Acid-Base Equilibria

Chapter 4
 Lesson Outcomes
• Students are able to:
– Define 3 main definition of base and acid
– Differenciate between acid,base and its
conjugates
– Write the ionization equilibrium
– Calculate the % dissociation
– Calculate the pH of weak acid and base solutions
– Calculate Ka, Kb, Kw
 ACID- PROPERTIES
• Acids have sour taste.
• Acids change the colour of litmus blue to red.
• Acids react with electropositive metals to liberate
hydrogen gas.
• Acids react with carbonate or bicarbonate to liberate
carbon dioxide gas.
• Acids react with bases form salt and water only.
•  
 BASE-PROPERTIES
• Bases are slippery to the touch.
• Bases change colour of red litmus to blue.
• Bases react with ammonium salt to produce
ammonia gas.
• Bases react with acid to form salt and water
only.
•  
 DEFINITION
• THREE MAIN DEFINITIONS
• Arrhenius’s Definition
• Bronsted-Lowry’s Definition
• Lewis Definition
 Arrhenius Acid & Base

Acids are substances that ionised in aqueous solution

to form hydrogen ions, thereby, increasing the
concentration of H+ (aq) ions

Acid: produces H+ in aqueous solution

Base: produces OH- in aqueous solution

HCl(aq)  H+ (aq) + Cl- (aq)

However, an H+ cannot exist by itself in water

HCl has an “acidic” H+, but by itself cannot act as an acid
However HCl(aq):
HCl (aq) + H2O (l)  H3O+ (aq) + Cl- (aq)

H3O+: hydronium ion

 Brønsted-Lowry Acids and Bases

An acid is a chemical substance which donates proton to another

substance Acid: proton donor

A base is a chemical substance which takes proton from another

substances Base: proton acceptor
substances.
 Brønsted-Lowry Acids and Bases

The H+ consists of 1 proton and 0 electron

HCN(aq) + NH3(aq)  NH4+(aq) + CN-(aq)
acid base

The H+ is transferred from HCN to NH3

HCN is a proton donor therefore it is an acid
NH3 is a proton acceptor therefore it is a base
 Examples
•  
1. CH3NH2 (aq) + H2O (l)  CH3NH3+ (aq) + OH- (aq)
•  
2. CO32- (aq) + H2O (l) HCO3- (aq) + OH- (aq)
•  
3. C2H5O- (aq) + H2O (l)  C2H5OH (aq) + OH- (aq)

4. NH3 (g) + HCl (g)  NH4Cl (s)

•  
5. NH3 (l) + HCl (l)  NH4Cl (l)
CCl4
•  In reaction 4 and 5 above, the ammonia molecule receives a proton from
hydrogen chloride molecule. Hence, ammonia is a base (proton acceptor)
while hydrogen chloride is an acid (proton donor).
 Conjugate Acid-Base Pair

• Consider the reaction of ethanoic acid and water.

•  
•  
•  
•
CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)
• Acid Base Conjugate base conjugate
acid
•
•  
•  
• The relationship of conjugate acid-base pair can be
represent by the equation
•  
Acid 1 + Base 2 Conjugate + Conjugate
Base 1 Acid 2

HA + B A- + HB+

A conjugate base is produce when an acid losses a proton.

• A conjugate acid is produce when a base accepts a proton.
 Conjugate Acids & Bases

HCN(aq) + H2O(l)  H3O+(aq) + CN-(aq)

acid conjugate base

CN- (aq) is the conjugate base of HCN

Brønsted-Lowry acids form conjugate bases

donates H+
Acid -----------> conjugate base
 Arrhenius vs Brønsted-Lowry
• Arrhenius definition restricted to water as a solvent
• However Brønsted-Lowry theory includes non-
aqueous solvents
• Brønsted-Lowry includes acid/base in the absence of
solvent
Protons can be transferred in the gas phase:
HCl(g) + NH3(g)  NH4Cl(s)
 Lewis Acids & Bases
A Lewis base donates a lone pair of electrons
A Lewis acid accepts a lone pair of electrons

Lewis acids/bases are a broader definition than the

Brønsted-Lowry definition

H+ is an electron pair acceptor; a Lewis acid

Soluble metal oxides are strong bases

 NH3 + H2O  NH4+ + OH-
base acid

Reactions between electron deficient and electron-rich molecules

BF3(g) + NH3(g)  F3B - NH3 (s)
Lewis acid Lewis base
B-N bond is called a coordinate covalent bond; formed by the
coordination of an electron-pair donor to an electron pair
acceptor
 SUMMARY

• ACID
• Arrhenius : H+ donor in (aq)
• Bronsted-Lowry : H+ donor
• Lewis : e- pair acceptor
• BASE
• Arrhenius : OH- donor in (aq)
• Bronsted-Lowry : H+ acceptor
• Lewis : e- pair donor
 Amphoteric / amphiprotic

• any compound that can act both as an acid

and a base
• ex) H2O, H2SO4 -, H2PO4 -, HPO4 -2
 Acid Strength
The strength of an acid is defined by the
equilibrium position of its dissociation
(ionization) reaction:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)

Strong Acid:
Acids that fully dissociate (100%) in water
Its equilibrium position lies far to the right. (HNO3)
Common strong acids are H2SO4, HCl, HNO3, HClO4
 Acid Strength
Weak Acid:
Acids that dissociate only partially in
water
Its equilibrium lies far to the left.
(CH3COOH)
Common weak acids are H3PO4, HNO2,
HOCl, organic acids (-COOH).
Strong Acid (a) and a Weak Acid (b) in Water
Fig. 18.1
Fig. 18.2
 Ionization and Percent ionization
Acid ionization (or acid dissociation) is the reaction
of an acid with water to produce hydronium ion
(hydrogen ion) and the conjugate base anion.
Percent ionization is used to specify the amount of
weak acid that has dissociated in achieving
equilibrium in an aqueous solution. The percent
dissociation is defined as follows:

a m o u n t d is s o c ia te d ( M )
% d is s o c ia tio n   100%
in itia l c o n c e n tr a tio n ( M )
 Acid-Ionization Equilibria
• For a weak acid, the equilibrium concentrations of
ions in solution are determined by the acid-
ionization constant (also called the acid-dissociation
constant) - Ka
Consider the generic monoprotic acid, HA.
 
HA(aq )  H 2O(l ) H 3O (aq )  A (aq )
 
[H 3O ][ A ]
Kc 
[HA][H 2O]
 acid-ionization constant, Ka
Since the concentration of water remains
relatively constant, we rearrange the equation
to get:
 
[H 3O ][ A ]
K a  [H 2O]K c 
[HA]
 
[H 3O ][A ]
Ka 
[HA]
base-ionization constant, Kb
B + H2O <--> BH+ + OH-

BOH <--> B+ + OH-


[OH ][B ]
Kb 
[BOH]
 Water as an Acid and a Base
A substance is said to be amphoteric if it can behave
either as an acid or as a base. Water is amphoteric
(it can behave either as an acid or a base).
H2O + H2O  H3O+ + OH
conj conj
acid 1 base 2 acid 2 base 1
 Writing the equilibrium constant :
K = [H3O+][OH-]
[H2O]
K [H2O] = [H3O+][OH-]
K [H2O] = Kw
Kw = [H3O+][OH-] = [H+][OH-] = 1  1014 at 25°C
Where, Kw is the ion-product constant or
dissociation constant for water.
[H+] = [OH-] = 1.0 x 10-7 M at 25oC in pure water.
 Kw = [H3O+(aq) ] [OH- (aq) ]

[H3O+(aq) ] [OH- (aq) ] = 1.0 x 10-14

Kw is an equilibrium constant; the product of the

concentrations of H3O+ and OH- is always equal to Kw.

In pure water [H3O+(aq) ] = [OH- (aq) ]

= 1.0 x 10-7 M at 298 K
Fig. 18.4
 The pH Scale
The pH scale provides a convenient way to
represent solution acidity. The pH is a log
scale based on 10.
pH  log[H+]
pH in water ranges from 0 to 14. The pH
decreases as [H+] increases.
Kw = 1.00  1014 = [H+] [OH]
pKw = -log Kw = 14.00 = pH + pOH
As pH rises, pOH falls (sum = 14.00).
pOH = -log [OH-]
 Calculating pH for weak acid
What is the pH at 25 oC of a solution obtained by
dissolving 0.325 g of acetylsalicylic acid (aspirin),
HC9H7O4, in 0.500 L of water? The acid is monoprotic
and Ka=3.3 x 10-4 at 25 oC. The molar mass of HC9H7O4
is 180.2 g.

Answer:
mol of acid in the sample = 0.00180 mol
the concentration of the acetylsalicylic acid is
0.00180 mol/0.500 L = 0.0036 M
Copyright © by Houghton
Mifflin Company. All rights
reserved.
Calculating Ka of a weak acid
Nicotinic acid is a weak monoprotic acid with the
formula HC6H4NO2. A 0.012 M solution of nicotinic
acid has a pH of 3.39 at 25 oC. Calculate the acid-
ionization constant for this acid at 25 oC.

Write the Ka expression

 
[H 3O ][Nic ]
Ka 
[HNic]

Copyright © by.
 Calculating Ka of a weak acid
Let x be the moles per liter of product formed.
 
HNic(aq)  H 2O(l ) H 3O (aq )  Nic (aq)
Starting 0.012 0 0
Change -x +x +x
Equilibrium 0.012-x x x

Substituting the expressions for the equilibrium

concentrations
2
x
Ka 
(0.012  x )
The value of x is obtained from the given pH value.


x  [H 3O ]  anti log( pH )
x  anti log(3.39)
4
x  4.1  10  0.00041
Substitute this value of x in our equilibrium
expression
2 2
x (0.00041) 5
Ka    1.4  10
(0.012  x) (0.012)
 Substitute this value of x in our equilibrium
expression
2 2
x (0.00041) 5
Ka    1.4  10
. ( 0. 012  x ) ( 0.012 )
 A Problem To Consider
Substitute this value of x in our equilibrium
expression.
Note first, however, that
(0.012  x )  (0.012  0.00041)  0.01159  0.012
the concentration of unionized acid remains
virtually unchanged.

Copyright © by Houghton
Mifflin Company. All rights
reserved.
 % of dissociation

To obtain the percent of ionizatin/dissociation

% dissociation = [H+] x 100
[HA]
0.00041
Degree of dissociation  x100  3.4%
0.012
• Lets as HAcs represents acetylsalicylic acid and x be
the amount of H3O+ formed per liter.

HAcs(aq)  H 2O(l ) H 3O  (aq)  Acs (aq)

 A Problem To Consider
What is the pH at 25 oC of a solution obtained by
dissolving 0.325 g of acetylsalicylic acid (aspirin),
HC9H7O4, in 0.500 L of water? The acid is monoprotic
and Ka=3.3 x 10-4 at 25 oC.

Note that
Ca
 0.0036 4  11
Ka 3.3  10
which is less than 100, so we must solve
the equilibrium equation exactly.
Copyright © by Houghton
Mifflin Company. All rights
reserved.
 A Problem To Consider
What is the pH at 25 oC of a solution obtained by
dissolving 0.325 g of acetylsalicylic acid (aspirin),
HC9H7O4, in 0.500 L of water? The acid is monoprotic
and Ka=3.3 x 10-4 at 25 oC.

We will abbreviate the formula for

acetylsalicylic acid as HAcs and let x be
the amount of H3O+ formed per liter.
The amount of acetylsalicylate ion is also x
mol; the amount of nonionized acetylsalicylic
acid
Copyright © by Houghtonis (0.0036-x) mol.
Mifflin Company. All rights
reserved.
 Ka and Kb

• Ka and Kb is inversely related

• Ka x Kb = Kw = 10-14
• pKa + pKb = pKw = 14