Chapter 4: Acids and Bases

Inorganic Chemistry II
Dr T. Tshabalala

Email: [email protected]
Office: Central Campus 233
Consultation Time: Mondays 10:00-12:00
Brønsted Acidity

• Brønsted acid: Proton donor

• Brønsted Base: Proton acceptor

• Acid-Base reaction: involves a proton transfer from one species to another

¿
HCl donates a proton to H2O NH3 accepts a proton from H2O

H2O acts as both acid and base (Amphiprotic substance)

Proton Transfer Equilibria In Water

Conjugate Acids and Bases

• A proton donor (i.e. acid) generates a conjugate base

• A proton acceptor (i.e. base) generates a conjugate acid

• Conjugate acids and bases are in equilibrium in solution

Examples
Identify the Brønsted acids and bases and their conjugate acids
and bases.

¿
 The Strength of the Brønsted acids and bases

• Brønsted Acid strength is measured by its acidity constant (Ka)

• Brønsted base strength is measured by its basicity constant (Kb)

HA  H 2O  H 3O   A
HF  H 2O  H 3O   F  𝐾 𝑎=¿ ¿
H O
For a Strong  NH
2 Acid: K >>1
a
3  NH 
 OH
This suggests
4

that [A-]>>[HA]
𝑲 𝒂 =¿ ¿
H 2O  NH 3  NH 4  OH 

But if Ka<<1 ….[HA]>>[A-] this implies that HA is a poor proton donor Acid1  Base2  Base1  Acid 2
  HA  H 2O  H 3O   A
HA
Acid H2O  H 3OBase
Base  A  Acid
𝐾 𝑏=¿ ¿
1 2 1 2
H 2O  B  HB   OH 
H 2O  NH 3  NH 4  OH 

For a Strong Base: Kb>>1 This suggests that [HB ]>>[B]

+
𝑲 𝒃=¿ ¿
Acid1  Base2  Base1  Acid 2
But if KbAcid1  Base2 +] thisBase
<<1 ….[B]>>[HB 1  that
implies AcidB2is a poor proton acceptor
 HNO3 (aq )  H 2O (l)  H 3O (aq )   NO
The Strength of the Brønsted acids and bases CO32 (aq)  H 2O(l )  HCO3 (aq )  OH
NH 3 ( aq)  H 2 S (aq )  NH 4 (aq )  HS 
• Autoprotolysis: proton transfer between water molecules 2 H 2O  H 3O   OH 
𝑲 𝒘 =¿

 
HAthe
• Autoprotolysis constant of a solvent is that it enables us to express  Hstrength
2O  Hof
3O a  A in terms
base
of the strength of its conjugate acid H O  NH  NH   OH 
2 3 4
 
NH  H 2O  H 3O  NH 3
4

Acid1  Base2  Base1  Acid 2

• The value of Kb for the ammonia equilibrium in which NH 3 acts as a base is related to the value of
Ka for the equilibrium
KaKb = Kw

• Larger the value of Kb, the smaller the value of Ka (stronger base, the weaker conjugate acid).

• The strengths of bases may be reported in terms of the acidity constants of their conjugate acids.
 The Strength of the Brønsted acids and bases
• pK =–Log (K)
• pKa + pKb = pKw = 14
Strong and Weak acids and bases

• A substance is classified as a strong acid if the proton transfer equilibrium lies strongly in favour of donation
of a proton to the solvent.
pKa < 0 (corresponding to Ka > 1 and usually to Ka >> 1)
• A substance is classified as a weak acid if the proton transfer equilibrium lies in favour of non-ionized acid.
pKa > 0 (corresponding to Ka < 1)
• A strong base reacts with water to become almost fully protonated. An example is the oxide ion, O 2- ,
which is immediately converted into OH– ions in water

• A weak base is only partially protonated in water. An example is NH3, which dissolves in water to give
only a small proportion of NH4+ ions.
Conjugate base of any strong acid is a weak base because it is
thermodynamically unfavourable for such a base to accept a proton.
 Polyprotic Acids
• Polyprotic acid: can donate more than one proton

[ H 3O  ][HS ]
 
H 2 S (aq )  H 2O (l)  H 3O ( aq )  HS (aq ) K a1   9.1108
[H2S ]

[ H 3O  ][S2 ]
  2
HS (aq )  H 2O (l )  H 3O ( aq )  S ( aq ) Ka2  
 1.110 19
[ HS ]

Example

Calculate the concentration of carbonate ions in 0.10 M

H2CO3(aq). Ka1 4,3x10-7; Ka2 4.6 × 10-11
 Periodic Trends in aqua acid Strength

• The strength of the aqua acids increases with increase in positive charge (oxidation state) of the
metal ion and with decrease in ionic radius.
2
z ξ: electrostatic parameter
  100 z: positive charge

r r: radius of the metal ion

Example
1. Arrange the following aqua acids in order of increasing in acidity.
[Na(OH2)6]+, [Sc(OH2)6]3+, [Mn(OH2)6]2+, and [Ni(OH2)6]2+
 Effect of Structure on Acid-Base Properties

Electronegativity Effect on Relative Strength of Oxo-Acids:

Same central atom, but different numbers of oxygen atoms:
HOClO3 > HOClO2 > HOClO > HOCl;

Same number of oxygen, but different central atoms:

• Trend of electronegativity: F > Cl > Br > I;

• Trend of relative acidity: HOF > HClO > HOBr > HOI

• Relative acidity: CF3COOH > CCl3COOH > CH3COOH

• Trend of electronegativity: Cl > S > P > Si

• Relative acidity: HClO4 > H2SO4 > H3PO4 > H4SiO4

 Acid-Base Properties of Oxides

• Nonmetal oxides are acidic;

N2O5 + H2O  2HNO3(aq);
SO3(g) + H2O  H2SO4(aq);
Cl2O7 + H2O  2HClO4(aq)
• Trends:
Acidity increases left to right across a period
SiO2 < P4O10 < SO3 < Cl2O7
Acidity decreases top-to-bottom in periodic table
N2O5 > P4O10 > As2O5 > Sb2O5
 Acid-Base Properties of Oxides

• Trend of acid-base properties of oxides in periodic table: from the most basic (on the left)
to the most acidic (on the right):

Na2O, MgO, Al2O3, SiO2, P4O10, SO3, Cl2O7

• Trend of acid-base properties going down a group: most acidic on the left to the most
basic on the right:
N2O5, P4O10 , As2O5, Sb2O5
 Effect of Structure on Acid-Base Properties
• A hydroxoacid, in which the acidic proton is on a hydroxyl group without a neighbouring
oxo group (=O).

• The key to the acidity of the oxoacids lies with electronegativity of the central atom (E).

• Higher the electronegativity of E, the more the electrons are drawn away from the H
atom and the more readily proton is lost. (HOI < HOBr < HOCI)

• The electronegativity of E increases ( I < Br < Cl), and the acid strength increases in the
same order.

• For a series of mononuclear oxoacids of an element E, the strength of the acids increases
with increasing number of O atoms. HOCl4 > HClO3 > HClO2 > HClO
H2SO4 >H2SO3 and HNO3 >HNO2.
 Effect of Structure on Acid-Base Properties
Substituted oxoacids
• Substituted oxoacids have strengths that may be rationalized in terms of the electron
withdrawing power of the substituent.

• By contrast, the –NH2 group, which has lone pair electrons, can donate electron density to
S by π bonding. This transfer of charge reduces the positive charge of the central atom
and weakens the acid.

• Fluorine is highly electronegative, it withdraws electrons from the central S atom and
confers on S a higher effective positive charge. As a result, the substituted acid is stronger
than O2S(OH)2.
 Amphoterism
• An amphoteric oxide is an oxide that reacts with both acids and bases
Al2O3  6 H 3O   3H 2O  2[ Al (OH 2 )6 ]3
Al2O3  2OH   3H 2O  2 Al (OH )4 

• From titanium to manganese and perhaps iron, oxidation

state +4 is amphoteric (with higher values on the border of
acidic and lower values of the border of basic).

• On the right of the block, amphoterism occurs at lower

oxidation numbers: the oxidation states +3 for cobalt and
nickel and +2 for copper and zinc are fully amphoteric.

The frontier between metals and non-metals in the periodic table is characterized by the
formation of amphoteric oxides; amphoterism also varies with the oxidation state of the element.
 Lewis Acidity

• Lewis Acid: substance that acts as an electron acceptor

• Lewis Base: substance that acts as an electron donor

A :B →AB

The fundamental reaction of Lewis acids and bases is the formation of a complex (or
adduct), A–B, in which A and :B bond together by sharing the electron pair supplied by
the base.
Sections 4.7 and 4.8 Self Study
 Hard-Soft Acid and Base (HSAB)
• The order of strengths (as measured by the equilibrium constant,
Kf, for the formation of the complex) with which they form
complexes with halide ion bases:
Hard acids bond in the order: I– < Br– < Cl– < F–
Soft acids bond in the order: F– < Cl– < Br– < I–
• Kf increase steeply from F– to I– when the acid is Hg2+, indicating
that Hg2+ is a soft acid.
• The trend is less steep but in the same direction for Pb2+, which
indicates that this ion is a borderline soft acid.
• The trend is in the opposite direction for Zn2+ , so this ion is a
borderline hard acid.

• The steep downward slope for Al3+ indicates that it is a hard acid.

Hard and soft acids and bases are identified empirically by the
trends in stabilities of the complexes that they form: hard acids
tend to bind to hard bases and soft acids tend to bind to soft bases.
• Hard cations such as Li+, Mg2+ , Ti3+ , and Cr3+ are found in
association with the hard base O2-.

• The soft cations Cd2+, Pb2+, Sb2+, and Bi2+ are found in
association with the soft anions S2– , Se2- , and Te2– .

• SCN–