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Chemical Equilibrium question

2022 · 26 Jun · Shift 2 · Q20
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Chemical Equilibrium question

2022 · 26 Jun · Shift 2 · Q20

JEE MainChemistryChemical EquilibriumNumerical+4 / −1
40% of HIHIHI undergoes decomposition to H2H_2H2​ and I2I_2I2​ at 300 K. Δ\DeltaΔ G Θ^\ThetaΘ for this decomposition reaction at one atmosphere pressure is ‾\underline{\hspace{2cm}}​ J mol −-− 1. [nearest integer] (Use R = 8.31 J K −-− 1 mol −-− 1 ; log 2 = 0.3010, ln 10 = 2.3, log 3 = 0.477)
Numerical answer
View written solutionFree

Correct answer: 5470

  1. Write the decomposition reaction

2HI(g)⇌H2(g)+I2(g)2HI(g) \rightleftharpoons H_2(g)+I_2(g)2HI(g)⇌H2​(g)+I2​(g)

We are told that at equilibrium, 40% of HI decomposes at 300 K300\,K300K.


  1. Take initial moles and find equilibrium moles

Assume initially:

HI=1 mol,H2=0,I2=0HI=1\text{ mol}, \qquad H_2=0, \qquad I_2=0HI=1 mol,H2​=0,I2​=0

If 40%40\%40% of HIHIHI decomposes, then moles of HIHIHI consumed are:

0.40.40.4

From

2HI→H2+I22HI \to H_2+I_22HI→H2​+I2​

if 0.40.40.4 mol of HIHIHI is consumed, then extent gives:

H2=I2=0.42=0.2H_2 = I_2 = \frac{0.4}{2}=0.2H2​=I2​=20.4​=0.2

So equilibrium moles are:

HI=0.6,H2=0.2,I2=0.2HI=0.6, \qquad H_2=0.2, \qquad I_2=0.2HI=0.6,H2​=0.2,I2​=0.2

Total moles at equilibrium:

0.6+0.2+0.2=1.00.6+0.2+0.2=1.00.6+0.2+0.2=1.0

Hence mole fractions are the same as the moles:

yHI=0.6,yH2=0.2,yI2=0.2y_{HI}=0.6, \quad y_{H_2}=0.2, \quad y_{I_2}=0.2yHI​=0.6,yH2​​=0.2,yI2​​=0.2

Since total pressure is 1 atm1\,\text{atm}1atm,

pHI=0.6 atm,pH2=0.2 atm,pI2=0.2 atmp_{HI}=0.6\,\text{atm}, \quad p_{H_2}=0.2\,\text{atm}, \quad p_{I_2}=0.2\,\text{atm}pHI​=0.6atm,pH2​​=0.2atm,pI2​​=0.2atm


  1. Find equilibrium constant

For the reaction

2HI(g)⇌H2(g)+I2(g)2HI(g) \rightleftharpoons H_2(g)+I_2(g)2HI(g)⇌H2​(g)+I2​(g)

Kp=pH2 pI2(pHI)2K_p=\frac{p_{H_2}\,p_{I_2}}{(p_{HI})^2}Kp​=(pHI​)2pH2​​pI2​​​

Substitute values:

Kp=(0.2)(0.2)(0.6)2K_p=\frac{(0.2)(0.2)}{(0.6)^2}Kp​=(0.6)2(0.2)(0.2)​

Kp=0.040.36=19K_p=\frac{0.04}{0.36}=\frac{1}{9}Kp​=0.360.04​=91​

Because Δn=(1+1)−2=0\Delta n = (1+1)-2=0Δn=(1+1)−2=0, we have:

Kp=KK_p=KKp​=K

So,

K=19K=\frac{1}{9}K=91​


  1. Use relation between standard Gibbs free energy and equilibrium constant

ΔG∘=−RTln⁡K\Delta G^\circ = -RT\ln KΔG∘=−RTlnK

Thus,

ΔG∘=−(8.31)(300)ln⁡(19)\Delta G^\circ = - (8.31)(300)\ln\left(\frac{1}{9}\right)ΔG∘=−(8.31)(300)ln(91​)

Since

ln⁡(19)=−ln⁡9\ln\left(\frac{1}{9}\right)=-\ln 9ln(91​)=−ln9

so

ΔG∘=(8.31)(300)ln⁡9\Delta G^\circ = (8.31)(300)\ln 9ΔG∘=(8.31)(300)ln9

Now,

ln⁡9=2ln⁡3\ln 9 = 2\ln 3ln9=2ln3

Given:

log⁡3=0.477,ln⁡10=2.3\log 3=0.477, \qquad \ln 10 = 2.3log3=0.477,ln10=2.3

Therefore,

ln⁡3=2.3×0.477=1.0971\ln 3 = 2.3\times 0.477 = 1.0971ln3=2.3×0.477=1.0971

Hence,

ln⁡9=2(1.0971)=2.1942\ln 9 = 2(1.0971)=2.1942ln9=2(1.0971)=2.1942

Now calculate:

ΔG∘=8.31×300×2.1942\Delta G^\circ = 8.31\times 300\times 2.1942ΔG∘=8.31×300×2.1942

8.31×300=24938.31\times 300 = 24938.31×300=2493

ΔG∘=2493×2.1942≈5470.14 J mol−1\Delta G^\circ = 2493 \times 2.1942 \approx 5470.14\,\text{J mol}^{-1}ΔG∘=2493×2.1942≈5470.14J mol−1

Nearest integer:

5470\boxed{5470}5470​


  1. Comparison with stored correct answer

Stored answer = 273527352735

My derived answer = 547054705470

The stored answer appears to be exactly half of the correct value, which may arise if one incorrectly writes the reaction as

HI⇌12H2+12I2HI \rightleftharpoons \frac12 H_2 + \frac12 I_2HI⇌21​H2​+21​I2​

and then uses the equilibrium constant expression inconsistently with the given decomposition percentage. But the standard decomposition reaction is

2HI⇌H2+I22HI \rightleftharpoons H_2 + I_22HI⇌H2​+I2​

for which the correct value is

5470 J mol−1\boxed{5470\,\text{J mol}^{-1}}5470J mol−1​

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