DEPARTMENT OF CHEMISTRY

MODULE: GENERAL CHEMISTRY 1

MODULE CODE: CHM
101 LECTURE TOPIC:

ELEMENTARY CONCEPTS OF ACIDITY AND BASICITY

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Introduction: Overview of Acids and Bases
Classically there are three major definitions of substances known as acids or bases.
These three lead to three classifications with different scopes.

1. The Arrhenius Theory of Acids and Bases (Svante Arrhenius, 1883)

(a) An acid is a substance that produces a hydrogen ion (H+) in solution while a base
is a substance that produces a hydroxide ion OH- in solution.
-Arrhenius definition is based on the fact that when dissolved in an aqueous solution,
certain ions were released into the solution.
-The Arrhenius theory is the simplest and narrowest description of acids and bases.

(i) An Arrhenius acid is a substance that increases the concentration of hydrogen ions
(H+) that are present when added to water.

HCl (aq)→ H+(aq) + Cl−(aq)

In this reaction, hydrochloric acid (ionized hydrogen chloride) (HCl) dissociates

completely into hydrogen (H+) and chlorine (Cl-) ions when dissolved in water, thereby
releasing H+ ions into solution.
Free hydrogen ions do not exist in water. They are hydrated by water molecules to form
the hydronium ion
(H3O+):

HCl (aq) + H2O (l) → H3O+(aq) + Cl−(aq)

Writing “H+ (aq)”, although formally correct does not convey enough information. The
formula H3O+ is much more adequate.

HBr(g) + H2O (l) → H3O+(aq) + Br−(aq).

Examples of Arrhenius acids include, HCl, HClO4 and HBr.

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(ii) An Arrhenius base is a compound that increases the concentration of hydroxide (OH-)
ions that are present
when added to water :

NaOH (aq) → Na+(aq) + OH−(aq).

In this reaction, sodium hydroxide (NaOH) disassociates into sodium ions (Na+) and
hydroxide (OH-) ions when dissolved in water, thereby releasing OH- ions into solution.

Examples of Arrhenius bases include NaOH, KOH, Mg(OH)2.

Achievement of Arrhenius Theory:

(i) It successfully describes neutralization (how acids and bases react with each other to
make water and salts).
(ii) It was able to explain salt hydrolysis.
(iii) It also explains strengths of acids and bases.

Limitations of the Arrhenius Theory

(i) It suggests that acids and bases must contain H+ and OH- ions respectively to be able to
release them. But these ions cannot exist the way they are but instead exist as hydrated
ions in solution.

(ii) It could not explain the acid character of substances which do not produce H+ ions
(eg CO2, SO2, SO3 ) and basic character bases that do not produce OH- ions ( eg CaO,
Na2CO3 ).

CaO(s) + H2O (l)---- > Ca2+(aq) + 2OH-(aq)

(iii) it does not explain why ammonia (NH3) which but does not contain OH- itself but in
the presence of water, releases hydroxide ions into solution and so is a base.
Hydrochloric acid is neutralized by ammonia solution (as with sodium hydroxide
solution) and in both cases, you get a salt, ammonium chloride,(just as sodium chloride).

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NaOH (aq) + HCl(aq) → NaCl(aq) +

H2O(l)NH3(aq) + HCl(aq) →

NH4Cl(aq)

You can explain this by saying that, when the ammonia reacts with the water, it is
dissolved in to produce ammonium ions and hydroxide ions:

NH3(aq) + H2O(l) ⇌ NH +(aq) + OH−(aq)

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(iv) It does not explain the reaction between an acid and a base in the absence of water.

Ammonia gas and hydrogen chloride gas form the same salt as with ammonia solution
and hydrochloric acid
even when, there are no hydrogen ions or hydroxide ions in solution - because there
isn't any solution.

NH3(g) + HCl(g) → NH4Cl(s)

Similarly: CaO(s) + SO2(g) CaSO4(s)

2. The Brønsted-Lowry Definition (Johannes Nicolaus Brønsted and Thomas Martin

Lowry,1923)

b. Acids are proton donors whereas bases are proton acceptors.

- This definition is based on the compounds' abilities to either donate or accept protons
(H+ ions).

-A substance no longer needed to be composed of hydrogen (H+) or hydroxide (OH-) ions

to be classified as an acid or base.
(i) A Brønsted-Lowry acid is a proton (hydrogen ion) donor.

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(ii) A Brønsted-Lowry base is a proton (hydrogen ion) acceptor.

-A compound that acts as both a Brønsted-Lowry acid and base together is said to be
amphoteric.

Illustration: Consider the chemical equation: HCl(aq) + NH3(aq) →4 NH +(aq) +

Cl−(aq)

Here, hydrochloric acid (HCl) "donates" a proton (H+) to ammonia (NH3) which
"accepts" it, forming a positively charged ammonium4 ion (NH +) and a negatively
charged chloride ion (Cl-).
Thus, HCl is a Brønsted-Lowry acid (donates a proton) while the ammonia is a Brønsted-
Lowry base (accepts a proton).
- A Brønsted acid dissociates by donating protons to water to increases the concentration
of hydrogen ions in the solution while a Brønsted bases dissociate by taking a proton
from water to generate hydroxide ions.

Eg Na+F-, generates OH ions in water by taking protons from water itself (to make
HF):

F−(aq) + H2O(l) ⇌ HF(aq) + OH-

Conjugate Acids, Conjugate Bases and Conjugate Pairs

Every Bronsted –Lowry acid (HA) has a conjugate base

(A−).Every Bronsted–Lowry base B has a conjugate acid
HB+.
The acid and its conjugate base or the base and its conjugate acid form a conjugate pair.

Acid + Base ⇌ Conjugate base + Conjugate acid. HA + B ⇌ A− + HB+

eg1. HCl(aq) + NH3(aq) → Cl−(aq) + NH

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+
(aq)

HCl is acid. NH3 is base. Cl- above is called the conjugate base of the acid, HCl while
NH4+ is called the conjugate acid of the base NH3. [The conjugate acid is what the
acid
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becomes after losing a proton while the conjugate base is what the base becomes after
accepting a proton].HCl and Cl- are a conjugate pair. NH3 and NH4 + are a conjugate pair.
eg2

[Determine the conjugate acid and the conjugate base of the following: F−(aq) + H2O(l)
⇌ HF(aq) + OH-]

Strong and Weak Acids and Bases

Acids and bases that ionize or dissociate completely into H+ ions and the anion A- are
said to be strong in aqueous solution;
−
e.g.: HClO4 (aq) → H+ (aq) + ClO4 .
Here the right-handed arrow (→) implies that the reaction goes to completion. That is, a
1.0 M solution of HClO4 in water actually contains 1.0 M H+(aq) and 1.0 M ClO 4-(aq),
and no undissociated HClO4.
[EXAMPLES OF STRONG ACIDS: HCl, HNO3, H2SO4, HBr, HI, HClO4]
[EXAMPLES OF STRONG BASES: The hydroxides of the Group I and Group II
metals such as LiOH, NaOH, KOH, RbOH, CsOH]

Weak acids and bases are ionize or dissociate partially in aqueous solution producing
few ions. Weak acids such as acetic acid (CH3COOH) and weak bases such as ammonia
(NH3) dissociate only slightly in water - typically a few percent, depending on their
concentration and exist mostly as the undissociated molecules.

[EXAMPLES OF WEAK ACIDS: All other acids, such as HCN, HF, H2S,

HCOOH] [EXAMPLES OF WEAK BASES: All other bases, such as NH3,

CH3NH2, C5H5N] NOTE:

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(1) Both strong acids/ bases and weak acids/bases can be concentrated or dilute
depending on the amount of water in its solution. Strength of acids/ bases is about the
degree of dissociation.

(2) The strength of a conjugate acid/base varies inversely with the strength of its parent
base/acid.
A strong acid will produce a weak conjugate base while a weak acid will have a strong
conjugate base.

Strong acids such as HCl dissociate to produce spectator ions (very weak conjugate
bases) such as Cl-, whereas for a weak acid such as acetic acid its conjugate base, the
acetate anion is a strong base.

CH3COOH + H2O ⇌ CH3COO− + H3O+

ACID DISSOCIATION AND DISSOCIATION CONSTANT (Ka)

Acid Dissociation: HA(aq) ⇌A−(aq) + H+(aq).

Equilibrium Constant Kc =[A−][H+]/[HA]=Ka
Ka is acid dissociation Constant (Note: square brackets,[ ], mean concentration).
−
Eg. HClO4 (aq)- → H+ (aq) + ClO
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Ka= [H+][Cl0 ]/[HCl0 ]
4 4
Note: Strong acid have high Ka values because they dissociate almost completely. The
stronger the acid the larger its Ka.
Weak acid have low Ka values since they produce few ions on dissociation.

Base Dissociation and Dissociation Constant (Kb)

Base dissociation: B(aq) + H2O(l) ⇌ HB+(aq) + OH
−
(aq) Equilibrium constant Kc =[HB+][OH−]/[B][H20]
But [H20] is practically constant per dm-3

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Thus Kc [H20] = [HB+][OH−]/[B] = Kb = Base Ionization Constant: Kb
Strong bases have high Kb since they produce plenty ions from complete dissociation.
Weak bases have low Kb since they produce few ions from partial dissociation.

Ionic Product of Water (Kw)

Being a weak acid water dissociates partially:
H2O(l) ⇌ H+(aq) + OH−(aq)
Equilibrium constant Kc is given
byKc = [H+][OH−]/[H20]
But [H20] is practically constant per
dm3 Thus [H2O]Kc = [H+][OH−] =Kw

Kw= [H+][OH−] = 1.00 x 10-14 mol2 dm-6 at 25°C is called the ionic product of
water. It can be easily shown that Ka x Kb = Kw. (thus: Kb = Kw/Ka,
Ka=Kw/Kb)
For strong acids and bases: Ka=Kb=1.00x10-7 at 25oC

The pH Scale
pH is a measure of hydrogen ion concentration, [H+], in an aqueous solution which is a
measure of strength of acidity and basicity. pH is determined by the formula:
pH = -log [H+] ie pH is the -log of hydrogen ion concentration,[H+]. A smaller pH
means a larger [H+].
The pH scale is often measured on a 1 to 14 range. A low pH value indicates acidity, a
pH=7 is exactly neutral, and a high pH value indicates alkalinity.
pH Scale of Common Substances

NOTES

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1. The higher the [H+], the lower the pH. Strong acids have low pH, strong bases have
high pH.

2. As with pH, pOH = - log [OH-] . At 25 degrees Celsius: pH + pOH =14

3. We may have pKa(=-logKa) and pKb (=-log Kb). They have inverse relationships
with Ka/Kb. Strong acids have low pKa. Strong bases have low pKb and high pKa.
4. When determining pH of a strong acid, [H+] is the same as the original concentration
of the acid since strong acids are fully dissociated.
5. For strong bases, [OH] is the concentration of the base, [H+] is determined from this
and ionic product of water.
5. When determining the pH of a weak acid or weak base, [H+] is first determined from
the pKa using the formula:

where [HA] =concentration of acid

Examples:
1. Determine the pH of an aqueous solution from the stomach of H+ concentration of 1x
10-2 mol dm-3.
pH = - log [H+] = - log 1x 10-2 mol dm-3 = 2

2. Determine the pH of 0.05mol dm-3 of NaOH

NaOH (aq) -------------------> Na+(aq) + OH-
(aq)

NaOH is a strong base thus [NaOH] = [Na+] = [OH-] =0.05mol

dm-3 Kw = [H+][OH-] = 1x10-14 mol2 dm-6
[H+] = Kw/[OH-] = 1x10-14/0.05 = 2 x 10-13 mol dm-3
Thus pH= -log [H+] = - log 2 x 10-13 =12.7

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Achievements of the Bronsted and Lowry Theory
(i) It did not limit acidity and basicity to molecules alone but includes ionic species.
(ii) It explained the basic character of substances like NH3 and Na2CO3 on the bases of
acceptance of proton.
(iii) It explained acid-base reactions in non-aqueous solutions or even in complete
absence of solvents.

Limitations of Bronsted and Lowry Theory

(i) It could not explain the reaction of acidic oxides (CO2, SO2, SO3) and basic
oxides (CaO, MgO, BaO) that occur in the absence of a solvent.
(ii) It could not account for the acidity of Lewis acids like that BF3, AlCl3 that cannot
give a proton.

3. Lewis Theory of Acids and Bases (G. N. Lewis, 1923)

Acids act as electron pair acceptors and bases act as electron pair donors.
-This definition doesn't mention anything about the hydrogen atom at all, unlike the
other definitions.

In the reaction between ammonia (NH3) and boron trifluoride (BF3):

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In this reaction, there is no transfer of hydrogen, but NH3 has a lone pair of electrons and
BF3 has an incomplete octet,(only has 6 electrons around boron), it can hold 2 more to
form an octet. BF3 is the Lewis acid, an
electron pair acceptor while NH3 the electron pair donor is the Lewis base. Lewis
structure of H3N-BF3 resulted from the coordinate covalent bond between nitrogen and
boron.
This is considered an acid-base reaction where NH3 (base) is donating the pair of
electrons to BF3. BF3 (acid) is accepting those electrons to form a new compound,
H3NBF3.
-Lewis bases include substances that have full negative charges (F-, OH-, CN-) and those
that have lone pairs (NH3, CH3NH2, ROH, H2O). They are sources of electron pairs.
- Lewis acids include electron deficient molecules (AlCl3, BF3 FeCl3), cations ( Ag+,Cu2+,
Fe 3+),molecules having central atoms with empty d orbitals (SiF4, PCl5, SnCl4) etc . They
can accept electron pairs.

Achievements of Lewis Theory

(i) It is more general; explains acidity and basicity of substances that other concept could
not explain.

Limitations of the Lewis Theory

(i) It could not explain the strength of acids and bases.
(ii) It is so general that it considers all reactions forming dative bond as acid –base but
this may not always be so.
(iii) Well known strong acids like HCl and H2SO4 do not form coordinate bond.
(iv) Acid –base reactions are usually very fast but formation of coordinate bonds by
Lewis concept is slow.

Acid –Base Reaction (Neutralization)

In an acid-base (or neutralization) reaction, the essential reaction is that H+ ions from the
acid and the OH- ions from the base react to create water (H2O). The other ions are
spectator ions. They form an ionic compound called a salt.
HCl(aq) + NaOH(aq) > NaCl(aq) + H2O(l)

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ie H+(aq) Cl- (aq) + Na+(aq) OH-(aq) -------> Na+(aq) Cl-(aq) + H2O(l)
Na+ and Cl- are spectator ions (did not participate in the reaction and remained
unchanged)
The essential reaction is:
H+(aq) + OH –(aq) ------ > H2O(l)
Thus an acid-base reaction is the production of water molecules from the hydrogen ions of
the acid and hydroxide ions of the base.

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