Acids & Bases

Md. Kaium Hossain

Assistant Professor
Department of Chemistry, BUET.
Reference Book
• Inorganic Chemistry by Gary L. Miessler and Donald A. Tarr
• Modern Inorganic Chemistry R.D. MADAN

2
Acid-Base Concepts:

• Antoine Lavoisier was one of the first chemists to try to explain what makes a
substance acidic. In 1776 he proposed that oxygen was an essential element in
acids. (Oxygen, which he named, means “acid-former” in Greek.)

• But in 1808 Humphry Davy showed that hydrogen chloride, which dissolves in
water to give hydrochloric acid, contains only hydrogen and chlorine.

• By the early 19th century, many acids that do not contain oxygen were known.
By 1838, Liebig defined acids as "compounds containing hydrogen, in which the
hydrogen can be replaced by a metal,"

• Chemists then noted that hydrogen, not oxygen, must be the essential
constituent of acids. The cause of acidity and basicity was first explained in 1894
by Svante Arrhenius.
 Arrhenius Concept of Acids and Bases

An acid is a substance that, when dissolved in water,

increases the concentration of hydronium ion, H O+ (aq). 3

For simplicity, chemists frequently use the notation H+(aq) for the
H3O+(aq) ion, and call it the hydrogen ion. of water molecules. One
such species is shown in Figure
The hydronium ion, H3O+ A base is a substance that, when dissolved in water, increases the
concentration of hydroxide ion, OH
-(aq).
The species is shown here
hydrogen bonded to three
water molecules.
The positive charge shown is
actually distributed over the
ion.
 Arrhenius Concept of Acids and Bases
The special role of the hydronium ion (or hydrogen ion) and the hydroxide ion in
aqueous solutions arises from the following reaction:

The addition of acids and bases alters the concentrations of these ions in water.
In Arrhenius’s theory , a strong acid is a substance that completely ionizes in aqueous
solution to give H3O+(aq) and an anion. An example is perchloric acid, HClO4.

Other examples of strong acids are

Strong base completely ionizes in aqueous
solution to give OH− and a cation.
Sodium hydroxide is an example of a strong
base.
Evidence for the Arrhenius theory comes from the heat of reaction, ∆H°, for the
neutralization of a strong acid by a strong base. This neutralization is essentially the
reaction of H3O+ (aq) with OH- (aq) and should therefore always give the same ∆H° per mole
of water formed.

For example, if you write the neutralization of HClO4 with NaOH in ionic form, you have

Experimentally, it is found that all neutralizations involving strong acids and bases
have the same ∆H°: -55.90 kJ per mole of H+. This indicates that the same
reaction occurs in each neutralization, as Arrhenius’s theory predicts.
Limitations:
• HCl is regarded as an acid only when dissolved in H2O and not in some other
solvent such as C6H6 or when it exists in the gaseous state.
• It cannot account for the acidic and basic character of the materials in non-
aqueous solvents e. g. NH4NO3 in liquid NH3 acts as an acid though it does not
give H+ ions. Similarly many organic materials and NH3 which do not have OH-
ions at all are actually known to show basic character.
• Neutralization process is limited to occur in aqueous solutions only, although
reactions involving salt formation do occur in many other solvents and even in
the absence of solvents.
• It can not explain the acidic character of certain salts such as AlCl3 in aqueous
solution.
 Brønsted-Lowry Concept of Acids and Bases
In 1923 the Danish chemist Johannes N. Brønsted (1879–1947) and, independently, the
British chemist Thomas M. Lowry (1874–1936) pointed out that acid–base reactions can
be seen as proton-transfer reactions and that acids and bases can be defined in terms of this
proton H+ transfer. According to the Brønsted–Lowry concept,

An acid is the species donating a proton in a proton-transfer reaction. A base is the species
accepting the proton in a proton-transfer reaction
Consider, for example, the reaction of hydrochloric acid with ammonia.

After canceling Cl-, you obtain the net ionic equation.

In any reversible acid–base reaction, both forward and reverse reactions involve proton
transfers. Consider the reaction of NH 3 with H2O.

• Note that NH3 and NH4+ differ by a proton.

• That is, NH3 becomes the NH4+ ion by gaining a proton, whereas the NH4+ ion
becomes the NH3 molecule by losing a proton.
• The species NH4+ and NH3 are a conjugate acid–base pair. A conjugate acid–
base pair consists of two species in an acid–base reaction, one acid and one base, that
differ by the loss or gain of a proton.
• The acid in such a pair is called the conjugate acid of the base, whereas the base is the
conjugate base of the acid. Here NH4+ is the conjugate acid of NH3, and NH3 is the
conjugate base of NH4+
In the following equations, label each species as an acid or a base. Show the conjugate
acid–base pairs.
An amphiprotic species
A species that can act as either an acid or a base (it can lose or gain a proton),
depending on the other reactant. For example, HCO3 acts as an acid in the
presence of OH- but as a base in the presence of HF. Anions with ionizable
hydrogens, such as HCO3, and certain solvents, such as water, are amphiprotic.
The amphiprotic characteristic of water is important in the acid–base properties
of aqueous solutions. Consider, for example, the reactions of water with the base NH3
and with the acid HC2H3O2 (acetic acid).
 Acid-Base Properties of Water

H2O (l) H+ (aq) + OH- (aq)

autoionization of water

+ -
H O + H O [H O H ] + H O
H H H

conjugate
base
acid
H2 O + H 2 O H3O+ + OH-
acid conjugate
base
14
15
Molecular Structure and Acid Strength
H X H+ + X-

The The
stronger weaker
the bond the acid

HF << HCl < HBr < HI

16
 Molecular Structure and Acid Strength
- +
Z O H Z O- + H+

The O-H bond will be more polar and easier to break if:
• Z is very electronegative or
• Z is in a high oxidation state

17
 Molecular Structure and Acid Strength

1. Oxoacids having different central atoms (Z) that are from

the same group and that have the same oxidation number.

Acid strength increases with increasing electronegativity of Z

••
•• ••
••

••
••
O O
•• •• •• ••
••

••
H O Cl O H O Br O
•• •• •• •• •• ••

Cl is more electronegative than Br

HClO3 > HBrO3

18
 Molecular Structure and Acid Strength

2. Oxoacids having the same central atom (Z) but different

numbers of attached groups.

Acid strength increases as the oxidation number of Z increases.

HClO4 > HClO3 > HClO2 > HClO

19
20
21
22
23
Utility of Solvent System Concept:
• Explain acid-base reactions occurring in aqueous and non-aqueous solvents.
Limitations:
• It does not explain acid-base reactions which may occur in the absence of solvent.

24
 Lux-Flood Concept
• Proposed by Lux (1939) and extended by Flood (1947).
• An acid (like SiO2, CO2 etc.) is an oxide ion acceptor while a base (CaO, BaO etc.) is an oxide ion donor.
 Lewis Concept of Acids and Bases
Certain reactions have the characteristics of acid–base reactions but do not fit the
Brønsted–Lowry concept. An example is the reaction of the basic oxide Na2O with
the acidic oxide SO3 to give the salt Na2SO4

A Lewis acid is a species that can form a covalent bond by accepting an electron pair
from another species; a Lewis base is a species that can form a covalent bond by
donating an electron pair to another species.
Consider again the neutralization of NH3 by HCl in aqueous solution, mentioned earlier. It
consists of the reaction of a proton from H3O+ with NH3:

Here the red arrow shows the proton accepting an electron pair
from NH3 and an H—N bond being formed. The proton is an
electron-pair acceptor, so it is a Lewis acid. Ammonia, NH3, which
has a lone pair of electrons, is an electron-pair donor and therefore
a Lewis base.
 Now let us look at the reaction of Na2O with SO3. It involves the reaction of the
oxide ion, O2 from the ionic solid, Na2O, with SO3.

Here SO3 accepts the electron pair from the O2- ion. At the same time, an electron pair from the
S=O bond moves to the O atom. Thus, O2- is the Lewis base and SO3 is the Lewis acid.
30
Utility of the Concept:
• Includes those reactions in which no protons are involved.
• More general than the Bronsted-Lowry concept; not dependent on the presence
of particular element or on the presence or absence of a solvent.
• Explains the long accepted basic properties of metallic oxides and acidic
properties of non-metallic oxides.
Limitations:
• Since the strength of Lewis acid and base found to depend on the type of
reaction, it is not possible to arrange them in any order of their relative strength.
• According to the phenomenological criteria, an acid base reaction should be a
rapid reaction. However, many Lewis acid-base reactions are slow.
 Usanovich Concept
• Proposed by Russian chemist, Usanovich in 1939.
• An acid is any chemical species which is capable of combining with anions or
electrons or giving up cations. Conversely a base is any chemical substances
which is capable of giving up anions or electrons or combining with cations.
Utility of the Concept:
• This concept is particularly advantageous in classifying together all examples of
acids and bases. It is thus the most general of all acid-base concepts.
Limitations:
• This is like a synthesis of all the previous acid-base concepts and hence in this
respect this concept becomes extremely general.
• This theory considers all the chemical reactions as acid-base reactions.
35
36
37
38
39
Reaction Mechanisms
How do the atoms of the reactant molecules
rearrange to form the product molecules?
What is the sequence of bond breaking and
bond making?

What are the energetics of the process?

How do the electrons flow?

What molecular orbitals are involved?

40
 How do you analyze a mechanism?

Follow the Electrons. Push your arrows.

H F

+ H F N
N
H H
H H
H H

What orbitals are involved?

What are the important MOs

of HF and NH3?
41
Restating the Lewis Acid-Base Definition:

a) Base: has e- pair in HOMO of

correct energy and symmetry

b) Acid: has LUMO of correct energy

and symmetry

42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
Classes of Lewis bases (Ligands)
• Monodentate Ligands - A ligand that donates only one electron pair to a single
metal
• One of the best examples is NH3.

• Bridging Ligands - A ligand that donates one or more electron pairs to two or
more metals
• Halides and hydroxide are good examples, since each possesses two or more electron pairs
on the donor atom
• As we considered before, one of the steps to forming insoluble hydroxide and oxo
compounds is the bridging of two metals in the course of hydroysis.

57
Classes of Lewis bases – con’t
• Ambidentate Ligands - Ligands that possess two or more donor atoms
can act as a monodentate ligand through either donor atom, or
bridge two metals.
The pseudohalides such as cyanide, azide and thiocyanate are good
examples.

58
Denticity
• The number of potential donor interactions is called the denticity
• ligands are classified as bidentate chelating ligands (as for
ethylenediamine), hexadentate chelating ligands (as for
ethylenediaminetetraacetic acid; EDTA) and so forth.
H2N H2N NH2 H2N NH2
NH2 N
H

ethylenediamine (en) propylenediamine (prn) diethylenetriamine (dien)

H
H2N N
N NH2
H

triethylenetetramine (trien)

59
Chelating ligands
• ethylenediamine (on the left) yields
a five-membered ring
• acetylacetonate (on the right) yields
a six-membered ring

N O

Ni Ni

N O

60
 Self-Ionization of Water
• Pure water is often considered a nonelectrolyte, precise measurements do show a very
small conduction.
• This conduction results from self-ionization (or autoionization), a reaction in which two
like molecules react to give ions.
• In the case of water, a proton from one H2O molecule is transferred to another H2O
molecule, leaving behind an OH − ion and forming a hydronium ion, H3O+ (aq).

Because the concentration of ions formed is very small, the concentration of H2O remains
essentially constant
We call the equilibrium value of the ion product [H3O+][OH−] the ion-product constant for
water, which is written Kw. At 25°C, the value of Kw is 1.0×10-14. Like any equilibrium constant,
Kw varies with temperature. At body temperature(37°C), Kw equals 2.5 × 10−14.
Kw =[H3O+][OH−] Because we often write
=[H+][OH−] H+(aq) for H3O+(aq)

Using Kw, you can calculate the concentrations of [H3O+] and [OH−] ions in pure water.
These ions are produced in equal numbers in pure water, so their concentrations are equal.
Let X=[H3O+]=[OH−] . Then, substituting into the equation for the ion product constant,

Kw = [H3O+][OH−] = X2
1.0×10-14 = X2
X = 1.0×10-7
Problem: Calculate [𝐻 + ] or [𝑂𝐻− ] of the following solution at 25℃ and state whether the
solution is neutral, acidic or basic.
a) 1.0 × 10−5 𝑀 𝑂𝐻−
𝐾𝑤 = H + × OH −
−14 −14
1.0 × 10 1.0 × 10
∴ H+ = −
= −5
= 1.0 × 10 −9
M
OH 1.0 × 10
Since 𝑂𝐻− > 𝐻 + , the solution is basic
b) 1.0 × 10−7 M OH −
c) 10.0 M H +

Problem: At 60℃, the value of 𝐾𝑤 = 1 × 10−13 . Predict whether the reaction

2𝐻2 𝑂 𝑙 ⇌ 𝐻3 𝑂+𝑎𝑞 + 𝑂𝐻−𝑎𝑞 is
i. Exothermic or endothermic?
ii. Calculate [𝐻 +] and [𝑂𝐻− ] in a neutral solution at 60℃

i. 𝐾𝑤 1 × 10−13 is increased at 60℃ than 25℃ 1.0 × 10−14 . So the process must be
endothermic.
ii. At 60℃: H + × OH − = 1 × 10−13
for a neutral solution: H + = OH − = 1 × 10−13
= 3 × 10−7 M
 Solutions of a Strong Acid or Base
Consider an aqueous solution of a strong acid or base. Suppose you dissolve 0.10 mol
HCl in 1.0 L of aqueous solution, giving 0.10 M HCl. In addition of self-ionization ,
following reaction will also happen

As HCl is strong acid, 0.10 mol HCl in 1.0 L of solution will produce 0.10 mol [H3O+], so
the concentration of [H3O+] ion from HCl is 0.10 M.

In pure water, the concentration of [H3O+] produced is 1.0×10-7 M; in an acid solution,

the contribution of [H3O+] from water will be even smaller. Hence, according to Le
Chatelier’s by adding an acid, the self-ionization of water reverses until a new
equilibrium is obtained.
Consequently, the concentration of [H3O+] produced by the self-ionization of water
(1.0×10-7 M) is negligible in comparison with that produced from HCl (0.10 M). So, 0.10
M HCl has a concentration of H3O+ ion equal to 0.10 M.

In a solution of a strong acid, you can normally ignore the self-ionization of water as a
source of [H3O+] . The H3O+ concentration is usually determined by the strong acid
concentration.
Although you normally ignore the self-ionization of water in calculating the [H3O+]
concentration in a solution of a strong acid, the self-ionization equilibrium still exists and is
responsible for a small concentration of OH−ion.
Now consider a solution of a strong base, such as 0.010 M NaOH.
The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.

The presence of a common ion suppresses

the ionization of a weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).
CH3COONa (s) Na+ (aq) + CH3COO- (aq)
common
CH3COOH (aq) H+ (aq) + CH3COO- (aq) ion

16.2
The pH Scale

[H+] in an aqueous solution is quite small. Thus, pH scale provides a convenient way to

present solution acidity.

pH = - log [H+]

Thus, for a solution where [H+] = 1.0 × 10-7 M

pH = - ( - 7.00) = 7.00

Similarly, Log scales are also used for:

pOH = - log [OH-]

pK = - log K

pH of a solution is measured using a pH meter.

pH meter: an electronic device , contains acidic solution enclosed by a special glass membrane that
allows migration of H+ ions . If the test sample solution has a different pH than the solution of the
pH meter, an electric potential results , which is converted to pH in the meter.

We know,

Kw = [H+][OH-]

→ log Kw = log [H+] + log [OH-]

→ - log kw = - log [H+] - log [OH-]

→ pKw = pH + pOH

Since, Kw = 1.00 × 10-14

pKw = - log(1.00 × 10-14) = 14.00

Thus, for any aqueous solution at 25°C, pH and pOH added upto 14.00.

So, pH + pOH = 14.00

pH scale is based on this concept.

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 ?
If a solution has a pH of 7.41, determine its H+ concentration.
If a solution has a pH of 5.50 at 25°C, calculate its [OH–].
The pH of a solution of HCl is 2. Find out the amount of acid present in
a litre of the solution.
Determine the pH of 0.10 M NaOH solution.
Calculate the pH of a 0.020 M Ba(OH)2 solution.

0.04 M
 Do Your Self:
The pH of human arterial blood is 7.40. What is the hydronium-ion concentration?
3.98×10-8 M
A brand of carbonated beverage has a pH of 3.16. What is the hydronium-ion
concentration of the beverage?
6.92×10-4 M
A 0.010 M solution of ammonia, NH3, has a pH of 10.6 at 25°C. What is the
concentration of hydroxide ion?
3.98×10-4 M
Morphine is a narcotic that is used to relieve pain. A solution of morphine has
a pH of 9.61 at 25°C. What is the hydroxide-ion concentration?
13.16
A 1.00-L aqueous solution contained 6.78 g of barium hydroxide, Ba(OH) 2. What
was the pH of the solution at 25°C?
12.90
 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.
where Ka is called the acid dissociation constant. In dilute solution of the acid (HA) we
note that the concentration of liquid water remains essentially constant. Therefore, the
terms included in the equilibrium expression (3).

The strength of an acid is defined as the concentration of H+

ions in its aqueous solution at a given temperature.
From the equilibrium (3), it is evident that the concentration of H+ ions, [H+], depends
on the value of Ka. Therefore,
the value of Ka for a particular acid is
a measure of its acid strength or acidity.
Calculation of Relative strength of Weak acids from Ka
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.
 Calculating the pH of Weak Acid
Since a weak acid dissolved in water can be viewed as a prototype of almost any Equilibrium occurring in
aqueous solution, we will proceed carefully and systematically. Although some of the procedures we develop
here may seem unnecessary, they will become essential as the problems become more complicated. We will
develop the necessary strategies by calculating the pH of a 1.00-M solution of HF (Ka =7.2 ×10-4).

Step-1: finding the major species in the solution.

From its small Ka value, we know that hydrofluoric acid is a weak acid and will be dissociated only to a slight
extent. Thus when we write the major species, the hydrofluoric acid will be represented in its dominant form,
as HF. The major species in solution are HF and H2O.

Step-2: writing the possible equilibrium equation

The next step (since this is a pH problem) is to decide which of the major species can furnish H+ ions.
Actually, both major species can do so:
Step-3: determining the dominant acid
By comparing Ka for HF with Kw for H2O, we see that hydrofluoric acid, although weak, is
still a much stronger acid than water. Thus we will assume that hydrofluoric acid will be the
dominant source of H+. We will ignore the tiny contribution by water.
Step-4: writing the equilibrium equation

Step-5: writing the initial concentration

First, we list the initial concentrations, the concentrations before the reaction of interest has
proceeded to equilibrium. Before any HF dissociates, the concentrations of the species in
the equilibrium are
(Note that the zero value for [H+]0 is an approximation, since we are neglecting the H+
ions from the autoionization of water.)
Step-6: writing the equilibrium equation
The next step is to determine the change required to reach equilibrium. Since some HF will
dissociate to come to equilibrium (but this amount is presently unknown), we let x be the
change in the concentration of HF that is required to achieve equilibrium. That is, we assume
that x mol/L HF will dissociate to produce x mol/L H+ and x mol/L F- as the system adjusts to its
equilibrium position. Now the equilibrium concentrations can be defined in terms of x:
If x is very small compared to 1.00, the term in the denominator can be approximated as follows:
How valid is the approximation that [HF] 5 1.00 M? Because this question will
arise often in connection with acid–base equilibrium calculations, we will consider it
carefully. The validity of the approximation depends on how much accuracy we demand
for the calculated value of [H+]. Typically, the Ka values for acids are known to
an accuracy of only about ±5%. It is reasonable therefore to apply this figure when
determining the validity of the approximation
Calculate the pH of 0.1 M CH3COOH. The dissociation constant of acetic acid is 1.8 ×
10– 5.
The pH of Weak Acid Mixtures
Polyprotic Acid: Dissociates in a stepwise manner.

e.g. Carbonic Acid 𝐻2 𝐶𝑂3 :

𝐻2 𝐶𝑂3 𝑎𝑞 ⇌ 𝐻 +𝑎𝑞 + 𝐻𝐶𝑂3− 𝑎𝑞 , 𝐾𝑎 1 = 4.3 × 10−7
𝐻𝐶𝑂3− 𝑎𝑞 ⇌ 𝐻 +𝑎𝑞 + 𝐶𝑂3−2𝑎𝑞 , 𝐾𝑎 2 = 5.6 × 10−11

Phosphoric acid 𝐻3 𝑃𝑂4

+ −
𝐻3 𝑃𝑂4 𝑎𝑞 ⇌ 𝐻 𝑎𝑞 + 𝐻2 𝑃𝑂4 𝑎𝑞 , 𝐾𝑎 1 = 7.5 × 10−3
𝐻2 𝑃𝑂4− 𝑎𝑞 ⇌ 𝐻 +𝑎𝑞 + 𝐻𝑃𝑂4−2𝑎𝑞 , 𝐾𝑎 2 = 6.2 × 10−8
𝐻𝑃𝑂4−2𝑎𝑞 ⇌ 𝐻 +𝑎𝑞 + 𝑃𝑂4−3𝑎𝑞 , 𝐾𝑎 3 = 4.8 × 10−13
Sulfuric Acid
Calculate the PH of a 1.0M H2SO4 solution
Major species : H+ , H2SO4- , H2O
H2SO4 (aq) H+(aq) + HSO4- (aq) , Ka1 = very large
HSO4- (aq) H+(aq) + SO4- (aq) , Ka2 = 1.2x10-2
The conc. Of H+ in the solution will be at least 1.0M , since
This amount is produce by the complete first dissociation step (Ka1)
Now , the question is—does HSO4- dissociate enough to produce a significant
contribution to the concentration of H+ ?
This can be answered by calculating the equation conc.s of the dissociation
reaction :
H2SO
HSO4 4 (aq)
- ⇌ H+(aq) + SO4-2 (aq)
Ka2 = 1.2x10-2 = [H+] [SO4-3]/ [HSO4-] = (1.0+X)(X)/(1.0-X) = (1.0)(X) / 1.0
X ≈ 1.2x10-2
Since 1.2x10-2 is 1.2% of 1, the approximation is valid
[H+] = 1.0M + (1.0x10-2) M
≈ 1.0M
Thus dissociation of HSO4- does not make a significant
contribution to the Concerntration of H+ and
[H+] = 1.0M
PH = 0.00
Prob. Calculate the pH of a 1.00x10-2M H2SO4 .
Major species: H+ , HSO4- and H2O
H2SO4(aq) ↔ H+(aq) + SO42-(aq)
Initial : 0.0100 0.0100 0
change: -x +x +x
Equilibrium: 0.0100-x 0.0100+x x
(0.0100 +𝑥)(𝑥) 0.0100𝑥
ka2=1.2x10-2= ≈
0.0100−𝑥 0.0100

x=0.012
now x is larger than 0.01 thus we cannot make the usual approximation and
must instead solve the quadratic equation :
(0.0100 +𝑥)∗𝑥
1.2x10-2=
0.0100 −𝑥

Leads to (1.2x10-2)(0.0100-x)=(0.0100+x)*x
(1.2x10-4)-(1.2x10-2)x=(1.0x10-2)x+x2
X2+(2.2x10-2)x - (1.2x10-4)=0
This equation can be solved by using quardratic formula :

−𝑏 ± 𝑏 2 − 4𝑎𝑐
𝑥=
2𝑎
X2+(2.2x10-2)x - (1.2x10-4)=0

Where a=1 ,b=2.2x10-2 ,c=-1.2x10-4

Quadratic formula gives one negative root (which cannot be correct)
And one positive root
X= 4.5x10-3
[H+]=0.0100+0.0045=0.0145
pH=1.84
#note that in this case, 2nd dissociation step produces about half as many H+ ion
as the initial step does .
 What Is A Buffer Solution?

A buffer solution is one which maintains its pH fairly constant even upon the
addition of small amounts of acid or base.

Two common types of buffer solutions are:

1) A weak acid together with a salt of the same acid with a strong base. These are
called Acid buffers e.g., CH3COOH + CH3COONa.

2) A weak base and its salt with a strong acid. These are called Basic buffers. e.g.,
NH4OH + NH4Cl.
 How A Buffer Operates ?

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 decrease of pH of the buffer solution on
addition of HCl.
(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
 What is the pH of a solution containing 0.30 M HCOOH
and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x
[HCOO-]
Common ion effect pH = pKa + log
[HCOOH]
0.30 – x  0.30
[0.52]
0.52 + x  0.52 pH = 3.77 + log
[0.30]
= 4.01

HCOOH pKa = 3.77

16.2
 HCl H+ + Cl-
HCl + CH3COO- CH3COOH + Cl-

16.3
 Which of the following are buffer systems?
(a) KBr/HBr, (b) Na2CO3/NaHCO3

(a) HBr is a strong acid

not a buffer solution
(b) CO32- is a weak base and HCO3- is its conjugate acid
buffer solution

16.3
 Titrations
In a titration a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.

Equivalence point – the point at which the reaction is complete

Indicator – substance that changes color at (or near) the
equivalence point

Slowly add base

to unknown acid
UNTIL
The indicator
changes color
(pink) 4.7
Strong Acid-Strong Base Titrations
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

OH- (aq) + H+ (aq) H2O (l)

16.4
Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

16.4
Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4Cl (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

16.4
 Acid-Base Indicators
HIn (aq) H+ (aq) + In- (aq)
[HIn]
-  10 Color of acid (HIn) predominates
[In ]
[HIn]
 0.1 Color of conjugate base (In -) predominates
[In-]

16.5
The titration curve of a strong acid with a strong base.

16.5
 Which indicator(s) would you use for a titration of HNO2
with KOH ?

Weak acid titrated with strong base.

At equivalence point, will have conjugate base of weak acid.
At equivalence point, pH > 7
Use cresol red or phenolphthalein
 Leveling Effect:
The leveling effect refers to the phenomenon in which the acidity or basicity
of a substance is limited by the solvent used in the reaction. In other words, a
solvent can "level" the acidity or basicity of a substance, preventing it from
exhibiting stronger acidic or basic properties.
For example, in aqueous solutions, strong acids such as hydrochloric acid
(HCl) and sulfuric acid (H2SO4) are completely ionized, and their acidic
strength cannot be distinguished.
This is because water is a strong proton acceptor and the presence of excess
water molecules in the solution prevents any acid stronger than the
hydronium ion (H3O+) from exhibiting its full acidic strength.
Similarly, in basic aqueous solutions, strong bases such as sodium hydroxide
(NaOH) and potassium hydroxide (KOH) are fully ionized and cannot exhibit
any greater basic strength.
 Hammett Acidity Function:
The Hammett acidity function is a measure of the acidity of a
substance based on its ability to donate a proton (H+ ion). It is defined
as the logarithm of the equilibrium constant for the reaction of an
acid with a standard base in a non-aqueous solvent:
H0 = -log(Ka/K0)
where Ka is the acid dissociation constant in the solvent of
interest, and K0 is the acid dissociation constant in a reference
solvent such as water.
The Hammett acidity function is used to compare the relative
strengths of acids in non-aqueous solvents, as it considers the effect
of the solvent on the acidity of the acid. A more negative Hammett
acidity function indicates a stronger acid, while a less negative
Hammett acidity function indicates a weaker acid.
For example, the Hammett acidity function can be
used to compare the relative strengths of carboxylic
acids in different solvents. In chloroform, the
Hammett acidity function for acetic acid is 13.1, while
the Hammett acidity function for trifluoroacetic acid is
-16.4. This indicates that trifluoroacetic acid is a
stronger acid than acetic acid in chloroform
Superacid:
A superacid is an acid with an acidity greater than that of 100% sulfuric
acid (H2SO4). Superacids are typically composed of strong Lewis acids such
as trifluoromethanesulfonic acid (CF3SO3H) or fluorosulfonic acid (HSO3F)
and a weaker Brønsted-Lowry acid such as hydrogen fluoride (HF).

Superacids are extremely reactive and can protonate even inert

hydrocarbons, making them useful in organic synthesis reactions. They are
also used in the study of reaction mechanisms and as catalysts for various
chemical reactions.

For example, a mixture of trifluoromethanesulfonic acid and hydrogen

fluoride is a superacid with an acidity greater than that of 100% sulfuric
acid. This superacid can be used to protonate hydrocarbons and initiate
reactions that are difficult to achieve with other acids.