CH2113 Principles of Inorganic Chemistry

Lecture 2

ACIDS & BASES

05 September 2023
Instructor: Dr. R. Vaidhyanathan 11.a.m.-12.p.m.
 Lewis Concept of acids and bases

Lewis' theory used electron transfer instead of proton transfer and specifically stated that an acid is a

species that accepts an electron pair while a base is a species that donates an electron pair.

A coordinate covalently bonded

compound, also known as an adduct

•Lewis Acid: a species that accepts an electron pair (i.e., an electrophile) and will have vacant orbitals

•Lewis Base: a species that donates an electron pair (i.e., a nucleophile) and will have lone-pair electrons
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• Lewis Acids are Electrophilic meaning that they are electron attracting. When bonding with a
base the acid uses its lowest unoccupied molecular orbital or LUMO (Figure below).

• Lewis Bases are Nucleophilic meaning that they “attack” a positive charge with their lone pair. They
utilize the highest occupied molecular orbital or HOMO (Figure below). An atom, ion, or molecule with
a lone-pair of electrons can thus be a Lewis base.

Is there anything not so correct about the above figure?

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 Lewis Acids
• Various species can act as Lewis acids. All cations are Lewis acids since they are able to accept electrons.
(e.g., Cu2+, Fe2+, Fe3+)
• An atom, ion, or molecule with an incomplete octet of electrons can act as an Lewis acid (e.g., BF3, AlF3).
• Molecules where the central atom can have more than 8 valence shell electrons can be electron acceptors,
and thus are classified as Lewis acids (e.g., SiBr4, SiF4).
• Molecules that have multiple bonds between two atoms of different electronegativities (e.g., CO2, SO2)

Lewis Bases
• An atom, ion, or molecule with a lone-pair of electrons can be a Lewis base. Each of the following anions
can "give up" their electrons to an acid, e.g., OH−, CN−, CH3COO−, :NH3, H2O:, CO:
• Lewis base's HOMO (highest occupied molecular orbital) interacts with the Lewis acid's LUMO (lowest
unoccupied molecular orbital) to create bonded molecular orbitals. Both Lewis Acids and Bases contain
HOMO and LUMOs but only the HOMO is considered for Bases and only the LUMO is considered for Acids.
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SiF62- d2sp3 – has six bonds and an octahedral shape

CO2 = O=C=O

CO32- =

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 A&B Assignment 4:

Molecules where the central atom can have more than 8 valence shell
electrons can be electron acceptors, and thus are classified as Lewis acids
(e.g., SiBr4, SiF4).

Explain the above with a suitable chemical reaction!

What are the requirement for an atom to be able to have the hypervalency?

Show how OH- acts as a Lewis base? 6

Complex Ion / Coordination Compounds
Complex ions are polyatomic ions, which are formed from a central metal ion that has other smaller ions joined around it. While
Brønsted theory can't explain this reaction Lewis acid-base theory can help. A Lewis Base is often the ligand of a coordination
compound with the metal acting as the Lewis Acid.

Al3+ + 6 H2O ⇌ [Al(H2O)6]3+

This is an example of a Lewis acid-base reaction. The Lewis structure of water suggests that this molecule has
nonbonding pairs of valence electrons and can therefore act as a Lewis base. The electron configuration of the
Al3+ ion suggests that this ion has empty 3s, 3p, and 3d orbitals that can be used to hold pairs of nonbonding
electrons donated by neighboring water molecules.

Al3+ = [Ne] 3s0 3p0 3d0

Thus, the Al(H2O)63+ ion is formed when an Al3+ ion acting as a Lewis acid picks up six pairs of electrons from
neighboring water molecules acting as Lewis bases to give an acid-base complex, or complex ion.

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A&B Assignment 5:

Explain the HOMO and LUMO involved and the MO diagram for

[Al(H2O)6]3+?

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Another case where Lewis acid-base theory can explain the resulting compound
is the reaction of ammonia with Zn2+.

Zn2+ + 4 NH3 → [Zn(NH3)4]2+

Lewis Acid and Base Theory allows us to explain the formation of other species
and complex ions which do not ordinarily contain hydronium or hydroxide ions. –
Expands the acid and base definition

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 A&B Assignment 6:

Draw the electronic configuration of Ag+ and explain what would be the

product of its reaction with NH3, use Lewis dot structure?

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Amphoterism
• Some substances can be both an acid and a base.
• Water can act as an acid by donating its proton to the base and thus becoming its conjugate base, OH-.
However, water can also act as a base by accepting a proton from an acid to become its conjugate acid, H3O+.

• Water acting as an Acid:

H2O + NH3 → NH4+ + OH− (Conjugate base of water)
• Water acting as a Base:
H2O + HCl → Cl− + H3O+ (Conjugate acid of water)

• The degree to which a molecule acts depends on the medium in which the molecule has been placed in.

• Water does not act as an acid in an acid medium

A&B Assignment 7: Explain the amphoterism shown by Al(OH)3? 11

• Lewis acid-base theory explains the reaction of BF3 with ammonia.

• BF3 is a trigonal-planar molecule and is sp2 hybridized, which leaves an empty 2pz orbital on the
boron atom.
• BF3 can therefore act as an electron-pair acceptor, or Lewis acid.

• BF3 uses its empty 2pz orbital to pick up a pair of nonbonding electrons from a Lewis
base, NH3, to form a covalent bond.

A&B Assignment 8: How does non-metal oxide CO2 react with water? Is it an lewis acid or base? 12
 Usanovich acid-base definition
Mikhail Usanovich developed a general theory that does not restrict acidity to hydrogen-containing compounds,
and his approach, published in 1938, was even more general than the Lewis theory.
• Usanovich's theory: An acid is something that
• All acids or oxidants, while all base are reductants!!
(i) accepts negative species – Anions or Electrons
Or
• This definition applies to the concept of redox reactions
(ii) donates positive ones, Cations or Protons and (oxidation-reduction) as a special case of acid-base reactions
a base as the reverse.
Examples:
Na2O ( ) + SO3 ( ) → 2Na+ + SO42- (species exchanged: ) => SO3 accepts
3(NH4)2S ( ) + Sb2S5 ( ) → 6NH4+ + 2SbS43- (species exchanged: ) => Sb2S5 accepts
2Na ( ) + Cl2 ( ) → 2Na+ + 2Cl- (species exchanged: ) => reaction
Cl2 ( ) + 2K ( ) → 2KCl => 2K minus 2e- = 2K+; Cl2 + 2e- = 2Cl- => reaction (species exchanged: )
HCl (acid) + NH3 (base) → NH4Cl (species exchanged: )

A comparison of the above definitions of Acids and Bases shows that the Usanovich concept encompasses all of the 13
others but some feel that because of this it is too general to be useful.
 Usanovich acid-base definition

Mikhail Usanovich developed a general theory that does not restrict acidity to hydrogen-containing compounds,
and his approach, published in 1938, was even more general than the Lewis theory.
• Usanovich's theory: An acid is something that
• All acids or oxidants, while all base are reductants!!
(i) accepts negative species – Anions or Electrons
Or
• This definition applies to the concept of redox reactions
(ii) donates positive ones, Cations or Protons and (oxidation-reduction) as a special case of acid-base reactions
a base as the reverse.
Examples:
Na2O (base) + SO3 (acid) → 2Na+ + SO42- (species exchanged: anion O2- ) => SO3 accepts oxide ion
3(NH4)2S (base) + Sb2S5 (acid) → 6NH4+ + 2SbS43- (species exchanged: anion S2- ) => Sb2S5 accepts sulfide ion
2Na (base) + Cl2 (acid) → 2Na+ + 2Cl- (species exchanged: electron) => Redox reaction
Cl2 (acid) + 2K (base) → 2KCl => 2K minus 2e- = 2K+; Cl2 + 2e- = 2Cl- => Redox reaction (species exchanged: electron)
HCl (acid) + NH3 (base) → NH4Cl => Exchanged species is H+ (HCl donates a proton, while NH3 accepts it.)

A comparison of the above definitions of Acids and Bases shows that the Usanovich concept encompasses all of the 14
others but some feel that because of this it is too general to be useful.
 Acidity constant- an equilibrium constant

HF + H2O ⇌ H3O+ + F-
Acid1 + Base1 ⇌ Acid2 + Base2

How fast the equilibrium is reached reflects the speed of the proton transfer reaction.
This is different for each species that is involved.

A typical PT has a time scale of ______. The rate constants for a strong acid transferring proton to water is ______

Strengths of acids and bases

For Bronsted acids such as HF it is given by the acidity constant Ka

HF(aq) + H2O (l) ⇌ H3O+ (aq) + F- (aq)

[F-] = Molar concentration

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Acidity constant- an equilibrium constant

HF + H2O ⇌ H3O+ + F-
Acid1 + Base1 ⇌ Acid2 + Base2

How fast the equilibrium is reached reflects the speed of the proton transfer reaction.
This is different for each species that is involved.

A typical PT has a time scale of 100 fs. The rate constants for a strong acid transferring proton to water is ~1013 s-1

Strengths of acids and bases

For Bronsted acids such as HF it is given by the acidity constant Ka.

HF(aq) + H2O (l) ⇌ H3O+ (aq) + F- (aq)

[F-] = Molar concentration

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Ka << 1 => [HF] >> [F-]

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Ka = acidity constant or acid dissociation constant

pKa = - log10(Ka)

For example, the Ka of HF = 3.5 x 10-4

Then, the pKa of HF = -log10(3.5x10-4) = 3.46

Smaller the ‘pKa’ value => stronger the acid

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 Concept of pH
Aim: To express the strength of an acid

The strength of an acid is always relative

When an acidic species dissolves in water it releases protons, H+. Now, how many proton it
releases decides its strength

The concentration of H+, [H+] or [H3O+] gives the quantification of acid’s strength in moles/litre

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Now for any acid, if we know the Ka or pKa or pH, the other can be calculated!
End of Lectures 1 and 2: Acids and Bases

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