Final Exam 12/16/96 R=8.314 J.K -1.

mol -1 Question 1: (25 points)

CHEM 3615 Name: ___________________ ID#: _____________________

The Clausius-Clapeyron equation given below describes the change in vapor pressure above the liquid as the temperature is changed:

dP vap H dT = P R T2
1) Write down the corresponding equation for the change in vapor pressure above a solid as a function of temperature. dP sub H dT = P R T2 2) The vapor pressure of benzene liquid fits the following expression between 10C and 30C: log(P) = 7.960 - 1780/T where log is the decimal logarithm, p is given in torr and T in Kelvin. Calculate the enthalpy of vaporization. The Clausius-Clapeyron equation can be integrated assuming that the heat of vaporization is independent of temperature to yield: 1 P vap H 1 ln = T T * P * R Which implies that ln(P) = ln(P*) + vapH/(RT*) vapH/(RT)

Furthermore log(X) = ln(X)/ln(10) where ln(10) = 2.303 Therefore: log(P) = log(P*) +

vapH/(2.303RT*)

vapH/(2.303RT)

Which leads to: 1780 = vapH/(2.303R) The final answer is then:

vapH

= 2.303Rx1780 = 34 kJ/mol

Question 2: (25 points)

Benzene and toluene form an ideal solution. Calculate the molar free energy of mixing, the molar enthalpy of mixing, the molar entropy of mixing and the change in molar volume upon mixing for a solution exhibiting a mole fraction of benzene equal to 0.5 at a temperature of 300 K.
mix

G = RT (n B ln(x B) + n T ln(x T))

since n B and n T must be such that n B + n T = 1 mol and x B = 0.5 then n T = n B = 0 . 5 . and: mix G = 8.3145x300x(0.5 ln(0.5) + 0.5 ln(0.5)) J/mol Since the solution is ideal, mix H = mix V = 0 and mix S = mix G/T = 300 ln(0.5) J/(K.mol)

Question 3: (25 points).

How does the melting temperature, the boiling temperature of a material A change when a very small quantity of B is added to A ? Assume that A and B form an ideal solution, that A and B do not mix in the solid crystalline state and that B has a negligible vapor pressure. Justify your answer with either equations or a graph ( versus Temperature). The melting temperature of component A decreases when a small amount of B is added. The boiling temperature of A is elevated when a small amount of A is added. Pure Solid A Pure Liquid A

Vapor A Mixed Liquid A

Tm(A) mixed A

Tm(A) pure A

Tb (A) pure A

Tb (A) mixed A

Question 4: (25 points)

Consider the following reaction: PbO (s, red) + CO (g) --------> Pb (s) + CO 2 (g) a) Calculate using the appropriate table the value of rG and the equilibrium constant for this reaction at 298 K. Using the formation free energies of PbO, CO, Pb, CO 2 , the reaction free energy is calculated to be -68.26 kJ/mol Therefore the equilibrium constant at 298K is calculated to be: lnK = - RG 0 /RT = 27.55 which leads to K = 9.2 10 11 b) Assuming that this reaction occurs at a pressure of 1 bar and at 298 K and that initially only CO is present in the gas phase, determine the partial pressures, P(CO) and P(CO2 ) at equilibrium (i.e. after the reaction appears to stop). K = P(CO 2 )/P(CO) and P(CO 2 )+P(CO) = P T Therefore, P(CO) = P T / (1+K)= 10 -12 bar and P(CO 2 ) = 1 bar. c) Assuming that the enthalpy of reaction is independent of temperature, determine the value of the equilibrium constant for a reaction temperature equal to 400 K. lnK(400K) = lnK(298K) - ( RH/R)*(1/400-1/298) = 20.96 K(400K) = 1.3 10 9 d) What would be the value of the equilibrium constant, if the reaction occurs at 298 K but under a pressure of 2 bars instead of 1 bar ? The same as in a) since the equilibrium constant (and RG 0 ) does not depend on pressure (since it is defined at 1 bar).