Dr.

VISHAL BADGUJAR
Faculty of Pharmacy and Health Sciences
UniKL, Royal College of Medicine Perak
Date: 12th & 17th Sep. 2013
 LEARNING OUTCOME

 By the end of this topic you should be able to:

 Define Acid and base

 Discuss Acid and base by Arrhenius, Lewis and Bronsted – lowry theory

 Differentiate between various types of acids and bases.

 Draw a graph of titration between various acids and bases

 Importance of pH and pOH its relation with pKa value

 Discuss indicator and its types.

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 What is Acid-base titration?

 An acid-base titration is a titration method in which the

reaction between the analyte and titrant is an acid-base
reaction.

Example: It may be between

Strong acid: HCl, H2SO4

Weak acid: CH3COOH, HNO3

Strong base: NaOH, KOH

Weak base: NH3

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 What is Acid-base titration?

 Acidimetric titration:
Alkaline substance is titrated with standard acid is called as acidimetric
titration.

 Alkalimetric titration:
Acidic substance is titrated with standard base is called as alkalimetric
titration.

 Non-aqueous titration:
Substances which can not be titrated satisfactorily either by acidimetry or
alkalimetry in aqueous solution are titrated by non-aqueous solvents and
called as non-aqueous titration.

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 ACID-BASE THEORIES

Arrhenius, Bronsted and Lowry, Lewis

 Arrhenius theory:
 Acid : HA H+ + A-
Acid are species which produce PROTON, H+ hydrogen ions in solution.

 Base: BOH B+ + OH-

Base are species that produce HYDROXIDE (OH-) ions in solution.

 Neutralisation is the reaction between an acid and a base :

H+ + OH- H 2O
It happens because acid and base reacts to produce water

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 ACID-BASE THEORIES

 Bronsted and Lowry Theory:

 Acid: it donates proton, H+

H2O + HCl H3O+ + Cl-

 Base: it accepts proton, H+

NH3 + HCl NH4 + Cl-

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 ACID-BASE THEORIES

 Conjugate pairs:
 When hydrogen chloride dissolves in water, almost 100% of it reacts with the
water to produce hydroxonium ions and chloride ions. Hydrogen chloride is a
strong acid, and we tend to write this as a one-way reaction:

H2O + HCl H3O+ + Cl-

In fact, the reaction between HCl and water is reversible, but only to a very
minor extent. In order to generalise, consider an acid HA, and think of the
reaction as being reversible.

HA + H2O H3O+ + A-

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 ACID-BASE THEORIES

 Thinking about the forward reaction:

 The HA is an acid because it is donating a proton (hydrogen ion) to the water.
 The water is a base because it is accepting a proton from the HA.
 But there is also a back reaction between the hydroxonium ion and the A- ion:
 The H3O+ is an acid because it is donating a proton (hydrogen ion) to the A- ion.
 The A- ion is a base because it is accepting a proton from the H3O+.
 The reversible reaction contains two acids and two bases. We think of them in
pairs, called conjugate pairs.

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 ACID-BASE THEORIES

 When the acid, HA, loses a proton it forms a base, A-. When the base, A-,
accepts a proton back again, it obviously refoms the acid, HA. These two
are a conjugate pair.

 Members of a conjugate pair differ from each other by the presence or

absence of the transferable hydrogen ion.

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 ACID-BASE THEORIES

 A second example of conjugate pairs

 This is the reaction between ammonia and water that we looked at earlier:

 In forward reaction. Ammonia is a base because it is accepting hydrogen ions from

the water. The ammonium ion is its conjugate acid - it can release that hydrogen ion
again to reform the ammonia.
 The water is acting as an acid, and its conjugate base is the hydroxide ion. The
hydroxide ion can accept a hydrogen ion to reform the water.
 Looking at it from the other side, the ammonium ion is an acid, and ammonia is its
conjugate base. The hydroxide ion is a base and water is its conjugate acid.
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 ACID-BASE THEORIES

 Amphoteric substances: A substance which can act as either an

acid or a base is described as being amphoteric.

 In one of the last two examples, water was acting as a base, whereas in
the other one it was acting as an acid.

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 ACID-BASE THEORIES

 The Lewis Theory of Acids and Bases:

This theory extends well beyond the things you normally think of as acids
and bases.

Acid: An acid is an electron pair acceptor.

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 ACID-BASE THEORIES

Base:
A base is an
electron pair donor.

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 Types of Acid-Base

 Monoprotic, Diprotic, Triprotic

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Types of Acid-Base

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Types of Acid-Base

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 STRENGTH OF ACID AND BASES

Strong Electrolyte – 100% dissociation

H 2O
HCl H+ (aq) + Cl- (aq)
Weak Electrolyte – partiallly dissociated
CH3COOH CH3COO- (aq) + H+ (aq)

Strong Acids are strong electrolytes

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

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)
H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)
 STRENGTH OF ACID AND BASES

Weak Acids are weak electrolytes

HF (aq) + H2O (l) H3O+ (aq) + F- (aq)
HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)
HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq)
H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)
Strong Bases are strong electrolytes
H 2O
NaOH (s) Na+ (aq) + OH- (aq)
H 2O
KOH (s) K+ (aq) + OH- (aq)
H 2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq) 18
 STRENGTH OF ACID AND BASES

Weak Bases are weak electrolytes

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

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

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 STRENGTH OF ACID AND BASES

 It is important that you don't confuse the words strong and weak with the
terms concentrated and dilute.

 The strength of an acid is related to the proportion of it which has reacted

with water to produce ions.

 The concentration tells you about how much of the original acid is
dissolved in the solution.

 It is perfectly possible to have a concentrated solution of a weak acid, or a

dilute solution of a strong acid.

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 STRENGTH OF ACID AND BASES

 Strong acids
 Explaining the term "strong acid”

 We are going to use the Bronsted-Lowry definition of an acid.

 When an acid dissolves in water, a proton (hydrogen ion) is transferred to
a water molecule to produce a hydroxonium ion and a negative ion
depending on what acid you are starting from.
 In the general case . . . HA + H2O H3O+ + A-

 These reactions are all reversible, but in some cases, the acid is so good
at giving away hydrogen ions that we can think of the reaction as being
one-way. The acid is virtually 100% ionised.

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 STRENGTH OF ACID AND BASES

 For example, when hydrogen chloride dissolves in water to make hydrochloric

acid, so little of the reverse reaction happens that we can write:
H2O (l) + HCl (g) H3O+ (aq.)+ Cl- (aq.)

At any one time, virtually 100% of the hydrogen chloride will have reacted to
produce hydroxonium ions and chloride ions. Hydrogen chloride is described as
a strong acid.
 A strong acid is one which is virtually 100% ionised in solution.
 Other common strong acids include sulphuric acid and nitric acid.
 You may find the equation for the ionisation written in a simplified form:
HCl H+(aq) + Cl- (aq)
 This shows the hydrogen chloride dissolved in the water splitting to give hydrogen
ions in solution and chloride ions in solution.
 This version is often used in this work just to make things look easier. If you use it,
remember that the water is actually involved, and that when you write H+(aq) what
you really mean is a hydroxonium ion, H3O+. 22
 pH and pOH

 Strong acids and pH

pH is a measure of the concentration of hydrogen ions in a solution. Strong
acids like hydrochloric acid have a pH around 0 to 1. The lower the pH, the
higher the concentration of hydrogen ions in the solution.
 Defining pH:
-ve log of H+Ion concentration to base 10

 Defining pOH
-ve log of OH-Ion concentration to base10

 pH + pOH = 14

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 STRENGTH OF ACID AND BASES

 Weak acids
 Explaining the term "weak acid"
A weak acid is one which doesn't ionise fully when it is dissolved in water.
 Ethanoic acid is a typical weak acid. It reacts with water to produce
hydroxonium ions and ethanoate ions, but the back reaction is more
successful than the forward one. The ions react very easily to reform the
acid and the water.

At any one time, only about 1% of the ethanoic acid molecules have
converted into ions. The rest remain as simple ethanoic acid molecules.
 Most organic acids are weak. Hydrogen fluoride (dissolving in water to
produce hydrofluoric acid) is also a weak inorganic acid.
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The acid ionization (dissociation) constant, Ka

HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

HA (aq) H+ (aq) + A- (aq)

[H+][A-]
Ka =
[HA]

Ka is the acid ionization (dissociation) constant

weak acid
Ka strength
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 The acid ionization (dissociation) constant, Ka

 The table shows some values of Ka for some simple acids:

Acid Ka (mol dm-3)

Hydrofluoric acid 5.6 x 10-4 L

Methanoic acid 1.6 x 10-4
o
w
Ethanoic acid 1.7 x 10-5
e
Hydrogen sulphide 8.9 x 10-8
r
These are all weak acids because the values for Ka are very small.
They are listed in order of decreasing acid strength - the Ka values get
smaller as you go down the table.
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 An introduction to pKa

 pKa bears exactly the same relationship to Ka as pH does to the hydrogen ion
concentration:
pKa = -log10 Ka
 If you use your calculator on all the Ka values in the table above and convert them
into pKa values, you get:

Acid Ka (mol dm-3) pKa

Hydrofluoric acid 5.6 x 10-4 3.3 H
Methanoic acid 1.6 x 10-4 3.8 i
g
Ethanoic acid 1.7 x 10-5 4.8
h
Hydrogen sulphide 8.9 x 10-8 7.1 e
r
The weaker the acid, the larger the value of pKa.
Remember this:
The lower the value for pKa, the stronger the acid.
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The higher the value for pKa, the weaker the acid.
 PERCENT IONIZATION

percent ionization = Ionized acid concentration at equilibrium x 100%

Initial concentration of acid

For a monoprotic acid HA

[H+]
Percent ionization = x 100%
[HA]0

[HA]0 = initial concentration

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 The Bases and
Base Ionization (Dissociation) Constants

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

[NH4+][OH-]
Kb =
[NH3]

Kb is the base ionization constant

weak base
Kb
strength
+].
Solve weak base problems like weak acids except solve for [OH-] instead of [H29
 Ionization Constants of Conjugate Acid-Base
Pairs

HA (aq) H+ (aq) + A- (aq) Ka

A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb

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

KaKb = Kw

Weak Acid and Its Conjugate Base

Kw Kw
Ka = Kb =
Kb Ka 30
 TYPES OF NEUTRALIZATION TITRATION

Strong Acid-Strong Base Titrations

NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

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

0.10 M NaOH
added to 25 mL of 0.10 M HCl

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 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)

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 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)

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 Equivalence Point Detection Methods

(1) Indicator method: Based on color change of indicator

• Most commonly used

•A dye whose color change depends on pH

(2) Potentiometric method: Based on sudden change in

voltage or current between a pair of electrodes
Ex. Alkalinity lab (pH change depends on voltage change)

(3) Absorbance method: Based on absorbance of light

Ex. Product absorbs light => absorption increases as product forms
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 ACID BASE INDICATORS

 How simple indicators work

Indicators as weak acids
Litmus
Litmus is a weak acid. It has a seriously complicated molecule which we will simplify
to HLit. The "H" is the proton which can be given away to something else. The "Lit" is
the rest of the weak acid molecule.
 There will be an equilibrium established when this acid dissolves in water. Taking the
simplified version of this equilibrium:

H Lit(aq) H +(aq) + Lit (aq)

 The un-ionised litmus is red, whereas the ion is blue.

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ACID BASE INDICATORS

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 ACID BASE INDICATORS

 If the concentrations of HLit and Lit - are equal:

 At some point during the movement of the position of equilibrium, the
concentrations of the two colours will become equal. The colour you see will
be a mixture of the two.

“Neutral colour”

 The reason for the inverted commas around "neutral" is that there is no
reason why the two concentrations should become equal at pH 7. For litmus,
it so happens that the 50 / 50 colour does occur at close to pH 7 - that's why
litmus is commonly used to test for acids and alkalis. As you will see below,
that isn't true for other indicators.

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 ACID BASE INDICATORS

 Methyl orange
Methyl orange is one of the indicators commonly used in titrations. In an
alkaline solution, methyl orange is yellow and the structure is:

Now, you might think that when you add an acid, the
hydrogen ion would be picked up by the negatively
charged oxygen. That's the obvious place for it to go.
Not so!

In fact, the hydrogen ion attaches to one of

the nitrogens in the nitrogen-nitrogen
double bond to give a structure which
might be drawn like this: 38
 ACID BASE INDICATORS

 The same sort of equilibrium between the two forms of methyl orange as in the
litmus case - but the colours are different.

 In the methyl orange case, the half-way stage where the mixture of red and yellow
produces an orange colour happens at pH 3.7 – no where near neutral.

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 ACID BASE INDICATORS

 Phenolphthalein:
Phenolphthalein is another commonly used indicator for titrations, and is
another weak acid.

 The weak acid is colourless and its ion is bright pink. Adding extra hydrogen ions
shifts the position of equilibrium to the left, and turns the indicator colourless. Adding
hydroxide ions removes the hydrogen ions from the equilibrium which tips to the right
to replace them - turning the indicator pink.

 The half-way stage happens at pH 9.3. Since a mixture of pink and colourless is
simply a paler pink, this is difficult to detect with any accuracy! 40
 ACID BASE INDICATORS

HIn (aq) H+ (aq) + In- (aq)

[HIn]
 10/1
[In-]

Color of acid (HIn)

predominates

[HIn]
 1/10
[In-]

Color of conjugate base

(In-) predominates 41
 ACID BASE INDICATORS

 The pH range of indicators

 The importance of pKind
Think about a general indicator, HInd - where "Ind" is all the rest of the
indicator apart from the hydrogen ion which is given away:

 Because this is just like any other weak acid, you can write an
expression for Ka for it. We will call it Kind to stress that we are talking
about the indicator.

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 ACID BASE INDICATORS

 Think of what happens half-way through the colour change. At this point the
concentrations of the acid and its ion are equal. In that case, they will cancel out of
the Kind expression.

 You can use this to work out what the pH is at this half-way point. If you re-arrange
the last equation so that the hydrogen ion concentration is on the left-hand side, and
then convert to pH and pKind, you get:

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 ACID BASE INDICATORS

 That means that the end point for the indicator depends entirely on what its
pKind value is. For the indicators we've looked at above, these are:

indicator pKind
litmus 6.5
methyl orange 3.7
phenolphthalein 9.3

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The pH range of indicators

Indicator pKind pH range

Litmus 6.5 5-8
Methyl orange 3.7 3.1 - 4.4
Phenolphthalein 9.3 8.3 - 10.0

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 Choosing indicators for titrations

 Strong acid v strong base:

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 Choosing indicators for titrations

 Strong acid v weak base:

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 Choosing indicators for titrations

 Weak acid v strong base:

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 Weak acid v weak base

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 Applications acid - base titration

 KJeldahl Analysis of Organic Nitrogen

This method is used

 in the analysis of caffeine
 saccharin in pharmaceutical products
 analysis of proteins, fertilizers, sludges, sediments

 Quantitative Analysis of Drug

Weak base
 Antihistamine drug : chlorpheniramin maleate
 Alkaloid : morphine, caffeine, quinine
 N – heterocyclic compound : bisacodyl, dextrometorphane

Weak acid
 Barbituric acid : chlordiazepoxide
 Phenol
 Organic acid : benzoic acid, citric acid 50
 REFERENCES..

 Kenkel, J. (2003). Analytical chemistry for Technician. 3rd edition. CRC

Press.

 Harvey D. (2000) Modern Analytical Chemistry. International edition. Mc

Graw-Hill. Book Co-Singapore

 Vogel’s text book of Quantitaitve Chemical analysis, Fifth edition,

Longmann, New York,

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