Chemical Equilibrium: Tricky Questions Solved (7)

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Question

For the reaction N2(g)+3H2(g)2NH3(g)N_2(g) + 3H_2(g) \rightleftharpoons 2NH_3(g), Kc=0.5K_c = 0.5 at 400 K400 \text{ K}. Initially, 1 mol1 \text{ mol} of N2N_2 and 3 mol3 \text{ mol} of H2H_2 are placed in a 2 L2 \text{ L} container. Find the equilibrium concentrations and the percentage conversion of N2N_2.

Solution — Step by Step

Initial concentrations:

  • [N2]0=1/2=0.5 M[N_2]_0 = 1/2 = 0.5 \text{ M}
  • [H2]0=3/2=1.5 M[H_2]_0 = 3/2 = 1.5 \text{ M}
  • [NH3]0=0[NH_3]_0 = 0

Let xx = mol/L of N2N_2 that reacts. By stoichiometry, 3x3x of H2H_2 reacts and 2x2x of NH3NH_3 forms.

SpeciesInitialChangeEquilibrium
N2N_20.50.5x-x0.5x0.5 - x
H2H_21.51.53x-3x1.53x1.5 - 3x
NH3NH_300+2x+2x2x2x

Kc=[NH3]2[N2][H2]3=(2x)2(0.5x)(1.53x)3=0.5K_c = \frac{[NH_3]^2}{[N_2][H_2]^3} = \frac{(2x)^2}{(0.5-x)(1.5-3x)^3} = 0.5

This is a high-order polynomial — generally messy. We try a smart simplification: notice that 1.53x=3(0.5x)1.5 - 3x = 3(0.5 - x). Substitute:

Kc=4x2(0.5x)27(0.5x)3=4x227(0.5x)4K_c = \frac{4x^2}{(0.5 - x) \cdot 27(0.5 - x)^3} = \frac{4x^2}{27(0.5 - x)^4}

4x227(0.5x)4=0.5    4x2=13.5(0.5x)4\frac{4x^2}{27(0.5-x)^4} = 0.5 \implies 4x^2 = 13.5 (0.5-x)^4

Take square roots (positive on both sides):

2x=13.5(0.5x)23.674(0.5x)22x = \sqrt{13.5}\,(0.5 - x)^2 \approx 3.674\,(0.5 - x)^2

Let u=0.5xu = 0.5 - x. Then x=0.5ux = 0.5 - u, so 2(0.5u)=3.674u22(0.5 - u) = 3.674 u^2, i.e. 12u=3.674u21 - 2u = 3.674 u^2, or 3.674u2+2u1=03.674 u^2 + 2u - 1 = 0.

Quadratic formula:

u=2+4+14.6962×3.674=2+4.3247.3480.316u = \frac{-2 + \sqrt{4 + 14.696}}{2 \times 3.674} = \frac{-2 + 4.324}{7.348} \approx 0.316

So x=0.50.3160.184 Mx = 0.5 - 0.316 \approx 0.184 \text{ M}.

  • [N2]eq=0.50.184=0.316 M[N_2]_{eq} = 0.5 - 0.184 = 0.316 \text{ M}
  • [H2]eq=1.53(0.184)=0.948 M[H_2]_{eq} = 1.5 - 3(0.184) = 0.948 \text{ M}
  • [NH3]eq=2(0.184)=0.368 M[NH_3]_{eq} = 2(0.184) = 0.368 \text{ M}

Percent conversion of N2N_2: 0.184/0.5×100%=36.8%0.184/0.5 \times 100\% = 36.8\%.

Quick sanity check on KcK_c: (0.368)2/[(0.316)(0.948)3]=0.1354/[0.316×0.853]=0.1354/0.2700.50(0.368)^2 / [(0.316)(0.948)^3] = 0.1354 / [0.316 \times 0.853] = 0.1354/0.270 \approx 0.50

Why This Works

The ICE table organises stoichiometry: how much each species changes is locked together by the balanced equation. The trick we used — recognising 1.5=3×0.51.5 = 3 \times 0.5 which means the reactants are in stoichiometric ratio — collapses the cubic and quartic terms into one variable.

Whenever the problem gives initial moles in the exact stoichiometric ratio, you can always factor like this. Otherwise you’re stuck with a messy polynomial that needs numerical methods.

Alternative Method

For approximate problems, the “small xx” approximation works when KK is small: assume x0.5x \ll 0.5, simplify denominators to 0.50.5 and 1.51.5, solve for xx, then check whether the assumption holds. Here x0.18x \approx 0.18 which is 36%36\% of 0.50.5 — too large for the approximation to hold accurately. The full quadratic was needed.

For ammonia synthesis problems specifically, NEET often gives stoichiometric initial ratios. Recognising this and substituting [H2]=3[N2][H_2] = 3[N_2] early collapses the algebra dramatically.

Common Mistake

The two killer errors:

  1. Forgetting the stoichiometric coefficients in the change row. If xx mol/L of N2N_2 reacts, then 3x3x of H2H_2 reacts (not xx) and 2x2x of NH3NH_3 forms (not xx). Always read the balanced equation carefully.

  2. Mixing KcK_c and KpK_p. KcK_c uses concentrations; KpK_p uses partial pressures. They differ by a factor of (RT)Δn(RT)^{\Delta n}. For this reaction Δn=24=2\Delta n = 2 - 4 = -2. Don’t substitute partial pressures into a KcK_c expression.

Final answer: [N2]=0.316 M[N_2] = 0.316 \text{ M}, [H2]=0.948 M[H_2] = 0.948 \text{ M}, [NH3]=0.368 M[NH_3] = 0.368 \text{ M}, 36.8%36.8\% conversion.

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