ACID , BASE , PH

 There are two concepts of acids and bases in current use :-

a) Arrhenius concept
b) Bronsted-Lowry concept
c) Lewis concept
Arrhenius concept
Svante August Arrhenius (1884) proposed his concept of acids and bases . This
theory is also known as classical or old theory. According to this concept, an
acid is a compound that releases H+ ions in water ; and a base is a compound
that releases OH- ions in water .

For example, HCl is an Arrhenius acid and NaOH is an Arrhenius base.

HCl (aq)→ H+(aq)+Cl-(aq)
NaOH (aq) → Na+(aq)+OH-(aq)
Limitations of Arrhenius concept:- Arrhenius concept of acids and bases proved
to very useful in the study of chemical reactions .

I. Free H+ and OH- ions do not exist in water :

The H+ and OH- ions are produced by acids and bases. Respectively do not exist
in water in the free state. They are associated with water molecules to form
complex ions through hydrogen bonding .Thus the H+ ion forms a hydronium
ion:

Similarly, OH- ion forms the complex H3O2- .

II. Limited to water only :-Arrhenius defined acids and bases as compounds
producing H+ and OH- ions in water only .But a truly general concept of acids
and bases should be appropriate to other solvent as well .
For example, HCl is acid only in water ,no other solvent like Benzene (C6H6) or in
gaseous state .

III. Some bases do not contain OH-:-According to Arrhenius, base is one that
produces OH- ions in water .Yet, there are some compounds like CaO , Na2CO3,
PH3 etc. that are bases but contains no OH- ions.

IV. Some Chemical compounds have OH- ions in their original formulation
but do not work as base.

V. Some compounds have Hydrogen in their molecular formula but does not
shows acidic character .Example, CH4

VI. This concept cannot explain the acidic character of certain salts like AlCl 3;
In aqueous solution.

Bronsted - Lowry concept or Protonic theory or Modern theory

In 1923, J.N Bronsted and J.M Lowry independently proposed a broader concept
of acids and bases .According to this theory ,

 An acid is ,any molecule or ion that can donate a proton (H+)

Example, Molecule → HCl, HBr
Cation → NH4+,H3O+
Anion → HSO4-, HCO3-
(Bi sulphate) (Bi carbonate)

 A base is any substance or ion that can accept a proton (H+)

Example, Molecule → NH3 ,H2O
Cation → [Fe(H2O)5OH]2+ [Pentaaquahydroxy Iron(III) ion]
Anion → Cl-, Br-,OH-,CO32
For brevity we can say that , an acid is a proton donor while a base a proton
acceptor.
Examples of Bronsted acids and bases :-

I. HCl gas and H2O: When dry HCl gas dissolves in water, each HCl molecule
donates a proton to a water molecule to produce hydronium ion .
Thus, HCl gas is Bronsted Acid and H2O that accepts a proton is a Bronsted Base
II. HCl and NH3 : HCl reacts with NH3 to form solid NH4Cl.

HCl is a proton donor and hence a Bronsted Acid while NH3 is a Proton acceptor
and a Bronsted Base.

III. Cao and H2O : When CaO is dissolves in water, it is converted to Ca(OH)2.
Here a water molecule donates a proton to oxide ion (O2-) and becomes
Bronsted Acid . The oxide ion accepts a proton and gives 2(OH-) ions hence, is a
Bronsted Base.

Bronsted Lowry’s concept is superior to Arrhenius concept :

1. Much wider scope: Arrhenius concept of acids and bases is restricted to the
study of substance which can release H+ or OH- ions in water, but in Bronsted
Lowry concept includes all molecules and ions that can donate a proton (H+) and
those who can accept a proton (Base).
2. Not limited to aqueous solutions : The Bronsted Lowry theory is not limited
to aqueous solutions as is the case of with Arrhenius theory . It can be extended
to the gas phase !

3. Release of OH- not necessary to qualify as a base in Bronsted Lowry theory

release of OH- is not necessary to qualify as a base but in Arrhenius it is
necessary .
NH3 + H+ → 𝑁𝐻4 +
4. The idea of conjugate acid base is absent in Arrhenius theory but given and
present in Bronsted Lowry theory
Limitations:
1. To act as acid/base molecules must have proton or H+.
2. According to this theory without transferring proton no substance can act as
either acid or base; but there are many substances acts as an acid or base don’t
transfer or exchange proton .Example, CuSO4(acid), CaO etc.

Conjugate Acid-Base pairs

In an Acid-Base reaction the acid (HA) gives us its proton (H+) and produces a
new base (A-). The new base that is related to the original acid is called a
conjugate base. Similarly the original base (B-) after accepting a proton (H+)
gives a new acid (HB) which is called a conjugate acid.

Example 1, let us consider the reaction between HCl(aq) & NH3(aq) :-

 In the reaction Cl-(base) has formed by the loose of one proton H+ form HCL
and is called the conjugate of HCL .This HCL and CL- is a conjugate acid
base pair Similarly, if we consider the reverse reaction in NH3(base) formed
by the loose of one proton (H+) from NH4+(acid) and is called the Base of
conjugate Acid. Thus NH4+ and NH3 is another or the second Acid-Base
conjugate pair.
Example 2 :Now, let us consider the reaction between Acetic Acid (CH3−COOH)
and water(H2O) to form conjugate base CH3−COO- and the conjugate acid H3O+ :

A weak acid (CH3−COOH) produces a strong conjugate base (CH3−COO-) and a

weaker base (H2O) gives a stronger acid (H3O+)

Classes of Bronsted acids and bases

Bronsted Acids:-
1. Monoprotic Acids: Which are capable of donating one proton only.
Example,
A. HF→H++F-
B. CH3−COOH→ CH3−COO-+ H+
2. Polyprotic Acids: Which are capable of donating two or more protons.
Example: H2SO4,H3PO4,H2CO3 etc.
A. H2O→2H++S2-
B. COOH−COOH→2H++ COO-− COO-
Similarly, there are Bronsted Bases:-
1. Monoprotic Bases: Which are accept one proton.
A. HS-+H+ → H2S
B. H20+H+→ H3O+
2. Polyprotic Bases: Which can accept two or more protons. Example,
A. SO42-+2H+→H2SO4
B. PO43-+3H+→H3PO4
 Lewis concept of Acids and Bases
In the early 1930s, G.N. Lewis proposed even a more general model of acids and
bases. According to Lewis theory,
 “An acid is an electron-pair acceptor”
 “A base is an electron-pair donor”

 Examples of Lewis reactions:

1. Between H+ and NH3:-

2. Between H+ and OH- :-

3. Between BF3 and NH3 :-

4. Hydration of Al3+ :-
 Superiority of Lewis concept on Arrhenius
1. Arrhenius theory is dependent on solvent ,but Lewis theory is independent on
solvent.
2. To act as an acid H+ lon must contained by the compound in Arrhenius theory;
but not in Lewis theory.
3. To act as a base the compound or molecule must contain OH- ion in Arrhenius
theory; but it is not necessary in Lewis theory.
4. Acids-Bases determinator of many compound in Arrhenius theory may be do
do not prove by other theory but may easily prove in lewis theory.
Example:- AlCl3 .

The PH of Solutions
The term pH was first described by Danish biochemical Sorensen in 1909. PH is
an abbreviation for “power of hydrogen” where P is short for the German word
for power, poten3 and H is the element symbol for hydrogen.

The pH of a solution is a measure of the molar concentration of hydrogen

ions in the solution and as such is a measure of the acidity or basicity of the
solution. It is define as the negative of the base -10 logarithm (log) of the H+
concetration mathematically it may be expressed as :−
PH = −𝒍𝒐𝒈 [𝑯+ ] {where [H+] is the concentration of hydrogen ions
𝟏 𝒎𝒐𝒍
Or, PH = 𝒍𝒐𝒈 In mols per liter or, M or, }
[𝑯+ ] 𝐿
[𝐇 + ] = 𝟏𝟎 −𝑷𝑯

Measurement of (pH)
The pH is usually measured with a pH meter, which translates into pH readings
the difference in electromotive force (Electrical potential or Voltage) between
suitable electrodes paced in the solution to be tested. Fundamentally, a p H
meter consists of a voltmeter attach to a pH responsive electrode and a
reference electrode. The pH responsive electrode is usually glass and the
reference is usually a mercury-mercuries chloride (calomel) electrode, although
a silver-silver chloride are immersed in a solution, they act as a battery. The
glass electrode develops an electric potential (charge) that is directly related to
the hydrogen ion activity in the solution and the voltmeter measures the
potential difference between the glass and reference electrodes.
“By using pH paper indicator that turns color corresponding to a pH on a color
key.”
pH Scale
The scale on which pH values are computed is called the pH scale. In order to
express the hydrogen ion concentration or acidity of a solution. A pH scale was
evolved. The pH is defined as :−
PH = −𝒍𝒐𝒈 [𝑯+ ]
𝟏
Or, PH = 𝒍𝒐𝒈 +
[𝑯 ]
H
These p values were computed on a scale taking water as the reference
substance. Water dissociates to [H+] and OH- ions to a very small degree. So
that,

………………………..(1)
We can write the equilibrium express ion as,
+ −]
K= [𝑯 [𝐻][OH
𝑂]
……………………………. (2)
2

Since water is so little dissociated, the concentration of un dissociated

molecules [H2O], is presumed to constant. So, from the equation (2):−
[H+]×[OH-]=K[H2O]=Kw=(A CONSTANT)

Where Kw is called the water dissociation constant or water ionization

constant. Where the concentration of H+ and OH- ions in water are expressed in
mole per liter. The value of Kw found experimentally is 𝟏. 𝟎 × 𝟏𝟎−𝟏𝟒 .
From the equation (1) it is obvious that one molecule of water dissociates
to give one H+ and one OH- in pure water is equal.
From equation (3), [𝐻 + ][𝑂𝐻 − ] = √𝐾𝑤 = √1.0 × 10−14
∴ [𝐻 + ] = [𝑂𝐻 − ] = 1.0 × 10−7 𝑚𝑜𝑙/𝐿
Thus the H+ ion and OH- ion concentrations in pure water are both
10−7 𝑚𝑜𝑙/𝐿 at 25℃ and it is said to be neutral. On this scale value range from 0
to 14. All solutions having pH less than 7 are Acidic and those with pH greater
than 7 are
Basie. “So pH decreases with the increases of [H+]. The lower the pH, higher is
the [H+] or acidic.