CRITICAL BOOK REPORT

ACID–BASE EQUILIBRA

THE LECTURER

ELFRIDA GINTING, S.Si.,M.Sc

ARRANGED BY

FIRDA NUR HIDAYAH

419131005

CHEMICAL EDUCATION A 19

FACULTY OF MATH AND SCIENCE

MEDAN STATE UNIVERSITY

2019
BOOK IDENTITY

1. Book Title : Chemistry

2. Publisher : Palgrave Macmilan
3. Author : Rob Lewis and Wynne Evans
4. Publisher Year : 2006
5. Print : Third Edition
6. Thick Pagen : 479 Couloms
7. No. ISBN : 978-0-230-00011-7
 ABSTRACK OF UNIT 16

I.1 Ionic equilibria in water

A. Ionization of water

Pure water is a very poor conductor of electricity. This shows that there are
virtually no ions present. However, there are some, and these play a very important role
in the equilibria of aqueous solutions.

At room temperature about one water molecule in every 1 000 000 000 is
ionized:

H2O(l) H2O(l) \===\ H3O(aq) OH (aq)

In this reaction, a proton is being transferred from one water molecule to

another. The equilibrium expression for this reaction is:

Kc(T)

[H3O(aq)][OH (aq)]

[H2O(l)]2

But [H2O(l)], the concentration of a pure liquid, is constant. This gives

Kw(T) [H3O(aq)][OH (aq)].

where Kw(T), which equals Kc(T)[H2O(l)]2, is known as the ionic product constant (or
autoionization constant) of water.

Table 1 shows the values of Kw at various temperatures.

Table 1 The ionic product constant of water at various temperatures

Temperature/°C 1014 Kw/mol2dm6

000 00.114
010 00.293
020 00.681
025 01.008
030 01.471
040 02.916
050 05.476
100 51.3
From Table 1, at 25°C
 Kw
1.0 10 14 mol2dm 6

When the concentration of hydroxide and hydronium ions in water or in aqueous

solutions are multiplied together, the product is always 1.0 10 14 mol2dm 6 at 25°C.

Definitions of neutral, acidic and basic solutions

Neutral solution

A neutral solution is one where the concentrations of hydroxide and hydronium

ions are equal. At 25°C, the pH of a neutral solution is 7.

Acidic solution

An acidic solution is one where the concentration of hydronium ions is greater

than the concentration of hydroxide ions. At 25°C, the pH of an acidic solution is less
than 7.

Basic solution

A basic (or alkaline) solution is one where the concentration of hydroxide ions is greater
than the concentration of hydronium ions. At 25°C, the pH of a basic solution is greater
than 7.

Calculations using the ionic product constant of water

The ionic product constant of water (Kw) may be used to calculate the
hydroxide ion concentration in solutions of acids. It may also be used to calculate the
hydronium ion concentration in solutions of bases.

pH, pOH and pKw

log Kw = log [H3O_(aq)] + log [OH_(aq)]

Multiplying throughout by 1 gives

-log Kw=log [H3O_(aq)] -log [OH_(aq)]

We know that pH log [H3O(aq)]. We similarly define pOH and pKw as

 pOHlog[OH (aq)] and pKwlogKw

from which we see that

pKw pH pOH

This expression is just another form of equation (16.2), and also applies to all aqueous
solutions. At 25°C, pKw–log (1.0 10–14 14, so that

pH+ pOH= 14

Acids and bases in aqueous solution

Strong acids

Hydrochloric acid is made by dissolving hydrogen chloride gas in water. The dissolved
HCl (symbolized HCl(aq)) then reacts with water as follows:

HCl(aq) H2O(l) H3O(aq) Cl (aq)

A strong acid is completely ionized in solution

This means that if 0.1 mol of HCl(g) is dissolved in water and made up to 1dm3, the
concentration of both H3Oand Cl ions is also 0.1 moldm3. There are only a few strong
acids. Apart from HCl(aq), the list includes:

 perchloric acid (HClO4(aq)), and cheerfully referred to as the ‘strongest known

acid’ in TV quizzes;
 nitric acid (HNO3(aq)), whose ancient name, aqua fortis, means ‘strong water’;
 hydrobromic acid (HBr(aq)) and hydriodic acid (HI(aq)).

Weak acids
Ethanoic acid is only partially ionized in aqueous solution:
CH3COOH(aq) _ H2O(l) \===\ CH3COO_(aq) _ H3O_(aq)
and is therefore termed a weak acid:
a weak acid is incompletely ionized in solution
equilibrium expression becomes
Ka(T) =[CH3COO_(aq)][H3O_(aq)]
________________________
[CH3COOH(aq)]

Hydrogen
fluoride:
HF(aq) _ H2O(l) \===\ F_(aq) _ H3O_(aq)
hydrogen
fluoride hydrofluoric acid
is also a weak acid with Ka(25°C) =3.510_4 moldm_3.

Symbolizing the
acids as AH, the acidity constants are the equilibrium constants for the general reaction
AH(aq) +H2O(l) \===\ A(aq) +H3O(aq)

The higher the Ka value, the stronger the acid.

The acidity constants of strong acids are difficult to determine experimentally
because the concentration of unionized molecules is minute, but there is no doubt that
the acidity constants of strong acids are much higher than those of the weaker acids
listed in Table 16.2. This reflects the fact that the acid molecules are almost entirely
dissociated in solution. We may also define pKa, where
pKa= -log Ka

The stronger the acid, the lower is its pKa.

In equation (16.4), the acid is donating a hydrogen ion (a proton) to a water
molecule to produce a H3O_(aq) ion. This means that we can look at a Ka value as an
indicator of the proton-donating power of that acid molecule toward the water molecule:
The greater the Ka value, the greater the proton donor ability of the acid
towards water.
The species A_(aq) in equation (16.4) is referred to as the conjugate base of the acid
AH(aq). This is because the A_(aq) ion acts like a base in that it accepts a proton from
H3O_(aq) in the reverse of reaction (16.4). For example, the conjugate base of ethanoic
acid is the ethanoate ion CH3COO_(aq).

Calculating the pH of solutions of weak acids

We shall use ethanoic acid as an example of a weak acid which contains one
acidic hydrogen atom. We will symbolize the initial concentration of ethanoic acid in a
solution as CA moldm_3.
The H3O_(aq) concentration of a very weak acid with one acidic hydrogen can be
estimated by re-arranging the following equation:
Ka(T) =[H3O_(aq)]2
___________
CA
The equation is a good approximation provided the percentage of acid molecules that
are ionized,
percentage of acid molecules ionized =[H3O_(aq)]
_________ 100
CA
does not exceed about 5%.
Sulfuric acid – a diprotic acid
Sulfuric acid possesses two acidic hydrogens and is said to be diprotic. There are
two ionization steps, with sulfuric acid itself being the acid in the first step, and the
hydrogensulfate ion being the acid in the second step:
First ionization:
H2SO4(aq) __H2O(l) \===\ H3O_(aq) _+HSO4(aq) Ka(298 K) =large

Second ionization
HSO4 _(aq) +H2O(l) \===\ H3O_(aq) + SO4 2_(aq) Ka(298 K) =0.012 moldm_3

The net reaction is the sum of both steps:

H2SO4(l) +2H2O(l) \===\ 2H3O_(aq) + SO4 2_(aq)

Strong and weak bases

The commonest strong bases are the water-soluble hydroxides of sodium,
potassium, calcium, barium and lithium. These are all ionic solids. Since they are strong
basesn they are completely ionized in water. For example, NaOH(s) breaks up
completely in water producing Na_(aq) and OH_(aq):
H2O Na_,OH_(s) —_ Na_(aq) +OH_(aq)

A second category of bases are those which produce hydroxide ions in solution
by reaction with water. An example is ammonia:
NH3(aq) + H2O(l) \===\ NH4_(aq) + OH_(aq)
Ammonia is a weak base because it is incompletely ionized in solution, and
Kb(T) = [NH4_(aq)][OH_(aq)]
________________
[NH3(g)]
where Kb(T) is the basicity constant (or dissociation constant) of ammonia at
temperature T. Generalizing, the basicity constant for a base B is the equilibrium
constant for the reaction:
B(aq) _ H2O(l) \===\ BH_(aq) _ OH_(aq)
Any solution which contains the hydroxide ion (such as NaOH(aq) or NH3(aq)) will
neutralize acids in the reaction:
H3O_(aq) _ OH_(aq) _ 2H2O(l)
Selected Kb values are included in Table 16.2, with triethylamine being the strongest
base listed because it has the biggest Kb value. By coincidence, Kb for ammonia (one of
the commonest weak bases) is numerically equal to Ka for ethanoic acid at 25 _C.
Books often tabulate pKb values where
pKb=logKb
The self-ionization of water,
H2O(l) _ H2O(l) \===\ H3O_(aq) _ OH_(aq)
involves one molecule of water donating a proton to another. This makes water both
a proton donor and a proton acceptor.
When calculating the pH of a weak base, we follow the same pattern as for an acid,
Kb(T) =[OH_(aq)]2/CB

Hydrolysis of salts
pH of solutions of salts
A salt is produced when a base and acid neutralize each other. On this basis, four
classes of salts are possible:
1. a salt of a strong acid and a strong base (SA–SB);
2. a salt of a weak acid and a strong base (WA–SB);
3. a salt of a strong acid and a weak base (SA–WB);
4. a salt of a weak acid and a weak base (WA–WB).
Sodium chloride solution (made with pure water), is neutral with a pH of 7 at 25
°C. This may lead us to suppose that solutions of all ionic salts are neutral. In fact, only
solutions of salts made from strong acids and strong bases are always neutral. Solutions
of other salts are usually either acidic or basic. The reasons for this behaviour are that:
1. These salts react with the water producing a weak acid or a weak base.
2. Since the weak acid or weak base is only partially ionized in water, formation of
these molecules ties up hydroxide or hydronium ions.
3. This produces unequal concentrations of hydronium and hydroxide ions, and
the resulting solution of salt is then acidic or basic.

Hydrolysis of a salt of a weak acid and a strong base

Using sodium ethanoate (CH3COO_,Na_) as an example, the ions present in an
aqueous solution of this salt are
H2O CH3COO_,Na_(s) —_ CH3COO_(aq) _ Na_(aq) (from the salt)
2H2O(l) \===\ H3O_(aq) _ OH_(aq) (from the water)
The potential products of any reaction between the ions in solution are NaOH
(from the reaction of Na_(aq) and OH_(aq)) and CH3COOH (from the reaction of
CH3COO_(aq) and H3O_(aq)). The NaOH is fully ionized in solution, but the ethanoic
acid is only partially ionized. This means that [OH_(aq)] _ [H3O_(aq)] and the solution
is basic.

Buffer solutions
Adding small amounts of acids or alkalis may lead to drastic changes in solution pH
The addition of even one drop of dilute hydrochloric acid to water drastically
changes its pH (Box 16.2). Such changes in pH can be troublesome in the laboratory,
and catastrophic in living cells. Changes in pH due to trace contamination with acids or
bases can be prevented using a buffer solution (usually simply called a ‘buffer”.

How buffers work

Buffers either consist of a weak base and one of its salts, or a weak acid and one of its
salts. As an example, we look at a mixture containing ethanoic acid and sodium
ethanoate. The ions present in such a mixture are shown by the following equations:
CH3COO_,Na_(s) —_ CH3COO_(aq) _ Na_(aq)
CH3COOH(aq) _ H2O(l) \===\ CH3COO_(aq) _ H3O_(aq)
 The salt (since it is an ionic compound) is fully ionized, and generates a
relatively high concentration of ethanoate ions.
Now consider the ionization of ethanoic acid in the presence of
sodiumethanoate. The expression for the acidity constant of ethanoic acid is:
Ka(T) =[CH3COO_(aq)][H3O_(aq)]
_______________________
[CH3COOH(aq)]
How does the buffer mixture resist changes in pH? The explanation is as follows.
 Suppose we add some hydrochloric acid to the mixture. The equilibrium
composition shifts, with ethanoate and hydronium ions combining together in
the reverse of equation. This mops up the added H3O(aq) ions, and there is no
change in pH. (The same conclusion is arrived at using Le Chatelier’s principle.)
 If we add hydroxide ions (e.g. by adding sodium hydroxide solution), the tiny
amount of [H3O(aq)] at equilibrium in the buffer mixture reacts with OH (aq) in
the neutralisation reaction

Calculating the pH of a buffer solution

We can easily obtain an expression with which to estimate the pH of a buffer,
starting with equation. Since virtually all the ethanoate ions in the buffer come from the
sodium ethanoate, we are justified in substituting Cs for [CH3COO (aq)]. Since so little
ethanoic acid is ionized in the buffer, we are also justified in taking the equilibrium
concentration of ethanoic acid, [CH3COOH(aq)], to be equal to the initial concentration
of acid, CA.

Data for the sodium ethanoate–ethanoic acid buffer

Let us use equation (16.11) to calculate the pH of an ethanoate–ethanoic acid
buffer at 25°C made by mixing 25cm3 of 0.100 moldm3 sodium ethanoate solution with
25cm3 of 0.100 moldm3 ethanoic acid solution. Since the volume doubles, the
concentrations are halved and CA Cs 0.050 moldm3. Ka for ethanoic acid at 25°C
1.8105 moldm3.

Buffer capacity
The amount of acid or alkali that needs to be added before the pH of a buffer
changes is called the buffer capacity of the buffer. The buffer capacity of a buffer
containing a relatively high number of moles of acid and salt is greater than the capacity
of a buffer with a lower number of moles of acid and salt. As we have already noted, the
buffer capacity of the buffer in Fig. 16.2 is equivalently to roughly 3cm3 of 0.1 moldm3
HCl or 3cm3 of 0.1 moldm3 NaOH.

Acid–base indicators
Acid–base indicators, such as methyl orange, phenolphthalein and litmus, show
two extreme colours, one at lower pH and the other at higher pH.
Indicators are sometimes absorbed into paper strips (e.g. litmus paper). The
indicator known as ‘universal indicator’ is a mixture of selected indicators which
displays different colours at different pH values. (To demonstrate this, place a large
crystal of tartaric acid in a small flask. Add dilute universal indicator solution and one
drop of NaOH solution. Upon gently swirling the flask, the acid slowly dissolves, and
the indicator passes through an impressive sequence of colours.)

Buffering action of carbon dioxide in water

Carbon dioxide in water
Carbon dioxide is fairly soluble in water, and a small amount of the dissolved CO2
reacts with water as follows:
CO2(aq) 2H2O(l) \===\ HCO3 (aq) H3O(aq)
Buffers in the body
The CO2–water equilibrium is also the main buffer present in blood. Excess
H3O(aq) in blood, due to the presence of lactic acid produced by the metabolism of
food, is removed by the reaction of the back reaction of equation (16.12). In this way,
the pH of blood is maintained at 7.4. Variations in arterial blood pH of more than about
0.4 can be fatal.
The hydrogencarbonate buffer in blood would soon become exhausted if there
was not a way for the body to get rid of waste. Excess carbon dioxide and excess acid
are removed by the lungs and kidneys, respectively. In this way, the hydrogencarbonate
ions in the blood are released to act as a buffer once again.