CH 4.

Acid-Base Theories and the Solvent System

Arrhenius
Bronsted-Lowry
Lewis
Lux-Flood
Usanovich
Cady- Esley
 INTRODUCTION
 There are so called theories of acids and bases, but they are not really
theories but merely different definitions of what we choose to call an acid
or base.

 Since it is only a matter of definition, no theory is more right or wrong than

any other, and we use the most convenient theory for a particular chemical
situation.
 Which is the most useful theory of acids and bases?

 The answer for this depends on whether we are considering ionic reactions
in aqueous solution, in non-aqueous solution, or in a fused melt, and whether
we require a measure of the strengths of acids and bases.

 Because of this we need to know several theories.

 Acid-Base theories and the solvent system
Acids:
 Arrhenius acid: Any substance that, when dissolved in water,
increases the concentration of hydronium ion (H3O+)
 Bronsted-Lowry acid: A proton donor
 Lewis acid: An electron acceptor
 Lux-Flood acid: An oxide ion (O2-) acceptor
 Usanovich acid: gives up cations, or combines with anions or
accepts anions or electrons or neutralizing a base to give salt
Bases:
 Arrhenius base: Any substance that, when dissolved in water,
increases the concentration of hydroxide ion (OH-)
 Bronsted-Lowery base: A proton acceptor
 Lewis base: An electron donor
 Lux-Flood base: An oxide ion (O2-) donor
 Usanovich Base: gives up anions or electrons or combines with
cations or neutralizing an acid to give a salt.
 Acid-Base theories: Arrhenius Acids and Bases
In 1887, the Swedish chemist Svante Arrhenius proposed a new way
of defining and thinking about acids and bases.
According to Arrhenius, acids are hydrogen-containing compounds
that ionize to yield H+ ions in aqueous solution. Bases are compounds
that ionize to yield hydroxide OH– ions in aqueous solution.

Arrhenius Acids Arrhenius Bases

 Acid-Base theories: Brønsted-Lowry Acids and Bases
Na2CO3 and NH3 be a base by the Arrhenius definition.

What distinguishes an acid from a base in the Brønsted-Lowry theory?

According to the Brønsted-Lowry theory, an acid is a H+ ion donor and a

base is a H+ ion acceptor.
•This theory includes all the acids and bases that Arrhenius defined.
•It also includes some compounds that Arrhenius did not classify as bases

In the Brønsted-Lowry definition, an acid-base reaction is a proton transfer process.

HCl + H 2O Cl- + H 3 O+
NH3 + H 2O NH4+ + OH-
 The Conjugate Acid-Base Pair
H2S + NH3 HS- + NH4+
H2S and HS- are a conjugate acid-base pair.
HS- is the conjugate base of the acid H2S.

NH3 and NH4+ are a conjugate acid-base pair.

NH4+ is the conjugate acid of the base NH3.

A Bronsted-Lowry acid-base reaction occurs when an acid and a base

react to form their conjugate base and conjugate acid, respectively.

An acid reactant produces a base product & the two constitute an acid-base conjugate pair.

acid1 + base2 base1 + acid2

 Conjugate Pairs in Some Acid-Base Reactions
conjugate pair

acid1 + base2 base1 + acid2

conjugate pair

reaction 1 HF + H2 O F- + H3 O +

reaction 2 HCOOH + CN- HCOO- + HCN

reaction 3 NH4+ + CO32- NH3 + HCO3-

reaction 4 H2PO4- + OH- HPO42- + H2 O

reaction 5 H2SO4 + N2 H5 + HSO4- + N2H62+

reaction 6 HPO42- + SO32- PO43- + HSO3-

Relative Acid-Base Strength and Reaction Direction
Strong acid:
 Ionization equilibrium lies far to the right.
 Yields a weak conjugate base.
Weak acid:
 Ionization equilibrium lies far to the left.
 Weaker the acid, stronger its conjugate base.

8
 Various Ways to Describe Acid Strength

What is the equilibrium constant expression for an acid acting in water?

HA(aq) + H2O(l) H3O+(aq) + A-(aq)

acid base conjugate acid conjugate base

H3O   A  
K =
HA 
9
 Q1. If water is a better base than A–, do products or reactants
dominate at equilibrium?
Q2. Does this mean HA is a strong or weak acid?
Q3. Is the value for Ka greater or less than 1?

General Rule: An acid-base reaction proceeds to the greater extent in the direction
in which a stronger acid and stronger base form a weaker acid and a weaker base.
a b b a
H2S + NH3 HS- + NH4+ Kc > 1

A competition for the proton between the two bases!

a b b a
HF + H2O F - + H3O+ Kc < 1
PROBLEM: The following reactions are important environmental processes.
Identify the conjugate acid-base pairs.

(a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq)

(b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq)

10
 The Lewis Acid-Base Definition

An acid is an electron-pair acceptor. A base is an electron-pair donor.

BF3 + F- ⇌ BF4-
NH3 + H+ ⇌ NH4+
BF3 + NH3 ⇌ BF3NH3

The adduct contains a

Acid Base new covalent bond.
F F
H
H
B + N
B N
F HH F
F F HH
PROBLEM: Identify the Lewis acids and Lewis bases in the following reactions:
(a) H+ + OH- H2 O
(b) Cl- + BCl3 BCl4-
(c) K+ + 6H2O K(H2O)6+

Lux-Flood Acid-Base
This theory was a revival of the oxygen theory of acids & bases proposed by German
chemist Hermann Lux in 1939 and further improved by Hakon Flood in 1947. It is
still used in modern geochemistry and for the electrochemistry of molten salts

An acid is an oxide O2- ion acceptor. A base is an O2- ion donor.

For example:
MgO (base) + CO2 (acid) ⇌ MgCO3
CaO (base) + SiO2 (acid) ⇌ CaSiO3
 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 acid: gives up cations, or combines with anions or
accepts anions or electrons or neutralizing a base to give salt

Usanovich Base: gives up anions or electrons or combines

with cations or neutralizing an acid to give a salt.

For example:
Na2O (b) + SO3 (a) → 2Na+ + SO42- (species exchanged: anion O2- )
3(NH4)2S (b) + Sb2S5 (a) → 6NH4+ + 2SbS43- (species exchanged: anion S2-)
2Na (b) + Cl2 (a) → 2Na+ + 2Cl- (species exchanged: electron)

This definition could even be applied to the concept of redox reactions

(oxidation-reduction) as a special case of acid-base reactions.
 The solvent system
Auto ionization Cocept
Although many inorganic reactions take place in aqueous solution, water is not
always the most suitable solvent; some reagents react violently or decompose in
water (e.g. the alkali metals) and non-polar molecules are often insoluble in water.
The solvent system concept was introduced by Franklin in 1905 and was
extended by Cady- Esley in 1928. The definition of acids and bases given by this
concept can be applied for protonic as well as for non-protonic solvents.
According to this concept, the solvents usually undergo self ionization (auto-
ionization) and give rise to cations and anions which are called solvent cations and
solvent anions, respectively.

Acids are defined as substances that increase the concentration of the

positive ions characteristics of the solvent.
Bases are substances that increase the concentration of the negative ions
characteristics of the solvent.
 The solvent system
Auto Ionization
water is an extremely weak electrolyte, the electrical conductive of tap
water is due to dissolved ions. The reason is that water itself dissociate
into ions very slightly in an equilibrium process known as auto ionization

2H2O (l) H3O+ + OH-

HCl gives H+ or H3O+ ions in water, hence; it behaves as an acid in aqueous solution.
HCl + H2O(l) Cl- + H3O+

Similarly, NaOH, which furnish OH– ions in its aqueous solution, acts as a base
H2O(l)
NaOH OH- + Na+
Likewise, for a solvent system of BrF3, the autoionization reaction is-
2BrF3 BrF4- + BrF2+
Hence, according to solvent system concept, the substance which can give BrF2+
in BrF3 is acid and the substance which can form BrF4- is base.
SbF5 + BrF3 BrF2+ + SbF6–
Acid

KF + BrF3 BrF4– + K+
Base
Many solvent undergo self ionization such as NH3, N2O4, HF, H2SO4,
& SO2 etc. and form positive and negative ions in a similar way to water:

Liquid dinitrogen tetraoxide, N2O4, undergoes the self ionization

Nitrosyl salts such as [NO][ClO4] behave as acids,

and metal nitrates (e.g. NaNO3) behave as bases.
 The solvent system

Advantages of solvent system concept:

1. The definition of acids and bases given by solvent system concept can be used for
both protonic (e.g. H2O, NH3 etc.) as well as non-protonic (e.g. SO2, SOCl2 etc.)
solvents.
2. The definition is applicable for aqueous (H2O) as well as non-aqueous solvents
(NH3, HF, H2SO4 etc).

Limitations solvent system concept:

1. The definition of acids and bases is based on the nature of the solvent cation and
solvent anion obtained by auto-ionization of the solvent.
2. Acid base reaction taking place in the absence of a solvent can’t be explained, i.e.,
acid-base reaction takes place only in presence of solvent.
3. The concept can’t account for the acid-base reaction occurring in non- ionizing
solvents like C6H6, CHCl3 etc.
 The solvent system
Levelling and differentiating effects

 Water has only a weak tendency to donate a proton.

 Thus in aqueous solutions the mineral acids all donate protons to the
water
 Thus behaving as acids, and in the process the mineral acids ionize
completely.

 If liquid ammonia used as solvent, the acids which were strong,

slightly less strong and even weak acids in water all react completely
with the ammonia.
 The acid strengths have all been leveled by the solvent liquid
ammonia. Thus, this solvent is called a leveling solvent.
 The solvent system
Levelling and differentiating effects

In water, the strongest acid possible is H3O+ and the

strongest base possible is OH-.

Any acid stronger than H3O+ donates its proton to H2O, and any base stronger
than OH- accepts a proton from H2O; thus, water exerts a leveling effect
(levels the strengths of all strong acids and bases).
To rank strong acids: must dissolve in a solvent that is a weaker base than
water (i.e., one that accepts their protons less readily).

HCl(g) + CH3COOH(l) Cl-(acet) + CH3COOH2+(acet)

HBr(g) + CH3COOH(l) Br-(acet) + CH3COOH2+(acet)
HI(g) + CH3COOH(l) I-(acet) + CH3COOH2+(acet)
KHI > KHBr > KHCl
 The solvent system
Levelling and differentiating effects
In a basic solvent, all acids are strong. The solvent is said to exhibit a leveling effect on the acid

In an acidic solvent (e.g. H2SO4), ionization of bases is facilitated; most acids

are relatively weak under these conditions, and some even ionize as bases.

In acetic acid the extent of ionization of the three hydrogen halides varies along
the series: HI > HBr > HCl.

Thus, acetic acid exerts a differentiating effect on the acidic behaviour of HCl,
HBr and HI, whereas water does not.

For acids, strong bases are levelling solvents, weak bases are differentiating solvents.
 Hard and Soft Acids and Bases
Pearson’s HSAB
This theory proposes that soft acids react faster and form stronger bonds with
soft bases, whereas hard acids react faster and form stronger bonds with
hard bases, all other factors being equal. The classification in the original work
was largely based on equilibrium constants for the reaction of two Lewis bases
competing for a Lewis acid.