S.K.

Sinha
By :
IIT CHEMISTRY
A CENTRE FOR CONCEPTUAL & SYSTEMATIC STUDY
B.O.-1 D 10 TALWANDI, .COMMERCE
COLLEGE Main Road .KOTA
MASTERING
H.O.- 2-N12 Rangbari Yojana Kota.
SINHA'S
PART-D
IONIC EQUILLIBRIA
Mo- 93149-05055 Ph- 0744 - 2407.906
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MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
Ph-0744-2407906 Mo-93149-05055.
1
ACIDS AND BASES

The Nature of Acids and Bases

Arrhenius concept:
Acid a substance that produces hydrogen ion in aqueous solution.
Base a substance that produces hydroxide ion in aqueous solution.

Examples of Acids:
1. HCl
(aq)
 H
+
(aq)
+ Cl
-
(aq)
; (a strong acid)
2. HNO
3(aq)
 H
+
(aq)
+ NO
3
-
(aq)
; (a strong acid)
3. CH
3
COOH
(aq)
⇋ H
+
(aq)
+ CH
3
COO
-
(aq)
; (a weak acid)

Examples of bases:
1. NaOH
(aq)
 Na
+
(aq)
+ OH
-
(aq)
; (a strong base)
2. Ba(OH)
2(aq)
 Ba
2+
(aq)
+ 2OH
-
(aq)
; (a moderately strong base)
8. NH
3(aq)
+ H
2
O ⇋ NH
4
+
(aq)
+ OH
-
(aq)
; (a weak base)
* All hydroxides and oxides of metal are bases.
(Oxides of metals in veryhigh O.N. is acidic. Ex CrO
3
, Mn
2
O
7 .


The Brønsted-Lowry concept:
Acid a substance that acts as a proton donor in chemical reaction;
Base a substance that acts as a proton acceptor in chemical reaction;

* Reactions that involve the transfer of protons (H
+
) are acid-base reactions.

The Bronsted-Lowry acid-base reaction can be represented as follows:
HA + B ⇋ BH
+
+ A
-

acid
1
base
2
conjugate conjugate
acid
2
base
1

For examples:
1. HCl + H
2
O  H
3
O
+
(aq)
+ Cl
-
(aq)

acid
1
base
2
conjugate conjugate
acid
2
base
1

2. HC
2
H
3
O
2
+ H
2
O ⇋ H
3
O
+
(aq)
+ C
2
H
3
O
2
-
(aq)
;
acid
1
base
2
conjugate conjugate
acid
2
base
1
3. NH
3
+ H
2
O ⇋ NH
4
+
(aq)
+ OH
-
(aq)
;
base
1
acid
2
conjugate conjugate
acid
1
base
2


In each reaction, a conjugate base is what remains of the acid molecule after it loses a
proton (H
+
), and a conjugate acid is what becomes of the base after it gains a proton.
acid
1
- conjugate base
1
and acid
2
- conjugate base
2
are called conjugate acid-base pairs;
they are a pair of species that are related to each other by the loss or gain of a single
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MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
Ph-0744-2407906 Mo-93149-05055.
2
proton (H
+
). Thus, H
2
O and H
3
O
+
are conjugate acid-base pair; H
3
O
+
is called hydronium
ion.

A BrØnsted-Lowry acid-base reaction involves a competition between two bases for a
proton, in which the stronger base ends up being the most protonated at equilibrium.

In the reaction: HCl + H
2
O  H
3
O
+
(aq)
+ Cl
-
(aq)
,
- H
2
O is a stronger base than Cl
-
; at equilibrium, a solution of hydrochloric acid
contains mostly H
3
O
+
and Cl
-
ions.

In reaction: HC
2
H
3
O
2
+ H
2
O ⇋ H
3
O
+
(aq)
+ C
2
H
3
O
2
-
(aq)
;
- C
2
H
3
O
2
-
is the stronger base; at equilibrium, a solution of acetic acid contains mostly
HC
2
H
3
O
2
and a small amount of H
3
O
+
and C
2
H
3
O
2
-
ions.

In the reaction: NH
3
+ H
2
O ⇋ NH
4
+
(aq)
+ OH
-
(aq)
,
- water is an acid. The competition for protons is between NH
3
and OH
-
, in which OH
-

is the strong base; the above equilibrium shifts to the left. That is, an aqueous
ammonia solution contains mostly NH
3
molecule and a small amount of NH
4
OH,
NH
4
+
, and OH
-
.
Exercises:
1. Write the conjugate base for each of the following acids:
(a) H
2
PO
4
-
; (b) H
2
C
2
O
4
; (c) [Al(H
2
O)
6
]
3+
; (d) NH
3
;

2. Write the conjugate acid for each of the following bases:
(a) NH
3
(b) [Al(H
2
O)
2
(OH
-
)
4
]
-
(c) SO
3
2-
(d) (CH
3
)
3
N:
The fects of Structure of Acid-Base Properties
The Relative Strength of Acids
The strength of acids is determined by a combination of various factors, such as the
strength and polarity of X÷H bond in the molecule, and the hydration energy of the ionic
species in aqueous solution.

For binary acids such as HF, HCl, HBr, and HI, H÷X bond strength decreases down
the group. The weaker the bond, the easier the molecule ionizes in aqueous solution.
Hence, the stronger will be the acid. Thus, for this group of acids, their strength increases
down the group:
HF < HCl < HBr < HI; H
2
O < H
2
S < H
2
Se < H
2
Te
Among the hydrohalic acids, HF is the only weak acid; the others are strong acids. The
relative strength of HCl, HBr, and HI cannot be differentiated in aqueous solution, because
each of them dissociates almost completely. Less polar solvents are used to determine their
relative strength. For example, HCl, HBr and HI ionize only partially in acetone or
methanol, which have a weaker ionizing strength than water. The ionization of HCl in
acetone can be represented by the following equilibrium:
(CH
3
)
2
CO
(l)
+ HCl
(acetone)
⇋ (CH
3
)
2
COH
+
(acetone)
+ Cl
-
(acetone)


The degree of ionization in acetone increases in the order of HCl < HBr < HI. Based on this
observation, it was determined that the acidity of hydrogen halides increases down the
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
Ph-0744-2407906 Mo-93149-05055.
3
group: HF < HCl < HBr < HI. A similar trend of relative acidity is also observed for the
hydrides of Group VIA elements, such that, H
2
O < H
2
S < H
2
Se < H
2
Te.

For the same period hydrides, the relative acidity increases from left to right, such that:
CH
4
< NH
3
< H
2
O < HF; PH
3
< H
2
S << HCl

Water is a stronger acid than ammonia, and in acid-base reaction, H
2
O acts as a BrØnsted-
Lowry acid, which donates a proton to NH
3
:
H
2
O
(l)
+ NH
3(aq)
⇋ NH
4
+
(aq)
+ OH
-
(aq)


In reaction with HF, water acts as a BrØnsted-Lowry base, which accept a proton:
HF
(aq)
+ H
2
O
(l)
⇋ H
3
O
+
(aq)
+ F
-
(aq)

The Relative Strength of Oxo-acids
Oxo-acids are acids that contain one or more O÷H groups covalently bonded to a
central atom, which can be a metal or a nonmetal. The OH group ionizes completely or
partially in aqueous solution producing hydrogen ions. Some common examples of oxo-acids
are H
2
CO
3
, HNO
3
, H
3
PO
4
, H
2
SO
4
, HClO
4
, and HC
2
H
3
O
2
:

O O O
| | |
H÷O÷S÷O÷H H÷O÷P÷O÷H O÷Cl÷O÷H
| | |
O O O
|
H
For these type of acids, their relative strengths depend on the electronegativity of
the central atoms. The more electronegative the central atom, the more polarized the O÷H
bond and the more readily it ionizes in aqueous solution to release the H
+
ion. For
example, N, S, and Cl are more electronegative than P, and HNO
3
, H
2
SO
4
, and HClO
4
are
stronger acids compared to H
3
PO
4
. The relative acid strengths are: HNO
3
> H
2
SO
4
> H
3
PO
4
.

For oxo-acids with central atoms from the same group, their relative strength decreases
from top to bottom as the electronegativity of the central atom decreases:

HOCl > HOBr > HOI; HOClO > HOBrO > HOIO; HOClO
2
> HOBrO
2
> HOIO
2


For oxo-acids containing identical central atom, acidity increases as more oxygen atoms are
bonded to it. For example, acidity increases in the following order:

HOCl < HOClO < HOClO
2
< HOClO
3
; H
2
SO
4
> H
2
SO
3
; HNO
3
> HNO
2


Oxygen is a very electronegative atom; when more oxygen atoms are bonded to the
central atom, the O÷H group in the molecule becomes more polarized (due to inductive
effect), and the more readily it ionizes to release H
+
ion.

Acetic acid is an organic acid, which contains the acidic carboxyl group, -COOH.
When acetic acid (CH
3
COOH) ionizes, only the O÷H bond of the carboxyl group breaks, but
not the C÷H bonds. However, if one or more of the hydrogen atoms in the methyl group (-
CH
3
) is substituted with a more electronegative atom, the O÷H of -COOH group becomes
more polarized and ionizes more readily, and increasing the acidity. The following K
a
values
illustrate the effect on the acidity of COOH when one or more of the methyl hydrogen is
substituted with more electronegative atoms:
CH
3
COOH
(aq)
⇋ CH
3
COO
-
(aq)
+ H
+
(aq)
; K
a
= 1.8 x 10
-5

MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
Ph-0744-2407906 Mo-93149-05055.
4
ClCH
2
COOH
(aq)
⇋ ClCH
2
COO
-
(aq)
+ H
+
(aq)
; K
a
= 1.4 x 10
-3

chloroacetic acid
FCH
2
COOH
(aq)
⇋ FCH
2
COO
-
(aq)
+ H
+
(aq)
; K
a
= 2.6 x 10
-3

fluoroacetic acid
CCl
3
COOH
(aq)
⇋ CCl
3
COO
-
(aq)
+ H
+
(aq)
; K
a
= 3.0 x 10
-1

trichloroacetic acid
Exercise:
1. Rank the following acids in order of increasing strength:
(a) CH
3
COOH, CH
3
CH
2
COOH, HCOOH;
(b) CH
3
COOH, ClCH
2
COOH, CHCl
2
COOH, CCl
3
COOH, CF
3
COOH
2. Rank the following bases in order of increasing strength:
(a) NH
3
, CH
3
NH
2
, (CH
3
)
2
NH
2
, (CH
3
)
3
N, (CH
3
CH
2
)
3
N
________________________________________________________________________
Acid-Base Properties of Oxides
Metal oxides are either basic or have amphoteric properties. The oxides the Group IA
metals are strongly basic because they are generally very soluble in water. Other metal
oxides are less soluble, but they react with strong acids:

Na
2
O
(s)
+ H
2
O
(l)
 2NaOH
(aq)
;
BaO
(s)
+ H
2
O
(l)
 Ba(OH)
2(aq)

MgO
(s)
+ 2HCl
(aq)
 MgCl
2(aq)
+ H
2
O
(l)


The oxide ion, O
2-
, has a very strong affinity for protons and reacts with water to produce
hydroxide ions:
O
2-
(aq)
+ H
2
O
(l)
 2OH
-
(aq)

Some metal oxides are amphoteric; for example, Al
2
O
3
, Cr
2
O
3
, PbO, SnO, and ZnO. They
react with both strong acids and strong bases:

Al
2
O
3(s)
+ 6HCl
(aq)
 2AlCl
3(aq)
+ 3H
2
O
(l)
;
Al
2
O
3(s)
+ 2NaOH
(aq)
+ 3H
2
O
(l)
 2Na[Al(OH)
4
]
(aq)
;

Oxides of nonmetals are acidic. They form acidic solution when dissolved in water.
CO
2(g)
+ H
2
O
(l)
⇋ H
2
CO
3(aq)
⇋ H
+
(aq)
+ HCO
3
-
(aq)
;
SO
2(g)
+ H
2
O
(l)
⇋ H
2
SO
3(aq)
⇋ H
+
(aq)
+ HSO
3
-
(aq)
;
P
4
O
10(g)
+ 6H
2
O
(l)
⇋ 4H
3
PO
4(aq)
; H
3
PO
4(aq)
 H
+
(aq)
+ H
2
PO
4
-
(aq)
;

Metal Hydroxides and Hydrides
Hydroxides of Group IA metals are strongly basic. For example, LiOH, NaOH, and
KOH, are strong bases. The basicity of other metal hydroxides is limited by their low
solubility. The hydroxides of some metals exhibit amphoteric properties. For example,
aluminum hydroxide, Al(OH)
3
is an amphoteric hydroxides.
Al(OH)
3(s)
+ OH
-
(aq)
⇋ Al(OH)
4
-
(aq)
;
Al(OH)
3(s)
+ 3H
3
O
+
(aq)
⇋ [Al(H
2
O)
6
]
3+
(aq)

Cr(OH)
3
, Zn(OH)
2
, Sn(OH)
2
, and Pb(OH)
2
are also amphoteric hydroxides.

MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
Ph-0744-2407906 Mo-93149-05055.
5
The hydrides of reactive metals, such as NaH and CaH
2
, are strong bases. The
hydride ion has a strong affinity for protons and reacts with water to produce hydroxide ions
and hydrogen gas:
H
-
(aq)
+ H
2
O
(l)
 H
2(g)
+ OH
-
(aq)

The Lewis Acids and Bases
According to G.N. Lewis, an acid is the reactant that is capable of sharing a pair of
electrons from another reactant to form a covalent bond; a base is the reactant that
provides the pair of electrons to be shared to form a covalent bond.
Based on the Lewis’s definition, hydrogen ion (H
+
) is considered a Lewis acid and water and
ammonia are the Lewis bases in the following reactions:

H
+
+ H
2
O  H
3
O
+
; H
+
+ NH
3
 NH
4
+
;
Lewis Lewis Lewis Lewis
acid base acid base
Species with incomplete octet (or electron deficient species) may act as Lewis acid and
those with lone pair of electrons may act as Lewis bases. For example, in the following
reactions, BF
3
, AlCl
3
, and FeBr
3
are Lewis acids; while NH
3
, Cl
-
, and Br
-
are Lewis bases.

BF
3
+ NH
3
 F
3
B:NH
3
; AlCl
3
+ Cl
-
 AlCl
4
-
; FeBr
3
+ Br
-
 FeBr
4
-
;
In the formation of complex ions, the positive ions act as Lewis acids and the ligands
(anions or small molecules) are Lewis bases:
Cu
2+
(aq)
+ 4NH
3(aq)
⇋ Cu(NH
3
)
4
2+
(aq);
Lewis acid Lewis base
Al
3+
(aq)
+ 6H
2
O
(l)
⇋ [Al(H
2
O)
6
]
3+
(aq)
;
Exercise
1. Determine the Lewis acids and Lewis bases in the following reactions:
(a) CO
2(g)
+ H
2
O
(l)
⇋ H
2
CO
3(aq)

(b) SO
3(g)
+ H
2
O
(l)
⇋ H
2
SO
4(aq)

(c) AlCl
3
+ (CH
3
)
3
N: ⇋ (CH
3
)
3
N:AlCl
3
(d) Zn(OH)
2(s)
+ 2OH
-
(aq)
⇋ Zn(OH)
4
2-
(aq)
;

(e) AuCl
3
(s) + Cl
-
(aq) ⇋ AuCl
4
-
(aq)
Acids Strength
The strength of an acid is defined by the extent of its dissociation (ionization) in
aqueous solution.
HA
(aq)
+ H
2
O H
3
O
+
(aq)
+ A
-
(aq)


Strong acids, such as HClO
4
, HCl, HNO
3
, and H
2
SO
4
, are those that are considered to
completely ionize at 1 M concentration. The above equilibrium would lie far to the right.
Acids that are only partially ionized at this concentration, such as HC
2
H
3
O
2
, HF, HNO
2
,
H
2
SO
3
, H
3
PO
4
, and HClO, are considered weak acids. Their dissociation equilibria would lie
far to the left.

The equilibrium constant, K
a
, for the acid ionization is given by the following expression:
[H
3
O
+
][A
-
] [H
+
][A
-
]
K
a
= ÷÷÷÷÷÷ = ÷÷÷÷÷
[HA] [HA]
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
Ph-0744-2407906 Mo-93149-05055.
6
For strong acids, K
a
would have a very large value; for weak acids, K
a
< 10
-1
. The following
are the K
a
values of some weak acids:
1. HF
(aq)
⇋ H
+
(aq)
+ F
-
(aq)
; K
a
= [H
+
][F
-
] = 7.2 x 10
-4
[HF]
2. HNO
2(aq)
⇋ H
+
(aq)
+ NO
2
-
(aq)
; K
a
= [H
+
][NO
2
-
] = 4.0 x 10
-4
[HNO
2
]
3. HC
2
H
3
O
2(aq)
⇋ H
+
(aq)
+ C
2
H
3
O
2
-
(aq)
; K
a
= [H
+
][ C
2
H
3
O
2
-
] = 1.8 x 10
-5
[HC
2
H
3
O
2
]
4. HOCl
(aq)
⇋ H
+
(aq)
+ ClO
-
(aq)
; K
a
= [H
+
][ClO
-
] = 3.5 x 10
-8
[HOCl]
5. HCN
(aq)
⇋ H
+
(aq)
+ CN
-
(aq)
; K
a
= [H
+
][CN
-
] = 6.2 x 10
-10
[HCN]
The value of K
a
is a measure of the extent of acid dissociation; hence, the strength of the
acid. A stronger acids have larger K
a
values. For strong acids such as HClO
4
, HCl, H
2
SO
4
,
and HNO
3
, their K
a
’s are very large (not given in any tables of K
a
values).

The Conjugate Acid-Base Relationships
Strong acids have weak conjugate bases, and weak acids have strong conjugate
bases; the weaker the acid, the stronger will be its conjugate base. Likewise, weak bases
have strong conjugate acids; the weaker the base, the stronger will be its conjugate acid.
Examples:
- HCl is a strong acid and Cl
-
is a very weak base;
- HF is a weak acid, and F
-
is a stronger conjugate base than Cl
-
.
According to BrØnsted-Lowry, acid-base reactions favor the direction from strong acid-
strong base combinations to weak acid-weak base combinations:

The following acid-base reactions go completely in the forward direction:
1. HClO
4(aq)
+ H
2
O
(l)
 H
3
O
+
(aq)
+ ClO
4
-
(aq)
; (HClO
4
is a very strong acid)
2. HCl
(aq)
+ NH
3(aq)
 NH
4
+
(aq)
+ Cl
-
(aq)
; (HCl is a strong acid)
3. HSO
4
-
(aq)
+ CN
-
(aq)
 HCN
(aq)
+ SO
4
2-
(aq)
; (HSO
4
-
is a stronger than HCN)
Many acid-base reactions reach a state of equilibrium. The following acid-base reactions do
not go to completion; their equilibrium positions may shift to the right or to the left,
depending on the relative strength of the acid:
1. H
2
PO
4
-
(aq)
+ C
2
H
3
O
2
-
(aq)
⇋ HC
2
H
3
O
2(aq)
+ HPO
4
2-
(aq)
;
Equilibrium shifts left; HC
2
H
3
O
2
is the stronger acid and HPO
4
2-
is the stronger base.
2. HNO
2(aq)
+ C
2
H
3
O
2
-
(aq)
⇋ HC
2
H
3
O
2(aq)
+ NO
2
-
(aq)
;
Equilibrium shifts right; HNO
2
is the stronger acid, C
2
H
3
O
2
-
is the stronger base.

Water as an Acid and a Base
Water is amphoteric because it can behave as an acid and a base. The following
equilibrium occurs in pure water:

H
2
O + H
2
O ⇋ H
3
O
+
(aq)
+ OH
-
(aq)
;
Acid
1
base
1
conjugate conjugate
acid
2
base
1
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
Ph-0744-2407906 Mo-93149-05055.
7
The above equilibrium can be simplified as follows, which is also called the auto-ionization of
water:
H
2
O ⇋ H
+
(aq)
+ OH
-
(aq)
; K
w
= [H
+
][OH
-
] = 1.0 x 10
-14
at 25
o
C.
K
w
is called the ion product constant for water.
An aqueous solution contains both H
+
(in the form of H
3
O
+
) and OH
-
, such that the product
of their concentrations is constant equal to 1.0 x 10
-14
at 25
o
C. In pure water (or in a
neutral solution,
[H
+
] = [OH
-
] = 1.0 x 10
-7
M.
If [H
+
] increases (> 1.0 x 10
-7
M), [OH
-
] will decreases (< 1.0 x 10
-7
M), and vice versa.
Thus, a solution with:
- [H
+
] > 1.0 x 10
-7
M, or [H
+
] > [OH
-
],  the solution is acidic;
- [H+] < 1.0 x 10
-7
M, or [H
+
] < [OH
-
],  the solution is basic;
- [H+] = [OH
-
] = 1.0 x 10
-7
M,  the solution is neutral;

Exercise-2:
1. What is [OH
-
] if [H
+
] = 0.0050 M? Is the solution acidic, basic or neutral?
2. What is the [H
+
] if [OH
-
] = 6.0 x 10
-4
M? Is the solution acidic, basic or neutral?
________________________________________________________________________
The pH Scale
pH is a scale that measures the acidity of an aqueous solution where [H
+
] is very small.
pH = -log[H
+
],

If [H
+
] = 1.0 x 10
-7
M, pH = -log(1.0 x 10
-7
) = -(-7.00) = 7.00

We can also express basicity using the log scale for [OH
-
], such that pOH = -log[OH
-
]
That is, if a solution has [OH
-
] = 1.0 x 10
-7
M, pOH = -log(1.0 x 10
-7
) = -(7.00) = 7.00
Since, at 25
o
C, K
w
= [H
+
][OH
-
] = 1.0 x 10
-14

pK
w
= -log K
w
= -log[H
+
] + (-log[OH
-
]) = -log(1.0 x 10
-14
) = -(-14.00) = 14.00
pK
w
= pH + pOH = 14.00; and pOH = 14.00 – pH

Thus, in aqueous solutions, if pH > 7.00  pOH < 7.00, and vice versa;
In neutral solution, [H
+
] = [OH
-
] = 1.0 x 10
-7
M, and pH = pOH = 7.00;
- [H
+
] > 1.0 x 10
-7
M,  pH < 7.00, the solution is acidic.
- [H
+
] < 1.0 x 10
-7
M,  pH > 7.00, the solution is basic.
_________________________________________________________________________.
Calculating the pH of Strong Acid and Strong Base Solutions
Strong acids are assumed to ionize completely in aqueous solution. For monoprotic
acids (that is, those acids with a single ionizable hydrogen atom), the concentration of
hydrogen ion in solution is the same as the molar concentration of the acid. That is
[H
+
] = [HA]

For example, in 0.10 M HCl(aq), [H
+
] = 0.10 M, and pH = -log(0.10) = 1.00.

A strong base such as NaOH, contains OH
-
which concentration is equal to that of dissolved
NaOH. That is, a solution of 0.10 M NaOH(aq) contains [OH
-
] = 0.10 M

pOH = -log[OH
-
] = -log(0.10) = 1.00; pH = 14.00 – 1.00 = 13.00

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A strong base such as Ba(OH)
2
produces twice the concentration of OH
-
as the concentration
of Ba(OH)
2
in solution. Ba(OH)
2
dissociates as follows:

Ba(OH)
2(aq)
 Ba
2+
(aq)
+ 2OH
-
(aq)
;
[OH
-
] = 2 x [Ba(OH)
2
]

In a solution of 0.010 M Ba(OH)
2
, [OH
-
] = 0.020 M, pOH = 1.70, and pH = 12.30
Exercise-3:
1. Calculate the pH of the following solutions:
(a) 0.0050 M HCl; (b) 0.00060 M NaOH.
2. What is [H
+
] and [OH
-
], respectively, in a solution where,
(a) pH = 4.50; (b) pOH = 5.40
3. The pH of an HCl solution is found to be 3.00. To what final volume must a 100.-mL
sample of this acid be diluted so that the pH of the solution becomes 3.50? (316 mL)

4. What is the pH of a saturated aqueous solution of Ca(OH)
2
in which 0.165 g of Ca(OH)
2

is dissolved in 100. mL solution at 25
o
C? (Answer: pH = 11.65)
_________________________________________________________________________.
Calculating the pH of Weak Acid Solutions

Weak acids do not ionize completely. At equilibrium, [H
+
] is much less than the
concentration of the acid. The concentration of H
+
in a weak acid solution depends on the
initial acid concentration and the K
a
of the acid. To determine [H
+
] of a weak acid we can
set up the “ICE” table as follows:
Consider a solution of 0.10 M acetic acid and its ionization products:
Concentration: HC
3
H
3
O
2(aq)
⇋ H
+
(aq)
+ C
2
H
3
O
2
-
(aq)

÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
Initial [ ], M: 0.10 0.00 0.00
Change, A[ ], M: -x +x +x
Equilibrium [ ], M : (0.10 - x) x x
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
The acid ionization constant, K
a
, is given by the expression:
K
a
= [H
+
][C
2
H
3
O
2
-
] = x
2
= 1.8 x 10
-5

[HC
2
H
3
O
2
] (0.10 – x)

Since K
a
<< 0.10, we can use the approximation that x << 0.10, and (0.10 – x) ~ 0.10
Then, K
a
= x
2
~ x
2
/0.10 = 1.8 x 10
-5
;
(0.10 – x)
 x
2
= (0.10)(1.8 x 10
-5
); x = \(1.8 x 10
-6
) = 1.3 x 10
-3

Note that, x = [H
+
] = 1.3 x 10
-3
M;  pH = - log(1.3 x 10
-3
) = 2.89

Percent Dissociation
The percent dissociation (or degree of ionization) of a weak acid is defined as
follows:
Percent dissociation = Amount of acid that dissociate (mol/L)
Initial concentration of acid (mol/L)
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For strong acids, the percent dissociation at equilibrium is almost 100%. For weak acids, the
percent dissociation depends on K
a
of the acid and their initial concentration. For example,
the percent dissociation of acetic acid (HC
2
H
3
O
2
, K
a
= 1.8 x 10
-5
) at 0.10 M concentration is,

(1.3 x 10
-3
M/0.10 M) x 100% = 1.3 %

K
a
or pK
a
is a measure of the acid strength. The stronger the acid, the more of it
ionizes, and the greater its K
a
(or the lower its pK
a
). The percent dissociation of a weak acid
then depends on its K
a
and also on the degree of dilution. In the more dilute acid, a higher
percentage of the molecules will ionize.

Now consider a solution of 0.010 M acetic acid and its ionization products:
Concentration: HC
3
H
3
O
2(aq)
⇋ H
+
(aq)
+ C
2
H
3
O
2
-
(aq)

÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
Initial [ ], M: 0.010 0.00 0.00
Change, A[ ], M: -x +x +x
Equilibrium [ ], M : (0.010 - x) x x
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷

The acid ionization constant, K
a
, is given by the expression:
K
a
= [H
+
][C
2
H
3
O
2
-
] = x
2
= 1.8 x 10
-5

[HC
2
H
3
O
2
] (0.010 – x)

K
a
<< 0.010, we can still use the approximation that x << 0.010, and (0.010 – x) ~ 0.010

Then, K
a
= x
2
~ x
2
/0.010 = 1.8 x 10
-5
;
(0.010 – x)
 x
2
= (0.010)(1.8 x 10
-5
); x = \(1.8 x 10
-7
) = 4.2 x 10
-4

Note that, x = [H
+
] = 4.2 x 10
-4
M;  pH = - log(4.2 x 10
-4
) = 3.37

The degree of ionization of acetic acid at this concentration is,
4.2 x 10
-4
M x 100% = 4.2 %
0.010 M
Note that, the degree of ionization of the acid is higher in the more dilute acid solution. In
fact, in 1.0 M acetic acid, the percent dissociation is only 0.42%, which is a 10-fold lower
than in 0.010 M acid solution.
Exercise:
1. What is [H
+
] in 0.10 M HNO
2
solution and the pH of the solution? K
a
= 4.0 x 10
-4
?
(Answer: [H
=
] = 6.3 x 10
-3
M; pH = 2.20)

2. A 0.10 M aqueous solution of lactic acid, HC
3
H
5
O
3
, has a pH = 2.43. Determine [H
+
] in
this solution and the K
a
of lactic acid. (Answer: [H
+
] = 3.7 x 10
-3
M; K
a
= 1.4 x 10
-4
)

3. If a 0.10 M benzoic acid, HC
7
H
5
O
2
is 2.5% ionized, what is [H
+
] and pH of 0.10 M
benzoic acid? Calculate the K
a
of benzoic acid.
(Answer: [H
+
] = 2.5 x 10
-3
M; pH = 2.60; K
a
= 6.4 x 10
-5
)
_________________________________________________________________________
Bases
Strong Bases:
- Hydroxides of Group IA metals (LiOH, NaOH, KOH, RbOH, and CsOH) are strong
bases, but only NaOH and KOH are commercially important and are common
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10
laboratory bases, since the others are quite expensive. These bases are quite soluble
in water and they completely dissociate in aqueous solution, producing a high
concentration of hydroxide ions. A moderately dilute solution of NaOH contains [OH
-
]
= Initial [NaOH].

NaOH
(s)
 Na
+
(aq)
+ OH
-
(aq)

A 0.10 M solution of NaOH contains [OH
-
] = 0.10 M.

- Among the hydroxides of the alkaline earth metals, Ca(OH)
2
, Sr(OH)
2
, and Ba(OH)
2

are also relatively strong bases. When completely dissolved, these bases produce
two moles of OH
-
per mole of the base:

Ba(OH)
2(aq)
 Ba
2+
(aq)
+ 2 OH
-
(aq)

A 0.10 M Ba(OH)
2
solution contains 0.20 M of OH
-
ions.

- The hydroxides of other metals are only slightly soluble. Even in a saturated solution,
the concentration of OH
-
is still quite low. For example, a saturated solution of
Mg(OH)
2
has [OH
-
] ~ 3.1 x 10
-4
M.
Weak Bases
Ammonia is the only weak base that is of commercial importance. Ammonia is very
soluble in water and ionizes as follows:
NH
3(aq)
+ H
2
O
(l)
⇋ NH
4
+
(aq)
+ OH
-
(aq)

The base dissociation constant, K
b
, is given by the expression:
K
b
=
] NH [
3
]
-
OH ][
4
[NH
+
= 1.8 x 10
-5

The concentration of OH
-
of a weak base solution, such as NH
3
(aq), depends on its K
b
and
the initial concentration of the base. For example, to determine [OH
-
], pOH and pH of 0.10
M NH
3
(aq), we can set up the following “ICE” table:

Concentration: NH
3(aq)
+ H
2
O
(l)
⇋ NH
4
+
(aq)
+ OH
-
(aq)

÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
Initial [ ], M: 0.10 0.00 0.00
Change, A[ ], M: -x + x + x
Equilibrium [ ], M : (0.10 - x) x x
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
K
b
= [NH
4
+
][OH
-
] = x
2
= 1.8 x 10
-5

[NH
3
] (0.10 – x)
Using approximation, K
b
= x
2
~ x
2
/0.10 = 1.8 x 10
-5
;
(0.10 – x)
 x
2
= (0.10)(1.8 x 10
-5
); x = \(1.8 x 10
-6
) = 1.3 x 10
-3

where, x = [OH
-
] = 1.3 x 10
-3
M;  pOH = - log(1.3 x 10
-3
) = 2.87;  pH = 11.13
For ammonia solution at 0.10 M concentration, the percent dissociation is:
Percent dissociation = 1.3 x 10
-3
M x 100% = 1.3%
0.10 M

MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
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Like weak acids, the percent dissociation of weak bases depends on the K
b
of the base and
the degree of dilution – larger K
b
and higher dilution  higher percent dissociation.

Exercise:
1. What is [OH
-
] in 0.0055 M KOH and what is the pH of the solution?

2. What is [OH
-
] in a 0.020 M solution of Ba(OH)
2
? What is the pH of this solution?

3. A 0.10 M solution of methylamine, CH
3
NH
2
is 6.5% ionized at 25
o
C. Determine the K
b

for methylamine? What is the pH of this solution? (Answer: K
b
= 4.5 x 10
-4
; pH =
11.81)
CH
3
NH
2(aq)
+ H
2
O
(l)
⇋ CH
3
NH
3
+
(aq)
+ OH
-
(aq)

_____________________________________________________________________
Polyprotic Acids
Acids such as HCl, HF, HOCl, HNO
2
, HC
2
H
3
O
2
, and other similar type of acids are
called monoprotic acids - each contains a single ionizable hydrogen ion. Some acids contain
more than one ionizable hydrogen, and they are called polyprotic acids. Examples of
polyprotic acids are H
2
SO
4
, H
2
SO
3
, H
2
C
2
O
4
, and H
3
PO
4
. In each case, the hydrogen ionizes in
stages and with different ionization constant, such as the following example with H
3
PO
4
:
H
3
PO
4(aq)
⇋ H
+
(aq)
+ H
2
PO
4
-
(aq)
; K
a1
= 7.5 x 10
-3
;
H
2
PO
4
-
(aq)
⇋ H
+
(aq)
+ HPO
4
2-
(aq)
; K
a2
= 6.2 x 10
-8
;
HPO
4
2-
(aq)
⇋ H
+
(aq)
+ PO
4
3-
(aq)
; K
a3
= 4.8 x 10
-13
;
Acid strength decreases in the order: H
3
PO
4
>> H
2
PO
4
-
>> HPO
4
2-
;

Sulfuric acid is a strong acid because the first hydrogen ionizes completely:
H
2
SO
4
(aq)  H
+
(aq) + HSO
4
-
(aq); K
a1
= very large
However, the second hydrogen does not dissociate complete. Thus, HSO
4
-
is a weak acid,
which dissociates as follows:
HSO
4
-
(aq)
⇋ H
+
(aq)
+ SO
4
2-
(aq)
; K
a2
= 1.2 x 10
-2

Exercise:
1. What is [H
+
], [HSO
4
-
], and [SO
4
2-
] in 0.10 M H
2
SO
4
(aq)? What is the pH of the
solution? (K
a1
is very large; K
a2
= 1.2 x 10
-2
) (Answer: pH = 0.96)

2. What is the pH of 0.10 M oxalic acid, H
2
C
2
O
4
, and what is [C
2
O
4
2-
] in this solution?
(K
a1
= 6.5 x 10
-2
; K
a2
= 6.1 x 10
-5
)
(Answer: [H
+
] = 0.054 M; pH = 1.26; [C
2
O
4
2-
] = 6.1 x 10
-5
M)
_________________________________________________________________________

Acid-Base Properties of Salts
When salts (ionic compounds) dissolve in water, we assume that they completely dissociate
into separate ions. Some of these ions can react with water and behave as acids or bases.
Salts are also products of acid-base reactions. The acidic or basic nature of a salt solution
depends on whether it is a product of:
- a strong acid-strong base reaction;
- a weak acid-strong base reaction;
- a strong acid-weak base reaction, or
- a weak acid-weak base reaction.

MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
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Salts of Strong Acid-Strong Base Reactions: such as NaCl, NaNO
3
, KBr, etc.
- This type of salt forms a solution that is neutral, because neither the cation ion nor
the anion reacts with water and offset the equilibrium between the H
3
O
+
and OH
-

concentrations in the aqueous solution.

Salts of Weak Acid-Strong Base Reactions: such as NaF, NaNO
2
, NaC
2
H
3
O
2
, etc.
- A salt that is the product of a reaction between a weak acid and a strong base will
form an aqueous solution that is basic in nature.

- the anion of such salt reacts with water to increase [OH
-
].
For example, Sodium acetate (NaC
2
H
3
O
2
) is a product of reaction between a weak acid
(HC
2
H
3
O
2
) and a strong base (NaOH).

HC
2
H
3
O
2(aq)
+ NaOH
(aq)
 NaC
2
H
3
O
2(aq)
+ H
2
O
(l)


When sodium acetate is dissolved in water, it dissociates into sodium and acetate ions:
NaC
2
H
3
O
2(aq)
 Na
+
(aq)
+ C
2
H
3
O
2
-
(aq)


The acetate ion undergoes hydrolysis in aqueous solution as follows:
C
2
H
3
O
2
-
(aq)
+ H
2
O
(l)
⇋ HC
2
H
3
O
2(aq)
+ OH
-
(aq)
; K
b
= [HC
2
H
3
O
2
][OH
-
]
[C
2
H
3
O
2
-
]
Note the for the dissociation of acetic acid:
HC
2
H
3
O
2(aq)
+ H
2
O
(l)
⇋ H
3
O
+
(aq)
+ C
2
H
3
O
2
-
(aq)
; K
a
= [H
3
O
+
][C
2
H
3
O
2
-
]
[HC
2
H
3
O
2
]
K
a
x K
b
= [H
3
O
+
][C
2
H
3
O
2
-
] x [HC
2
H
3
O
2
][OH
-
] = [H
3
O
+
][OH
-
] = K
w
= 1.0 x 10
-14

[HC
2
H
3
O
2
] [C
2
H
3
O
2
-
]
Thus, for C
2
H
3
O
2
-
, K
b
(for = K
w
= 1.0 x 10
-14
= 5.6 x 10
-10

K
a

(for HC2H3O2)
1.8 x 10
-5
Thus, the hydrolysis of acetate ion has K
b
= 5.6 x 10
-10
(> K
w
), which implies that the
solution of sodium acetate will be basic (pH > 7).
Salts of Strong Acid-Weak Base Reactions: NH
4
Cl, NH
4
NO
3
, (CH
3
)
2
NH
2
Cl, C
5
H
5
NHCl.
- Aqueous solutions of this type of salts are acidic, because the cation (such as NH
4
+

ion) is the conjugate acid of a weak base (NH
3
)
- the cations react with water, which increases [H
3
O
+
] in solutions.

For example, ammonium chloride, NH
4
Cl, is produced by the reaction of a strong acid HCl
and a weak base NH
3
.

HCl
(aq)
+ NH
3(aq)
 NH
4
Cl
(aq)
 NH
4
+
(aq)
+ Cl
-
(aq)


In an aqueous solution, ammonium ion (NH
4
+
) establishes the following equilibrium that
increases [H
3
O
+
] and makes the solution acidic:
NH
4
+
(aq)
+ H
2
O
(l)
⇋ H
3
O
+
(aq)
+ NH
3(aq)
; K
a
= [H
3
O
+
][NH
3
]
[NH
4
+
]
For the reaction of NH
3
with water, the following equilibrium occurs:
NH
3(aq)
+ H
2
O
(l)
⇋ NH
4
+
(aq)
+ OH
-
(aq)
; K
b
= [NH
4
+
][OH
-
]
[NH
3
]
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
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Ph-0744-2407906 Mo-93149-05055.
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K
a
x K
b
= [H
3
O
+
][NH
3
] x [NH
4
+
][OH
-
] = [H
3
O
+
][OH
-
] = K
w
= 1.0 x 10
-14

[NH
4
+
] [NH
3
]
Thus, for NH
4
+
, K
a
= K
w
= 1.0 x 10
-14
= 5.6 x 10
-10

K
b
(for NH
3
) 1.8 x 10
-5
Thus, the hydrolysis of ammonium ion has K
a
= 5.6 x 10
-10
(> K
w
), which implies that
aqueous solution of ammonium chloride will be acidic (pH < 7).

Salts of Weak Acid-Weak Base Reactions: such as NH
4
C
2
H
3
O
2
, NH
4
CN, NH
4
NO
2
, etc..
- Aqueous solutions of this type of salts can either be neutral, acidic, or basic,
depending on the relative magnitude of the K
a
of the weak acid and the K
b
of the
weak base.
- If K
a
~ K
b
, the salt solution will be approximately neutral;
- If K
a
> K
b
, the salt solution will be acidic, and
- If K
a
< K
b
, the salt solution will be basic.

For example, K
a
of HC
2
H
3
O
2
= 1.8 x 10
-5
, K
b
of NH
3
= 1.8 x 10
-5
, and aqueous solution of
ammonium acetate, NH
4
C
2
H
3
O
2
, is approximately neutral.

NH
4
C
2
H
3
O
2(aq)
 NH
4
+
(aq)
+ C
2
H
3
CO
2
-
(aq)

NH
4
+
(aq)
+ H
2
O
(l)
⇋ H
3
O
+
(aq)
+ NH
3(aq)
; K
a
= 5.6 x 10
-10
;
C
2
H
3
O
2
-
(aq)
+ H
2
O
(l)
⇋ HC
2
H
3
O
2(aq)
+ OH
-
(aq)
; K
b
= 5.6 x 10
-10
;
K
a
=K
b
 a neutral solution, because the hydrolyses result in a solution with [H
3
O
+
] = [OH
-
].

For NH
4
CN, K
a
(HCN) = 6.2 x 10
-10
, K
b
(NH
3
) = 1.8 x 10
-5
, and aqueous solution of NH
4
CN
will be basic.
NH
4
CN
(aq)
 NH
4
+
(aq)
+ CN
-
(aq)

NH
4
+
(aq)
+ H
2
O
(l)
⇋ H
3
O
+
(aq)
+ NH
3(aq)
; K
a
= 5.6 x 10
-10
;
CN
-
(aq)
+ H
2
O
(l)
⇋ HCN
(aq)
+ OH
-
(aq)
; K
b
= 1.6 x 10
-5
; K
a
< K
b
 basic
solution, because the hydrolyses result in a solution in which [H
3
O
+
] < [OH
-
].
For NH
4
NO
2
, K
a
(HNO
2
) = 4.0 x 10
-4
, K
b
(NH
3
) = 1.8 x 10
-5
, and aqueous solution of NH
4
NO
2

will be acidic.
NH
4
NO
2(aq)
 NH
4
+
(aq)
+ NO
2
-
(aq)

NH
4
+
(aq)
+ H
2
O
(l)
⇋ H
3
O
+
(aq)
+ NH
3(aq)
; K
a
= 5.6 x 10
-10
;
NO
2
-
(aq) + H
2
O
(l)
⇋ HNO
2(aq)
+ OH
-
(aq)
; K
b
= 2.5 x 10
-11
;
K
a
> K
b
 acidic solution, because the hydrolyses result in a solution with [H
3
O
+
] > [OH
-
].

Calculating the pH of a Basic or an Acidic salt Solution
1. Consider a solution of 0.050 M sodium acetate, which dissociates completely as follows:
NaC
2
H
3
O
2(aq)
 Na
+
(aq)
+ C
2
H
3
O
2
-
(aq)


The acetate ion undergoes hydrolysis in aqueous solution as follows:
C
2
H
3
O
2
-
(aq)
+ H
2
O
(l)
⇋ HC
2
H
3
O
2(aq)
+ OH
-
(aq)
; K
b
= [HC
2
H
3
O
2
][OH
-
] = 5.6 x 10
-10

[C
2
H
3
O
2
-
]
By approximation, [OH
-
] = \(K
b
[C
2
H
3
O
2
-
]) = \{(5.6 x 10
-10
)(0.050)} = 5.3 x 10
-6
M
pOH = -log(5.3 x 10
-6
) = 5.28, and pH = 8.72, ( a basic solution)
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
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14

2. Consider a solution of 0.050 M NH
4
Cl, which dissociates as follows:
NH
4
Cl
(aq)
 NH
4
+
(aq)
+ Cl
-
(aq)

In an aqueous solution, the following equilibrium occurs:
NH
4
+
(aq)
+ H
2
O
(l)
⇋ H
3
O
+
(aq)
+ NH
3(aq)
; K
a
= [H
3
O
+
][NH
3
] = 5.6 x 10
-10

[NH
4
+
]
By approximation, [H
3
O
+
] = \(K
a
[NH
4
+
]) = \{(5.6 x 10
-10
)(0.050)} = 5.3 x 10
-6
M
pH = -log(5.3 x 10
-6
) = 5.28, ( an acidic solution)
Exercise:
1. Predict whether aqueous solution of each of the following salts is acidic, basic, or
neutral?
(a) KNO
3
(b) CH
3
NH
3
Cl (c) Na
2
SO
3
(d) (NH
4
)
2
HPO
4

K
a
(for HSO
3
-
) = 1.0 x 10
-7
; K
a
(for H
2
PO
4
-
) = 6.2 x 10
-8
; K
b
(for CH
3
NH
2
) = 4.4 x 10
-4


2. Calculate the pH of a solution that is 0.10 M in sodium cyanide, NaCN(aq).
(K
a
for HCN = 6.2 x 10
-10
) (Answer: pH = 11.10)

3. What is the pH of a solution containing 1.5 g of pyridinium chloride, C
5
H
5
NHCl, in
100.0 mL solution? (K
b
of C
5
H
5
N = 1.7 x 10
-9
) In aqueous solution C
5
H
5
NHCl
dissociates as follows:
C
5
H
5
NHCl(aq)  C
5
H
5
NH
+
(aq) + Cl
-
(aq) (Answer: pH = 3.56)
________________________________________________________________________
The Common Ion Effect in Acid-Base Equilibria

Common ions are ions produced by more than one solute in the same solution. For
example, in a solution containing sodium acetate and acetic acid, the acetate ion (C
2
H
3
O
2
-
)
is the common ion. According to the Le Chatelier's principle, the following equilibrium for
acetic acid:
HC
2
H
3
O
2(aq)
+ H
2
O
(l)
⇌ H
3
O
+
(aq)
+ C
2
H
3
O
2
-
(aq)


will shift to the left if C
2
H
3
O
2
-
(from another source) is added to the solution. This will reduce
the acid dissociation, which lowers [H
3
O
+
] and increases the pH of the solution.

Addition of ammonium chloride, NH
4
Cl, to ammonia solution will cause the following
equilibrium to shift to the left:
NH
3(aq)
+ H
2
O
(l)
⇌ NH
4
+
(aq)
+ OH
-
(aq)

NH
4
Cl dissociates to produce NH
4
+
and Cl
-
ions, where NH
4
+
is a common ion in the
equilibrium of ammonia solution. The introduction of NH
4
+
ion reduces the ionization of NH
3
,
which decreases [OH
-
] and lowers the pH of the solution.

Calculating [H
+
] and pH of a solution containing weak acid and the salt of its
conjugate base.
Consider a solution containing 0.10 M HNO
2
and 0.050 M NaNO
2
, where the latter
dissociates completely as follows:
NaNO
2(aq)
 Na
+
(aq)
+ NO
2
-
(aq)


The concentration of H
+
can be calculated using the following “ICE” table:
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
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Concentration: HNO
2(aq)
⇌ H
+
(aq)
+ NO
2
-
(aq)

÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
Initial [ ], M 0.10 0.00 0.050 (from salt)
Change, A[ ], M -x +x +x
Equilibrium [ ], M (0.10 – x) x (0.050 + x)
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷

K
a
=
] [HNO
] ][NO [H
2
-
2
+
=
) - (0.10
) )(0.050 (
x
x x +
= 4.0 x 10
-4

Since K
a
<< 0.10, x is assumed to very small, and by approximation,

) - 0.10 (
) )(0.050 (
x
x x +
~
(0.10)
)(0.050) (x
= 4.0 x 10
-4
;  x = 8.0 x 10
-4

where x = [H
+
] = 8.0 x 10
-4
M, and pH = -log(8.0 x 10
-4
) = 3.10
In general, for a solution containing a weak acid HX, with an dissociation constant K
a
, and
the salt NaX, [H
+
] can be calculated by approximation, such that,
[H
+
] = K
a
x
] [
] [
÷
X
HX

Exercises:
1. What are [H
+
] and pH of a solution containing 4.0 g of sodium acetate (NaC
2
H
3
O
2
) in
1.0 L of 0.050 M HC
2
H
3
O
2(aq)
? (K
a
= 1.8 x 10
-5
for acetic acid)
2. What are [OH
-
], [H
+
], and pH of a solution containing 2.5 g of NH
4
Cl dissolved in 1.0 L
of 0.050 M NH
3(aq)
? (K
b
= 1.8 x 10
-5
for NH
3
)
Buffered Solutions

A buffered solution is one that has the ability to maintain its pH relatively constant even
when a small amount of strong acid or strong base is added.

Buffered solutions contain a comparable amount of weak acid and its conjugate base (or a
weak base and its conjugate acid).

Consider a buffer made up of acetic acid and sodium acetate, in which the major species
present in solution are HC
2
H
3
O
2
and C
2
H
3
O
2
-
.

If a little HCl is added to this solution, most of H
+
(from HCl) is absorbed by the conjugate
base, C
2
H
3
O
2
-
, in the following reaction:

H
+
(aq)
+ C
2
H
3
O
2
-
(aq)
 HC
2
H
3
O
2
-
(aq)


Since C
2
H
3
O
2
-
is present in a much larger quantity than the added H
+
, the above reaction is
considered to go almost completely to the right. This buffering reaction prevents a
significant increase in [H
+
] and minimizes the change in its pH.

If a strong base such as NaOH is added, most of the OH
-
ions (from NaOH) are reacted by
the acid component of the buffer as follows:

OH
-
(aq)
+ HC
2
H
3
O
2(aq)
 H
2
O + C
2
H
3
O
2
-
(aq)
.
Again, because of the larger concentration of HC
2
H
3
O
2

compared to OH
-
, this reaction also
goes almost to completion. This buffering reaction prevents a large increase in the [OH
-
]
and minimizes any change in the pH of the solution.

MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
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Buffer solution is generally prepared by dissolving a mixture of either a weak acid and a
"salt" that contains its conjugate base, or a weak base and a "salt" that contains its
conjugate acid, in the desired molar ratio to obtain the correct pH. A given buffer is effective
within a range of pH that is typically within approximately ±1 of the pK
a
of its acid
component.

Examples of some common buffer systems:
Buffer pK
a
pH Range_____
HCHO
2
– NaCHO
2
3.74 2.75 – 4.75
HC
2
H
3
O
2
– NaC
2
H
3
O
2
4.74 3.75 – 5.75
KH
2
PO
4
- K
2
HPO
4
7.21 6.20 – 8.20 (one of the buffer systems in blood);
CO
2
/H
2
O – NaHCO
3
6.37 5.40 – 7.40 (one of the buffer systems in blood)
NH
3
- NH
4
Cl 9.25 8.25 – 10.25
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷

Calculating The [H
+
] and pH of Buffer Solutions:
For a buffer containing the weak acid HB and the salt NaB, such that B
-
is the
conjugate base to the acid, the concentration [H
+
] and pH of the buffer depend on the
dissociation constant, K
a
, of the acid component and the concentration ratio [B
-
]/[HB] in the
buffer solution.
Consider the equilibrium: HX
(aq)
⇌ H
+
(aq)
+ X
-
(aq)
; K
a
=
] [
] ][ [
HX
X H
÷ +

Re-arranging, we obtain, [H
+
] = K
a
x
] [
] [
÷
X
HX
;  pH = pK
a
+ log(
] [
] [
÷
X
HX
)
The last expression is called the Henderson-Hasselbalch equation, which is useful for
calculation the pH of solutions when the ratio [X
-
]/[HX] is known. For a given buffer
system, [H
+
] and pH varies with the ratio: [Base]/[Acid].
Exercise:
1. A 100.0 mL buffer solution contains 5.0 g of 0.038 mol acetic acid and 0.061 mol of
sodium acetate. Calculate the pH of the buffer? (K
a
= 1.8 x 10
-5
for acetic acid)
If 0.0050 mol of HCl is added to the buffer, what is the final pH of the solution?
(Assume that the volume of buffer does not change when HCl(aq) is added.)

2. A buffer solution is prepared by mixing 25 mL of 0.20 M H
2
SO
3
and 75 mL of 0.20 M
NaHSO
3
. Calculate the pH of this buffer. (K
a
= 1.5 x 10
-2
for H
2
SO
3
)

3. (a) Suppose you want to prepare a 100-mL buffer solution with pH = 7.30, which
buffer system would you consider? [Hint: look for acids that have pK
a
close to the
buffer pH.] (b) Calculate the ratio [Base]/[Acid] that the buffer should have. (c) If the
concentration of the acid is 0.50 M, what should be the base concentration?
(d) Assuming your starting materials are solids, how many grams of each must be
dissolved to make the 100. mL buffer solution? (Both acid and its conjugate base may
be in the form of sodium or potassium salts)
Buffering Capacity
The buffering capacity of a solution represents the amount of H
+
and/or OH
-
the
buffer solution can absorb without significantly altering its pH. A buffer that contains large
concentrations of buffering components and able to absorb significant quantities of strong
acid or strong base with little change in its pH is said to have a large buffering capacity.
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
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Ph-0744-2407906 Mo-93149-05055.
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Whereas the pH of a buffered solution is determined by the ratio [X
-
]/[HX], buffer capacity is
determined by the sizes of [HX] and [X
-
] in the buffer.

Calculating the change in pH of buffered solution after a strong acid is added:
1. Calculate the change in pH that occurs when 0.010 mol of HCl is added to 1.0 L of each
of the following buffers:

Buffer-A: 1.0 M HC
2
H
3
O
2
+ 1.0 M NaC
2
H
3
O
2
;
Buffer-B: 0.020 M HC
2
H
3
O
2
+ 0.020 M NaC
2
H
3
O
2

Solutions
For these buffers the pH can be calculated using the Henderson-Hasselbalch equation:
pH = pK
a
+ log([C
2
H
3
O
2
-
]/[HC
2
H
3
O
2
]) = -log(1.8 x 10
-5
) + log(1) = 4.74

When 0.010 mol HCl is added to Buffer-A, the following reaction takes place:
H
+
(aq)
+ C
2
H
3
O
2
-
(aq)
( HC2H3O2(aq)

[ ] before reaction: 0.010 M 1.0 M 1.0 M
[ ] after reaction: 0 0.99 M 1.01 M

The new pH = 4.74 + log(0.99/1.01) = 4.74 - 0.010 = 4.73 (pH is hardly changed ~ 0.21%)

When 0.010 mol HCl is added to Buffer-B, the following reaction takes place:
H+(aq) + C2H3O2-(aq) ( HC2H3O2(aq)
[ ] before reaction: 0.010 M 0.020 M 0.020 M
[ ] after reaction: 0 0.010 M 0.030 M
New pH = 4.74 + log(0.010/0.030) = 4.74 – 0.48 = 4.26 (pH decreases by 0.48 unit or 10%)
This shows that Buffer-A, which contains larger quantities of buffering components, has a much
higher buffering capacity that Buffer-B. For the Buffer-A to decrease its pH by 0.48 unit (or
10%), it would have to absorb the equivalent of 0.50 mol of HCl.

Exercise
1. An acetate buffer solution is prepared by mixing 35.0 mL of 1.0 M HC2H3O2 and 65.0 mL
of 1.0 M NaC2H3O2. Calculate the pH of this buffer. If 1.0 mL of 6.0 M HCl is added to the
buffer solution, what will be the new pH of the buffer.

2. A 100-mL buffer solution contains 0.20 M KH
2
PO
4
and 0.32 M K
2
HPO
4
. What is the pH
of the buffer? If 0.0050 mol of HCl is added to the buffer without changing its volume,
what is the final pH of the buffer? (K
a
= 6.2 x 10
-8
for H
2
PO
4
-
)
_________________________________________________________________________

Titration and pH Curves
A pH curve is a graph of pH versus the volume of titrant in an acid-base titration.
The data used to plot a pH curve may be obtained either by computation or by measuring
the pH directly with a pH meter during titration.

There are four types of pH curves for the different types of acid-base titration:
- 1. strong acid - strong base titration.
- 2. strong acid - weak base titration.
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
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18
- 3. weak acid - strong base titration.
- 4. weak acid - weak base titration.
(MEMORIZE AND UNDERSTAND THE GENERAL SHAPES AND FEATURES OF EACH pH
CURVES!)
Strong Acid-Strong Base Titration
Net reaction: H
+
(aq)
+ OH
-
(aq)
 H
2
O
(l)

Calculating The pH of Solutions During Titration:
Consider the titration of 20.0 mL of 0.100 M HCl with 0.100 M NaOH solution.
Calculate the pH of the solution: (a) before any of the NaOH is added; (b) after 15.0 mL of
NaOH is added; (c) after 19.5 mL of NaOH is added; (d) after 20.0 mL of NaOH is added;
(e) after 21.0 mL of NaOH is added.

(a) Before titration, [H
+
] = 0.100 M,  pH = 1.000

(b) After 15.0 mL of NaOH is added, calculation of [H
+
] will be as follows:
H
+
(aq)
+ OH
-
(aq)
 H
2
O
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
[ ] before mixing: 0.100 M 0.100 M
[ ] after mixing, but
before reaction: 0.057 M 0.043 M
[ ] after reaction: 0.014 M 0.000
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
[H
+
] = 0.014 M,  pH = -log(0.014) = 1.85
(c) After 19.0 mL of NaOH is added, calculation of [H
+
] will be as follows:
H
+
(aq)
+ OH
-
(aq)
 H
2
O
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
[ ] before mixing: 0.100 M 0.100 M
[ ] after mixing, but
before reaction: 0.051 M 0.049 M
[ ] after reaction: 0.002 M 0.000
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷

[H
+
] = 0.002 M,  pH = -log(0.002) = 2.70
(d) After 20.0 mL of NaOH is added, calculation of [H
+
] will be as follows:
H
+
(aq)
+ OH
-
(aq)
( H2O
[ ] before mixing: 0.100 M 0.100 M
[ ] after mixing, but
before reaction: 0.050 M 0.050 M
[ ] after reaction: 0.000 M 0.000

At this point, the solution contains only water and salt (NaCl) and [H+] = [OH-] = 1.0 x 10-7 M,
which is due to water ionization. The pH of the solution will be 7.00 (pH of neutral solution)

(e) When 21.0 mL of 0.100 M NaOH has been added, there will be excess OH-:
H+(aq) + OH-(aq) ( H2O
[ ] after mixing, but
before reaction: 0.049 M 0.051 M
[ ] after reaction: 0.000 0.002 M
[OH-] = 0.002 M, ( pOH = 2.70, and pH = 11.30
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
H.O-2 N 12 Rangbari Yojana , Kota B.O-1D 10 Talwandi main Road, Kota
Ph-0744-2407906 Mo-93149-05055.
19
Note that in strong acid-strong base titration, an abrupt change from about pH 3 to 11 occurs
within (0.5 mL of NaOH added near the equivalent point. All strong acid-strong base titration
have the same pH curves.
Weak Acid-Strong Base Titration
Net reaction: HX(aq) + OH-(aq) ( H2O + X-(aq)
For example, when acetic acid is titrated with sodium hydroxide, the net reaction is
HC2H3O2(aq) + OH-(aq) ( C2H3O2-(aq) + H2O

1. Consider the titration of 20.0 mL of 0.100 M HC2H
3
O
2
with 0.100 M NaOH solution.
Calculate the pH of the solution: (a) before any of the NaOH is added; (b) after 10.0 mL
of NaOH is added; (c) after 15.0 mL of NaOH is added; (d) after 20.0 mL of NaOH is
added; (e) after 25.0 mL of NaOH is added.

Solution:
(a) Before titration, [H
+
] = \{(0.100 M)(1.8 x 10
-5
)} = 1.34 x 10
-3
M,
pH = -log(1.34 x 10
-3
) = 2.873

(b) After adding 10.0 mL of 0.100 M NaOH, [H
+
] is calculated as follows:
Concentration, M: HC
2
H
3
O
2(aq)
+ OH
-
(aq)
 C
2
H
3
O
2
-
(aq)
+ H
2
O
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
Before mixing: 0.100 0.100 0.000
After mixing, before rxn: 0.0667 0.0333 0.000
After reaction: 0.0333 0.000 0.0333
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
Using Henderson-Hasselbalch equation,
[H
+
] = K
a
x
] O H [C
] O H [HC
-
2 3 2
2 3 2
= 1.8 x 10
-5
x
M) (0.033
M) 033 . 0 (
= 1.8 x 10
-5
M
pH = pK
a
+ log(
] O H [C
] O H [C
2 3 2
-
2 3 2
= 4.74 + log(1) = 4.74

When a weak acid is half-neutralized, 50% of the acid is converted to its conjugate base.
That is, at half-way to the equivalent point of the titration, [C
2
H
3
O
2
-
] = [HC
2
H
3
O
2
]. Under
this condition, [H
+
] = K
a
, and pH = pK
a
.

(c) At the equivalent point (when 20.0 mL of 0.100 M NaOH has been added), all of the acid
is converted to its conjugate base. The latter undergoes hydrolysis as follows:
C
2
H
3
O
2
-
(aq)
+ H
2
O
(l)
⇌ HC
2
H
3
O
2(aq)
+ OH
-
(aq)

———————————————————————————————————
Initial [ ], M: 0.0500 0.000 0.000
Change, A[ ], M: -x +x +x
Equilibrium [ ], M: (0.0500 – x) x x
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
By approximation, [OH
-
] = x =
0
-
2 3 2
] O H [C x
b
K = )(0.050) 10 x 5.6 (
-10
= 5.3 x 10
-6
M
pOH = -log(5.3 x10
-6
) = 5.28;  pH = 8.72

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The hydrolysi of the conjugate base of a weak acid produces OH
-
, which leads to pH > 7 at
the equivalent point. In the case of acetic-NaOH titration, the pH at the equivalent point is
about 8.72. The larger the K
a
of the weak acid, the closer the pH to 7 at equivalent point.
The smaller K
a
, the higher the pH than 7 at equivalent point.

Exercise
1. In a titration of 20.00 mL of 0.100 M formic acid, HCHO
2
, with 0.100 M NaOH,
calculate the pH: (a) before NaOH was added; (b) after 15.00 mL of NaOH is added;
(b) after 20.00 mL of NaOH is added. (K
a
= 1.8 x 10
-4
for HCHO
2
)

2. In a titration of 20.00 mL of 0.100 M NH
3
(aq) with 0.100 M HCl(aq), calculate the pH:
(a) before titration begins; (b) after 10.0 mL of HCl(aq) is added; (c) at equivalent
point, that is after 20.0 mL of HCl(aq) is added. (K
b
= 1.8 x 10
-5
for NH
3
)

_________________________________________________________________________

The Use of Indicators in Acid-Base Titration
- An indicator - a substance that changes color to mark the end-point of a titration.
- Most indicators used in acid-base titration are weak organic acids.
- Indicators exhibit one color in the acid or protonated form (HIn) and another in the
base or deprotonated form (In
-
).
- Each indicator has a range of pH = pK
a
± 1, where the change of colors occurs;
- A suitable indicator gives the end-point that corresponds to the equivalent point of
the titration; this would be one with a range of pH that falls within the sharp increase
(or decrease) of pH in the titration curves.

Like a weak acid, an indicator exhibits the following equilibrium in aqueous solution:
HIn
(aq)
⇌ H
+
(aq)
+ In
-
(aq)
;
K
a
=
[HIn]
] ][In [H
- +
;
Re-arranging, we obtain [H
+
] = K
a
x ([HIn]/[In
-
]);  pH = pK
a
+ log(
[HIn]
] In [
-
)
When [HIn] = 10 x [In
-
],
pH = pK
a
+ log(
[HIn]
] In [
-
) = pK
a
- 1; indicator assumes the color of acid form

When [In
-
] = 10 x [HIn],
pH = pK
a
+ log(
[HIn]
] In [
-
) = pKa + 1; indicator assumes the color of base.

Phenolphthalein, which is the most common acid-base indicator, has K
a
~ 10
-9
. Its acid form
(HIn) is colorless and the conjugate base form (In
-
) is pink. It is colorless when the solution
pH < 8, that is when 90% or more of the species are in the acid form (HIn), and pink at pH
> 10, when 90% or more of the species are in the conjugate base form (In
-
). The pH range
at which an indicator changes depends on the K
a
. For phenolphthalein with K
a
~ 10
-9
, its
color changes at pH = 8 – 10. It is suitable for strong acid-strong base titration and weak
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acid-strong base titration. The range of pH for other common acid-base indicators are listed
below:
Indicators: Acid Color Base Color pH Range Type of Titration
Methyl orange orange yellow 3.2 – 4.5 strong acid-strong base
strong acid-weak base
Bromocresol green yellow blue 3.8 – 5.4 strong acid-strong base
strong acid-weak base
Methyl red Red Yellow 4.5 - 6.0 strong acid-strong base
strong acid-weak base
Bromothymol blue Yellow blue 6.0 - 7.6 strong acid-strong base
Phenol Red orange red 6.8 – 8.2 strong acid-strong base
weak acid-strong base
Solubility Equilibria

Solubility Equilibria and the Solubility Product Constants
When a slightly soluble salt such as silver chloride, AgCl, is dissolved in water, a
saturated is quickly obtained, because only a very small amount of the solid dissolves, while the
rest remains undissolved. The following equilibrium between solid AgCl and the free ions occurs
in solution:
AgCl(s) ⇌ Ag+(aq) + Cl-(aq);
K
sp
= [Ag
+
][Cl
-
]

K
sp
is called the solubility product constant or just solubility product.

General Expressions of Solubility Product Constant, K
sp

For solubility equilibrium: M
a
X
b(s)
⇌ aM
b+
(aq)
+ bX
a-
(aq)
,
K
sp
= [M
b+
]
a
[X
a-
]
b
A. For ionic equilibria of the type: MX
(s)
⇌ M
n+
(aq)
+ X
n-
(aq)
; K
sp
= [M
n+
][X
n-
]
If the solubility of compounds is S mol/L, K
sp
= S
2
;  S = \(K
sp
)
For example, the solubility equilibrium for BaSO
4
is
BaSO
4(s)
⇌ Ba
2+
(aq)
+ SO
4
2-
(aq)
; K
sp
= [Ba
2+
][SO
4
2-
] = 1.5 x 10
-9

If the solubility of BaSO
4
is S mol/L, a saturated solution of BaSO
4
has
[Ba
2+
] = [SO
4
2-
] = S mol/L, K
sp
= S
2
; and S = \(K
sp
) = \(1.5 x 10
-9
) = 3.9 x 10
-5

mol/L

B. For ionic equilibria of the type: MX
2(s)
⇌ M
2+
(aq)
+ 2X
-
(aq)
, K
sp
= [M
2+
][X
-
]
2
;
and for the type: M
2
X
(s)
⇌ 2 M
+
(aq)
+ X
2-
(aq)
; K
sp
= [M
+
]
2
[X
2-
]
For both types, if the solubility is S mol/L, K
sp
= 4S
3
;  S = (K
sp
/4)
1/3
For example, CaF
2(s)
⇌ Ca
2+
(aq)
+ 2F
-
(aq)
; K
sp
= [Ca
2+
][F
-
]
2
= 4.0 x 10
-11

The solubility of calcium fluoride is S = (K
sp
/4)
1/3
= (4.0 x 10
-11
/4)
1/3
= 2.2 x 10
-4
mol/L
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C. For solubility equilibria of the type: MX
3(s)
⇌ M
3+
(aq)
+ 3X
-
(aq)
, K
sp
= [M
3+
][X
-
]
3

Or one of the type: M
3
X
(s)
⇌ 3 M
+
(aq)
+ X
3-
(aq)
, K
sp
= [M
+
]
3
[X
3-
]
If the solubility of the compound (MX
3
or M
3
X) is S mol/L, K
sp
= 27S
4
;  S =
4
) 27 / (
sp
K

For example, Ag
3
PO
4(s)
⇌ 3Ag
+
(aq)
+ PO
4
3-
(aq)
; K
sp
= [Ag
+
]
3
[PO
4
3-
] = 1.8 x 10
-18

The solubility of silver phosphate is
S =
4
) 27 / (
sp
K =
4
-18
)/27 10 x (1.8 = 1.6 x 10
-5
mol/L

D. For solubility equilibria: M
2
X
3(s)
⇌ 2M
3+
(aq)
+ 3X
2-
(aq)
, K
sp
= [M
3+
]
2
[X
2-
]
3

OR, one of the type: M
3
X
2(s)
⇌ 3M
2+
(aq)
+ 2X
3-
(aq)
, K
sp
= [M
2+
]
3
[X
3-
]
2
If the solubility of the compound M
3
X
2
is S mol/L, then [M
2+
] = 3S, and [X
3-
] = 2S;
K
sp
= (3S)
3
(2S)
2
= 108S
5
;  S =
5
108 /
sp
K
For example, Ca
3
(PO
4
)
2(s)
⇌ 3Ca
2+
(aq)
+ 2PO
4
3-
(aq)
,
K
sp
= [Ca
2+
]
3
[PO
4
3-
]
2
= 1.3 x 10
-32
;
 the solubility of Ca
3
(PO
4
)
2
is S =
5
-32
)/108 10 x (1.3 = 1.6 x 10
-7
mol/L

Calculating K
sp
from Solubility
1. Suppose the solubility of PbSO
4
in water is 4.3 x 10
-3
g/100 mL solution at 25
o
C. What
is the K
sp
of PbSO
4
at 25
o
C?

Solution:
Solubility of PbSO
4
in mol/L = 4.3 x 10
-3
g x 1000 mL/L = 1.40 x 10
-4
mol/L
100. mL 303.26 g/mol
That is, a saturated solution of PbSO
4
, contains [Pb
2+
] = [SO
4
2-
] = 1.4 x 10
-4
mol/L
For the equilibrium: PbSO
4(s)
⇌ Pb
2+
(aq)
+ SO
4
2-
(aq)
;
K
sp
= [Pb
2+
][SO
4
2-
] = S
2
= (1.4 x 10
-4
mol/L)
2
= 2.0 x 10
-8


Exercise
1. If the solubility of MgF
2
is 7.3 x 10
-3
g/100 mL solution at 25
o
C, what is the K
sp
of
MgF
2
?

2. A saturated solution of calcium hydroxide has a pH = 12.17. Calculate the solubility of
Ca(OH)
2
and its K
sp
at 25
o
C.

_________________________________________________________________________
Determining Solubility from K
sp

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1. If the K
sp
of Mg(OH)
2
is 6.3 x 10
-10
at 25
o
C, what is its solubility at 25
o
C (a) in mol/L,
and (b) in g/100 mL solution at 25
o
C?

(a) Solubility equilibrium for Mg(OH)
2
is: Mg(OH)
2(s)
⇌ Mg
2+
(aq)
+ 2 OH
-
(aq)

K
sp
= [Mg
2+
][OH
-
]
2
= 4S
3
= 6.3 x 10
-10

Solubility of Mg(OH)
2
: S =
3
4 /
sp
K =
3
-10
)/4 10 x 6.3 ( = 5.4 x 10
-4
mol/L

(b) Solubility in g/100 mL solution = (5.4 x 10
-4
mol/L)(58.32 g/mol)(0.1L/100 mL)
= 3.1 x 10
-3
g/100 mL solution.
Exercise:
1. The K
sp
of PbI
2
is 1.4 x 10
-8
. What is its solubility in grams per 100. mL of solution at
25
o
C?
2. Calcium hydroxide, Ca(OH)
2
, has K
sp
= 1.3 x 10
-6
. How many grams of Ca(OH)
2
can be
dissolved in 250-mL solution to make a saturated solution at 25
o
C?
_________________________________________________________________________
Relative Solubility from K
sp

For compounds whose formula yields the same number of ions, their K
sp
value can be
used to determine relative solubility. That is, larger K
sp
implies greater solubility.

Common Ion Effect of Solubility
The presence of common ion decreases the solubility of a slightly soluble ionic
compound. For example, in the following equilibrium
PbCl
2(s)
⇌ Pb
2+
(aq)
+ 2 Cl
-
(aq)

If some NaCl is added to a saturated solution of PbCl
2
, the [Cl
-
] will increase, and according
to Le Chateliler’s principle, the equilibrium will shift in the direction that tends to reduce [Cl
-
]. In this case, the equilibrium will shift left, to form more PbCl
2
solid, hence decreasing the
amount of PbCl
2
that dissolves into solution.
Sample Problem
The K
sp
of BaSO
4
is 1.5 x 10
-9
at 25
o
C. (a) What is its solubility in water at 25
o
C? (b)
What is the solubility in 0.10 M Na
2
SO
4
at 25
o
C?
Solubility equilibrium for BaSO
4
: BaSO
4(s)
⇌ Ba
2+
(aq)
+ SO
4
2-
(aq)
;
K
sp
= [Ba
2+
][SO
4
2-
] = S
2
= 1.5 x 10
-9

Solubility of BaSO
4
in water is S = \(K
sp
) = \ (1.1 x 10
-10
) = 3.9 x 10
-5
mol/L
Let the solubility of BaSO
4
in 0.10 M Na
2
SO
4
be x mol/L
Then, the solution contains [Ba
2+
] = x mol/L and [SO
4
2-
] = (0.10 + x) mol/L
K
sp
= [Ba
2+
][SO
4
2-
] = (x)(0.10 + x) = 1.5 x 10
-9

By approximation, since x << 0.10 M, (0.10 + x) ~ 0.10, and
K
sp
= (x)(0.10 + x) ~ (x)(0.10) = 1.5 x 10
-9
;  x = 1.5 x 10
-8
mol/L

The Effect of pH on Solubility
pH affect the solubility of slightly soluble compounds containing anions that are
conjugate bases of weak acids, such as F
-
, NO
2
-
, OH
-
, SO
3
2-
, and PO
4
3-
, but not those
containing anions which are conjugate bases of strong acids, such as SO
4
2-
, Cl
-
, Br
-
. For
example, in a saturated solution of calcium fluoride, CaF
2
, the following equilibrium exists:
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CaF
2(s)
⇌ Ca
2+
(aq)
+ 2F
-
(aq)

When a strong acid is added to the saturated solution, the following reaction occurs:
H
+
(aq)
+ F
-
(aq)
 HF
(aq)

This reaction has the net effect of reducing the concentration of F
-
ions, which causes the
equilibrium to shift to the right and resulting in more of CaF
2
to dissolve.

Exercise
1. Calculate the solubility of PbCl
2
(K
sp
= 1.6 x 10
-5
) and AgCl (K
sp
= 1.6 x 10
-10
) in 0.010
M NaCl solution.
2. What is the solubility of CuS (K
sp
= 4 x 10
-37
) and ZnS (K
sp
= 2 x 10
-25
), respectively,
in solution buffered at pH = 8.00? (For H
2
S, K
a1
= 1 x 10
-7
; K
a2
= 1 x 10
-19
)
_________________________________________________________________________
Precipitation and Qualitative Analysis
For solubility equilibrium: M
a
X
b(s)
⇌ aM
+
(aq)
+ bX
-
(aq)
,
We can express the ion product, Q, as follows: Q = [M
+
]
o
a
[X
-
]
o
b
Where [ ]
o
is the initial concentration of each ion in solution.
For a given pair of ions pertaining to a slightly soluble compound, if:
- Q = K
sp
;  solution is saturated, but no precipitate is formed.
- Q > K
sp
;  solution is saturated and a precipitate is formed.
- Q < K
sp
;  solution is not saturated

Sample problem:
If 20.0 mL of 0.050 M Pb(NO
3
)
2
is mixed with 30.0 mL of 0.10 M NaCl, will PbCl
2

precipitate form? K
sp
of PbCl
2
= 1.6 x 10
-5
.
Pb
2+
(aq)
+ 2Cl
-
(aq)
⇌ PbCl
2(s)

[ ] after mixing 0.020 M 0.060 M
Q
sp
= [Pb
2+
][Cl
-
]
2
= (0.020)(0.060)
2
= 7.2 x 10
-5
> K
sp

Q
sp
> K
sp
 PbCl
2
ppt will form.

Exercise:
1. At what pH a solution containg 0.10 M Ca
2+
ions will form a precipitate of Ca(OH)
2
?
(K
sp
= 1.3 x 10
-6
at 25
o
C for Ca(OH)
2
)
2. Will Ag
2
SO
4
precipitate if 30.0 mL of 0.050 M AgNO
3
is added to 20.0 mL of 0.10 M of
Na
2
SO
4
solution? K
sp
= 1.2 x 10
-5
for Ag
2
SO
4
at 25
o
C.
_________________________________________________________________________
Practical Application of Ionic Equilibria
Qualitative Analysis
The presence of certain ions, such as Cl
-
, I
-
, SO
4
2-
, Ag
+
, etc. in water can be
determined qualitatively and quantitatively by precipitation method. Cl
-
and I
-
can be
precipitated as AgCl and AgI, respectively, by adding AgNO
3
solution.

Synthesis
Certain industrial chemicals, such as AgCl, AgBr, AgI, that are needed in
photographic industries are prepared by precipitation.

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AgNO
3(aq)
+ NaBr
(aq)
 AgBr
(s)
+ NaNO
3(aq)

Since the K
sp
of these compounds are very small, the precipitation reaction practically goes
to completion. The separation and purification processes are simple.

Selective Precipitation
Because of the different solubility of compounds, the separation of ions from a
mixture of solution can be accomplished by selectively precipitation. This selective
precipitation is carried out by adding the precipitating ion until the ion product, Q
,
of the
more soluble compound is almost equal to its K
sp
, but the K
sp
of the less soluble compound
is exceeded as much as possible. For example, because of the different solubility of CaSO
4

(K
sp
= 6.1 x 10
-5
), and BaSO
4
(K
sp
= 1.5 x 10
-9
), Ca
2+
and Ba
2+
can be separated from a
solution by selectively precipitating BaSO
4
using Na
2
SO
4
or H
2
SO
4
solution.

Sample problem-3:
An aqueous solution contains Ca
2+
and Ba
2+
ions at concentrations 0.10 M and 0.010
M, respectively. What concentration of SO
4
2-
must be present so that the maximum amount
of Ba
2+
ion precipitates as BaSO
4
, but Ca
2+
remains in solution ? K
sp
of CaSO
4
= 6.1 x 10
-5
;
K
sp
of BaSO
4
= 1.5 x 10
-9
.

Exercise-9:
1. How many grams of AgCl will precipitate out when 50.0 mL of 0.050 M AgNO
3
is added
to 50.0 mL of 0.10 M NaCl? What is the concentration of Ag
+
that remains in solution
after the precipitation? K
sp
= 1.6 x 10
-10
at 25
o
C for AgCl.

2. A solution contains 0.10 M in Cl
-
and 0.010 M in I
-
. At what concentration of Ag
+

would (a) AgI begin to precipitate; (b) AgCl begins to precipitate? What is the
concentration of I
-
when AgCl begins to precipitate? (K
sp
[AgCl] = 1.6 x 10
-10
and
K
sp
[AgI] = 1.5 x 10
-16
)

3. Sea water contains Mg
2+
at a concentration of about 0.015 M. Would precipitate of
Mg(OH)
2
form if a sample of sea water is added to a saturated solution of Ca(OH)
2
?
What concentrion of Mg
2+
is present when the solution is just saturated with Ca(OH)
2
?
(K
sp
= 1.3 x 10
-6
for Ca(OH)
2
; K
sp
= 8.9 x 10
-12
.

÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷

Qualitative Analysis: Identifying Ions in Mixtures of Cations
The separation and identification of ions in a mixture is called qualitative analysis.
The technique employs the different solubility of ionic compounds in aqueous solution as
well as the ability of certain cations to form complex ion with ligands. For many transition
metals, their complex ions are often colored, which can be used in their identification.

Separation into Groups
The general approach in the qualitative analysis of cations is to separate them into
various ion groups.

Ion group 1: Insoluble chlorides. Treating the mixture with 6 M HCl will precipitate Ag
+
,
Hg
2
2+
, and Pb
2+
ions as chlorides, leaving other cations in solution. The formation of a white
precipitate indicates the presence of at least one of these cations in the mixture.

Ion group 2: Acid-insoluble sulfides. The supernatant from the above treatment with HCl is
adjusted to pH ~ 0.5 and then treated with aqueous H
2
S. The high [H
3
O
+
] in solution keeps
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[HS
-
] very low, which precipitates only the following group of cations: Cu
2+
, Cd
2+
, Hg
2+
,
Sn
2+
, and Bi
3+
. Centrifuging and decanting gives the next solution.

Ion group 3: Base-insoluble sulfides. The supernatant from acidic sulfide treatment is
treated with NH
3
/NH
4
+
buffer to make the solution slightly basic (pH~8). The excess OH
-
in
solution increases [HS
-
], which causes the precipitation of the more soluble sulfides and
some hydroxides. The cations that precipitate under this condition are: Zn
2+
, Mn
2+
, Ni
2+
,
Fe
2+
, Co
2+
, as sulfides, and Al
3+
, Cr
3+
, and Fe
3+
as hydroxides. The precipitate is centrifuged
and the supernatant decanted to give the next solution.

Ion group 4: Insoluble phosphates. The slightly basic supernatant separated from the
group 3 ions is treated with (NH
4
)
2
HPO
4
, which precipitates Mg
3
(PO
4
)
2
, Ca
3
(PO
4
)
2
, and
Ba
3
(PO
4
)
2
.

Ion group 5: Alkali metal and ammonium ions. The final solution contains any of the
following ions: Na
+
, K
+
, and NH
4
+
.

Sample qualitative analysis.
A solution contains a mixture of Ag
+
, Al
3+
, Cu
2+
, and Fe
3+
ions. Devise a scheme to
separate and identify each of these cations.

Mixture: Ag
+
, Al
3+
, Cu
2+
, Fe
3+
(colored solution)
add 3 M HCl,
centrifuge



Precipitate (white) Supernatant (colored)
AgCl (Al
3+
, Cu
2+
, Fe
3+
)

add 6 M NaOH,
centrifuge




Precipitates Supernatant (colorless)
(Cu(OH)
2
& Fe(OH)
3
) Al(OH)
4
-

add 6 M NH
3





Precipitate Supernatant
Fe(OH)
3
Cu(NH
3
)
4
2+

(dark brown) (dark blue)
______________________________________________________________________________


Complex Ion Equilibria

15.8 Equilibria Involving Complex Ions
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A complex ion consists of a central metal ion that is covalently bonded to two or
more ligands, which can be anions such as OH
-
, Cl
-
, F
-
, CN
-
, etc. or neutral molecules such
as H
2
O, CO, and NH
3
. For example, in the complex ion [Cu(NH
3
)4]
2+
, Cu
2+
is the central
metal ion with four NH
3
molecules covalently bonded to it.

All complex ions are Lewis adducts; the metal ions act as Lewis acids (electron-pair
acceptors) and the ligands are Lewis bases (electron-pair donors). Only species with at least
one lone-pair electrons can be a ligand.

The Formation of Complex Ion
In aqueous solutions, metal ions form complex ions with water molecules as ligands.
When another ligand is introduced into the solution, ligand exchanges occur and equilibrium
is established. For example, when NH
3
is added to aqueous solution containing Cu
2+
ion, the
following equilibrium occurs:
Cu(H
2
O)
6
2+
(aq)
+ 4 NH
3(aq)
⇌ [Cu(NH
3
)
4
]
2+
(aq)
+ 6H
2
O
K
f
=
4
3
2
6 2
2
4 3
] ][NH O) [Cu(H
] ) [Cu(NH
+
+


At molecular level, the ligand exchange process occurs in stepwise manner; water
molecule is replace with NH
3
molecule one at a time to give a series of intermediate species,
each with its own formation constant. For convenience, the water molecules can be omitted
from the equation.
1. Cu
2+
(aq)
+ NH
3(aq)
⇌ Cu(NH
3
)
2+
(aq)
;
K
f1
=
] ][NH [Cu
] ) [Cu(NH
3
2
2
3
+
+

2. Cu(NH
3
)
2+
(aq)
+ NH
3(aq)
⇌ Cu(NH
3
)
2
2+
(aq)
;
K
f2
=
] ][NH ) [Cu(NH
] ) [Cu(NH
3
2
3
2
2 3
+
+

3. Cu(NH
3
)
3
2+
(aq)
+ NH
3(aq)
⇌ Cu(NH
3
)
4
2+
(aq)
;
K
f4
=
] ][NH ) [Cu(NH
] ) [Cu(NH
3
2
3 3
2
4 3
+
+

The overall formation constant is the product of all intermediate formation constants:
K
f
= K
f1
x K
f2
x K
f3
x K
f4
=
4
3
2
2
4 3
] ][NH [Cu
] ) [Cu(NH
+
+

K
f
is called the formation constant for the complex equilibrium.


Sample problem-4:
If a 30.0-mL solution containing 0.020 M Cu
2+
is mixed with 20.0 mL of 0.20 M NH
3

solution, what is the concentration of Cu
2+
in solution? K
f
= 5.0 x 10
12


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Solution: First calculate the concentration of each species in the solution after mixing, but
before formation of complex ion Cu(NH
3
)
4
2+
:

[Cu
2+
] = 0.020 M x (30.0 mL/50.0 mL) = 0.012 M
[NH
3
] = 0.20 M x (20.0 mL/50.0 mL) = 0.080 M
Write the equilibrium expression:
Cu
2+
(aq)
+ 4 NH
3(aq)
⇌ Cu(NH
3
)
4
2+
(aq)
+ 4 H
2
O
Since K
f
is very large, we can assume that all of Cu
2+
is converted to Cu(NH
3
)
4
2+
.
Then, [Cu(NH
3
)
4
2+
] = 0.012 M and [NH
3
] = 0.080 M – (4 x 0.012 M) = 0.032 M
Next, consider the following (reverse) equilibrium:
Cu(NH
3
)
4
2+
(aq)
⇌ Cu
2+
(aq)
+ 4NH
3(aq)

K
c
=
] ) [Cu(NH
] ][NH [Cu
2
4 3
4
3
2
+
+
= 1/K
f
= 1/(5.0 x 10
12
) = 2.0 x 10
-13
Set up the following equilibrium table:
Concentration (M) Cu(NH
3
)
4
2+
(aq)
⇌ Cu
2+
(aq)
+ 4 NH
3(aq)

÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
Initial: 0.012 M 0.000 0.032 M
Change: - x + x + x
Equilibrium: (0.012 – x) x (0.032 + x)
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷
Since K
c
is very small, we assume that x << 0.012 M,
Then, (0.012 – x) ~ 0.012, and (0.032 + x) ~ 0.032
K
c
=
(0.012)
0.032) )( (
4
x
= 2.0 x 10
-13
;
 x = [Cu
2+
] =
4
-13
(0.032)
)(0.012) 10 x 0 . 2 (
= 2.3 x 10
-9
M
Formation of Complex Ions and the Effect on Solubility
Ligand increases the solubility of slightly soluble ionic compounds if they form
complex ions with the metal ions. For example, silver chloride, AgCl, is more soluble in
ammonia solution because silver ions form complex ions with NH
3
:
AgCl
(s)
⇌ Ag
+
(aq)
+ Cl
-
(aq)
; K
sp
= 1.6 x 10
-10
;
Ag
+
(aq)
+ 2NH
3(aq)
⇌ Ag(NH
3
)
2
+
(aq)
; K
f
= 1.7 x 10
7
;
AgCl
(s)
+ 2NH
3(aq)
⇌ Ag(NH
3
)
2
+
(aq)
+ Cl
-
(aq)
;
K
net
= K
sp
x K
f
= (1.6 x 10
-10
)(1.7 x 10
7
) = 2.7 x 10
-3

Exercise:
1. Calculate the solubility (a) in mol/L and (b) in g/L of AgCl in 2.0 M NH
3(aq)
. What is the
concentration of Ag
+
in this solution? (K
sp
= 1.6 x 10
-10
; K
f
= 1.7 x 10
7
for Ag(NH
3
)
2
+
)

2. Will AgCl precipitates form if 5.0 mL of 0.10 M AgNO
3
is added to 5.0 mL of solution
containing 0.10 NaCl and 2.0 M NH
3
? (b) Will precipitate form if [NH
3
] = 1.0 M?

MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
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3. Calculate the concentrations of Ag
+
, Ag(S
2
O
3
)
-
, and Ag(S
2
O
3
)
2
3-
in a solution prepared
by mixing 20.0 mL of 0.010 M AgNO
3
and 30.0 mL of 2.0 M Na
2
S
2
O
3
?
Ag
+
(aq)
+ S
2
O
3
2-
(aq)
⇌ Ag(S
2
O
3
)
-
; K
f1
= 7.4 x 10
8

Ag(S
2
O
3
)
-
(aq)
+ S
2
O
3
2-
(aq)
⇌ Ag(S
2
O
3
)
2
3-
(aq)
; K
f2
= 3.9 x 10
4

Ag
+
(aq)
+ 2S
2
O
3
2-
(aq)
⇌ Ag(S
2
O
3
)
2
3-
(aq)
; K
f
= 2.9 x 10
13

Miscellenius Problems
PROBLEM. 1. A chemist needs to prepare about 400 mL of a buffer solution of pH
5.0 using acetic acid. What should the weight of sodium acetate (MW 82.034 g/mole)
should be added to 400 mL of 0.1 M acetic acid (MW 60.052 g/mole) solution to prepare
the buffer? (K
a
=1.75X10
-5
for acetic acid.)
Ans 5.76 gram
PROBLEM. 2 20 mL of a diprotic acid, H
2
A, is titrated with 0.1 M NaOH titrant. The
resulting titration curve is shown below.

(a) Label the two points where the solution has the maximum buffer capacity and label
first and second equivalence points as .
(b) Estimate the formal concentration of H
2
A from the graph.
(c) There are simple expressions for the pH at points A, B, and C. Give the equations
below.
(d) Estimate K
a1
and K
a2
for this acid from your estimate of pH at points A, B, and C.
(e) At what indicator pH would you want your color-change indicator to have in order to
titrate to the second equivalence point?
Ans (a) Buffer capacity at A & C
1
st
equivalence point at B 2
nd
at D.
(b) 0.1 M
©
MASTERING PHYSICAL CHEMISTRY By-- S.K.SINHA
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Ph-0744-2407906 Mo-93149-05055.
30

(D)


(e)At pH=10
PROBLEM. 3.Calomel, Hg
2
Cl
2
, (MW 472.09) dissolves to form Hg
2
2+
and chloride with
a K
sp
=1.2? 10
-18
. Calculate the mass of calomel that will dissolve in...
A. 1.00 L pure water Ans. 3.16 x 10
-4
gram
The equilibrium equation is Hg
2
Cl
2
s)<=>Hg
2
2+
(aq) + 2Cl
-
(aq)
B. 1.00 L of a 0.030 M solution of NaCl . ans 6.29 x 10
-13
gram

PROBLEM. 4. Which of the following would be most suitable for preparing a
buffer of pH 2.5? Show your work and briefly state why you chose that species.
1) H
2
C
2
O
4
(K
a1
=5.60? 10
-2
K
a2
=5.42? 10
-5
) 2) H
3
PO
4
(K
a1
=7.11? 10
-3
K
a2
=6.32? 10
-8
)
3) B(OH)
3
(K
a1
=5.81? 10
-10
K
a2
=1.82? 10
-13
) 4) H
2
CO
3
(K
a1
=4.45? 10
-7
K
a2
=1.69? 10
-9
)
Ans
The best acid to use is the one with a pK
a=
pH. Of the choices, H
3
PO
4
, with pK
a1
=2.15,
is the closest to the target value of pH=2.5
Problem-5 A solution was prepared by addition of 0.050 mole NaOH to 500 mL of
a 0.10 M acetic acid (K
a
=1.75? 10
-5
) solution and then diluted to 1 L. Find the pH of
the resulting buffer. Ans 8.7
Problem-6 . 50 mL of a solution containing Cl
-
and Br
-
are titrated with 0.01 M
AgNO
3
solution. The two equivalence points, found using an electrochemical
apparatus, occur at 12.5 mL and 18.0 mL total volume of titrant added. What are
the molar concentrations of Cl
-
and Br
-
in the unknown solution? The silver-halide
solubility products are 1.8? 10
-10
for AgCl and 5.0? 10
-13
for AgBr.
Ans Br- =0.0025 M Cl-= 0.0011 M
PROBLEM-6 . Lanthanum iodate, La(IO
3
)
3
, (M.W. 663.62) has K
sp
=1.0?10
-11
. How many
grams lanthanum iodate will dissolve in...
A) 1.00 L pure water ?
The equilibrium equation is La(IO
3
)
3
(s) ? La
3+
(aq) + 3IO
3
-
(aq) Ans 0.518 gram
B) A solution is prepared by dissolving 9.88 g trichloroacetic acid (M.W. 163.39) in 500
mL solution. At this concentration, the acid is 70% dissociated. What is the Molarity of
trichloroacetate ion? Ans 0.036 Molar