CHE 101, Chemistry

Ishmam Ibnul Arabi

Lecturer
Department of Textile Engineering
Green University of Bangladesh
 Chapter 5

Acid-Base Theories &

the Concept of PH
 Acids and Bases

There are three concepts of acids and bases in current use. Each has its
own peculiar advantages. They are:
(a) Arrhenius concept
(b) Bronsted-Lowry concept
(c) Lewis concept
 Arrhenius Concept
Svante Arrhenius (1884) proposed his concept of acids and bases. According to this
concept, an acid is a compound that releases H+ ions in water; and a base is a
compound that releases OH– ions in water.
For example, HCl is an Arrhenius acid and NaOH is an
Arrhenius base.
HCl(aq) ⎯⎯→ H+ (aq ) + Cl– (aq)

NaOH(aq) OH– (aq) + Na+ (aq)

 Limitations of Arrhenius Concept

Arrhenius concept of acids and bases proved to be very useful in the study of chemical
reactions. However, it has the following limitations :
(1) Free H+ and OH– ions do not exist in water. The H+ and OH– ions produced by acids
and bases respectively do not exist in water in the free state. They are associated with water
molecules to form complex ions through hydrogen bonding. Thus the H+ ion forms a
hydronium ion :

Similarly, OH– ion forms the complex H3O−2 .

(2) Limited to water only. Arrhenius defined acids and bases as compounds producing
H+ and OH– ions in water only. But a truly general concept of acids and bases should be
appropriate to other solvents as well.
(3) Some bases do not contain OH–. Arrhenius base is one that produces OH– ions in
water. Yet there are compounds like ammonia (NH3) and calcium oxide (CaO) that are
bases but contain no OH– ions in their original formulation. Arrhenius models of acids
and bases, no doubt, proved very helpful in interpreting their action. However on
account of its limitations the Arrhenius concept needed to be modified.
 BRONSTED–LOWRY CONCEPT

In 1923 J.N. Bronsted and T.M. Lowry independently proposed a broader concept
of acids and bases. According to this theory, an acid is any molecule or ion that
can donate a proton (H+)and a base is any molecule or ion that can accept a
proton
For brevity we can say that an acid is a proton donor while a base is a proton
acceptor.
An acid qualifying Bronsted-Lowry concept is termed a Bronsted-Lowry acid or
simply Bronsted acid.
A base qualifying Bronsted-Lowry concept is termed a Bronsted-Lowry base or
simply Bronsted
base.
Examples of Bronsted acids and bases

(1) HCl gas and H2O. When dry HCl gas dissolves in water, each HCl molecule
donates a proton to a water molecule to produce hydronium ion.

Thus HCl gas is a Bronsted acid and water that accepts a proton is a Bronsted base.
(2) HCl and Ammonia,NH3. HCl gas reacts with ammonia (NH3) to form solid NH4Cl

HCl is a proton donor and hence a Bronsted acid, while NH3 is a proton
acceptor and a Bronsted base.
 Bronsted-Lowry concept is superior to Arrhenius concept

(1) M uch wider scope. Arrhenius concept of acids and bases is restricted to the study of
substances which can release H+ or OH– ions in water. Bronsted-Lowry concept embraces
all molecules and ions that can donate a proton (acids) and those which can accept a proton
(bases).
(2) Not limited to aqueous solutions. The Bronsted-Lowry model is not limited to aqueous
solutions as is the case with Arrhenius model. It can be extended even to the gas phase. For
example, gaseous ammonia (a Bronsted base) can react with hydrogen chloride gas (a
Bronsted acid) to give ammonium chloride.

Here a proton is donated by HCl to NH3 as shown above. Note that this is not considered as an acid-base reaction according to
Arrhenius concept.
(3) Release of OH– not necessary to qualify as a base. Arrhenius base is a substance
that releases OH– ions in water. On the other hand, Bronsted base is a substance that
accepts a proton. Thus liquid ammonia (NH3) does not produce OH– ions in water but it is
a recognized base. But according to Bronsted-Lowry model, it qualifies as a base since it
can accept a proton to form NH4+ (an acid).
In an acid-base reaction the acid (HA) gives up its proton (H+) and produces a new base (A–).
The new base that is related to the original acid is called a conjugate (meaning related) base.
Similarly the original base (B–) after accepting a proton (H+) gives a new acid (HB) which is
called a conjugate acid. A hypothetical reaction between the acid HA and the base B– will
illustrate the above definitions

The acid (HA)and the conjugate base (A–)that are related to each other by donatingand acceptinga single proton,
are said to constitute a conjugate Acid-Base pair.
Examples of Conjugate Acid-base pairs

A weak acid (CH COOH)

produces a strong conjugate
base (CH3COO-); and a
weaker base
(H2O) gives a stronger
conjugate acid (H3O+ ).
 Classes of Bronsted acids and bases

There are a variety of Bronsted acids :

(1) M onoprotic acids which are capable of donating one proton only e.g.,
HF ⎯⎯→ H+ + F−
CH3COOH ⎯⎯→ H + + CH3COO –
(2) Polyprotic acids which are capable of donating two or more protons e.g., H2SO4, H3PO4, carbonic acid
(H2CO3), hydrosulphuric acid, etc.
H2S ⎯⎯→ 2H+ + S2-
Similarly, there are Bronsted bases

(1) M onoprotic bases which can accept one proton

(2) Polyprotic bases which can accept two or more protons e.g., anions of
diprotic and triprotic acids.
 Amphiprotic substances
Molecules or ions that can behave both as Bronsted acid and base are called amphiprotic
substances. For example, with HCl, water acts as a base in accepting a proton from the
acid.
 LEWIS CONCEPT OF ACIDS AND BASES

In the early 1930s, G.N. Lewis proposed even a more general model of acids and bases.
According to Lewis theory,
an acid is an electron-pair acceptor
a base is an electron-pair donor
Lewis pictured an acid and base as sharing the electron pair provided by the base. This
creates a covalent bond (or coordinate bond) between the Lewis acid and the Lewis base.
The resulting combination is called a Complex. If the Lewis acid be denoted by A and the
Lewis base by B, then the fundamental equation of the Lewis theory can be written as :

It may be noted that : (1) all cations or molecules short of an electron-pair act as Lewis acids; and (2) all anions or molecules
having a lone electron-pair act as Lewis bases.
 Examples of Lewis reactions

(1) Between H+ and NH3. Proton (H+) is a Lewis acid as it can accept an electron-pair.
Ammonia molecule (: NH3) has an electron-pair which it can donate and is a Lewis base.
Thus the Lewis reaction between H+ and NH3 can be written as:

(2) Between H+ and OH–. A proton (H+) is an electron-pair acceptor and, therefore, a Lewis
acid. The OH– is an electron-pair donor and hence a Lewis base. Thus Lewis reaction
between H+ and OH– can be written as:
(3) Between BF3 and NH3. BF3 has six valence electrons with B atom which can
accept an electron-pair and is a Lewis acid. The N atom of :NH3 has a lone electron-
pair and is a Lewis base. Lewis reaction between BF3 and NH3 may be written as:
 Water can act both as an acid and a base
Water is an amphoteric substance. It can behave either as an acid or a base. One molecule of
water transfers a proton to another molecule. There results a hydronium ion (H3O+) and a
hydroxyl ion (OH–).
Auto-ionisation of water.
The above reaction in which water
molecules interact to produce a
hydronium ion and a OH– ion is
called auto-ionisation of water. It
may be written as
 RELATIVE STRENGTH OF ACIDS

The strength of an acid depends on its ability to transfer its proton (H+) to a base to form its
conjugate base. When a monoprotic acid (HA) dissolves in water, it transfers its proton to
water (a Bronsted base) to form hydronium ion (H3O+) and a conjugate base.

The value of acid dissociation

constant is large for a strong
acid while it is small for a weak
acid.

Ka is called the acid dissociation constant

 Relative strength of Weak acids from Ka

For an acid in aqueous solution we have, HA   H+ + A–

Let C moles per liter be the concentration of the acid and α its degree of dissociation. Then,

Substituting the values in the equilibrium expression we have

This expression relates to the
degree of dissociation of
electrolytes with dilution. This is
called Ostwald’s dilution law.
 Ostwald Dilution Law
Ostwald’s dilution law states that “The degree of dissociation of a weak electrolyte is inversely
proportional to the square root of molar concentration or directly proportional to the square root
of volume holding one mole of the solute for a weak electrolyte.”

SOLVED PROBLEM 1. The dissociation constants of formic acid and acetic acid are 21.4 ×
10– 5 and 1.81 × 10– 5 respectively. Find the relative strengths of the acids.
SOLVED PROBLEM 2. Two hypothetical acids HA and HB have the dissociation constants
1 × 10– 3 and 1 × 10– 5 respectively in water at 25°C. Calculate the strength of HA with respect
to HB
 THE pH OF SOLUTIONS
Hydrogen ion concentrations are typically quite small numbers. Therefore, chemists report the hydrogen ion concentration
of a solution in terms of pH . It is defined as the negative of the base-10 logarithm (log)of the H+ concentration.
Mathematically it may be expressed as
pH = – log[H+]
where [H+] is the concentration of hydrogen ions in moles per liter.
Alternative and more useful forms of pH definition are :
pH = log1/
[H ]+
and [H+]= 10– pH

The pH concept is very convenient for expressing hydrogen ion concentration. It was introduced by Sorensen in 1909. It is now
used as a general way of expressing other quantities also, for example,
(a) Concentration of OH– ions in aqueous solution of a base is expressed as
p [OH–]= – log[OH–]
 (b) Equilibrium constant for water is written as
pKw = – log[Kw]
For any quantity X, we can write
pX = – logX
The “p” in these expression means “– logof the quantity”

pH Scale
In order to express the hydrogen ion concentration or acidity of a solution, a pH scale was evolved. The pH is defined as
pH = – log[H+]or [H+]= 10– pH
The hydrogen ion concentration of different acidic solutions was determined experimentally.
These were converted to pH values using the above relations. Then these pH values were computed on a scale taking water
as the reference substance. The scale on which pH values are computed is called the pH scale.
Water dissociates to H+ and OH– ions to a very small degree so that we have the equilibrium.
H2O   H+ + OH– ...(1)
 We can write the equilibrium expression as

Since water is so little dissociated, the concentration of undissociated molecules, [H2O], is presumed to be
constant. Therefore from expression (2) we can write
[H+][OH–]= K [H2O]= Kw = a constant. ...(3)

where Kw is called the water dissociation constant or the water ionization constant

The value of Kw found experimentally is 1.0 × 10– 14.

From the equation (1) it is obvious that one molecule of water dissociates to give one H+ ion and one OH– ion. This
means that the concentration of H+ and OH– ions in pure water is equal. Using the expression (3), we have
Relation between pH and pOH
 Problems
1. The hydrogen ion concentration of a fruit juice is 3.3 × 10– 2 M. What is the pH of the juice? Is it acidic or
basic?
2. If a solution has a pH of 7.41, determine its H+ concentration.
3. If a solution has a pH of 5.50 at 25°C, calculate its [OH–].
3. Calculate the pH of 0.001 M HCl.
4. The pH of a solution of HCl is 2. Find out the amount of acid present in a liter of the solution.
5. Determine the pH of 0.10 M NaOH solution.
6. Calculate the pH of a 0.020 M Ba(OH)2 solution.
7. Calculate the pH of 0.1 M CH3COOH. The dissociation constant of acetic acid is 1.8 × 10– 5.
8. Find out the pH of a 0.002 M acetic acid solution if it is 2.3% ionized at this dilution.
 BUFFER SOLUTIONS

A buffer is a solution that can resist pH change upon the addition of an acidic or basic components. It is
able to neutralize small amounts of added acid or base, thus maintaining the pH of the solution relatively
stable. This is important for processes and/or reactions which require specific and stable pH ranges. Buffer
solutions have a working pH range and capacity which dictate how much acid/base can be neutralized
before pH changes, and the amount by which it will change.

To effectively maintain a pH range, a buffer must consist of a weak conjugate acid-base pair, meaning
either a. a weak acid and its conjugate base, or b. a weak base and its conjugate acid. The use of one or the
other will simply depend upon the desired pH when preparing the buffer. For example, the following could
function as buffers when together in solution:

•Acetic acid (weak organic acid w/ formula CH3COOH) and a salt containing its conjugate base, the acetate
anion (CH3COO-), such as sodium acetate (CH3COONa).

•Ammonia (weak base w/ formula NH3) and a salt containing its conjugate acid, the ammonium cation,
such as Ammonium Hydroxide (NH4OH)
 HOW A BUFFER OPERATES ?

The pH of the buffer is governed by the equilibrium

CH3COOH   CH3COO– + H+
(1) Addition of HCl. Upon the addition of HCl, the increase of H+ ions is counteracted by association with the
excess of acetate ions to form unionized CH3COOH. Thus the added H+ ions are neutralized and the pH of the
buffer solution remains virtually unchanged. However owing to the increased concentration of CH3COOH, the
equilibrium (1) shifts slightly to the right to increase H+ ions. This explains the marginal increase of pH of the
buffer solution on addition of HCl (Fig.)
(2) Addition of NaOH. When NaOH is added to the buffer solution, the additional OH– ions combine with H+ ions of
the buffer to form water molecules. As a result the equilibrium (1) shifts to the right to produce more and more H+ ions
till practically all the excess OH– ions are neutralized and the original buffer pH restored. However, a new equilibrium
system is set up in which [CH3COOH] is lower than it was in the original buffer. Consequently [H+] is also slightly less
and pH slightly higher than the buffer pH values (Fig)
Operation of a Basic buffer as NH4OH/NH4Cl can also be explained on the same lines as of an acid buffer (Fig.) upon
addition of HCl the H+ ions combine with OH– ions of the buffer to form water molecules. The equilibrium,
NH4OH  NH4+ + OH −
is shifted to the right till all the additional H+ ions are neutralized and the original buffer pH restored. When NaOH is
added to the buffer solution, OH– ions associate with excess of NH4+ ions to form unassociated NH4OH. Thus the pH of
the buffer is maintained approximately constant.
 Henderson-Hasselbalch equation

The pH of an acid buffer can be calculated from the dissociation constant, Ka, of the weak acid and the concentrations of
the acid and the salt used. The dissociation expression of the weak acid, HA, may be represented as

The weak acid is only slightly dissociated and its dissociation is further depressed by the addition of the salt (Na+A–)
which provides A– ions (Common ion effect). As a result the equilibrium concentration of the unionized acid is nearly
equal to the initial concentration of the acid. The equilibrium concentration [A–] is presumed to be equal to the initial
concentration of the salt added since it is completely dissociated. Thus we can write the equation (1) as
where [acid] is the initial concentration of the added acid and [salt] that of the salt used. Taking negative
logs of both sides of the equation (2), we have

This relationship is called the Henderson-Hasselbalch equation or simply Henderson equation.

In a similar way,the Henderson-Hasselbalch equation for a basic buffer can be derived. This can be stated as :
 Problems
1. Find the pH of a buffer solution containing 0.20 mole per liter CH3COONa and 0.15 mole per liter CH3COOH. Ka
for acetic acid is 1.8 × 10– 5.
2. Estimate the pH at 25°C containing 0.10 M sodium acetate and 0.03 M acetic acid pKa for CH3COOH = 4.57.
3. Calculate the pH of a buffer solution that is 0.250 M in formic acid, HCOOH, and 0.100 M in sodium formate,
HCOONa. Ka for formic acid is 1.8 × 10– 4.
4. The Ka of propionic acid is 1.34 × 10– 5. What is the pH of a solution containing 0.5 M propionic acid, C2H5COOH,
and 0.5 M sodium propionate, C2H5COONa. What happens to the pH of this solution when volume is doubled by the
addition of water?
5. A buffer solution contains 0.25 M NH3 and 0.40 M NH4Cl. Calculate the pH of the solution. Kb for ammonia = 1.8
× 10– 5.