Acids and Bases

 Arhenius concept
 Bronsted-Lowry concept
 Autoionization of water
 The pH scale
 Ionization constant of
acids and bases
 Problem solving using Ka
and Kb
 Lewis acids and bases
 Background and History
 Aqueous solution (Environment/living organisms) – almost acidic or basic
 Photosynthesis & Respiration – biological process on earth
 CO2 – acid producing compound in Nature
 Acid rain (Dissolved CO2) – acidification by SO2 & NO2
 Oceans, ground and surface water – slightly basic
 Natural water – acidic (more acidic, metals like lead can be easily be dissolved

 1677-Antoine Lavoisier – proposed Oxygen made an acid, acidic – Greek word

meaning Acid Former
 1808-discovered, gaseous HCl dissolve in water give HCl, which do not contain Oxygen
 Later – Hydrogen common to all acids in solutions
 Aqueous soln. Acids/Bases conduct electrical current-Electrolytes (release Ions)
General properties
ACIDS BASES
• Taste sour • Taste bitter
• Turn litmus • Turn litmus
• React with active metals – Fe, • Feel soapy or slippery
Zn (react with fats to make
soap)
• React with acids

• React with bases

blue to red red to blue

Definitions
• Acids – produce H+
Arrehenius
• Bases - produce OH-
only in water

Bronsted-Lowry • Acids – donate H+

• Bases – accept H+
any solvent

Lewis • Acids – accept e- pair

used in organic chemistry, • Bases – donate e- pair
wider range of substances
Limitations of Arhenius concept

• An acid is expected to be an acid in any solvent. But

that’s not the case nowadays. For example HCL acts
as an Arrhenius acid when dissolved in water.
However when HCl is dissolved in benzene there is
no dissociation. This is against Arrhenius theory;
Arrhenius states that dissociation occurs in any
aqueous solution. The properties of acid and bases
play a critical role.
• In Arrhenius theory all salts should produce solutions that
are neither acidic nor basic. But there are some exceptions
against this theory. For example if equal amounts of HCl
and ammonia react, the solution is slightly acidic. If equal
amounts of acetic acid and sodium hydroxide react, the
resulting solution is basic. Arrhenius theory does not
include any explanation for this

• It offered no satisfactory explanation for the acid

property of various substances such as AlCl3,
NH4NO3, etc.
Limitations of Lowry bransted concepts
• This theory works for all protic solvents (acetic
acid, water, liquid ammonia, etc.), not only for
water as Arrhenius’ theory. But it does not explain
the acid-base behavior in aprotic solvents such as
benzene and dioxane.
Bronsted-Lowry Concept
Test yourself
Water role as Acid and Base

Test yourself
Bronsted-Lowry concept is superior to Arrhenius concept

(1) Much wider scope.

• Arrhenius concept of acids and bases is restricted to the study of
substances which can release H+ or OH– ions in water.
(2) Not limited to aqueous solutions.
• The Bronsted-Lowry model is not limited to aqueous solutions as is
the case with Arrhenius model.
Conjugate acid-base pairs.

• In every acid-base reaction involving H+ transfer,

there are two acid-base conjugate pairs.
• A weak acid produces a strong conjugate base and a
weaker base gives a stronger conjugate acid.
Test yourself
 The hydrogen ion in aqueous solution
H+ + H2O  H3O+ (hydronium ion)

Examples

Arrhenius HCl NaOH

Bronsted-Lowry HCl HCN NH3

Lewis BF3 :NH3

Does pure water conduct electrical current?
Water is a very, very, very weak electrolyte.

H2O  H+ + OH-
How are (H+) and (OH-) related?

(H+)(OH-) = 10-14

For pure water: (H+) = (OH-) = 10-7M

This is neutrality and at 25oC is

a pH = 7.

water
 Let’s examine the behavior of an acid, HA, in
aqueous solution.

HA

What happens to the HA molecules in solution?

 100% dissociation of HA

HA

H+
Strong Acid
A-
Would the
solution be
conductive?
 Partial dissociation of HA

HA

H+
Weak Acid
A-
Would the
solution be
conductive?
 HA  H+ + A-

HA

H+
Weak Acid
A- At any one time,
only a fraction of
the molecules are
dissociated.
Strong and Weak Acids/Bases
Strong acids/bases – 100% dissociation into ions

HCl NaOH
HNO3 KOH
H2SO4
Weak acids/bases – partial dissociation,
both ions and molecules

CH3COOH NH3
Acids and Bases
 Relative Strengths of Acids and Bases
 Strong acids are better H+ ions donors than weak acids similarly,
strong bases are better H+ ion acceptors than weak bases.
 So, stronger acids have weaker conjugate bases and weaker acids
have stronger conjugate bases.
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)

HF(aq) + H2O(l) H3O+(aq) + F-(aq)

 In a dilute solution (<1.0 M) the ionization of HCl is virtually 100%;
all HCl molecules react with water to form H3O+ and Cl-. The Cl-
ion has no tendency to accept H+ from H3O+. While, the reverse of
ionization of HF is significant; F- ion readily accepts H+ from H3O+
 As acid strength decreases, conjugate base
strength increases, the weaker the acid, the
stronger its conjugate base.
 As base strength decreases, conjugate acid
strength increases, the weaker the base, the
stronger its conjugate acid.

o Knowing the relative acid & base strength

of the reactants, we can predict the direction
of an acid-base reaction.
 The stronger acid & stronger base will
always react to form a weaker conjugate
base and a weaker conjugate acid.
Strong Bronsted-Lowry Weak Bronsted-Lowry Bases
Bases

Hydride ion (H-) Cyanide (CN-)

Sulfide ion (S2-) Fluoride (F-)
Oxide ion (O2-) Acetate (CH3COO-)
Amide ion (NH2-)
Hydroxide ion (OH-)
H-(aq) + H2O(l) H2(g) + OH-(aq)

CaH2(aq) + H2O(l) H2(g) + Ca(OH)2(aq)

 Acid-Base reaction favour going from stronger

to weaker member of each conjugate acid-base pair

 From table, it shows that bisulfate(HSO4-) stronger is acid than

bicarbonate(HCO3-) and carbonate(CO32- is stronger base sulfate(SO42-).
So, the reaction will proceed in forward direction.
 The Autoionization of Water
 Pure water conducts a very small electrical current, which indicates
that water contains a very small concentration of ions. These ions are
formed when water molecules react to produce H3O+ ions and OH-.
This process is called Autoionization.

 At equilibrium reaction, an equilibrium expression can be written as:

 Kw is know as ionization constant for water.
 Electrical conductivity of pure water is:
[H3O+) = [OH-] = 1.0 x 10-7 at 25 °C.

o So,
Kw = [H3O+][OH-] = (1.0 x 10-7)(1.0 x 10-7)
= 1.0 x 10-14 (at 25 °C)

 The equation Kw = [H3O+][OH-] applies to

pure water and all aqueous solutions.
 Points to remember
 Kw(product of H3O+ ion times OH- ion) concentration will always be
same at given temperature.
 If H3O+ ion concentration increases due to addition of an acid, then
OH- ion concentration will decrease and vice versa.
 If we know one concentration, we can calculate the other.
 The relative concentrations of H3O+ and OH- also indicate the acidic,
neutral or basic nature of the aqueous solution.
There are three(3) possibilities for all aqueous solutions.

Neutral solution: [H3O+] = [OH-] both equal to 1.0 x 10-7 at 25 °C

Acidic solution: [H3O+] > 1.0 x 10-7 M [OH-] < 1.0 x 10-7 M
Basic solution: [H3O+] < 1.0 x 10-7 M [OH-] > 1.0 x 10-7 M
Hydronium and Hydroxide Concentrations
Calculate:
(a) The hydroxide ion concentration at 25 C in 0.10 M HCl, a strong acid
(b) The hydronium ion concentration at 25 C in 0.010 M KOH, a strong base
o Based on calculation, explain why 0.10 M HCl solution is acidic and
0.010 M KOH solution is basic

So, the 0.10 M HCl soln is acidic because its hydronium concentration is
Greater than its hydroxide conctration; [H 3O+] > [OH-]. The 0.010 M KOH
Soln is basic because [OH-] > [H3O+].

Explanation: we know the relation that [H3O+] [OH-] = 1.0 x 10-14

(a) As strong acid (HCl) ionizes 100%, so the [H3O+] is 1.0 x 10-1
The [OH-] can readily be calculated…
[H3O+][OH-] = 1.0 x 10-14 = (1.0 x 10-1 M) [OH-]

(b) The strong base KOH is completely ionized and the [OH -] is 1.0 x 10-2 M.
The hydronium concentration can be calculated directly:

Problem solving:
 Problem solving:
 [H3O+] and [OH-] concentrations
Calculate the hydroxide ion concentration at 25 C in 6.0 M HNO 3 and the
Hydronium ion concentration in 6.0 M NaOH.
 Explanation: assume that nitric acid and sodium hydroxide are strong
electrolytes, i.e. 100% ionized. Therefore, a 6.0 M nitric acid solution has
[H3O+] = 6.0 M and its [OH-] can be calculated as:

 For NaOH:
 NaOH is strong base, so 6.0 M sodium hydroxide has [OH-] = 6.0 M

 Practice problem
 The pH Scale
 [H3O+] and [OH-] concentrations vary in solution depends on acid and
base present in solution.
 Generally, [H3O+] in aqueous soln. can range from 10 mol/L to 10 -15 mol/L
and the [OH-] can also vary in same range.
 As the concentrations can be so small i.e. with very large negative exponents.
 For convenience, we express the concentration in terms of logarithms.

 So, pH of as solution is the negative of the base 10 logarithm (log) of the

hydronium ion concentration (mol/L)
pH = - log[H3O+]
The negative logarithm of small concentration values is used as it gives a
Positive pH value. The pH of pure water at 25 C is given by
pH = -log[1.0 x 10-7] = -[log(1.0) + log(10-7)
= -[0 + (-7.00)] = 7.00
 Fig. shows the pH values along with corresponding
H3O+ and OH- concentration of some common
solutions, e.g. –log(1 x 10-x) = x

 One pH unit represents a ten-fold change in H3O+

concentration, a change of two pH units represents
100-fold as so on.
In above example, [H3O+] in lemon juice (pH=2) is 1000
Times greater than in black coffee(pH=5)
  For solutions in which [H3O+] or [OH-] has value other than an exact
power of 10 (1, 1x10-1, 1x10-2,…) a calculator is convenient for
finding the pH.
e.g. the pH is 2.35 for a solution that contains 0.0045 mol of the strong
acid HNO3 per litre. 0.0045 = 4.5 x 10-3

pH = -log(4.5 x 10-3) = 2.35

 Problem solving:
calculating pH from [H3O+]

Calculate the pH of an aqueous HNO3 solution that has a volume of 250.

mL and contains 0.4649 g HNO3
 Strategy: first calculate the moles of HNO3 , then [H3O+] from Molarity
equation