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Electrochemistry question

2012 · Shift 2 · Q3
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  5. /2012 · Shift 2 · Q3

Electrochemistry question

2012 · Shift 2 · Q3

JEE AdvancedChemistryElectrochemistryMCQ+4 / −1
The electrochemical cell shown below is a concentration cell. M | M2+M^{2+}M2+ (saturated solution of a sparingly soluble salt, MX2MX_2MX2​) || M2+M^{2+}M2+ (0.001 mol dm–3) | M The emf of the cell depends on the difference in concentrations of M2+M^{2+}M2+ ions at the two electrodes. The emf of the cell at 298 K is 0.059 V. The solubility product (KspKspKsp; mol3 dm–9) of MX2MX_2MX2​ at 298 K based on the information available for the given concentration cell is (take 2.303 ×\times× R ×\times× 298/F = 0.059 V)
  1. A
    1 ×\times× 10–15
  2. B
    4 ×\times× 10–15
  3. C
    1 ×\times× 10–12
  4. D
    4 ×\times× 10–12
View written solutionFree

Correct answer: B

  1. Identify the cell and the electrode reaction

The cell is:

M∣M2+(saturated from MX2)  ∣∣  M2+(0.001 mol dm−3)∣M\text{M} \mid \text{M}^{2+}(\text{saturated from } MX_2) \;||\; \text{M}^{2+}(0.001\,\text{mol dm}^{-3}) \mid \text{M}M∣M2+(saturated from MX2​)∣∣M2+(0.001mol dm−3)∣M

For the electrode

M2++2e−⇌M\text{M}^{2+} + 2e^- \rightleftharpoons \text{M}M2++2e−⇌M

this is a concentration cell, so the emf depends only on the difference in M2+\text{M}^{2+}M2+ concentration.


  1. Use Nernst equation for concentration cell

For a concentration cell with same metal electrodes:

E=0.059nlog⁡[M2+]higher[M2+]lowerE = \frac{0.059}{n} \log \frac{[\text{M}^{2+}]_{\text{higher}}}{[\text{M}^{2+}]_{\text{lower}}}E=n0.059​log[M2+]lower​[M2+]higher​​

Here, n=2n=2n=2.

Given:

E=0.059 VE = 0.059\,\text{V}E=0.059V

So,

0.059=0.0592log⁡[M2+]higher[M2+]lower0.059 = \frac{0.059}{2} \log \frac{[\text{M}^{2+}]_{\text{higher}}}{[\text{M}^{2+}]_{\text{lower}}}0.059=20.059​log[M2+]lower​[M2+]higher​​

Hence,

1=12log⁡[M2+]higher[M2+]lower1 = \frac{1}{2} \log \frac{[\text{M}^{2+}]_{\text{higher}}}{[\text{M}^{2+}]_{\text{lower}}}1=21​log[M2+]lower​[M2+]higher​​

log⁡[M2+]higher[M2+]lower=2\log \frac{[\text{M}^{2+}]_{\text{higher}}}{[\text{M}^{2+}]_{\text{lower}}} = 2log[M2+]lower​[M2+]higher​​=2

[M2+]higher[M2+]lower=102=100\frac{[\text{M}^{2+}]_{\text{higher}}}{[\text{M}^{2+}]_{\text{lower}}} = 10^2 = 100[M2+]lower​[M2+]higher​​=102=100

One side has

[M2+]=0.001=10−3 mol dm−3[\text{M}^{2+}] = 0.001 = 10^{-3}\,\text{mol dm}^{-3}[M2+]=0.001=10−3mol dm−3

The saturated solution of sparingly soluble salt must have the lower concentration. Therefore,

10−3[M2+]sat=100\frac{10^{-3}}{[\text{M}^{2+}]_{\text{sat}}} = 100[M2+]sat​10−3​=100

So,

[M2+]sat=10−5 mol dm−3[\text{M}^{2+}]_{\text{sat}} = 10^{-5}\,\text{mol dm}^{-3}[M2+]sat​=10−5mol dm−3


  1. Relate solubility to KspK_{sp}Ksp​

For

MX2(s)⇌M2++2X−MX_2(s) \rightleftharpoons M^{2+} + 2X^-MX2​(s)⇌M2++2X−

Let solubility be sss mol dm−3^{-3}−3.

Then,

[M2+]=s,[X−]=2s[M^{2+}] = s, \qquad [X^-] = 2s[M2+]=s,[X−]=2s

Given saturated solution has

[M2+]=s=10−5[M^{2+}] = s = 10^{-5}[M2+]=s=10−5

Thus,

Ksp=[M2+][X−]2=s(2s)2=4s3K_{sp} = [M^{2+}][X^-]^2 = s(2s)^2 = 4s^3Ksp​=[M2+][X−]2=s(2s)2=4s3

Ksp=4(10−5)3=4×10−15K_{sp} = 4(10^{-5})^3 = 4 \times 10^{-15}Ksp​=4(10−5)3=4×10−15


  1. Match with options

Ksp=4×10−15K_{sp} = 4 \times 10^{-15}Ksp​=4×10−15

So the correct option is B.


  1. Comparison with stored answer

Stored correct answer: B

Derived answer: B

They agree.

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