Chem 10171 Fall 2017 Problem Set 10 Due November 17, 2017

(1) Some thermodynamic properties of aluminum trichloride are given in the table below (all
listed values at 298 K). For the purposes of this problem, you may assume that changes
in enthalpy and entropy are independent of temperature.
Hf (kJ/mol) S (J/molK) Gf (kJ/mol)
AlCl3 (s) 704.2 110.67 628.8
(a) The heat of fusion of AlCl3 is +35.0 kJ/mol:
AlCl3 (s) AlCl3 (l) H = +35.0 kJ/mol
Calculate Hf of AlCl3 (l) (at 298 K).
(b) The melting point of AlCl3 is 192.4 C. Using the information in part (a) what is the
Sfus ?
(c) Assume that Sfus does not change with temperature, calculate S of AlCl3 (l) (at 298
K).
(d) Calculate Gf of AlCl3 (l) (at 298 K).

(2) Elemental sulfur in its most stable form exists as cyclic S8 molecules. There are two
different crystalline phases of S8 (s), a rhombic phase (Hf = 0.00 kJ/mol, S = 254.4
J/molK) and a monoclinic phase (Hf = 2.40 kJ/mol, S = 260.8 J/molK).
(a) Calculate H and S for the reaction S8 (s, rhombic) S8 (s, monoclinic).
(b) Which phase is stable at lower temperature, which phase at higher temperature, and at
what temperature are the two phases in equilibrium? (Assume that H and S are
independent of temperature.)
(c) Gaseous S8 has Hf = 102.3 kJ/mol, S = 430.87 J/molK. Estimate the sublimation
point of monoclinic sulfur.
(d) Monoatomic sulfur, S (g), has Hf = 278.80 kJ/mol. Calculate the average bond
dissociation enthalpy for a S-S bond in S8 (g).
(e) Other forms of sulfur with different ring sizes from n = 5-12 are known, but all of these
are thermodynamically unstable with respect to S8. In other words, Sn will
spontaneously transform into S8 for n 8. What conclusions, if any, can you draw
about the strength (i.e., bond dissociation enthalpy) of the S-S bond in these other
cyclo-sulfurs compared to the S-S bonds in S8? Does your conclusion vary with the
ring size of the cyclo-sulfur in question?
Chem 10171 Fall 2017 Problem Set 10 Due November 17, 2017

(3) For each set of three substances, rank them in order of increasing boiling point, and
justify your ranking.
(a) Br2, Cl2, F2

(b)

(c) CH3NH2, CH3OH, CH3F

(d) CH3CH2CH2CH3, CH3CH2CH2OH, HOCH2CH2OH