Chapter Four: Acid Base Chemistry

Acids and Bases are substance we find in our every day

life

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 Acid-Base Theories
• Acid base reaction is chemical reaction that occurs
between an acid and a base.

• Several concepts/theories that provide alternative

definitions for the reaction mechanisms involved and
their application in solving related problems were
developed.

• Some of the important acid- base theories are:

 Theories/Models of Acid Base chemistry
• Several models have been developed to classify, rationalize
and predict the reactivity of acid-base pairs (or donor-
acceptor pairs).
1. Arrhenius Model
2. Brønsted-Lowry Model
3. Lewis Model
4. Solvent System Model
5. Lux-Flood Model
6. Usanovich Model
 Arrhenius Acid Base Concept
• The first modern approach to acid-base concept was
developed in 1878 by Swedish chemist Svante
Arrhenius.
According to Arrhenius concept;
• An acid is defined as a hydrogen compound which dissociated in
water to give hydrogen ions.
HCl (g) + H2O H+(ag) + Cl-(ag)

• A base is a substance which dissociates in to hydroxyl ions when

dissolved in water
NaOH + H2O Na+(ag) + OH-(ag)

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 Cont…

– Acids that contain one ionizable hydrogen, such as

nitric acid (HNO3), are called monoprotic acids.
– Acids that contain two ionizable hydrogens, such
as sulfuric acid (H2SO4), are called diprotic acids.

– Acids that contain three ionizable hydrogens, such

as phosphoric acid (H3PO4) are called triprotic
acids
 Types of Arrhenius Acids
• In terms of chemical structure, Arrhenius acids can
be divided into several different subcategories.
• The major ones include: binary acids, oxyacids, and
organic acids.
• The binary acids are HF(aq), HCl(aq), HBr(aq), and
HI(aq); all have the general formula of HX(aq), where
X is one of the first four halogens.
• The most common binary acid is hydrochloric acid,
HCl(aq)
 Cont…
• Oxyacids (often called oxoacids) are molecular substances
that have the general formula HaXbOc.
• Oxyacids contain hydrogen, oxygen, and one other
element represented by X; the a, b, and c represent
subscripts.
• The most common oxyacids in the chemical laboratory are
nitric acid, HNO3, and sulfuric acid, H2SO4.
• Organic acid such as Acetic acid, with the formula HC2H3O2,
CH3CO2H, or CH3COOH also fits the criteria for classification
as an oxyacid, but it is more commonly described as an
organic (or carbon‑based) acid.
Cont…
 Limitation of the Arrhenius theory
• The reactions of an acid with a base represented a
neutralization of the characteristics of both.
• The Arrhenius theory has been subjected to many
objections, the chief among them beings:
– Acid-base reactions could take place in non-aqueous
media (ammonia, sulfur trioxide)
– Acidic property of salts such as AlCl3 is ignored
– A bare proton cannot exist in solution
– Many substances contain no hydroxyl group but they
are bases (eg. NH3)

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 Brønsted-Lowry Acid Base concept
• Although the Arrhenius definitions of acid, base, and
acid‑base reaction are very useful, an alternate set of
definitions is also commonly employed.
• The Brønsted-Lowry theory was proposed in 1923.
• It is more general than the Arrhenius theory, i.e., all
Arrhenius acids/bases are also Brønsted-Lowry
acids/bases (but not necessarily vice versa).
– A Brønsted-Lowry acid is a proton (H+) donor.
– A Brønsted-Lowry base is a proton (H+) acceptor
– A Brønsted-Lowry acid-base reaction results in the transfer
of a proton from an acid to a base

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 Cont…
Conjugate Acids and Bases
• A conjugate acid is the particle formed when a base
gains a hydrogen ion.
• A conjugate base is the particle that remains when an
acid has donated a hydrogen ion
 Cont…

• A conjugate acid-base pair consists of two

substances related by the loss or gain of a single
hydrogen ion.

• A substance that can act as both an acid and a base is

said to be amphoteric
Example

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Conjugate Pairs in Some Acid-Base Reactions

conjugate pair

acid1 + base2 base1 + acid2

conjugate pair

reaction 1 HF + H2O F- + H3O+

reaction 2 HCOOH + CN- HCOO- + HCN

reaction 3 NH4+ + CO32- NH3 + HCO3-

reaction 4 H2PO4- + OH- HPO42- + H2O

reaction 5 H2SO4 + N2H5+ HSO4- + N2H62+

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

 Acid strength
• Acid strength is the tendency of an acid to donate a proton.
• The more readily a compound donates a proton, the stronger
an acid it is.
• Acidity is measured by an equilibrium constant.
• When a Brønsted-Lowry acid H—A is dissolved in water, an
acid-base reaction occurs, and an equilibrium constant can be
written for the reaction.

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 Acid-Base strength

Strong acids dissociate completely into ions in water.

HA(g or l) + H2O(l) H3O+ (aq) + A- (aq) Kc >> 1

Weak acids dissociate very slightly into ions in water.

HA(aq) + H2O(l) H3O+ (aq) + A- (aq) Kc << 1

Defining the acid dissociation constant

[H3O+][A-]
Kc =
[H2O][HA]
stronger acid, higher [H3O+],
larger Ka
[H3O+][A-]
Kc[H2O] = Ka = [HA] weaker acid, lower [H3O+],
smaller Ka
 Cont…
 Because the concentration of the solvent H2O is essentially
constant, the equation can be rearranged and a new
equilibrium constant, called the acidity constant, Ka, can be
defined

It is generally more convenient when describing acid strength to use “pKa”

values than Ka values.

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19
 Factors that Affect Acid Strength
• Anything that stabilizes a conjugate base A:- makes the
starting acid H—A more acidic.
• Four factors affect the acidity of H—A. These are:
– Element effects
– Inductive effects
– Resonance effects
– Hybridization effects
• No matter which factor is discussed, the same procedure is
always followed. To compare the acidity of any two acids:
– Always draw the conjugate bases.
– Determine which conjugate base is more stable.
– The more stable the conjugate base, the more acidic the
acid.

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 Factors that affect Acid Strength-Element Effect
• Across a row of the periodic table, the acidity of H—A increases as
the electronegativity of A increases

Positive or negative charge is stabilized when it is spread over a larger

volume.

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 Cont…
• Down a column of the periodic table, the acidity of H—A increases
as the size of A increases

• Size, and not electronegativity, determines acidity down a column.

• The acidity of H—A increases both left-to-right across a row and
down a column of the periodic table.
• Although four factors determine the overall acidity of a particular
hydrogen atom, element effects—the identity of A—is the single
most important factor in determining the acidity of the H—A
bond.

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 Trends in Bronsted Acid strength
1. Polyprotic acids: They are capable of dissociating into more
than one proton e.g. H2SO4, H3PO4. They dissociate in steps. The
tendency to dissociate in water follows the order;
• H2SO4 > HSO4-
• H3 PO4 > H2PO4 - > HPO4-
2. In acids with the same central atom containing different number
of oxygen atoms, the acid strength increases as the oxidation
number of central atom increases:
HClO4> HClO3 > HClO2 > HClO
H2SO4 > H2SO3
HNO3 > HNO2
The more positive central atom will attract its bonding electrons
with the oxygen to a greater extent than does the hydrogen atom.
 Cont…

3. Acids with different central atoms containing oxygen:

• All oxygen atoms attached to central atom, lesser the number of
hydrogenated oxygen atoms, greater the acid strength.
HClO4 > H2SO4 > H3AsO3
4. Acids containing oxygen and central atoms having the same
oxidation state: The acid strength decreases as the size of the central
atom increases.
HClO4 > HBrO4> HIO4
H2SO4 > H2SeO4 > H2TeO4
H3PO4 > H3AsO4

• Smaller the size of central atom greater is the charge density,

the more easily it will attract electrons from the electronegative
oxygen.
 Cont…
5. Hydrogen acids
• The acid strength increases with increase in the size of
atoms. The per cent ionic character of the bonds in these
compounds is in the reverse order to their acid strengths,
e.g.
– HI > HBr > HCl > HF
– H2Te > H2Se > H2S > H2O

• The gas phase acidity increases across a period and down

a group in the p-block binary acids, HF is a stronger acid
than H2O and HI is the strongest of the hydrogen halides
 Cont…
6. Hydrides of the elements of a period:
Consider the hydrides of nitrogen, oxygen and fluorine of the second
period. The electronegativity of these element increases in the order.
N<O<F
And acid strength of the hydrides increases in the same order
NH3 < H2O < HF
Similarly, the electronegativities of the elements of the third period
change in the order
P < S < Cl
The acid strength of the hydrides of these elements increases in the
same order
PH3 < H2S < HCl
PH3 does not react with water, H 2S is a weaker acid and HCl is a strong
acid.
 Lewis Acid and Base Concept
• The Lewis definition of acids and bases is more general than
the BrØnsted-Lowry definition.
• A Lewis acid is an electron pair acceptor.
• A Lewis base is an electron pair donor.
 Cont…
• Lewis bases are structurally the same as BrØnsted-Lowry
bases. Both have an available electron pair—a lone pair or an
electron pair in a  bond.

• A BrØnsted-Lowry base always donates this electron pair to a

proton, but a Lewis base donates this electron pair to
anything that is electron deficient.
• A Lewis acid must be able to accept an electron pair.
• All BrØnsted-Lowry acids are also Lewis acids, but the reverse is
not necessarily true.
• Any species that is electron deficient and capable of accepting
an electron pair is also a Lewis acid.
• Common examples of Lewis acids (which are not BrØnsted-Lowry
acids) include BF3 and AlCl3. These compounds contain elements
in group 3A of the periodic table that can accept an electron pair
because they do not have filled valence shells of electrons.

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Cont…
Cont…
Cont…
 Cont…
Classifying Lewis acid behavior:
• All species with an electron pair accepting (vacant)
orbital and all species with full or partial positive
charge behave as Lewis Acids. Lewis Acid behaviour
is found amongst:
• Metal cations complexed by ligands
• Electrophiles (attacking Lewis acids)
• Classic electron deficient species such as BF 3 and AlCl3
• Cationic spectator counter ions
• Electron deficient π-systems which take part in
multicentre interactions
Cont…
• Lewis Base species have a pair of electrons to donate,
or an available HOMO.
• All species with full or partial charge behave as Lewis
Bases. Lone-pair donation behavior is found amongst:
• Anions
• Proton abstractors
• Conjugate Brønsted bases
• Nucleophiles
• Ligands
• Anionic counter ions
• Electron-rich π-systems
 The solvent system concept

• The 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.
 Cont…
• According to this concept,
– The substances which form solvent cations when dissolved
in that solvent are called acids and
– the substances which give solvent anions when dissolved
in that solvent are called bases
Cont…
 Lux-Flood acid base definition

• This acid-base theory was a revival of oxygen theory of acids

and bases, proposed by German chemist Hermann Lux in
1939, further improved by Håkon Flood Circa 1947 and is still
used in modern geochemistry and electrochemistry of molten
salts.
• This definition describes an acid as an oxide ion (O2−) acceptor
and a base as an oxide ion donor. Thus acid-base reaction
involves transfer of oxide ion (compared to transfer of proton
in the Bronsted-Lowry definition).
For example:
• MgO (base) + CO2 (acid) → MgCO3
• CaO (base) + SiO2 (acid) → CaSiO3

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 Usanovich Acid-Base concept

• According to this concept,

– “An acid is any species capable of giving cations, combining
with anions or electrons or neutralizing a base to give a salt
and
– A base is any species capable of giving up anions or electrons,
combining with cation or neutralizing an acid to form salt.”
• Examples:
• Usanovich Acids: SO3, Cl2, etc.
• Usanovich Bases: Na2O, Na, etc.
– This concept is useful in classifying all types of acids and
bases, as well as it also considers the oxidation-reduction
process.
 Cont…
• Na2O (base) + SO3(acid) → 2 Na+ + SO42− 
(O2−anion exchanged)
• 2Na (base) + Cl2 (acid) → 2Na+ + 2Cl−
(2 electrons exchanged)
• 3(NH4)2S (base) + Sb2S5 (acid) → 6NH4+ + 2SbS43- 
(S2- anion exchanged)
 THE HARD-SOFT ACID-BASE PRINCIPLE (HSAB)
• HSAB Theory is a qualitative concept introduced by Ralph
Pearson to explain the stability of metal complexes and the
mechanisms of their reactions .
• It was in that area that evidence of the principle that species
of similar electronic character interact best was first noted.
• As early as the 1950s, Ahrland, Chatt, and Davies had
classified metals as belonging to class A if they formed more
stable complexes with the first series elements in the periodic
group or to class B if they formed more stable complexes with
the heavier elements in that group.

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 Cont…
• Metals are classified as A or B based on the electronic character of
the donor atom they prefer to bond to.
• The donor strength of the ligands is determined by the stability of
the complexes they form with metals

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Cont…

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59
 Cont…
• The guiding principle regarding the interaction of electron pair
donors and acceptors is that the most favorable interactions
occur when the acid and base have similar electronic character

According to HSAB principle;

– Hard acids prefer binding to the hard bases to give ionic complexes,
whereas
– Soft acids prefer binding to soft bases to give covalent complexes.
* The large electronegativity differences between hard acids and
hard bases give rise to strong ionic interactions.
* The electronegativities of soft acids and soft bases are almost
same and hence have less ionic interactions. i.e., the interactions
between them are more covalent.

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 Cont…
• Hard acids (hard metal cations) form more stable complexes with
hard bases (hard ligands), while soft acids (soft metal cations) show
a preference for soft bases (soft ligands).

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 Cont…
• Soft acids and soft bases interact primarily by sharing electron density,
which is favored when the species have high polarizability
• MeHgF + HSO3- → MeHgSO3- + HF   Keq ~ 103

Soft-hard Hard-soft Soft-soft Hard-hard

• MeHgOH + HSO3- → MeHgSO3 － + H2O    Keq > 107

• Hard acids (such as Fe3+) tend to bind the halides in the order of
complex strength of F− >Cl− >Br−> I−, and soft acids (such
as Hg2+) in the reverse order of stability

• Hard acids (hard metal cations) form more stable complexes with hard
bases (hard ligands), while soft acids (soft metal cations) show a
preference for soft bases (soft ligands).

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 Cont…
• One example involves the long-established reaction of Co2+ andHg2+
together in solution with SCN−.
• The ligand has both a ‘soft’ donor (S) and a ‘hard’ donor (N)
available; although like-charged, Hg2+ is larger than Co2+ and further
across and down the Periodic Table, and thus ‘softer’.

• This reaction results in a crystalline solid

[(NCS)2Hg(μ-SCN)2Co(μ-NCS)2Hg(SCN)2],
with each metal in a square plane of thiocyanate donors, with four
S atoms bound to each Hg2+ and four N atoms bound to the central
Co2+.

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Applications of HSAB principle