Chapter # 7 

Solution and electrolytes 

 
 
 
 
 
 
 
 
 Contents page 
● Concentration of solution 1
● Hydration 3
● Hydrolysis 4
● Arrhenius theory of ionization 4
● Conduction of electricity through solution 5
● Electrolysis 6
● Electrode potential 7
i) Standard electrode potential of Zinc 7
ii) Standard electrode potential of copper 8
● Electrochemical series (ECS) 9
● Oxidation number 9
● Oxidation-Reduction reactions (Redox reaction) 10
● Indicators 11
● pH 12
● Buffer solution 14
● Neutralization and types of salt 15
● Scientific explanation 15
Concentration of solutions 
Definitions
“The amount of solute dissolved in a specific amount of solvent ( or solution ) is known
as concentration of solution.”
The greater the amount of solute present, the more will be the concentration of solution.
Amount of solute
Concentration = volume
WAYS OF EXPRESSING CONCENTRATION
The most frequently used the concentration units are normally, molarity and molality ( or mole
fraction).
1. ​NORMALITY
Definition
“The number of gram equivalent of a solute dissolve per dm​3​ or litre of solution is known
as Normality.”
Symbol
Normality is usually represented by the symbol of N.
Unit
The unit or normality is gram equivalent/ litre.
Formulae
Gram equivalent of solute
Normality = V olume in litres or dm3
And
W eight of solute
Gram equivalent = Equivalent weight
Use
In volumetric titrations, the concentration of solutions is usually expressed in terms of
Normality.
2. ​MOLARITY
Definitions
“ The number of moles of a solute dissolved per dm​3​ or litre of a solution is known as
Molarity.”
Symbol
Molarity is represented by the symbol of M.
Unit
The unit of molarity is moles / dm​3​ or mole / litre.
Formula
N o. of moles of solute
Molarity = V olume in litres or dm3
Use
 For fairly dilute solutions where the volume changes are not very significant with
temperature changes, we can specify concentration in terms of molarity.
Explanation
40 grams of NaOH when dissolved in 1 litre of solution is 1 molar solution of NaOH.
3. ​MOLALITY
Definition
“ The number of moles of a solute dissolved per kilogram (Kg) of a solvent is known as
Molality.”
Symbol
Molality is usually represented by the symbol m.
Unit
The unit molality is moles / Kg
Formula
N o. of moles of solute
Molality = W eight of solvent in Kg
Use
When measurements are to be made over a wide range of temperature, the concentration
is expressed as molality.
Explanation
40 grams of NaOH when dissolved in 1 kg of solvent is 1 molal solution of NaOH.
MULTIPLE CHOICE QUESTION (MCQ)
The molarity of 0.2N solution of H​2​SO​4​ is
a) ​0.1M b) 0.3M c) 0.2 M d) 0.04M
Interconversion of Normality And Molarity
Molarity x Acidity or Basicity = Normality
⇒ M x 2 = 0.2
⇒ M = 0.2
2
⇒ M = 0.1
Important
S.I unit of concentration of solution is mole / m​3​.
Hydrating 
Definitions
“The process in which water molecules surround and interact with solute ions or
molecules is known as Hydrating.”
Explanation
When an ionic compound dissolves in water, it dissolves into ions. Water molecules due
to their polar nature interact and surround the ions. This surrounding of the ions by water
molecules is known as hydration.
FACTORS ON WHICH HYDRATION DEPENDS
The formation of hydrates depends upon the following factors.
1. Magnitude of the charge on the ion.
2. Size of the ion.
The charge density is the ratio of the charge on the ion to the size of the ion, i.e.
Charge on the ion
Charge Density = Size of the ion
IOn with the small and high charge will have high charge densities and are easily hydrated. In
ionic compounds, cations are usually smaller in size than anions, that is why water molecules
prefer to surrounded cations; e.g. CuSO​4​.5H​2​O , Cu​=2​ ions is surrounded by four water molecules
and only one to sulphate ion.
Among Al​+3​, Mg​+2​, and Na​+​ ; The Al​+3​ ​ion due to greater charge small size has a high charge
density and therefore forms hydrate easily.
Examples
CuSO​4​.5H​2​O , FeSO​4​.7H​2​O
Examples
CuSO​4​.5H​2​O , FeSO​4​.7H​2​O , BaCl​2​.2H​2​O etc -------- (Hydrates)
CuSO​4 + 5H​2​O -------> CuSO​4​.5H​2​O -------(Hydration)
hydrolysis 
Definition
“The reactions of cations and anions (or both) of the salt with water so as to change to its
pH is known as Hydrolysis.”
Explanation
Certain ionic salts when dissolved in water react with water molecules,so the bonds
between Hydrogen and Oxygen water are broken and the solution either becomes acidic or
alkaline. The interaction between an ion (or ion) of a salt and the ions of water ( H​+​ and​ ​OH​-​) is
known as Hydrolysis. It is the reverse of neutralization.
EXAMPLES
1. Alkaline Solution
a) pH increases.
b) Salt of weak acid - strong base.
Na​2​CO​3​ + 2HOH H​2​CO​3 + 2NaOH
Weak acid Strong base
2. Acidic Solution
a) pH decreases.
b) Salt of strong acid - weak base
NH​4​Cl + HOH NH​4​OH + HCl
Weak base Strong acid
3. Neutral Solution
a) pH remain same.
b) Salt of strong acid - strong base or weak acid - weak base
NaCl + H​2​O Na​+​ + Cl​-​ + H​+​ + OH​-
CH​3​COONH​4​ + H​2​O NH​4​-​ + CH​3​COO​-​ + H​+​ + OH​-

Arrhenius theory of ionization 

Introduction
To account for the behaviour of solutions of electrolytes and to explain the phenomenon
of electrolysis, ionic theory was put forward by ​Arrhenius ​in ​1880​.
Assumptions
1. When an acid , base or a salt dissolved in water, it splits into its ions. Positive ions are called
cations and negative ions are called anions.
HCl​(aq)​ H​+​(Aq)​ + Cl​-​(Aq)
NaOH Na​+​(Aq)​ + OH​-​(Aq)
NaCl​(aq)​ Na​+​(Aq)​ + Cl​-​(Aq)
2. The number of positive and negative charges on the ions that must be equal so that the
solution as a whole remains neutral.
3. Ionization is a reversible process, i.e the ions can reunite to form neutral molecules.
4. Ionization is not affected by electric current.
5. When electric current is passed through a solution of an electrolyte, cations move towards the
cathode and anions move towards the anode and get discharged.
6. The extent of ionization ( degree of dissociation ) depends upon
a) Nature of electrolyte.
b) Dilution of solution.
c) Temperature.
7. Electrical conductivity through solution depends upon:
a) Numbers of ions.
b) Speed of ions.

Conduction of electricity through solution 

The substance that can conduct electricity are called electrolytes. The electrical
conductivity of the electrolytes depends upon the number of ions present in a solution. The
conductance of the electricity through electrolytic solution depends upon the following factors.
1. Dilution. 3. Pressure
2. Absolute velocity of ions 4. Temperature
5. Degree of ionization
Dilution
Conductance increases with dilution.
Absolute Velocity Of Ions
Conductance increases with the increase in absolute velocity of ions.
Effect of Pressure
The pressure has no clear effect on the conductance.
Effect of Temperature
Generally on increasing the temperature by 1 °C,the conductance increases by 2 to 2.5 %.
Degree of Ionization
Conductance increases with the increase in degree of ionization ( Classification of
electrolytes) . The degree of ionization is determined by the following relation.
N o . of ionized particles
Degree of Ionization = T otal no. of dissolved particles
Electrolytes are classified as,
i) Strong electrolytes ii) Weak electrolytes

electrolysis 
QUESTION
Define Electrolysis. Write all the electrode reactions involved in the electrolysis of CuCl​2.​

Definition
“The movement of cations and anions towards their respective electrodes under the
influence of electric current with accompanying chemical reactions in an electrolytic cell is
known as electrolysis.”
Explanation
CuCl​2​ is composed of ions, it may precisely be represented by Cu​++​, Cl​-​ , Cl​-​. On
dissolving in water, these ions are separated.

CuCl​2 ​(aq)​ Cu​++​(Aq)​ + 2Cl​-​(Aq)

These ions are free to move around randomly among water molecules when no electric current is
passed. As soon as the electric current is passed, the movement of these ions begins to take place.
Cu​++​ ions migrate towards the cathode and Cl​-​ ions migrate towards the anode.
At cathode , Cu​++​ ions are discharged as copper atims by the gain of electrons (reduction).

Cu​++​ + 2e​-​ Cu --------- Reduction at cathode

-​
At anode Cl​ ions are discharged as Cl​2​ by the loss of electrons (oxidation).

2Cl​-​ Cl​2​ + 2e​-​ ---------- Oxidation at anode

Thus, the reaction taking place in the electrolytic cell are oxidation - reduction reaction or redox
reaction. By combining the electrode reactions, the overall reaction of electrolysis is obtained as,

CuCl​2​(aq)​ Cu​++​(Aq) + 2Cl​-​(Aq)​ Cu ​(s)​ + Cl​2 (s)

CuCl​2 (Aq)​ Cu ​(S)​ + Cl​2 (s)

When the lions originally present have been Charged to neutral particles,the current can no
longer flow.
Electrode potential 
Definition
“The Difference of potential created between a metal and solution of its salt is known as
electrode potential.” It is a measure of the tendency of an electrode go lose ( or gain ) electrons.
Explanation
Since absolute electrode potential cannot be measured, we measured only standard
electrode potential. Generally hydrogen is taken as standard. Arbitrarily, the electrode potential
of hydrogen is 0.00 volts.

Salt Bridge
It is prevents mixing of two solutions. It is used to complete the circuit.
Standard hydrogen Electrode (SHE)
A hydrogen electrode is made up of a platinum (Pt) plate immersed in 1M H​2​SO​4​ or HCl.
Pure hydrogen gas (H​2​) is passed continuously at 25 °C and 1 atm pressure. Pt absorb H​2​ gas on
its surface and it behaves as if it were made entirely of H​2​ . The electrode potential of hydrogen
is 0.00 volts.

Standard electrode potential of zinc ( z​n​)

Construction
A voltaic cell is constructed in order to measure the standard electrode potential of zinc . Voltaic
cell consists of Zinc and Hydrogen electrodes.
Zinc electrode is a strip of zinc immersed in 1M ZnSO​4​ solution and hydrogen electrode
is made up of Pt plate dipped in 1M H​2​SO​4​ or HCl. Pure hydrogen gas (H​2​) is passed
continuouly at 25 °C and 1 atm pressure. Pt absorb H​2 ​ gas on its surface and it behaves as if it
were made entirely of H​2​. Arbitrarily, the electrode potential of hydrogen is 0.00 volts.
Salt bridge is made up of KCl jelly. It function is to prevent the mixing of solution and to
complete the circuit.

Electrode Potential ( Cell voltage )

Potentiometer reading gives voltage of the cell which is 0.76V. Since the standard
electrode potential of hydrogen is ( zero ) 0.00V, therefore standard oxidation potential of zinc
0.76V.
Direction of flow of electrons
In external circuit, electrons flow from hydrogen to Zn electrode.Thus, Zinc is anode and is
negative with respect to hydrogen.

Equations
Zn ​(s)​ - 2e​ ​ Zn​+2​(Aq)​ , E°​Oxidation​ ​= 0.76V
Reduction take place at hydrogen electrode;
2H​+​ + 2e H​2 (g)​ , E°​Reduction​ ​= 0.00V
The cell reaction is, therefore, obtained by adding the half reaction;
Zn​ ​(s)​ + 2H​+​(Aq)​ Zn​+2​(Aq)​ + H​2 (g)
Thus the standard reduction potential of zinc electrode is -0.76V.
Zn​+2​(Aq)​ + 2e Zn​ (s)​ ; E°​Reduction​ ​= -0.76V

Zn | Zn​+2​(aq)​ ​ ( 1M ) H​+​(Aq)​ (1M) | H​2 (g)​ (1atm) ; Pt

Standard electrode potential of copper (c​u​) 
Construction
A voltaic cell is constructed in order to measure the standard electrode potential of Copper .
Voltaic cell consists of Copper and Hydrogen electrodes.
Copper electrode is a strip of copper immersed in 1M ZnSO​4​ solution and hydrogen
electrode is made up of Pt plate dipped in 1M H​2​SO​4​ or HCl. Pure hydrogen gas (H​2​) is passed
continuouly at 25 °C and 1 atm pressure. Pt absorb H​2 ​ gas on its surface and it behaves as if it
were made entirely of H​2​. Arbitrarily, the electrode potential of hydrogen is 0.00 volts.
Salt bridge is made up of KCl jelly. It function is to prevent the mixing of solution and to
complete the circuit.

Electrode Potential ( Cell voltage )

Potentiometer reading gives voltage of the cell which is 0.34V. Since the standard
electrode potential of hydrogen is ( zero ) 0.00V, therefore standard oxidation potential of copper
is +0.34V.
Direction of flow of electrons
In external circuit, electrons flow from hydrogen to Cu electrode.Thus, Copper is cathode and is
positive with respect to hydrogen.

Equations
Cu​+2​(Aq)​ + 2e​-​ Cu​ ​ ; E°​Reduction​ ​= +0.34V

H​+​(Aq)​ (1M) | H​2 (g)​ (1atm) ; Pt Cu | Cu​+2​(aq)​ ​ ( 1M )

Electrochemical series (ecs) 
Definition
“ The list of standard reduction potentials at 25 °C and 1 atm pressure is known as
Electrochemical Series (ECS).”
Interference from series
1. Metals above hydrogen in ECS show oxidation and act as anode in the cell; and metals below
hydrogen in ECS show reduction and act as cathode in the cell.
2. Lithium (Li) is the strongest reducing agent and Fluorine (F) is the strongest oxidizing agent.
3. In the ECS the metals are placed in the order of reactivity and shows the displacement order.
Metals displace metals lying below them in the list from solutions of their salts.
4. All metals above the hydrogen have negative electrode potentials.
Oxidation number 
Definition
“The apparent charge (formal charge), positive or negative , which an atom would have
in a compound is known as Oxidation number.”
● In the concept of oxidation number, all the compounds are imagined to be completely
ionic.
● In electrovalent compound, the oxidation number is equal to the charge on the ion.
Examples
● In MgCl​2​, the oxidation number of Mg = +2 and Cl = -1. In covalent compounds , the
electrons in each bond are assigned to the more electronegative atom.
● In H​2​O, the Oxygen is more electronegative than Hydrogen. Therefore, two electrons one
fom each atom are considered to be gained by Oxygen, giving rise to two negative
charges on Oxygen.
Oxidation number of O is -2 and H is +1.
Rules For Assigning Oxidation Number
1. The oxidation number of a free element is always zero.
E.g. N a0 , O02 , Br02 , P 0 .
2. The sum of oxidation number of all elements in an ionic compound or molecule is zero.
E.g. N a+1 Cl−1 , C −4 H 4+4 .
3. In a polyatomic ion, the sum of the oxidation number of the elements is equal to the charge on
the ion.
E.g. M nO4− , M n−7 O4+8 = ​- -7 + 8 = -
4. The oxidation number of H is +1 when combined with a non metal, e.g. H​+1​F​-1​ . When H is
combined with a metal it is -1 , e.g. Na​+1​H​-1​.
5. The oxidation number of O is -2 except in peroxides, H​2​O​2​ and F​2​O , where it is -1 and +2
respectively.
6. Group I , II , III elements show the oxidation number of +1 , +2 , and +3 respectively in their
compounds.
E.g. K​+1​Cl​-1​ , Ca​+2​F​-2​ , Al+3 Cl3−3 .
Oxidation - reduction reactions (r​edox ​r​eactions​)
Oxidation
“ A chemical process in which electrons are lost by an atom or ion is known as
Oxidation.”
OR
“ A chemical process in which oxidation number of an element is increased is known as
Oxidation.”
Example
Cu​0​ Cu​+2​ + 2e​- (Oxidation)
Reduction
“ A chemical process in which electrons are gained by an atom or ion is known as
Reduction.”
OR
“ A chemical process in which oxidation number of an element is decreased is known as
Reduction.”
Example
Cl​0​ + e​-​ Cl​- ( Reduction)
Oxidizing Agent
“The substance which reduces itself but oxidizes the others is known as Oxidizing Agent
(Oxidant).”
Reducing Agent
“The substance which oxidizes itself but reduces the others is known as Reducing
Agent.”
Redox Reaction
“The chemical reaction between the oxidizing agent and reducing agent is known as
Oxidation Reduction reaction or Redox reaction.”
Example

Indicators 
Definition
“ The organic substance which changes colour as the pH of the solution changes are
known as Indicators.”
The indicators are weak acids or bases.
Use
The end point of an acid - base titration is often denoted by means of an indicator.
( Table for MCQS )

Indicator Colour In Acid Colour In Base Colour When Neutral

Litmus Red Blue Purple

Methyl Orange Red Yellow Orange

Phenolphthalein Colourless Pink Colourless

Universal Indicator Red Purple Green

Behaviour (Mechanism) Of Indicator

It is a matter of fact that an unionized molecule of an indicator and its ion possess
different colours. One may be coloured and the other colourless.
Example
Hln (methyl orange indicator )dissociate to gives its anion ln​-​.
Hln H​+​ + ln​-
(Red) ( Yellow )
Undissociated molecular Hln, say is red and the anion ln​-​ yellow.
a) If [H​+​] is high, the equilibrium will shift to towards backward direction and the solution will
become red.
b) If [OH​-​] is high, the [H​+​] is reduced so the equilbrium will shift towards forward direction and
the solution will become yellow.
When thre is equal concentration of Hln and ln​-​ , the indicator will be in its neutral position and it
will appear orange.

pH
Introduction
The small value of the concentration of hydrogen ion (H​+​) that we have encountered with
solutions of slightly dissociated acid led ​Sorensan​ in ​1909 ​to introduc the conception of pH.
Definition Of pH
“ The pH of a solution is the negative logarithm of the hydrogen ion concentration.”
Formula
pH = -log [H​+​] = log [H1+ ]
Definition Of pOH
“ The pOH of a solution is the negative logarithm of the hydroxyl ion concentration.”
Formula
1
pOH = -log [OH​-​] = log [OH −
]
Amphoteric (Dual) Nature Of Water
Water acts as an acid as well as a base. For example , if we add NH​3​ to H​2​O , water acts
as a proton donor or acid forming N H 4+ . It also acts as a proton acceptor or base forming H​3​+​O,
if an acid is added to it.
H​2​O + N​..​H​3​ NH​4​+​ + OH​-
H​2​O + H δ + - Cl δ − H​3​+​O + Cl​-
Ionic Product Of Water
Careful measurements have shown that pure water ionizes slightly to produce ions of H​+
and OH​-​. Electrical conductance measurement of water at 25 °C have indicated the concentration
of 1.0x10​-7​M each of H​+​ and OH​-​. The ionic product of water is therefore,
K​w​ = [H​+​][OH​-​] = 1x10​-14​M.
Consider,
[H​+​][OH​-​] = 10​-14​ M.
Taking log and changing sign on both sides,
➔ -log ([H​+​][OH​-​]) = -log (10​-14​)
➔ (-log [H​+​]) + (-log[OH​-​]) = 14 log 10
pH + pOH = 14
Explanation
In acidic solution, the concentration of H​+​ is always greater than that of OH​-​ and in basic
solutions, the concentration of H​+​ is always less than that of OH​-​.
Thus for water in which [H​+​] = 1x 10​-7​ M.
pH = -log ( 1.0x10​-7​)
➔ pH = ( -log 1.0 ) + ( -log 10​-7​)
➔ pH = 0.00 + 7.00
pH = 7.00
The pH of 7.00 represents the point of neutrality. Clearly, acidic solutions will have pH values
which are less than 7, and basic solutions have pH values which are high .i.e greater than 7.
pH scale ( important for MCQs)
[H​+​] 10​0​ 10​1​ 10​2​ 10​3​ 10​4​ 10​5​ 10​6 10​-7 10​8​ 10​9​ 10​10​ 10​11​ 10​12​ 10​13​ 10​14​ M

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Acidic Neutral Basic
Thus, acidity is measured on a scale from 0 ( very acidic ) to 14 ( very alkaline ). This is the pH
scale. pH scale should be thought of simply as numbers which indicate acidity moles / dm​3​.
Universal Indicator
pH of a solution is determined using universal indicator. By mixing together various
indicators which change colour at slightly different acidities, chemical manufacturers have
developed a universal indicator which goes through a spectrum of colours as the acidity changes.
pH numbers are related to universal indicator colours as follows.
Red Orange Yellow Gree blue Deep blue Purple
0 3 6 7 8 10 14
pH of a solution can be determined by adding a few drops of universal indicator solution, the
reading off the pH number from the corresponding colour. Colour charts are provided by the
manufacturer for this purpose.
Glass Electrode pH Meter ( Digital pH Meter )
For more precise measurements, pH meters are available. These are used with a delicate
glass electrode which when dipped into a solution will give a direct reading of pH on the meter.
Some Common pH Values

Buffer solution 
Definition
“A solution which tends to resist changes in pH is known as a Buffer Solution.”
Examples
CH​3​COOH + CH​3​COONa = Buffer solution
(Acetic Acid) (SodiumAcetate)
NH​4​OH + NH​4​Cl = Buffer solution
(Ammonium Hydroxide) (AmmoniumChloride)
Functioning Of Buffer System (Solution) (Preparation Of Buffer Solution)
We can illustrate the functioning of a buffer system by the dissociation equilibrium of a
weak acid.
CH​3​COOH CH​3​COO​-​ + H​+
The buffer also contains the salt sodium acetate which is fully dissociated to give acetate ions.
CH​3​COONa CH​3​COO​-​ + Na​+
Due to increase in concentration of acetate ions, the acetic acid equilibrium is pushed towards
backward direction forming undissociated acetic acid. Even if small amounts of acid or alkali are
added, there is very little in pH of the mixture.
If Acid Is Added
In case of added acid, the additional H​+​ ions in the solution will combine with CH​3​COO​-
to produce undissociated acetic acid and pH will remain about original level.
CH​3​COO​-​ + H​+​ CH​3​COOH
If Base Is Added
Small amount of base ( NaOH ) added to buffer solution will be neutralized by reactions
with weak acid and pH will remain at about original level.
H​+​ + OH​-​ H​2​O

Neutralization and type of salt 

Definition
“When no substances (acid and base) having opposed properties are allowed to react, salt
and water are produced. This reaction is known as Neutralization.”
Examples
HCl + NaOH NaCl + H​2​O
(Acid) (Base) (Salt) (Water)
Salt
It is neutralized product of acid and base along with water.

Acidic Salts
Salts formed by the partial neutralization of acids and bases are known as acidic salts.
Example
H​2​SO​4​ + NaOH NaHSO​4​ + H​2​O
Basic Salts
Salts formed by the partial neutralization of bases and acids are known as basic salts.
Example
Mg(OH)​2​ + HCl Mg(OH)Cl + H​2​O
Neutral Salts
Salts formed by the complete neutralization of acids and bases are known as neutral salts.
Example
HCl + NaOH NaCl + H​2​O