This document summarizes key concepts in electrochemistry. It defines galvanic and electrolytic cells, and describes how standard cell potential is related to standard Gibbs free energy and equilibrium constants. It also discusses concentration dependence based on the Nernst equation, conductivity of electrolytic solutions, and Faraday's laws of electrolysis. Common electrochemical cells and batteries are briefly described. Some sample questions and answers are provided at the end.
This document summarizes key concepts in electrochemistry. It defines galvanic and electrolytic cells, and describes how standard cell potential is related to standard Gibbs free energy and equilibrium constants. It also discusses concentration dependence based on the Nernst equation, conductivity of electrolytic solutions, and Faraday's laws of electrolysis. Common electrochemical cells and batteries are briefly described. Some sample questions and answers are provided at the end.
This document summarizes key concepts in electrochemistry. It defines galvanic and electrolytic cells, and describes how standard cell potential is related to standard Gibbs free energy and equilibrium constants. It also discusses concentration dependence based on the Nernst equation, conductivity of electrolytic solutions, and Faraday's laws of electrolysis. Common electrochemical cells and batteries are briefly described. Some sample questions and answers are provided at the end.
This document summarizes key concepts in electrochemistry. It defines galvanic and electrolytic cells, and describes how standard cell potential is related to standard Gibbs free energy and equilibrium constants. It also discusses concentration dependence based on the Nernst equation, conductivity of electrolytic solutions, and Faraday's laws of electrolysis. Common electrochemical cells and batteries are briefly described. Some sample questions and answers are provided at the end.
Key Concepts A cell is of two types:- I. Galvanic Cell II. Electrolytic cell. In Galvanic cell the chemical energy of a spontaneous redox reaction is converted into electrical work. Batteries and fuel cells are very useful forms of galvanic cells In Electrolytic cell electrical energy is used to carry out a non-spontaneous redox reaction.
E0cell = E0cathode-E0anode The standard potential of the cells are related of standard Gibbs energy. ∆rG0 = -n FE0cell The standard potential of the cells is related to equilibrium constant. ∆rG = -RT ln k Concentration dependence of the potentials of the electrodes and the cells are given by Nernst equation. aA + bB → cC + dD
The conductivity, K of an electrolytic solution depends on the concentration of the
electrolyte, nature of solvent and temperature. Molar Conductivity, m, is defined by sp /C where C is the concentration in mol L-1
k 1000 m or M M
the unit of molar conductivity is Ω -1 cm2 mol-1. Conductivity(Specific conductance)
decreases but molar conductivity increases with decrease in concentration. It increases slowly with decrease in concentration for strong electrolyte . there is sharp increase in molar conductivity of weak electrolyte on decreasing concentration or increasing dilution. Kohlrausch law of independent migration of ions. The law states that limiting conductivity of an electrolyte can be represented as the sum of the individual contribution to the anion and cation of the electrolyte.
Faraday’s laws of Electrolysis
I. The amount of chemical reaction which occurs at any electrode during electrolysis by a current is proportional to the quantity of electricity passed through the electrolyte. II. The amount of different substances liberated by the same quantity of electricity passing through the electrolytic solution is proportional to their chemical equivalent weights. Cells and Batteries: Cells are of two types: (a) Primary Cell (b)Secondary cell
There are mainly two types of batteries.
(a)Primary Corrosion of metals is an electrochemical phenomenon In corrosion metal is oxidized by loss of electrons to oxygen and formation of oxides. Anode (Oxidation): 2Fe(s) 2Fe2+ + 4e- Cathode (Reduction): O2(g) + 4H+(aq) + 4e- 2H2O
1. Name the factor on which emf of a cell depends:-
Ans. Emf of a cell depends on following factor- a. Nature of reactants. b. Concentration of solution in two half cells. c. Temperature d. Pressure of gas. 2. What are the units of molar conductivity? ( cm2 ohm-1 mol-1 or Scm2mol-1)
3. What is the EMF of the cell when the cell reaction attains equilibrium? Ans. Zero 4. What is the electrolyte used in a dry cell? Ans. A paste of NH4Cl, MnO2 and C 8. How is cell constant calculated from conductance values? Ans. Cell constant= specific conductance/ observed conductance. 9. What flows in the internal circuit of a galvanic cell? Ans. Ions 10. Define electrochemical series. Ans. The arrangement of various electrodes in the decreasing or increasing order of their standard reduction potentials is called electrochemical series.
QUESTIONS CARRYING TWO MARKS
1. Calculate emf of the following cell at 298K Zn/Zn2+ (10-4 M) || Cu2+ (10-2M)/Cu Given E0 Zn2+/Zn=-0.76V E0Cu2+/Cu=+0.34V Ans. Cell reaction is as follows. Zn(s) + Cu2+(aq)→ Zn2+(aq) + Cu(s) n=2 T=298K Ecell= (E0Cu2+/Cu-E0Zn2+/Zn) -0.0591V log[Zn2+(aq)] [Cu2+(aq)]
= 0.34V-(-0.76)-0.02955Vlog10-4 10-2 = 1.10V-0.02955V log 10-2 = 1.10V+2 X 0.02955V = 1.10V + 0.0591 V = 1.1591V
2. Electrolysis of KBr (aq) gives Br2 at anode but KF(aq) does not give F2. Give reason. Ans. Oxidation takes place at anode. Now higher the oxidation Potential, easier to oxidize. Oxidation potential of Br -, H2O, F- are in the following order. Br- > H2O > F- Therefore in aq. Solution of KBr. Br - ions are oxidized to Br2 in preference to H2O. On the other hand, in aq. Solution of KF, H2O is oxidized in preference to F-. Thus in this case, oxidation of H2O at anode gives O2 and no F2 is produced.
3. Define corrosion. Write chemical formula of rust.
Corrosion is a process of deterioration of metal as a result of its reaction with air and water, surrounding it. It is due to formation of sulphides, oxides, carbonates, hydroxides, etc. Formula of rust- Fe2O3.xH2O 4. Why mercury cell gives the constant voltage. Ans. Mercury cell gives a constant voltage in its life because the overall reaction does not involve any ion in solution whose concentration can change during its life time. 5. What is fuel cell? Write reaction involved in H2-O2 fuel cell. Ans. Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen, methane, methanol, etc. directly into electrical energy are called fuel cells.
Reactions involved in H2 - O2 fuel cell can be presented as follows:-
QUESTION CARRYING THREE MARKS
1. Write any three differences between potential difference and E.M.F.
E.M.F POTENTIAL DIFFERENCE 1.It is difference between 1.It is difference of potential electrode potential of two electrodes between electrode in a closed when no current is flowing through circuit. circuit. 2. It is the maximum voltage obtained 2.It is less than maximum voltage From a cell. Obtained from a cell. 3. It is responsible for steady flow of 3.It is not responsible for steady Current. Flow of current.
2. For the standard cell
Cu(s)/Cu2+(aq)|| Ag+(aq)/Ag(s) E0 Cu2+/Cu = +0.34 V E0 Ag+/Ag =+0.80 V i. Identify the cathode and the anode as the current is drawn from the cell. ii. Write the reaction taking place at the electrodes. iii. Calculate the standard cell potential.
Ans. From the cell representation
Ag/Ag+ electrode is cathode and Cu/Cu2+ electrode is anode. Reaction at anode: Cu(s)→ Cu2+ ( aq )+2e- Reaction at cathode: 2Ag+(aq) + 2e →2Ag(s) E0 cell = E0 cathode – E0 anode = E0 Ag+/Ag – E0 Cu2+ /Cu = +.80 V – (+0.34V) = +0.80V-0.34V = 0.46V 3. Can we store copper sulphate in (i)Zinc vessel (ii) Silver vessel? Give reasons. Given E0 Cu2+/Cu = +0.34V, E0Zn2+/Zn= -0.76V) , E0Ag+/Ag = +0.80V Ans.(i) No (ii) Yes Explanation:A metal having lower reduction potential can displace a metal having higher reduction potential from solution of its salt. Since standard reduction potential of Zn2+(E0Zn2+/Zn = -0.76V) is less than the standard reduction potential of Cu2+ (E0Cu2+/Cu=+0.34V), Zn can displace copper from copper sulphate solution. Thus, CuSO4 solution can be stored in silver vessel. 4. How many grams of chlorine can be produced by the electrolysis of molten NaCl with a current of 1.02 A for 15 min? 2NaCl(l) →2Na+(l)+2Cl-(l) 2 Cl- (g) →Cl2(g) + 2e- 2 mole 1mol Q= n f Q= 2 x 96500 C/mol= 1.93 x 105C Quantity of electricity used = I x t = 1.02 A X (15 X 60) s = 900 C Molar mass of Cl2 = 2 X 35.5 = 71 gmol-1 X 105 C of charge produce chlorine = 71g 1.93 X 105 C of charge produce chlorine = 71g 900 C of charge produce chlorine 71 X 900 1.93 X 105 = 0.331 g
