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Practice
EquilibriumNational 2024

A mixture containing CO(g)\ce{CO(g)}, HX2O(g)\ce{H2O(g)}, COX2(g)\ce{CO2(g)}, and HX2(g)\ce{H2(g)} is allowed to reach equilibrium at 120 °C in a container that maintains a constant total pressure of 1.0 bar. CO(g)+HX2O(g)⇌COX2(g)+HX2(g)\ce{CO(g) + H2O(g) <=> CO2(g) + H2(g)} 5.0 g of HX2O\ce{H2O} is added to this container, which is allowed to reattain equilibrium (still at 120 °C and 1 bar total pressure). How does the partial pressure of HX2(g)\ce{H2(g)} change as a result of the addition of HX2O\ce{H2O}?

9% of national qualifiers got this right

Explanation

draft

Setting up the equilibrium expression

For CO(g)+HX2O(g)⇌COX2(g)+HX2(g)\ce{CO(g) + H2O(g) <=> CO2(g) + H2(g)}, the number of moles of gas is the same on both sides (Δn=0\Delta n = 0). If we write KpK_p in terms of partial pressures,

Kp=PCO2 PH2PCO PH2OK_p=\dfrac{P_{CO2}\,P_{H2}}{P_{CO}\,P_{H2O}}

Since the total pressure is fixed at 1.0 bar, each partial pressure equals (mole fraction) × (1.0 bar), so

Kp=xCO2 xH2xCO xH2OK_p=\dfrac{x_{CO2}\,x_{H2}}{x_{CO}\,x_{H2O}}

This expression contains no explicit total-pressure dependence, so adding HX2O\ce{H2O} at constant total PP does not simply push the reaction in one obvious direction the way a volume change would for a reaction with Δn≠0\Delta n \neq 0.

Why the direction can't be predicted

Adding HX2O\ce{H2O} increases xH2Ox_{H2O} instantaneously, which momentarily makes the reaction quotient Qp<KpQ_p < K_p, so the system shifts forward, consuming some CO\ce{CO} and HX2O\ce{H2O} and producing more COX2\ce{CO2} and HX2\ce{H2}. However, because the total pressure is re-fixed at 1.0 bar (the container must re-adjust volume), the new equilibrium mole fractions—and therefore the new partial pressure of HX2\ce{H2}—depend on the specific initial amounts of all four species and the numerical value of KK, none of which are given.

Without knowing the initial composition (moles of CO\ce{CO}, HX2O\ce{H2O}, COX2\ce{CO2}, HX2\ce{H2} present before the 5.0 g of water was added) or the value of KpK_p at 120 °C, we cannot calculate whether xH2x_{H2} (and hence PH2P_{H2}) ends up larger, smaller, or unchanged after the shift. The qualitative Le Chatelier shift tells us the reaction moves forward, but the magnitude relative to how much the total pressure redistributes among all species determines whether PH2P_{H2} actually rises or falls — this cannot be pinned down from the information given.

Conclusion: The correct answer is (D) — the effect cannot be determined without knowing the initial composition and/or KK.

A

Assumes that because the reaction shifts forward (more HX2\ce{H2} produced) upon adding HX2O\ce{H2O}, the partial pressure of HX2\ce{H2} must simply increase — ignoring that total pressure is held constant, so mole fractions (and thus PH2P_{H2}) depend on the unspecified initial composition and KK.

B

Mistakenly focuses on the increase in HX2O\ce{H2O} diluting the mixture and assumes this must decrease PH2P_{H2}, without recognizing that the reaction shifts forward, producing more HX2\ce{H2}, and that the net effect on PH2P_{H2} cannot be judged from dilution reasoning alone.

C

Incorrectly reasons that because Δn=0\Delta n = 0 for the reaction, the equilibrium position (and hence all partial pressures) must be completely unaffected by adding a reactant — this confuses insensitivity of KpK_p to total pressure changes with insensitivity of the equilibrium position to concentration changes.

D

Correct: since KpK_p depends only on mole fractions (as Δn=0\Delta n=0) and total pressure is fixed, determining the new PH2P_{H2} requires knowing the initial mole amounts of all species and the numerical value of KK, which are not provided.

Concept · Le Chatelier's principle with constant total pressure and Δn = 0 equilibria

USNCO 2024 National Part I exam, question 35. © American Chemical Society; reproduced for non-commercial practice.