aq)
 

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