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chap 4

The document discusses the properties and definitions of acids and bases, including their behavior in aqueous and non-aqueous solutions. It highlights the limitations of using water as a solvent for titrations and introduces non-aqueous titration as a solution for weak acids and bases. Additionally, it covers the classification of non-aqueous solvents and the concepts of leveling and differentiating effects in acid-base reactions.

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Ahmanur Sule
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8 views

chap 4

The document discusses the properties and definitions of acids and bases, including their behavior in aqueous and non-aqueous solutions. It highlights the limitations of using water as a solvent for titrations and introduces non-aqueous titration as a solution for weak acids and bases. Additionally, it covers the classification of non-aqueous solvents and the concepts of leveling and differentiating effects in acid-base reactions.

Uploaded by

Ahmanur Sule
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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ACIDS AND BASES

Acids:
acids are sour tasting
Arrhenius acid: Any substance that, when dissolved in water,
increases the concentration of hydronium ion (H3O+)
Bronsted-Lowry acid: A proton donor
Lewis acid: An electron acceptor
Bases:
bases are bitter tasting and slippery
Arrhenius base: Any substance that, when dissolved in water,
increases the concentration of hydroxide ion (OH-)
Bronsted-Lowery base: A proton acceptor
Lewis acid: An electron donor
INTRODUCTION
Water is a most convenient solvent, for it can act as a second
acid-base pair both for acids (in which case it functions as a
base) and for bases (when it functions as an acid)
The major limitation of water as a titration medium, however, is
also due to this amphoteric behavior.

In aqueous solution one of these bases is water


If the other base is relatively weak, it will not compete
effectively with the solvent for the proton
In practical terms, it will not be titratable
In aqueous media
In an aqueous solution of a weak acid, the titration
situation can be described as a competition of the
solute acid and the solvent acid for the titrant base.

Thus neither weakly acidic nor weakly basic substances


can be titrated easily in aqueous solution
The simplest solution to this problem is to replace the
solvent
If the solute is a weakly basic , successful titration is
blocked by the basic character of the solvent water
If water is replaced by a relatively non-basic solvent,
this undesirable competition is effectively eliminated
or at least reduced, and the solute base can now be
titrated, a similar situation holds for weakly acidic
solutes.
Titration in non aqueous media is called non aqueous

titration

Non aqueous titration: It is the most common titrimetric

procedure used in pharmacopoeial assays and serves a

double purpose
Substances which give poor end points due to being

weak acids or bases in aqueous solution

give far more satisfactory end points when titrations

are carried out in non-aqueous media

An additional advantage is that many substances which

are insoluble in water are sufficiently soluble in

organic solvents permit their titration in these non-

aqueous media
They are also of particular value for determining the
proportions of individual components in mixtures of
either acids or of bases. These differential titrations
are carried out in solvents which do not exert leveling
effect.
SOLVENTS FOR NON AQUEOUS TITRATION

In the Brunsted-Lowry theory, any acid (HB) is


considered to dissociate in solution to give a proton
(H') and a conjugate base (B-);
whilst any base (B) will combine with a proton to
produce a conjugate acid (HB').
The ability of substances to act as acids or bases will depend very
much upon the nature of the solvent system which is employed
Non-aqueous solvents are classified into the four groups: aprotic
solvents, protophilic solvents, protogenic solvents, and
amphiprotic solvents

Protophilic solvents:
Philic-loving

They are basic solvents,

more basic than water and have high ability to accept protons
e.g. liquid ammonia, amines, ethers and ketones

HA + S == SH+ + A-

They enhance the strength of weak acids ( e.g. acetic and formic
acid). so that they have the same strength as strong bases
(Leveling effect)
Protogenic solvents: (Genic=producing)
They are acidic solvents, more acidic than water ,have the affinity
to donate protons

e.g. sulfuric acid : H2SO4 + 2B → SO42- + 2BH+

They enhance the strength of weak bases so that they have the same
strength as strong bases (Leveling effect)
Amphiprotic solvents:
They are liquids that ionized to a slight extent

exhibit both protogenic and protophilic properties .

e.g. alcohols, water, acetic acid

They have both leveling and differentiating effects.


Leveling effect
It is impossible experimentally to distinguish any
difference between the strength of two acid such as
perchloric and hydrochloric acids in aqueous media.

Thus, water is said to exert leveling effect on HClO4 and


HCl since both acids are much stronger acids than
H3O+ (or because H2O is a stronger base than either

HCIO4 or HCl). - +
HCIO4 + H2O ClO4 + H3O

+
HCl + H2O Cl- + H3O
Differentiating effect
It is the capability of a solvent to differentiate the strength of two
acid or two bases:

Thus, acetic acid is said to exert differentiating effect on HClO 4

and HCl since CH3COOH2+ is a stronger acid than H3O+ (or


acetic acid is a much weaker base than water).

The reaction of HClO4 in acetic acid, however, shows a higher


degree of completion than the reaction of HCl with acetic acid.
- +
HClO4 + CH3COOH ClO 4 + CH3COOH2

- +
HCl + CH3COOH Cl + CH3COOH2
RELATIVITY OF ACIDITY AND BASICITY

An acidic substance can only function as an acid in the presence


of a base, and basic substance can only act as a base in
presence of an acid.
Examples :
+ -
CH3COOH + H2O H3O CH3COO
(a) Water : +

NH4+ + H2O H3O + + NH3


H2PO 4- + H2O H3O + + HPO 42-

- -
CH3COO + H2O HO + CH3COOH
- +
NH3 + H2O HO + NH4
- -
HPO 42- + H2O HO + H2PO 4
(C) HCN is very weak acid , it has a low tendency to
transfer a proton to water as a solvent.

HCN + H2O == H 3 O+ + CN-

The same acid might dissociate to a much greater


degree in more basic solvents e.g. amines and
ammonia.

HCN + NH3 === NH4+ + CN-

This mean that we can enhance the acidity by


choosing a solvent more basic (less acidic) than
water.
A substance which acts as an acid in one solvent does not
necessary reacts in the same way in another solvent
A substance reacts as an acid if it is more acidic than the used
solvent and as a base if it is more basic than the used solvent.
Titration of a Weak Acid with a Strong Base
– Addition of a strong base to a weak acid forms a Buffer
Solution
• HA + OH- A- + H2O
• If not enough base has been added to complete the reaction:
HA/A- buffer
B.Important Points
• pH increases more rapidly at the start than for a strong acid
2)pH levels off near pKa due to HA/A- buffering effect
pH = pKa + log([A-]/[HA]) = pKa + log(1) = pKa
(when [A-] = [HA])
3)Curve is steepest near equivalence point. Equivalence Point
> 7.0
4)Curve is similar to strong acid—strong base after eq. pt.
where OH- is major
III.Titration of a Weak Base with a Strong Acid
– Similar problem to the titration of a weak acid with a strong
base
• Determine major species from the stoichiometry
• Calculate pH from weak acid, buffer, or weak base
accordingly

– Example: Titrate 100 ml of 0.10 M NH3 (Kb = 1.8 x 10-5)


with 0.1 M HCl.
END POINT DETECTION
The end point is determined in different ways
depending on the titration, in the following way as
illustrated below.
TITRATION SOLUTION pH range limit

Strong acid-strong 0.1N solutions or 4.5 to 9.5


base stronger
Weak acid-Strong ----------- All alkaline pH
base (phenolphthalein,
thymol blue etc.)
Weak base-strong ----------- All acidic pH
acid (methyl red, methyl
orange, methyl
yellow)
Weak acid-Weak ------------ Very limited pH
base range (neutral red +
methylene blue)
APPLICATIONS
Substances which are of insufficient basic or acidic strengths to
give sharp end points in aqueous solutions .
Analysis of mixtures of acids or bases which can not be
differentiated in aqueous solutions. e.g. HCl and HClO4 in
methyl-isobutyl ketone as solvent.
Substances which are insoluble in water.

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