Acids and Bases Zapper Pres

Acids and bases in
Inorganic Chemistry
By the way: You will be allowed to bring
molecular modelling kits into exams.
You can find a link to the retailer’s website

on Blackboard.
What am I talking about?
“It can be described as a proton acceptor”
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1. An acid
2. A base
3. A buffer
4. An indicator
An acid A base A buffer An indicator
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“This is a substance which changes colour at
a particular pH value”
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1. An acid
2. A base
3. A buffer
4. An indicator
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“It can be described as a proton donor”
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1. An acid
2. A base
3. A buffer
4. An indicator
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Some definitions...
Svante Arrhenius
• acids produce H+ ions in aqueous solutions

• bases produce OH- ions in aqueous solutions
• water required, so only allows for aqueous
solutions
• only protic acids are allowed; required to produce
hydrogen ions
• only hydroxide bases are allowed
Some definitions...
Johannes Nicolaus Brønsted - Thomas Martin Lowry
• acids are proton donors

• bases are proton acceptors
• aqueous solutions are permissible
• bases besides hydroxides are permissible
• only protic acids are allowed
Some definitions...
Gilbert Newton Lewis
• acids are electron pair acceptors

• bases are electron pair donors
• least restrictive of acid-base definitions
Brønsted-Lowry acids and bases
Keq = [H3O
HA + H2O A- + H3O+
[AH
Hydronium ion
Write an expression for Keq (the equilibrium constant)

Keq = [H3O+][A-]
HA + H2O A- + H3O+
[AH][H2O]
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B. I got it wrong, but now
understand it
C. I’m not sure about this
I got it right I got it wrong, b... I’m not sure abou...
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Keq = [H3O+][A-]
HA + H2O A- + H3O+
[AH][H2O]
As the concentration of water remains relatively constant at

55.56 moldm-3 for dilute solutions of acids, and the effect of the
equilibrium is negligible, a new equilibrium constant, the acidity
constant (Ka) is defined.
HA + H2O A- + H3O+ Ka = [H3O+][A-]

[AH]
pKa
The strength of an acid can be measured by the value of K a,
or alternatively pKa where “p” means -log10
Polyprotic acids
Acid Formula Ka pKa
phosphoric acid H3PO4 K1 = 7.1 x 10-3 2.12
H2PO4- K2 = 6.2 x 10-8 7.21
HPO42- K3 = 4.6 x 10-13 12.34
[H3O+][H2PO4-]
H3PO4 + H2O H2PO4- + H3O+ K1 =
[H3PO4]
[H3O+][HPO42-]
H2PO4- + H2O HPO42- + H3O+ K2 =
[H2PO4-]
HPO42- + H2O PO43- + H3 O+ K3 = [H3O+][PO43-]

[HPO42-]
Polyprotic acids
Acid Formula Ka pKa
phosphoric acid H3PO4 K1 = 7.1 x 10-3 2.12
H2PO4- K2 = 6.2 x 10-8 7.21
HPO42- K3 = 4.6 x 10-13 12.34
Predicting the acidity of oxo-
acids
See Shriver & Atkins
• Pauling’s rules: p.120 - 122
• For a formula EOp(OH)q,
• Ka = 105p-8 which gives: pKa = 8-5p
• If q > 1, successive Ka values for additional ionisations are 10 -5 smaller

(or pKa 5 units larger)
Example: H2SO4 or SO2(OH)2 p=2 and q=2
K1 = 105x2-8 = 102 and pKa = 8 - (5 x 2) = -2
K2 = 102 x 10-5 = 10-3 (Experimental value 10-1.9)

Predicting the acidity of oxo-
acids
• Pauling’s rules:
• For a formula EOp(OH)q,
• Ka = 105p-8 which gives: pKa = 8-5p
• If q > 1, successive Ka values for additional ionisations are 10 -5 smaller

(or pKa 5 units larger)
Work out K1 and K2 for H2SO3 (or SO(OH)2) p=1 and q=2
K1 = 10(5 x 1)-8 = 10-3 (Experimental value = 1.2 x 10-2)
K2 = 10-3 x 10-5 = 10-8 (Experimental value = 6.6 x 10-3)

Predicting the acidity of oxo-acids
Work out K1 and K2 for H2SO3 (or SO(OH)2) p=1 and q=2
K1 = 10(5 x 1)-8 = 10-3
K2 = 10-3 x 10-5 = 10-8

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Conjugate Acids and Bases
• Consider the following system...when hydrofluoric acid is added
to water, there is an increase in the hydrogen ion
concentration...
HF + H2O H3O+ + F- (1)
But the reaction does not go to completion. The four species

are in equilibrium - so which is the acid and which is the
base?
H3O+ + F- HF + H2O (2)

Conjugate Acids and Bases
Conjugate Acid
HF + H2O H3O+ + F- (1)

Acid Base Conjugate Base
Conjugate Acid
H3O+ + F- HF + H2O (2)

Acid Base
Conjugate Base
Which is the conjugate base?
Base Conjugate Acid
NH3 + H2O NH4+ + OH-
Acid Conjugate Base

A. NH4+ 0%
B. OH-
C. NH3
D. H2O
0 of 136 NH4+ OH- NH3 H2O

Which is the correct term for describing the
role of water in this equilibrium?
Base Conjugate Acid
NH4+ + H2O H3O+ + NH3

Acid Conjugate Base
A. Conjugate acid 0%
B. Acid
C. Base
D. Conjugate base
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Which is the conjugate acid?
Base Conjugate Acid
OEt- + CH3COOH EtOH + CH3COO-
Acid Conjugate Base
0%
A. OEt-
B. CH3COOH
C. EtOH
D. CH3COO-
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Acidity of oxides in water
Classifications of oxides:
Acidic:
e.g. SO3 + H2O H+ + HSO4-
Basic:
e.g. CaO + H2O Ca2+ + 2 OH-
Amphoteric:
in acid:
Al2O3 + 6 H3O+ + 3 H2O 2 [Al(OH2)6]3+
and in base: Al = amphoteric

Al2O3 + 2 OH- + 3 H2O 2 [Al(OH)4]-
As = AsV acidic; AsIII basic
See Shriver & Atkins The elements in circles have amphoteric oxides even in
their highest oxidation states. The elements in boxes
p.122 have acidic oxides in their maximum oxidation states and
amphoteric oxides in their lower oxidation states
Acidity of oxides in water
Amphoteric:
in acid:
Al2O3 + 6 H3O+ + 3 H2O 2 [Al(OH2)6]3+
and in base:
Al2O3 + 2 OH- + 3 H2O 2 [Al(OH)4]-
Acids and Bases in Other Solvent Systems
1) Solvent systems similar to water, in which self-ionisation
involves proton transfer.
In the case of water: 2H2O H3O+ + OH-
An acid is a species which increases the concentration of

H3O+, while a base is a species which increases the
concentration of OH-.
Also, species which react with the solvent to give changes

in H3O+ or OH- concentration can similarly be classified as
an acids or bases
e.g the OEt- ion in NaOEt would be a base, because:

OEt- + H2O  EtOH + OH-
Acids and Bases in Other Solvent Systems
Liquid ammonia is another solvent which, like water,

can undergo self-ionisation.
Write an equation for the self-ionisation of

ammonia.
Liquid Ammonia
The self-ionisation reaction is: 2NH3 NH4+ + NH2-
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Liquid Ammonia
An acid will increase the
concentration of the cationic species
The self-ionisation reaction is: 2NH3 NH4+ + NH2-
A base will increase the concentration

of the anionic species
Ammonium salts (e.g. NH4Cl) are acids because

they increase the concentration of NH4+.
Alkali metal amides (e.g. NaNH2) are bases because

they increase the concentration of NH2-.
Species which can protonate H2O to form H3O+ (e.g. HCl)
will protonate NH3 to give NH4+.
Liquid HF
The self-ionisation reaction is: 3HF H2F+ + HF2-

Some species which are acids in water will also be acids in liquid
HF:
e.g. H2SO4 + HF  H2F+ + HSO4-
But, some species which are only weakly acidic in water can act as
bases in HF:
e.g. CH3COOH + 2HF  CH3COOH2+ + HF2-
Liquid HF
The
Theself-ionisation
self-ionisationreaction
reactionis: 3HF  HH22FF++ ++ HF
is:3HF HF22- -

Fluoride ion donors (e.g. NaF) become bases:
F- + HF  HF2-
Fluoride ion acceptors (e.g. SbF5) become acids:
e.g. SbF5 + 2HF  SbF6- + H2F+

[ ]
•-
See Shriver & Atkins
Lewis acids and bases p.125 - 134
When we talk about Lewis acidity and basicity, the
thing being donated or accepted is an electron pair
(not a proton!).
A Lewis acid is an electron pair acceptor.
A Lewis base is an electron pair donor.
This definition extends the range of interactions which can

be described as “acid-base” reactions to include a wide
range of donor-acceptor behaviour.
Examples you know about:
Dative covalent (co-ordinate) bonding
Transition metal – ligand complexes
Lewis acids and bases
Bronsted acids and bases are also Lewis acids and bases.
Consider:
NH3 + H2O  NH4+ + OH-
NH3 is a Bronsted base as it accepts a proton.
At the same time:

NH3 is a Lewis base as it donates a pair of electrons.
Lewis acids and bases
Bronsted acids and bases are also Lewis acids and
bases.
Consider:
[ ]
•-
SbF5 is a Lewis acid as it accepts a pair of electrons from

a fluoride ion. The fluoride ion donates a pair of electrons
so is a Lewis base.
Other examples of donor-acceptor complexes
“Hard” and “soft” acids and bases
The strength of the donor-acceptor interaction in Lewis acid-base complexes can be measured
quantitatively in terms of the stability constant K.
A + B AB
High K indicates a strong interaction

Low K indicates a weak interaction
[AB] a
K=
Why does the interaction change for different complexes?
[A] x [B]
Hard acids and bases
These tend to be small and not easily polarised.
e.g Hard acids: H+, Li+, Na+, Mg2+, Ca3+, Al3+, BF3
Hard bases: F-, OH-, O2-, H2O, NH3, NO3-

Soft acids and bases
These tend to be large and more easily polarised.
e.g Soft acids: Cu+, Ag+, Hg+, Hg2+, Cd2+, BH3
Soft bases: H-, I-, CN-, SCN-, CO, PR3

Remember this:
Hard acids tend to bind to hard bases

(high ionic character)
Soft acids tend to bind to soft bases

(high covalent character)
[AB] a
A + B AB K=
[A] x [B]
Hard – Hard  High K

Soft – Soft  High K
Hard – Soft  Low K

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Acids and bases in

You can find a link to the retailer’s website

An acid A base A buffer An indicator

An acid A base A buffer An indicator

An acid A base A buffer An indicator

• acids produce H+ ions in aqueous solutions

• acids are proton donors

Gilbert Newton Lewis

• acids are electron pair acceptors

Write an expression for Keq (the equilibrium constant)

I got it right I got it wrong, b... I’m not sure abou...

As the concentration of water remains relatively constant at

HA + H2O A- + H3O+ Ka = [H3O+][A-]

HPO42- + H2O PO43- + H3 O+ K3 = [H3O+][PO43-]

• Ka = 105p-8 which gives: pKa = 8-5p

• If q > 1, successive Ka values for additional ionisations are 10 -5 smaller

Example: H2SO4 or SO2(OH)2 p=2 and q=2

K1 = 105x2-8 = 102 and pKa = 8 - (5 x 2) = -2

K2 = 102 x 10-5 = 10-3 (Experimental value 10-1.9)

• For a formula EOp(OH)q,

• Ka = 105p-8 which gives: pKa = 8-5p

• If q > 1, successive Ka values for additional ionisations are 10 -5 smaller

K1 = 10(5 x 1)-8 = 10-3 (Experimental value = 1.2 x 10-2)

K2 = 10-3 x 10-5 = 10-8 (Experimental value = 6.6 x 10-3)

K2 = 10-3 x 10-5 = 10-8

I got it right I got it wrong, b... I’m not sure abou...

HF + H2O H3O+ + F- (1)

But the reaction does not go to completion. The four species

H3O+ + F- HF + H2O (2)

HF + H2O H3O+ + F- (1)

H3O+ + F- HF + H2O (2)

NH3 + H2O NH4+ + OH-

Acid Conjugate Base

0 of 136 NH4+ OH- NH3 H2O

NH4+ + H2O H3O+ + NH3

OEt- + CH3COOH EtOH + CH3COO-

Acid Conjugate Base

and in base: Al = amphoteric

In the case of water: 2H2O H3O+ + OH-

An acid is a species which increases the concentration of

Also, species which react with the solvent to give changes

e.g the OEt- ion in NaOEt would be a base, because:

Liquid ammonia is another solvent which, like water,

Write an equation for the self-ionisation of

The self-ionisation reaction is: 2NH3 NH4+ + NH2-

The self-ionisation reaction is: 2NH3 NH4+ + NH2-

A base will increase the concentration

Ammonium salts (e.g. NH4Cl) are acids because

Alkali metal amides (e.g. NaNH2) are bases because

The self-ionisation reaction is: 3HF H2F+ + HF2-

A base will increase the concentration

A base will increase the concentration

Fluoride ion acceptors (e.g. SbF5) become acids:

e.g. SbF5 + 2HF  SbF6- + H2F+

This definition extends the range of interactions which can

NH3 is a Bronsted base as it accepts a proton.

At the same time:

SbF5 is a Lewis acid as it accepts a pair of electrons from

High K indicates a strong interaction