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Crackiitjee - In: Various Concepts of Acids and Bases
Crackiitjee - In: Various Concepts of Acids and Bases
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Electrolytes when dissolved in water splits up into charged particles called ions. The
process is called ionisation or dissociation. Certain electrolytes such as NaCl, KCl, HCl are
almost completely ionised in solutions, whereas electrolytes such as NH 4OH, CH3COOH
etc. are weakly ionised. The electrolytes which are almost completely ionised in their
solutions are called strong electrolytes. On the other hand, electrolytes which are
weakly ionised in their solutions are called weak electrolytes. In case of solutions of
weak electrolytes, the ions produced by dissociation of electrolyte are in equilibrium
with undissociated molecules of the electrolyte. The equations for dissociation of strong
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electrolytes are written with only a single arrow directed to the right.
KCl(aq) K+ (aq) + Cl (aq)
NH4Cl(aq) NH4+ (aq) + Cl(aq)
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On the other hand, equations for the dissociation of weak electrolytes are written with
double arrows
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CH3COOH(aq) + H2O(l) H3O+ (aq) + CH3COO(aq)
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Acids such as HCl and HNO3 which are almost completely ionised in aqueous solution
are termed as strong acids whereas acids such as CH3COOH which are weakly ionised
are called weak acids .
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Similarly, bases which are almost completely ionised in aqueous solution are called
Strong bases, for example, NaOH and KOH. The bases such as NH4OH are only slightly
ionised are called weak bases. ee
According to Arrhenius theory, neutralisation of acids and bases is basically a reaction
between H+ and OH ions in solutions.
H + + OH H2O
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Nature of Hydrogen ion in aqueous solutions
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Hydrogen atom contains one proton and one electron. H + ion is formed by loss of this
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electron. Therefore H+ ion is simply a proton. Charge density of this unshielded proton is
very high. Therefore, it is not likely to exist as H+ ion. In an aqueous solution, H+ ion is
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Acids, such as hydrochloric acid, and bases, such as potassium hydroxide, that have a
great tendency to dissociate in water are completely ionized in solution; they are called
strong acids or strong bases.
Acids, such as acetic acid, and bases, such as ammonia, that are reluctant to dissociate
in water are only partially ionized in solution; they are called weak acids or weak bases.
Strong acids in solution produce a high concentration of hydrogen ions, and strong
bases in solution produce a high concentration of hydroxide ions and a correspondingly
low concentration of hydrogen ions.
The hydrogen ion concentration is often expressed in terms of its negative logarithm or
pH. Strong acids and strong bases make very good electrolytes, i.e., their solutions
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readily conduct electricity. Weak acids and weak bases make poor electrolytes.
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ACID-BASE NEUTRALISATION-SALTS
When aqueous solutions of hydrochloric acid and sodium hydroxide are mixed in the
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proper proportion, a reaction takes place to form sodium chloride and water.
HCl(aq) + NaOH(aqr) NaCl(aq) + H2O(l)
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Sodium chloride
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Such a reaction is termed neutralisation because both acidic (H +) and basic (OH-)
properties are eliminated during the reaction. The hydrogen ion, which is responsible
for the acidic properties, has reacted with the hydroxyl ion which is responsible for the
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basic properties, producing neutral water. The Na + and CI- ions have undergone no
chemical change and appear in the form of crystalline sodium chloride upon evapo-
ration of the solution. Sodium chloride is an example of the class of compounds called
salts.
HCl(aq) + Cl-(aq) + Na+(aq) H2O(l) + Na+(aq) + Cl-(aq)
or H+(aq) + OH-(aq) H2O(l)
Thus, the neutralisation of a base with an acid involves the interaction between OH - and
H+ ions.
or
The reaction between an acid and a base to form salt and water is termed
neutralisation.
The process of neutralization does not produce the resulting solution always neutral; no
doubt it involves the interaction of H+ and OH- ions. The nature of the resulting solution
depends on the particular acid and a particular base involved in the reaction. The
following examples illustrate this point when equivalent amounts of acids and bases are
reacted in aqueous solution.
(i) A strong acid plus a strong base gives a neutral solution because both are completely
ionised and the reaction goes to completion.
H+ + CI- + Na+ + OH- H2O + Na+ + CI-
(ii) A strong acid plus a weak base gives an acidic solution as the weak base is not
completely ionised. The reaction does not go to completion and there is an excess of
hydrogen ions in solution.
H+ + CI- + NH4OH H2O + NH4+ + Cl-
(iii) A weak acid plus a strong base gives a basic solution as the weak acid is not
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completely ionised. The reaction does not go to completion and there is an excess of
hydroxyl ions in solution.
CH3COOH + Na+ + OH- H2O + CH3COO- + Na+
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(iv) A weak acid plus a weak base gives an acidic or a basic or a neutral solution
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depending on the relative strength of acid and base. In case both have equal strength,
the resulting solution is neutral in nature.
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SALTS:
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Salts are regarded as compounds made up of positive and negative ions. The
positive part comes from a base while negative part from an acid. Salts are ionic
compounds. Salts may taste salty, sour, bitter, astringent or sweet or tasteless. Solutions
of salts may be acidic, basic or neutral. Fused salts and aqueous solutions of salts
conduct electricity and undergo electrolysis. The properties of salts in aqueous solutions
are the properties of ions. The salts are generally crystalline solids.
The salts are classified into the following classes:
1. SIMPLE SALTS
The salt formed by the neutralization process, i.e., interaction between acid and base, is
termed as simple salt. These are of three types:
a) Normal salts: The salts formed by the loss of all
possible protons (replaceable hydrogen atoms as H+) are called normal salts. Such a
salt does not contain either replaceable hydrogen or a hydroxyl group.
Examples are: NaCl, NaNO3, K2SO4, Ca3(PO4)2, Na3BO3, Na2HPO3 (one H atom is not
replaceable as H3PO3 is a dibasic acid), NaH2PO2 (both H atoms are not replaceable
as H3PO2 is a monobasic acid), etc.
b) Acid salts: Salts formed by incomplete neutralization of poly-basic acids are called
acid salts. Such salts still contain one or more replaceable hydrogen atoms. These
salts when neutralised by bases form normal salts.
Examples are: NaHCO3, NaHSO4, NaH2PO4, Na2HPO4, etc.,
c) Basic salts: Salts formed by incomplete neutralization of poly acidic bases are called
basic salts. Such salts still contain one or more hydroxyl groups. These salts when
neutralised by acids form normal salts.
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Examples are: Zn(OH)Cl, Mg(OH)Cl, Fe(OH)2Cl, Bi(OH)2Cl, etc.
2. DOUBLE SALTS
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The addition compounds formed by the combination of two simple salts are termed
double salts. Such salts are stable in solid state only.
Examples are: Ferrous ammonium sulphate, FeS0 4-(NH4)2SO4.6H2O, Potash alum,
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K2SO4Al2(SO4)3.24H2O, and other alums.
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Properties:
a) When dissolved in water, it furnishes all the ions present in the simple salts from
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3. COMPLEX SALTS
These are formed by combination of simple salts or molecular compounds. These
are stable in solid state as well as in solutions.
K4Fe(CN)6 + K2SO4
Simple salt Complex salt
CoSO4 + 6NH3 Co(NH3)6SO4
Simple salt Molecular Complex salt compound
In 1923, Bronsted and Lowry independently proposed new definitions for acids and
bases.
They proposed that: An acid is a substance that can donate a proton.
A base is a substance that can accept a proton.
These definitions are more general because according to these definitions even ions can
behave as acids or bases. Moreover, these definitions are not restricted to reactions
taking place in aqueous solutions only. In order to understand this concept of acids and
bases , consider some specific example :
HCl(aq) + H2 O(l) H3O+(aq) + Cl(aq)
acid base
NH4 (aq) + H2 O(l) H3O+(aq) + NH3(aq)
+
acid base
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H2 O(l) + NH3(aq) NH4+(aq) + OH(aq)
acid base
H2 O(l) + CO 3(aq) HCO3(aq) + OH(aq)
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acid base
From the above equations, it is obvious that acid base reactions according to Bronsted-
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Lowry concept involve transfer of proton from the acid to a base. A substance can act as
an acid only if another substance capable of accepting a proton is present.
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becomes an acid. For example, consider the reaction between water and ammonia as
represented by the following equilibrium:
In the forward reaction, water donates a proton to ammonia (base) and acts as acid. In
the reverse reaction NH4+ ions donate a proton to OH ions (base) and acts as acid. A
base formed by the loss of proton by an acid is called conjugate base of the acid,
whereas an acid formed by gain of a proton by the base is called conjugate acid of the
base. In the above example, OH ion is the conjugate base of H2O and NH4+ ion is the
conjugate acid of NH3 . Acid- base pairs such as H2 O OH and NH4+ NH3 which are
formed by loss or gain of proton are called conjugate acid-base pairs.
A strong acid would have large tendency to donate a proton. Thus, conjugate base of a
strong acid would be a weak base. Similarly, a conjugate base of a weak acid would be a
strong base.
Some more conjugate acid - base pairs has been given in the following equations:
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It may be noted that in equation
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a) H2O is behaving as a base whereas in equation
b) it is behaving as an acid. Similarly HCO3 ion in equation
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c) acts as an acid and in equation
d) it acts as a base. Such substances which act as acids as well as bases are called
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amphoteric substances.
In both Arrhenius and Bronsted concepts, acids are sources of protons. Hence all
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Arrhenius acids are also Bronsted acids. However, there is a difference in the definition
of bases. Arrhenius theory requires base to the source of OH ions in aqueous medium,
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but Bronsted theory requires base to be a proton acceptor. Hence Arrhenius bases may
not be Bronsted bases. For example, NaOH is a base according to Arrhenius theory
because it gives OH ions in aqueous solution, but NaOH does not accept proton as such.
Hence it may not be classified as a base according to Bronsted theory.
Strengths of acids and bases
Strength of an acid is measured in terms of its tendency to lose proton whereas strength
of a base is measured in terms of its tendency to accept proton. The conjugate base of a
strong acid is a weak base.
HCl(aq) + H2 O(l) H3O+(aq) + Cl(aq)
strong acid weak base
On the other hand, conjugate base of a weak acid is a strong base.
CH3COOH(aq) + H2O(l) H3O+ (aq) + CH3COO(aq)
weak acid strong base
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THE LEWIS ACIDS AND BASES
Although Bronsted-Lowry theory was more general than Arrhenius theory of acids and
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bases , but failed to explain the acid base reactions which do not involve transfer of
protons. For example it fails to explain how acidic oxides such as anhydrous CO 2 , SO2 ,
SO3 etc. can neutralise basic oxides such as CaO, BaO etc. even in absence of solvent.
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Lewis proposed a more general definition for acids and bases, which do not require the
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Acid-base reactions according to this concept involve the donation of electron pair by a
base to an acid to form a co-ordinate bond. Lewis bases can be neutral molecules such
as :
HA H+ + A-
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[ ][ ]
Ka =
[
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Higher the Ka, stronger is the acid
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BOH B+ + OH-
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[ ][ ]
Kb =
[ ]
For salts
SALT HYDROLYSIS
Pure water is a weak electrolyte and neutral in nature, i.e., H + ion concentration is
exactly equal to OH" ion concentration
[H+] = [OH-]
When this condition is disturbed by decreasing the concentration of either of the two
ions, the neutral nature changes into acidic or basic.
When [H+] > [OH-], the water becomes acidic and when [H+] < [OH-], the water acquires
basic nature. This is exactly the change which occurs during the phenomenon known as
salt hydrolysis. It is defined as a reaction in which the cation or anion or both of a salt
react with water to produce acidity or alkalinity.
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Salts are strong electrolytes. When dissolved in water, they dissociate almost
completely into ions. In some salts, cations are more reactive in comparison to anions
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and these react with water to produce H+ ions. Thus, the solution acquires acidic nature.
M+ + H2O MOH + H+
Weak base
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In other salts, anions may be more reactive in comparison to cations and these react
with water to produce OH- ions. Thus, the solution becomes basic.
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A- + H2O HA + OH-
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Weak acid
The process of salt hydrolysis is actually the reverse of neutralization.
Salt + Water Acid + Base
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If acid is stronger than base, the solution is acidic and in case base is stronger than acid,
the solution is alkaline. When both the acid and the base are either strong or weak, the
solution is generally neutral in nature.
As the nature of the cation or the anion of the salt determines whether its solution will
be acidic or basic, it is proper to divide the salts into four categories.
1. Salt of a strong acid and a weak base.
Examples: FeCl3, CuCl2, AlCl3, NH4Cl, CuSO4, etc.
2. Salt of a strong base and a weak acid.
Examples: CH3COONa, NaCN, NaHCO3, Na2CO3, etc.
3. Salt of a weak acid and a weak base.
Examples: CH3COONH4, (NH4)2CO3, NH4HCO3, etc.
4. Salt of a strong acid and a strong base.
Examples: NaCl, K2SO4, NaNO3, NaBr, etc.
It was pointed out by Ostwald that like chemical equilibrium, law of mass action van be
applied to such systems also.
Consider a binary electrolyte AB which dissociates into A + and B- ions and the
equilibrium state is represented by the equation:
AB A+ + B-
Initially t = o C 0 0
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At equilibrium C(1-) C C
So, dissociation constant may be given as
K = [A+][B-]/[AB] = (C * C)/C(1-)
= C2 /(1-)
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For very weak electrolytes,
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<<< 1, (1 - ) = 1
.. K = C2
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The law holds good only for weak electrolytes and fails completely in the case of strong
electrolytes. The value of '' is determined by conductivity measurements by applying
the formula /. The value of '' determined at various dilutions of an electrolyte
when substituted in Eq. (i) gives a constant value of K only in the case of weak
electrolytes like CH3COOH, NH4OH, etc. the cause of failure of Ostwald's dilution law in
the case of strong electrolytes is due to the following factors"
I. The law is based on the fact that only a portion of the electrolyte is dissociated
into ions at ordinary dilution and completely at infinite dilution. Strong
electrolytes are almost completely ionized at all dilutions and / does not give
accurate value of ''.
II. When concentration of the ions is very high, the presence of charges on the ions
appreciably effects the equilibrium. Hence, law of mass action its simple form
cannot be strictly applied in the case of string electrolytes.
SOME EXAMPLES
K = 2/(1-)V
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= 0.05, V = 1/0.01 = 100 litres
Hence,
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Ka = 0.05 * 0.05/ (1-0.05)100 = 2.63 * 10-5
Example 2: Calculate the H+ ion concentration of a 0.02 N weak monobasic acid. The
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value of dissociation constant is 4.0 10-10.
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Solution: HA H+ + A-
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= kaV
BUFFER SOLUTIONS
For several purposes, we need solutions which should have constant pH. Many
reactions, particularly the biochemical reactions, are to be carried out at a constant pH.
But it is observed that solutions and even pure water (pH = 7) cannot retain the constant
pH for long. If the solution comes in contact with air, it will absorb CO 2 and becomes
more acidic. If the solution is stored in a glass bottle, alkaline impurities dissolve from
glass and the solution becomes alkaline.
A solution whose pH is not altered to any great extent by the addition of small
quantities of either an acid (H+ ions) or a base (OH- ions) is called the buffer solution. It
can also be defined as a solution of reserve acidity or alkalinity which resists change of
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pH upon the addition of small amount of acid or alkali.
General characteristics of a buffer solution
a. It has a definite pH, i.e., it has reserve acidity or alkalinity.
b. Its pH does not change on standing for long.
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c. Its pH does not change on dilution.
d. Its pH is slightly changed by the addition of small quantity of an acid or a base.
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i. CH3COOH + CH3COONa
ii. Boric acid + Borax
iii. Phthalic acid + Potassium acid phthalate
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2. by mixing a weak base with its salt with a strong acid, e.g;
i. PNH4OH + NH4Cl
ii. Glycine + Glycine hydrochloride
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effect in the overall H+ ion concentration or pH value.
When a drop of NaOH is added, it will react with free acid to form undissociated
water molecules.
CH3COOH + OH- CH3COO- + H2O
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Thus, OH- ions furnished by a base are removed and pH of the solution is
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practically unaltered.
B. Basic buffer:
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Consider the case of the solution containing NH4OH and its salt NH4Cl. The
solution will have NH4OH molecule, ions, Cl- ions, OH- ions and H+ ions
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When a drop of NaOH is added, the added OH- ion combine with NH4 ions to
form feebly ionised NH4OH whose ionisation is further suppressed due to
common ion effect. Thus pH is not disturbed considerably.
NH4 + OH- NH4OH
(From strong base)
When a drop of HCl is added, the added H+ ions combine with NH4OH to form
undissociated water molecules.
NH4OH + H+ NH+4 + H2O
(From strong acid)
Thus pH of the buffer is practically unaffected.
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Base Buffer (NH4OH + NH4Cl) ee
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