Acids and bases in Inorganic Chemistry

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What am I talking about?

It can be described as a proton acceptor
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1. 2. 3. 4.

An acid A base A buffer An indicator

An acid

A base

A buffer

An indicator

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What am I talking about?

This is a substance which changes colour at a particular pH value
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1. 2. 3. 4.

An acid A base A buffer An indicator

An acid

A base

A buffer

An indicator

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What am I talking about?

It can be described as a proton donor
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1. 2. 3. 4.

An acid A base A buffer An indicator

An acid

A base

A buffer

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 Brnsted - 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

Brnsted-Lowry acids and bases

HA + H2O A+ H3O+

Keq = [H3O

[AH

Hydronium ion Write an expression for Keq (the equilibrium constant)

Brnsted-Lowry acids and bases

HA + H2O A- + H3O+
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Keq = [H3O+][A-] [AH][H2O]

A. I got it right B. I got it wrong, but now

understand it C. Im not sure about this

I got it right

I got it wrong, b...

Im not sure abou...

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Brnsted-Lowry acids and bases

HA + H2O A- + H3O+ Keq = [H3O+][A-] [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 Ka, or alternatively pKa where p means -log10

Polyprotic acids
Acid Formula H3PO4 Ka K1 = 7.1 x 10-3 pKa 2.12 phosphoric acid

H2PO4-

K2 = 6.2 x 10-8
HPO42-

7.21
12.34

K3 = 4.6 x 10-13

H3PO4 + H2O

H2PO4- + H3O+

K1 =

[H3O+][H2PO4-] [H3PO4]

H2PO4- + H2O

HPO42- + H3O+

K2 =

[H3O+][HPO42-] [H2PO4-]

HPO42-

+ H2O

PO43-

+ H3

O+

K3 =

[H3O+][PO43-] [HPO42-]

Polyprotic acids
Acid Formula H3PO4 Ka K1 = 7.1 x 10-3 pKa 2.12 phosphoric acid

H2PO4-

K2 = 6.2 x 10-8
HPO42-

7.21
12.34

K3 = 4.6 x 10-13

Predicting the acidity of oxoacids

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

See Shriver & Atkins p.120 - 122

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 oxoacids

Paulings 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) K1 = 10(5 x 1)-8 = 10-3 K2 = 10-3 x 10-5 = 10-8
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p=1 and q=2

A. I got it right B. I got it wrong, but now

understand it C. Im not sure about this

I got it right

I got it wrong, b...

Im not sure abou...

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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
Acid Base

H3O+ + FConjugate Base

(1)

Conjugate Acid

H3O+ + FAcid Base

HF + H2O
Conjugate Base

(2)

Which is the conjugate base?

Base Conjugate Acid

NH3 + H2O
Acid

NH4+ + OHConjugate Base

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A. NH4+

B. OHC. NH3

D. H2O
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NH4+ OHNH3 H2O

Which is the correct term for describing the role of water in this equilibrium?
Base Conjugate Acid

NH4+ + H2O
Acid

H3O+ + NH3
Conjugate Base

A. Conjugate acid B. Acid C. Base D. Conjugate base

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Which is the conjugate acid?

Base Conjugate Acid

OEt- + CH3COOH
Acid

EtOH + CH3COOConjugate Base

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A. OEtB. CH3COOH C. EtOH D. CH3COO0 of 136

Acidity of oxides in water

Classifications of oxides: Acidic: e.g. SO3 + H2O H+ + HSO4Basic: e.g. CaO + H2O

Ca2+ + 2 OH-

Amphoteric: in acid: Al2O3 + 6 H3O+ + 3 H2O and in base: Al2O3 + 2 OH- + 3 H2O

2 [Al(OH2)6]3+

2 [Al(OH)4

]-

Al

= amphoteric

As = AsV acidic; AsIII basic

See Shriver & Atkins p.122

The elements in circles have amphoteric oxides even in their highest oxidation states. The elements in boxes 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
and in base: Al2O3 + 2 OH- + 3 H2O 2 [Al(OH2)6]3+

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
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NH4+ + NH2-

A. I got it right
B. I got it wrong, but
now understand it

C. I dont get it
A B C

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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
An acid will increase the concentration of the cationic species

The self-ionisation reaction is: 3HF

H2F+ + HF2-

A base will increase the concentration of the anionic species

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
An acid will increase the concentration of the cationic species

The self-ionisation reaction is: 3HF H22F+ + HF22H F+ + HF The self-ionisation reaction is: 3HF
A base will increase the concentration of the anionic species
Fluoride ion donors (e.g. NaF) become bases: F- + HF HF2Fluoride ion acceptors (e.g. SbF5) become acids: e.g. SbF5 + 2HF SbF6- + H2F+

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Lewis acids and bases

See Shriver & Atkins 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+ + OHNH3 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

Other examples of donor-acceptor complexes

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

[AB] a K= [A] x [B]

High K indicates a strong interaction Low K indicates a weak interaction Why does the interaction change for different complexes?

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

Hard acids and bases Remember this:

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

Hard acids and bases

A + B AB
[AB] a K= [A] x [B]

Hard Hard High K Soft Soft High K Hard Soft Low K