Acid–Bases Theory

and
Solvent System
 Acid–Bases Theory

Acid Base
• Acid as substance • Base as substance
whose aqueous solution whose aqueous
turned blue litmus red solution turned red
• Acids are sour in test Litmus blue
• Neutralized with bases • Base are biter in test
• It react with active • Neutralized with Acids
metals evolving • It have soupy in touch
Hydrogen gas
 Acid-Base Theories
o Different scholars define acid and bases in different manner

1. Arrhenius Theory
o Acid is gives hydrogen ions, and bases gives hydroxide ions when
dissolved in water.
• The definition is limited to aqueous system
• No explanation for the acidity of various salts, like AlCl 3, NH3NO3, etc.
• NH3, Pyridine basic properties although they contain no –OH groups
but base
• The restriction of the term base to only OH compounds was another
serious limitation of Arrhenius definition
• These concepts were not applicable to reaction in the gas phase
where no solvent in present
3
 Cont…
2. Brønsted-Lowry(1923)
o Proton theory is retained, but the definition is independent on
solvents
• An acid is a proton donor, and a base is a proton acceptor.

Acid Base + H+
Base + H+ Acid
• For every acid to loss proton, there should be a base that can
accept a proton, acid-base conjugate pairs.
o Give examples of acid and bases!

4
Conjugated Acid-Base Pairs
Acid Base Conjugated Acid Conjugated base

HCl + H 2O H 3O+ + Cl-

HSO4- + NH3 NH4+ + SO42-

NH4+ + H20 H 3O + + NH3

Types of Bronsted –Lowry acids and bases

Type Acid Bases

Molecular HCl,HBr,HClO4,H2SO4 NH3, N2H4, amines
H3PO4,H2O Pyridine, H2O

Cationic NH4+,[Fe(H2O)6]3+, [Fe(H2O)5(OH)]2+,

[Al(H2O)6]3+, [Al(H2O)5(OH)]2+,
5
Anionic HS ,HCO ,HSO
- - -
Cl ,Br ,OH ,HSO
- - - -
 Cont…
o Some species can acts either as an acids or bases,
depending on the way they behave in a given
reaction.
o These species are called amphoteric or amphiprotic
substances. Give examples!

HCl + H2O H3O + + Cl-

NH3 + H2O NH4+ + OH-

6
 Strength of Acids and Bases
• According to Brown-Lowery concept, a strong acid is one
which has a strong tendency to donate a proton
• A comparison of acid strength is generally done by water
HA + H2O H3O+ + A-

Ka = [H3O+] [A-]/[HA]
Larger the value of ka the stronger Acid vice versa
• Thus if we compare the relative acidic strength of CH3COOH
(Ka = 1.8 X 10-5) and HCN (Ka = 7.2 X 10-10)
• Acetic Acid is strong Acid than Hydrogen cyanide
 Cont…
• For Base B may similarly write the equilibrium reaction
B + H2O BH+ + OH-
Kb = [BH+] [OH-]/[B]
Kb measure the strength of the base
• B is a stronger base than OH- if it can extract proton from H2O
• Larger the value of Kb stronger is the base
• It generally more convenient to express Ka and Kb values in
terms of their negative logarithms, i.e.
Pka = - log Ka and Pkb = - log Kb
• Than smaller values of Pka means the strong Acid
• Similarly smaller values of Pkb means the strong Base
 Strength of Hydrides
• The relative Acidic strength of hydrides influence by two
factors
 The electronegativity of the elements
 The Atomic size of the elements
Hydrides of the elements of the periods
o Consider the hydrides of nitrogen, oxygen and fluorine of the
second period
• The electronegativity of these elements increases in the order
N<O<F
• And acid strength increase in the same order
NH3 < H2O < HF
• Electronegativity of the third period elements
P < S < Cl
The acidic strength of the hydrides of these elements
PH3 < H2S < HCl
 Cont….
o The acidity of the hydrides of the elements of a group increases
with increases size of central atom
• Considered the hydrides of group VI and VII A elements
H2O < H2S < H2Se < H2Te
HF < HCl < HBr < HI
o This order is the reverse of that expected on the basis of EN
o This can explain two factors
 Stability of the conjugated base: Charge density on the
conjugated base is in the order
F-> Cl -> Br- > I- and O2- >S2- > Se2- > Te2-
• Greater charge density on the conjugated base will result in
grater proton attraction by the conjugated base

 Moreover a larger anion will be more stabilized by solvation

leading to more ionization of the acid.
 Strength of oxyacids
o Oxyacids are acid which contain hydrogen, oxygen and other
atom and are derived from oxyanions by simply adding one
or more protons to the ion

nH+ + XOn-m HnXOm

were X = B, Si, Ge, N, P, As, S, Se, F, Cl, Br, I

• When the oxyacid is dissolved in water the proton normally

bonded to the oxygen atoms, may be transferred from the
acid to the solvent.
• An oxyacid which is a good proton donor is termed as strong
acid.
• One that is a poor proton donor is a weak acid

H2O + HnXOm H3O+ + Hn-1XO-m

 Cont….

o The extent to which proton are transferred to water may be

correlated with the structure of the oxyanion and with ionic
potential of the central ion
H O Z
• Cleavage of the O-H bond in aqueous solution is characteristic
of Acid (Z = More electronegative element)
• Cleavage of the O-Z bond in aqueous solution is characteristic
of Base (Z = Less electronegative element)
• When either of the two bonds can be cleaved by an
appropriate reagent, the substance is amphoteric
 Oxy Acid given elements
o The rules described above may be summarized as follow
• For a given element increase in the oxidation number of the
central atom X increases the acidity

HClO < HClO2 < HClO3 < HClO4

+1 +3 +5 +7

HNO3 > HNO2, H2SO4 > H2SO3

• For oxyacid within a period group having identical oxidation
number, the acidic strength decreases with increases in size of
the central atom Z
Oxidation number
HOCl > HOBr > HOI +1
HClO3 > HBrO3 > HIO3 +5
HNO3 > HPO3 > HAsO3 +5
Oxyacid of Elements in a group
• oxyacids derived from elements within group, in which the
central atoms have identical oxidation state, as size of the
elements increases acidic strength decreases
HClO> HBrO > HlO,
H2SO4> H2SeO4 > H2TeO4

HNO3> HPO3 > HAsO3

Oxyacid of Elements in a Period
• The strength of oxyacid formed by elements in a given period
may be increases from left to right with same oxidation state
of the element
 Cont…
3. Lux-Flood Concept
o Acid base reactions are also feasible in oxide systems without
the acid of protons (Lux)
o This concept was extended by Flood and applied to non-
protonic system which were not covered by the Bronsted-
Lowry concept
• Acid is an oxide acceptor, and a base is an oxide donor

CaO + SiO2 CaSiO3

BaO + CO2 BaCO3

15
 Cont….
• Substance may be classified as amphoteric in
terms of Lux-Flood definition

ZnO + S2O7 2- Zn (SO4)2

Na2O + ZnO Na2ZnO2

• Acid-base reactions in oxide systems can be

extended to any negative ions

3NaF + AlF3 [Na3AlF6]2-

16
Na S + CS [ Na CS ]2-
 Cont…
4. Lewis Theory (1923)
o Acid is an electron pair acceptor, and base is an
electron pair donor (avoid proton system).

Example

17
 Cont…
• All metal cations in donor solvents are Lewis acid
interacting with solvent molecules which act as Lewis
bases
• A Lewis acid is often described as an electrophile
(electron loving) and a base is nucleophile (electron
excess).

18
 Cont….

• Molecule containing a central atom incomplete octet

BF3 + O(C2H5)2 F3B O(C2H5)2

AlCl3 + NC5H5 Cl3Al NC5H5

• Molecule containing vacant d-orbital on the central atom

SnCl4 + 2Cl- [SnCL6]2-

SbF3 + 2F- [SbF6]2-

• Molecule with multiple bonds between atom

Eg.CO2,SO3 19
 Solvent System
5. Solvent System Concept(Cady and Elsey 1928)
o Acid is a solute that, either by direct dissociation or by reaction with the solvent
gives the anion characteristic of the solvent
o Base is a solute that, either by direct dissociation or by reaction with solvent,
gives the cation characteristic of solvent.
• The definition applies to all solvents that can dissociate into a cation and anion
(autoionisation).
Acid Base Acid Base

H2O + H2O H3O+ + 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 base
20
 Cont…
• Similarly in N2O4 as non protonic solvent
Acid Base Acid Base
N2O4 + N2O4 ˂-----˃2NO+ + 2NO3-

• Auto-ionisation of some protonic and non –protonic solvents is

shown bellow
H2O + H2O ˂-----˃ H3O+ + OH-
Protonic NH + NH ˂-----˃ NH + + NH -
3 3 4 2
solvent CH COOH + CH COOH ˂-----˃ CH3COOH2+ + CH3COO-
3 3

Non protonic SO2 + SO 2 ˂--------˃ SO 2+

+ SO 3
2-

solvent BrF 3 + BrF 3

˂--------˃ BrF 2
+
+ BrF 4
-

N2O4 + N2O4 ˂---------˃ 2NO+ + 2NO3-

 Cont…
• Neutralization is a reaction between an acid and a base to produce a
salt and the solve
Acid Base Salt Solvent
In lid NH3 : NH4Cl + NaNH2 ˂-----˃ NaCl + 2NH3

In N2O4 : NOCl + NaNO3 ˂-----˃ NaCl + N2O4

In CH3COOH: HCl + CH3COONa ˂-----˃ NaCl + CH3COOH

In liq.SO2 : SOCl2 + [N(CH3)4]2SO3 ˂-----˃ 2[N(CH3)4] Cl + SO2

Limitations: 1) this theory does not consider a number of acid-base reactions

included in the protonic definition.
2. It limits acid-base phenomena to solvent system only. Thus it does not
explain the acid-base reactions which may occurs in the absence of solvent
 Cont…
6. Usanovich Concepts
o This is a broad acid-base definition

• An acid is a species capable of giving cations,

combining with anions or electron or neutralising a
base to give a salt
• A base is defined as any species capable of giving up
anions or electrons, combining with cation or
neutralising an acid to give a salt

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 Cont……
Acid + Base Salt
Eg .1 SO3 + Na2O Na2SO4

• Na2O gives O2- ion; SO3 combines with O2- ion

Na2O 2Na+ + O2-

SO3 + O2- SO42-

2Na+ + SO42- Na2SO4

Eg.2 Fe(CN)2+ 4KCN K4[Fe(CN)6]

• KCN gives CN- ion, Fe(CN)2 combine with CN- ion

4KCN 4K+ + 4 CN –
Fe(CN)2 + 4 CN- [Fe(CN)6]4-
 Hard and soft acid and base principle (HSAB)
o According Bronsted -Lowery the strength of acid and base
measured based on magnitude of the dissociation constant (K)
• Acid with higher value of Ka are stronger while Base with higher
value of Kb are stronger

o According to Lewis definition, a strong acid is one that easily

receive electron pair and a strong base is that one that can
donate electron pair easily

o Unfortunately, there is no simple measure of electron transfer

between Lewis acid and bases.

o The relatively strength of Lewis acid and bases can be estimated

by soft and hard acids and bases (HSAB) principle.
Classification of Lewis Acids and Bases into Hard and Soft and Acid
and Bases

Hard Acids: Hard Lewis bases are those

 Have smaller electron accept atom
 High positive charge
 Don’t contain unshared pairs of electron
 High electro-negativity
 Low polarizability
Soft Acid : Soft Lewis acids are those
 Have large electron acceptor atom
 Low positive charge
 Easily polarized
 Low electro-negativity
 May contain unshared electron pair
 Cont….

Borderline
Hard Acid (intermediate) acid Soft acids

H+,Li+,Na+,K+,Be2+Sr2+,  Fe2+, Co2+, Ni2+, Cu2+,  Cu2+, Ag+ , Au+

Mn2+,Al3+,Ga3+,La3+, Zn2+, pb2+, Sn2+, Sb2+, Ti+, Pb2+ ,Cd2+,
Lu3+,Cr3+, Co3+, Rh3+, SO2, NO+ Pt2+, Hg2+, Tl3+,
Fe3+,As3+, BH3,GaCl3,InCl2,
Si4+,Ti4+,Th4+,U4+, Ce4+, I+
Sn4+
 Cont…

Hard Base:

 Donor atoms is N, O, F
 Highly electronegativity donor atoms
 Low polarizability
 Valency electron hold tightly

Soft Base:

 Donor atoms is P, S, I, Br, Cl, C

 Low electronegativity donor atoms
 High polarizability
 Valency electron hold loosely
 Cont…

Borderline
Hard Base (intermediate) Base Soft Base

H2O, OH-, F-,  C6H5NH2, C5H5N,  R2S, RSH, RS-, I-,

CH3COO-, SO42-, Cl-, NO2-, SO3- ,N2 SCN-, S2O32-, R3P,
CO3-, ClO4-, ROH, R3As, (RO)3P, CN-,
RO-,R2O, NH3, RNH2, RCN-, CO, C2H4,
N2H4 C6H6,H-
 Cont…
o The typical Lewis acid and base reaction can be generalized
as
A + B A : B
Lewis acid Lewis base Adduct
(acceptor) (donor)
o Both Lewis acid and base are hard given complex stable
e.g. AgI2 more stable than AgF2
• Ag is soft acid and F hard base unstable but AgI is
combination of soft acid and base stable
o CoF63- (Hard acid + Hard base) is more stable than CoI63-
(hard acid + soft base)
o HgS (soft acid + soft base)more stable than Hg(OH)2 (soft
acid + hard base)
• More stability of HgS than that of Hg(OH)2 explain why
Hg(OH)2 dissolves readily in acidic aqueous solution but
HgS does not