A mixture containing , , , and is allowed to reach equilibrium at 120 °C in a container that maintains a constant total pressure of 1.0 bar. 5.0 g of 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 change as a result of the addition of ?
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Explanation
draftSetting up the equilibrium expression
For , the number of moles of gas is the same on both sides (). If we write in terms of partial pressures,
Since the total pressure is fixed at 1.0 bar, each partial pressure equals (mole fraction) × (1.0 bar), so
This expression contains no explicit total-pressure dependence, so adding at constant total does not simply push the reaction in one obvious direction the way a volume change would for a reaction with .
Why the direction can't be predicted
Adding increases instantaneously, which momentarily makes the reaction quotient , so the system shifts forward, consuming some and and producing more and . 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 —depend on the specific initial amounts of all four species and the numerical value of , none of which are given.
Without knowing the initial composition (moles of , , , present before the 5.0 g of water was added) or the value of at 120 °C, we cannot calculate whether (and hence ) 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 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 .
Assumes that because the reaction shifts forward (more produced) upon adding , the partial pressure of must simply increase — ignoring that total pressure is held constant, so mole fractions (and thus ) depend on the unspecified initial composition and .
Mistakenly focuses on the increase in diluting the mixture and assumes this must decrease , without recognizing that the reaction shifts forward, producing more , and that the net effect on cannot be judged from dilution reasoning alone.
Incorrectly reasons that because for the reaction, the equilibrium position (and hence all partial pressures) must be completely unaffected by adding a reactant — this confuses insensitivity of to total pressure changes with insensitivity of the equilibrium position to concentration changes.
Correct: since depends only on mole fractions (as ) and total pressure is fixed, determining the new requires knowing the initial mole amounts of all species and the numerical value of , which are not provided.
USNCO 2024 National Part I exam, question 35. © American Chemical Society; reproduced for non-commercial practice.