Acids and Bases

Presented By
Sabita Subedi
Lecturer
Tri-Chandra Multiple Campus
 Lewis Acids and Bases
• According to the Lewis theory of acid-base reactions, acids react
with bases to share a pair of electrons in which bases donate and
acids accept electrons.

• A Lewis acid is therefore any substance that can accept one or

more pair of electrons. In other words, a Lewis acid is an electron-
pair acceptor. Hence it is an electron deficient species which is
also called electrophile.

• A Lewis base is any substance that can donate a pair of electrons.

A Lewis base is therefore an electron-pair donor. Hence it is an
electron rich species which is also called nucleophile.
 Lewis Acids and Bases
• The principal advantage of the Lewis theory is the way it expands the
number of acid-base reactions.

For example,
• Al3+ ions form bonds to six water molecules to give a complex ion
which can be explained by Lewis Acid-Base Concept.
Al3+(aq) + 6 H2O(l) ⇌ Al(H2O)63+(aq)
• This is an example of a Lewis acid-base reaction.

• Water has nonbonding pairs of valence electrons and can therefore

act as a Lewis base while Al3+ ion is electron deficient which makes it
Lewis Acid.

• Thus, Al(H2O)63+ ion is formed when an Al3+ ion acting as a Lewis acid
picks up six pairs of electrons from neighboring water molecules
acting as Lewis bases to give an acid-base complex, or complex ion.
 Lewis Acids and Bases
The Lewis acid-base theory explains why BF reacts with ammonia.
• 3

• The lone pair of electrons on the N-atom of NH3 makes it electron pair
donor or Lewis base. Likewise BF3 act as an electron-pair acceptor, or
Lewis acid since it contains empty 2pz orbital which can pick up a pair of
nonbonding electrons from a Lewis base to form a coordinate covalent
bond. BF3 therefore reacts with Lewis bases such as NH3 to form acid-
base complexes.
NH3 + BF3 H3N BF3
• Thus, ammonia (NH3), organic amines (RNH2), ethers (R2O), alcohols
(ROH), hydroxyl ions (OH-) etc. which are capable of donating electron
pair through formation of coordinate bonds are examples of Lewis bases.

• Compounds like BF3, BCl3, AlCl3, SiF4 etc. and positively charged ions
which are capable of accepting electron pair through formation of
coordinate bonds are examples of Lewis Acids.
 Types of Lewis Acids
• According to Lewis concept, the following species can act as Lewis acids.
A. Simple Cations:
All cations behave as Lewis Acids as they have tendency to accept
electron pairs. Smaller cations such as H+, Li+, Be++ etc. act as stronger Lewis
acid due to their higher tendency to accept electrons while larger cations
act as weaker Lewis Acids due to their lesser tendency to accept electrons.
Higher charged cations such as Fe3+, Sn4+ etc. are stronger Lewis Acids
compared to lower charged ones such as Fe2+, Sn2+ etc. due to their higher
tendency to accept electrons than the latter counterparts.

B. Molecules in which central atom has incomplete octet

The central atoms in BF3, AlCl3, FeCl3 molecules have only six electrons, and
they show the tendency to accept electrons in order to complete their octet.
Hence, these molecules are considered Lewis Acids.
Cl– (Lewis base) + AlCl3 (Lewis acid) → [Cl → AlCl3]+
 Types of Lewis Acids
C. Molecules containing central atom with vacant d-orbitals
The central atom of the molecules such as SiX4, GeX4, TiCl4, SnX4 etc. have vacant d-
orbitals, i.e. deficient with electrons, hence they can extend their valence shell and
accommodate more electrons.
SiF4 (Lewis acid) + 2F– (Lewis base) → [SiF6]2-
SnCl4 (Lewis acid) + 2Cl– (Lewis base) → [SnCl6]2-

D. Molecules having a multiple bond between atoms of dissimilar electro negativity

 Examples of this class include CO2, SO2 and SO3.
 In these compounds, Oxygen atoms are more electronegative than S or C atoms due
to which electron density of л-electrons is displaced away from C or S atoms towards
O-atom. The C or S atoms thus become electron deficient and are able to accept
electron from Lewis base such as OH- ions to form covalent bond.
CO2 + H2O → H2CO3
(In this reaction, oxygen of water molecule (Lewis base) donates electron to carbon atom
of carbon dioxide)
 Types of Lewis Bases
A. Neutral species having at least one unshared or
lone pair of electrons:
Examples of this class include water (H2O:),
ammonia (:NH3), ether (R2O:) etc. since they are able
to donate electrons to the electron deficient
species.
B. Negatively charged species or anions
Examples include oxides (O2-), hydroxides (OH-),
halides (X-) etc. since they have tendency to donate
electrons. Higher is the charge density, stronger is
the tendency to donate electrons.
 Hard and Soft Acids
• Lewis acids and bases are classified as hard and soft acids and bases.
• Hard acids are alkali metal ions, alkaline earth metal ions and lighter transition
metal ions which possess following properties:
 Small size
 high positive charge
 high polarizing power (ability to distort electron charge cloud of anion)
 contain empty orbitals in valence shell which are not easily distorted or
polarized
• Hard acids are Type (a) metals which include smaller ions from group 1 and 2 and
the left hand side of the transition metals having high positive charge and no or
less d-electrons. For example, K+, Mg2+, Al3+, Ti4+, Fe3+, Co3+ etc.

• Soft Acids include heavier transition metal ions which possess following
properties:
 Large size
 Low positive oxidation state
 Low polarizing power
 Outer orbitals or electrons are easily distorted or polarized
• Soft Acids are Type (b) metals which include ions from right hand side of the
transition series having smaller positive charge and sufficient d-electrons. For
+ + 2+ 2+
 Hard and Soft Bases
• Hard bases are Lewis bases which hold their electrons strongly.
• These have donor atoms which possess following properties
 Smaller size
 Less Polarizable
 High electronegativity
• Examples include OH-, F-, H2O, NH3 etc.

• Soft bases are Lewis bases in which the position of electrons are easily polarized or
removed.
• These have donor atoms which possess following properties
 Larger size
 Easily Polarizable
 Low electronegativity
• Examples include I-, SCN-, CN-, thioether etc.

• In a group of the periodic table, softness of the Lewis base increase with the increase in
size of the donor atom. Softness of Lewis Base increases
F - < Cl- <Br- <I-
 Examples of Hard and Soft Acids and Bases
Acid/Base EXAMPLES

H+, Li+, Na+, K+, Be2+, Mg2+, Ca2+, Sr2+, Sn2+

Hard acids Al3+, Ga3+, In3+, Cr3+, Co3+, Fe3+, Ir3+, La3+, Si4+, Ti4+, Zr4+, Th4+,U4+, VO2+ , UO22+

BeMe2, BF3, BCl3, B(OR)3, AlMe3

Cu+, Ag+, Au+, Hg+ , Cs+ , Tl+ , Hg2+ , Pd2+, Cd2+ , Pt2+

Soft acids Metal atoms in zero oxidation states

BH3

H2O, OH-, F-, Cl-, CH3CO2-, PO43-, SO42-, CO32-, NO3-, ClO4-, ROH, RO-, R2O, NH3,
Hard bases
RNH2, N2H4
S2-, RSH, RS-, R2S, I-, CN-, SCN-, S2O3-, R3P, R3As,
Soft bases
(RO)3P, RNC, CO, C2H4, C6H6, R-, H-
Hard and Soft Acids and Bases (HSAB) Principle
• Hard and Soft Acids and Bases (HSAB) Principle is a qualitative concept introduced by Ralph
Pearson to explain the stability of metal complexes and the mechanisms of their reactions.

• According to HSAB concept, hard Lewis acids prefer binding to the hard Lewis bases to give
stable ionic complexes, whereas the soft Lewis acids prefer binding to soft Lewis bases to
give stable covalent complexes.

• The large electronegativity differences between hard acids and hard bases give rise to
strong ionic interactions.
• The electronegativities of soft acids and soft bases are almost same and hence have less
ionic interactions. i.e., the interactions between them are more covalent.
• 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.

• Examples:
 AgI2- exist as a stable compound but AgF2- is not stable because Ag+ , being a soft acid, prefer to
interact with I- ion which is soft Lewis base in order to form stable covalent complex but F - ion,
being a hard base, form unstable complex(AgF2-) with Ag+.

 [Ag(CN)2]- exist as a stable compound but [AgCl2]- is not stable because Ag+ , being a soft acid,
prefer to interact with CN- ion which is soft Lewis base in order to form stable covalent
complex but Cl- ion, being a hard base, form unstable complex(AgCl2-) with Ag+.
 Applications of HSAB Principle
• With the help of HSAB, a large number of chemical reactions can be understood.
A. Relative strength of Hydracids HF,HCl,HBr and HI:
 In aqueous solution the relative strength of HF, HCI, HBr and HI can be predicted.
 The reaction of acids with water is:
HX+H2O→H3O++X-
 The hardest base F- will be most successfully and strongly bonded to the hard acid
H+. Hence HF will be highly stable. It is therefore least dissociated.
 Hence acid strength increases as : HF < HCI < HBr < HI

B. Relative stabilities of complexes in Aqueous Solutions:

 HSAB explains the special stability of complexes formed by hard-hard and soft-soft
interactions.
 For eg., [ Cd(CN)4 )] 2- is more stable that [Cd(NH3)4]2+. According to HSAB principle
hard acid prefers hard base and soft acid prefers soft base . Hence the soft acid
Cd2+ will prefer to combine with soft base CN-.
 AgI2- exist as a stable compound but AgF2- is not stable because Ag+ , being a soft
acid, prefer to interact with I- ion which is soft Lewis base in order to form stable
covalent complex but F- ion, being a hard base, form unstable complex(AgF 2-) with
Ag+.
 Applications of HSAB Principle
C. To Predict the Course of Reaction:
HSAB principle can be used to predict the course of reaction.
For example,
i) H+ + CH3HgOH→H2O+CH3Hg+
ii) H+ +CH3HgSH→H2S + CH3Hg+
The reaction (i) goes to right as the hard acid H+ binds strongly to hard base OH - to
produce stable product H2O. On the other hand the reaction (ii) is favoured to left where
soft base SH- will tend to remain combined with soft acid CH3Hg+ instead of joining to
hard acid H+.

• The reaction between LiI and CsF always proceed to give LiF and CsI since Li and F are
hard acid and base respectively while Cs and I are soft acid and base respectively and
as per HSAB principle, there is always greater stability for hard-hard and soft-soft
interactions.
LiI + CsF LiF + CsI
D. Occurrence of Minerals:
• Hard Acids such as Mg2+,Ca2+, Al3+ etc. occur in nature as a compound MgCO3, CaCO3,
Al2O3 etc. with hard bases such as CO32-, O2- etc. respectively. These metal ions do not
occur in nature as a compound MgS, CaS etc. with soft bases. Likewise soft acids such
+ + + 2-
 Applications of HSAB Principle
E. In hydrogen bonding:
• The strong hydrogen bond is possible in cases of H2O, 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.

F. 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.
 Relative Strengths of Acids and Bases
• According to Bronsted-Lowry theory, the strength of an acid is measured from its tendency
to donote proton .
• The relative strengths of acids is determined by measuring their equilibrium constants in aqueous
solutions.
• In solutions of the same concentration, stronger acids ionize to a greater extent, and so yield higher
concentrations of hydronium ions than do weaker acids. The equilibrium constant for an acid is
called the acid-ionization constant, Ka.
• For the reaction of an acid HA:
HA + H2O ⇌ H3O+ + A−,
• The equation for the ionization constant is written as:
Ka=[H3O+][A−]/[HA]
• Although water is a reactant in the reaction, it is solvent and its concentration is very large, so,
[H2O] is not included in the equation.
• The numerical value of ka determines the strength of the acid. Larger the value of Ka of an acid,
stronger is the acid since the concentration of H3O+ and A− is larger relative to the concentration of
the non ionized acid, HA.
• Thus a stronger acid has a larger ionization constant than does a weaker acid. The ionization
constants increase as the strengths of the acids increase.
• The strength of an acid is also expressed in terms of pKa value.
• pKa=-logKa
• Smaller the value of pKa, stronger is the acid and vice-versa.
 Relative Strengths of Acids and Bases
• According to Bronsted-Lowry theory, the strength of a base is measured from its tendency to accept
proton.

• The relative strengths of bases are also determined by measuring their equilibrium constants in
aqueous solutions.
• The equilibrium constant for base is called the base-ionization constant, Kb.
• For the reaction of a base B:
B + H2O ⇌ BH+ + OH−,
• The equation for the ionization constant is written as:
Kb=[BH+][OH−]/[B]
• Although water is a reactant in the reaction, it is solvent and its concentration is very large, so,
[H2O] is not included in the equation.
• The numerical value of kb determines the strength of the base. Larger the value of Kb of a base,
stronger is the base since the concentration of OH- and BH+ is larger relative to the concentration of
the non ionized base , B.
• Thus a stronger base has a larger ionization constant than does a weaker base. The ionization
constants increase as the strengths of the bases increase.

• The strength of an base is also expressed in terms of pKb value.

pKb= -logKb
• Smaller the value of pKb, stronger is the base and vice-versa.
 Effect of Substituents on relative strengths of
acids
Several factors that affect relative strength of acids
are as follows:
1) Electronegativity: Acidity increases as you go
left to right across the periodic table.
2) Anion size: Acidity increases as you go from top
to bottom in a group of the periodic table.
3)Inductive effect: Electron withdrawing
substitution will increase the acidity of a
compound.
 Effect of Electronegativity on Strength of acids
• For a series of compounds of the general formula HE, as
the electronegativity of E increases, the E–H bond becomes
more polar, favoring dissociation to form E− and H+.

• The more likely the bond is to break to form H+ ions and

thus the more acidic the molecule.

• For binary acids within the same row such as CH4 , NH3 ,
H2O, and HF, the hydrogen atom is bonded to (C, N, O and
F) becomes more electronegative as proceed across the
period and this tends to weaken the bond to H. Thus these
binary acids become more acidic as proceed from left to
right within a period.
Most acidic: HF > H2O > NH3 > CH4 :Least acidic.
 Effect of Size of Atom on Strength of acids
• The larger the atom to which H is bonded, the weaker the
bond. Any factor that weakens the bond to hydrogen, makes
the substance more acidic.

• For binary acids within the same group such as HCl, HF, HI,
and HBr, the atom bonded to hydrogen (F, Cl, Br, I) becomes
larger as proceed down the periodic table and this tends to
weaken the bond to H. Thus, binary acids become more
acidic as proceed from top to bottom with a column.
Most acidic: HI > HBr > HCl > HF :Least acidic;
Most acidic: H2Te > H2S > H2O :Least acidic.

• The order of acidity for the binary hydrides of Group 16

elements is as follows due to the same reason:
H O<H S<H Se<H Te
 Effect of Inductive Effect on Strength of acids
• When an atom or group of atoms is substituted for another
atom or group of atoms in a molecule, the distribution of
electron density changes. The effect of the new atom or
group of atoms on this electron density distribution is
termed the "inductive effect" of the atom or group.

• If the new atom or group of atoms (the substituent) is more

electronegative than the one that it replaced then electrons
will be withdrawn from other parts of the molecule toward
the new substituent. This is electron-withdrawing inductive
effect, also known as -I effect.

• On the other hand, if the new substituent is less

electronegative than the group that it replaced then the
electron density will increase in the rest of the molecule.
 Effect of Inductive Effect on Strength of acids
• Electron-withdrawing groups (EWG) increase the acidity of a compound and
electron-donating group decrease the acidity of a compound.

Relative strengths of oxyacids depend on two major factors:

A) Electronegativity of the central atom:
• A more electronegative substituent increases the acidity of an oxy (or hydroxy)
acid XO-H by greater withdrawal of electron density from the oxygen-hydrogen
bond. This both weakens the O-H bond and increases the positive charge on
hydrogen.

HOCl (most acidic) > HOBr (moderate acidic) > HOI (least acidic)
• As the electronegativity of the central atom increases from I through Br to Cl, the
O-H bond strength weakens and the acidity increases.

• Furthermore, presence of a more electronegative substituent stabilizes the

conjugate base (XO-) by withdrawing charge from the oxygen and effectively
delocalizing the charge over more of the molecule.

• However, electron donating group destabilizes conjugate base because of inter-

 Effect of Inductive Effect on Strength of acids
B) Number of Oxygen atoms around the central atom:
• Within an oxyacid series such as HClO, HClO3, HClO2 and HClO4 , the relative strengths
of acids follows the order:
HClO4 (perchloric acid)> HClO3 (chloric acid)> HClO2 (chlorous acid)> HClO
(hypochlorous acid).

• Since Oxygen is more electronegative than chlorine, with an increase in the number
of O atoms attached to Cl, more electrons are pulled away from O−H bond, thereby
causing a weakening of the O-H bond strength and an increase in the acidity.

• Furthermore, as the number of terminal oxygen atoms increases, single negative

charge is delocalized over successively more oxygen atoms. Such electron
delocalization in the conjugate base increases acid strength.

• For example, in the perchlorate ion (ClO4-), the single negative charge is delocalized
over all four oxygen atoms, whereas in the hypochlorite ion (OCl−), the negative
charge is largely localized on a single oxygen atom. As a result, the perchlorate ion
has no localized negative charge to which a proton can bind. Consequently, the
perchlorate anion has a much lower affinity for a proton than does the hypochlorite
ion, and perchloric acid is the strongest acid.
 Peculiar examples of Relative Strength of Acids
• The correct order for the decrease in relative acidity of boron
halides is BI3>BBr3​>BCl3​>BF3​
Reason
• We know that the electronegativity of halogens decreases from
fluorine to iodine as we move down the group.

• Hence, according to this, BF3​should be the most Lewis acidic due

to the electron withdrawing nature of fluorine atoms.

• However, the order is just the opposite due to back-bonding.

• Back bonding due to the lone pair of electrons of halogen atom

increases electron density on B centre, thereby, reducing its lewis
acid character. This back bonding is more in case of BF3​due to
similar size of orbitals of boron and fluorine atoms, whereas it
decreases down the group due to the increasing size of orbitals as
 Solvent Effects on Acid-Base strength
Leveling and Differentiating effect refers to the effect of solvent on the properties of
acids and bases. If more than one acids or bases are showing same acidic or basic
strength in same solvent it is called levelling effect and the solvent is called levelling
solvent.
Likewise, If more than one acids or bases are showing different acidic or basic strength
in same solvent it is called Differentiating effect and the solvent is called
Differentiating solvent.

Effect of solvents on acid strength (Levelling and Differentiating Effect)

• In order to illustrate the effects of solvents on strength of acids, three solvents,
namely acetic acid, water and liquid ammonia of increasing basic strength may be
considered.
A. Ionization in acetic acid (weakly basic solvent)
• Since acetic acid (weak base) has very poor tendency to accept protons, strong
acids are ionized to different extent and thus have different strength in acetic acid,.
This is called differentiating effect and acetic acid is differentiating solvent for
strong acids.
• Some common acids have been arranged in order of decreasing strength in acetic
acid:
HClO4 > HBr > H2SO4 >HCl > HNO3
 Solvent Effects on Acid-Base strength
B. Ionization in water (moderately basic solvent)
• Water is a much stronger base than acetic acid. Hence the equilibrium of strong acids in water is
expressed as:
HA + H2O ⇌ H3O+ + A−
• Stronger acids ionize completely in water to give H 3O+. Thus when all the acids like HClO 4, HCl,
HBr, HNO3 etc. which are stronger than H 3O+ are added to water, they appear to have equal
strength since all these acids are levelled to the strength of H 3O+ ion which is left in the solution
and is common to all. This is called levelling effect of the solvent because the solvent, water levels
strong acids to the same strength. Hence H 2O is a levelling solvent for strong acids.

• However, water does not show levelling effect for weak acids because they are ionized to different
extent in water. Therefore it is possible to distinguish between their relative strength in water. This
effect is called differentiating effect and water is differentiating solvent. for weak acids.

C. Ionization in liquid ammonia (strongly basic solvent)

• Ammonia is a strong base than H 2O, i.e. it has strong tendency to accept protons. Hence even
weak acids ionize to a considerable extent in NH 3 to give ammonium ion (NH4+) and behave as
strong acids.
CH3COOH + NH3 ⇌ NH4+ + CH3COO-

• Since the strongest acid is ammonium (NH4+), both strong and weak acids appear to be of same
strength in liquid NH3). Hence, liquid ammonia shows levelling effect to both strong and weak
acids; in other words, liquid ammonia is levelling solvent for strong and weak acids.
 Solvent Effects on Acid-Base strength
Effect of solvents on base strength
• The nature of solvent plays equally an important role in ionization and relative strength of bases.
A. Ionization in Water
• Strong bases, i.e., NaOH, KOH Ca(OH)2 etc. exert same basic strength in water. The equilibrium of
strong bases in water is expressed as:
B + H2O ⇌ BH+ + OH−
• Stronger bases ionize completely in water to give OH-. Thus when all the bases like NaOH, KOH etc.
which are stronger than OH- are added to water, they appear to have equal strength since all these bases
are levelled to the strength of OH- ion which is left in the solution and is common to all. This is called
levelling effect of the solvent because the solvent, water levels strong bases to the same strength. Hence
H2O is a levelling solvent for strong bases.
• However, water does not show levelling effect for weak bases because they are ionized to different
extent in water. Therefore it is possible to distinguish between their relative strength in water. This
effect is called differentiating effect and water is differentiating solvent for weak bases.

B. Ionization in acetic acid

• When the solvent is slightly acidic (acetic acid), it will not be possible to distinguish the strength of
different bases.
• Aniline is a weak base and Sodium Hydroxide is a very strong base in water. Both appear to be equally
strong bases in acetic acid solvents. Thus acetic acid is a levelling solvent for bases.

C. Ionization in ammonia
• Since ammonia (strong base) has very poor tendency to donate protons, strong bases are ionized to
different extent and thus have different strength in ammonia. This is called differentiating effect and
ammonia is differentiating solvent for strong bases. For eg., NaNH2 is a far more basic reagent in