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Thermodynamics question

2009 · Shift 0 · Q7
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Thermodynamics question

2009 · Shift 0 · Q7

JEE MainChemistryThermodynamicsMCQ+4 / −1
On the basis of the following thermochemical data : (ΔfGoH(aq)+\Delta _fG^oH^+_{(aq)}Δf​GoH(aq)+​= 0) H2OH_2OH2​O(l) →\to→ H+H^+H+(aq) + OH−OH^-OH−(aq); ΔH\Delta HΔH= 57.32 kJ H2H_2H2​(g) +12O2(g)→{1 \over 2} O_2(g) \to21​O2​(g)→ H2OH_2OH2​O(l); ΔH\Delta HΔH = -286.20 kJ The value of enthalpy of formation of OH−OH^-OH− ion at 25oC is :
  1. A
    -22.88 kJ
  2. B
    -228.88 kJ
  3. C
    +228.88 kJ
  4. D
    -343.52 kJ
View written solutionFree

Correct answer: B

  1. Given thermochemical equations

    We are given:

    H2O(l)→H+(aq)+OH−(aq)ΔH=+57.32 kJ\mathrm{H_2O(l) \rightarrow H^+(aq) + OH^-(aq)} \qquad \Delta H = +57.32\,\text{kJ}H2​O(l)→H+(aq)+OH−(aq)ΔH=+57.32kJ

    and

    H2(g)+12O2(g)→H2O(l)ΔH=−286.20 kJ\mathrm{H_2(g) + \tfrac12 O_2(g) \rightarrow H_2O(l)} \qquad \Delta H = -286.20\,\text{kJ}H2​(g)+21​O2​(g)→H2​O(l)ΔH=−286.20kJ

    Also,

    ΔfH∘(H+(aq))=0\Delta_f H^\circ\big(\mathrm{H^+(aq)}\big)=0Δf​H∘(H+(aq))=0

  2. Target reaction

    We need the enthalpy of formation of OH−(aq)\mathrm{OH^- (aq)}OH−(aq), i.e. for the reaction:

    12H2(g)+12O2(g)→OH−(aq)\mathrm{\tfrac12 H_2(g) + \tfrac12 O_2(g) \rightarrow OH^-(aq)}21​H2​(g)+21​O2​(g)→OH−(aq)

    Strictly in aqueous convention, this can be viewed through Hess's law using ΔfH∘(H+)=0\Delta_f H^\circ(\mathrm{H^+})=0Δf​H∘(H+)=0.

  3. Apply Hess's law

    Add the two given equations:

    • Formation of water: H2(g)+12O2(g)→H2O(l)ΔH=−286.20\mathrm{H_2(g) + \tfrac12 O_2(g) \rightarrow H_2O(l)} \qquad \Delta H=-286.20H2​(g)+21​O2​(g)→H2​O(l)ΔH=−286.20

    • Ionization of water: H2O(l)→H+(aq)+OH−(aq)ΔH=+57.32\mathrm{H_2O(l) \rightarrow H^+(aq) + OH^-(aq)} \qquad \Delta H=+57.32H2​O(l)→H+(aq)+OH−(aq)ΔH=+57.32

    On adding, H2O(l)\mathrm{H_2O(l)}H2​O(l) cancels:

    H2(g)+12O2(g)→H+(aq)+OH−(aq)\mathrm{H_2(g) + \tfrac12 O_2(g) \rightarrow H^+(aq) + OH^-(aq)}H2​(g)+21​O2​(g)→H+(aq)+OH−(aq)

    Therefore,

    ΔH=−286.20+57.32=−228.88 kJ\Delta H = -286.20 + 57.32 = -228.88\,\text{kJ}ΔH=−286.20+57.32=−228.88kJ

  4. Use standard enthalpy of formation relation

    For the above reaction,

    ΔH=ΔfH∘(H+)+ΔfH∘(OH−)\Delta H = \Delta_f H^\circ(\mathrm{H^+}) + \Delta_f H^\circ(\mathrm{OH^-})ΔH=Δf​H∘(H+)+Δf​H∘(OH−)

    since reactants are elements in standard state.

    Given:

    ΔfH∘(H+)=0\Delta_f H^\circ(\mathrm{H^+})=0Δf​H∘(H+)=0

    Hence,

    ΔfH∘(OH−)=−228.88 kJ mol−1\Delta_f H^\circ(\mathrm{OH^-}) = -228.88\,\text{kJ mol}^{-1}Δf​H∘(OH−)=−228.88kJ mol−1

  5. Option check

    • A: −22.88-22.88−22.88 kJ ❌
    • B: −228.88-228.88−228.88 kJ ✅
    • C: +228.88+228.88+228.88 kJ ❌
    • D: −343.52-343.52−343.52 kJ ❌

Final answer: Option B.

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