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St.

Andrews Junior College H2 Chemistry 2012 Redox Reactions

Tutorial 4: Redox Reactions Basic Questions

1. State the oxidation number of: (a) N in N2O, NO, NO2, NO3-, NH3, N2H2 +1 +2 +4 +5 -3 ClO3-, +5 -1 ClO4-, Na3AlCl6 +7 -1 (b) Cl in HCl, HClO, -1 +1 ClO2-, +3

2. Which of the following equations represent redox reactions? Explain your answer in terms of changes in oxidation number. (a) 2FeCl2 + Cl2 2FeCl3 (b) 2CrO42- + 2H+ Cr2O72- + H2O (c) Cl2 + 2NaOH NaCl + NaClO + H2O

3. Balance the following equations: (a) I- + ClO- I3- + Cl- (in acidic medium)

(b) C6H5CH3 + MnO4- Mn2+ + C6H5COOH (in acidic medium)

(c) MnO4- + H2O2 MnO2 + O2 (in alkaline medium)

(d) MnO4- + SO32- MnO42- + SO42- (in alkaline medium) 4. Write redox equations for the following reactions: (a) When aqueous potassium iodide, KI is added to acidified hydrogen peroxide, H2O2, a brown solution of iodine, I2 is formed.

(b)

When sodium sulfite, Na2SO3 is added to acidified potassium dichromate (VI), K2Cr2O7 solution, the orange solution turns to green Cr3+ ions.

5. In an experiment, 50 cm3 of a 0.100 mol dm-3 solution of a metallic salt reacted exactly with 25 cm3 of 0.1 mol dm-3 aqueous sodium sulfite, Na2SO3 . (a) Write down the half-equation for oxidation of sulfite, given it was oxidized to sulfate, SO42-. (b) If the original oxidation number of the metal in the salt was +3, what would be the new oxidation number of the metal after reaction with Na2SO3? [Answer: (b) +2 ] SO32- + H2O SO42- + 2H+ + 2e

5(a)

(b) No of moles of SO32- = 0.025 x 0.1 = 0.0025 mol No of moles of metallic salt = 0.05 x 0.1 = 0.005 mol Mole ratio of SO32- to metallic salt = 1: 2 Since 1 mol of SO32- lost 2 mol electrons, 2 mol of electrons is gained by 2 mol of metallic salt. 1 mol of metallic salt (M3+) gained 1 mol electrons. Final oxidation state of M = +2 M3+ + e M2+

6. 20.0 cm3 of 0.0500 mol dm-3 iron(II) sulfate is titrated against 0.0200 mol dm-3 aqueous KMnO4 in the presence of an excess of fluoride and hydrogen ions. Iron(II) ions is oxidized to iron(III) in the process. 12.50 cm3 of the KMnO4 solution is required to reach the end point. What is the oxidation number of the manganese at the end point? No of moles of Fe2+ = 0.02 x 0.05 = 0.001 mol No of moles of MnO4- = 0.0125 x 0.02 = 0.00025 mol Mole ratio of MnO4- to Fe2+ = 1: 4 Fe2+ Fe3+ + e Since 4 mol of Fe2+ loses 4 mol electrons, 4 mol of electrons is gained by 1 mol of MnO4-. Since initial oxidation state of Mn is +7, final oxidation state of Mn = +3. Mn(+7) + 4e Mn(+3) [Answer: +3]

7. 50 cm3 of solution of hydrogen peroxide were diluted to 1 dm3 with water. 25.0 cm3 of this solution, when acidified with dilute sulfuric acid, reacted with 20.25 cm3 of 0.02 mol dm-3 KMnO4. What is the concentration of the original hydrogen peroxide solution in mol dm-3? [Answer: 0.810 mol dm-3] No of moles of KMnO4 = 0.02025 x 0.02 = 4.05 x 10-4 mol 2MnO4- + 6H+ + 5H2O2 2Mn2+ + 8H2O + 5O2 No of moles of H2O2 in 25.0 cm3 = 5/2 x 4.05 x 10-4 = 1.0125 x 10-3 mol No of moles of H2O2 in 1 dm3 of diluted solution = 1000/25 x 1.0125 x 10-3 = 0.0405 mol No of moles of H2O2 in 50 cm of original solution = 0.0405 mol Concentration of original H2O2 = 0.0405 / 0.05 = 0.810 mol dm-3 More Difficult Questions
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8. Iodine and chlorine react together to form compound X (ICln). When 0.0010 mol of X was reacted with an excess of KI(aq), all of its iodide was converted to I2. The iodine liberated required 40.0 cm3 of 0.10 mol dm-3 sodium thiosulfate, Na2S2O3, for complete reaction. (a) Calculate the amount (in moles) of iodine produced. [I2 + 2S2O32- 2I- + S4O62-] (b) Hence calculate the value of n in ICln. (c) Write a balanced equation for the reaction between Cl2 and I2. [N03/III/5(c)] [Answer: (a) 0.002 mol; (b) n=3] No. of moles of sodium thiosulfate = 40/1000 x 0.10 = 0.004 mol No. of moles of iodine = x 0.004 = 0.002 mol (b) ICln + nI-

(n 1) I2 + nCl2
0.001 0.002

No. of moles of ICln No. of moles of I2 (c)

1 (n + 1)/2

n=3 3Cl2 + I2 2ICl3

9. 28.3 g of a sample of haematite iron ore [iron(III) oxide, Fe2O3] is dissolved in concentrated hydrochloric acid and the solution diluted to 250 cm3. 25.0 cm3 of this solution was reduced with tin(II) chloride (which is oxidised to Sn4+ in the process) to form a solution of iron(II) ions. This solution required 26.40 cm3 of 0.02 mol dm-3 potassium dichromate(VI) for oxidation. (a) Given the half-reactions Sn4+ + 2e Sn2+ and Cr2O72- + 14H+ + 6e 2Cr3+ + 7H2O deduce the fully balanced redox equations for the reactions of (i) the reduction of iron(III) ions by tin(II) ions (ii) the oxidation of iron(II) ions by the dichromate(VI) ion. (b) Calculate the percentage of iron(III) oxide in the ore. (c) Why isn't potassium manganate(VII) used for this titration? [Answer: (b) 8.93%] (a)(i) 2Fe3+ + Sn2+ (ii) (b) 2Fe2+ + Sn4+ 6Fe2+ + Cr2O72- + 14H+ 2Cr3+ + 7H2O + 6Fe3+ No of moles of Cr2O72- = 0.0264 x 0.02 = 5.28 x 10-4 mol No of moles of Fe2+ in 25.0 cm3 = 6 x 5.28 x 10-4 = 3.168 x 10-3 mol No of moles of Fe3+ in 25.0 cm3 = 3.168 x 10-3 mol No of moles of Fe3+ in 250 cm3 = 250/25.0 x 3.168 x 10-3 = 3.168 x 10-2 mol Fe2O3 2Fe3+ + 3O2No of moles of Fe2O3 = x 3.168 x 10-2 = 0.01584 mol Mass of Fe2O3 = 0.01584 x (55.8 x 2 + 16 x 3) = 2.528 g % of Fe2O3 = 2.528/28.3 x 100 = 8.93% (c) KMnO4 is not suitable as besides oxidising Fe2+, it will oxidise Cl- (from concentrated HCl) which is present in the solution as well.

10.

Given the half-cell reaction: IO3 + 6H+ + 5e- (a) (b)

/2 I2 + 3H2O

Deduce the redox equation for iodate(V) ions oxidising iodide ions. 25.0 cm3 of the potassium iodate solution were added to excess potassium iodide.

On acidification, the liberated iodine needed 24.10 cm3 of 0.05 mol dm-3 sodium thiosulfate solution for titration. Calculate the concentration of potassium iodate(V) in g dm-3. [Answer: (b) 1.72 g dm-3] 10. (a) (b)

IO3- + 5I- + 6H+


2S2O32- + I2

3I2 + 3H2O

S4O62- + 2I-

No of moles of IO3- : I2 : S2O32- = 1 : 3 : 6 No of moles of S2O32- = 0.0241 x 0.05 = 1.205 x 10-3 mol No of moles of IO3- in 25.0 cm3 = 1/6 x 1.205 x 10-3 = 2.008 x 10-4 mol Concentration of IO3- = 2.008 x 10-4 / 0.025 = 8.033 x 10-3 mol dm-3 Concentration of KIO3 = 8.033 x 10-3 x 214 = 1.72 g dm-3

Assignment Questions

11.

Balance the following equations: (a) HClO + Fe2+ Cl2 + Fe3+ (in acidic medium)

(b)

CH3OH + MnO4- CO2 + MnO2 (in alkaline medium)

12.

1.50 g of ammonium chromate(VI), (NH4)2CrO4, is dissolved in dilute sulfuric acid and water is added to make 250 cm3 of solution, FB 11. The acid present in the solution converts CrO42- ions into orange Cr2O72-. 25.0 cm3 of FB 10 which is an aqueous solution of iron(II) sulfate, require 12.50 cm3 of FB 11 for complete reaction. (a) (b) (c) Write (i) (ii) equation of the reaction between acid H+ and CrO42-. equation of the reaction between Fe2+ and Cr2O72-.

Calculate the mass of Fe2+ ions present in 1 dm3 of FB 10; Calculate mass of FeSO4 used to make 1 dm3 of FB 10. [Answer: (b) 3.30 g; (c) 8.99 g]

13.

A 0.450 g impure sample of sodium azide was dissolved in water and made up to 100 cm3. To a 25.0 cm3 portion of this solution, 25.0 cm3 of acidified 0.050 mol dm3 I2 were added. The equation for the reaction is as follows: 2N3 + I2 3N2 + 2I + excess I2. The excess of iodine required 18.50 cm3 of 0.050 mol dm-3 sodium thiosulfate for complete reaction. Calculate the percentage purity of sodium azide. [Answer: 91.0%]

Tutorial: Redox Reactions SOLUTIONS Basic Questions N in N2O, NO, NO2, NO3-, NH3, N2H2 +1 +2 +4 +5 -3 -1

1 (a)

(b) Cl in HCl, HClO, ClO2-, ClO3-, ClO4-, Na3AlCl6 -1 +1 +3 +5 +7 -1

2(a)

2FeCl2 + Cl2 2FeCl3 Redox as O.N. of Fe increased from +2 to +3; O.N. of Cl decreased from 0 to -1. 2CrO42- + 2H+ Cr2O72- + H2O Not redox as there is no change in oxidation state. Cr remains as +6, H as +1 and O as -2.

(b)

(c)

Cl2 + 2NaOH NaCl + NaClO + H2O Redox as O.N. of Cl decreased from 0 (Cl2) to -1(NaCl) and increased from 0 (Cl2) to +1(NaClO). Disproportionation 3I- I3- + 2e ClO- + 2H+ + 2e Cl- + H2O 3I- + ClO- + 2H+ I3- + Cl- + H2O (b) C6H5CH3 + 2H2O C6H5COOH + 6H+ + 6e MnO4- + 8H+ + 5e Mn2+ + 4H2O 5C6H5CH3 + 6MnO4- + 18H+ 5C6H5COOH + 6Mn2+ + 14H2O (c) MnO4- + 2H2O + 3e MnO2 + 4OHH2O2 + 2OH- O2 + 2H2O + 2e 2MnO4- + 3H2O2 2MnO2 + 2H2O + 3O2 + 2OH(in alkaline medium) (d) MnO4- + e MnO42SO32- + 2OH- (in alkaline medium) SO42- + 2H2O + 2e 2MnO4- + SO32- + 2OH- 2MnO42- + SO42- + H2O

3 (a)

4 (a)

2I- I2 + 2e H2O2 + 2H+ + 2e 2H2O 2I- + H2O2 + 2H+ I2 + 2H2O SO32- + H2O SO42- + 2H+ + 2e 2Cr3+ + 7H2O + 4H2O

(b)

Cr2O72- + 14H+ + 6e

3SO32- + 3H2O + Cr2O72- + 14H+ 2Cr3+ + 7H2O + 3SO42- + 6H+ 3SO32- + Cr2O72- + 8H+ 2Cr3+ + 3SO42-

6.

(a)(i) (ii) (b)

2Fe3+ + Sn2+

2Fe2+ + Sn4+

6Fe2+ + Cr2O72- + 14H+ 2Cr3+ + 7H2O + 6Fe3+ No of moles of Cr2O72- = 0.0264 x 0.02 = 5.28 x 10-4 mol No of moles of Fe2+ in 25.0 cm3 = 6 x 5.28 x 10-4 = 3.168 x 10-3 mol No of moles of Fe3+ in 25.0 cm3 = 3.168 x 10-3 mol No of moles of Fe3+ in 250 cm3 = 250/25.0 x 3.168 x 10-3 = 3.168 x 10-2 mol Fe2O3 2Fe3+ + 3O2No of moles of Fe2O3 = x 3.168 x 10-2 = 0.01584 mol Mass of Fe2O3 = 0.01584 x (55.8 x 2 + 16 x 3) = 2.528 g % of Fe2O3 = 2.528/28.3 x 100 = 8.93%

(c)

KMnO4 is not suitable as besides oxidising Fe2+, it will oxidise Cl- (from concentrated HCl) which is present in the solution as well.

More Difficult Questions

8.(a)

No. of moles of sodium thiosulfate = 40/1000 x 0.10 = 0.004 mol No. of moles of iodine = x 0.004 = 0.002 mol (b) ICln + nI-

(n 1) I2 + nCl2
0.001 0.002

No. of moles of ICln No. of moles of I2 (c)

1 (n + 1)/2

n=3 3Cl2 + I2 2ICl3

9.

10.

(a) (b)

IO3- + 5I- + 6H+


2S2O32- + I2

3I2 + 3H2O

S4O62- + 2I-

No of moles of IO3- : I2 : S2O32- = 1 : 3 : 6 No of moles of S2O32- = 0.0241 x 0.05 = 1.205 x 10-3 mol No of moles of IO3- in 25.0 cm3 = 1/6 x 1.205 x 10-3 = 2.008 x 10-4 mol Concentration of IO3- = 2.008 x 10-4 / 0.025 = 8.033 x 10-3 mol dm-3 Concentration of KIO3 = 8.033 x 10-3 x 214 = 1.72 g dm-3 Assignment Questions 11. (a) 2HClO + 2H+ + 2Fe2+ Cl2 + 2H2O + 2Fe3+ (in acidic medium) (b) CH3OH + 2MnO4- CO2 + 2MnO2 + H2O + 2OH- (in alkaline medium) 12. (a) (i) (ii) 2H+ + 2CrO42- Cr2O72- + H2O 6Fe2+ + Cr2O72- + 14H+ 2Cr3+ + 7H2O + 6Fe3+

(b)

No of moles of (NH4)2CrO4 = 1.50/152.0 = 9.868 x 10-3 mol No of moles of CrO42- in 250 cm3 = 9.868 x 10-3 mol No of moles of Cr2O72- in 250 cm3 = x 9.868 x 10-3 = 4.934 x 10-3 mol No of moles of Cr2O72- in 12.50 cm3 = 12.50/250 x 4.934 x 10-3 = 2.467 x 10-4 mol No of moles of Fe2+ in 25.0 cm3 = 2.467 x 10-4 x 6 = 1.48 x 10-3 mol No of moles of Fe2+ in 1 dm3 = 1.480 x 10-3 x 1000/25 = 0.0592 mol Mass of Fe2+ in 1 dm3 = 0.0592 x 55.8 = 3.30 g No of moles of FeSO4 in 1 dm3 = 0.0592 mol Mass of FeSO4 in 1 dm3 = 0.0592 x (55.8 + 32.1 + 16 x 4 ) = 0.0592 x 151.9 = 8.99 g

(c)

13..

No of moles of S2O32- = 0.0185 x 0.05 = 9.25 x 10-4 mol No of moles of excess I2 = x 9.25 x 10-4 = 4.625 x 10-4 mol No of moles of I2 added = 0.025 x 0.05 = 1.25 x 10-3 mol No of moles of I2 reacted with N3- = 1.25 x 10-3 - 4.625 x 10-4 = 7.875 x 10-4 mol No of moles of N3- in 25.0 cm3 = 2 x 7.875 x 10-4 = 1.575 x 10-3 mol No of moles of NaN3 in 100 cm3 = 1.575 x 10-3 x 100/25.0 = 6.30 x 10-3 mol

10

Mass of NaN3 = 6.30 x 10-3 x 65 = 0.4095 g % purity = 0.4095/0.450 x 100% = 91.0 %

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