Acids & Bases L - 1-Merged
Acids & Bases L - 1-Merged
Acids & Bases L - 1-Merged
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.
Oxyacids: H-O-Y- Electronegativity of Y atom is large → H-O bond polarity increases → H-O bond strength decreases
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
the acid
• 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.
• [ 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.
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).
Soft acids are readily polarized. These have a larger size, low positive charge or zero charge.
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.
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)
• 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:
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
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