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CHEM10003 2014
INORGANIC CHEMISTRY

Brendan Abrahams
bfa@unimelb.edu.au
Room 267 Chemistry
2
Lecture 1
CHEM10003 (inorganic chemistry)

1.# Acids and Bases


2.# Trends in the Periodic Table
3.# Molecular Structure and Bonding
4.# Ionic Compounds and their Solutions
5.# Structures of Solids
6.# Main Group Chemistry
3
Acids and Bases

Lewis Acidity and Basicity

A Lewis base is an electron pair donor.

e.g. ammonia, cyanide, hydroxide, water, chloride,


carbon monoxide, amine etc.

All of these species are capable of donating a pair


of electrons.
4
Consider the reaction between aqueous HCl and NaOH

H
+
(aq)
+Cl
-
(aq)
+Na
+
(aq)
+ OH
-
(aq)
! H
2
O
(l)
+ Cl
-
(aq)
+ Na
+
(aq)

In this reaction the base is hydroxide and it acts as a


Lewis base by donating a pair of electrons.

It acts as a Bronsted base by accepting a proton.

Hydrogen chloride is a Lewis acid because it accepts a


pair of electrons (from the hydroxide) and it is a Bronsted
acid because it is a proton donor.

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Thus Bronsted acids and bases are a special
class of Lewis acids and bases involving
hydrogen ions or protons.
A Bronsted acid is a proton donor.

A Bronsted base is a proton acceptor.

Thus the Bronsted acid-base reaction is a


proton transfer reaction.
6
Consider the ionization of a strong acid such as
HCl in water.
It may be represented as:

HCl H
+
(aq)
+ Cl
-
(aq)

or H
2
O + HCl H
3
O
+
(aq)
+ Cl
-
(aq)

H
2
O
Such representations are simplications.
Representations of the hydrated proton
Copyright:Houghton Mifin
7
The hydrogen ion does not exist as a "naked proton" in
aqueous solution.

It is hydrated but the degree of hydration is uncertain.

The ion may exist as H


5
O
2
+
, H
7
O
3
+
, H
9
O
4
+
etc.
The proton is often represented as a simple hydrated proton
- the hydronium ion - H
3
O
+
.

The hydrogen ion is represented as both H


+
and H
3
O
+
.

Both representations are acceptable.


8
Conjugate Acid-Base Pairs

Consider the reaction between a base, B and an acid,


HA:
B + HA HB
+
+ A
-
HA is the acid HB
+
is the conjugate acid
B is the base A
-
is the conjugate base

In the reverse reaction HB


+
would be the acid and A
-

would be the base.

Note that the weak acid-base pair is always favoured


in the equilibrium.
HB
+
+ A
-


B + HA
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The Ionization of Water

Pure water undergoes self-ionization:

2H
2
O H
3
O
+
+ OH
-

Water is behaving as both an acid and a base.

Since water is only a weak acid and a weak base,


the reaction lies predominantly to the left.
Copyright:Houghton Mifin
10
The extent of the ionization can be expressed in
terms of an ionization constant K
w
.

K
w
= [H
+
][OH
-
] = 10
-14
at 25 C
In pure water, [H
+
] = [OH
-
] = 10
-7
M

When [H
+
] = [OH
-
] the solution is said to be neutral.
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If [H
+
] > 10
-7
M then the solution is acidic.

If [OH
-
] > 10
-7
M then the solution is basic.
The addition of other substances may change [H
+
]
and [OH
-
] but the product of their concentrations is
always constant (for a given temperature).

Thus if [H
+
] = 10
-1
M then the [OH
-
] = 10
-13
M.

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The pH and pOH Scales

Not always convenient to express very small


concentrations of H
+
and OH
-
in terms of mol L
-1

An alternative is to express acidity in terms of a log


scale.
pH = -log[H
+
]
pOH = -log[OH
-
]
If [H
+
] = 10
-1
M then the pH = 1 and since [OH
-
] =
10
-13
M the pOH = 13.
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K
w
= [H
+
][OH
-
] = 10
-14

-log([H
+
][OH
-
])= -log(10
-14
)

-log[H
+
] + (-log[OH
-
])= -log(10
-14
)

pH + pOH = 14

Thus if we know the pH we can calculate the pOH.

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pH - Important points to keep in mind
pH = -log
10
[H
+
]
The pH scale is logarithmic.

This means when pH changes from say, 5 to 2,


that the [H
+
] increases by a factor of 1,000.

In the neutralization of a strong acid, it takes a great deal


more strong base to raise the pH from 1 to 2 than it does
from 2 to 7.

pH 1 ! 2; [H
+
] = 0.1 ! 0.01 M; # = 0.09 M
pH 2 ! 5; [H
+
] = 0.01 ! 0.00001 M; # = 0.00999 M

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Acids and bases exhibit a variety of strengths.
Copyright:Houghton Mifin, 2003
Copyright:Houghton Mifin, 2003
16
Quantifying acid strength

Equilibrium constants can be used to express


the strengths of acids and bases.

For acids:
H
2
O + HA H
3
O
+
(aq)
+ A
-
(aq)
K
a
=
[H
3
O
+
][A
-
]


[HA]
pK
a
= -log
10
K
a

Strong acids have high K


a
s and small pK
a
s
K
a
- acid dissociation constant
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Quantifying base strength

Equilibrium constants can be used to express


the strengths of acids and bases.

For bases:
H
2
O + B HO
-
(aq)
+ BH
+
(aq)

K
b
=
[HO
-
][BH
+
]


[B]
pK
b
= -log
10
K
b

Strong bases have high K


b
s and small pK
b
s
K
b
- base equilibrium constant
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Strong acids include HCl, HBr, H
2
SO
4
, HClO
4
, HBF
4
.

The anions of these acids are very weak bases.


i.e. the conjugate base of a strong acid is a very weak base.
Strong Acids

A strong acid ionizes almost completely in aqueous


solution.

Recall that the following reaction for a strong acid, HA


lies very much to the right - K
a
is large.

H
2
O + HA H
3
O
+
+ A
-

Copyright:Houghton Mifin
19
Strong Acids

The acids are so strong we can assume 100% ionization.

i.e. The following equilibrium lies completely to the right.

H
2
O + HA H
3
O
+
+ A
-

The H
3
O
+
concentration is thus equal to the acid
concentration.

If the HA concentration was 0.0010 M then the [H


3
O
+
] =
0.0010 M and the pH = 3.
Copyright:Houghton Mifin
20
Exercise:

Calculate the pH and pOH of a 1 x 10


-5
M solution of
NaOH.

Ans: pH = 9; pOH = 5
Similarly, for strong bases such as NaOH, we can
assume that the concentration of the base is equal to
the HO
-
concentration.

If the concentration of NaOH is 0.010 M then the pOH


= 2 and the pH = 12.
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Weak Acids

Weak acids tend to undergo only a small degree of


dissociation.

Carboxylic acids are examples of weak acids.

In the reaction below, ionisation only occurs to a small extent.

RCOOH + H
2
O RCOO
-
(aq)
+ H
3
O
+
(aq)

i.e. the equilibrium lies well to the left.

Ammonium ions are also examples of weak acids:


NH
4
+
+ H
2
O NH
3 (aq)
+ H
3
O
+
(aq)

R-C
OH
O
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Weak Acids

The pH of a strong acid solution is easily calculated


because of complete dissociation.

e.g. A 0.010 M solution of HCl has a pH of 2.0.


A weak acid only dissociates to its conjugate base and a
proton to a small extent.

Calculation of pH is not as simple for a weak acid.

e.g. A 0.010 M solution of acetic acid has a pH of 3.4.

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A representation of the difference in the degree of
ionization of a strong acid and a weak acid.
Copyright:Houghton Mifin
Strong acid Weak acid
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Calculation of the pH of solutions of weak acids:
i) Write the chemical equation:

HA + H
2
O H
3
O
+
+ A
-
ii) Write the acidity constant:

K
a
= [H
3
O
+
][A
-
]
/
[HA]
iii) If only an acid has been added then [H
3
O
+
] = [A
-
].

K
a
= [H
3
O
+
]
2
/ [HA]

[H
3
O
+
] = $(K
a
[HA])
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iv) Take negative logs of both sides:

pH = - log{$(K
a
[HA])}

This may also be represented as:

pH = 1/2 pK
a
- 1/2 log [HA]
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Example

Calculate the pH of a solution in which 0.00200


moles of HCN is dissolved in 1.0 L of water.

HCN has K
a
of 4.93 x 10
-10
.

i) Write the chemical equation:

HCN + H
2
O ! H
3
O
+
(aq)
+ CN
-
(aq)
ii) Write the acidity constant:

K
a
= [H
3
O
+
][CN
-
]
/
[HCN]
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iii) If an acid only has been added then [H
3
O
+
] = [CN
-
].

Simplify the expression:


K
a
= [H
3
O
+
]
2
/
[HCN]
But what is [HCN] ?
HCN + H
2
O H
3
O
+
+ CN
-

start 0.00200 0.000 0.000


change -X X X
equilibrium0.00200-X X X

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Thus: K
a
= X
2
/
0.00200-X

X
2
+ K
a
X - 0.00200 K
a
= 0
Substituting in our value for K
a
we can solve our
quadratic equation.

This results in X = 9.93 x 10


-7
M

pH = -log 9.93 x 10
-7

= 6.00

Although the calculation is correct, it is tedious and time


consuming.
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We can make a simplifying assumption if the acid is
weak.

K
a
tells us that the degree of dissociation is very
small.

Assume that the concentration of HCN in the solution


at equilibrium is very close to the number of mole of
HCN added divided by the volume.
Thus we assume that [HCN] at equilibrium is ~0.00200
M.
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The problem is now greatly simplied.

[H
3
O
+
] = $(K
a
[HCN])
= $(4.93 x10
-10
x 0.00200)
= 9.93 x10
-7
M
iv) Take negative logs of both sides:

pH = 6.00
The similarity in the answers is a consequence of the very weak
nature of the acid.

When the acid is not quite as weak, the assumption is less valid
and the estimation of pH is cruder.

Nevertheless the assumption is worth making for weak acids.


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Example:

Determine the pH of a 0.100 M formic acid solution


using
i) a quadratic solution
ii) a simplifying assumption.

Formic acid has a K


a
of 1.76 x10
-4
.

Ans = 2.39, 2.38

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How do we know if the acid is weak enough to use the
approximation???

Use the 5% rule.

If dissociation is < 5%, approximation is valid.

For example consider formic acid example.

pH = 2.39, [H
+
] = 10
-2.39
= 4.07 x10
-3
M

% dissociation = 4.07 x10
-3
/0.1000
= 4.1%

% dissociation is < 5% - approximation is valid.


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For the 0.00200 M HCN problem in which pH = 6

% dissociation = 1 x10
-6
/0.00200 = 0.05%

Approximation is valid.

The percentage dissociation is sometimes useful


information in its own right.
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Weak Bases

Weak bases tend to undergo only a small degree of protonation.

Ammonia and amines are examples of weak bases.

In the reaction below, ionisation only occurs to a small extent.

NR
3
+ H
2
O HNR
3
+
+ OH
-

i.e. the equilibrium lies well to the left.

Carboxylate ions are also examples of weak bases:



RCOO
-
+ H
2
O RCOOH + OH
-
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ii) Write the basicity constant:
K
b
= [HO
-
][BH
+
]
/
[B]
iii) If only a base has been added then [BH
+
] = [HO
-
].

Simplify the expression:


K
b
= [HO
-
]
2
/
[B]

[HO
-
] = $(K
b
[B])
Calculation of the pH for weak bases:

i) Write the chemical equation:

B + H
2
O HO
-
+ BH
+

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iv) Take negative logs of both sides:

pOH = - log{$(K
b
[B])}

This may also be represented as:

pOH = 1/2 pK
b
- 1/2 log [B]

37
Determine the pOH and pH of a 0.050 M ammonia
solution.

Ammonia has a K
b
of 1.77 x 10
-5
.

i) Write the chemical equation


NH
3
+ H
2
O NH
4
+
+ OH
-

ii) Write the basicity constant:

K
b
= [NH
4
+
][OH
-
]
/
[NH
3
]

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iii) If only ammonia has been added then [NH
4
+
] = [OH
-
].

Simplify the expression:


K
b
= [OH
-
]
2
/
[NH
3
]

iv)
NH
3
+ H
2
O NH
4
+
+ OH
-

start 0.050 0.000 0.000


change -X X X
equilibrium0.050-X X X
Make approximation 0.050-X = 0.050 (K
b
= 1.77 x10
-5
)

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K
b
= [OH
-
]
2
/
[NH
3
]
1.77 x 10
-5
= [OH
-
]
2
/

0.0500

[OH-] = $(1.77 x 10
-5
x 0.050)
= 9.41 x 10
-4


pOH = -log 9.41 x 10
-4

= 3.0
pH = 11.0

Check validity of approximation


[NH
4
+
]/[NH
3
] = 9.41 x10
-4
/0.050
= 1.9% (valid approxn)
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Calculation of the pK
a
of a conjugate acid from the
pK
b
of the base (and vice versa).
If K
b
= [HO
-
][BH
+
]
/
[B]

then K
a
for the conjugate acid (BH
+
) may be dened
as:
K
a
= [B][H
+
]
/
[BH
+
]
If K
a
and K
b
are multiplied together:

K
a
x K
b
= ([B][H
+
]
/
[BH
+
]) x ([HO
-
][BH
+
]
/
[B])

We are left with:


K
a
x K
b
= [H
+
][HO
-
] = 10
-14
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Thus:
K
a
x K
b
= K
w
.

and

pK
a
+ pK
b
= 14

Note K
a
and K
b
must be for an acid and conjugate
base.
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Read Burrows
Sections 7.1, 7.2

Problems 7.1-7.6.
After today!s lecture