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NCERT Class XI Chemistry Redox Reactions Solutions

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Question : 14 of 30
Marks: +1, -0
Consider the reactions :
2S2O32(aq)+I2(s)\mathrm{2S_2O_3^{2-}\,\text{(aq)} + I_2\,\text{(s)}}S4O6(aq)2+2I(aq)\mathrm{{S_4O_6}^{2-}_{(aq)} + 2{I}^{-}_{(aq)}}
S2O32(aq)+2Br2(l)+5H2O(l)\mathrm{ {S_2O_3^{2-}}_{(aq)} + 2{Br_2}_{(l)} + 5{H_2O}_{(l)} }2SO4(aq)2+4Br(aq)+10H(aq)+\mathrm{2SO_{4(aq)}^{2-} + 4Br_{(aq)}^{-} + 10H_{(aq)}^{+}}
Why does the same reductant, thiosulphate react differently with iodine and bromine?
Solution:  
The average O.N. of S in S2O32\mathrm{S_2O_3^{2-}} is +2 while in S4O62\mathrm{S_4O_6^{2-}} it is +2.5. The O.N. of S in SO42\mathrm{SO_4^{2-}} is +6. Since Br2\mathrm{Br_2} is a stronger oxidising agent, it oxidises S of S2O32\mathrm{S_2O_3^{2-}} to a higher oxidation state of +6 and hence forms SO42\mathrm{SO_4^{2-}} ion. I2\mathrm{I_2}, however, being a weaker oxidising agent oxidises S of S2O32\mathrm{S_2O_3^{2-}} ion to a lower oxidation state of + 2.5 in S4O62\mathrm{S_4O_6^{2-}} ion.
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