Concepts of Acids and Bases-Theory & Exercise

CONCEPTS OF ACIDS & BASES
1. SYLLABUS
Various concepts of Acids and Bases, Relative Strengths of Inorganic and Organic Acids
and Bases.
2. INTRODUCTION
The general public is regularly exposed to ideas about acids and bases. The environmental
problems of “acid rain” is a popular topics in newspaper and magazines, and television
commercials mention “pH” in relation to a variety of products, such as deodorants,
shampoos and antacids.
Chemists have been classifying substances as acids and bases for a long time. Lavosier
thought that the common element in all acids was oxygen, a fact conveyed by its name.
Oxygen means “acid former” in Greek. In 1810, Humphry Davy showed that hydrogen is
the elements that acids have in common. In this chapter we will discuss various theories, no
theory is more right or wrong than any other, and we use the most convenient theory for a
particular chemical situation.
3. ARRHENIUS CONCEPT
Swedish chemist Svante Arrhenius gave his theory of ionic dissociation in his Ph..D. thesis.
Threatened with a low passing grade on thesis because his examiners did not understand
his theory. He sent his thesis to several scientists who defended it. This thesis earned
Arrhenius the 1903 Noble prize in chemistry.
According to Arrhenius
a) Acid : A substance which furnishes H+ ions in aqueous solution i.e. when dissolved in
water. e.g. HCl, CH3COOH.
 H+(aq) + Cl–(aq)
HCl (aq) 
 K+(aq) + H+(aq) + SO 24  (aq)
KHSO4 (aq) 
b) Base : A substance which furnishes OH– ions in aqueous solution i.e. when dissolved
in water. e.g. NH4OH, KOH etc.
 K+(aq) + OH–(aq)
KOH (aq) 
NH4OH (aq) NH 4 (aq) + OH–(aq)
Chemistry : Concepts of Acids & Bases
c) Strength of acids and bases according to Arrhenius concepts: Acids and bases
which are almost completely ionized in aqueous solution are termed as strong acids &
strong bases respectively where as acids and bases which are weakly ionized in
aqueous solution are called weak acids & weak bases respectively.
Strong Acid  H+(aq) + Cl–(aq)
HCl(aq) 
Weak Acid CH3COOH(aq) H+(aq) + CH3COO–(aq)
Strong Base  Na+(aq) + OH– (aq)
NaOH(aq) 
Weak Base NH4OH (aq) NH 4 (aq) + OH–(aq) .
d) According to Arrhenius concept, neutralization of acids and bases is basically a
reaction between H+ and OH– ions in solutions :
H+ (aq) + OH– (aq) 
 H2O (l)
3.1 OUTCOME OF ARRHENIUS CONCEPTS
i) Since the reaction representing neutralisation process involves the combination of H+
and OH– ions, the approximately constant molar heat of neutralisation would be
expected. Thus the constant heat of neutralisation of a strong acid by a strong base is
readily understandable in terms of this concept.
ii) This concept has offered a means of correlating catalytic behaviour with the
concentration of the H+ ion.
3.2 LIMITATIONS OF ARRHENIUS THEORY
i) The acid or base property of a substance was not inherent in it, but was dependent on
the presence of water. According to this concept, HCl is regarded as an acid only when
dissolved in H2O and not in some other solvent such as C6H6 or when it exists in the
gaseous form.
ii) The neutralisation process is limited to those reactions which can occur in aqueous
solution only, although reactions involving salt formation do occur in many other
solvents and even in the absence of solvents.
iii) It cannot explain the acidic character of certain salts such as AlCl3 in aqueous solution.
4. BRONSTED - LOWRY THEORY

THE PROTON - DONOR - ACCEPTOR SYSTEM
Bronsted and Lowry in 1923 independently proposed a more general definition of acids
and bases. According to them, an acid is defined as any hydrogen containing material (a
molecule or a cation or an anion) that can release a proton (H+) to any other substance,
whereas a base is any substance (a molecule or a cation or an anion) that can accept a
proton from any other substance. In short, an acid is a proton -donor and a base is a proton
- acceptor.
It may be summarized as below :
a) Acid: An acid is a substance (a molecule or a cation or an anion) that can furnish
proton i.e. H+ ion i.e. proton donor
Acid   H+ + [Base]
Molecular species : HCl   H+ + Cl–

Cationic species: [Al(H2O)6]3+ 
 H+ + [(Al(H2O)5OH]2+
 H+ + CO32 
Anionic species: HCO3 
Base: A base is a substance ( a molecule or a cation or an anion) that can accept proton
i.e. H+ ion i.e. Proton acceptor. e.g.
Base + H+   [Acid]
Molecular species : H2O + H+   H3 O+
Cationic species : CO32  + H+ 
 HCO3
Anionic species : CN– + H+   HCN.
b) Lowry-Bronsted concept does not vary appreciably from Arrhenius concept for acids,
but in case of bases, it vary and need not contain OH– ions only. Therefore, ions like
Cl–, CH3COO–, Br– are bases, although OH– ions are absent in them e.g.
HBr   H   Br 
Acid Base
c) Conjugate Acid-Base Pairs : Chemical species, that is formed from the base by the
gain of proton or H+ ion e.g.
Base  H    [conjugate acid] e.g. H 2 O  H  
 H 3O 
Conjugate Base : Chemical species, that is formed from the acid by the loss of proton
or H+ ion e.g.
Acid   H+ + [conjugate base] e.g. HCl   H+ + Cl–.
d) Formation of conjugate acids and bases are simultaneous process.
Conjugage Acid-Base pair
Acid1  Base 2 Acid 2  Base1

(HCl) (H 2O) (H3O  ) (Cl )
Conjugage Acid-Base pair
4.1 TWO IMPORTANT OUTCOMES OF THE BRONSTED CONCEPT AND

POSITION OF EQUILIBRIUM IN ACID-BASE REACTIONS
In the equilibrium mixture two acid HCl and H3O+ ion are competing to donate protons to a
base. Since HCl wins, it is the stronger acid. Similarly two bases, H2O and Cl– ion, are
competing to accept protons. Here H2O is the stronger base. It will be seen that the stronger
acid, HCl, has the weaker conjugate base Cl– ion and the stronger base, H2O, has weaker
conjugate acid, H3O+ ion. The stronger acid and weaker base form one conjugate acid -
base pair and weaker acid and stronger base form another conjugate acid base pair. It is
quite evident that HClO4 is the strongest acid; its conjugate base ClO4 ion, is consequently
the weakest base. CH4 and H2 are the weakest acids; their conjugate bases, CH3 ion and H–
ion respectively, are consequently the strongest bases. The position of equilibrium is
illustrated through a illustration given below:
4.2 RELATIVE STRENGTH OF CONJUGATE ACID – BASE PAIR
HCl H 2 O H3O  Cl

acid1 base2 acid 2 base1
In the above reaction, two acids (HCl & H3O+ ion) are competing to donate protons, since
the acid HCl wins, it is stronger acid. Similary H2O accepts proton more readily than Cl–,
therefore H2O is stronger base than Cl–. Hence, we conclude that :
a) Stronger acid 
 weak conjugate base & vice-versa
b) Stronger base 
 weak conjugate acid & vice-versa
Conjugate Acid-Base pair
Stronger acid + Stronger Base Weaker acid + Weaker Base
Conjugate Acid-Base pair
Relative Strengths of Conjugate Acid-base Pairs

Acid Conjugate Base
HClO 4 (perchloric acid) ClO 4– (perchlorate ion)
HI (hydroiodic acid) I– (iodide ion)
Strong acids
HBr (hydrobromic acid) Br– (bromide ion)

HCl (hydrochloric acid) Cl – (chloride ion)
H 2SO 4 (sulfuric acid) HSO 4– (hydrogen sulfate ion)
Acid strength increases
Base strength increases

HNO 3 (nitric acid) NO 3– (nitrate ion)
H 3O + (hydronium ion) H 2O (water)
HSO 4– (hydrogen sulfate ion) SO 4 2– (sulfate ion)
HF (hydrofluoric acid) F– (fluoride ion)
HNO 2 (nitrous acid) NO 2– (nitrite ion)
Weak acids
HCOOH (formic acid) HCOO – (formate ion)

CH 3COOH (acetic acid) CH 3COO – (acetate ion)
NH 4+ (ammonium ion) NH 3(ammonia)
HCN (hydrocyanic acid) CN – (cyanide ion)
H 2O (water) OH – (hydroxide ion)
NH 3 (ammonia) NH 2– (amide ion)
Illustration 1 : Write a balanced equation for the dissociation of each of the following
Bronsted-Lowry acids in water :
(a) H2SO4; (b) H 3 O+
(c) HSO4–
Solution : a) H 2SO4  H 2O H3O  HSO –

4
acid 1 base 2 acid 2 base 1 (conjugate)
b) H 3O   H 2 O H3O  HO 2
acid 1 base 2 acid 2 base 1 (conjugate)
c) HSO 4–  H 2O H3O  SO 2–
4
acid 1 base 2 acid 2 base 1(conjugate)
Illustration 2 : Predict the direction of the following reaction in aqueous solution:

HNO2 (aq) + CN – (aq) HCN(aq) + NO2– (aq)
Solution : HCN is a weak acid, hence, its conjugate base CN – is strong. HNO 2 is a
strong acid, hence its conjugate base NO2– is weak. When following reaction
takes place
HNO2 (aq)  CN – (aq) HCN(aq)  NO2– (aq)
stronger acid stronger base wea ker acid wea ker base
There is formation of weaker acid and weaker base, thus, this reaction is
shifted in forward side.
5. PERIODIC VARIATIONS OF ACIDIC & BASIC PROEPRTIES

Protonic acid may be classified as :
Hydra acid : Acid in which acidic hydrogen atom is directly linked to the second element
is called Hydra acid e.g. –
Binary hydrides: HF, HCl, H2S etc.
5.1 RELATIVE STRENGTH OF HYDRA ACIDS
1. Hydra acids of the elements of the same period :
We know that, if the charge is spread over larger volume then,
(i) Smaller is the charge density.
(ii) Smaller is the basic character of the ion to attract a proton.
(iii) Larger is the acidity of the conjugate acid.
Now, consider the hydracids of 2nd period CH4, NH3, H2O, FH.
We find that, from left to right
(i) Size of central atom over which the negative charge is present is decreasing
(ii) The volume of central atom overlapped by hydrogen is 3/4th, 2/3rd, ½ and 1
respectively.
C– N– O– F–
H H H H H
– –
CH 3 NH 2 OH – F–
Increasing volume available to electron
Increasing electron delocalisation
Decreasing electron density
Decreasing basicity
(iii) Volume available for negative charge is increasing in the conjugate bases
(CH 3  NH3  OH   F )
(iv) Charge density of the conjugate bases is decreasing
(v) Basicity of the conjugate bases is decreasing
(vi) Acidity of the acids is increasing
(vii) Stability of conjugate bases is increasing (CH 3  NH3  OH   F )
(viii) Acidity constant is increasing CH4 (10–58) < NH3 (10–35) < H2O (10–14)< HF
(10–4)
(ix) Basicity constant is decreasing
(x) Therefore, the acidic character is increasing (CH 4  NH 3  H 2 O  HF) .
2. Hydra acids of the elements of the same group:
In each Group : from top to bottom
(i) Atomic size of the central atom is increasing.
(ii) Volume available for the negative charge is increasing
(iii) Charge density is decreasing
(iv) Basicity of the ions is decreasing
(v) Acidity of conjugate acids is increasing
(vi) Acidity constant is increasing
(vii) Basicity constant is decreasing
Therefore; order of acidic character can also be explained as following alongwith the
above reasons
a) VII A group (Halogens)
HF < HCl < HBr < HI
(Due to decreasing bond energy of H — X bond).
b) VI A group
H2O < H2S < H2Se < H2Te
(Due to decreasing trend in electron donor ability of OH–, HS–, HSe–, HTe– ions).
c) V A group
NH3 < PH3 < AsH3 < BiH3

(Due to decreasing order of electron density).
d) IV A group
CH4 < SiH4 < GeH4 < SnH4 < PbH4
(Due to decreasing order of electro negativity.)
e) III A group
BH3 < AlH3 < GaH3 < InH3 < TlH3
(Due to decreasing order of electro negativity.)
3. Among hydrides of elements with same electro negativity, acidic strength increases
with size of the central atom e.g.
CH 4  H 2S  HI .
4. The ability of Borontrihalides to act as Lewis acid increases in the order of BF3 < BCl3
< BBr3 < BI3 due to decreasing order of strength of  bond when halide forms X-B
bond.
5. Acids that require only one electron pair to complete an outer shell are stronger than
those require two. Thus
GaCl3 > ZnCl2.
5.2 OXY ACID
Acid in which acidic hydrogen is linked to central atom via an oxygen atom e.g. –
O
O S
H2SO4, HNO3, HO OH
What is meant by strength of acids and bases:
According to Lowry-Bronsted concept, a stronger acid has a greater tendency to donate a
proton and a strong base has a greater tendency to accept a proton.
Quantitatively, the magnitude of strength of Bronsted acid & Bronsted base in aqueous
solution is expressed by acidity constant (Ka) and basicity constant (Kb) respectively.
a) For acid: HF(aq) + H2O(  ) H3O+ (aq) + F–(aq)
[H3O ] [F ]
Ka  and thus, pKa = – log Ka
[HF]
If K a   , given substance is a strong acid.
If K a  1 or pKa > 0, given substance is a weak acid.
5.3 IONIZATION CONSTANTS OF SOME WEAK ACIDS AT 25°C

Name of acid Formula Ka Conjugate Base Kb
–4 –
Hydrofluoric acid HF 7.1 × 10 F 1.4 × 10–11
Nitrous acid HNO2 4.5 × 10–4 NO2– 2.2 × 10–11
Acetysalicylic acid (aspirin) C9H8O4 3.0 × 10–4 C9H7O4– 3.3 × 10–11
Formic acid HCOOH 1.7 × 10–4 HCOO– 5.9 × 10–11
Ascrobic acid C6H8O6 8.0 × 10–5 C6H7O6– 1.3 × 10–10
Benzoic acid C6H5COOH 6.5 × 10–5 C6H5COO– 1.5 × 10–10
Acetic acid CH3COOH 1.8 × 10–5 CH3COO– 5.6 × 10–10
Hydrocyanic acid HCN 4.9 × 10–10 CN– 2.0 × 10–5
Phenol C6H5OH 1.3 × 10–10 C6H5O– 7.7 × 10–5
b) For Base : NH3(aq) + H2O (  ) NH 4 (aq) + OH–(aq)
[NH 4 ][OH  ]
Kb  and Thus pKb = –log Kb.
[NH 3 ]
If K b   , given substance is a strong base.
If K b   1 or pKb > 0, given substance is a weak base.
5.4 IONISATION CONSTANTS OF SOME COMMON WEAK BASES AT 25°C

Name of base Formula Kb Conjugate acid Ka
Ethylamine C2H5NH2 5.6 × 10–4 C2H5N+H3 1.8 × 10–11
Methylamine CH3NH2 4.4 × 10–4 CH3N+H3 2.3 × 10–11
Caffeine C8H10N4O2 4.1 × 10–4 C8H11N4+O2 2.4 × 10–11
Ammonia NH3 1.8 × 10–5 NH4+ 5.6 × 10–11
Pyridine C5H5N 1.7 × 10–5 C5H5N+H 5.9 × 10–10
Aniline C6H5NH2 3.8 × 10–5 C6H5N+H3 2.6 × 10–10
Urea N2H4CO 1.5 × 10–5 H2NCON+H3 0.67×10–10
c) Polyprotic Acids: substance that can donate more than one proton. e.g. H2S.
For polyprotic acids.
K a1  K a 2
pK a1  pK a 2
For cis-Butanedioic (maleic) acid, pK a1  1.92, pK a 2  6.23
For trans-Butanedioic (fumaric) acid, pK a1  3.02, pK a 2  4.38

Thus, it is also seen that cis-butanedioic (maleic) acid is much stronger acid than trans-
butanedioic (fumaric) acid due to intramolecular H-bonding which stabilize conjugate
base.
5.5 IONISATION CONSTANTS OF SOME COMMON DIPROTIC AND
POLYPROTIC ACIDS IN WATER AT 25°C
Name of acid Formula Ka Conjugate Base Kb
–
Sulfuric acid H2SO4 very large HSO4 very small
– –2 2–
Hydrogen sulfate ion HSO4 1.3 × 10 SO4 7.7 × 10–13
Oxalic acid C2H2O4 6.5 × 10–2 C2HO4– 1.5 × 10–13
Hydrogen oxalate ion C2HO4– 6.1 × 10–5 C2O42– 1.6 × 10–10
Sulfurous acid H2SO3 1.3 × 10–2 HSO3– 7.7 × 10–13
Hydrogen sulfite ion HSO3– 6.3 × 10–8 SO32– 1.6 × 10–7
Carbonic acid H2CO3 4.2 × 10–7 HCO3– 2.4 × 10–8
Hydrogen carbonate ion HCO3– 4.8 × 10–11 CO32– 2.1 × 10–4
Hydrosulfuric acid H2 S 9.5 × 10–8 HS– 1.1 × 10–7
Hydrogen sulfide ion HS– 1 × 10–19 S2– 1 × 105
Phosphoric acid H3PO4 7.5 × 10–3 H2PO4– 1.3 × 10–12
Dihydrogen phosphate ion H2PO4– 6.2 × 10–8 HPO42– 1.6 × 10–7
Hydrogen phosphate ion HPO42– 4.8 × 10–13 PO43– 2.1 × 10–2
5.6 RELATIVE STRENGTH OF OXYACIDS

1. Oxyacids with same central atom in different oxidation state:
Among oxyacids of the same central atom having general formula. (HO)m ZOn
Where z = central atom
m = no of oxygen atoms attached to Z and attached to H.
n = No of oxygen atoms attached to Z but not attached to H.
Acidic strength increases with increasing no of n or increasing oxidation no e.g.-
1 3 5 7
a) HO Cl  HO Cl O  HO Cl O 2  HO Cl O3
very weak weak strong very strong
They give OCl, OClO, OClO 2 , OClO3 anions after removal of a proton. The species
which have more than one oxygen atom show resonance.
We see that from left to right, acidic strength increases
Due to:
 More the number of oxygen atoms, more the resonance.
 Volume available for the negative charge is increasing
 Charge density is decreasing
 Basicity of the anion is decreasing
 Acidity of the conjugate acid is increasing.
4 6
b) H 2SO3  H 2SO 4
3 5
c) H NO2  H NO3
d) When the oxidation state rule as given above is applied to the oxyacids of phosphorus
 3 5
viz. H 3 P O 2  H 3PO3  H3P O 4 , but the experimental observation suggest the reverse
order viz H3PO2 > H3PO3  H3PO4.
Explanation : The experimental order can be explained when we consider the
structures of these acids as given below. In these the number of protonated and
unprotonated oxygen atoms have also been indicated. The oxygen atom attached with
a proton is called protonated oxygen while that attached directly with phosphorus
(central atom) is known as unprotonated oxygen.
O—H H O—H H—O O—H
H
P P P
Structure : H O—H O—H
O O O
H3PO2 H3PO3 H3PO4
Nature of the acid: Monobasic Dibasic Tribasic

No. of protonated oxygen 1 2 3
atoms
No. of unprotonated oxygen 1 1 1
atoms:
The proton attached to any oxygen atom has a far greater chance of dissociation than
that linked directly with phosphorus atoms (which is the central atom). Thus in this
series, since the number of protonated oxygen atoms and consequently the number of
dissociable protons increases from one in H3PO2 to three in H3PO4, the acidity of these
acids decrease in the order : H3PO2 > H3PO3  H3PO4
2. Oxyacids with different central atom of same oxidation state and same configuration.
Acid will be stronger if central atom is more electronegative
a) HOI < HOBr < HOCl
b) HIO4 < HBrO4 < HClO4
c) HPO3 < HNO3
d) H3AsO4 < H3PO4.
Among above; acidity increases from left to right due to moving towards top in the
group.
Due to:
 Decreasing size of the central atom
 Increasing order of the electro negativity
 Increasing order of pull of electron of O—X bond towards X.
 Resulting into increasing positive character on O.
 Ultimately, increasing order of release of H+.
3. The strength of oxyacids increases from left to right across a period e.g. –
H2SiO4 < H3PO4 < H2SO4 < HClO4,
Which is attributable to increase in electronegativity of the central atom,
4. Hydrated metal ions
Under favourable conditions, one or more protons may dissociate to form the
coordinated aqua groups.
[M(H 2O) 6 ]n   H 2 O 
 [M(H2O)5OH]n–1 + H3O+
(Hydrated metal ion)
Al(H 2O)63  H2O 

 Al(OH)(H 2O)52 _  H 3O 
In principle, all metal ions react with water to produce an acidic solution. However,
because the extent of hydrolysis is most pronounced for the small and highly charged metal
cations such as Al3+, Cr3+, Fe3+ and Be2+, we generally neglect the relatively small
interaction of alkali metal ions and most alkaline earth metal ions with water. When
aluminium chloride (AlCl3) dissolves in water, the Al3+ ions take the hydrated form
Al(H2O)63+. Let us consider one bond between the metal ion and an oxygen atom from one
of the six water molecules in Al(H 2 O)36 .
H
H O
H
3+
The positively charged Al ion draws electron density toward itself, increasing the polarity
of the O – H bonds. Consequently, the H atoms have a greater tendency to ionize than
those in water molecules not involved in hydration. The resulting ionization process can be
written as
Al(H 2O)63 (aq)  H 2 O(l) Al(OH)(H 2O)52 (aq)  H 3O  (aq)
or simply Al(H 2O)63 (aq) Al(OH)(H 2O)52 (aq)  H  (aq)

The equilibrium constant for the metal cation hydrolysis is given by
[Al(OH)(H 2O)52 ][H  ]
Ka  3
 1.3  10 5
[Al(H 2 O)6 ]
Note that Al(OH)(H 2O)52 can undergo further ionization
Al(OH)(H 2 O)52 (aq) Al(OH)2 (H 2 O)4 (aq)  H  (aq)

and so on. However, it is generally sufficient to take into account only the first stage of
hydrolysis.
For hydrated metal ion or aqua acids, acidity increases with the increase of positive charge
of the central metal ion and with decreasing ionic radius.
[Fe(H2O)6]3+ > [Fe(H2O)6]2+.
Exceptions are some times seen due to the effect of covalent bonding.
[Fe(OH 2 )6 ]2  [Fe(OH 2 )6 ]3  [Al(OH 2 ) 6 ]3  [Hg(OH 2 )6 ]2
Illustration-3 Account for the fact that there is very little difference in acid strength in the
series H 3 PO4 , H 3 PO3 and H 3 PO2 .
Solution : The hydrogens in these acids are not all bonded to oxygens. From the Lewis
structures,
O O O
H —O —P—O—H H—O—P—O—H H—P—O—H
O H H
H
It is seen that the number of terminal oxygen atoms is 1 in all three acids. The
electronegativities of P and H are almost the same. Thus, no great difference in
acidity are expected.
Illustration-4 Why sulphuric acid is stronger than sulphurous acid?

Solution : Sulphuric acid is stronger than sulphurous since the sulphur atom in sulphuric acid
has more coordinated oxygen atoms.
O
O O O O
H S H H S H
O O
Sulphurous acid Sulphuric acid
Illustration-5 Explain
F– is a strong base
Solution : F– is a conjugate base of acid HF. HF is a weak acid. Weaker the acid, stronger the
conjugate base.
Illustration-6 Compare the acidity between HClO4 and H3AsO3.

Solution : HClO4 is much stronger than H3AsO3, conjugate base of it more stabilised than
conjugate base of H3AsO3.
5.7 LEVELLING SOLVENTS
Whenever an acid is dissolved in water, it acts as an acid only if the solvent acts as a base.
That is, if we dissolve acids like HCl, HNO3 etc in water, their acidic strength is almost the
same since water acts as a base for both these acids. Infact, it is known that all strong acids
show equal acidic strength when dissolved in water. This is because, water acts as a base to all
these acids and thus forces them to donate almost the same amount of protons irrespective of
their chemical nature. Since water levels the acidic strength of strong acids, it is referred to as
a levelling solvent. In order to measure the strength of strong acids, they are dissolved in
glacial acetic acid and the amount of protons are measured by conductometry. It is found that
the strength of acids varies as
HClO4 > HBr> H2SO4 > HCl > HNO3
5.8 AMPHIPROTIC SPECIES
Many molecules and ions can behave like water and may either gain or lose a proton under the
appropriate conditions. Such species are said to be amphiprotic. eg.
Acid1 Base2 Acid2 Base1
- -
HS + OH H2O + S2-
HBr + HS- H2S + Br-
HCO3 + CN- HCN + CO23 
H3O+ + HCO3 H2CO3 + H2O
5.9 OUTCOME OF BRONSTED CONCEPT

i) It defines acids and bases in terms of the substances themselves and not in terms of
their ions in aqueous solution. Thus HCl is an acid because of the fact that it can give a
H+ ion.
HCl H+ + Cl–
ii) The Bronsted concept recognises that acid-base behaviour is neither restricted to, nor
depends on, any particular, solvent
iii) This concept is useful in accounting for the hydrolysis of salt solution. When a salt is
dissolved in water, an unbalance in the concentration of the solvent cation (H3O+) and
anion (OH–) will result, if the salt cation and anion differ in their proton-donor and
proton-acceptor properties towards H2O. This point can be illustrated by considering
the aqueous solution of FeCl3. Aqueous hydrated ferric ion, [Fe(H2O)x]3+, exceeds the
proton-acceptor ability of Cl– ion and a considerable excess of H3O+ ion is produced in
the solution, making FeCl3 acidic.
FeCl3 + xH2O [Fe(H2O)x]3+ + 3Cl–
Aqueous solution of a Na2CO3 is alkaline in character, because the proton acceptor
ability of CO32  ion exceeds the proton-donor ability of hydrated sodium ion,
[Na(H2O)x]+.
2xH2O + Na2CO3 2[Na(H2O)x]+ + CO32 
5.10 LIMITATIONS OF BRONSTED CONCEPT

i) This concept lays excessive emphasis on the proton - transfer. Although it is true that
most common acids are protonic in nature, yet there are many which are not. It fails to
explain the acidic character of many substances which do not contain any proton (e.g.
SO3, AlCl3).
ii) There are a number of acid-base reactions in which no proton transfer takes place,
e.g. SO2 + SO2 SO2+ + SO32 
Acid1 + Base2 Acid2 + Base1
Thus the protonic definition cannot be used to explain the reactions occurring in non-
protonic solvents such as COCl2,SO2, N2O4 and BrF3.
6. GENERAL THEORY OF SOLVENT SYSTEM

The protonic definition of acids and bases given by Bronsted can be extended to the
reactions occurring in non-aqueous solvents containing hydrogen such as NH3, N2H4,HF,
H2SO4, CH3COOH, HCN and alcohols.
In an attempt to have a more general definition of acids and bases applicable to protonic
and non-protonic solvents, several definitions have been proposed. One of these is due to
Cady and Elsey (1928) according to whom an acid is solute that, either by direct
dissociation or by reaction with the solvent gives the anion characteristic of the solvent and
a base is a solute that, either by direct association or by reaction with the solvent, gives the
cation characteristic of the solvent. If for example, we consider the solvent H2O, its
characteristic cation and anion are H3O+ and OH– respectively as shown below:
acid base acid base
H 2O  H 2 O H 3O   OH 
Thus all those compounds which can give H3O+ ions in H2O will act as acids and all the
compounds which can give OH– ions in H2O will behave as bases.
Similarly in N2O4 as solvent substance such as NOCl which yield NO+ ions are acids and
the substances such as NaNO3 which yield NO3– ions are bases.
Acid Base Acid Base
N 2O 4 + N 2O 4 2NO  + 2NO3
Evidently this definition of acids applies equally well to protonic and non-protonic
solvents.
The auto-ionisation of some protonic and non-protonic solvents is shown below.

Acid Base Acid Base

Protonic solvents H2 O + H2 O H3O+ + OH–
NH3 + NH3 NH4+ + NH2–
CH3COOH + CH3COOH CH3COOH2+ + CH3COO–
Non-protonic
SO2 + SO2 SO2+ + SO32 
solvents
COCl2 + COCl2 (COCl.COCl2)+ + Cl–
BrF3 + BrF3 BrF2+ + BrF4–
N2 O4 + N2 O4 2NO+ + 2NO3–
Just as with the Arrhenius definition, neutralisation is a reaction between an acid and a base
to produce a salt and the solvent. Neutralisation reaction in some non-aqueous solvents are
given below:
Acid Base Salt Solvent
In liq. NH3 : NH4Cl + NaNH2 NaCl + 2NH3

In N2O4 : NOCl + NaNO3 NaCl + N2O4
In CH3COOH : HCl + CH3COONa NaCl + CH3COOH
In liq. SO2 : SOCl2 + [N(CH3)4]2 SO3 2[N(CH3)4]Cl + 2SO2
It may be seen from the following reactions that there is a complete analogy between the
solvolytic acid and amphoteric behaviours in aqueous solvents.
Solvolytic behaviour In liq. NH3: AlCl3 + NH3  [Al(NH2)]2+ + H+ + 3Cl–
In H2O: AlCl3 + H2O  [Al(OH)]2+ + H+ + 3Cl–
Amphoteric behaviour In liq. NH3: Zn(NH2)2 + 2NH2–  [Zn(NH2)4]2–
In H2O Zn(OH2) + 2OH–  [Zn(OH)4]2–
6.1 UTILITY OF SOLVENT SYSTEM THEORY

Evidently this concept of solvent system can be used to explain the acid-base reactions
occurring in aqueous solvents (protonic and non-protonic both). It also includes many
nonaqueous acidbase systems.
6.2 LIMITATIONS OF SOLVENT SYSTEMS THEORY

i) This theory does not consider a number of acid base reactions included in the protonic
definition.
ii) It limits acid base phenomena to solvent systems only. Thus it does not explain the
acid - base reactions which may occur in the absence of solvent.
iii) It cannot explain the neutralisation reactions occurring without the presence of ions.
Thus this theory can simply be said to be an extension of the Arrhenius water - ion system.
7. LEWIS CONCEPT
a) Lewis acid: species which can accept electron pair(s).
b) Lewis base: species which can donate electron pair(s)
: NH  BF3 
3  H 3 N  BF3
Lewis base Lewis acid
c) All Bronsted bases are Lewis bases but all Bronsted acids are not Lewis acids because
Bronsted acid can give a proton, but may not be capable of accepting a pair of
electron. e.g HCl, H2SO4.
Conditions for Lewis Acid
1. Molecules whose central atom have an incomplete octet e.g. BF3, AlCl3.
H H H H
BMe3  N N N N BMe3
H H H H
+ +
2. Simple cations : e.g. H , Ag .
..
2 N H3 + Ag+   [H3N  Ag  NH3]+
3. Compounds in which the central atom has empty d-orbital and or other orbitals (s and
p) of suitable energy and may acquire more than an octet of valence electrons e.g. PF3 .
SiF4.
SiF4  2 F 
 [SiF6 ]2 
4. Molecules containing multiple bonds. e.g. between atoms of dissimilar electro
negativity e.g. CO2, SO2.
OH
 –
O  C  O  OH 

Lewis acid Lewis base
O O
5. A closed shell molecule may be able to use one of the unoccupied antibonding
molecular orbitals to accommodate an incoming electron pair. e.g. – Tetracyano
ethane.
Conditions for Lewis Bases

1. Molecule(s) whose central atom has unshared pair(s) of electrons e.g. –
H 2 O , NH3 , ROH, ROR
2. Multiple bonded compounds which form coordination compounds with transition
metals e.g. CO, NO, ethylene.
3. Simple negative anions : Cl , F etc.
Illustration-7 How do you account for the formation of S2 O32– from SO32– and S in terms of
Lewis acid theory?
Solution : A sulfur atom is electron deficient and can thus be regarded as an acid. SO32– , for
which an octet structure can be written, is the base.
8. HARD AND SOFT ACIDS AND BASES

Lewis acids and bases are classified as hard and soft acids and bases. A firmly held
electron cloud with low poarisability makes a species “ hard” while an easily polarisable
electron cloud characterizes the species as soft. A third category with intermediate
character appears in the border line. Thus.
Hard Acid : Those species in which electron accepting atom is small with a high positive
charge and no electron which are easily polarized or removed.
Soft Acid : Those species in which the acceptor atom is large, carries a low positive charge
or it has electron in orbitals which are easily polarized or distorted.
Hard Base : Those Lewis base which holds its electrons strongly.
Soft Base : Those Lewis base in which the position of electrons is easily polarized or
removed.
Hard acids Soft acids
i) Small size i) large size
ii) high positive oxidation state ii) zero or low positive oxidation state
iii) absence of any outer electron which are iii) several easily excitable valence
easily excited to higher states electrons
iv) high electronegativity iv) low electronegativity
v) low polarisability v) high polarisability
+ + + +
H , Li , Na , K Cu+, Ag+, Hg+
Be2+, Mg2+, Ca2+, Sr2+ Cd2+, Pt2+, Hg2+, Pt4+
Al3+, Fe3+, Co3+, Cr3+ I+, I2, Br2, Br+
CO2,SO3 Cl, Br, I, N
HX (hydrogen –bonding molecules) M° (metal atoms) and bulk metals
Hard Bases Soft bases
i) high electronegativity i) low electronegativity
ii) low polarisability ii) high polarisability
iii) Presence of filled orbitals; iii) partially filled orbitals;
iv) empty orbitals may exist at high energy iv) empty orbitals are low lying.
level
H2O, OH–, F–, Cl– H–, I–
CH3CO 2 , PO34 , SO24 SCN–, CN–, S2O23 
NO3 , CO23 , ClO 4 R2S, RSH, RS–
NH3, N2H4, RNH2 R3P, R3As.
9. ORIGIN OF ACIDITY OR BASICITY IN ORGANIC COMPOUNDS

Acid vs Electrophile : An electron acceptor or electron deficient species is called Lewis
acid as well as electrophile. They can be neutral or cation. e.g. BH3, BF3, AlCl3, ZnCl2. Br+
An electron deficient species is called electrophile if it tends to make bond with carbon. In
other situations the species is known as acid.
Electrophile
Br   
  H
Br
Acid 
 BrOH  H 
Br  H 2O 
It should be noted that all Lewis acids are electrophiles and vice versa. They differ only in
the mode of action as stated above.
Bases Vs Nucleophile : An electron donar is called lewis base as well as nucleophile.
e.g. H2O, NH3, CH3OH, CN–, NO2–, X–
An electron rich species is called nucleophile if it tends to make bond with carbon
otherwise it is called lewis base.
Base HO   H  
 H 2O
Nucleophile OH   CH3I 
 CH 3OH  I
Nucleophilicity vs Basicity : All bases are nucleophiles and vice versa, but a strong base
need not be a strong nucleophile, similarly a poor base need not be a poor nucleophile.
This is because nucleophilicity/electrophilicity is kinetically controlled property but
acidity/basicity are thermodynamically controlled property.
Therefore,
1
Acidity 
Basicity of conjugate base
or Acidity  Stability of conjugate base

Similarly,
Basicity  Stability of conjutate acid
Illustration-8 Which of the following will be more acidic

a) CH3COOH; (b) CCl3COOH
Solution : a) O O
H3 C H3C  H+
OH O
(i)
Cl O Cl O
Cl Cl  H+
Cl OH Cl O
(ii)
Since (ii) is more stable than (i) so

b) will be more acidic than (a)
Periodic Table correlation of Basicity and Nucleophilicity : In a period there is no

significant change in size therefore electronegativity is the controlling factor.
CH 3  NH 2  OH   F (due to electronegativity)
On the other hand in a group there is a very high change in size of atoms so in a group
atomic size becomes controlling factor.
F  Cl   Br   I
Decreasing order of basic strength
If active atom falls in a period Basicity If active atom falls in a group

order (B.O.) = Nucleophilicity order (N.O.)
In gas phase In aprotic polar solvent In protic polar solvent

B.O. = N.O. B.O. = N.O. B.O.  N.O.
Example
O
B.O. F–  Cl–  Br–  I– H3C O
N H3C S
N.O. in gas phase F–  Cl–  Br–  I–
H3C H CH3
N.O. in DMF or DMSO F–  Cl–  Br–  I– D.M.F. D.M.S.O.
N.O. in H2O/CH3OH I–  Br–  Cl–  F–
Solvent effect on Nucleophilicity : In protic polar solvent (H2O, CH3OH), solvation of
Nucleophile occurs through H-bonding. Since O  H  F bond is strongest F– is solvated to
the maximum extent. But I– is solvated by few water molecules.

H OH
O O  
H H I H H F H OH

H OH
–
Availability of I as nucleophilicity in protic polar solvent is high. That is why in protic
polar solvents nucleophilicity order is
I  Br   Cl  F
On the other hand in aprotic polar solvents, nucleophile dissolves but they are not highly
solvated since H-bonding is not possible. That is why in solvents like DMF or DMSO
nucleophilicity order does not change.
9.1 RELATIVE STRENGTH OF ORGANIC ACIDS

1. % s-character
a) Hydrocarbons: Hydrogen atom attached to sp-hybridised carbon is more acidic than
that on sp2 hybridised carbon which in turn is more acidic than that on sp3.
In other words, acidity increases with percentage (%) s-character. This is because,
higher the s-character closer the electrons to the nucleus of C and farther the electrons
go from H, and easily can H be removed as H+.
Thus, HC  CH  H 2C  CH 2  H3C — CH3
sp sp2 sp3
b) Carboxylic Acids: Acidity of carboxylic acids increases with increasing % s-character

CH  C  CH 2 COOH  CH 2  CH  CH 2 COOH  CH 3CH 2CH 2COOH 2.
Due to resonance of conjugate Base
a) Phenol (C6H5OH) is acidic while ethanol (C2H5OH) is neutral. Because conjugate base
of phenol i.e. phenoxide ion (C6H5O–) can stablise through resonance while that of
alcohol i.e. alkoxide ion (C2H5O–) can not.
OH OH
3 more resonating structrue
–H  (Charge seperation is present, not much stable)
O O O O O
(No charge seperation, more stablization by resonance)
b) Similarly, C6H5COOH > CH3COOH. Because C 6 H5 COO is more stablised than

CH3COO .
c) Phenols are less acidic than carboxylic acids because Phenoxide ion ( C 6 H5 O ) is less
stable than carboxylate ion RCOO
d) R—COOH > R—OH
Because carboxylate anion RCOO is more resonance stablised than alkoxide
anion C 2 H5O .
O O
R C OH R C R C
O O
O
R — CH 2 — OH 
 R — CH 2 — O
The same effect is found in other compounds containing a C=O or C  N group. Thus,
amides (RCONH 2 ) are more acidic than amines (RCH 2 NH 2 ) ;
Esters (RCH 2COOR ) than ethers ( RCH 2CH 2OR ); and
Ketones (RCH 2 COR ) than alkanes (RCH 2 CH 2 R ) .
The effect is enhanced when two carbonyl groups are attached to the same carbon
(because of additional resonance and spreading of charge). E.g.  -keto esters are more
acidic than simple ketones or carboxylic esters.
R C CH2 C OR R C CH C OR R C CH C OR
O O O O O O
R C CH C OR
O O
e) CH 3 — COOH  C6 H 5 — COOH
Because Benzoate anion ( C 6 H5 COO  ) shows more resonance than carboxylate anion
( RCOO ).
Exception: C6H5COOH < HCOOH. (Because there is no destablising factor for
formate ion.)
3. Inductive Effect: In Carboxylic Acids
a) –I Effect: An electron withdrawing group (–I group) withdraws electrons and hence if
present in a carboxylic acid, it stablises the anion and thus increase the acidity. e.g.
i) CH3 — COOH  ClCH 2 — COOH  Cl 2CH — COOH  Cl3C — COOH
ii) Cl
H3C
COOH 
Cl H3C COOH
This is due to the fact that nearer the Cl is placed to COOH group, more is the acidity.
iii) Acidic strength increases in the order CHF3 < CHCl3 < CHBr3 < CHI3 due to
decreasing electronegativity of halogen atoms.
b) +I Effect : An electron releasing group (+I group) releases electrons and hence when
present destablises the anion and thus decreases acidity of carboxylic acids.
H—COOH < CH3—COOH.
4. Alcohols are more acidic than CH4 because oxygen is more electronegative than C and
consequently O—H bond easily give H+ ion than C—H bond.
H3C—H < CH3O—H.
Illustration-9 Arrange the following in the increasing order of acidic strength.

COOH COOH COOH COOH COOH
NO2 CH3 NH2 Cl

(I) (II) (III) (IV) (V)
Solution : I  V  IV  II  III
9.2 RELATIVE STRENGTH OF ORGANIC BASES

Higher the electron density on nitrogen, more is the basic character of amine
[A] Aliphatic Amines [R—NH2]
1. Inductive Effect :
a) Presence of electron releasing group (+I group) on nitrogen release electrons and
hence increases availability of electrons at nitrogen i.e.increases basicity. Thus methyl
amine is stronger base than ammonia. However, if the nitrogen atom having lone pair
of electrons is having three alkyl (bulky) groups, the availability of these electrons to
protons decreases (steric effect) and thus tertiary amines are weak bases than the
secondary and even than the primary amines.
R2NH > RNH2 > R3N > NH3
e.g. (Me)2NH > MeNH2 > (Me)3N > NH3.
(Et)2 NH > Et NH2 > (Et)3 N > NH3.
Thus pK a value for the following is observed as :
CH3 CH 3
CH3 NH 2 NH CH 3 N
(10.64) CH3 (10.77) CH 3 (9.80)
NH 3
(9.25)
C2 H 5 C 2 H5
C2 H 5 NH 2 NH C 2 H5 N
(10.67) C2 H5 (10.93) C 2 H5 (10.88)
The basic strength of an amine in water is determined not only by electron –

availability on the nitrogen atom, but also by the extent to which the cation, formed by
uptake of a proton, can undergo solvation and so become stablised. The more
hydrogen atoms attached to nitrogen in the cation, the greater is the possibilities of
powerful solvation via hydrogen bonding between these and water.
OH2 H OH2 H OH2 H
-
R N H OH2 > N R > R N R
OH2 H OH2 H R
Decreasing stablisation by solvation
b) Introduction of alkyl (e.g Me group) on the nitrogen atom of aniline results in small
increase in pKa due to the +I effect of alkyl groups. e.g.
C6H5 NH2 < C6H5 NHMe < C6H5 NMe2.
2. Resonance: A compound is basic in nature, if its conjugate acid can stabilize through
resonance e.g.
NH2
Guanidine H2N NH is strong alkali because its conjugate acid is very

much stablised through resonance.
NH2 NH2 NH2
C C C
H2N NH2 H2 N NH2 H2N NH2
[B] Aromatic Amines

1. Resonance: Aniline is weaker base than the primary aliphatic amines due to resonance
which decreases availability of lone pair of electrons on nitrogen.
C 6 H5 — NH 2  R — NH 2 .
NH 2 NH2 NH2 NH 2
2. Inductive effect
a) +I Effect: Presence of +I group like alkyl group in the NH2 NH2
benzene nucleus of aniline increases the basicity. This
effect is more when the alkyl group is in O– and P–
position than in m-position.
–I Effect: Presence of –I group like –NO2 and
b) Halogen in the benzene nucleus of aniline decreases N N
the basicity. This effect is much more in O– and O O O O
p– position than in m position.
Electron withdrawal is intensified when the nitro group is in the O– or P– position, for
the interaction of the unshared pair of the amino nitrogen with the delocalized 
orbital system of the benzene nucleus is then enhanced. The neutral molecule is thus
stablised even further with respect to the cation, resulting in further weakening as a
base.
The extra base-weakening effect,when the substituent is in the O–position, is due to
the short distance over which its inductive effect is operating, and also to direct
interaction, both steric and by hydrogen bonding with the NH 2 group.
3. Steric Effect
a) N-alkylated anilines are stronger bases than aniline because of steric effect which
decreases the resonance of the lone pair of electrons on nitrogen and hence makes it
more available for protonation.
b) Ethyl group, being bigger than methyl has more steric effect, so N– ethylaniline is
stronger base than N–methylaniline.
4. Introduction of phenyl groups on nitrogen lowers basicity because the substituted
amine becomes much more stable than the ion.
Ph2 NH < PhNH2.
5. 2, 4, 6-trinitro – N, N-dimethylaniline is 40000 times sronger base than 2, 4, 6-
trinitroaniline because NMe2 group is sufficiently large to interfere sterically with the
very large NO2 groups in both o-positions.
Me Me
O N O
N N
O O
N
O O
Illustration-10 N-ethyl aniline is more basic than N methyl aniline why?

Solution : N-alkylated anilines are stronger bases than aniline because of steric effects
which decrease the resonance of the lone pair of electron on nitrogen and
hence makes it more available for protonation. Ethyl group is bigger than the
methyl group so N-ethyl aniline is stronger base than N-methyl aniline.
10. FACTORS AFFECTING THE STRENGTH OF ACIDS AND BASES

[A] Effect of structure :
1. Field effect (–I effect and +I effect) 
2. Resonance effect 

 Already discussed
3. Periodic Table correlations 
4. Steric hinderance 
5. Hybridisation
6. Statistical Effects : In a symmetrical diprotic acid, the first dissocation constant is

twice as large as expected, since there are two equivalent ionizable hydrogens, while
the second constant is only half as large as expected because the conjugate base can
accept a proton at two equivalent sites. So k1/k2 should be 4. Similar arguments hold
good for basic groups.
7. Hydrogen Bonding: p-hydroxy benzoic acid  o  hydroxy benzoic acid
pk a  4.58 pk a  2.98
(k a 10–5 ) (k a 10 –3 )
Intra molecular hydrogen bonding between the OH and COO groups of the conjugate
base of the ortho isomer stablizes it and results in an increased acivity.
[B] The Effect of Medium or Solvent
a) If a base is more solvated than its conjugate acid, its stability is increased relative
to the conjugate acid. e.g.
MeNH 2  NH 3 .
b) Aniline in the gaseous phase is a stronger base than NH3 but its much lower
basicity in aqueous solution is caused by similar solvation effects and not by
resonance and field electron withdrawing effect of a phenyl group.
Similarly,
Pyridine and pyrrole < NH3 (In aqueous solution)
Pyridine and pyrrole > NH3 (In gaseous phase)
c) For simple alcohols, following order of acidity is due to solvation effect.
H2O > MeCH2OH > Me2CHOH > Me3COH (in solution)
H2O > MeCH2OH < MeCHOH > Me3COH (In gaseous phases)
d) A change from a protic to an aprotic solvent can also effect the acidity or basicity
because there is a difference in solvation of anions by a protic solvent and an
aprotic one e.g.
In DMF : Picric acid is stronger than HBr
In water : HBr is stronger than picric acid
SECTION-I
SUBJECTIVE TYPE PROBLEMS
Problem 1. (a) Is a solution of AlCl3 in water acidic, basic or neutral ?
(b) Write a net equation to support your answer.
Solution : (a) Acidic
(b) Al(H 2 O)63 [Al(H 2 O)5 OH]2  H  or
Al(H 2 O)63  H 2O [Al(H 2 O)5 OH]2  H 3O 

Problem 2. Identify conjugate acid base pair in the following reactions.
C 6 H 5 OH + H 2 O H 3O + + C6 H 5O -
HCl + OH - H 2 O + Cl -
Solution :  H3O  (Conjugate acid)

H 2O(base) 
 C6 H5 O (Conjugate base)
C6 H 5OH(acid) 
 Cl  (Conjugate base)
HCl(acid) 
OH  (base) 
 H 2O (Conjugate acid)
Problem 3. Why pyrrole is less basic than pyridine.

Solution : Pyrrole uses lone pair of electron on nitrogen atom in delocalisation hence less
electrons are available for protonation, hence less basic than pyridine.
Problem 4. Which is the stronger base towards a proton NH 2 or PH 2 and why ?
Solution : Bond energy (N – H > P – H) ionization suggests that NH 2 will be stronger base.
This is constituents with the relative strengths of the respective conjugate acid
NH3 < PH3
Problem 5. Arrange according to increasing Lewis acid character,
B(n–Bu)3, B(t–Bu)3
Solution: The highly branched tertiary butyl group involve appreciable back – strain (B-strain)
when the boron atom changes to pyramidal environment on adduct formation. This
destabilizes the adduct. Hence the order is
B(t–Bu)3 < B(n–Bu)3
Problem 6. Compare the basic strengths of ortho, meta and para isomers of nitroaniline
and predict the decreasing order of basicity.
Solution: The –NO2 group which is a powerful electron withdrawing inductive effect when
present at ortho and para positions for the interaction of the unshared pair of the
amino nitrogen with the delocalised p-orbital system of the benzene nucleus is
then enhanced. The neutral molecule is thus stabilized even further with respect to
the cation, resulting in further weakening as a base. Thus the order of basicity of
nitroanilines is as
m-NO2C6H4NH2  p-NO2C6H4NH2  o-NO2C6 H4NH2.
Problem7. On the basis of H-bonding explain that the second ionization constant K2 for
fumaric acid is greater than for maleic acid.
Solution: We know that H-bonding involving acidic H has an acid weakening effect and H-
bonding in conjugate base has an acid strengthening effect.
Both dicarboxylic acids have two ionisable hydrogen atoms. Considering second
ionization step.
O O
C H C
H
O O
C C
H
C OH C O
H C H C
O O
Fumarate monoanion Maleate monoanion
(no H-bonding) (H-bonding)
Since the second ionisable H of the Maleate participates in H-bonding and more
energy is needed to remove this H because the H-bond must be broken. The
maleate mono anion is, therefore, the weaker acid.
Problem 8. Predict the nature of change, if any on the acidity of the solution consequent to
the addition (i) HgO to an aqueous solution of KI. (ii) CuSO4 to an aq. solution
of (NH4)2SO4, (iii) Al(OH)3 to aqueous caustic soda solution.
Solution: i) Due to the formation of the stable complex HgI42 species, the concentration of
OH– increase according to the reaction
HgO + 4KI + H2O  HgI4 + 2OH– + 4K+
Hence acidity decreases
ii) Due to the formation of Cu(NH3)4+2 complex ion increases H+ ion
concentration. Hence the acidity increases acid to the reaction
Cu2+(aq) + 4NH4+(aq)  Cu(NH3 )42 + 4H+(aq)
iii) Formation of the complex Al(OH)4 anion consumes. OH– ions. Hence acidity
increases.

Al(OH)3(s) + OH– (aq)  Al  OH 4
Problem 9. HF is the weakest acid of halogen acids in aqueous solution. Explain.

Solution : Hydrogen fluoride (HF) ionizes only slightly in dilute aqueous solution:
H O
HF(aq) 2
H  (aq)  F– (aq)
However, HCl, HBr and HI ionize completely in dilute aqueous solutions because
the H—X bonds are much weaker.
H O
HX(aq) 2
H  (aq)  X – (aq) (X = Cl, Br, I)
The order of bond strengths for hydrogen halides is
HF > > HCl > HBr > HI
To understand why HF is so much weaker an acid than the other hydrogen
halides, let us consider the following factors:
a) In HF, the electronegativity difference is 1.9 compared with 0.9 in HCl, 0.7 in
HBr, and 0.4 in HI. We might expect the very polar H—F bond in HF to
ionize easily. The fact that HF is the weakest of these acids suggests that this
effect must be of minor importance.
b) The bond strength is considerably greater in HF than in the other three acids
(HCl, HBr, HI). This tells us that H—F bond is harder to break than the H—
Cl, H—Br and H—I bonds.
c) the small, highly charged F – ion, formed when HF ionizes, causes increased
ordering of the water molecules and thus ionization of the acid is not favoured.
d) The net result of all factors is that the order of acid strength is
HF << HCl < HBr < HI
e) The dilute aqueous solutions, HCl , HBr and HI are completely ionized and all
show the same apparent acid strength. Water is sufficiently basic that it does
not distinguish among the acid strengths of HCl, HBr and HI and thus is the
leveling solvent for these acids. However, when these compounds dissolve in
anhydrous CH 3COOH or other solvents less basic than H 2 O acid strength is
in order:
HCl < HBr < HI
As a result of the leveling effect of water, H 3 O  ion is the strongest acid and
OH – is the strongest base that can exist in aqueous solution.
Problem 10. In the tradiational scheme of qualitative analysis, a solution of metal ions is
oxidized and then aqueous ammonia is added to raise the pH. The ions Fe3+,
Ce3+, Al3+, Cr3+, and V3+ precipitate as hydroxides. The addition of H2O2 and
NaOH redissolves the aluminum, chromium, and vanadium. Discuss these steps
in terms of the acidities of oxides.
Solution : When the oxidation number is +3, all the metal oxides are sufficiently basic to be
insoluble in a pH  10 solution. Aluminum (III) is amphoteric acid redissolves in
strong base to give aluminate ions, [Al(OH) 4 ]– . Vanadium (III) and chromium
(III) are oxidized by H 2 O 2 to give vanadate ions, [VO 4 ]3– , and chromate ions,
[CrO 4 ]2– , which are the anions derived from the acidic oxides V2 O5 and CrO3 ,
respectively.
SECTION-II
SINGLE CHOICE PROBLEMS
Problem 1. Which of the following is the soft base?
(a) CO32– ion (b) CO
3+
(c) Ce (d) Pb2+
Solution : (b)
Problem 2. Which among the following is the strongest base
(a) Be(OH)2 (b) Mg(OH)2
(c) Ba(OH)2 (d) Sr(OH)2
Solution : (c)
Problem 3. The conjugate acid of NH3 is
(a) NH2– (b) NH2OH
(c) NH4+ (d) N2H4
Solution : (c)
Problem 4. In the equilibrium CH3COOH + HF CH3COOH2 + F–
(a) F– is the conjugate acid of CH3COOH
(b) F– is the conjugate base of HF
(c) CH3COOH is the conjugate acid of CH3COOH2
(d) CH3COOH2 is the conjugate base of CH3COOH.
Solution : (b)
Problem 5. Which of the following statements is/are correct?
(a) Maleic acid is a stronger acid than fumaric acid but maleate monoanion is a
weaker acid than fumarate monoanion
(b) Maleic acid is a stronger acid than fumaric acid and also maleate
monoanion is a stronger acid than fumarate monoanion
(c) Maleic acid is a weaker acid than fumaric acid but maleate monoanion is a
stronger acid than fumarate monoanion
(d) Maleic acid is a weaker acid than Fumaric acid and also maleate
monoanion is a weaker acid than fumarate monoanion.
Solution : (a)
Problem 6. Which of the following is the strongest acid
(a) HNO3 (b) H2SO4
(c) HNO2 (d) All have same strength
Solution : (b)
Problem 7 : In Mond’s process, CO(g) is passed over Ni(s) when volatile complex Ni (CO ) 4
escapes.
Ni ( s )  4CO ( g ) 
 Ni (CO ) 4 ( g )
In this reaction, which one is correct.
(a) Ni(s) is a Lewis base and CO(g) is a Lewis acid
(b) Ni(s) is a Lewis acid and CO(g) is a Lewis base
(c) Ni(s) as well as CO(g) behaves as amphoteric
(d) It is not Lewis acid-base reaction.
Solution: (b)
Problem 8: The compound HCl behaves as …. in the reaction
HCl + HF  H2+Cl + F–
(a) Strong acid (b) Strong base
(c) Weak acid (d) Weak base
Solution : HCl is accepting proton in HF medium and acts as weak base.
 (d)
Problem 9: Which of the following statements is true for a 0.1 M solution of a weak
acid HA?
(a) the pH is 1.00 (b) the pH is less than 1
(c) [ H  ]  [ A – ] (d) [ H  ]   [ A – ] .
Solution: (c)
Problem 10: The anhydride of H3PO4 is
(a) P2O5 (b) P2O3
(c) PO2 (d) None
Solution : P has +5 oxidation numbers in P2O5 and H3PO4
 (a)
Problem 11: The conjugate base of hydrazoic acid is
(a) HN3– (b) N3H
(c) N 3– (d) N2–

Solution : N3H  N3–
H
 (c)
Problem 12: Strongest conjugate base is :

COO COO
CH3
(a) (b)
COO O
NO2
(c) (d)
Solution: (d)
Problem 13: Which of the following orders regarding acid strength is correct?
(a) HCOOH < CH3COOH < PhCOOH
(b) HCOOH > PhCOOH > CH3COOH
(c) HCOOH > CH3COOH > PhCOOH
(d) CH3COOH > HCOOH > PhCOOH
Solution: (b)
Problem 14: In the following compounds, the correct order of basicity is
O
N N N N
H H H
(I) (II) (III) (IV)
(a) IV > I > III > II (b) III > I > IV > II
(c) II > I > III > IV (d) I > III > II > IV
Solution: (d)
Problem 15: Arrange the following ions in increasing order of acidity.
[Na (H2O)6]+, [Al (H2O)6]3+,[Mn (H2O)6]2+, [Ni (H2O)6]2+
(I) (II) (III) (IV)
(a) I < II < III < IV (b) I < III < IV < II
(c) I < III < II < IV (d) II < IV < III < II
Solution : (b)
Problem 16 : The following acids have been arranged in order of increasing acid strength.
Identify the correct order.
ClOH (I) BrOH (II) IOH (III)
(a) I  II  III (b) II  I  III
(c) III  II  I (d) I  III  II
Solution : Higher the electronegativity of the atom attached with oxygen greater the acidity.
So order is III  II  I
 (c)
Problem 17 : Among the following compounds, the strongest acid is
(a) HC  CH (b) C6H6
(c) C2H6 (d) CH3OH
Solution : Hydrogen atom attached with oxygen is maximum acidic.
 (d)
Problem 18 : The conjugate acid of HPO42– is
(a) PO43– (b) H2PO4–
(c) H3PO4 (d) HPO32 
Solution: Conjugate acid and base differs by one proton hence the conjugate acid of HPO42– is
H2PO4–
 (b)
Problem 19 : The anhydride of HClO4 is
(a) ClO2 (b) Cl2O3
(c) Cl2O7 (d) None
Solution : Cl has +7 oxidation state in Cl2O7 and HClO4
 Anhydride is Cl2O7
 (c)
Problem 20 : The conjugate acid of azide ion is
(a) NH3 (b) N3H
(c) N2H4 (d) N2–
Solution: N3– + H+ N3H
 (b)
SECTION - III
MULTIPLE CHOICE QUESTIONS
(with one or more than one correct answer)
Problem 1 : Which does not react with NaOH ?

(a) NaH2PO2 (b) Na2HPO3
(c) Na2HPO4 (d) NaH2PO3
Solution: (b, a)
Problem 2 : Which of the following will supress the ionisation of phthalic acid
(a) KCl (b) H2SO4
(c) HNO3 (d) NaOH
Solution: (b, c)
Problem 3 : Which of the following salts are acidic in aqueous solutions ?

(a) (NH4 )2SO4 (b) NaHCO3
(c) CuSO4 (d) AgNO3
Solution: (a, b, c)
Problem 4 : Which of the following species can act as Bronsted base as well as a Lewis base ?
(a) NO3 (b) CN
(c) NH3 (d) BF3

Solution: (a, b, c)
Problem 5 : Which of the following compounds / ions can act as Bronsted acid as well as a
Bronsted base ?
(a) HCO3 (b) K2CO3
(c) H2SO4 (d) H 2 PO4
Solution: (a, d)
Problem 6 : Which of the following is not amphi protic ?

(a) H 2 PO2 (b) HPO32
(c) H 3 PO4 (d) H 2 PO4
Solution: (a, b, c)
Problem 7 : Which of the following acids is diprotic ?

(a) oxalic acid (b) phthalic acid
(c) carbonic acid (d) orthophosphorous acid
Solution: (a, b, c, d)
Problem 8 : Which of the following give correct order of acid strength ?

(a) HClO < HClO2 < HClO3 < HClO4
(b) HF < HCl < HBr < HI
(c) HClO3 < HBrO3 < HIO3
(d) HClO4 < HBrO4 < HIO4
Solution: (a, b, d)
Problem 9 : Which of the following is (are) stronger acid(s) as compared to hydronium ion
(H3O+) ?
(a) HF (b) HCl
(c) HBr (d) NH3
Solution: (b, c)
Problem 10 : Which of the following behave(s) as stronger bases than NaOH when dissolved in
water ?
(a) Na2O2 (b) NaH
(c) Na3N (d) NaN3
Solution: (a, b, c)
SECTION - IV
COMPREHENSION TYPE PROBLEMS
I. WRITE-UP
Acid rain is a regional phenomenon. The low pH in heavily industrilized and populated
areas is thought to be caused by the acidic oxides SO2, NO and NO2. pH isopleths are the
regions in which the parcipitation has the same pH. The primary acid present is H2CO3,
which results from the dissolution of atmospheric CO2, an acidic oxide in water the serious
pollutants in acid rain are strong acid. Atmospheric nitrogen and oxygen can react to form
NO at the high temperature of automobile internal composition gives and electric power
stations.
N 2 (g)  O2 (g) 
 2NO(g)
NO is not very soluble in water, but it is oxidised further in air to form NO2
2NO(g)  O 2 (g) 
 2NO 2 (g)
There NO2 reacts with water, forming nitric acid and nitric oxide.
 2H3O  (aq)  2NO 3 (aq)  NO(g)
3NO2 (g)  3H 2 O(l ) 
Catalytic convertors in automobiles reduces the nitrogen in NO to N2.
SO2 directly combines with water to give sulphurous acid,
SO 2 (g)  H 2O(l ) 
 H 2SO3 (aq)
Problem 1 : The lines drawn on map on which the precipitation have same pH are called
(a) Isoperks (b) Iso pHs
(c) Isoplethes (d) none of these
Solution: (c)
Problem 2 : Which non metallic oxides gives its presence in acid rain and therby maintain low
pH ?
(a) SO2 (b) SO3
(c) N2O3 (d) S2O3
Solution: (a)
Problem 3 : What effort is made to avoid formation of HNO3 in acid rain.

(a) sprinkling of SO3 gas from atmoshphere
(b) not to let NO oxidised into NO2
(c) not to let NO reduced into N2O
(d) not to let NO converted into N2
Solution: (b)
II. WRITE-UP
X Y  H  , Explanation goes as the relative strength of the acid X and the base Y by
the relative amount of each substance present when the system is in equilibrium. The
stronger the acid X, larger the equilibrium constant K. The stronger the base Y, smaller the
equilibrium constant K. A practical definition of acid and base strength requires an
equilibrium, which must include another acid base conjugate pair to accept the proton from
the acid and to donate the proton to the base
Problem 4 : Identify the strongest acid among the following

(a) NaOH (b) Mg(OH)2
(c) B(OH)3 (d) Fe(OH)3
Solution: (c)
Problem 5 : Which one of the following statement is correct

(a) Water acting as an acid makes all strong bases appear equally strong by
forming –OH
+
(b) C 5 H 5 N H is weak conjugate acid of respective strong base
+
(c) N H 2  N H 3 is neither acid nor base
+
(d) Glycine N H 3  CH 2  COO  is cationic being more reactive centre.
Solution: (a)
Problem 6 : Which of the following species is an ampholyte ?

(a) CH3COO– (b) H2O
+
(c) NH 4 (d) C6H5COOH
Solution: (b)
MATCHING TYPE PROBLEMS

Problem 7 : HCl + H2O — H3O+ + Cl–
+
NH3 + HCl — NH 4 + Cl–
CH3COOH + H2O —CH3COO– + H3O+
Question is, compound in column-I is stronger than in column-II.
Column-I Column-II
(a) HCl (p) H3O+
+
(b) H2O (q) NH 4
(c) NH3 (r) Cl–
(d) CH3COOH (s) CH3COO–
Match the above two columns based on above question. From the column-I, more
than one options may be correct in column-II
Solution: (a) – (p, q, r, s); (b) – (q, r); (c) – (s); (d) – (p, q, s)
ASSERTION – REASONING TYPE PROBLEMS

The following questions consist of two statements, one labelled as ASSERTION (A) and REASON (R).
Use the following key to choose the correct appropriate answer.
(a) If both (A) and (R) are correct, and (R) is the correct explanation of (A).
(b) If both (A) and (R) are correct, but (R) is not the correct explanation of (A).
(c) If (A) is correct, but (R) is incorrect.
(d) If (A) is incorrect, but (R) is correct.
Problem 8. ASSERTION (A) : H2SO4 acts as a base in presence of HClO4.

REASONING (R) : Perchloric Acid is a stronger acid than H2SO4.
Solution : (a)
Problem 9. ASSERTION (A) : I2 + I– — I3–-, I2 is a Lewis base in the reaction.
REASONING (R) : Electron pair acceptor is a Lewis base
Solution : (d)
Problem 10. ASSERTION (A) : pH of a neutral solution is always 7.
REASONING (R) : pH of a solution does not depend upon temperature.
Solution : (d)
ASSIGNMENTS
SECTION - I
SUBJECTIVE QUESTIONS
LEVEL-I
1. Which of the following reagents are strong electrolytes?

(a) NH3 (b) NH 4Cl (c) HC 2 H 3O 2 (d) NaC 2 H3O 2 , (e) HCl (f) NaCl.
2. Draw an electron dot diagram to illustrate that “ammonium hydroxide” could not exist as a
weak base. Explain the weakly basic properties of a solution of ammonia in water.
3. The amino acid glycine exists predominantly in the form  NH 3CH 2 COO – . Write formulas
for (a) the conjugate base and (b) the conjugate acid glycine.
4. Write the equation representing self-ionisation of POCl3 and BrF3 as non-aqueous solvents.
5. Using the Lewis acid-base concept determine the trend in the acid strengths in the series:
(a) HClO4, HClO3, HClO2 (b) H3PO2, H3PO3, H3PO4
6. Rationalize the relative Lewis basicities (H3Si)2O < (H3C)2O; (b) (H3Si)3N < (H3C)3N.
7. Be(OH)2 exhibits amphoterism. Explain by reactions.
8. Write down the conjugate base of the following
(i) NH3, (ii) CH3COOH
–
(iii) OH , (iv) H2NCONH3+
9. Predict the relative acidic strength among the following:
HI, HIO4, ICl.
10. Among CH4, H2S, HI which one is most acidic? Justify your answer
LEVEL-II
1. Which way would the pH shift when AlCl3 is added to pure water ? Write a net ionic
equation to support your answer.
2. If you mix equal concentration of reactants and products which of the following reactions
proceed to the right and which proceed to the left ?
a) H 2SO4 (aq)  NH 3 (aq) NH 4 (aq)  HSO 4– (aq)
b) HCO3– (aq)  SO42– (aq) HSO –4 (aq)  CO32– (aq)

3. In the acid of the type HA, at 25°C [H3O+] = 1  10–2 M. What is [OH–]?
4. Hydration of CuSO4 is a Lewis acid-base reaction. Explain.

5. NO 2 (nitronium ion) is formed from the mixture of concentrated H2SO4 and HNO3;
explain.
6. Account for the trend in acidity
[Fe(OH 2 ) 6 ]2   [Fe(OH 2 ) 6 ]3  [Al(OH 2 ) 6 ]3  [Hg(OH 2 ) n ]2
7. Silver perchlorate, AgClO4, is significantly more soluble in benzene than in alkane
solvents. Account for this observation in terms of Lews acid-base properties.
8. The common ores of nickel and copper are sulfides. In contrast, aluminium is obtained
from the oxide and calcium from the carbonate. Can these observations be explained in
terms of hardness?
9. What is the order of increasing strength of -chloro butanoic acid, -chloro butanoic acid,
-chloro butanoic acid and n – butanoic acid?
10. Among different hydroxy benzoic acids, o-hydroxybenzoic acid is the strongest compared
to m-and p-isomers considerably. Why?
LEVEL-III
1. Arrange the following in increasing order of basicity

Phenol, o-nitrophenol, cresol
2. Arrange according to increasing Lewis acid character,
SiF4, SiCl4, SiBr4, Sil4
3. Among N,N dimethyl aniline and N,N,2,6 – tetramethyl aniline which one is a stronger
base and why.
4. For the acid-base reaction
HA (aq) + OH– (aq) A– (aq) + H2O(l), K = 1  109
What is equilibrium constant for the
HA (aq) + H2O (l) A– (aq) + H3O+ (aq)?
5. Which way would the pH shift when CuSO4 is added to pure water. Write a net ionic equation
to support your answer.
6. Write the cation, anion and the neutralisation reaction if thionyl chloride reacts with
sodium sulphite.
7. N-ethyl aniline is more basic than N methyl aniline why?
8. Arrange the following in the order of their basic strength. Justify your answer
NH2NH2,NH3,NH2OH
9. Arrange the following in the order of their decreasing acidic strength
CH4 , LiH, BeH2, H2O, HF, NH3
10. Why CHCl3 is more acidic than CHF3?
SECTION - II
SINGLE CHOICE QUESTIONS
1. Which of the following are not Lewis bases ?
(a) Ag+ (b) H2O
(c) CN– (d) CH3
2. Which anion is the weakest base ?
(a) C2H5O– (b) NO3
(c) F– (d) CH3OO–
3. The strongest base that can exist in aqueous solution is :
(a) NH 4 (b) Cl –
(c) OH – (d) H 2 F .
4. Select correct statement:
(a) NF3 is stronger base than NH3
(b) NH3 is stronger base than NF3
(c) NH3 is always a base and NF3 an acid
(d) NH3 is always an acid and NF3 a base.
5. Among the following compounds, the strongest acid is
(a) HC  CH (b) C6H6
(c) C2H6 (d) CH3OH
6. Amongst the following the most basic compound is
(a) Benzyl amine (b) Aniline
(c) Acetanilide (d) p –nitro aniline
7. What is the decreasing order of strength of bases
(a) CH3 – CH2  NH2 > H – C  C > OH
(b) H – C  C > CH3- CH2 > NH2 > OH
(c) OH > NH2 > H- C  C > CH3CH2
(d) NH2 > H – C  C > OH > CH3 -CH2
8. Of the following orders regarding basicity, which one is correct
(a) CH3CH2NH2 > PhCONH2 > CH3CONH2
(b) CH3CH2NH2 > PhCONH2 < CH3CONH2
(c) CH3CH2NH2 > PhCONH2 < CH3CONH2
(d) CH3CH2NH2 < PhCONH2 < CH3CONH2
9. Which among the following is the strongest base

(a) aniline (b) N,N dimethyl aniline
(c) para nitro aniline (d) meta nitro aniline
+
10. The correct order of increasing [H3O ] in the following aqueous solution is
(a) 0.01 MH2S < 0.01 MH2SO4 < 0.01 M NaCl < 0.01 MNaNO2
(b) 0.01 M NaCl < 0.01 MNaNO2 < 0.01 MH2S < 0.01 MH2SO4
(c) 0.01 MNaNO2 < 0.01 M NaCl < 0.01 MH2S < 0.01 MH2SO4
(d) 0.01 MH2S < 0.01 MNaNO2 < 0.01 M NaCl < 0.01 MH2SO4
SECTION - III
(with one or more than one correct answer)
1. Select the correct answers :

(a) On the basis of Arrhenius concept of acids and bases, all hydrogen compounds are
acids.
(b) Proton donors are called Bronsted acids.
(c) A substance which donates an electron pair acts as a Lewis base.
(d) All Lewis bases contain OH groups.
(a) Strong acids have strong conjugate bases.
(b) Among the halides ions, I– is the weakest base.
(c) CH3COOH can never act as a base.
(d) AlCl3 is a Lewis acid.
(a) CCl4 and SiCl4 can act as Lewis acids.
(b) All Arrhenius acids are Bronsted acids.
(c) HSO 4 ion can act as amphiprotic.
(d) Cl– ion is stronger base than Br– ion.
[Cu(H 2 O)3 (OH)]  [Al(H 2 O)6 ]3 
[Cu(H 2 O)4 ]2   [Al(H 2 O)5 (OH)]2
4.
A1 A2 A3 A4
(a) A1 is an acid and A2 is a base
(b) A1 is a base and A2 is an acid
(c) A3 is conjugate acid of A1 and A4 is conjugate base of A2
(d) A3 is conjugate base of A1 and A4 is conjugate acid of A2
5. For H3PO3 and H3PO4 the in correct choices are :
(a) H3PO3 is dibasic and reducing

(b) H3PO3 is diabasic and non-reducing
(c) H3PO4 is tribasic and reducing
(d) H3PO3 is tribasic and non-reducing
SECTION - IV
COMPREHENSION TYPE QUESTIONS
I. Acid strength is measured by the position of equilibrium of ionization in water. In other

words acid strength is the function of the stability of conjugate base of the acid. More is the
stability of conjugate base of the acid, more is the acidity of acid.
1. Arrange the following compounds in decreasing order of acidity ?
OH
(I) C6 H 5  OH (II) Cl
Cl
Cl
(III) OH (IV) OH
Select the correct answer from the codes given below :
(a) III > II > IV > I (b) III > II > I > IV
(c) II > III > I > IV (d) II > III > IV > I
2. Which one of the following is the strongest acid ?
(a) CH 3  CH — COOH (b) CH 3  C — COOH
(c) CH 3 — CH 2 — COOH (d) CH 3 — COOH
3. Which one of the following is strongest acid ?
(a) Cl — CH2 —CH2 — COOH (b) Cl — CH2 — COOH
(c) Cl — CH2 — CH2 — CH2 — COOH (d) CH3 — COOH
II. Basicity of nitrogen containing compounds are determined by the relative availability of the
non-bonding electrons on nitrogen atom to a proton donor or Lewis acid and by the
stabilization of the positive charged nitrogen atom by solvation or, in some special cases by
resonance.
4. Consider the following bases :

(I) aniline (II) o-nitroaniline
(III) m-nitroaniline (IV) p-nitroaniline
(a) I > II > IV > III (b) I > II > III > IV
(c) IV > III > II > I (d) III > II > I > IV
5. Consider the basicity of the following aromatic amines :
(I) aniline (II) p-nitroaniline
(III) p-methoxyaniline (IV) p-methylaniline
(a) III > IV > I > II (b) III > IV > II > I
(c) I > II > III > IV (d) IV > III > II > I
6. Which one of the following is least basic in character ?
N
N N H
(a) H (b)
N N
(c) H (d) H
MATCHING TYPE QUESTIONS

7. Match the following
(P) Monobasic acid (w) Ag+
(Q) Soft acid (x) Cationic Bronsted base
(R) Hard base (y) H   OH H 2O
(S) Neutralisation (z) H3PO2
P Q R S
(a) z y w x
(b) z w x y
(c) z w y x
(d) w z x y
8. Match the following

(P) H3PO4 (w) Tribasic acid

(Q) H3BO3 (x) Dibasic acid
(R) H3PO2 (y) Lewis monobasic acid
(S) H3PO3 (z) Monobasic acid
P Q R S
(a) y x w z
(b) x y w z
(c) w y z x
(d) w y x z
MISCELLANEOUS TYPE QUESTIONS

Fill in the blanks
9. In the reaction, BCl3 + PH3  Cl3B : PH3, the Lewis base is …………
10. In the reaction, SnCl2 + 2Cl–  SnCl4 + 2e, the Lewis acid is …………
11. The conjugate acid of HPO32 is …………
12. A solvent which is neither proton donor nor proton acceptor is called …………
13. The bonding between hard acid and hard base is ………… in nature.
True or False
14. A Lewis base which holds the electrons strongly is called a hard base
15. The bonding between soft acids and soft bases is mainly ionic.
16. CsOH is the strongest alkali
17. Molecules containing an electron deficient atom act as Lewis acids.
18. In the oxy-acids H3PO2, H3PO3 and H3PO4, the acidic nature increases as the oxidation
number of P increases.
SECTION - V
1. Which of the following is a weakest base ?
(a) NaOH (b) Zn(OH)2
(c) KOH (d) Ca(OH)2
2. The compound that is not a Lewis acid is
(a) BF3 (b) BaCl2
(c) AlCl3 (d) SnCl4
3. The following equilibrium is established when HCl is dissolved the acetic acid,
HCl + CH3COOH Cl– + CH3COOH2+
The set that characterizes the conjugate acid-base pairs is
(a) (HCl, CH 3COOH) and (Cl ,CH3COOH 2 )
(b) (HCl, CH 3COOH 2 ) and (CH3COOH, Cl )
(c) (CH 3COOH 2 , HCl) and ( Cl , CH 3COOH)
(d) ( HCl, Cl ) and (CH3COOH 2 ,CH 3COOH)

4. Among the trihalides of nitrogen, which one is the least basic ?
(a) NI3 (b) NBr3
(c) NCl3 (d) NF3
5. H3BO3 is :
(a) Monobasic and weak Lewis acid
(b) Monobasic and weak Bronsted acid
(c) Monobasic acid and strong Lewis acid
(d) Tribasic and weak Bronsted acid
6. For H3PO3 and H3PO4 the correct choice is :
(a) H3PO3 is dibasic and reducing
(b) H3PO3 is diabasic and non-reducing
(c) H3PO4 is tribasic and reducing
(d) H3PO3 is tribasic and non-reducing
7. Match the Ka values
Compound Ka
(a) Benzoic acid 3.3 × 10–5
(b) O2N COOH 6.3 × 10–5
(c) Cl COOH 30.6 × 10–5
(d) H3CO COOH 6.4 × 10–5
(e) H3C COOH 4.2 × 10–5

8. Arrange in order of increasing acidic strength
+ +
H3 N NH3
Z Y
COOH
X
(a) X > Z > Y (b) Z < X > Y

(c) X > Y > Z (d) Z < X > Y
ANSWERS
SECTION – I
SUBJECTIVE ASSIGNMENTS
Level-I
1. (b), (d), (e) and (f). All salts (b, d, and f), soluble hydroxides, and the acids (e) HCl,
HClO3 , HClO4 , HBr, HI, HNO3 and H 2SO4 (first proton) are strong electrolytes.
Note that the added sodium acetate merely shifted this equilibrium to the left.
2. H
H N H O H–
H
The diagram shows that there is no covalent bonding of the OH – ion to the NH 4 ion.
Since solutions of ammonia in water do not act as strong bases, this representation must be
incorrect. The fact that ammonia acts as a weak base is explained by the equilibrium.
NH 3  H 2 O NH 4  OH –
3. (a) NH 2 CH 2 COO – (b)  NH 3CH 2 COOH
4. 2POCl3 POCl2  POCl 4–
2BrF3 BrF2  BrF4–
5. As a general rule, the greater the number of terminal oxygens in the Lewis structure of oxy
acid, the greater is its acidity. Thus, in
a) O
H O Cl O H O Cl O H O Cl O
O O
three terminal two terminal one terminal
oxygen oxygen oxygen
b) O H O H O H
H P H H P O H H O P O H
O O O
one H bonded to O, two H bonded to O three H bonded to O
All have only one terminal oxygen. Also electronegativity of H and P are also
approximately same. Hence, there is not large difference in the strengths of the acids.
6. Nonmetallic elements in period 3 and below can expand their valence shells by
delocalization of the O or N lone paris (27), so the silyl ether and silyl amine are the
weaker Lewis bases in each pair.
7. Be(OH) 2 is an amphoteric hydroxide since it reacts with both acids and bases.
8. To form a conjugate base means removal of a proton

So answer is
(i) NH2– (ii) CH3COO–
(iii) H2O (iv) H2NCONH2
9. IO4- is more stable than I- and I+ is unstable. Hence HIO4 will be strongest acid.
HIO4  HI> ICI
10. Acidic nature
CH4  H2S  HI
Size of the central atoms is greatest in HI hence it is most acidic.
Level-II
1. AlCl3  3H 2 O Al(OH) 3  3H   3Cl
As it is clear from the above equation that solution of AlCl3 is acidic, so pH will shift
below 7.
2. a) From H 2SO 4 is stronger acid than NH 4 and NH3 is stronger base than HSO –4 . Thus,
H 2SO4 (aq)  NH3 (aq) NH 4 (aq)  HSO 4– (aq)

Since proton transfer takes place from stronger acid to stronger base, the reaction
proceeds from left to right.
b) HCO3– (aq)  SO 42– (aq) HSO –4 (aq)  CO 32– (aq)

This is reverse of (a), hence, proceeds right to left.

3. HA(aq)  H 2 O() H3O (aq)  A – (aq)
Since, [H 3O  ][OH – ]  K w  1 10 –14 at 25°C
and [H 3O  ]  110 –2 M,
Kw 1 10 –14
hence, [OH – ]    110 –12 M
[H3O ] 1 10 –2
4. Hydration of metal ions in solution is in itself a Lewis acid-base reaction. Thus, when
CuSO 4 dissolves in water, each Cu 2  ion is associated with six water molecules as
Cu(H 2 O) 62  . In this case, the Cu 2  ion acts as the acid and the H 2O molecules at as the
base.
CuSO 4  6H 2 O 
 [Cu(H 2O) 6 ]SO 4 (aq)
acid base
5. In concentrated H2SO4, HNO3 behaves as a base (proton acceptor) and H2SO4 as an acid
(proton donor).
 H 2 NO3  HSO4–
H 2SO 4  HNO3 
acid base
H 2 NO 3 gives NO 2 (nitronium ion) which is used in nitration of aromatic compounds.
H 2 NO 3 
 H 2 O  NO 2
NO2

 NO 

2
6. The weakest acid is the Fe2  complex on account of its relatively large radius and low
charge. The increase of charge to +3 increases the acid strength. the greater acidity of Al3
can be explained by its smaller radius. the anomalous ion in the series is the Hg 2 
complex. This complex reflects the failure of an ionic model, for in this complex there is a
large transfer of positive charge to oxygen as a result of covalent bonding.
7. The  electrons of benzene, a soft base, are available for complex formation with the
empty orbitals of the cation Ag  , a soft acid (recall 19). The species [Ag –C 6 H 6 ] is the
complex of the acid Ag  with  electrons of the weak base benzene.
8. We know that O 2– and CO 32– are hard bases; S2– is a soft base. The cations Ni2  and
Cu 2  are considerably softer acids than Al3 or Ca 2  . Hence the hard=hard and soft-soft
rule accounts for the sorting observed properties.
9. CH3 – CH2 – CHCl –COOH  CH3 – CHCl – CH2 – COOH  CH2Cl – CH2 – CH2 –
COOH  CH3 – CH2 – CH2 – COOH
10. o–hydroxy benzoate anion is stabilized by chelation due to hydrogen bonding which is
absent in meta and para isomers.
O
||
C –
O
H
O
Level-III
1. o-nitrophenol  phenol  cresol
2. The order in this case is the reverse of that for BX3. -conjugation from the halogen p-orbital
to the Si-d orbital is not as intense as in the case of BX3 and the order of acidity follows the
increase in electron withdrawing power of the halogen from I to F. Hence the order is
SiI4 < SiBr4 < SiCl4 < SiF4
3. Me Me Me Me
N N
Me Me
In N,N-2,6 – tetramethyl aniline the methyl groups on nitrogen and the ortho position are
very close to each other resulting in a steric crowding. Now to avoid steric crowding the
C—N bond rotates and becomes perpendicular to the benzene ring. In this process the lone
pair on nitrogen becomes perpendicular to the p-orbitals of benzene ring thereby inhibiting
resonance. But in N,N dimethyl aniline there is no steric hindrance, so the lone pair is in
the same plane as the benzene ring and undergoes resonance. Therefore the lone pair on
the tetramethyl derivative is more available and hence it is more basic.
4. HA(aq)  OH – (aq) A – (aq)  H 2 O
[A – ]
K –
 1109 . Also, [H 3O  ][OH – ]  K w  1 10 –14
[HA][OH ]
HA(aq)  H 2O() A – (aq)  H 3O (aq)
[A – ][H3O ]
K 
[HA]
[A – ][H 3O  ]
 KwK   1 10 –5
[HA]
 K   1 10 –5
5. The pH will shift down below 7. It is clear from the following equation.
CuSO4 + H2O Cu(OH)2 + SO42– + 2H+
6. Reaction SOCl2 + Na2SO3  2NaCl + 2SO2
Cation SO++
Anion SO32–
7. N-alkylated anilines are stronger bases than aniline because of steric effects which decrease
the resonance of the lone pair of electron on nitrogen and hence makes it more available for
protonation. Ethyl group is bigger than the methyl group so N-ethyl aniline is stronger base
than N-methyl aniline.
8. NH3  NH2 NH2  NH2OH
9. HF  H2O  NH3  CH4  BeH2  LiH
10. Cl3C–: is less basic than F3C–: because fluroine can disperse charge only by an inductive
effect. White Cl (having empty 3d orbitals) disperses charge by inductive effect as well as
by p - d bonding delocalisatioin. Fluorine is a second period element with no 2d orbital.
SECTION – II
SINGLE CHOICE QUESTIONS
1. (a) 2. (b) 3. (b) 4. (b) 5. (d)
6. (a) 7. (a) 8. (a) 9. (b) 10. (b)
SECTION – III
1. (b, c) 2. (b, d) 3. (b, c, d) 4. (b, c) 5. (a)
SECTION – IV
COMPREHENSION TYPE QUESTIONS
1. (d) 2. (b) 3. (b) 4. (c) 5. (a)
6. (a)
MATCHING TYPE QUESTIONS

7. (b) 8. (c)
MISCELLANEOUS TYPE QUESTIONS

Fill in the blanks
9. PH3 10. SnCl2
11. H2PO3– 12. Aprotic
13. Ionic
True & False

14. True 15. False
16. True 17. True
18. False
SECTION - V
QUESTION ASKED IN IIT-JEE
1. (b)
2. (b)
3. (d)
4. (d)
5. (a)
6. (a)
7. (a) – (iii), (b) – (iv), (c) – (ii), (d) – (v) (e) – (i)
8. (a)

Concepts of Acids and Bases-Theory &amp; Exercise

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CONCEPTS OF ACIDS & BASES

4. BRONSTED - LOWRY THEORY

Molecular species : HCl   H+ + Cl–

Acid1  Base 2 Acid 2  Base1

4.1 TWO IMPORTANT OUTCOMES OF THE BRONSTED CONCEPT AND

HCl H 2 O H3O  Cl

Conjugate Acid-Base pair

Stronger acid + Stronger Base Weaker acid + Weaker Base

Conjugate Acid-Base pair

Relative Strengths of Conjugate Acid-base Pairs

HBr (hydrobromic acid) Br– (bromide ion)

Base strength increases

HCOOH (formic acid) HCOO – (formate ion)

Solution : a) H 2SO4  H 2O H3O  HSO –

Illustration 2 : Predict the direction of the following reaction in aqueous solution:

5. PERIODIC VARIATIONS OF ACIDIC & BASIC PROEPRTIES

NH3 < PH3 < AsH3 < BiH3

5.3 IONIZATION CONSTANTS OF SOME WEAK ACIDS AT 25°C

5.4 IONISATION CONSTANTS OF SOME COMMON WEAK BASES AT 25°C

For trans-Butanedioic (fumaric) acid, pK a1  3.02, pK a 2  4.38

5.6 RELATIVE STRENGTH OF OXYACIDS

Nature of the acid: Monobasic Dibasic Tribasic

Al(H 2O)63  H2O 

or simply Al(H 2O)63 (aq) Al(OH)(H 2O)52 (aq)  H  (aq)

Al(OH)(H 2 O)52 (aq) Al(OH)2 (H 2 O)4 (aq)  H  (aq)

H —O —P—O—H H—O—P—O—H H—P—O—H

Illustration-4 Why sulphuric acid is stronger than sulphurous acid?

Illustration-6 Compare the acidity between HClO4 and H3AsO3.

H3O+ + HCO3 H2CO3 + H2O

5.9 OUTCOME OF BRONSTED CONCEPT

5.10 LIMITATIONS OF BRONSTED CONCEPT

6. GENERAL THEORY OF SOLVENT SYSTEM

The auto-ionisation of some protonic and non-protonic solvents is shown below.

Acid Base Acid Base

In liq. NH3 : NH4Cl + NaNH2 NaCl + 2NH3

6.1 UTILITY OF SOLVENT SYSTEM THEORY

6.2 LIMITATIONS OF SOLVENT SYSTEMS THEORY

Conditions for Lewis Bases

8. HARD AND SOFT ACIDS AND BASES

9. ORIGIN OF ACIDITY OR BASICITY IN ORGANIC COMPOUNDS

or Acidity  Stability of conjugate base

Illustration-8 Which of the following will be more acidic

Since (ii) is more stable than (i) so

Periodic Table correlation of Basicity and Nucleophilicity : In a period there is no

If active atom falls in a period Basicity If active atom falls in a group

In gas phase In aprotic polar solvent In protic polar solvent

9.1 RELATIVE STRENGTH OF ORGANIC ACIDS

b) Carboxylic Acids: Acidity of carboxylic acids increases with increasing % s-character

3 more resonating structrue

–H  (Charge seperation is present, not much stable)

(No charge seperation, more stablization by resonance)

b) Similarly, C6H5COOH > CH3COOH. Because C 6 H5 COO is more stablised than

Illustration-9 Arrange the following in the increasing order of acidic strength.

NO2 CH3 NH2 Cl

9.2 RELATIVE STRENGTH OF ORGANIC BASES

The basic strength of an amine in water is determined not only by electron –

Decreasing stablisation by solvation

Guanidine H2N NH is strong alkali because its conjugate acid is very

NH2 NH2 NH2

[B] Aromatic Amines

Illustration-10 N-ethyl aniline is more basic than N methyl aniline why?

10. FACTORS AFFECTING THE STRENGTH OF ACIDS AND BASES

6. Statistical Effects : In a symmetrical diprotic acid, the first dissocation constant is

Al(H 2 O)63  H 2O [Al(H 2 O)5 OH]2  H 3O 

Concepts of Acids and Bases-Theory & Exercise

Concepts of Acids and Bases-Theory & Exercise