Relative volatility versus pressure: For a typical binary mixture in distillation, how does the relative volatility α generally change with increasing system pressure?

Difficulty: Medium

Correct Answer: Decreases

Explanation:


Introduction / Context:
Relative volatility α measures the ease of separating two components by distillation. Higher α indicates a larger volatility difference and easier separation. Pressure affects vapor–liquid equilibrium (VLE), which in turn influences α.


Given Data / Assumptions:

  • Binary, non-azeotropic mixture over practical pressure ranges.
  • No strong associating or pressure-activated complex formation.
  • Comparison at the same temperature approach (or along operating range).


Concept / Approach:
As pressure increases, vapor-phase non-ideality and saturation pressures shift such that K-values (y/x ratios) of components tend to converge. This convergence usually lowers relative volatility (α = K_A / K_B), making separation more difficult. Hence low-pressure operation often improves α and reduces stages.


Step-by-Step Solution:
Define α = (y_A/x_A) / (y_B/x_B) = K_A / K_B.Note that with increasing pressure, K-values often move closer to 1 and to each other.Therefore, α generally decreases as pressure rises.Select 'Decreases' as the most representative trend.


Verification / Alternative check:
VLE charts and process simulators commonly show increased column difficulty (more stages/higher reflux) at higher pressures for many hydrocarbon pairs, consistent with reduced α.


Why Other Options Are Wrong:
'Increases' is uncommon except for special systems; 'remains the same' ignores VLE pressure sensitivity; 'either/or' is too vague for the general rule-of-thumb expected in fundamentals.


Common Pitfalls:

  • For azeotropic/associating systems, trends can deviate; the question seeks the general case.
  • Confusing α changes due to pressure with temperature effects along the column.


Final Answer:
Decreases

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