2011 DHS Year 6 H2 Chemistry

TUTORIAL: ELECTROCHEMISTRY

Differences between an Electrochemical and an Electrolytic cell

Electrochemical cell Diagram
Voltmeter V Anode (+) + Electron Flow

Electrolytic cell

Salt Bridge

Cathode ()

Anions
Cations

Anode ()

Cathode (+)

Electrolyte

Light Bulb or Voltmeter Present Battery Emf Energy conversion Cathode No Battery Generated by the cell Chemical Electrical Reduction occur Positive (+) Oxidation occur Negative () From anode to cathode

No Light Bulb or Voltmeter Present Battery required Supplied to the cell by battery Electrical Chemical Reduction occur Negative () [due to connection to battery] Oxidation occur Positive (+) From anode to cathode

Anode Electron flow

2010 DHS Year 6 H2 Chemistry

Part I : Electrochemical Cell

1. Method to write cell notation: Determine the which halfcell undergoes reduction and oxidation Draw the salt bridge, Reduction halfcell to be written on the right Oxidation halfcell to be written on the left The species with the higher oxidation number to be written next to the salt bridge Include phase boundary, or use comma , Electrode always at the extreme ends Include state symbols for all species, including the electrodes 2. Calculate Ecell:

Ecell = Ered Eox

3. Equation Arrows:

Anode/cathode/oxidation/reduction Overall chemical equation Use , include state symbols Use

reactions,

halfequation,

Overall

reaction

or

will be penalised (0 marks)

4. Draw labelled diagram to measure standard electrode potential using SHE Standard qn! Labels: anode, cathode, polarity, ions/metal/gas, electrode Standard conditions: Aqueous solution 1 mol dm3 Gas 298 K or 25C, 1 atm Salt bridge: open end, not closed Gas arrow always points into gas column not out! Direction of electron flow: only if asked for Use ruler!

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2010 DHS Year 6 H2 Chemistry

1. (i) (ii) (iii)

Given the following sets of half equations, for the spontaneous reaction that will occur: Write the cell diagram Write the overall cell reaction Calculate E cell

[+1.10V, +2.51V, +0.98V, +0.70V]

(a) Given

Eox
Zn + 2e Cu
2+ 2+

Zn Cu

E = 0.76 V E = +0.34 V

+ 2e

Ered

E (Cu2+ /Cu) is more positive, Cu2+ is more readily reduced.

Therefore: E cell = E red E oxid = +0.34 ( 0.76) = + 1.10 v Reduction: Oxidation: Cell diagram: Cu2+ + 2e Cu Zn Zn2+ + 2e (1) (2)

Zn (s) Zn2+ (aq) Cu2+ (aq) Cu (s)

Overall Cell equation: (1) + (2) Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq) (b) Given Mn
2+

Eox
+ 2e Mn 2Cr3+ + H2O E = 1.18 V E = +1.33 V

Cr2O72 + 14H+ + 6e

Ered

E(Cr2O72- /Cr3+ ) is more positive, Cr2O72 is more readily reduced.

E cell = E red E oxid = +1.33 (1.18) = +2.51 V Therefore Reduction: Oxidation: Cell diagram: Cr2O72 + 14H+ + 6e Mn Mn2+ + 2e 2Cr3+ + H2O (1) (2)

Mn (s) Mn2+ (aq) Cr2O72 (aq), Cr3+ (aq) Pt (s)

Overall Cell equation: (1) + (2)x 3 3Mn (s) + Cr2O72 (aq) + 14H+ (aq) 3Mn2+ (aq) + 2Cr3+ (aq) + 7H2O (l)

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2010 DHS Year 6 H2 Chemistry

(c)

Given Sn
4+

Ered
Sn
2+

+ 2e

E = +0.15 V E = 0.83 V

2H2O + 2e

H2 + 2OH

Eox

E (Sn4+ /Sn2+ ) is more positive, Sn4+ is more readily reduced.

E cell = E red E oxid Reduction: Oxidation: = +0.15 (0.83) = +0.98 V (1) (2) E cell >0 reaction is feasible Sn4+ + 2e Sn2+ 2OH + H2 2H2O + 2e

Cell diagram: Pt (s) H2 (g) H2O (aq) Sn4+ (aq), Sn2+ (aq) Pt (s) Overall Cell equation: (1) + (2) Sn4+ (aq) + 2OH (aq) + H2 (g) Sn2+ (aq) + 2H2O (l)

(d)

Given Fe
3+

Eox
Fe
2+

+ e

E = +0.77 V Pb2+ + 2H2O E = +1.47 V

PbO2 + 4H+ + 2e

Ered

E(PbO2/Pb2+ ) is more positive, PbO

E cell = E red E oxid Reduction: Oxidation:

is more readily reduced. = +0.70 V E cell >0 reaction is feasible (1) (2)

= +1.47 0.77

PbO2 + 4H+ + 2e Fe2+ Fe3+ + e

Pb2+ + 2H2O

Cell diagram: Pt (s) Fe2+ (aq), Fe3+ (aq) PbO2 (s) Pb2+ (aq) Pt (s) Overall Cell equation: (1) + (2) x 2 PbO2 (s) + 4H+ (aq) + 2Fe2+ (aq) Pb2+ (aq) + 2H2O (l) + 2Fe3+ (aq)

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2010 DHS Year 6 H2 Chemistry

2. N99/I/3 (a) Draw a labeled diagram of the standard hydrogen electrode and describe how it may be used to measure the standard electrode potential for Fe3+ (aq)/ Fe2+ (aq).

platinised Pt (s) The standard hydrogen electrode potential for Fe3+/Fe2+ is measured with reference to the standard hydrogen electrode which has a potential of 0.00 V The standard Fe3+/Fe2+ halfcell is connected to the standard hydrogen electrode by a salt bridge, which completes the circuit by allowing the passage of electricity between electrodes but physically separating the two halfcells. From the voltmeter reading at 25oC, Ecell is found to be 0.77 V. Since reduction occurs at the Fe3+/Fe2+ halfcell, the standard electrode potential for Fe3+/Fe2+ is therefore +0.77V. (b) By calculating the relevant oxidation number, determine which elements undergo oxidation, and which undergo reduction, during the following reactions. 2HNO2 + 2HI 2NO + I2+ 2H2O

(i)

+3

+2

Nitrogen undergoes reduction (O.N. decreases from +3 in HNO2 to +2 in NO) Iodine undergoes oxidation (O.N. increases from 1 in HI to 0 in I2) (ii) NO2 + NaClO3 NaNO3 + ClO2

+4

+5

+5

+4

Nitrogen undergoes oxidation (O.N. increases from +4 in NO2 to +5 in NO3) Chlorine undergoes reduction (O.N. decreases from +5 in ClO3 to +4 in ClO2)

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2010 DHS Year 6 H2 Chemistry

(c)

The oxidation number of vanadium in a complex ion was determined as follows. A 0.013 mol sample of the complex was dissolved in water and the solution made up to 100 cm3. A 10 cm3 portion of this solution required 20.8cm3 of 0.025 mol dm3 KMnO4 to oxidise all the vanadium to the +5 state. Use these data to calculate the original oxidation number of the vanadium. Concentration of vanadium complex = [+3]

0.013 100 1000

= 0.130 mol dm3

No of mole of complex in 10 cm3 =

10 0.130 1000 20 .8 0.025 1000

= 1.30 x 103

No of mole of KMnO4 in 20.8 cm3 = Ratio of complex : KMnO4

= 5.20 x 104

1.30 x 103 : 5.20 x 104 1 : 0.4 5:2

No of electrons gained by KMnO4 = 2 x 5 = 10 (since MnO4 + 8H+ + 5e Mn2+ + 4H2O) no. of electrons lost by 5 mol of complex = 10

no of electrons lost by 1 mol of complex = original oxidation state of V = +52 =

10 =2 5

+3

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2010 DHS Year 6 H2 Chemistry

3.

Predict which of the following reactions is expected to proceed under standard conditions. Steps for Prediction of the Feasibility of a Chemical Reaction: Step 1: Step 2: Step 3: Step 4: Step 5: Identify the reactants and its corresponding products. For the reactant undergoing reduction, assign its E value from the Data Booklet as Ered. For the reactant undergoing oxidation, assign its E value from the Data Booklet as Eox. Calculate the overall Ecell value using formula: Ecell = Ered - Eox Check the sign of Ecell. If Ecell > 0, then the reaction is feasible. If Ecell < 0, then the reaction is not feasible.

(a) NO3 (aq) + 3H+(aq) + Cu(s) HNO2 (aq) + H2O (l) + Cu2+ (aq)

[+0.60V]

Reduction
From Data Booklet: NO3 + 3H+ + 2e Cu2+ + 2e Cu HNO2 + H2O

Oxidation

E = +0.94 V E = +0.34 V

Since question state that reduction have to occur from NO3 to HNO2, Ered = +0.94 V Thus, Eoxd = +0.34 V Ecell = Ered Eoxd = +0.94 (+0.34) = +0.60 V E cell >0 reaction is feasible

(b) I2 (s) + 2Fe2+ (aq) 2I (aq) + 2Fe3+ (aq)

[0.23V]

Reduction
From Data Booklet: Fe3+ + e I2 + 2e Fe2+ 2I

Oxidation

E = +0.77 V E = +0.54 V

Since question state that reduction have to occur from I2 to I, Ered = +0.54 V Thus, Eoxd = +0.77 V Ecell = Ered Eoxd = +0.54 0.77 = 0.23V E cell<0 reaction is not feasible

reaction is not feasible

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2010 DHS Year 6 H2 Chemistry

(c) Cr2O72 (aq) +14H+ (aq) + 6Cl (aq) 2Cr3+ (aq) + 7H2O (l) + 3Cl2 (g) [0.03V]

Reduction
From Data Booklet: Cl2 + 2e 2Cl 2Cr3+ + 7H2O

Oxidation

E = +1.36 V E = +1.33 V

Cr2O72 + 14H+ + 6e

Since question state that reduction have to occur from Cr2O72 to Cr3+, Ered = +1.33 V Thus, Eoxd = +1.36 V Ecell = Ered Eoxd = +1.33 1.36 = 0.03 V E cell <0 reaction is not feasible

(d)

2V3+ (aq) + Cu2+ (aq) + 2H2O (l) 2VO2+ (aq) + 4H+ (aq) + Cu (s) [0.00V]

Reduction Oxidation
From Data Booklet: Cu2+ + 2e VO2+ + 2H+ + e Ecell = Ered Eoxd Cu V3+ + H2O E = +0.34 V E = +0.34 V

= +0.34 0.34

= 0.00 V

Since E cell = 0.00 V reaction is feasible but will proceed until equilibrium is reached. Overall eqn: 2V3+ (aq) + 2H2O (l) + Cu2+ (aq) 2VO2+ (aq) + 4H+ (aq) + Cu (s)

4.

The standard redox potential for hydrazine in acidic solution N2 (g) + 5H+(aq) + 4e N2H5+ (aq)

is 0.17V. By using this, and any other necessary information from your Data Booklet, predict the outcome of the reaction of chlorine with hydrazine in acidic solution and write a balanced equation for the overall reaction. [+1.53V] From Data Booklet: Cl2 (g) + 2e Given in question: N2 (g) + 5H+(aq) + 4e N2H5+ (aq) E = 0.17 V 2Cl (aq) E = +1.36 V

Since question mentioned chlorine reacting with hydrazine Ered = +1.36 V Eoxd = 0.17 V Ecell = Ered Eoxd = +1.36 (0.17) = +1.53 V
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E cell >0 reaction is feasible

2010 DHS Year 6 H2 Chemistry

Reduction: Oxidation:

Cl2 + 2e 2Cl (1) + N2H5 (aq) N2 (g) + 5H+ (aq) + 4e (2)

Overall equation: (1) x 2 + (2) 2Cl2 (g) + N2H5+ (aq) 4Cl (aq) + N2 (g) + 5H+ (aq) 5. A cell consisting of a Cu2+ (aq) Cu(s) half cell and a Fe3+ (aq), Fe2+ (aq) Pt (s) halfcell is shown below, using the conventional notation: Cu (s) Cu2+ (aq) Fe3+ (aq), Fe2+ (aq) Pt (s)

reduction

oxidation

(a) Predict the effect on the standard potential, E of this cell if aqueous sodium hydroxide is added to the Cu2+ (aq) Cu (s) halfcell. Cu2+(aq) + 2e Cu (s) Eoxid (1)

Addition of OH causes precipitation of Cu2+ as Cu(OH)2 hence decreasing [Cu2+] By Le Chateliers Principle, the equilibrium in (1) shift left to increase the [Cu2+] Eoxid will become less positive/decrease, oxidation is favoured Since Ecell = Ered Eoxd Overall Ecell will increase / become more positive.

(a)** Predict the effect on the standard potential, E of this cell if aqueous potassium iodide is added to the Fe3+ (aq) , Fe2+ (aq) halfcell.

(b)

It is not possible to use E values reliably to decide whether a chemical reaction will occur: Suggest why it is nevertheless probable that the reaction for which you have written an in (a) will proceed if performed in a testtube.

Two reasons why the reaction will proceed: 1. Reaction is kinetically feasible though not thermodynamically feasible. 2. Reaction takes place under nonstandard conditions (c) Suggest a replacement halfcell for Cu2+ (aq) Cu (s) which would reverse the direction of the electron flow in the Fe3+ (aq), Fe2+ (aq) Pt (s) halfcell. Your answer needs to state both the electrode and reagents of your new halfcell. Ag electrode dipped in AgNO3 solution Reason: From Data Booklet: Ag + e Fe
3+ +

Ag Fe
2+

(+0.80V) (+0.77V) (+0.34V)

+e

From the E value, to reverse the direction of electron flow, there is a need to cause oxidation to take place at the Fe3+ (aq), Fe2+ (aq) Pt (s) halfcell. Choose halfcell with E value > +0.77 V, so that Ecell will be > 0.
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Cu2+ + e

Cu

2010 DHS Year 6 H2 Chemistry

6. A simple rechargeable cell may be constructed by dipping two lead electrodes into aqueous lead (II) nitrate and passing a current for a few minutes. During the process, lead (IV) oxide is deposited on one of the electrode. When the power source is disconnected and a bulb is connected across the two electrodes, the bulb lights for a time as the cell discharges. (a) By reference to the Data Booklet, choose two halfcell equations to construct the full equation for the reaction that occurs during discharge. Calculate the value of E for this cell reaction. [+1.60V] During charging the Pb2+ is being oxidised to PbO2. When the power source is disconnected, the cell will discharge and PbO2 will be reduced to Pb2+ From the Data Booklet For reduction: PbO2 + 4H+ + 2e Pb4+ + 2e Pb2+ Pb2+ + 2H2O +1.47 V +1.69 V (1)

(The first halfequation is selected since the question mentioned lead (IV) oxide) For oxidation: Pb2+ + 2e Pb 0.13 V (2)

During discharge PbO2 will be reduced to Pb2+ (NB: reduction of NO3 will not take place.) Ecell = Ered Eoxd = +1.47 (0.13) = +1.60 V

(1) + (2): PbO2 + 4H+ + 2e Pb2+ + 2H2O +1.47 V Pb Pb2+ + 2e 0.13 V PbO2 (s) + 4H+ (aq) Pb (s) 2Pb2+ (aq) + 2H2O (l) (b) In a leadacid battery, similar reactions takes place but the electrolytes of dilute sulfuric acid causes the lead (II) ions to be precipitated as PbSO4 (s), which coat the electrode. The e.m.f. of the cell is 2.0V. Explain the difference between this e.m.f. and the E calculated in (a) by reference to the concentrations of relevant aqueous ions. When Pb2+ is precipitated out as PbSO4, the [Pb2+] decreases Hence the equilibrium of the reaction will shift right according to Le Chatelier's principle to increase [Pb2+] PbO2 + 4H+ + 2e Pb2+ + 2H2O Ered

In addition, the increase in [H+] due to presence of H2SO4 further shifts the equilibrium to the right. Ered will increase and since Ecell = Ered Eoxd, new Ecell value will increase
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2010 DHS Year 6 H2 Chemistry

7.

(a) Describe the components in any one fuel cell and the reactions taking place at the electrodes. Suggest one advantage of fuel cells as source of energy. Anode: Cathode: Electrolyte Anode reaction Cathode reaction Overall reaction Graphite impregnated with finely powdered Pd catalyst Graphite impregnated with finely divided cobalt (II) oxide and Pt as catalyst Aqueous KOH 2H2(g) + 4OH(aq) 4H2O (l) + 4e O2 (g) + 2H2O (l) + 4e 4OH (aq) 2H2 (g) + O2 (g) 2H2O (l)

Advantages: Pollution free High power to mass ratio Highly efficient (75% efficiency) Easy maintenance

Any One

Industrial use of Fuel

Futuristic MP3 player from Toshiba which make use of Fuel Cell Technology

Hydrogen Fuel Cell used in rockets to propel space craft into orbit

Fuel Cell Technology used in hybrid cars

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2010 DHS Year 6 H2 Chemistry

(b) Hydrogen and oxygen can be used in a fuel cell. By choosing suitable electrode reactions from Data Booklet, calculate the e.m.f. of a cell consisting of oxygen electrode and a hydrogen electrode, each under acidic conditions. [+1.23V] From the Data Booklet choose: O2 + 4H+ + 4e 2H+ + 2e H2 2H2O +1.23 V 0.00 V

In the case of hydrogen and oxygen fuel cell, from the E values, reduction of O2 and oxidation of hydrogen will occur Thus, Ecell = Ered Eoxd = +1.23 0.00 = +1.23 V

(c) One type of rechargeable battery makes use of the nickelcadmium cell, in which nickel and cadmium electrodes, coated with their respective hydroxides, are immersed in potassium hydroxide solution. In normal use, the cadmium electrode is the one that releases electrons to the external circuit. The relevant electrode reactions are: Cd(OH)2 (s) + 2e NiO(OH) (s) + H2O (l) + e Cd (s) + 2OH (aq) Ni(OH)2 (s) + OH (aq)

Write a cell diagram for this arrangement, showing the polarity of the electrodes, and construct a balanced equation for the reaction that occurs during the discharge. Since cadmium electrode is the one that releases electrons to the external circuit oxidation must occur at the cadmium electrode and it must be the anode () Nickel electrode must be the cathode (+) where reduction occurs. Cell Diagram: Cd (s), Cd(OH)2 (s) NiO(OH) (s), Ni(OH)2 (s), Ni (s) Reduction: Oxidation: NiO(OH) (s) + H2O (l) + e Ni(OH)2 (s) + OH (aq) Cd (s) + 2OH (aq) Cd(OH)2 (s) + 2e

Overall equation: Cd (s) + 2NiO(OH) (s) + 2H2O (l) Cd(OH)2 (s) + 2Ni(OH)2 (s)

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2010 DHS Year 6 H2 Chemistry

SelfAttempt Questions 8. Use the standard electrode potential data in your Data booklet, to calculate the standard e.m.f of the cell: [+0.48V] Sn (s) Sn2+ (aq) Cu2+ (aq) Cu (s)

and write a balanced equation for the reaction. From the Data Booklet: Cu2+ + 2e Sn2+ + 2e Cu Sn E = +0.34 V E = 0.14 V

Ered Eox
= +0.48 v E cell >0 reaction is feasible

E cell = E red E oxid From the cell diagram Reduction: Oxidation:

= +0.34 (0.14)

Cu2+ + 2e Cu Sn Sn2+ + 2e

(1) (2)

Overall Cell equation: (1) + (2) Cu2+ (aq) + Sn (s) Cu (s) + Sn2+ (aq)

9.

Use the half equations in the Data Booklet to construct a balanced equation, under conditions of low pH, for each of the reactions between (a) manganate (VII) and iron (II) ions From Data Booklet: MnO4 + 8H+ + 5e Fe3+ + e Ered = +1.52 V Eoxd = +0.77 V Ecell = Ered Eoxd = +1.52 (+0.77) = +0.75 V E cell >0 reaction is feasible (1) (2) Fe2+ Mn2+ + 4H2O E = +1.52 V E = +0.77 V [+0.75V]

Reduction: MnO4 + 8H+ + 5e Mn2+ + 4H2O Oxidation: Fe2+ Fe3+ + e

Overall reaction (1) + [(2) x 5] MnO4 (aq) + 8H+ (aq) + 5Fe2+ (aq) Mn2+ (aq)+ 4H2O (l) + 5Fe3+ (aq)

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2010 DHS Year 6 H2 Chemistry

(b)

dichromate (VI) and iron (II) ions From Data Booklet: Cr2O72 + 14H+ + 6e Fe3+ + e Ered = +1.33 V Eoxd = +0.77 V Ecell = Ered Eoxd = +1.33 (+0.77) = +0.56 V Fe2+ 2Cr3+ + 7H2O E = +1.33 V E = +0.77 V

[+0.56V]

E cell >0 reaction is feasible (1) (2)

Reduction: Cr2O72 + 14H+ + 6e 2Cr3+ + 7H2O Oxidation: Fe2+ Fe3+ + e

Overall reaction (1) + [(2) x 6] Cr2O72 (aq) + 14H+ (aq) + 6Fe2+ (aq) 2Cr3+ (aq) + 7H2O (l) + 6Fe3+ (aq) Suggest why potassium manganate (VII) rather than potassium dichromate (VI) is used to titrate Fe (II) in volumetric analysis. [i.e. consider the titration procedure] If MnO4 is used, a distinct endpoint of yellow (due to mostly Fe3+) pale orange (due to mixing one drop of purple MnO4 in excess with yellow Fe3+) is seen. If Cr2O72 is used, the endpoint of yellowgreen (due to mostly Fe3+ + Cr3+) not distinct. Hence MnO4 is used. orangegreen is

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2010 DHS Year 6 H2 Chemistry

10. (a) (i) Describe the experimental procedure you would use to measure the standard electrode potential of I2 (aq) /I (aq) system. A standard I2 (aq) / I (aq) halfcell (which consists of a Pt electrode dipping into a solution of I of concentration 1 mol dm3) is connected to a standard hydrogen electrode via a salt bridge. The electrode potential is measured using a voltmeter. (Need not draw diagram to illustrate since question specifically mention describe). (ii) What effect would an increase in the concentration of iodide ions have in the Ecell of this system? I2 + 2e 2I Ered = +0.54 V

When [I] increases, equilibrium shift to the left by LeChaterliers Principle to decrease [I] oxidation process is favoured, Ered becomes less positive Ecell becomes decreases

(b) Use the Data Booklet to predict the reaction that would occur when the following pairs of solutions are mixed. Calculate the Ecell and write an equation for each reaction. State the observation if reaction occurs. (i) acidified manganate (VII) and aqueous sulfur dioxide. From the Data Booklet: MnO4 + 8H+ + 5e SO42 + 4H+ + 2e Ecell = Ered Eoxd Reduction: Oxidation: Mn2+ + 4H2O SO2 + 2H2O E = +1.52 V E = +0.17 V [+1.35V]

Ered Eoxd

= +1.52 (+0.17)

= +1.35 V

E cell >0 reaction is feasible

MnO4 + 8H+ + 5e Mn2+ + 4H2O (1) (2) SO2 + 2H2O SO42 + 4H+ + 2e

Overall reaction: [(1) x 2] + [(2) x 5] 2MnO4 (aq) + 2H2O (l) + 5SO2 (g) 2Mn2+ (aq) + 5SO42 (aq) + 4H+ (aq)

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2010 DHS Year 6 H2 Chemistry

Part II : Electrolytic Cell

Important Concept: Selective discharge of ions With an aqueous solution as electrolyte, there may be more than one type of ions E.g. NaCl (aq) contains Na+ and Cl from NaCl and H+ and OH from autoionisation of water. The orders in which ions are discharged at the electrodes depend on three factors: (1) (2) (3) Nature of the electrode (reactive or inert e.g. platinum or graphite) Concentration of the ions in the electrolyte Nature of aqueous electrolyte (Comparing E values)

General Steps for Calculations involving Electrolysis Step 1 : Step 2 : Step 3 : Step 4 : Step 5 : Write the half equation for the reaction occurring at the cathode or anode Determine the no. of mol of electrons required Calculate the quantity of electricity, Q Calculate the no. of moles of substance (=

Q ) no. of Faradays

Calculate the mass / volume of substance

H 2O Na+ SO42

1(a)

A current of 3.20 A passed through dilute aqueous sodium sulfate for 50 minutes. Calculate the volume of gas (measured at room temperature and pressure) liberated at the anode.

Analysis: Why not SO42? From Data Booklet SO42 + 4H+ + 2e S2O8 + 2e O2 + 4H+ + 4e
2

SO2 + 2H2O 2SO42 2 H2O

+0.17 +2.01 +1.23V

Since oxidation must occur at anode, ion concerned must be on the right hand side. Thus first equation is out, since it shows SO42 being reduced. Since oxidation have to occur, the half equation with a less positive E value will be favoured. Thats why SO42 did not under go oxidation Step 1: Analysis, at anode: 2 H2O (l) O2 (g) + 4H+ (aq) + 4e Step 2: 2F is required to liberate one mole of O2 gas Step 3: Quantity of electricity passed Q = I x t = 3.20 x (50 x 60) = 9600 C

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2010 DHS Year 6 H2 Chemistry

Step 4: No of moles of O2 gas liberated =

Q no. of Faradays

9600 9600 = 0.02487 mol = 4F 4 96500

= 0.597 dm3

Step 5: Volume of gas liberated at r.t.p. = n x Molar volume = 0.02487 x 24.0 (b)

A layer of chromium is electroplated on an automobile bumper by a passing constant current of 250 A through a cell that contains Cr3+ (aq). Calculate the time taken in minutes to deposit 250 g of chromium.

Step 1: Analysis, at Cathode: Cr3+ + 3e Cr Step 2: 3F is required to deposit 1 mol of Cr Step 3: Quantity of electricity passed Q = I x t Step 4: No of moles Cr deposited = = 250 x t

250 t Q = 3 96500 no. of Faradays

Step 5: Determining time to deposit 250 g of Cr Since n=m/Mr

250 250 t = 52 3 96500

t = 5567.3 s 92.8 min

(c)

In an experiment, 0.80 g of element Europium was discharged at the cathode by the passage of 0.50 A of current for 2000 seconds. Europium has relative atomic mass of 152. Calculate the charge on the europium ion.

Using

m Q 0.80 0.50 2000 = = Mr n F 152 n 96500

n = 1.96 2

Since 2F is required to discharge 1 mol of Europium ion, Therefore, charge on Europium ion = 2

2. The following pairs of electrolysis experiments were carried out. In each case, determine which experiment produces the bigger increase in the mass of the cathode (Show all relevant working).
(a)

Exp I : 3.00 A for 60 minutes through 1.0 mol dm3 Na2SO4 (aq) using platinum electrodes. Exp II : 5.00 A for 10 minutes through 1.0 mol dm3 CuSO4 (aq) using copper electrodes.

For Expt 1: Analysis: Current 3.0 A, time 60 min, given Na2SO4 (aq)
(1) At the cathode: 2 H2O (l) + 2e H2 (g) + 2OH (aq) (2) 2 Faraday is required to discharge 1 mol of H2 (g) (3) Q = I x t = 3 x 60 x 60 = 10800 C
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Na+ SO42 H2O

2010 DHS Year 6 H2 Chemistry

(4) No of mole of H2 liberated =

Q 10800 = = 0.05595 2F 2 96500

(5) Volume of H2 liberated = 0.05595 x 24 = 1.34 dm3 Thus, reduction of Na+ to Na will not occur at the cathode.

Mass of cathode remains unchanged (since no Na metal is deposited) For Expt 2: Analysis: Current 5.0 A, time 10 min, given CuSO4 (aq)
(1) At the cathode: Cu2+ (aq) + 2e Cu (s) (2) 2 Faraday is required to deposit 1 mol of Cu (3) Q = I x t = 5 x 10 x 60 = 3000 C

Cu2+ SO42 H 2O

(4) No of mole Cu deposited = Q / 2F

3000 2 96500

= 0.0155

(5) Mass of Cu deposited = 0.0155 x 63.5 = 0.987 g

Expt 2 will show the greater increase in the mass of the cathode.
(b)

Exp I : 0.2 A for 30 minutes through PbBr2 (aq) using carbon electrodes. Exp II : 0.2 A for 30 minutes through AgNO3 (aq) using silver electrodes

For Expt 1: Analysis: Current 0.2 A, time 30 min, given PbBr2 (aq)
(1) At the cathode: Pb2+ (aq) + 2e Pb(s)

Pb2+ Br H2O

(2) 2 Faraday is required to discharge 1 mol of Pb2+(aq)

(3) Q = I x t = 0.2 x 30 x 60 = 360 C

(4) No of mole of H2 liberated =

Q 360 = = 1.18 x103 2F 2 96500

(5) mass of Pb deposited = 1.18 x 103 x 207.2 = 0.244 g

For Expt 2: Analysis: Current 0.2 A, time 30 min, given AgNO3 (aq)
(1) At the cathode: Ag+ (aq) + e Ag (s) (2) 1 Faraday is required to deposit 1 mol of Ag

Ag+ NO3 H2O

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2010 DHS Year 6 H2 Chemistry

(3) Q = I x t = 0.2 x 30 x 60

= 360 C

(4) No of mole Ag deposited = Q / F = (5) Mass of Ag deposited =

360 96500

360 x 108 = 0.403 g 96500

Expt 2 will show the greater increase in the mass of the cathode.
(c) When a current if 0.25 A was passed through dilute aqueous NaCl for 32 minutes and 10 seconds at s.t.p., 56 cm3 of gas was evolved at the cathode. Calculate the Faraday constant from these data and hence derive a value for the Avogadros constant, obtaining any other data from the Data Booklet. Analysis: I = 0.25 A t = 32 min 10 sec Given NaCl (aq) Na+, Cl , H2O are present

(1) Cathode reaction: 2 H2O (l) + 2e H2 (g) + 2OH (aq) (2) 2 Faraday is required to discharge 1 mol of H2 (g) (3) Q = I x t = 0.25 x [(32 x 60) + 10] = 482.5 C (4) no. of mole of H2 evolved at s.t.p. =

H2O discharged due to more +ve E value compared to Na+

0.056 = 2.5 10 3 22.4

2.5 x 103 mol of H2 required 482.5 C of electricity to discharge.

Using the formula: no. of mole of H2 =

Q 2F

F=

Q 482.5 = 96500 C mol1 Proven = 2 nH2 2(2.5 10 3 )

Since F = L x e Where L is Avogadros Constant and e is charge of electron and from the Data Booklet e = 1.60x1019 C L=

F 96500 = = 6.03 10 23 e 1.6 10 19

Proven

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2010 DHS Year 6 H2 Chemistry

3. (a)

Draw and label the apparatus used to electrolyse molten lead (II) bromide in an evaporating basin using graphite electrodes and including an ammeter in the circuit.

Ammeter A Graphite electrode Graphite electrode Label: Electrode Electrolyte State symbols cathode/anode +/

Cathode () (Reduction) Pb2+ (l) + 2e Pb (s) Electrolyte PbBr2 (l)

(b) (i) (ii)

Anode (+) (Oxidation) 2Br (l) Br2 (l) + 2e

Give the ionelectron equations for the reaction occuring at the anode cathode Suggest how you would detect the product formed at the anode. 2Br (l) Br2 (l) + 2e Pb2+ (l) + 2e Pb (s) [grey solid]

Anode: Cathode:

The electrolyte turns reddishbrown to show the formation of the Br2 at the anode.

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2010 DHS Year 6 H2 Chemistry

(c) When a current of 4.0 A was passed for 30 minutes, a bead of lead of mass 6.90 g was obtained. (i) How many coulombs were passed? (ii) In this experiment, how many coulombs would be required to deposit one mole of lead? (i) (ii) Q =Ixt = 4 x 30 x 60 = 7200 C

mass of Pb deposited = 6.90 g No. of mole of Pb deposited = 6.90/ 207 = 0.0333 Therefore quantity of electricity required to deposit 1 mol of Pb = 7200 0.0333 = 2.16 x 105 C

4.

J03/IV/1
Because of its increased scarcity, cheaper copper ornaments are no longer made from the solid metal, but from iron that has been copper plated.

(a)

Draw a diagram to show the set up for a copper electroplating process. Show clearly the polarity (+/) of the power source, and suggest a suitable electrolyte.

Object to be plated

A +
Cu (s) electrode

Electrolyte: CuSO4 (aq)

NB: The object to be plated must always be the cathode i.e. reduction take place Cu2+ (aq) + 2e Cu (s)
(b) A current of 0.500 A is passed through the electroplating cell. Calculate the time required to deposit a mass of 0.500 g of copper on to the ornament. [50.6 min]

Cu2+ (aq) + 2e Cu (s) No of mole of Cu deposited =

0.500 = 7.874 10 3 63.5

Q 2F

No of Faraday to produce 1 mol of Cu = 2F Therefore, using no. of mole =

Q = no. of mol x 2F = 7.874 x 103 x 2 x 96500 = 1519.6 C

Since Q = I x t

t=

Q 1519.6 = = 3039 seconds I 0.500

50.7 min

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2010 DHS Year 6 H2 Chemistry

5.(a) When a current is passed through a cell containing aqueous silver nitrate (using inert electrodes ), silver is deposited at the cathode and oxygen is evolved at the anode. What volume of oxygen, at s.t.p, would be produced if the current were passed for a sufficient time to deposit 0.60 g of silver?

At Cathode: Ag+ + e Ag At Anode: 4OH (aq) 2H2O (l) + O2 (g) + 4e No. of mole of silver deposited =
0.60 = 5.555 x 103 = no. of mole of electron 108

Since the two electrodes are connected in series, the same no. of mole of electron must pass through both electrodes at the same time. 4e O2 No. of mole of O2 evolved =
5.555 10 3 = 1.388 x 103 4

Volume of O2 evolved at s.t.p = 1.388 x 103 x 22.4 = 0.0311 dm3

(b)

Calculate the ratio of the mass of silver to the mass of nickel deposited on the cathodes when the current is passed through electrolytic cells containing silver (I) nitrate and aqueous nickel (II) sulfate, connected in series.

Ni2+ + 2e Ni (1) Ag+ + e Ag (2) Since the two electrolytic cells are connected in series, the same no. of mole of electron must pass through both cells at the same time. Eqn (2) x 2: 2Ag+ + 2e 2Ag Hence no. of mole of Ag deposited : no. of mole of Ni deposited = 2 : 1 Mass of Ag deposited : Mass of Ni deposited = 108 x 2 : 58.7 = 3.68 : 1

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2010 DHS Year 6 H2 Chemistry

6. (a)

Integrated Question N2006/III/1

Predict the products formed at the anode, and at the cathode, when the following liquids are electrolysed using inert electrodes. In each case explain your reasoning, using data from the Data Booklet. [6] NaBr (l)

(i)

Only Na+ (l) and Br (l) are present as ions to be discharged at the cathode and anode respectively.
Products are: Na (s) at the cathode and Br2 (l) at the anode (ii) NaBr (aq) 2H2O + 2e Na+ + e Since the E
(H2O/H2 )

At the cathode:

H2 + 2OH 0.83V Na 2.71 V

is more positive / less negative, H2O is more readily reduced.

H2 (g) is produced at the cathode.

At the anode: O2 + 4H+ + 4e Br2 + 2e 2 H2O +1.23V 2Br +1.07 V

Since the E (Br- /Br2 ) is less positive, Br is more readily oxidised.

Br2 (aq) is produced at the anode.

(iii)

CuF2 (aq) 2H2O (l) + 2e Cu

2+

At the cathode:

H2 (g) + 2OH Cu

0.83V +0.34 V

+ 2e

Since the E

(Cu/Cu2 + )

is more positive / less negative, Cu2+ is more readily reduced.

Cu (s) is produced at the cathode.

O2 + 4H+ + 4e F2 + 2e Since the E
(H2O/O2 )

At the anode:

2 H2O +1.23V 2F +2.87 V

is less positive, H2O is more readily oxidised.

O2 (g) is produced at the anode.

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2010 DHS Year 6 H2 Chemistry

(b)

The electrolysis of a solution of potassium fluoride, KF, in a mixed solvent of hydrogen fluoride and water produces a colourless triatomic gas A at the anode. When 0.900 g of A is introduced into an evacuated vessel of 1.00 dm3 capacity at a temperature of 282 K, it produces a pressure of 3.90 x 104 Pa. Calculate the Mr of A.

(i)

M=

mRT (0.900)(8.31)(282) = = 54.1 g mol1 4 3 PV (3.90 10 )(1.00 10 )

Mr = 54.1 (answer to question!) (ii) Suggest the molecular formula and the shape of A. [4]

Analysis:
KF (electrolysed) + HF + H2O colourless triatomic (three atoms!) gas A at anode

suspect F oxidised (since at anode) to F2 remaining atom in A is oxygen (since triatomic).

Mr of 54 2(19) (due to F2) + 16

Possible molecule formula of A is F2O. Shape: Bent about O atom. [like H2O]

7.

Copper often occurs in the Earths crust as the sulfide, Cu2S, associated with the sulfides of zinc, ZnS, and silver, Ag2S. The copper is extracted from its ores by partial airoxidation to copper (I) oxide and sulfur dioxide, followed by the reaction between this copper (I) oxide and unchanged copper (I) sulfide to give copper metal and more sulfur dioxide. Write balanced chemical equations for these two reactions.

(a)

The first stage produces copper containing some zinc and silver as impurities. Reaction 1: Reaction 2: (b) Cu2S (s) + 3/2 O2 (g) Cu2O (s) + SO2 (g) 2Cu2O (s) + Cu2S (s) 6Cu (s) + SO2 (g)

Describe in detail with the aid of relevant equations and diagram, how this impure copper is purified electrolytically, explaining what happens to the zinc and silver impurities. The use of relevant E data from the Data Booklet is recommended.

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2010 DHS Year 6 H2 Chemistry

In the electrochemical purification of copper:

Anode: Crude copper Cathode: Pure copper Electrolyte used: Copper (II) sulfate From the Data Booklet: Ag+ + 2e Cu
+ 2+

Ag Cu H2 Zn

+0.80V +0.34V 0.00 V 0.76V

+ 2e + 2e

H +e Zn
2+

When an electric current is applied, both zinc and copper are oxidised to Zn2+ and Cu2+ respectively. Silver, due to its more positive (E) reduction potential will not be oxidised. Silver will drop to the electrolytic bed as elemental silver. H+, Zn2+ and Cu2+ migrate to the cathode. Only Cu2+ is reduced to copper due to its more positive reduction potential and higher concentration. H+ and Zn2+ remains in the solution.

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2010 DHS Year 6 H2 Chemistry

SelfAttempt Questions

Cu2+ NO3

8. An aqueous solution of copper (II) nitrate is electrolysed for 20 minutes with a constant current of 2.40 A. Calculate the mass of copper deposited at the electrode. Step 1: Analysis, at Cathode: Cu2+ (aq) + 2e Cu (s) Step 2: 2F is required to deposit 1 mol of Cu Step 3: Quantity of electricity passed Q = I x t = 2.40 x (20 x 60) = 2880 C 2880 2880 Q Step 4: No of moles of Copper deposited = = = = 0.014922 2F 2 96500 no. of Faradays Step 5: Mass of copper deposited = n x Ar = 0.014922 x 63.5 = 0.94756 = 0.948 g

9. State and explain, with the aid of the Data booklet where necessary, what would happen in the following experiment: (a) Dilute aqueous potassium bromide using C electrodes.

H2O

K+ Br

Inert electrode

At the cathode (reduction takes place): K+ and H2O migrate

From the Data Booklet: E/ V K+ + e K 2.92 V

2H2O + 2e

H2 + 2OH

0.83V

Since the E (H2O/H2 ) is more positive, H2O is more readily reduced.

Cathode reaction:

2 H2O (l) + 2e H2 (g) + 2OH (aq)

(1)

At the anode (oxidation takes place): Br and H2O migrate

From the Data Booklet: E/ V Br2 + 2e 2Br + O2 + 4H + 4e Since the E
(Br- /Br2 )

2 H2O

+1.07 V +1.23V

is less positive, Br is more readily oxidised. 2Br (aq) Br2 (aq) + 2e

(2)

Anode reaction:

Overall reaction (1) + (2): 2H2O (l) + 2Br (aq) 2H2 (g) + 2OH (aq) + Br2 (aq) Observation: Effervescence of H2 is seen at the cathode and solution turns reddish brown.
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2010 DHS Year 6 H2 Chemistry

(b) Concentrated aqueous copper (II) chloride is electrolysed between graphite electrodes.

H2O Cu2+ Cl
At the cathode (reduction takes place): Cu2+ and H2O migrate
From the Data Booklet: E/ V Cu2+ + 2e 2H2O + 2e Cu +0.34 H2 + 2OH 0.83V

Inert electrode

E (Cu 2+ /Cu) is more positive, Cu2+ is more readily reduced.

Cathode reaction:
Cu2+(aq) + 2e Cu (s) (1)

At the anode (oxidation takes place): Cl and H2O migrate

Cl ions are preferentially discharged instead of H2O since there is a high concentration of Cl ions. Chlorine gas is liberated.

Anode reaction: Overall reaction (1) + (2):

2Cl (aq) Cl2 (g) + 2e

(2)

Cu2+ (aq) + 2Cl (aq) Cu (s) + Cl2 (g)

Observation: Effervescence of greenishyellow gas of Cl2 is seen at the anode and pink solid of copper metal will appear at the cathode. Decolourisation of blue solution.

(c) Molten lead (II) oxide using C electrodes.

Pb2+ O2
At the cathode: only Pb2+ migrate Cathode reaction: Pb2+ (l) + 2e Pb (s)

At the anode: only O2 migrate Anode reaction: 2O2 (l) O2 (g) + 4e

Observation: Grey solid deposited at the cathode and effervescence observed at the anode

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2010 DHS Year 6 H2 Chemistry

Multiple Choice Questions Q1

A weedkiller can be prepared by heating a bleach solution 3NaClO 2NaCl + NaClO3 bleach weedkiller

A B C D Q2

What are the oxidation states of chlorine in these compounds? 1 1 +5 +1 1 +5 +1 1 +7 +2 1 +7 The equations for three reactions are given below: Cl2 (g) + 2H2O (l) + SO2 (g) 2HCl (aq) + H2SO4 (aq) Cl2 (g) + H2S (g) 2HCl (g) + S (s) SO2 (g) + 2H2S (g) 2H2O (l) + 3S (s) What is the correct order of strength of the three reacting gases as reducing agents? Strongest Weakest Hydrogen sulfide Sulfur dioxide Sulfur dioxide Hydrogen sulfide Sulfur dioxide Hydrogen sulfide Chlorine Chlorine

A B C D Q3

Chlorine Chlorine Hydrogen sulfide Sulfur dioxide

Four standard electrode potentials are listed below: Cu2+(aq) + 2e Cu(s) AgCl(s) + e Ag(s) + Cl (aq) H+ (aq) + e H2 (g) Zn2+ (aq) + 2e Zn (s) +0.34V +0.22V 0.00V 0.76V

Which cell potential could be obtained by combining two of these standard electrodes?

A B C D E

0.39 V 0.42 V 0.54 V 0.56 V 0.98 V

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2010 DHS Year 6 H2 Chemistry

Q4

The use of the Data Booklet is relevant to this question. Sir Humphrey Davy showed that the corrosion of copper hulls of sea going ships could be prevented by placing strips of sacrificial metals on the hulls Which of these metals is least likely to dissolve when attached to the copper hull of a sea going ship?

A B C D Q5

Iron Magnesium Tin Zinc In the construction of heart pacemakers, it is possible to use a tiny magnesium electrode which creates an electrical cell with the inhaled oxygen. The relevant halfcells are as follows Mg2+ + 2e Mg O2 + 2H+ + 2e H2O E = 2.38V E = +1.23V

Under standard conditions, the cell emf would be 3.61 V, but in the body a potential of 3.25 V is more than usual. What is the best explanation of this lower emf?

A B C D Q6

The small size of the magnesium electrode. The low concentration of Mg2+ ions surrounding the magnesium electrode. The high resistance of the body fluids surrounding the electrodes. The pH of between 7 and 8 of the body fluid surrounding the electrodes. A current of 8A is passed for 100 minutes through molten aluminium oxide using inert electrodes. What will be the approximate volume of gas liberated, measured at s.t.p?

A B C D E

2.8 dm3 5.6 dm3 8.4 dm3 11.2 dm3 22.4 dm3

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2010 DHS Year 6 H2 Chemistry

Q7

The standard cell potentials for the redox equilibria of aqueous vanadiumcontaining ions and the colours of these ions are below. VO2+ + 2H+ + e Yellow VO2+ + 2H+ + e Blue V3+ + e Green V2+ purple H2O + VO2+ blue H2O + V3+ green E = +1.00 V

E = +0.34 V

E = 0.26 V

What is likely to the final colour when metallic tin is added to a solution containing VO2+? (Sn2+ + 2e Colourless Sn E = 0.14 V)

A B C D

Yellow Blue Green Purple

Q8

Aqueous sodium chloride (brine) is electrolysed by using inert electrodes in a cell which is stirred so that the products of electrolysis are able to react. The cell is kept cold. Which one of the following pairs of substances is among the final products?

A B C D E

Hydrogen and chlorine only Hydrogen and sodium chlorate (I) Hydrogen and sodium chlorate (V) Hydrogen chloride and sodium chlorate (I) Sodium hydroxide and chlorine only

Answers: 1. B 2. C 3. E 4. C 5. D 6. B 7. C 8. B

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