2.

Electrochemistry Electrochemistry is the branch of chemistry which deals with conversion of electrical energy into chemical energy and vice versa. Mechanism of Conduction:
Conductor: - It is a substance, which allows the electric current to pass through it. Insulator: - It is a substance, which does not allow the electric current to pass through it. Electrolyte: - The substance which is in the fused state or in aqueous state allows passing the electric current, resulting chemical decomposition is called as electrolytic conductor or electrolytes. e.g. all acids, all bases & all salts.

1. Cations: When the atom donates the electron, it acquire charge, these positively charged atom is called as cations. Na Na++ eCa Ca2+ + 2eAl Al3+ +3eCation has smallest size than its parent atom. 2. Anions: When the atom accepts the electron, it acquire charge, these negatively charged atom is called as anions. Cl+ eClF + eFS +2eS-2 Anion has greater size than its parent atom. Difference between atom and ion: Atom Ion
1. It carries no electrical charge i.e. neutral particle 2 . The outermost shell is incomplete. 3. Atoms react with solvent. 4. Atoms take part in molecular

positive

negative

1. It carries electrical charge either +ve or ve. 2. Outermost shell is complete. 3. Ions do not react with solvent. 4. Ions take part in ionic reaction. Mr. S.M. Patange

reaction. 5. e.g. Na, Ca etc

+ 2+ 4+ 5. e.g. Na , Ca , NH ,Cl etc

Ionization:The process of splitting up or breaking up of substance into its ions called as Ionization. Electrolytic Dissociation: The process of splitting up or breaking up of electrovalent substance into its ions when dissolved in water called as Electrolytic Dissociation. Arrhenius theory: (theory of ionization) The Swedish scientist Svante Arrhenius proposed the theory of ionization in 1887. For this theory he was awarded by Nobel Prize in 1903. Assumptions or principles or postulates: 1. When a molecule of electrolyte (acid/base/salt) is dissolved in water, produces positive ions (cations) and negative ions (anions), e.g. NaCl Na+ + Cl 2. Cations are obtained by the loss of electrons from metallic atoms, e.g. Na Na++ 1e Anions are obtained by the gain of electrons from non- metallic atoms, e.g. Cl + 1e Cl 3. In the solution, the total number of positive charges on cations is equal to the total number of negative charges on anions. Hence solution as a whole is electrically neutral. 4. The number of positive or negative charges on ions indicates the valency of the element from which the ion is derived. 5. Molecules of electrolyte constantly split into ions and the ions present in the solution constantly recombine to form electrolyte molecules. Thus all the molecules of an electrolyte in the solution is not dissociated. Hence the process of electrolytic dissociation is a reversible process. e.g . NaCl Na+ + Cl
Degree of ionization or dissociation:

The fraction of the total number of molecules of an electrolyte that ionizes in solution called the degree of ionization. OR It is the ration of number of molecules dissociated to the number of molecules dissolved.

Factors affecting degree of ionization (any three) 1. Nature of Solute: - Ionic compounds such as acids, bases & salts are highly ionized in solution. e.g. strong acids like HCl, H2SO4 & strong bases like NaOH, KOH are highly ionized in solution. Weak acids like CH3COOH & weak bases NH4OH are weakly ionized in solution. 2. Nature of Solvent: - In polar solvents like water & ammonia, degree of ionizations is more. In non-polar solvents degree of ionization is less. 3. Concentration of the solution: - If concentration of solution is more, then degree of ionization is less. 4. Temperature:-At higher temperature molecules acquire thermal energy hence degree of ionization increases with increase in temperature. ELECTROLYSIS Terms involved in electrolysis: 1) Electrolysis: Process of chemical decomposition of electrovalent substance by passing electric current through its aqueous solution or in fused state. Mr. S.M. Patange

2) Electrolytic Cell: The device in which external voltages used to bring the chemical change is called as electrolytic cell. It is made up of glass. It is also known as voltammeter. 3) Electric current: Battery is the source of electric current. It has two poles, Positive and negative poles. The potential difference is exists between the two poles. 4) Electrode: In order to conduct the electric current two metallic conductors are dipped into the solution is called as electrode. It is in the form of rod, foil, plate. Electrodes are electron carriers. The electrode connected to positive terminal of battery is called as anode. (Positive electrode).The electrode connected to negative terminal of battery is called as cathode.(Negative electrode). Mechanism of Electrolysis: Decomposition of electrovalent substance by the passing electric current through its aqueous solution or in fused state is called as electrolysis. The electrolytic cell contains fused NaCl as electrolyte. It is in the form of ions.(Na+&Cl-). Initially these ions are in random motion. (Free to move).

i) When key is closed the positively charged ions (Na+) travels towards the cathode. The negatively charged ions ( Cl) travels towards the anode. The reactions are as follows. 1) Reaction at cathode: Na+ ions migrate at cathode. It accepts one electron from cathode and become neutral atom. [ Na+] Na+ + e Na. 2) Reaction at anode: Cl ions migrate towards the anode. It losses one electron at anode and becomes neutral. 2Cl Cl2+ 2e

Electrochemical / Activity series of ions.

1. The series in which ions are arranged from top to bottom according to their increasing order of activity. 2. So, ion with highest activity placed at top & ion with lowest activity placed at the bottom of the series. 3. Therefore less active cation is Au+3 & most active cation is K+ & less active anion is I &most active anion is SO42. Cation: Anion K+ SO42 + Na NO3 ++ Ca OH Mr. S.M. Patange

Mg++ Cl +++ Al Br ++ Zn S2 ++ Cr I ++ Fe Cd+++ H+ Cu++ Ag+ Au+3 Examples of electrolysis: A) Electrolysis of CuSO4 solution using platinum electrode: Mechanism: 1. An aqueous solution of CuSO4 contains

Cu,SO4 ,H ,OHions

present

in

solution. 2. According to the activity series, Cu, ions are discharged in preference to + H ions & Cu deposited at cathode. 3. At anode, OHions are discharged in preference to S O 4 ions& oxygen as is liberated at anode. Schematic representation of electrolysis of CuSO4:-

Net result of electrolysis:i) The deposition of Cu metal at cathode electrode ii) The liberation of O2 at anode electrode. + -2 iii) The remaining ions (H &SO4 ) increased in the soln. These ions combined to form H2SO4 Electrolysis of CuSO4 solution using copper electrode: 1. An aqueous solution of CuSO4contains

Cu,SO4 ,H ,OHions

present

in

solution. 2. According to the activity series, Cu, ions are discharged in preference to + H ions & Cu deposited at cathode. 3. Anode itself dissolves in solution.

Schematic representation of electrolysis of CuSO4:

Mr. S.M. Patange

Net result of electrolysis :i) The deposition of Cu metal at cathode electrode ii) Anode itself dissolves. Application of electrolysis: i) Electroplating ii) Electro-refining Electroplating: The process of deposition of superior metal over the inferior base metal with the help of electric current is called as electroplating. Purpose: i) Protection of metal:In order to avoid the corrosion of metal or rusting of iron, the electroplating is performed. ii) Decoration:For increasing the beautiful and attractive appearance electroplating is performed. Also for increasing commercial and decorative value electroplating is performed. iii) Repairing: The broken pieces or warn out machine parts can be repaired by electroplating. iv) Achievement of specific properties: To achieve specific functional properties, such as electrical conductivity, wear resistance etc. Process:1. The surface of the article to be electroplated is first cleaned. 2. It is washed with hot solution of alkali or soaps to remove the greases. 3. Then it is treated with dilute acid to remove the oxide layer called as pickling.

4. Then it is washed with water to remove acid and alkali. Then it is carefully polished. 5. The cleaned article is made as cathode. The anode is the pure metal. 6. These two electrodes are placed in electrolytic cell containing electrolyte which is the salt solution of metal to be electroplated. 7. On passing the electric current, the metallic ions from the electrolytes deposited on cathode. 8. The anode gets dissolved in the form of metal ions. 9. A smooth and bright deposition is obtained. Electroplating of silver on iron spoon Construction 1. A plating of silver on iron spoon is done in a steel tank. 2. Iron spoon is first thoroughly cleaned by boiling with caustic soda (KOH) to remove grease &dirt. 3. Then it is washed with water to remove caustic soda. 4. Then it is treated with dilute hydrochloric acid to remove any oxide layer. 5. Again it is washed with water and polished carefully.

Mr. S.M. Patange

S Working: 1. The iron spoon is then made as cathode. 2. The pure plate of silver metal whose coating is desired is made as anode. 3. The cathode and anode both are immersed in cell of potassium argento cyanide, K[Ag (CN)2]. 4. When current is passed, the iron spoon gets plated with a smooth and bright deposit of silver. 5. The silver anode gets slowly dissolved in solution. Net result of electrolysis: 1. The silver ions from the electrolyte, K[Ag(CN)2] and which are formed by dissolution of anode get discharged at the cathode and silver gets deposited on the iron spoon. Ag++ 1e Ag . reduction 2. Anode itself dissolves in solution. Ag Ag+ + 1e . Oxidation Electro-refining Electrorefining: - The process in which a pure metal can be obtained from the impure metal by the method of electrolysis is known as electrorefining. Or The process of purification of metal into its most pure form by the passage of electric current is called electrorefining. Electrorefining: Impure copper contains about3-5%impuritieslikeZn, S, As, Ni, Au etc. such impure copper is not fit to be used as an electrical conductor. Copper with100%purityisrequired for electrical conductivity. Hence, the crude (impure) copper is refined by the process of electrorefining. Consider electrorefining of impure copper rod. a)Anode electrode :-Impure metal (Cu) rod (thick) b) Cathode electrode :- pure metal rod(Thin) c) Electrolyte:-Solution of salt of metal. 1. By the passage of electric current, the anode of impure metal goes in solution in the form of metal ions. 2. The electrolyte breaks up into positively charged metal ions & negative ions. 3. Positively charged metal ions go to the cathode & are deposited thereafter neutralizing their charge.

Mr. S.M. Patange

4. The negatively charged ions go to the anode & take an equivalent amount of pure metal & again change into electrolyte. 5. The process is continued till whole of the pure metal gets transferred to cathode. 6. As a result of electrolysis, the anode gets dissolved & impurities get settled down below the anode as anode mud. 7. The cathode is refined metal. It is washed, dried & put to use 8. The schematic representation of electrolysis is

Concept of electrode potential - reduction potential &oxidation potential: A metal consists of metal ions with valency electrons that bind them together. if metal is in contact with a solution of its own salt ,then there are two opposing process takes place. 1. Oxidation Potential: - The tendency of a metal electrode to go into the solution as metallic ions leaves behind an equivalent number of electrons on the metal electrode. Thus the metal acquires negative charge. Hence a potential difference develops between the electrode & electrolyte due to oxidation is called oxidation potential. e.g. Zn in ZnSO4 solution. M Mn+ + ne(Loss of electron)

2. Reduction Potential: The tendency of a positive metallic ions present in the solution have tendency to accept electrons from metal electrode & form neutral metal atom that enters the metallic lattice . Thus the metal acquires positive charge. Hence a potential difference develops between the electrolyte & electrode due to reduction is called reduction potential. e.g. Cu in CuSO4 solution n+ M + neM (Gain of electron) Faradays law of electrolysis: Faradays 1stlaw of electrolysis: This law states that the weight of a substance liberated or deposited at the electrode is directly proportional to Mr. S.M. Patange

the quantity of electricity passed through the electrolyte solution. Let, W = Amount of substance deposited at electrode. Q = Quantity of electricity passed through the electrolyte. According to law, W Q W= Z C t. ( 1 ) Where, Z = Proportionality constant, called as electrochemical equivalent. C= Current in ampere, t = Time in second. If t = 1 sec. and C = 1 amp. eqn ( 1 ) becomes, W = Z The electrochemical equivalent (Z) is defined as the amount of substance deposited or liberated when one ampere current is passed for one second through the electrolyte. Faradays second law of electrolysis: This law states that, when the same quantity of electricity is passed through the different electrolyte solutions which are connected in series, the amount of the substance deposited or liberated at the electrodes are directly proportional to their chemical equivalents (c.e.)or equivalent weights. Consider two electrolytes CuSO4 and AgNO3. Weight of Cu deposited (W1) Chemical equivalence of Cu ( E1) Weight of Ag deposited (W2) Chemical equivalence of Ag ( E2) Weight of Cu deposited (W1) Weight of Ag deposited (W2) Chemical equivalence of Cu ( E1) Chemical equivalence of Ag ( E2) W1 E1 W2 E2

Relation between (E.C.E.):-

chemical

equivalent

(C.E.)

and

electrochemical

equivalent

1. The quantity of electricity, 96500 coulombs required to liberate or deposit 1 gm equivalent of a substance. 2. One coulomb liberates/deposits the quantity of same substance (in grams) equal to its electrochemical equivalent. 3. Thus, equivalent weight of a substance is 96,500 times the electrochemical equivalent. Therefore C.E. (Eq. Wt.) = 96,500 x E.C.E. pH & pOH 1. Knowledge of the concentration of hydrogen ions is of the greatest importance in chemistry. 2. Hydrogen ion concentrations are typically quite small numbers. 3. Therefore, chemists report the hydrogen ion concentration of a solution in terms of PH. Definition: pH=Negative logarithm of the base ten of the H+ concentration. pH = - log10 [H+] pOH = Negative logarithm of the base ten of the OHconcentration. Mr. S.M. Patange

pOH = -log10[OH-] Relation between pH and pOH Let us consider the log form of the expression [H+] [OH]= Kw where Kw = ionic product of water By taking log on both sides log [H+] + log [OH] = log Kw On changing signs on both sides log [H+] log [OH]= log Kw Since Kw = 1.0 1014, at 25oC But, PH = - log10[H+] &POH = - log10[OH-] pH + pOH= log (1.0 1014) pH+ pOH= 14 Hence, for any aqueous solution at 25oC, pH and pOH add up to 14.00. Ionic Product of Water The product of the ionic concentration of hydrogen ions and hydroxide ions in pure water or in any aqueous solution is called ionic product of water. It is constant at any given temperature. At 25oC it is 1.01014. Ionic product of water is Kw = [H+] [OH-]. pH Scale The scale on which pH values are computed is called the pH scale.

Solutions having pH less than 7 are acidic; those with PH greater than 7 are basic & with 7 are neutral. Problems 1. Calculate the time in seconds in which 0.3 gms of copper is liberated from copper sulphate solution when a current of0.5 ampere is passed (equivalent weight of copper= 31.6) i ] E.C.E. of Copper = Eq. Wt. of Copper/ 96500 = 31.6 / 96500 = 0.000327 gms /coulomb ii] From 1st law of Faraday, w =Zct t = 0.3 / 0.000327 X 0.5 t = 1832 seconds. 2. A current of 0.5 amperes was passed through a solution of copper sulphate, calculate time required to deposits 0.3 gm of copper. (Given equivalent weight of copper= 31.6)

Given: W=0.3 gm c =0.5 ampere Equivalent weight of Cu=31.6 Time =? E.C.E. of copper Eq. wt. of copper

96,500 31.6 96,500 0.000327gm./c. Solution: From1stlawofFaraday, W ZCt 0.30.0003270.5t 0.3 t 0.0003270.5
Mr. S.M. Patange

t1832seconds
3. A current of 2 amperes was passed through a solution of copper sulphate for 16 minutes& 5 seconds. Calculate the amount of copper deposited at cathode. (Given atomic weight of copper= 63.5) Given: C=2 amperes t= 16 minutes & 5 seconds= 965 seconds At. wt. of Cu= 63.5 Valency = 2 To calculate: w =? Step i) Atomic weight = equivalent weight x valency Equivalent weight (c. e.) = Atomic weight/ valency Equivalent weight (c. e.) = 63.5 / 2 = 31.75 Step ii) c. e. = 96,500 x e. c. e. (z) e. c. e. (z) = c. e. / 96,500 e. c. e. (z) = 31.75 / 96,500 = 3.29 x 10-4 Step iii) w = z x c x t w = 3.29 x 10-4 x 2 x 965 w = 0.635 4. A solution has pH 4.2596. Find out hydrogen ion concentration. Given: pH = 4.2596 [H +] = ? Solution: pH = - log 10 [H +]

4.2596 = - log 10 [H +] [H +] [H +] = antilog ( -4.2596) = 5.50 x 10-4 moles/ lit.

5. Calculate the pH value of solution having hydrogen ion concentration 1x10-3 gm ions per liter. pH = - log10[H+] pH = - log10[1x10-3] pH = - [log10(1) +(-3) log10 (10)] pH = 3 [but log10 (10) = 1]

6. A current of 0.4 amperes was passed through a solution of CuSO4 for 1 hour. Find out the weight of copper deposited on the cathode. (Electrochemical equivalent of copper = 0.000326) Given: C= 0.4 amperes t = 1 hour= 60 x 60 = 3600 seconds z = 0.000326 To calculate: w =? w=zct w= 0.000326 x 0.4 x 3600 w= 0.469 g Question Bank 1. Write the difference between atom and ion. 2. Write any four postulates of Arrhenius theory. 3. Define degree of ionization & explain factors affecting degree of ionization. 4. Describe the mechanism of electrolysis. 5. Explain electrolysis of i) CuSO4 solution by using platinum electrode. ii) CuSO4 solution by using copper electrode. 6. State and explain Faradays first law of electrolysis. 7. State and explain Faradays second law of electrolysis. 8. Derive the relation between faradays and coulomb. Mr. S.M. Patange

9. Derive the relation between chemical equivalence (C.E.) and electrochemical equivalence (E.C.E.). 10. Describe the following. i) Electroplating of iron spoon by silver. ii) Electro-refining of blister copper. 11. Define pH & POH. 12. Obtain relation between pH & pOH. 13. What is pH scale? 14. Same quantity of current is passed through CuSO4 & AgNO3 solution. If 3.207 g of Cu is deposited, calculate weight of silver deposited. (equivalent weight of copper= 31.77 & equivalent weight of silver = 108) 15. Calculate pH of 0.0034N HCl assuming complete ioniosation. 16. When the same amount of current is passed through the solution of CuSO4 and ZnSO4, then 0.7 and 0.7164 gms of Cu and Zn get deposited on respective electrodes. Calculate equivalent weight of Zn( atomic wt. Of Cu= 63.5). 17. Which of the following substance will conduct electric current? Give reasons. i) Solid NaCl, Fused NaCl ii) Solid ZnSO4, Solution of ZnSO4 iii) Solid CuSO4, Solution of CuSO4 iv) Benzene, Alcohol. i ) Solid NaCl, Fused NaCl : Solid NaCl will not conduct electric current because it does not produces ions but fused NaCl will conduct electric current as it gives Na+ and Cl - ions on dissociation. ii ) Solid ZnSO4, Solution of ZnSO4 : Solid ZnSO4 will not conduct electric current because it does not produces ions but solution of ZnSO4 will conduct electric current as it gives Zn++ and SO4 - - ions on dissociation. iii ) Solid CuSO4, Solution of CuSO4 : Solid CuSO4 will not conduct electric current because it does not produces ions but solution of CuSO4 will conduct electric current as it gives Cu++ and SO4 - - ions on dissociation. iv) Benzene, Alcohol: Benzene and alcohol will not conduct electric current because both are non polar solvents (does not undergo dissociation / ionisation).

I have been so electrically occupied of late that I feel as if hungry for a little chemistry: but then the conviction crosses my mind that these things hang together under one law & that the more haste we make onwards each in his own path the sooner we shall arrive, and meet each other, at that state of knowledge of natural causes from which all varieties of effects may be understood & enjoyed Michael Faraday
Mr. S.M. Patange