Acids, Bases & Buffers - Copy-1
Acids, Bases & Buffers - Copy-1
Introduction
• Acids and bases are the most important pharmaceutical
substances.
• Many active pharmaceutical ingredients are insoluble in water
and aqueous solutions of such agents cannot be prepared.
• Many acid and bases are use in the preparation od suitable
salt of drugs.
• E.g. Diclofenac sodium, atropine sulphate
• Almost 80% of drugs are in suitable salt form.
• Buffers are equally important in case of pharmaceutical
formulations.
• Body has its own buffer system and it gets altered giving rise
to certain ailments.
Various concepts of Acids and Bases
• Although various concepts have been evolved for acids
and bases, all have certain limitation and wherever these
theories are applicable, they can be applied with equal
confidence.
• Earlier concept of Acid And Base:
• An Acid – any substance which has a sour taste and its
aqueous solution turns blue litmus red.
• A Base - any substance which has a bitter taste and its
aqueous solution turns red litmus blue.
Various concepts of Acids and Bases
• Arrhenius Concept:
• The concept of acid and base was first of all introduced by
Arrhenius.
• According to him,
• Acid – any substance that produce H+ ions in aqueous
solution or any substance capable of providing hydrogen ions
(Protons, H+) in aqueous solution.
• Base - any substance that contain OH group or any substance
capable of providing hydroxyl ions (OH-) in aqueous solution.
HCl ↔ H+ + Cl-
NaOH ↔ Na + + OH-
Various concepts of Acids and Bases
• Arrhenius Concept:
• According to him, the neutralization process can be
represented by a reaction involving the combination of H+
and OH- ions to form water.
H+ + OH- ↔ H2O
• Limitations:
• Although the Arrhenius acid base theory is most simple and
convenient in explaining the reaction in aqueous solution.
– The definitions of acids and bases are only in terms of aqueous
solution and not in terms of substances.
– Theory cannot explain acidic and basic properties of substances in
non-aqueous solvents. E.g. NH4NO3 in liquid NH3 acts as an acid,
though it does not give H+ ions
• Limitations:
– The neutralization of acid and base in absence of solvent could
not be explained.
– few basic substances which do not have OH- ions can not be
explained by the theory. E.g. NH3
– It cannot explain the acidic character of certain slats such as
AlCl3 in aqueous solution.
Various concepts of Acids and Bases
• Bronsted Lowry Concept:
• According to them,
• Acids – any particle that donate proton in a chemical reaction.
• Bases - any particle that accept proton in a chemical reaction.
HCl ↔ H+ + Cl-
Acid: donate Proton
H3O+ ↔ H+ + H2O
OH- + H + ↔H2O
Base: Accept Proton
NH3 + H + ↔ NH4 +
• Acids and bases exist side by side.
• This theory is not limited to water as a solvent.
• An acid and a base connected in this way are said to be
conjugated acid-base pair.
• Bronsted Lowry Concept:
• Bronsted acid ionizes to produce proton and conjugate base
of acid, which can be explained by following half reactions of
ionization.
Acid ↔ H+ + Conjugated base
HCl ↔ H+ + Cl-
H3O+ ↔ H+ + H2O
• On the other hand, bases are usually considered as neutral
molecules, or anions, and few cation accepting proton. The
species formed when base accepts proton is called as
conjugate acid. E.g.
Base + H + ↔ Conjugate acid
OH- + H + ↔H2O
NH3 + H + ↔ NH4 +
• The acid base pairs, the members of which can be formed
from each other mutually by the gain or loss of proton are
called conjugate acid base pair.
HCl + H2O ↔ H3O+ + Cl-
Acid1 + Base2 ↔ Base1+ Acid2
Acid1 + Base2 ↔ Conjugated Acid + Conjugated base
• Water can accept proton, thus acting as base and can also
give proton, thus acting as acid. Due to this property of water,
it is called as amphoteric substance.
Acid Base Conjugate Conjugate
Acid Base
HCl + H2O ↔ H3O+ + Cl-
H2SO4 + OH- ↔ H2O + HSO4-
• According to above description, a strong acid is one which
easily give away protons to base, so conjugate base of such
acids, must be weak.
• If conjugated base form is strong, then it will accept the
proton more easily and weaken the strength of acid.
• In general,
• strong acids have weak conjugate bases
• Strong base have weak conjugate acids.
• These concepts are important in the considerations of buffers
and buffer mechanisms.
• This theory is useful while considering the strength of acid
and measuring the pH and pKa.
• Advantage:
• Very simple and easy to apply to many acids and bases.
• The relative strength of acids and bases in aqueous solvent
can be very useful in developing suitable buffers.
• This theory can be applied while applying the calculation of
pH, pOH, pKa etc., which is important in deciding the
physiological characteristics and physiological behaviour of
acids and bases.
• Advantage:
• Very simple and easy to apply to many acids and bases.
• The relative strength of acids and bases in aqueous solvent
can be very useful in developing suitable buffers.
• This theory can be applied while applying the calculation of
pH, pOH, pKa etc., which is important in deciding the
physiological characteristics and physiological behaviour of
acids and bases.
• Lewis Concept:
• It is know as electron donor acceptor concept.
• Acid: any substance or species (molecule, ion or radical)
which can accept an electron pair to the form a coordinate
bond OR is an electron pair acceptor.
• Base: any substance or species (molecule, ion or radical)
which can donate an electron pair to the form a coordinate
bond OR is an electron pair donor.
• According to theory, the process of neutralization is simply
the formation of a coordinate bond between an acid and a
base.
H+ + :NH3 → H←NH3 (NH4+)
BF3 + :NH3 → BF3←NH3 (BF3NH3)
Lewis Concept:
• It is know as electron donor acceptor concept.
• Acid: H+, NH4+, Na+, K+,Cu+2, Al+3
• Base: NH3, H2O, OH-, Cl-, CN-,S-2
• Bronsted acid, the proton is also lewis acid but all lewis
acids are not bronsted acids, vice versa.
• Limitations:
• Substances that are not normally considered as acids, behave
as Lewis acids. Eg.BF3
• As the strength of an acid or a base varies with the solvent,
also depends upon the type of reaction, there can be no scale
of acid and basic strength.
Relative Strength of Acid and Bases
• Acids and bases can be identified as monoprotic or
polyprotic depending upon the numbers of dissociable
protons the acid contains or the number of protons with
which the base can combine.
• Irrespective of whether a substance is monoprotic or
polyprotic, the strength of an acid or base refers to the
efficiency with which the substance demonstrates the
properties of an acid or base.
• For acid – the ease with which it donates protons
• For base – the ease with which it accepts protons
• These properties of substance will be affected by its
environment.
Relative Strength of Acid and Bases
• With respect to strength, there are two general classes
• Strong – are ones which are almost completely dissociated in
dilute aqueous media
• Weak – are ones which are only partially dissociated in dilute
aqueous media
• The strength of acid or base is most frequently determined
by the dissociation constant “K”.
• Strength of Acid – Ka
• Strength of Base – Kb or Ka of its conjugate acid
Images: Strong Acids, Department of Chemistry, CSU From the Virtual Cell Biology Classroom on ScienceProfOnline.com
From the Virtual Cell Biology Classroom on ScienceProfOnline.com
Relative Strength of Acid and Bases
• Strength of Acid – is usually based on the degree of
dissociation of proton from conjugate base when acid is
dissolved in water.
• Ka is ionisation constant for acid. it is expressed as product of
equilibrium constant and concentration of water.
HA + H2O ↔H3O+ + A-
Keq = [H3O +] [A-] / [HA] [H2O]
Ka = Keq [H2O] = [H3O+] [A-] / [HA]
• pKa = - log Ka
• pKb = - log Kb
HA(aq)
H
A
Ka
H A
HA
(aq) (aq)
HA
pK a pH log
A
HA
pH pK a log
base
acid
pH pK a when A HA
-
If pH = pKa, [HA] = [A-]
If pH < pKa, [HA] > [A-]
If pH > pKa, [HA] < [A-]
Measurement of acidity and basicity
• pH: is a method of expressing the hydrogen ion
concentration [H+] or hydronium ion [H3O+] concentration
in solution. It is equal to the negative log of the molar
hydrogen concentration .
pH = -log[H+]
Sr. Acidity or
Substance Formula Ka pKa Kb pKb
No Basicity
• The amount of
H+ or OH-
• that buffered
solution can
• absorb without a
significant
• change in pH
• The plot of buffer capacity versus pH for
acetate buffer is represented below:
4.5
1. Boric acid
2. Hydrochloric acid
3. Dilute Hydrochloric acid
4. Sulphuric acid
5. Dilute Sulphuric acid
6. Phosphoric acid
Boric Acid
• Synonym: Biracic acid, orthoboric acid
• Formula: HH3BO3
• It is having NLT 99.5 % H3BO3
• Preparation:
• It is prepared from native borax and from borates by reacting
them with HCl / H2SO4.
• 1) in the laboratory, it is obtained by adding a mixture of
Conc. H2SO4 and water (1:5) to a boiling solution of Borax
(60gm in 160 ml of water).
Na2B4O7 + H2SO4 + 5H2O → Na2SO4 + 4H3BO3
• The solution is filtered and kept a side for crystallisation. The
crystals of boric acid are separated and then washed until
they become free from sulphate ions. Finally, they are dried at
room temperature.
Boric Acid
• Assay:
An accurately wieghed quantity of boric acid (2g) is dissolved in
a mixture of 50 ml of water + 100ml glycerin
• Storage:
• Must be stored in tightly closed containers as it absorbs
moisture and carbon dioxide.
Sodium Hydroxide
• Synonym: Caustic soda
• Formula: NaOH
• M. Wt: 40.00 gm
• It contains NLT 95 % of total alkali calculated as NaOH
including NMT 3% of Na2CO3.
• Preparation:
• It is obtained by the soda lime process in which sodium
carbonate is heated with milk of lime in large tanks.
Na2CO3 + Ca(OH)2 → CaCO3↓ + 2NaOH
• The product is removed immediately to disallow the reversal
of the reaction. The mother liquor is removed. Then, it is
filtered and evaporated and the mass is processed into flakes,
pellets or sticks.
• Assay:
An accurately quantity of NaOh (1.5g) is put in flask which is
already having 40 ml od Carbon free water
• Storage:
• Must be stored in tightly closed containers as it absorbs
moisture and carbon dioxide.
Potassium Hydroxide
• Formula: KOH
• M. Wt: 56.10 gm
• It contains NLT 85 % of total alkali calculated as KOH including
NMT 4% of K2CO3.
• Preparation:
• It is obtained by causticizing potassium carbonate with milk of
lime.
K2CO3 + Ca(OH)2 → CaCO3↓ + 2KOH
• The product is removed immediately to disallow the reversal
of the reaction. The mother liquor is removed. Then, it is
filtered and evaporated and the mass is processed into flakes,
pellets or sticks.
• Assay:
An accurately quantity of KOH (2g) is dissolved in 25 ml of water
• Storage:
• Must be stored in well closed containers.
• Great care has to be taken in handling hyroxide, because it is
highly destructive to tissue.