Acids & Bases

Applications in Textile industries:

Acids:
• H2SO4: Washing, Mordanting, carbonizing of wool, dyeing on wool, Remove metal imperfections on fabric
• HCl: washing and dyeing, Diazotization, Souring
• CH3COOH: Dyeing and Neutralization
• C2H2O4: Remove metallic stain from fabric
• CH3COOLi: Catalyst in polyester production, Corrosion inhibitor
Bases:
• NaOH: Electrolyte in Reactive dyeing, Bleaching process
• Na2CO3: Reactive dyeing
• Ca(OH)2: Remove hardness of water, Formation of bleaching chemicals, mordant, indigo Vat etc.
• NH3: Making textile fibers
Concepts of Acids & Bases
• Arrhenius : H+ & OH- in aqueous solution
• Bronsted-Lowry/Protonic concept: (Transfer of H+)
• Lewis Electronic concept: (Pair of Electrons)
• Lux-Flood concept: (Transfer of oxide ions O2-)
Arrhenius concept
Acids: Contain H+
• Dissolved in water →Increases H+ in aqueous solution
• Strong Acid: Completely ionizes in aqueous solution to give H3O+ and an Anion
• HCl(aq)→ H+ (aq) + Cl− (aq)
• Examples: HClO4, H2SO4, HI, HBr, HCl, HNO3
Arrhenius concept:
• Bases: Contain HO-
• Dissolved in water →Increases HO- in aqueous solution
• Strong Base: Completely ionizes in aqueous solution to give HO- and a Cation
• NaOH(aq)→ Na+(aq) + OH− (aq)
• Examples: LiOH, NaOH, KOH, Ca(OH)2, etc. [Hydroxides of Group ΙA elements
and Group ΙΙA elements (except Be)]
Neutralization reaction:

This concept explains the constant heat of neutralization of any strong acid and strong base as all these reactions
involve only the combination of hydrogen and hydroxide ion.
Arrhenius concept
• Limitations:
1. Not all acids and bases contain H+ and HO-.
2. Non aqueous solvents
Bronsted-Lowry/Protonic concept
• Not limited to aqueous solvents
• Acids: Donate proton in a proton-transfer reaction
• Bases: Accepts proton in a proton-transfer reaction
• Conjugate acid-base pair: Associated with loss or gain of proton
• Acid – H+→ Conjugate Base
• Base + H+ → Conjugate acid
The acid – base
pair which can
be formed from
each other
mutually by
gain or loss of
proton
Bronsted-Lowry/Protonic concept
• Limitation
1. Extent to act as acid/base depends on solvent (Amphiprotic species)
2. Not all species contain protons
POLYPROTIC ACIDS:-
Acids containing one proton which can be donated are monoprotic acids or monobasic acids .

Those acid which contain more then one donate able proton are known as Polyprotic Acids or

polybasic acids.

HCI ,HNO3, HCN etc are the monoprotic acids. whereas H3PO4, H2SO4 are polyprotic acids.
Lewis Electronic theory
• Acids: Accept electron pairs
• Bases: Donate electron pairs
According to Lewis Concept, Acids: Accept electron pairs, Bases: Donate electron pairs
Lewis Electronic theory
• Lewis Acid:
• Compounds having less than a full octet: BF3, AlCl3
• Positive ions: Ag+, Co3+
• Compounds having polar double/triple bond: CO2, SO2
• Compounds having central metal capable of expanding its valence shell: PCl5, SnCl4
• Lewis Base:
• Molecules containing two/less number of unpaired electrons: H2O, NH3
• Negative ions: Cl-, HO-
Lewis Electronic theory
• Limitations:
• No ions formed/no protons transferred
• Many substances are not acid but behaves as lewis acid (BF3)
• Almost all the reactions become acid-base reactions under this system
Lux-Flood concept
• Bases: A base give up Oxide ion (O2-).
• Acids: An acid gain Oxide ion (O2-).
CaO + SO3 ↔ Ca2+ + SO42-

CaO is base as it gives up O2- ions: CaO ↔ Ca2+ + O2- Here, Ca2+ is acid.

SO42- is base: SO42- ↔ SO3 + O2- and SO3 is acid.

Lux-Flood concept
• Bases: A base give up Oxide ion (O2-). These are oxides (CaO, BaO, Na2O) which
react with water, giving bases in water.
• Na2O + H2O → 2 NaOH
• Acids: An acid gain Oxide ion (O2-). They (SiO2, CO2, P4O10) react with water
giving acids.
• P4O10 + 6H2O → 4 H3PO4
•
Strength of acids
The Behavior of Polyprotic Acids
Acids with more than one ionizable proton are polyprotic acids. They undergo stepwise ionization reaction in solution.
Each dissociation step has a different Ka.
For example, phosphoric acid is a triprotic acid (three ionizable protons), so it ionization involves three steps and has
three K value.
The neutral molecule gives up the proton more readily than the negatively charged anions as the
negative charge tends to attract proton.
Hence, acid strength decreased.

HSO4- < H2SO4

 Strength of acids
An oxyacid is an acid that contains an oxygen atom bonded to a hydrogen atom

Oxyacids: H-O-Y- Electronegativity of Y atom is large → H-O bond polarity increases → H-O bond strength decreases

→ acid strength increases

HOI < HOBr < HOCl < HOF

The strength of these acids can be determined by the electronegativity of atom bonded to oxygen. Because F is the
most electronegative, it draws the bulk of the electrons in the HOF molecule toward itself strongly. Since H and F are
on opposite ends of the molecule, F pulls at the electrons in the H-O bond strongly, thereby weakening it. The weaker
the H-O bond, the more easily the H+ can ionize in water, and the stronger the acid. On moving down across a group
electronegativity of atoms decreases. So, Acidic strength also follows the same trend.
 Strength of acids
• Oxidation number: The acidic character of the oxy-acids having the central atom in
different oxidation number increases with the increase in the oxidation number of central
atom. Higher the oxidation number of the central atom, greater the pull on all the electron
pairs of O atom. Hence, weakens the O-H bond and gives off H+ ion easily.
• H2SO4 (+6) > H3PO4 (+5) > H2SO3 (+4)
• HClO4 (+7) > H2SO4 (+6) > HNO3 (+5) > H2SO3 (+4) > H3AsO3 (+2) > HClO (+1)
• For same oxidation number, Smaller the size of the central atom, greater its positive charge
density, greater pull on O –H bond electron, weaker the O-H bond, stronger the acids.
• H2SO3 > H2SeO3
Strength of acids
• Number of O and H: For (HO)mYOn, increasing n (No. of O atom excluding O atom

in OH), increases acid strength. Increasing non – hydrogenated O atom, increases

electronegativity of Y atom. Greater the pull on the electron of O –H bond, Stronger

the acid

• H2SO4 (SO2(OH)2) > H2SO3 (SO(OH)2)

Strength of acids
• HClO3 > HClO2 > HClO, H2SO4 > H2SO3, HNO3 > HNO2

• H2SO4 > H3PO4

• HNO3 > H2CO3

• HClO4 > H2SO4 > H3PO4 > H4SiO4

 Strength of Hydrides
• Acid strength in periodic table:
• Across a row: atomic radius decreases → Electronegativity increases → H-X bond polarity increases → acid
strength increases Here, X is a substituent

• HF > H2O > NH3 ( where X= F, O, N).

• On moving from left to right in a period, the acidic character of hydrides increases. NH3 is basic, H2O is
neutral and HF is acidic.
• Electronegativity of central atom increases from left to right in a period. The polarity of H-X bond increases
So the pull of H – X bond electrons toward X increases. The ease of losing a proton increases and acidity
increases.
 Acid strength of hydracids in periodic table:

Across a column: atomic radius increases → H-X bond strength decreases → acid strength increases
HF < HCl < HBr < HI
Atomic radius increases
Acidic Strength
❑ On moving down a group the acid strength increases because size of the nonmetal increases.
For example HI is stronger acid than HF, it is because I has greater size than F, meaning the
bonded H is far away from attractive nucleus of I than it is in F, So HX bond strength is weaker
for HI than that of HF. Hence, acid strength increases with increasing size of non-metal.

❑ Another reason is that the conjugate bases are more stable. As you move down in a column, the
atoms are larger and the negative charge density of the conjugate bases are less.
- -
F > Cl- > Br -
Conjugate base charge density decreases >I
Stability increases
Strength of bases
❑ Alkali metals: Alkali metal hydroxides (MOH) form strong bases and strength increases
with increasing metal ion size. A large ion with a small positive charge has little attraction
for the electrons of HO- ion.

LiOH < NaOH < KOH < CsOH

❑ Why ammonia is better Lewis base than water, Explain?

NH3 > H2O

Try the answer Yourself.

Neutralization reaction

• Acid + Base → Salt + water

• Neutralization is double displacement reaction.
• HCl + NaOH → NaCl + H2O
• Nature of salts:
• Strong acid + Strong Base → Neutral salt (NaCl)
• Strong acid + Weak Base → Acidic salt (NH4NO3)
• Weak acid + Strong Base → Basic salt (NaNO2)
• Weak acid + Weak Base → Neutral/Acidic/Basic salt (NH4CN- Basic)
 Nature of salts:
A salt consisting of the anion of a strong acid and the cation of a strong base yields a neutral solution
because the ions do not react with water.

• Strong acid + Strong Base → Neutral salt (NaCl)

• NaOH (aq) + HCl (aq) → NaCl (aq)+ H2O

• NaCl (aq) → Na+ (aq) + Cl- (aq)

The ions are hydrated, but do not react with water:

• Na+ + H2O → No reaction

• [ Na+ could be Lewis acid but small charge-large radius and it is conjugate acid of strong base NaOH. So, it
is weak acid]

• Cl- + H2O → No reaction [Cl- is conjugate base of strong acid HCl → weak base]

The cation is conjugate acid of strong base is hardly acidic & the anion is conjugate base of strong acid is
hardly basic. Hence they don`t react with water.
 The anions of weak acids are basic. On the other hand, the anions of strong acids have hardly any basic character;
that is, these ions do not hydrolyze.

The cations of weak bases are acidic. On the other hand, the cations of strong bases (metal ions of Groups IA
and IIA elements—except Be) have hardly any acidic character; that is, these ions do not hydrolyze.
Nature of salts:
A salt consisting of the anion of a strong acid and the cation of a weak base yields an acidic solution because
the cation of the salt is conjugate acid of weak base acts as an acid and the anion conjugate base of strong
acid does not react with water.

• Strong acid + Weak Base → Acidic salt (NH4NO3)

• HNO3 (aq) + NH4OH (aq) → NH4NO3 (aq) + H2O
• NH4NO3 (aq) → NH4+ (aq) + NO3- (aq)
• NH4+ + H2O → NH3 + H3O+ [ H3O+ → Strong acid] [NH4+ ion is conjugate acid of weak base]
Weak acid
• NO3- + H2O → No reaction [NO3- is conjugate base of strong acid HNO3 → weak base]
• The cation NH4+ produced from weak base acts as an acid. Hence enhances acidity of solution. But
the anion NO3- conjugate base of strong acid has hardly basic behavior & can`t react with
water.
Nature of salts:
A salt consisting of the anion of a strong acid and the cation of a weak base yields a basic solution because the anion is
conjugate base of weak acid acts as a base and the cation conjugate acid of strong acid does not react with water.

• Weak acid + Strong Base → Basic salt (NaNO2)

• NaOH (aq) + HNO2 (aq) → NaNO2 (aq) + H2O
• NaNO2 (aq) → Na+ (aq) + NO2- (aq)
• Na+ + H2O → No reaction
[ Na+ could be Lewis acid but small charge-large radius and it is conjugate acid of strong base NaOH.
So, it is weak acid]
• NO2- + H2O → HNO2 + HO- [HO- → Strong base] [NO2- conjugate base of weak acid]
Weak base

The anion produced from weak acid acts as a base. Hence enhances basicity of solution. But the cation
conjugate acid of strong base has hardly acidic behavior & can`t react with water.
Nature of salts: if the salt contains cation of a weak base and anion
of a weak acid then the overall pH of the solution depends on Kb & Ka. of separated ions
(cation and anion of the salt).

• Weak acid + Weak Base → Neutral/Acidic/Basic salt (NH4CN- Basic)

• NH4OH + HCN → NH4CN+ H2O
• NH4CN (aq) → NH4+ + CN-
NH4+ conjugate acid of a weak base NH3 itself is a acid.
NH4+ + H2O → NH3 + H3O+ [ H3O+ → Strong acid]
CN- conjugate base of a weak acid HCN itself is a base.
CN- + H2O → HCN + HO- [HO- → Strong base]

• In this case, Kb > Ka. Hence, NH4CN is Basic

 Hard-Soft Acid Base (HSAB)
Hard acids are difficult to polarize and those have smaller size, high positive charge .

Soft acids are readily polarized. These have a larger size, low positive charge or zero charge.

Factors Hard Acid Soft acid

Size Small Large
Polarizability Low High
Positive Charge High Low
Bond nature Ionic Covalent
Electronic configuration Absence of d electron in valence Nearly full d-orbital in valence
shell shell

Examples H+, s-block, alkaline, alkaline Ag+, Hg+2, Pd+2, Pt+2 Ti+1
earth metal ions Ni0
Ti++4
H , Li+, Be+2, Mg+2, Al+3, Fe+3
Cr +3 Ti+4 Ni3+
 Hard-Soft Acid Base (HSAB)
Hard bases are those in which the donor atoms have smaller size, low polarisabilities and have high electronegativity.
Soft bases are those in which the donor atoms are larger in size, easily polarized and have low electronegativity.

Factors Hard Base Soft Base

Size Small Large
Electronegativity High Low
Polarizability Low High
Bond nature Ionic Covalent
Electron Donating Capacity Low High
Examples F, O, N, Cl donor atom S, I, P, C donor atom
F-, Cl-, H2O, ROH, SO42-, I-, H2S, RSH, S2-, SCN, R3P, CO, CN-
O2-, NH3, RNH2, NCS
Acids

BASES
∙ Pearson principle:
Hard acids prefer to bond with hard bases and soft acids prefer to bind to soft bases.
∙ Hard Acid- Hard base complexes: Ionic bonding (Low polarization)

• Soft Acid – Soft base complexes: Covalent bonding (High polarization)

• Hard acid - soft base or soft acid - hard base: Mostly polar covalent bonding ( Unstable)
According to HSAB concept, hard acids prefer binding to the hard bases to give ionic complexes, whereas the soft acids
prefer binding to soft bases to give covalent complexes. It is sometimes referred to as Hard-Soft Interaction Principle
(HSIP).

HSAB Principle - Hard Acid - Hard Base - Soft Acid - Soft base interactions

* 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.

* The interactions between hard acid - soft base or soft acid - hard base are mostly polar covalent and tend to be more
reactive or less stable.
 ∙ HSAB theory application:

Solubility in water:
The compound formed due to soft acid-soft base combination is more covalent and less soluble in polar solvents
like water. For example, Silver iodide, AgI is insoluble in water as it has covalent nature since it is the combination
of soft acid, Ag+ and soft base, I-.
On the other hand, Lithium iodide, LiI is the result of a combination of Li+ (hard acid) and I- (soft base). Thus it is
polar covalent and thus soluble in water.

Solubility:

LiF > LiCl > LiBr> LiI Solubility in polar solvent

AgF > AgCl > AgBr> AgI Solubility in polar solvent

LiI Soluble in water due to Polar Covalent bond

AgI Insoluble due to covalent nature of bond

In hydrogen bonding:
The strong hydrogen bond is possible in cases of H 2O, NH3, and HF, since the donor atoms (F, O &
N) are hard Lewis bases and their interactions with partially positively charged H, which is a hard
acid, are stronger.

1. HSAB to predict direction of Inorganic reactions: HSAB principle is used to predict the outcome of few of the
reactions. We can predict whether a reaction proceeds to the right or left based on soft or hard acid/base
interactions.

The following reaction is possible since Mg2+ is harder acid than Ba2+ and O2- is harder base than S2-.

The following reaction is possible and proceeds to the right since As3+ is softer than P3+ and I- is softer than
F -.
Linkage of ambidentate ligands to metal atoms: The SCN- ligand is an ambidentate ligand and can be S-bound

to metal (M-SCN) or can be N-bound to metal (M-NCS). The choice among S-bound or N-bound is decided by

soft or hard acid base behavior. S is comparatively soft base than N atom. Hence soft metal ions are S-bound while

hard metal ions are N-bound.

1) SCN- bonds through sulfur atom (soft base) when bonded to Pt2+, a soft acid.

2) It bonds through nitrogen atom (a hard base) when linked to Cr3+, a hard acid.
Stability of complex: Hard acid-Hard base: Stable complex

FeCl3 > FeBr3 > FeI3 (Fe3+ Hard acid)

CoF3 > CoI3 (Co3+ Hard acid)