INORGANIC CHEMISTRY II

SMEP METALLURGICAL ENGINEERING

LECTURE SERIES
EQUILIBRIUM PRINCIPLES AND ITS
APPLICATIONS TO IONIC EQUILIBRIA IN
AQUEOUS SOLUTIONS
REACTION RATES
Reaction Rate- describes how fast the
concentration of a reactant or product changes
with time
Rate of change [A] = delta [A]/ delta time
Rate of reaction [A] = - rate of change [A]
Instantaneous Rate of Reaction- determined
from the slope of a tangent lines to a
concentration-time graph
Initial Rate of Reaction- reaction rate when
the reactants are first brought together.
RATE LAW
The rate of reaction depends on the concentrations of
reactants.

aA + bB + gG + hH

The exponents, m,n.. are not generally related to the
stoichiometric coefficients. They are the order of
reactions. The overall order of reaction is the sum of
all the exponents.

Rate constant, k- relates the rate of reaction to
reactant concentrations, the larger the value, the
faster the reaction goes.
ZERO ORDER REACTIONS
The zero-order reaction as a rate equation in which
the sum of the exponents m+n+.. is equal to 0.
A products
The concentration-time graph is a straight line with a
negative slope
The rate of reaction, which is equal to k and remains
constant throughout the reaction, is the negative of
the slope of this line.
The units of k are the same as the units of the rate of
a concentration (mol/L-s)
Integrated rate equation:
y= mx + b [A]t = -kt + [A]
0
FIRST ORDER REACTIONS
The first order reaction has a rate equation in
which the sum of the exponents is equal to 1. A
common type is a single reactant decomposes
into products.
A products

e.g. 2 H
2
O
2
2 H
2
O + O
2

Integrated rate equation:

Half life of a reaction is the time required for
one-half of a reactant to be consumed.

| | A k reaction of rate =
| |
2 2
O H k reaction of rate =
| |
| |
kt
A
A
t
=
0
ln
| | | |
0
ln ln A kt A
t
+ =
| |
k
t
2 ln
2 / 1
=
SECOND ORDER REACTIONS
The second order reaction has a rate
equation in which the sum of the
exponents is equal to 2.
A products

Integrated rate equation:
| |
2
A k reaction of rate =
| | | |
0
1 1
A
kt
A
t
+ =
THE EFFECT OF TEMPERATURE ON
REACTION RATES
RT E
a
Ae k
/
=
|
|
.
|

\
|
=
2 1 1
2
1 1
ln
T T R
E
k
k
a
ACIDS AND BASES
EQUILIBRIUM CONSTANT, K
c
- allows us
to calculate equilibrium concentrations of
reactants and products
aA + bB = gG +hH

When we reverse an equation, we invert the value of Kc
When we multiply the coefficients in a balanced equation
by a corresponding factor, we raise the equilibrium
constant to the corresponding power.
When we divide the coefficients in a balanced equation by
a common factor, we take the corresponding root of the
equilibrium constant.
| | | |
| | | |
b a
h g
c
B A
H G
K =
When the individual equations are combined their
equilibrium constants are multiplied to obtain the
equilibrium constant for the net reaction.
Equilibrium constant expressions do not contain
concentration terms for solid or liquid phase of a
single component (pure solids or liquids)
A reaction is most likely to reach a state of
equilibrium in which significant quantities of both
reactants and products are present if the numerical
value of Kc is neither very large nor very small,
roughly from about 10
-10
to 10
+10
.
When an equilibrium system is subjected to a change
in temperature, pressure, or concentration of reacting
species, the system responds by attaining a new
equilibrium that partially offsets the impact of the
change
Reaction quotient, Qc ratio of
initial concentrations in a reaction
mixture that has the same form as
the equilibrium constant expression
If Q
c
=K
c
a reaction is at equilibrium
If Q
c
<K
c
a net reaction proceeds from
left to right (forward reaction)
If Q
c
>K
c
a net reaction proceeds from
right to left (reverse direction)
ARRHENIUS THEORY
In aqueous solution a strong electrolyte exists only in
the form of ions, whereas a weak electrolyte exists
partly as ions and partly as molecules.
A neutralization reaction involves the combination of
hydrogen ions and hydroxide ions to form water.
HCl H
+
+ Cl
-
NaOH Na
+
+OH
-
Neutralization reaction:
H
+
+ Cl
-
+ Na
+
+OH
-
Na
+
+ Cl
-
+ H
2
O
Acid base salt
Net ionic equation: H
+
+ OH
-
H
2
O
BRONSTED-LOWRY THEORY
Acid is proton donor, and a base is a proton
acceptor
NH3 + H2O NH4+ + OH-
base acid acid base
amphiprotic substances- can act either as an
acid or a base (H
+
)
amphoteric substances- can act either as an
acidic or basic oxide (Al
2
O
3
), associated with
elements having electronegativities in an
intermediate range.
LEWIS ACID AND BASE THEORY
Lewis acid-base theory is not limited to
reactions involving H
+
and OH
-
, it
extends to reactions in gases and in
solids.
Lewis acid is a species (atom, ion or
molecule) that is an electron pair
acceptor and a Lewis base is a species
that is an electron pair donor.
SELF IONIZATION OF WATER AND THE pH SCALE
Self Ionization of water- for each H2O molecule that acts as
an acid another acts as base, and hydronium (H3O+) and
hydroxide (OH-) ions are formed.
H
2
O + H
2
O H3O
+
+ OH
-

K
c
=[ H
3
O
+
][OH
-
]

At 25
o
C: [ H3O+]=[OH-]= 1.0 x 10
-7
M
Kw= [ H3O+][OH-]=1.0 x 10
-14


pH- potential of hydrogen ion

pH= - log [H3O
+
]
pOH= - log [OH
-
]
pKw = pH + pOH= 14
Percent ionization- gives the proportion
of ionized molecules on a percentage basis.


Percent ionization of a weak acid or a weak
base increases as the solution becomes
more dilute.
Polyprotic or polybasic acids- acids with
more than one ionizable H atom per
molecule.
% 100
3
x
HA of molarity initial
HA from derived O H molarity
ionization percent
+
=
Hydrolysis- a reaction between an ion and
water
Salts of strong bases and strong acids do not
hydrolyze, pH=7
Salts of strong bases and weak acids hydrolyze,
pH>7 (anion acts as base)
Salts of weak bases and strong acids hydrolyze,
pH<7 (cation acts as acid)
Salts of weak bases and weak acids hydrolyze,
pH depends on the relative values of Ka and Kb
for the ions (cations are acids, anions are bases)
Solutions of Weak Acids/Bases and Strong
Acids/Bases
The common ion effect is the suppression of the
ionization of a weak electrolyte caused by the
addition of an ion that is also a product of the
ionization equilibrium of weak electrolyte.
When a strong electrolyte supplies the common ion
(H3O
+
for acids, and OH
-
for bases) the equilibrium
shifts.
Solutions of Weak Acids/Bases and Their Salts
The salt of a weak acid/base is a strong electrolyte-
its ions become completely dissociated from one
another in aqueous solution. The presence of the
common ion suppresses the ionization of the weak
acid/base.
Buffer solutions
The pH values of buffer solutions change only
very slightly on the addition of small amounts of
either an acid or a base.
Buffer solutions require two components, one of
which is able to neutralize acids and the other
able to neutralize bases, but the two
components must not neutralize each other.
Common buffer solutions are a mixture of a
weak acid and its conjugate base or a weak
base and its conjugate acid.
Buffer capacity- the amount of acid or base that a
buffer can neutralize before its pH change
appreciably. The maximum buffer capacity exists
when the concentration of a weak acid and its
conjugate base are kept large and approximately
equal to each other.
Buffer range- pH range in which a buffer effectively
neutralizes added acids and bases and maintains a
fairly constant pH.


A range of 2 pH units is the maximum range to which a
buffer solution should be exposed.
| |
| | acid
base conjugate
pK pH
a
log + =
Complex ion- is a polyatomic cation or anion
composed of a central metal ion to which other
groups (molecules or ions) are bonded. Substances
containing complex ions belong to a category of
compounds called coordination compounds.
Kf- formation constant is the equilibrium constant
that is used to deal with a complex ion equilibrium, it
describes the formation of a complex ion from a
central ion and its ligands.

K
f
are usually large numbers which distinguish K
f
from
other equilibrium constants.
POSITIVE IONS BEHAVIOR AND
DETERMINATION
Qualitative Analysis of Cations- aims at identifying the cations present in
a mixture but not their quantities
Cations are divided into five groups depending on differing solubilities of their
compounds.

Group I: Ag
+
, Hg
2
2+
, Pb
2+

Precipitated in 1 M HCl

Group II: Bi
3+
, Cd
2+
, Cu
2+
, Hg
2+
, (Pb
2+
), Sb
3+
and Sb
5+
, Sn
2+
and Sn
4+

Precipitated in 0.1 M H
2
S solution at pH 0.5

Group III: Al
3+
, (Cd
2+
), Co
2+
, Cr
3+
, Fe
2+
and Fe
3+
, Mn
2+
, Ni
2+
, Zn
2+

Precipitated in 0.1 M H
2
S solution at pH 9

Group IV: Ba
2+
, Ca
2+
, K
+
, Mg
2+
, Na
+
, NH
4+

Ba
2+
, Ca
2+
, and Mg+ are precipitated in 0.2 M (NH
4
)
2
CO
3
solution at pH 10;
the other ions are soluble

Group V: The resulting solution consists of the soluble ions in water, Na
+
,
K
+
, NH
4+
Dissolving Metal sulfides
Increase the solubility of any sulfide by allowing
it to react with acid.
Use an oxidizing acid such as HNO
3

3CuS
(s)
+ 8 H
+

(aq)
+ 2NO
3

(aq)
2 Cu
2+

(aq)
+ 3 S
(s)
+2 NO
(g)
+ 4 H
2
O

A few metal sulfides dissolve in basic solution
with a high concentration of HS-. The subgroup
consisting of HgS , PbS, CuS , Bi
2
S
3
and CdS
remains undissolved after treatment with an
alkaline solution with an excess of HS- but
As
2
S
3
. Sb
2
S
3
and SnS
2
dissolve.
VOLUMETRIC AND
GRAVIMETRIC ANALYSIS
Volumetric analysis- a technique that employs the
measurement of volumes to determine quantitatively
the amount of a substance in solution. In any reaction
between two or more species, the reaction equation
will show the stoichiometric ratio of reacting species.
Gravimetric analysis- based upon the measurement
of mass. The precipitation method of gravimetric
analysis involves isolation of an ion in solution by a
precipitation reaction, filtering, washing the
precipitate free of contaminants, conversion of the
precipitate to a product of known composition, and
finally weighing the precipitate and determining its
mass by difference. From the mass and known
composition of the precipitate, the amount of the
original ion can be determined.