Course : SCIE 6020 (Chemistry)

Effective Period : September 2017

ACID AND BASE

Session 10
ACID AND BASE
Learning Objectives

1. Ability to create a low of

rate of reactions and
constant equilibrium
reactions
2. Ability to classify a low rate
of reactions and constant
equilibrium reactions
 Contents

1. Bronsted-Lowrey Acid-Base
Model
2. The Ion Product of Water
3. pH and pOH
4. Weak Acids
 1. Bronsted-Lowry Acid-Base Model

The first acid-base model was proposed by Arrhenius (1884)

which state:
• an acid is a substance that produces an excess of H+ ions in
water.
• a base is a substance that forms excess OH- ions in water
solution.

Another acid-base model was developed by Lewis:

• acid is a species that can form a covalent bond by accepting
an electron pair from another species
• base is a species that can form a covalent bond by donating
an electron pair to another species
 1. Bronsted-Lowry Acid-Base Model

The Brønsted-Lowry model focuses on the nature of acids

and bases and the reactions that take place between them. It
considers that:
• an acid is a proton (H+ ion) donor.
• a base is a proton (H+ ion) acceptor.
• in an acid-base reaction, a proton is transferred from an acid
to a base

A Brønsted-Lowry acid-base reaction:

HB(aq) + A-(aq) ⇌ HA(aq) + B-(aq)

HB and HA = Brønsted-Lowry acid

A- and B- = Brønsted-Lowry base
 1. Bronsted-Lowry Acid-Base Model

Conjugate pairs
HB(aq) + A-(aq) ⇌ HA(aq) + B-(aq)

1. Conjugate base: the species formed when a proton is

removed from an acid
 B- is the conjugate base of HB.
Conjugate acid : the species formed when a proton is added
to a base
 HA is the conjugate acid of A-

Conjugate acid-base pairs differ only in the presence or absence

of a proton (H+). A conjugate acid has one more proton than
its conjugate base
 1. Bronsted-Lowry Acid-Base Model

2. A species that can either accept or donate a proton is

referred to as amphiprotic
Example: the H2O molecule,
- gain a proton to form the hydronium ion (H3O+) or
- lose a proton, leaving the hydroxide ion (OH-)
 1. Bronsted-Lowry Acid-Base Model

Example:
(a) What is the conjugate base of HNO2? The conjugate acid of
F-?
(b) The HCO3- ion, like the H2O molecule, is amphiprotic. What is
its conjugate base? Its conjugate acid?

Answer:
a. HNO2  H+ + NO2- (conjugate base)
F- + H+  HF (conjugate acid)
b. HCO3-  H+ + CO32- (conjugate base)
HCO3- + H+  H2CO3 (conjugate acid)
 1. The Ion Product of Water

The acidic and basic properties of aqueous solutions are

dependent on an equilibrium that involves the solvent water.

The reaction involved can be regarded as a Brønsted-Lowry

acid-base reaction in which the H2O molecule shows its
amphiprotic nature
H2O + H2O ⇌ H3O+(aq) + OH-(aq)

The reaction can be viewed as the ionization of a single H2O

molecule:
H2O ⇌ H+(aq) + OH-(aq)

In the ionization of water, the equilibrium constant expression

can be written*as the ion product of water (Kw), at 25oC:
Kw = [H+][OH-] = 1.0 x 10-14
 2. Ionisasi molekul H2O

The concentrations of H+ ([H+] = [H3O-]) ions and OH- ions in pure

water at 25oC are calculated from Kw

Kw = [H+][OH-] = [H+]2 = 1.0 x 10-14

[H+] = 1.0 x 10-7 M
[H+] = [OH-], [OH-] = 1.0 x 10-7 M

• If [H+] = [OH-] = 1.0 x 10-7  neutral solution

• If [H+] > 1.0 x 10-7 M, [OH-] < 1.0 x 10-7 M  acidic solution
• If [H+] < 1.0 x 10-7 M, [OH-] > 1.0 x 10-7 M  basic solution
 3. pH dan pOH

An acidity of a solution can be defined by a term called pH (for

“power of the hydrogen ion”):

The higher the pH, the less acidic the solution.

Most aqueous solutions have hydrogen ion concentrations
between 1 and 10-14 M and hence have a pH between 0 and 14.

• If pH < 7, solution is acidic

• If pH = 7, solution is neutral
• If pH > 7, solution is base
 3. pH dan pOH

At 25oC, [H+] [OH-] = 1.0 x 10-14:

pH + pOH = 14
3. pH dan pOH
 3. pH dan pOH

Calculate, at 25oC:
a. the [H+] and pH of a tap water sample in which [OH-] = 2.0 x 10-
7
.
b. the [H+] and [OH-] of human blood at pH 7.40.
c. the pOH of a solution in which [H+] = (5.0)[OH-].

Answer:

a. Kw = 1.0 x 10-14 = [H+][OH-] = [H+](2.0 x 10-7)

[H+] = 1.0 x 10-14 = 5.0 x 10-8 M
2.0 x 10-7

pH = -log10[H+] = -log10(5.0 x 10-8) = 7.30

 3. pH dan pOH

2. pH = -log10[H+] = 7.40
[H+] = 10-7.40 = 4.0 x 10-8 M

[H+] [OH-] = 1.0 x 10-14

(4.0 x 10-8) [OH-] = 1.0 x 10-14
[OH-] = 2.5 x 10-7 M

3. 1.0 x 10-14 = [OH-][H+]

= [OH-](5.0)[OH-]
1.0 x 10-14 = 5.0[OH-]2
[OH-]2 = 1.0 x 10-14 = 4.5 x 10-8 M
5.0
pOH = -log10[OH-] = -log10(4.5 x 10-8) = 7.35
 3. pH dan pOH

From the previous example, it is seen that the [H+] in blood

is very small, about 4.0 X 10-8 M
Small changes in [H+] can have dramatic physiological
effects
Many biological reactions depend on [H+]
An increase in [H+] from 4.0 X 10-8 to 4.0 X 10-7 can
increase the a reaction rate by a power of 10
Small increases in [H+] can lead to acidosis; small
decreases in [H+] can lead to alkalosis
Effective control of many physiological reactions depends
on pH control
 3. pH dan pOH

pH of Strong Acids and Strong Bases

• Strong acids and bases are completely ionized in water.
• Reaction of the strong acid, HCl, with water:
HCl(aq) + H 2O ⇌ H3O+(aq) + Cl-(aq)
0.1 M 0.1 M 0.1 M

Because this reaction goes to completion, a 0.10 M solution of HCl

will yield 0.10 M in both H3O+ (i.e., H+) and Cl- ions.

Strong acids: HCl HBr HI HClO4 HNO3 H2SO4*

 3. pH dan pOH

• Reaction of the strong base, NaOH, with water:

NaOH (aq) + 2H2O ⇌ Na+ + H3O+ + OH-(aq)

0.1 M 0.1 M 0.1 M

This reaction goes to completion, a 0.10 M solution of NaOH

will yield 0.10 M in both Na+ and OH- ions.

Strong bases: LiOH NaOH KOH

Ca(OH)2 Sr(OH)2 Ba(OH)2
 3. pH dan pOH

Example (p. 407):

Consider barium hydroxide, Ba(OH)2, a white, powdery
substance. Student A prepares a solution of Ba(OH)2 by
dissolving 4.23 g of Ba(OH)2 in enough water to make 455 mL of
solution.
a. What is the pH of Student A’s solution?
b. Student B was asked to prepare the same solution as Student
A. Student B’s solution had a pH of 13.51. Did Student B add
more or less Ba(OH)2 to his solution? How much more or less
Ba(OH)2 was added?
c. Student C was asked to add 0.60 g of NaOH to Student A’s
solution. What is the pH of Student C’s solution? (Assume no
volume change.)
 3. pH dan pOH

Answer :
a. Ba(OH)2  Ba2+ + 2OH-
0.0247 mol 0.0495 mol

[OH-] = 4.23/171 mol x 2 = 0.109 mol/L = 0.109 M

0.455 L
[H+] [OH-] = 1.0 x 10-14
[H+] = 1.0 x 10-14 = 1.0 x 10-14 = 9.17x 10-14
[OH-] 0.109
pH = - log10[H+] = - log (9.17x 10-14) = 13.04
 3. pH dan pOH

b. pH = - log10 [H+] = 13.51

[H+] = 10-13.51 = 3.1 x 10-14
[H+] [OH-] = 1.0 x 10-14
[OH-] = 1.0 x 10-14 = 0.32 M
3.1 x 10-14

Ba(OH)2  Ba2+ + 2OH-

Ba(OH)2 = 0.32 mol/L x ½ x 0.455 L = 0.0728 mol

= 0.0728 x 171 g = 12.45 g

Initial Ba(OH)2 = 4.23 g

Ba(OH)2 left = 12.45 g

Added Ba(OH)2 = 12.45 g - 4.23 g = 8.22 g

 3. pH dan pOH

c. Added NaOH = 0.6 g/40 = 0.015 mol

Total moles in solution
= mol OH- in Ba(OH)2 + mol OH- in NaOH
= 0.0495 + 0.015
= 0.0645 mol

[OH-] = 0.0645 mol = 0.14 M

0.455 L

[H+] = 1.0 x 10-14 = 1.0 x 10-14 = 7.14 x 10-14

[OH-] 0.14

pH = - log10(7.14 x 10-14) = 13.13

 3. pH dan pOH

Measuring pH
The pH of a solution can be measured by:
1. pH meter. A
pH meter translates the H+ ion concentration of a solution
into an electrical signal that is converted into either a
digital display or a deflection on a meter that reads pH
directly
2. Universal indicator
a mixture of acid-base indicators that shows changes in
color at different pH values. The measurement is less
accurate
3. pH paper
Has similar principle with universal indicator. Strips of this
paper are coated with a mixture of pH-sensitive dyes.
Depending on the indicators used, a test strip can measure
pH over a wide or narrow range.
 3. pH dan pOH

pH meter
Universal indicator
• Strongly acidic solution (upper left), pH < 6
• Neutral solution, pH 6-8 (yellow – green)
• Strongly basic solution, (lower right), pH>8
(deep violet)
3. pH dan pOH
3. pH dan pOH
 4. Weak Acids

Weak Acids and Their Equilibrium Constant

Weak acids ionize only partially (less than 1% of weak acid

molecules are converted into ions)

HB (aq) + H2O ⇌ H3O+ (aq) + B- (aq)

Most of weak acids are fall into 2 categories:

1. Molecules with an ionizable hydrogen atom
HNO2 (aq) + H2O ⇌ H3O+ (aq) + NO2- (aq)
2. Cations
NH4+ (aq) + H2O ⇌ H3O+ (aq) + NH3 (aq)

NH4+, behaves as a weak acid in water; the NH4+ ion has a

+1 charge; a 0.10 M solution of NH4Cl has a pH of about 5
 4. Asam lemah

Many metal cations act as weak acids in water solution:

Al(H2O)63+ (aq) + H2O ⇌ H3O+ (aq) + Al(H2O)53+(OH)2+(aq)

conjugate base

Zn(H2O)42+(aq) + H2O ⇌ H3O+ (aq) + Zn(H2O)3(OH)+ (aq)

conjugate base

The Equilibrium Constant for a Weak Acid

When a weak acid is added to water, there is proton transfer:

HB (aq) + H2O  H3O+ (aq) + B- (aq)

As a simple ionization:
HB (aq) + H2O  H+ (aq) + B- (aq)
 4. Weak Acids

 
[ H ][ B ]
Ka 
[ HB ]

Ka = acid equilibrium constant

Ka values are related to its strength

The weaker the acid, the smaller the value of Ka
e.g.: HCN (Ka = 5.8 x 10-10) is a weaker acid than HNO2
(Ka = 6.0 x 10-4).

pKa value of a weak acid

pKa = -log10Ka

HNO2 Ka = 6.0 x 10-4 pKa = 3.22

HCN Ka = 5.8 x 10-10 pKa = 9.24

 The smaller pK is, the stronger the acid

4. Weak Acids
 4. Weak Acids

Example (p. 412):

Consider acetic acid, HC2H3O2, and the hydrated zinc cation,
Zn(H2O)42+.
a. Write equations to show why these species are acidic.
b. Which is the stronger acid?
c. What is the pKa of Zn(H2O)42+?

Answer:
a. HC2H3O2 (aq) + H2O ⇌ C2H3O2- (aq) + H3O+
Zn(H2O)42+ (aq) + H2O ⇌ Zn(OH)(H2O)3+ (aq) + H3O+

b. Ka HC2H3O2 = 1.8x10-5 > Ka Zn(H2O)42+ = 3.3x10-10

HC2H3O2 is stronger than Zn(H2O)42+

-10
 4. Weak Acids

Percent ionization
HB (aq)  H+ (aq) + B- (aq)

% ionization = [H+]eq x 100%

[HB]o

[H+]eq = concentration at equilibrium

[HB]o = initial concentration

Percent ionization also depends on

the concentration of weak acid increasing
as the acid is diluted

The weaker the acid, the smaller the % ionization.

E.g.: Ibuprofen (Ka = 2.5 x 10-5), a weaker acid than aspirin, only
3.6% ionized compare with aspirin (Ka = 3.6 x 10-4) which 12%
ionized.
 4. Weak Acids

Calculation of [H+] in a Water Solution of a Weak Acid

The H+ concentration in solution is easy to calculate when the

ionization constant of a weak acid and its original concentration
are given.

Ka can be calculated by knowing [H+]; or, Ka is known and [H+]

can be calculated.

Example:
Nicotinic acid, HC6H4O2N (Ka = 1.4 x 10-5), is another name for
niacin, an important member of the vitamin B group. Determine
[H+] in a solution prepared by dissolving 3.0 g of nicotinic acid
(MM = 123.11 g/mol), HNic, in enough water to form 245 mL of
solution
 4. Weak Acids

Answer:
[HNic]o = 3 g/123.11 = 0.1 M
0.245

HNic (aq) ⇌ H+(aq) + Nic-(aq)

Ka = [H+] [Nic-] = (x)(x)

[HNic]eq (0.1-x)
(assume: %ionization <5%, 0.1 – x = 0.1)
1.4 x 10-5 = x2  x = 0.0012 M
0.1
 4. Weak Acids

In general, the value of Ka is seldom known more accurately than

+5%. Ka = x2
a-x
x = [H+]
a = original concentration of weak acid
Neglect the x in the denominator if doing so does not introduce an
error of more than 5%.

If x/a < 0.05 then a - x  a

x = [H+]eq and a = [HB]o.

Hence: x = [H+]eq
a [HB]o

x% = [H+]eq x 100%
a [HB]o
 4. Weak Acids

Example:
Calculate [H+] in 0.100 M HNO2 with Ka = 6.0 x 10-4.
Answer:
HNO2(aq) ⇌ H+(aq) + NO2-(aq)
[ ]o 0.1
Δ[ ] -x x x
[ ]eq 0.1-x x x

Ka = [H+][NO2-]
[HNO2]

6.0 x 10-4 =(x)(x) = x2  x = 0.0077 M = [H+]

(0.1-x) 0.1
% ionization = [H+]eq x 100% = 0.0077 x 100% = 7.7%
[HB]o 0.1

7.7% > 5%  the assumption that Ka < 5% is not correct,

then:
 4. Weak Acids

6.0 x 10-4 = (x)(x)

(0.1-x)

x = 0.0074 M
 4. Weak Acids

Polyprotic Weak Acids

Polyprotic acid: acid that contain more than one ionizable

hydrogen atom.

Such acids ionize in steps, with a separate equilibrium constant

for each step.
e.g.:
Oxalic acid, a weak organic acid sometimes used to remove
bloodstains, is diprotic:
H2C2O4(aq) ⇌ H+(aq) + HC2O4-(aq) Ka1 = 5.9 x 10-2
HC2O4-(aq) ⇌ H+(aq) + C2O42-(aq) Ka2 = 5.2 x 10-5

Phosphoric acid, a common ingredient of cola drinks, is triprotic:

H3PO4(aq) ⇌ H+(aq) + H2PO4-(aq) Ka1 = 7.1 x 10-3
H2PO4-(aq) ⇌ H+(aq) + HPO42-(aq) Ka2 = 6.2 x 10-8
HPO42-(aq) ⇌ H+(aq) + PO43-(aq) Ka3 = 4.5 x 10-13
 4. Weak Acids

The behavior of all polyprotic acids:

• the anion formed in one step (e.g., HC2O4-, H2PO4-) produces
another H+ ion in the next step.
• the acid equilibrium constant becomes smaller with each
successive step.
Ka1 > Ka2 > Ka3

The acids in successive steps become progressively weaker.

It is more difficult to remove a positively charged proton, H+,
from
a negatively charged species like H2PO4- than from a neutral
molecule like H3PO4
 4. Weak Acids

Example:
The distilled water you use in the laboratory is slightly acidic
because of dissolved CO2, which reacts to form carbonic acid,
H2CO3. Calculate the pH of a 0.0010 M solution of H2CO3 and [CO32-]
at equilibrium.
Answer:
H2CO3 (aq) ⇌ H+(aq) + HCO3-(aq) Ka = 4.4x10-7

4.4 x 10-7 = [H+][HCO3-] = x2

[H2CO3] 0.001-x

4.4 x 10-7 = x2
0.001

x2 = (0.001)(4.4 x 10-7)  x = 2.1x10-5 M

 4. Weak Acids

Check % ionization 

% ionization = [H+]eq x 100% = 2.1x10-5 x 100% = 2.1%

[H2CO3]o 0.0010

% ionization < 5%, the assumpiton is correct thus:

[H+] = [HCO3-] = 2.1x10-5 M  pH = 4.68

 Reference

Masterton, W.L. & Hurley, CN.

2007. Chemistry: Principles
and Reactions, 7th ed. ISBN
978–0–495–12671-3. US:
Brooks/Cole