ELECTROLYTES

Electrolyte is any substance that give ions when dissolved in water, that make the substance electrically conductive. These ionic solutions conduct electricity due to the mobility of the positive and negative ions, which are called cations and anions respectively.

ARRHENIUS THEORY OF ELECTOLYTIC DISSOCIATION

1.

An electrolyte, when dissolved in water, breaks up into two types of charged particles, one carrying a positive charge and the other a negative charge. These charged particles are called ions. Positively charged ions are termed cations and negatively charged as anions. AB --> A+ + BNaCl --> Na+ + ClK2SO4 --> 2K++ SO42-

2. The process of splitting of the molecules into ions of an

electrolyte is called ionization.The fraction of the total number of molecules present in solution as ions is known as degree of ionization or degree of dissociation. It is denoted by

Degree of ionization ( )
Number of dissociated molecules E! Total number of molecules of electrolyte before dissociation Number of dissociated molecules E % ! v 100% Total number of molecules of electrolyte before dissociation nearly 1 = strong electrolytes (0 < < 1) = weak electrolytes 0 = non-electrolytes the degree of dissociation concentration decreases with the increase of

Vant Hoff factor ( i )

i ! 1  (n  1)E )
n = number of ions = degree of dissociation i = the factor which is defined as the i ratio of the observed colligative property produced by the given concentration of electrolytic solution to the colligative property produced in the solution of non-electrolytes as the same concentration.

3. for weak electrolytes : Ions present in solution constantly re-unite to form neutral molecules and, thus, there is a state of dynamic equilibrium between the ionized and the non-ionized molecules, i.e., AB A+ + BApplying the law of mass action to above equilibrium [A+ ][B- ] /[AB] =K

4. When an electric current is passed through the electrolytic solution, the positive ions (cations) move towards cathode and the negative ions (anions) move towards anode and get discharged, i.e., electrolysis occurs.
Reaction at Catode 1. Ions from group IA, IIA, Al3+ ,Mn2+ 2H2O + 2e 2OH- + H2 2. Ions from other metals Mn+ + ne M 3. Ion H+ (acid) 2H+ + 2e H2 Reaction at Anode 1. Ions like SO42-, NO32H2O 4H+ + 4e +O2 2. Ions F- , Cl- , Br- , I2XX2 + 2e 3. Ion OH- (base) 4OH2H2O + 4e + O2

Electrolysis of sodium chloride solution: NaCl <--> Na+ + ClH2O <--> H+ + OHAt catode At Anode H+ + e- --> H Cl- --> Cl + e2H --> H2 2Cl --> Cl2 Electrolysis of copper sulphate solution using platinum electrodes: CuSO4 <--> Cu2+ + SO42H2O <--> H+ + OHAt catode At Anode Cu2+ + 2e- --> Cu 2OH- --> H2O + O + 2e-

5. The electrolytic solutions is always neutral in nature as the total charge on one set of ions is always equal to the total charge on the other set of ions. However, it is not necessary that the number of two sets of ions must be equal always. AB <--> A+ + B(Both ions are equal) NaCl <--> Na+ + Cl(Both ions are equal) AB2 <--> A2+ + 2B(Anions are double that of cations) BaCl2 <--> Ba2+ + 2Cl(Anions are double that of cations) A2B <--> 2a+ + B2(Anions are double that of cations) Na2SO4 <--> 2Na+ + (Anions are double that of cations)

6. The properties of electrolytes in solution are the properties of ions present in solution. For example, acidic solution always contains H+ ions while basic solution contains OH- ions and characteristic properties of solutions are those of H- ions and OH- ions respectively.

7. The ions act like molecules towards depressing the freezing point, elevating the boiling point, lowering the vapour pressure and establishing the osmotic pressure. 8. The conductively of the electrolytic solution depends on the nature and number of ions as the current is carried through solution by the movement of ions.

DEBYE HUCKEL THEORY OF INTERIONIC ATTRACTION

I. I.

The strong electrolytes is completely ionized at all dilution Anions and cations are not uniformly distributed in a solution of an electrolyte but that the cations tend to be found in the vicinity of anions and vice versa. Decrease in equivalent conductance with increase in concentration is due to fall in mobilities of the ions due to greater interionic effect and vice versa . the ratio of equivalent conductance at given concentration to the equivalent conductance at infinite dilution Pv does not correctly give the coefficient

I.

I.

P g only the conductance or conductance degree of dissociation of electrolytes, but

I.

Inspite of almost complete ionization

Pv is much less than Pg

Faradays Laws of Electrolysis

Faraday's First Law the weight of substance liberated or deposited at electrode during electrolysis is directly proportional to the quantity of electricity passed through the electrolytic cell If W be the mass of the substance deposited by passing Q coulomb of charge, then according to the law, we have the relation: W Q A coulomb is the quantity of charge when a current of one ampere is passed for one second. Thus, amount of charge in coulombs, Q = current in amperes time in seconds =It So W It or W=zIt

Faraday's Second Law When the same quantity of charge is passed through different electrolytes, then the masses of different substances deposited at the respective electrodes will be in the ratio of their equivalent masses

The law can be illustrated by passing same quantity of electric current through three voltametres containing solutions of H2SO4, CuSO4 and AgNO3 respectively as shown in Fig.12.1. In the first voltameter, hydrogen and oxygen will be liberated; in the second, copper will be deposited and in the third, silver will be deposited.

Example
How long has a current of 3 ampere to be applied through a solution of silver nitrate to coat a metal surface of 80 cm2 with 0.005 cm thick layer? Density of silver is 10.5 g/cm3. Solution: Mass of silver to be deposited = Volume density = Area thickness density Given: Area = 80 cm2, thickness = 0.0005 cm and density = 10.5 g/cm3 Mass of silver to be deposited = 80 0.0005 10.5 = 0.42 g Applying to silver E = Z 96500 Z = 108/96500 g Let the current be passed for r seconds. We know that W=ZIt So, 0.42 = 108/965003t or t = (0.42 96500)/(1083) = 125.09 second