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Two crystalline phases of white phosphorus are known. Both contain P4 molecules,

ID: 637723 • Letter: T

Question

Two crystalline phases of white phosphorus are known. Both contain P4 molecules, but the molecules are packed together in different ways. The a phase of the solid (P4 density 1.82 g/cm2) is always obtained when molten phosphorus crystallizes below the melting point (44.1 °C). However, when cooled below -76.9 °C, the a phase spontaneously converts to the B phase (P4; density 1.88 g/cm3). P4(s, a)P4(s, B) Indicate which of the following statements are true or false, with regard to the above process. ?At-76.9°CAG for this process is less than zero. The a phase has the more ordered crystalline structure The sign of AS for this process is negative. At-76.9°C, both solid phases can coexist indefinitely The sign of ?? for this process is positive. Above-76.9°C, the sign of 0G for this process is positive cf Section 10.7 "Free Energy pp 368-71 in Zumdahl Chemical Principles 8th ed.

Explanation / Answer

Statement 1 -

Equilibrium temperature T = - 76.9 °C

Gibbs free energy

?G = ?H - T?S

At equilibrium (T)

?G = 0

Statement 1 is false

Statement 2 -

Density of beta phase > density of alpha phase

Beta phase has the more ordered crystalline structure

Statement 2 is false

Statement 3 -

Since the beta phase has more ordered than alphas phase, there must be entropy loss. Entropy decreases as the order improves.

Entropy is negative for this process

Statement 3 Is true

Statement 4 -

Equilibrium temperature T = - 76.9 °C

?G = 0

Both solid phases can coexist indefinitely

Statement 4 is true

Statement 5 -

At equilibrium T = - 76.9 + 273 = 196.1 K

?H = T?S

?S for process < 0

Therefore

?H < 0

Statement 5 is false

Statement 6 -

T > (-76.9)°C

Let the temperature be T" > T

?G = ?H - T"?S

From the equillibrium relation

?G = T?S - T"?S = ?S(T - T")

?S < 0

(T - T") < 0

?G > 0

Statement 6 is true

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