CHAPTER – 2

ACIDS AND BASES

Outcomes covered -16,17,18,19,20

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 CHAPTER - 2
ACIDS AND BASES

Acid –base chemistry is important in a wide variety of everyday applications. There are complex
systems in our bodies that carefully control the acidity of our blood, since even small deviations
may lead to serious illness and death. Acids and bases are also important industrially .For
example a large quantity of sulphuric acid is used for the manufacture of fertilizers, polymers,
steel etc.

2.1 Properties of Acids

 taste sour , the word 'acid' comes from the Latin acere, which means 'sour'
 acids change litmus (a blue vegetable dye) from blue to red
 their aqueous (water) solutions conduct electric current (are electrolytes)
 react with bases to form salts and water
 evolve hydrogen gas (H2) upon reaction with an active metal (such as alkali metals,
alkaline earth metals, zinc, aluminum)

Properties of Bases

 taste bitter
 feel slippery or soapy (don't arbitrarily touch them!)
 bases don't change the color of litmus; they can turn red (acidified) litmus back to blue
 their aqueous (water) solutions conduct and electric current (are electrolytes)
 react with acids to form salts and water

Examples of Common Acids

 citric acid (from certain fruits and veggies, notably citrus fruits)
 ascorbic acid (vitamin C, as from certain fruits)
 vinegar (5% acetic acid)
 carbonic acid (for carbonation of soft drinks)
 lactic acid (in buttermilk)

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Examples of Common Bases

 detergents
 soap
 lye (NaOH)
 household ammonia (aqueous)

Strong vs. Weak Acids & Bases

 A Strong Acid is 100% dissociated at all concentrations up to 1M. Common strong acids
include:
o Nitric acid (HNO3)
o Hydrochloric acid (HCl)
o Sulfuric acid (H2SO4) for the first dissociation only: H2SO4 HSO4- + H+. The
second dissociation is weak, that is it hardly dissociates at 1M.
 A Weak Acid is only partly dissociated at 1M. The degree of dissociation varies widely,
from a few percent to an infinitesimal degree. Common weak acids include:
o Acetic acid (HC2H3O2 or CH3CO2H, etc.)
o Formic acid (HCO2H)
o Hydrofluoric acid (HF)
o Most acids of biological origin such as amino acids, fatty acids, metabolites,
nucleic acids etc.
 A Strong Base is 100% dissociated at all concentrations up to 1M. Common strong bases
include:
o Sodium hydroxide (NaOH)
o Potassium hydroxide (KOH)
 A Weak Base only partly reacts at 1M. The degree of dissociation varies widely, from a
few percent to an infinitesimal degree. Common weak bases include:
o Ammonia (NH3)
o Aluminum hydroxide (Al(OH)3)
o Magnesium hydroxide (Mg(OH)2)

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There are three concepts of acids and bases

2.2 Theories of Acids and Bases

Arrhenius Concept

According to Arrhenius concept, an acid is a substance that dissociates to give hydrogen ions
when dissolved in water. Thus, hydrogen chloride gas is an acid because when dissolved in
water, it gives hydrogen ions.
HCl (g) + water H+ (aq) + Cl- (aq)
The symbol aq indicates that the ions are hydrated, i.e., associated with one or more molecules of
water. Similarly, the substances such as HNO3, CH3COOH, H2SO4 etc., are acids because they
also furnish hydrogen ions when dissolved in water, as shown below.
HNO3 + water H+ (aq) + NO3- (aq)
CH3COOH + water H+ (aq) + CH3COO- (aq)
H2SO4 + water 2H+ (aq) + SO4,2- (aq)
According to Arrhenius concept, a base is a substance which dissociates into hydroxyl ions when
dissolved in water. Thus, NaOH, KOH, Ca(OH)2 etc., are bases because they furnish hydroxyl
ions in aqueous solution, as shown below.
NaOH + water Na+ (aq) + OH- (aq)
KOH + water K+ (aq) + OH- (aq)
Ca(OH)2 + water Ca2+ (aq) + 2OH- (aq)
Hydronium ion: Hydrogen ion is merely a proton. It is a unique ion in the sense that it has no
electron. It may be considered to have been derived from hydrogen atom by the loss of the
solitary electron. It is the smallest ion known and, therefore, has a strong tendency to get
hydrated. It exists largely as attached to a molecule of water forming H3O+ ion, viz., the
hydronium ion. The formation of hydronium ion is similar to the formation of ammonium ion.
H+ + H2O H3O+
H+ + NH3 NH4+

The dissociation of HCl or CH3COOH in water, therefore, is written as

HCl + H2O H3O+ + Cl-
CH3COOH + H2O H3O+ + CH3COO-

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Bronsted- Lowry Concept

Lowry and Bronsted suggested a more general definition of acids and bases which applies to
aqueous as well as to non-aqueous solutions. According to this concept, an acid is defined as a
substance which has a tendency to donate a proton to any other substance and a base as a
substance which has a tendency to accept a proton from any other substance. In other words, an
acid is a proton-donor and a base is a proton-acceptor.
When an acid loses a proton, the residual part of it has a tendency to regain the proton.
Therefore, it behaves as a base. An acid and a base may, therefore, be defined by the general
equation
Acid H+ + Base
(Proton)

The Brønsted-Lowry definition of acids: ACIDS are proton (H+) donors.

The Brønsted-Lowry definition of bases: BASES are proton (H+) acceptors.

Conjugate Acids and Bases: Consider ionization of acetic acid I in water which may be
represented as
CH3COOH + H2O H3O+ + CH3COO-
Acid Base (Solvent) Acid Base

It is evident that acetic acid donates a proton to water and thus acts as an acid. Water accepts
a proton and, therefore, acts as a base. In the reverse reaction, hydronium ion (H3O+) donates
a proton to the acetate ion and, therefore, acts as an acid. The acetate ion can accept a proton

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 and, therefore, behaves as a base.
Such pairs of substances which can be formed from one another by the gain or loss of a
proton are known as conjugate, acid-base pairs. Thus, acetic acid is the conjugate acid of
acetate ion and acetate ion is the conjugate base of acetic acid. Similarly, water is the
conjugate base of hydronium ion and hydronium ion is the conjugate acid of water.
The ionization of hydrochloric acid in water may be represented as

HCl + H2O H3O+ + Cl-

Acid Base Acid Base
(Solvent)

HCl is the conjugate acid of Cl-, and Cl- is the conjugate base of HCl.
b. H3O+ is the conjugate acid of H2O, and H2O is the conjugate base of H3O+.

3. In the reaction between NH3 and water, ammonia/ammonium ion are a conjugate acid-base
pair, and H2O/OH- are the other conjugate acid-base par.
a. NH3 is the conjugate base of NH4+, and NH4+ is the conjugate acid of NH3.
b. H2O is the conjugate acid of OH-, and OH- is the conjugate base of H3O+.

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Evidently, hydrochloric acid is the conjugate acid of chloride ion and chloride ion is the
conjugate base of hydrochloric acid.
In general, the ionization of an acid HA in water may be represented as
HA + H2O H3O+ A-
Just as an acid requires a solvent that can take up a proton (i.e., can act as a base) for its
ionization, similarly, a base requires a solvent that can give up a proton (i.e., that can act as an
acid) for its ionization. Water possesses both basic and acidic properties. Therefore, acids as well
as bases can ionize in water. Thus, water acts as an acid (a proton-donor) towards ammonia and
as a base (a proton-acceptor) towards acetic acid. Such substances are said to be Amphiprotic.
Consider ionization of ammonia in water which may be represented as
NH3 + H2O NH4+ + OH-
Basel Acid2 Acid1 Base2

Now ammonium (NH4+) ion is the conjugate acid (say Acid1) to the base NH3 (Base1) and
hydroxyl (OH-) ion is the conjugate base (Base2) to the acid H2O (Acid2). Thus, this equilibrium
also conforms to the usual pattern. Some typical cases of equilibrium between acids and bases
involving proton transfers are given in Table below.
Thus, as a general rule, the stronger an acid, the weaker must be its conjugate base and vice
versa. If an acid (e.g., HCl) is strong, its conjugate base (CI-) is weak. If a base (e.g., CH3COO-)
is strong, its conjugate acid (CH3COOH) is weak.

Water is a very weak base because its conjugate acid, hydronium ion (H3O+), is a very strong
acid. At the same time; water is a very weak acid because its conjugate base, hydroxide ion
(OH), is a very strong base.

Lewis Concept

In 1923, G.N. Lewis, in order to cover all types of neutralization reactions, gave more broad-
based definitions of acids and bases. According to Lewis concept, a base is defined as a
substance which can donate a pair of electrons whereas an acid is a substance which can accept a
pair of electrons. In other words, while a base is an electron pair-donor, an acid is an electron
pair-acceptor
A lone pair of electrons from oxygen of calcium oxide is donated to sulphur trioxide.

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Lewis definition of a base covers all substances which have unshared pairs of electrons in the
outer energy levels. These would also be classed as bases according to Lowry-Bronsted's
concept. On the other hand, Lewis acids include all substances which have vacant orbitals to
accept electron pairs. These include the following types of substances:

All cations are regarded as Lewis acids because they can accept electron pairs. While larger
cations such as Na+, K+, Ba2+, Ca2+, etc., behave as weak Lewis acids, smaller cations such as
H+, Ag+, Fe2+, etc., behave as strong Lewis acids. The smallest cation, viz., H+ ion, behaves as
the strongest Lewis acid.

H H
.. ..
+
H + : N: H H: N: H
.. ..
H H
Example:

Hydrogen chloride is a Lewis acid because it can accept a lone pair from a base such as water
though this is followed by ionization.

H2O + HCl  [ H2O:  HCl ]  H3O+ + Cl-

Example:

Many substances, such as BF3 or metal ions that are normally regarded as acids behave as Lewis
acids. This theory also includes reactions where no ions are formed and neither hydrogen ions
nor any other ions are transferred.

BF3 + NH3  [H3N:  BF3]

H+ + NH3 → [H ←:NH3]

Acid-dissociation equilibrium constant (Ka) - A measure of the relative strength of an

acid. Consider the dissociation of a weak acid HA in water,

HA+H2O↔ H3O+ + A-

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The acid-dissociation equilibrium constant is the mathematical product of the equilibrium
concentrations of the products of this reaction divided by the equilibrium concentration of the
original acid, In other words, Ka is the product of the concentrations of the products over the
concentration of the reactants (not including water):

Water is not included in the acid-dissociation equilibrium expression because the [H2O] has no
effect on the equilibrium.

As the Ka value of an acid increases, so does the strength of the acid. By definition:

 strong acid: Ka > 1

 weak acid: Ka < 1

Base-ionization equilibrium constant (Kb) - A measure of the relative strength of a

base. Consider the dissociation of a weak base in water,

B + H2O ↔ BH+ +OH-

The base-ionization equilibrium constant is the mathematical product of the equilibrium

concentrations of the products of this reaction divided by the equilibrium concentration of the
original base, In other words, Kb is the product of the concentrations of the products over the
concentration of the reactants (not including water):

Water is not included in the base-ionization equilibrium expression because the [H2O] has no
effect on the equilibrium.

As the Kb value of a base increases, so does the strength of the base.

 strong base: Kb > 1

 weak base: Kb < 1

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2.3 Ionic Product of water

The Self-Ionization of Water and the Ion Product Constant for water, Kw
a. Water can act as an acid or as a base.
b. As you can see from the reactions above, water can act as either an acid or a base,
depending on the situation. Such a substance is said to be “amphoteric” since it can
either accept or donate a proton under various conditions.
c. Pure water is not pure H2O! Can you believe it?!?! Water reacts with itself to make the
OH- ion (hydroxide ion) and the H3O+ ion (hydronium ion).

d. The concentrations of these ions in pure water at 25°C is always

[OH-] = [H3O+] = 1.00X 10-7 M
e. Also, we can write this chemical reaction as
2H2O (l)  OH- (aq) + H3O+ (aq)
Therefore, we can write the equilibrium constant (Keq) expression for this reaction as
Keq = [OH-][H3O+] = [10-7 M][10-7 M] = 10-14
Notice that we have left H2O out of the Keq expression because it is a liquid.
This equilibrium constant has a special name; it is called the ion product constant of water. It
is unit less. It is given a special symbol, too: Kw. This product will be true for any aqueous
solution – not just pure water – at 25°C, which is the only temperature which we will consider.
Acidic, basic, and neutral aqueous solutions always have an ion product constant that is
equal to 1.00 x 10-14.
The following is an important formula:
Kw = 1.00 X 10-14

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2.4 The pH Scale

pH is a measure of hydrogen ion concentration, a measure of the acidity or alkalinity of

a solution. The pH scale usually ranges from 0 to 14. Aqueous solutions at 25°C with a pH less
than 7 are acidic, while those with a pH greater than 7 are basic or alkaline. A pH level of 7.0 at
25°C is defined as "neutral" because the concentration of H3O+ equals the concentration of
OH− in pure water.

pH = -log [H+]

Remember also that the concentration of hydrogen ion in water is related to the concentration of
hydroxide ion due to the equilibrium dissociation of water:

H2O H+ + OH-, so

They are calculated using the dissociation constant or ion product for water:

Kw= [H+][OH-] = 1.0 x 10-14 at 25 °C

Example: 1
What is the pH of a solution of 0.015 M HCl?
Strong acid, so [H+] = 0.015 M
pH = - log [H+]
pH = - log 0.015 = - (- 1.824)
pH = 1.82

Example: 2

Find the pH of a 0.0025 M HCl solution. The HCl is a strong acid and is 100% ionized in
water. The hydronium ion concentration is 0.0025 M. Thus:

pH = - log (0.0025) = - ( - 2.60) = 2.60

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Calculating the Hydronium Ion Concentration from pH

The hydronium ion concentration can be found from the pH by the reverse of the mathematical
operation employed to find the pH.

[H3O+] = 10-pH or [H3O+] = antilog (- pH)

Example: 3

What is the hydronium ion concentration in a solution that has a pH of 8.34?

8.34 = - log [H3O+]

- 8.34 = log [H3O+]
[H3O ] = 10-8.34 = 4.57 x 10-9 M
+

On a calculator, calculate 10-8.34, or "inverse" log ( - 8.34).

Calculating pOH

To calculate the pOH of a solution you need to know the concentration of the hydroxide ion in
moles per liter (molarity). The pOH is then calculated using the expression:

pOH = - log [OH-]

Example: 4

What is the pOH of a solution that has a hydroxide ion concentration of 4.82 x 10-5 M?

pOH = - log [4.82 x 10-5] = - ( - 4.32) = 4.32

Calculating the Hydroxide Ion Concentration from pOH

The hydroxide ion concentration can be found from the pOH by the reverse mathematical
operation employed to find the pOH.

[OH-] = 10-pOH or [OH-] = antilog ( - pOH)

Example: 5

What is the hydroxide ion concentration in a solution that has a pOH of 5.70?

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 5.70 = - log [OH-]
-5.70 = log[OH-]
[OH-] = 10-5.70 = 2.00 x 10-6 M

On a calculator calculate 10-5.70, or "inverse" log (- 5.70).

Relationship Between pH and pOH

The pH and pOH of a water solution at 25oC are related by the following equation.

pH + pOH = 14

If either the pH or the pOH of a solution is known, the other can be quickly calculated.

Example: 6

A solution has a pOH of 11.76. What is the pH of this solution?

pH = 14 - pOH = 14 - 11.76 = 2.24

Calculating pKa

The pKa is calculated using the expression:

pKa = - log (Ka)

where "Ka" is the equilibrium constant for the ionization of the acid.

Example:7

What is the pKa of acetic acid, if Ka for acetic acid is 1.78 x 10-5?

pKa = - log (1.78 x 10-5) = - ( - 4.75) = 4.75

Example: 8

What is the pH of a solution of 0.067 M NaOH?

Strong base, so [OH-] = 0.067 M

Recall that [H+][OH-] = 1.0 x 10-14
Substituting, [H+][0.067] = 1.0 x 10-14

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 Rearranging, [H+] = (1.0 x 10-14) / 0.067 = 1.493 x 10-13
pH = - log (1.493 x 10-13) = - (- 12.83)
pH = 12.83

2.5 Acid-Base Titration and Hydrolysis

When a weak acid is titrated with a strong base it is found that the equivalence point always
occurs at a pH above neutrality (pH > 7), as seen in the figure for acetic acid titrated with
hydroxide ion:

Similarly, when a weak base is titrated with a strong acid the equivalence point always occurs at
a pH below neutrality (pH < 7).

2.6 Buffer Solutions

These are the solutions that resist pH change on adding small amount of acid or base.
There are two types of buffers.
1) Acid buffer - Weak acid with a salt of the same acid with a strong base.
e.g. CH3COOH and CH3COONa
2) Basic buffer - Weak base and its salt with a strong acid.
e.g. NH4Cl and NH4OH

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Buffers contain a significant amount of both a weak acid and its conjugate base (or weak base
and its conjugate acid).While a weak acid will partially ionize to produce its conjugate base, it
will not produce enough conjugate base to be considered a buffer. (The same problem occurs for
a weak base and its conjugate acid).In order to prepare a buffer solution, BOTH a weak acid and
its conjugate base must be added to solution or, a weak base and its conjugate acid.

Consider what would happen if a strong base was added to the previous example:
NaOH(aq) + CH3COOH(aq)  H2O(l) + CH3COONa(aq)
As long as the amount of NaOH added was small compared to the amount of HC 2H3O2 in
solution, the NaOH would be neutralized, and the pH change would be small.
Consider what would happen if a strong acid was added to the previous example:
HCl(aq) + CH3COONa(aq)  NaCl(aq) + CH3COOH(aq)
As long as the amount of HCl added was small compared to the amount of CH3COONa in
solution, the HCl would be neutralized, and the pH change would be small.

General characteristics of buffers:

1. Buffers resist pH changes.
2. Buffers contain significant amounts of both a conjugate acid and its weak base.
3. The weak acid neutralizes added base.
4. The conjugate base neutralizes added acid.

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Calculation of the pH of buffer solution

This calculation can be done by using Henderson-Hasselbalch Equation

pH = pKa + log ([salt]/[acid])

The equation can be rewritten to solve for pOH:

pOH = pKb + log ([salt]/[ base ])

pH of a buffer solution can be calculated using this equation

Example: 9
Applying the Henderson-Hasselbalch Equation
Calculate the pH of a buffer solution made from 0.20 M HC2H3O2 and 0.50 M C2H3O2 Na that
has an acid dissociation constant for HC2H3O2 of 1.8 x 10-5.
pH = pKa + log ([salt]/[acid])
pH = pKa + log ([C2H3O2Na] / [HC2H3O2])
pH = -log (1.8 x 10-5) + log (0.50 M / 0.20 M)
pH = -log (1.8 x 10-5) + log (2.5)
pH = 4.7 + 0.40
pH = 5.1

2.7 Stoichiometry
The quantitative relationship among reactants and products is called stoichiometry. The term
stoichiometry is derived from two Greek words: stoicheion (meaning "element") and metron
(meaning "measure"). On this subject, you often are required to calculate quantities of reactants
or products. Stoichiometry calculations are based on the fact that atoms are conserved. They
cannot be destroyed or created. Numbers and kinds of atoms before and after the reactions are
always the same. This is the basic law of nature.
Let us consider the combustion of methane. A balanced equation is given below
CH4+ 2 O2  CO2 + 2 H2O

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The coefficients 2 for O2 and H2O are called stoiometric coefficients. Similarly the coefficients
of CH4 and CO2 are one in each case. They represent the number of molecules (moles as well)
taking part in the reaction.

Example: 10

Calculate the amount of water produced by the combustion of 16g of methane.

Balanced equation
CH4+ 2 O2  CO2 + 2 H2O
16g of methane corresponds to one mole.
From the equation 1 mole of CH4 gives 2 moles of H2O
2 moles of H2O= 2x (2+16) = 36g

1.8 References:

1. Essentials of Physical Chemistry –Arun Bahl,B .S.Bahl,G.D.Tuli

2. http://www.chemistrylecturenotes.com/html/buffers.html
3. http://www.chemguide.co.uk/acids

Long Answer Type Questions:

1. Calculate the pH of a 0.54 M solution of NH4Cl. Kb = 1.8 x 10-5
2. Calculate the pH of a buffer solution that is 0.100 M in HC2H3O2 and 0.100 M in NaC2H3O2.
(Ka = 1.8 x 10-5)
3. Calculate the pH of a buffer made up by dissolving 0.0125 moles acetic acid (HOAc) and
0.0250 moles of sodium acetate (NaOAc) in enough water to make 1.000 L of solution. Ka =
1.8x 10-5
4. State and explain Bronsted- Lowry theory and Lewis theory of acids and bases.
5. How many grams of oxygen are required to burn completely 84.9 g of carbon?
C(s) + O2 (g) → CO2 (g)
6. In the decomposition of potassium chlorate, 82.6 g of oxygen are formed. How many grams
of potassium chloride are produced?

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Short Answer Type questions:
1. What is a buffer solution? Give an example.
2. Define pH.of a solution.What is its range for acidic, basic and neutral solutions?
3. Write the equation for the auto ionization of NH3.
4. Write the formulas for the conjugate bases of the following acids.
(a) HCN (b) HCO3- (c) N2H5+ (d) C2H5OH
5. Write the formulae for the conjugate acids of the following bases.
(a) HC2H3O2 (b) HCO3- ( c) C5H5N (d) N2H5+
6. Which one of the following reaction is Lewis acid-base reaction?
(a) NH3 + BF3  H3N:BF3 (b) Ca + S  Ca2+ + S2-
7. In the reaction of BeF2 with 2F- to form BeF42-, which reactant is the Lewis acid and which is
the Lewis base?
8. Which is the strongest acid of the following?
(a) NH3 (b) HClO (c) HClO2 (d) HClO3
9. Calculate the pH of a 0.01 M NH3 solution.
10. What is the H3O+ concentration of a solution of 0.600 N HC2H3O2?
11. What is the OH- concentration of a 0.20 M solution of NH3? ( Kb = 1.8 x 10-5)
Multiple choice questions:-
1. For the following reaction, which of the following is a conjugate acid-base pair?
HC2O4-(aq) + H2O(l) → H3O+(aq) + C2O42–(aq)
–
a. HC2O4 and H2O c. H2O and C2O42–
b. HC2O4– and H3O+ d. HC2O4– and C2O42–

2. In the following reaction, which is a Brønsted-Lowry base?

HC2O4–(aq) + H2O(l)→ H3O+(aq) + C2O42–(aq)
–
a. HC2O4 b. H2O c. H3O+ d. None of these
3. A Brønsted-Lowry base is defined as a substance that
a) acts as a proton donor. b) increases [H+] when placed in water.
c) acts as a proton acceptor. d) decreases [H+] when placed in water.

4. For the following reaction, which of the following is a conjugate acid-base pair?
H2PO4- (aq) + NH3 (aq) HPO42- (aq) + NH4+ (aq)
a) H2PO4- and NH3 b) HPO42- and NH4+
- 2-
c) H2PO4 and HPO4 d) None of the above

5. What is the pH of an aqueous solution at 25.0oC in which [OH–] is 0.00250 M.

a) +2.60 b) –2.60 c) +11.4 d) –11.4 e) –2.25

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6. A substance that is capable of acting as both an acid and as a base is _____.
a) amphiprotic b) conjugated c) autosomal d) binary acid-base

7. Strong acids:
a) Ionize completely and produce many hydrogen ions in solution
b) Ionize slightly and produce few hydrogen ions in solution
c) Ionize slightly and produce few hydroxide ions in solution
d) Ionize completely and produce many hydroxide ions in solution

8. What does the strength of an acid depend upon?

a). concentration of the acid b) time it takes the acid to neutralize a base
c) extent to which the acid ionizes d) volume of the acid

9. Which acts as an amphoteric species in aqueous solution?

a)HCO3- b)HNO3 c)PO43-- d)SO42-

10. A pH meter used to test a freshly opened carbonated soft drink gives a reading of 3.14. What
is the [H+]?
a.)7.2 x 10-2 mol/L b). 3.1 x 10-3 mol/L c). 7.2 x 10-4 mol/L d). 3.1 x 10-5 mol/L

Answer Key for Multiple Choice Questions:

1.d,2.b,3.c,.4.c,5.c,6.a,7.a,8.c,9.c,10.c

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