Ionic Equilibrium

Auto-ionisation of water, pH
& pOH, Acid-base concept in
non-aqueous medium
 Molecular Structure and
Acid Strength
• Consider polyprotic (more than one ionizable
proton) acids and their corresponding anions.

– Each successive H atom becomes more difficult to remove

(species is negatively charged therefore harder to pull
positive proton off).
– Therefore the acid strength of a polyprotic acid and its
anions decreases with increasing negative charge.
2 
HPO 4 < H 2 PO 4 < H 3 PO 4
weakest strongest
2
 Autoionization of Water
• Self-ionization is a reaction in which two like
molecules react to give ions (amphiprotic
therefore can react with self)
– In the case of water, the following equilibrium is
established.
H 2O ( l )  H 2O ( l ) H 3O  ( aq )  OH  ( aq )
– The equilibrium-constant expression for this
system is:  
[ H 3O ][OH ]
Kc  2
[ H 2O ]
3
4
Self-ionization of Water

– The concentration of ions is extremely

small (equal lies to far left), so the
concentration of H2O remains essentially
constant. This gives:
 
[ H 2O ] K c  [ H 3O ][OH ]
2

constant

5
 Self-ionization of Water
H 2O ( l )  H 2O ( l ) H 3O  ( aq )  OH  ( aq )

– We call the equilibrium value for the ion product

[H3O+][OH-] the ion-product constant for water,
which is written Kw.
 
K w  [ H 3O ][OH ]
– At 25 oC, the value of Kw is 1.0 x 10-14.
– Like any equilibrium constant, Kw varies with
temperature. Kw means water + water and basis
of acid/base scale in aqueous solutions

6
 Self-ionization of Water
– Because we often write H3O+ as H+, the ion-
product constant expression for water can be
written:
 
K w  [ H ][OH ]
– Using Kw you can calculate the concentrations of
H+ and OH- ions in pure water.

H 2O ( l )  H 2O ( l ) H 3O  ( aq )  OH  ( aq )
x x

  14
K w  [ H 3O ][OH ]  ( x)( x)  1.00 x10
7
 Self-ionization of Water
• These ions are produced in equal numbers in
pure water, so if we let x = [H+] = [OH-]
 14
1 . 0  10 x 2 o
at 25 C
x  1 .0  10  14  1 .0  10  7 M  [ H 3 O  ]  [ OH  ]

– Thus, the concentrations of H+ and OH- in pure

water are both 1.0 x 10-7 M. Baseline for what we
call a neutral solution with water as solvent.
– If you add acid or base to water they are no longer
equal but the Kw expression still holds. One goes
up other goes down to keep product equal to Kw
8
 Solutions of Strong Acid or
Base
• In a solution of a strong acid you can
normally ignore the self-ionization of water as
a source of H+(aq). You have the self
ionization equal and the strong acid
ionization; however one drop of strong acid
ionizes 100% and typically produces far
greater amount of hydronium ion than that
produced
– The H+(aq)from water itself.
concentration is usually determined by the
strong acid concentration.
– However, the self-ionization still exists and is
responsible for a small concentration of H3O+ ion but
we typically neglect it.
9
 Solutions of Strong Acid or
Base
• By dissolving substances in water, you can
alter the concentrations of H+(aq) and OH-(aq).

– In a neutral solution, the concentrations of H+(aq) and

OH-(aq) are equal, as they are in pure water.
[ H 3 O  ]  [ OH  ]  1 . 0  10  7 M
– In an acidic solution, the concentration of H+(aq) is
greater than that of OH-(aq).
[ H 3 O  ]  1 . 0  10  7 M  [ OH  ]
– In a basic solution, the concentration of OH-(aq) is
greater than that of H+(aq).
[ H 3 O  ]  1 . 0  10  7 M  [ OH  ]
10
Solutions of Strong Acid or
Base
• At 25°C, you observe the following
conditions.
– In an acidic solution, [H ] > 1.0 x 10 M.
+ -7

– In a neutral solution, [H+] = 1.0 x 10-7 M.

– In a basic solution, [H+] < 1.0 x 10-7 M.

Realize these definitions for acid/base/neutral

solutions is based as water as solvent. If
different solvent or temperature, the
concentration would be different.

11
 pH
• Although you can quantitatively describe the acidity of a
solution by its [H+], it is often more convenient to give
acidity in terms of pH (power/potential of the hydrogen
ion). Easier to see larger value: 10-7 vs 10-8

– The pH of a solution is defined as the negative logarithm of the

molar hydrogen-ion concentration.


pH   log[ H ]
– Basically changing 1.0 x 10-7 M to log scale.
1.0 number indicates where between the 10-6 and 10-7 --> 7.00

12
 The pH of a Solution
• For a solution in which the hydrogen-ion
concentration is 1.0 x 10-3 M, the pH is:
3
pH   log(1.0  10 )  3.00
– Note that the number of decimal places in the pH
equals the number of significant figures in the
hydrogen-ion concentration.

note: [H3O+] pH

13
 The pH of a Solution
• In a neutral solution, whose hydrogen-ion
concentration is 1.0 x 10-7 M, the pH =
7.00.

• For acidic solutions, the hydrogen-ion concentration is

greater than 1.0 x 10-7 M, so the pH is less than 7.00.

• Similarly, a basic solution has a pH greater than 7.00.

14
Figure : The pH Scale

Ebbing, D. D.; Gammon, S. D. General

Chemistry, 8th ed., Houghton Mifflin, New
15York, NY, 2005.
 A Problem to Consider
• A sample of orange juice has a hydrogen-ion
concentration of 2.9 x 10-4 M. What is the
pH?

pH   log[ H ]
4
pH   log( 2.9  10 )
pH  3.54

16
 A Problem to Consider
• The pH of human arterial blood is 7.40. What is
the hydrogen-ion concentration?
• calculator 2nd function log
[H+] = 10-pH

[ H ]  anti log(  pH )

[ H ]  anti log(  7.40 )
  7.40 8
[ H ]  10  4.0  10 M

17
 pOH
• A measurement of the hydroxide ion concentration,
similar to pH, is the pOH.
– The pOH of a solution is defined as the
negative logarithm of the molar hydroxide-ion
concentration.
pX   log[ X ]

pOH   log[OH ]
  pOH
[OH ]  10
18
 The pH of a Solution
– Using Kw = [H+][OH-] = 1.0 x 10-14 at 25 oC, we can
show another important eq
K w  1.0 x10 14  [ H  ][OH  ]
log K w  log1.0 x10 14  log[ H  ][OH  ]  log[ H  ]  log[OH  ]
 log K w   log1.0 x10 14   log[ H  ]  (  log[OH  ])
pK w  14.00  pH  pOH
[ H  ]  10  pH
[OH  ]  10  pOH
pH   log[ H  ]
pOH   log[OH  ]
K19w  [ H 3O  ][OH  ]  1.00 x10 14
 pH Scale
• Note that although Kw may change with
temperature, the variations in pH with
temperature are so small that we often ignore
it.
• pKw is a very important quantity for aqueous
solutions and controls the relative
concentrations of hydrogen and hydroxyl ions
as their product is a constant.
• It should be noted that as the pH scale is
logarithmic, a change in pH by just one unit
also means change in [H+] by a factor of 10.
• Similarly, when the hydrogen ion
concentration, [H+] changes by a factor of 100,
the value of pH changes20
by 2 units. Now you
can realise why the change in pH with
 pH Scale
• Measurement of pH of a solution is very
essential as its value should be known when
dealing with biological and cosmetic
applications.
• The pH of a solution can be found roughly with
the help of pH paper that has different colour
in solutions of different pH.
• For greater accuracy pH meters are used.
• pH meter is a device that measures the pH-
dependent electrical potential of the test
solution within 0.001 precision.
21
 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

pH (indicator) paper pH meter

22
A Problem to Consider
• An ammonia solution has a hydroxide-ion
concentration of 1.9 x 10-3 M. What is the pH of
the solution?
You first could calculate the pOH:
pOH   log(1 . 9  10  3 )  2 . 72
Then the pH is: pH  14.00  2.72  11.28
Optional way:

23
 The pH of a Solution

• The pH of a solution can accurately be

measured using a pH meter.

– Although less precise, acid-base indicators are

often used to measure pH because they usually
change color within a narrow pH range.

24
 pH of Strong Acids or Bases
• Calculate the [ H3O+],[OH- ], pH, and pOH in
0.10 M HCl.

0.10 M

25
 Calculating [H3O+] and [OH-] in an aqueous solution

A research chemist adds a measured amount of HCl gas

to pure water at 25 oC and obtains a solution with [H3O+]
= 3.0 x 10-4 M. Calculate [OH-]. Is the solution neutral,
acidic or basic?
PLAN: Use the Kw at 25 oC and the [H3O+] to find the
corresponding [OH-].
SOLUTION: Kw = 1.0 x 10-14 = [H3O+] [OH-]

[OH-] = Kw/ [H3O+] = 1.0 x 10-14/3.0 x 10-4 = 3.3 x 10-

11 M

[H3O+] > [OH-]; the solution is

acidic.
26
•Ex. Calculate the [ H3O+],[OH- ], pH, and pOH in solution
prepared by dissolving 10.0g of Ba(OH)2 per liter.
10.0 g 1 mol
[ Ba (OH ) 2 ]  x  0.0584M
1.0 L 171.3 g

0.0584 M 2(0.0584 M)

[OH  ]  2(0.0584)  0.117M

pOH   log[ OH  ]   log[ 0.117]  0.932

pH  14.00  pOH  14.00  0.932  13.07

[ H  ]  10 pH  1013.07  8.5x1014 M

27
 Acid-base concept in non-aqueous
media
• The protonic is definition of acid and bases given by
Bronsted can be extended to the reactions occurring
in non aqueous solvent containing hydrogen
(NH3,N2H4, HF, H2SO4, CH3COOH, HCN and
alcohol).
• According to Cady and Elsey, an acid is a solute that,
either by direct association or by reaction with the
solvent, gives the anion characteristic of the solvent
and a base is a solute that either by direct
association or by reaction with the solvent give the
cation characteristic of the solvent.
• If, for example, we consider the solvent H2O, its
characteristic cation and anion are H3O+ and OH-
respectively as shown below:
𝐻Acid Acid + Base −
2 𝑂 + 𝐻2 𝑂 ⇄ 𝐻3 𝑂 + 𝑂𝐻
Base
28
 Acid-base concept in non-aqueous
media
• Thus all those compounds which can give
H3O+ ion in H2O will act as acids and all
those compounds which can give OH- ions
in H2O will behave as bases.
• Similarly in N2O4 as solvent, substance such
as NOCl which yield NO+ ions are acids and
the substance such as NaNO3 which yield
NO3- ions are bases.
Acid Base Acid Base

𝑁2 𝑂4 + 𝑁2 𝑂4 ⇄ 2𝑁𝑂 + + 2𝑁𝑂3−
• Evidently this definition of acids apply
equally well to protonic and non protonic
solvent 29
 Acid-base concept in non-aqueous
media

Auto-ionisation of some protonic and non-protonic

solvents

30
 Acid-base concept in non-aqueous
media

• Just as with the Arrhenius definition,

neutralization reaction between an acid
and a base to produce a salt and the
solvent.
• Neutralization reaction in some non-
aqueous solvents are given below:

𝐼𝑛 𝐻2𝑂 ∶ 𝐻𝐶𝑙 + 𝑁𝑎𝑂𝐻 ⇌ 𝑁𝑎𝐶𝑙 + 𝐻2𝑂

31
Acid-base concept in non-aqueous
media

32
 Acid-base concept in non-aqueous
media

Acidic character of acetic acid in water and

liquid ammonia
 When acetic acid reacts with water and liquid
ammonia (solvents), water and liquid ammonia both
accept a proton from CH3COOH to produce H3O+ and
NH4+ ions.
 Due to the production of these ions CH3COOH
behaves as an acid in both the solvent

33
 Acid-base concept in non-aqueous
media
Acidic character of acetic acid in water and liquid ammonia

• Now since the proton accepting ability of H2O is

less than that of liquid ammonia, CH3COOH
behaves as weak acid in aqueous solution and
act as a strong acid in liquid ammonia.

34
 References
• NCERT, Class IX Chemistry
• Satyarakash’s Modern Inorganic
Chemistry – R. D. Madan, S. Chand
Publication, 2002.

35