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Thermodynamics / Acid-Base EquilibriumFRQ

Selected thermodynamic values for the ionization of ethanoic acid, H3CCOOH, and trichloroethanoic acThermodynamics / Acid-Base Equilibrium Chemistry Question

Problem Context

Selected thermodynamic values for the ionization of ethanoic acid, H3CCOOH, and trichloroethanoic acid, Cl3CCOOH, at 25 ˚C are given in the table below.

Use the given values to provide answers to the following questions.

a.

What is the ∆S˚ value for the ionization of H3CCOOH at 25 ˚C?

Model Answer

Go = Ho – T So
27120 = –2510 – 298.15 K × So
So = –99.4 K

b.

What is the Ka value for Cl3CCOOH at 25 ˚C?

Model Answer

Go = –RT ln K

ln (K) = –1.58
K = 2.0 × 10–1

c.

What is the Ka value for H3CCOOH at 35 ˚C?

Model Answer

ln ( ) = –301.9 × (0.003354–0.003245)
ln ( ) = –0.0329
( ) = 0.9677
K2 = 1.71 × 10–5

d.

Account for the difference in the Ka values of the two acids at 25 ˚C in terms of their molecular structures.

Model Answer

Cl3CCOOH has a greater K than H3CCOOH because the Cl atom draw electrons from C–OH, weakening the O–H bond.

e.

State whether the ∆S˚ values suggest an increase or a decrease in the order of the system upon ionization and offer an explanation in molecular-level terms.

Model Answer

So values are less than zero, suggesting an increase in order H+ and A– are solvated more tightly than HA with CH3CO2 – being solvated better than larger Cl3CO–.

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