NVAMediumJEE 2023Internal Energy & Enthalpy

JEE Chemistry 2023 Question with Solution

0.3g0.3 \, \text{g} of ethane undergoes combustion at 27C27^\circ \text{C} in a bomb calorimeter. The temperature of calorimeter system (including the water) is found to rise by 0.5C0.5^\circ \text{C}. The heat evolved during combustion of ethane at constant pressure is _____ kJ mol1\text{kJ mol}^{-1}. (Nearest integer)

[Given : The heat capacity of the calorimeter system is 20kJ K120 \, \text{kJ K}^{-1}, R=8.3J K1mol1R = 8.3 \, \text{J K}^{-1} \, \text{mol}^{-1}. Assume ideal gas behaviour. Atomic mass of C and H are 1212 and 1g mol11 \, \text{g mol}^{-1} respectively]

Answer

Correct answer:1006

Step-by-step solution

Standard Method

Given:

  • Mass of ethane = 0.3g0.3 \, \text{g}
  • Temperature rise = 0.5K0.5 \, \text{K}
  • Heat capacity of calorimeter system = 20kJ K120 \, \text{kJ K}^{-1}
  • R=8.3J K1mol1R = 8.3 \, \text{J K}^{-1} \, \text{mol}^{-1}
  • Temperature = 27C=300K27^\circ \text{C} = 300 \, \text{K}

Find: Heat evolved during combustion of ethane at constant pressure in kJ mol1\text{kJ mol}^{-1}.

Bomb calorimeter works at constant volume, so the measured heat gives ΔU\Delta U.

Heat released for the sample:

q=CcalΔT=20×0.5=10kJq = C_{cal} \Delta T = 20 \times 0.5 = 10 \, \text{kJ}

Molar mass of ethane C2H6C_2H_6 is:

2×12+6×1=30g mol12 \times 12 + 6 \times 1 = 30 \, \text{g mol}^{-1}

So, heat released by combustion of 11 mole:

ΔU=(100.3)×30=1000kJ mol1\Delta U = -\left(\frac{10}{0.3}\right) \times 30 = -1000 \, \text{kJ mol}^{-1}

Combustion reaction:

C2H6(g)+72O2(g)2CO2(g)+3H2O(l)C_2H_6(g) + \frac{7}{2} O_2(g) \rightarrow 2CO_2(g) + 3H_2O(l)

Change in moles of gaseous species:

Δng=2(1+72)=52\Delta n_g = 2 - \left(1 + \frac{7}{2}\right) = -\frac{5}{2}

Using the relation:

ΔH=ΔU+ΔngRT\Delta H = \Delta U + \Delta n_g RT

Substituting values as used in the solution:

ΔH=1000+(52)(8.3)(300)×103\Delta H = -1000 + \left(-\frac{5}{2}\right)(8.3)(300) \times 10^{-3} ΔH=10006.225\Delta H = -1000 - 6.225 ΔH1006kJ mol1\Delta H \approx -1006 \, \text{kJ mol}^{-1}

Therefore, the heat evolved at constant pressure is 1006kJ mol11006 \, \text{kJ mol}^{-1}, so the required numerical answer is 1006.

Energy Relation and Sign Convention

Given: Bomb calorimeter measures heat at constant volume.

At constant volume, the combustion heat corresponds to ΔU\Delta U, not ΔH\Delta H. Since the temperature of the calorimeter rises, the reaction releases heat, so the thermodynamic sign is negative for the system.

First calculate the heat absorbed by the calorimeter:

qcal=20×0.5=10kJq_{cal} = 20 \times 0.5 = 10 \, \text{kJ}

Hence for the reacting sample:

qrxn=10kJq_{rxn} = -10 \, \text{kJ}

Now convert sample mass into per mole basis. For ethane:

M=30g mol1M = 30 \, \text{g mol}^{-1}

So,

0.3g=0.330=0.01mol0.3 \, \text{g} = \frac{0.3}{30} = 0.01 \, \text{mol}

Therefore,

ΔU=100.01=1000kJ mol1\Delta U = \frac{-10}{0.01} = -1000 \, \text{kJ mol}^{-1}

Next convert ΔU\Delta U to ΔH\Delta H using:

ΔH=ΔU+ΔngRT\Delta H = \Delta U + \Delta n_g RT

From

C2H6(g)+72O2(g)2CO2(g)+3H2O(l)C_2H_6(g) + \frac{7}{2} O_2(g) \rightarrow 2CO_2(g) + 3H_2O(l)

only gaseous moles are counted, hence:

Δng=2(1+72)=52\Delta n_g = 2 - \left(1 + \frac{7}{2}\right) = -\frac{5}{2}

Using T=300KT = 300 \, \text{K} and R=8.3J K1mol1R = 8.3 \, \text{J K}^{-1} \, \text{mol}^{-1}:

ΔngRT=(52)(8.3)(300)×103=6.225kJ mol1\Delta n_g RT = \left(-\frac{5}{2}\right)(8.3)(300) \times 10^{-3} = -6.225 \, \text{kJ mol}^{-1}

Thus,

ΔH=10006.225=1006.225kJ mol1\Delta H = -1000 - 6.225 = -1006.225 \, \text{kJ mol}^{-1}

Nearest integer heat evolved = 1006.

Note: the provided the solution reaches the same final answer 1006, although its printed intermediate value for Δng\Delta n_g appears inconsistent; the final numerical conclusion matches ΔH1006kJ mol1\Delta H \approx -1006 \, \text{kJ mol}^{-1}.

Common mistakes

  • Using the calorimeter heat directly as ΔH\Delta H is incorrect because a bomb calorimeter operates at constant volume. The measured quantity is ΔU\Delta U. Convert to ΔH\Delta H using ΔH=ΔU+ΔngRT\Delta H = \Delta U + \Delta n_g RT.

  • Forgetting to convert 0.3g0.3 \, \text{g} of ethane into moles leads to a wrong molar heat of combustion. First use molar mass 30g mol130 \, \text{g mol}^{-1} to get 0.01mol0.01 \, \text{mol}, then scale the heat to one mole.

  • Counting liquid water in Δng\Delta n_g is wrong. Only gaseous species are included in Δng\Delta n_g. Here H2O(l)H_2O(l) must not be counted while evaluating Δng\Delta n_g.

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