Acid/Base Equilibria

Acid/Base Equilibria
Topics
• Acids and Bases
– Bronsted-Lowry Definition
– Conjugate Acids and Bases
– Lewis Definition
 Acid/Base Equilibria
Early Definitions of Acids and Bases
• Various attempts have been made to define exactly what acids and
bases are
• Some early definitions:
• Acids
– Have a sour taste
– React with bases and some other compounds to give salts
e.g. . 2HCl (aq) + CaO (s) CaCl2 (aq) + H2O (l)
acid base salt water

– Produce hydrogen ions (protons) in solution

e.g. water
. HCl (g) H+(aq) + Cl– (aq)
 Acid/Base Equilibria
Early Definitions of Acids and Bases
• Various attempts have been made to define exactly what acids and
bases are
• Some early definitions:
• Bases
– Have a bitter taste
– Alkalis (soluble bases) have a soapy detergent-like feel
– React with acids to give a salt and water
– Produce hydroxide ions in solution
water
. KOH (s) K+(aq) + OH– (aq)

– and neutralize acids by the reaction:

H+ + OH– H2O
 Acid/Base Equilibria
Problems with Early Definitions
• The H+ ion does not actually exist in solution. Instead it exists as a
hydrated proton, H3O+, called the oxonium ion (also referred to as
the hydrogen ion).
H+ + H2O H3O+
• Bases such as ammonia neutralize acids by picking up hydrogen
ions, rather than by providing hydroxide ions
NH3 + H+ NH4+
 Acid/Base Equilibria
Bronstead-Lowry Definition
• In 1923, Bronstead and Lowry proposed new definitions of acids
and bases:
• An acid is a proton donor (i.e. a substance which can donate a
proton to another substance)
• A base is a proton acceptor (i.e. a substance which can accept a
proton from another substance)
• Some substances such as H2O and HSO4– can act as either an acid
or a base. These are referred to as amphoteric
 Acid/Base Equilibria
Bronstead-Lowry Acids – Examples
H+ donated

. HCl (g) + H2O (l) H3O+ (aq) + Cl– (aq)

acid base

. HSO4– (g) + H2O (l) H3O+ (aq) + SO42– (aq)

acid base

. CH3CO2H (l) + H2O (l) H3O+ (aq) + CH3CO2– (aq)

acid base

. HCOOH + HClO2 HCOOH2+ + .ClO2–

base acid
 Acid/Base Equilibria
Bronstead-Lowry Bases – Examples
H+ accepted

. NH3 (g) + H2O (l) NH4+ (aq) + OH– (aq)

base acid

. RNH2 + H2O RNH3+ + OH–

base acid

HSO4–(aq) + H3O+ (aq) H2SO4 (aq) + H2O (l)

base acid

CH3CO2– + H3O+ CH3CO2H + H2O

base acid
 Acid/Base Equilibria
Conjugate Acid-Base Pairs
. Acid Base+ H+
• The acid and base that are related in this way, by the exchange of a
proton are called a conjugate acid-base pair

• A conjugate base is the base formed when an acid donates a proton

. HX + H2O H3O+ + X–
acid conjugate base
• A conjugate acid is the acid formed when a base accepts a proton
. B + H2O BH+ + OH–
base conjugate acid
 Acid/Base Equilibria
Conjugate Acid-Base Pairs
• Acid-Base reactions always generate another pair of acids and bases
that are the conjugate base and acid of the original reactants

Acid 1 + Base 2 Conjugate Base1 + Conjugate Acid 2

. HX + B BH+ + X–
acid base conjugate conjugate
acid base

conjugate conjugate acid base

acid base

• [Note that the original reactant acid and base are also the conjugate
acid and base to the product acid and base]
 Acid/Base Equilibria
Conjugate Acid-Base Pairs - Examples
H+ donated

. HCl (g) + H2O (l) H3O+ (aq) + Cl– (aq)

acid base conjugate conjugate
acid base
. CH3CO2H (l) + H2O (l) H3O+ (aq) + . CH3CO2– (aq)
acid base conjugate conjugate
acid base
. NH3 (g) + H2O (l) NH4+ (aq) + OH– (aq)
base acid conjugate conjugate
acid base
. HCOOH + HClO2 HCOOH2+ + .ClO2–
base acid conjugate conjugate
acid base
 Acid/Base Equilibria
Conjugate Acid-Base Pairs - Examples

Acid Base
H2O OH–
H3O+ H2O
H2SO4 HSO4–
HSO4– SO42–
CH3COOH CH3COO–
HNO3 NO3–
H2CO3 HCO3–
HCO3– CO32–
NH4+ NH3
 Acid/Base Equilibria
Lewis Definitions
• Around 1930 – 1940, G.N. Lewis proposed a new definition of acids and bases
to accommodate additional reactions that do not involve proton transfer, but
that seem intuitively to be acid-base reactions, e.g. :
CaO + SO3 CaSO4
NH3 + BF3 NH3BF3
• An acid is an electron acceptor
• A base is an electron donor
• A Lewis base donates a lone pair of electrons to a Lewis acid forming a
covalent bond
• Note: Lewis bases are also Bronsted-Lowry bases because a species with a
lone pair of electrons will accept a proton from a Bronsted-Lowry acid
• However, not all Lewis acids are Bronsted-Lowry acids e.g. BF3 and SO3 are
not acids in the Bronsted-Lowry sense because they cannot donate protons
• And, not all Bronsted-Lowry acids are Lewis acids e.g. HCl, H2SO4, and
CH3CO2H are not acids according to the Lewis definition because they cannot
readily accept electrons
 Acid/Base Equilibria
Lewis Acids & Bases – Examples
e–’s donated F
H F H
H N + B F H N B F

H F H F
(coordination compound)
base Lewis acid

F F
- -
F + B F F B F

F F
base Lewis acid

H H
+ +
H N + H H N H

H H
base Lewis acid
(also a Bronsted-Lowry acid)