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SMK KING GEORGE V SEREMBAN UPPER SIX CHEMISTRY QUESTIONS FOR UNDERSTANDING (ELECTROCHEMISTRY 3) FEBRUARY 2011 1.

(a)Draw an electrolysis cell for the electrolysis of molten lead(II) iodide using graphite electrodes. Label the electrodes anode and cathode and electrolyte .Is anode/ cathode +ve or ve.Write equations at each electrode battery cathode(-) Pb + 2e Pb(l)
2+

electrodes

anode( +) - oxidation 2Br-(l) Br2(g) + 2e

Electrolite (molten PbBr2) Pb2+(l) Br-(l)

Electrolite: an ionic compound in molten or aqueous solution that conducts electricity and can be decomposed by it Electrolysis: process of decomposing an electrolite by passage of an electric current
(d)

State differences between electrolytic and the electrochemical cells Electrochemical cell Spontaneous redox chemical reaction results in a flow of electric current . Chemical energy electrical energy Anode is vely charged Cathode is +vely charged

Electrolytic cell 1.electric current is passed to cause a non-spontaneous redox reaction to take place
2,anode

+ve charged Cathode vely charged

(e) State two similarities between electrolytic and electrochemical cells Electrons move from anode to cathode
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oxidation takes place at anode and reduction is at cathode


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Cathode: Na+, H2O Anode: SO42-; H2O Carbon cathode carbon anode

Na2SO4(aq) 2.(a) In the electrolysis of aqueous sodium sulphate solution, what are the species that move towards the (i) cathode: Na+ and H2O (ii) anode: SO42- and H2O (b) Write the two possible reaction equations at the cathode and state the the value of E for each reaction Na+(aq) + e Na E0 = -2.71V 2H2O + 2e H2 + 2OH- E0 = -0.83V (c) Which species will be selected to be discharged/ reduced and why? H2O selected to be reduced to form H2 gas since E0 for the reduction is the least ve. Note the more +ve or less ve value of E0, the easier reduction will occur. (d) Which anion cannot be discharged at the anode and why? Which other anion cannot be discharged at anode NO3- . At anode oxidation must take place. N in NO3- has +5 oxidation state and cannot be oxidised further (e) Write two posible reaction equations that may take place at the anode and the value of E for each reaction 2SO42- S2O82- + 2e E0 = -2.01V S2O82- + 2e 2SO42- E0= +2.01V 2H2O O2 + 4H+ + 4e E0 = -1.23V O2+ 4H+ + 4e 2H2O E0=+1.23V (e)Which ion will be discharged/oxidised and why? Of the above 2 oxidation reactions, the E 0 for oxidation of H2O to form O2 is the least ve and hence the most favourable to occur (f) Which species is oxidised at anode? H2O is selected to be oxidised at anode to O2.
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The products of electrolysis of Na2SO4(aq) is H2(cathode) and O2(anode) 3.(a) In electrolysis, what process always take place at: (i) anode: oxidation (ii) cathode: reduction (b) How do you determine which cation/ species will be selected to be discharged/ reduced at the cathode? The cation or species that has the most +ve E0 or least ve E0 for reduction will be selected. b) (ii) Arrange the following cations/species in order of being selected to be reduced at the cathode from the easiest to the most difficult: Mn2+, Ca2+,; Li+;Mg2+, Zn2+, Cu2+, Ag+; Sn2+, Pb2+; Fe2+, H+; H2O;Na+;Al3+ Ag+, Cu2+, H+, Pb2+, Sn2+, Fe2+, Zn2+, H2O, Mn2+, Al3+, Mg2+, Na+, Ca2+, Li+ (iii) Which species will be reduced under standard conditions: Al3+ or H2O H2O bec H2O(-0.83V) less ve compared with -1.66 V for Al3+ (iv) Which species will be reduced under standard conditions: Cu2+ or H2O Cu2+ bec Cu2+( +0.34V) is more +ve than -0.83V for H2O (c) How do you determine which species will be discharged/ oxidised at the anode? The anion or species that has the most +ve E0 or the least ve E0 for the oxidation reaction will be selected.
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ii) Arange the following anions in order of being discharged/oxidised form easiest to most difficult: Cl-, OH-, NO3-; I-, Br-, SO42-, OH-, I-, Br-, Cl-, SO42-, NO3(d) Given the following half-cell reactions and their E0 values, arrange species in order from easiest to the most dificult to be discharged at the anode O2 + 4H+ + 4e 2H2O + 1.23V 2S2O8 + 2e 2SO42- + 2.05V Cl2 + 2e 2Cl- + 1.36V S + 2e S2- -0.51V [Fe(CN) 6]3-(aq) + e [Fe(CN) 6]4(aq) + 0.36V Easiest -------------------------------------------------------------------------> Hardest S2-; S2O32-; [Fe(CN)6]4-; OH-; I- ; Br- ; H2O; Cl- ; SO42- ; F3

I2 + 2e 2I+ 0.54V Br2 + 2e 2Br + 1.07V F2 + 2e 2F- + 2.87V O2 + 2H2O + 4e 4OH- + 0.40V S4O62- + 2e 2S2O32- + 0.09V

(B) Concentration factor. Complete table below Electrolyt e 0.001M HCl(aq) Ions / species H+, H2O Cl- and H2O Pt cathode Probable reaction equation equation and product Reduction + 2H (aq) + 2e H2(g) 0.00V 2H2O + 2e H2 + 2OH-0.83V 2H+(aq) + 2e H2(g) 0.00V 2H2O + 2e H2 + 2OH-0.83V Pt anode Probable reaction equation equation and product Oxidation 2H2O O2 + 4H+ + 4e -1.23V 2Cl-(aq) Cl2(g) + 2e -1.36V 2Cl-(aq) Cl2(g) + 2e -1.36v 2H2O O2 + 4H+ + 4e -1.23V [ ] factor and O2 overvoltage 2H2O + 2e H2 + 2OH 2Cl-(aq) Cl2(g) + 2e -0.83V -1.36v + Na (aq) + e Na(s) -2.71V 2H2O O2 + 4H+ + 4e -1.23V 2H2O + 2e H2 + 2OH 2H2O O2 + 4H+ + 4e -0.83V - 1.23V + Na (aq) + e Na(s) -2.71V 2Cl-(aq) Cl2(g) + 2e -1.36v {o2 overvoltage} + Ag (aq) + e Ag 2H2O O2 + 4H+ + 4e +0.80V -1.23V 2+ Cu (aq) + 2e Cu(s) +0.34 NO3 cannot be oxidised 2H2O + 2e H2 + 2OH-0.83V 2H2O + 2e H2 + 2OH- 2H2O O2 + 4H+ + 4e -0.83V -1.23V + Na (aq) + e Na(s) -2.71V 2F-(aq)F2(g) +2e -2.87 2H2O + 2e H2 + 2OH- 2H2O O2 + 4H+ + 4e -0.83V -1.23V + Na (aq) + e Na(s) -2.71V 2F-(aq)F2(g) +2e -2.87 2H2O + 2e H2 + 2OH- 2Br- Br2 + 2e -0.83V -1.07V + K (aq) + eK(s) -2.92V 2H2O O2 + 4H+ + 4e 2H2O + 2e H2 + 2OH- 2Br- Br2 + 2e -0.83V -1.07V + K (aq) + eK(s) -2.92V 2H2O O2+ 4H++ 4e -1.23V
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2.0 M HCl(aq)

H+, H2O Cl- and H2O

5.0M NaCl(aq)

Na+, H2O Cl-, H2O

0.01M NaCl(aq)

Na+, H2O Cl-, H2O

2.0M AgNO3 + 2.0M Cu(NO3)2 Dilute NaF(aq) Conc NaF(aq) Conc KBr(aq) Dilute KBr(aq)

Ag+, H2O Cu2+, NO3- ,H2O

Na+, H2O F-, H2O Na+, H2O F-, H2O K+. H2O Br-, H2O K+. H2O Br-, H2O

(C)

Nature of electrode. Reaction equation at cathode Cu2+(aq) +2eCu(s) +0.34V 2H2O+2eH2(g) +2OH-0.83V Cu2+(aq) +2eCu(s) +0.34V 2H2O+2eH2(g) +2OH-0.83V

Electrolyte Electrodes Reaction equation at anode CuSO4(aq) Platinum 2H2O O2 + 4H+ + 4e 2+ Cu , H2O -1.23V 2SO4 H2O 2SO42-(aq) S2O82- +2e -2.05V CuSO4(aq) Copper 2H2O O2 + 4H+ + 4e 2+ Cu , H2O -1.23V 2SO4 H2O 2SO42-(aq) S2O82- +2e -2.05V Cu(s)Cu2+(aq) + 2e -0.34V ZnSO4(aq) Platinum 2H2O O2 + 4H+ + 4e 2+ Zn , H2O -1.23V 2SO4 H2O 2SO42-(aq) S2O82- +4e -2.05V ZnSO4(aq) Zinc 2H2O O2 + 4H+ + 4e 2+ Zn , H2O -1.23V 2SO4 H2O 2SO42-(aq) S2O82- +2e -2.05V Zn(s) Zn2+(aq) + 2e +0.76V Brine Anode2H2O O2 + 4H+ + 4e solution graphite -1.23V + Na , H2O Cathode 2Cl-(aq) Cl2(g) + 2e Cl-, H2O Hg -1.36V Brine graphite 2H2O O2 + 4H+ + 4e solution -1.23V + Na , H2O 2Cl-(aq) Cl2(g) + 2e Cl , H2O -1.36V
(D) Applications of Faradays laws

Zn2+(aq) +2eZn(s) -0.76V 2H2O+2eH2(g) +2OH-0.83V Zn2+(aq) +2eZn(s) -0.76V 2H2O+2eH2(g) +2OH-0.83V

2H2O+2eH2(g) +2OH-0.83V Na+(aq) + e Na(s) -2.71V 2H2O+2eH2(g) +2OH-0.83V Na+(aq) + e Na(s) -2.71V

1. State Faradays first law and write an equation to represent this law

Mass of subtance dissolved/formed at electrode is proportional to the quantity of electricity passed during electrolysis m Q
2. State Faradays second law and write an equation to represent this law

If same quantity of electricity is passed through different electrolytes, the number of moles of a substance dissolved/formed at an electrode during electrolysis is inversely proportional to the charge on the ion. n 1/ z Example Moles of metal deposited at cathode by 1F Ag+ 1 Cu2+ Al3+ 1/3

3. When an electric current is passed through an aqueous solution of silver nitrate for 7 minutes, 1.04 g of silver is deposited at the platinum cathode. What is the quantity of electricity in coulomb that is used in this electrolysis? Calculate the current used in amperes.( Faradays constant: 96,500C mol-1) [A: 929C , 2.21A] At cathode: Ag+(aq) + e Ag(s) 1 mol Ag produced by 1 F of electricity => 108 g of Ag produced by 96,500 C 1.04 g of Ag is produced by 1.04 x 96,500 = 929 C 108 Q=Ixt I = Q/t = 929 = 2.21 A 7 x 60 4. Calculate the time taken to deposit 0.90g of copper when a current of 0.15A is passed through an aqueous solution of copper(II) sulphate using carbon electrodes. [A: 18,200 s ] At cathode: Cu2+(aq) + 2e Cu(s) I mol of Cu is produced by 2F of electricity = > 63.5 g of Cu is produced by 2 x 96,500C 0.90 g of Cu is produced by 0.90 x 2 x 96, 500 63.5 = 2735.4 C Q=Ixt t = Q/I = 2735.4 = 18,236 s 0.15
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In an experiment, 280 cm3 of oxygen is liberated by 4825C during the electrolysis of dilute sulphuric acid at s.t.p. If the charge of an electron is 1.60 x 10-19 C, calculate the Avogadros constant. [A: 6.03 x 1023 mol-1] At anode: 2H2O O2 + 4H+ + 4e 1 mol of O2 is produced by 4F of electricity At s.t.p 22, 400 cm3 of O2 is produced by 4 x 96,500C
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4825 C liberates 280 cm3 of O2 at stp. 22,400 cm3 of O2 is liberated by 22,400 x 4825 = 386,000 C 280 Therefore 386,000C must be the charge of 4 mol e or 4F 4 x L x e = 386,000C L = 386,000 = 6.03 x 1023 mol-1 4 x 1.60 x 10-19 6. When 19,300C flows through a dilute solution of sulphuric acid, 1,120 cm3 of gas measured at s.t.p is liberated at the anode. Calculate a value for Avogadros constant. [ A: 6.03 x 1023 mol-1] At anode: 2H2O O2 + 4H+ + 4e 1,120 cm3 gas O2 is liberated by 19,300 C At stp 1mol gas (22,400 cm3) is liberated by 22,400 x 19,300 1,120 = 386,000 C According to equation 1 mol of O2 is produced by 4F of electricity 4 F = 386,000 C 4 x L x e = 386,000C L = 386,000 = 6.03 x 1023 mol-1 4 x 1.60 x 10-19 7. When a certain amount of electricity flows through aqueous silver nitrate, 3.24 g of Ag is deposited at the cathode. Claculate (a) the mass of copper and (b) mass of aluminium that will be deposited by the same quantity of electricity. [A: 0.953g Cu and 0.27g Al.] At cathode : Ag+(aq) + e Ag(s) 1 mol Ag (108 g) is produced 1 F (96,500 C) 3.24 g of Ag is produced by 3.24 x 96,500 = 2895 C 108 (a) Cu2+(aq) + 2e Cu(s) 2 x 96,500C ------ > 63.5 g Cu 2895 C ---- > 2895 x 63.5 2 x 96,500 = 0.953 g Cu (b) Al3+(aq) + 3e Al(s) 3 x 96,500C ----- > 27.0 g Al 2895 C ----- > 2895 x 27.0 3 x 96,500 = 0.27 g Al

8. When 3.22 A flows throgh an aqueous solution containing Aun+ ions for 20 minutes, 2.628g of gold is deposited. Calculate (a) the charge on the gold ion (b) the mass of copper deposited by the same amount of electric
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charge through 0.10 mol dm-3 of copper(II) sulphate solution. [A (a) +3 (b) 1.27 g ] Q=Ixt = 3.22 x 20 x 60 = 3864 C 3864 C deposits 2.628 g Au 1 mol of Au is deposited by 197 x 3864 = 289,652 C 2.628 n+ Au + ne Au 1 mol Au is produced by n F 289,652 C = n x F = n x 96,500 n = 289,652 = 3 96,500 Charge on gold cation is Au3+
(b)

Cu2+(aq) + 2e Cu(s) 2 x 96,500C produces 1 mol (63.5 g) Cu 3864 C produces 3864 x 63.5 = 2 x 96,500

1.27 g Cu

9. A metal consists of 2 isotopes with relative masses 63 and 65 in the ratio 3:1. When an aqueous solution containing ions of the metal is electrolysed by a current of 0.5A for 110 minutes, 0,988 g of the metal is deposited at the cathode. Calculate the charge on the metal ion. [A: +2. ] R.A.M of M = 63 x 3 + 65 x 1 = 63.5 4 Q =Ixt = 0.5 x 110 x 60 = 3300 C 0.988 g of metal M is produced by 3300 C 63,5 g ( 1 mol of M) is produced by 3300 x 63.5 = 190,846 C 0.988 190,846 C = n x 96,500 n = 190,846 = 1.97 96,500 n must be whole number, n = 2

Charge of metal ion = M2+ 10. In an anodisation experiment, the thickness of the oxide layer of an aluminium object with a total surface area of 2500cm2 is to be increased by

0.005cm. Calculate the quantity of electricity required, given that the density of Al2O3 is 4.00 gcm-3. [A: 2.84 x 105 C ] Volume of oxide layer = 2500 x 0.005 = 12.5 cm3 Mass of Al2O3 formed = 12.5 x 4.00 = 50.0 g 1 mol of Al2O3 (102 g)contains 2 mol of Al = 27.0 x 2 = 54.0 g of Al 50.0 g of Al2O3 contains 50.0 x 54.4 = 26.47 g Al 102 3+ At cathode: Al (aq) + 3e Al(s) 1 mol of Al = 27.0 g is produced by 3 x 96,500 C 26.47 g of Al is produced by 26.47 x 3 x 96,500 27.0 = 2.84 x 105 C Industrial Application Extraction of Al from Bauxite; chlorine from brine solution 1. (a) How is aluminium extracted from bauxite? Electrolysis of molten pure bauxite (Al2O3) (b) What is bauxite? hydrated aluminium oxide Al2O3.xH2O (c) In the extraction of Al from bauxite in industry, state what the cathode and anode is made of and what is the electrolyte used Both cathode and anode are made of graphite Electrolyte: molten Al2O3 mixed with cryolite (d) State the chemical name of cryolite. Why is it added to the electrolyte? Chemical name is sodium hexafluoroaluminate Na3AlF6 It is added to reduce the melting temperature of bauxite from 20500C to ~ 9000C and to increase electrical conductivity (e) Write equations for all reactions taking place at the (i) anode:. 2O2-(l) O2(g) + 4e (ii) cathode:. Al3+(l) + 3e Al(l) * Why recycle? answer on last page 2. (a) What is anodising? Process of coating Al objects with a layer of Al2O3 by electrolysis / increasing the thickness of Al2O3 by electrolysis (b) Name the substance used as anode and as cathode in anodising experiments. What is the electrolyte used? Anode is Al object; cathode is inert electrode like C or Pt Electrolyte is dilute sulphuric acid

(c) Write equations for reactions at (i) anode: 2H2O(l) O2(g) + 4H+(aq) + 4e; 2Al(s) + 3/2O2(g) Al2O3(s) (ii) cathode: 2H+(aq) + 2e H2(g) .(iii) Overall equation:.. 2Al(s) + H2O(l) + O2(g) Al2O3(s) + H2(g) 3. In the electrolysis of brine using a diaphragm cell state (a) electrolyte: saturated brine solution (b) anode and equation of reaction:..Titanium : 2Cl-(aq) Cl2(g) + 2e (c) cathode and equation of reaction: steel: 2H2O(l) + 2e H2(g) + 2OH(d) write overall equation of reaction: .2NaCl(aq) + 2H2O(l) 2NaOH(aq) + H2(g) + Cl2(g) (e) What is the diaphragm made of: asbestos (f) What is the purpose of using the diaphragm? To separate the anode and cathode compartments so that the products of electrolysis are not allowed to mix with each other. To allow the Na+(aq) ions to flow from cathode to anode (g) Why does the OH- ions in the cathode compartment not able to enter the anode compartment where Cl2 is produced The brine electrolyte solution in anode compartment is at higher pressure so the OH- ions are prevented from entering the anode compartment through the asbestos diaphragm * Electroplating of plastics in text book 4. (a) Name some heavy metal ions found in waste water discharged by factories. Ni2+ ; Cd2+; Cr3+; Co2+ (b) How can the concentrations of such toxic heavy metal ions in the effluent be significantly reduced? Electrolysis of the affluent before being discharged out of factory (c) Write an equation to show how one of these heavy metal ions is removed from the effluent Cd2+(aq) + 2e Cd(s)

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#Advantages to recycling Al 1. saves energy costs 2. conserves natural resources 3. protects the environment reduces soil erosion and landslides by reducing mining activities

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