Chem 113: Chemical Thermodynamics and Kinetics, Spring 2014 Assignment 6 - Solutions

1. The slope of the coexistance line between solids and liquids is very steep for many substances. At the triple point, usually a slight increase (or in some cases decrease) in the temperature along the coexistance line brings you to the normal freezing point. 2. Think of a solid piece of item. When you increase the pressure, the item will compress into a smaller size, but the mass is still the same. So if you increase the pressure at constant temperature, the density increases. This means that ice I has the lower density. 3. To solve for part a, rst solve for the change in molar volumes. Since we are considering ice melting to water, Vm = Vm,liq Vm,sol . Vm = Vm,liq Vm,sol ml 18.02g ml 18.02 =( )( ) 0.997g mol 0.920g mol ml L = 1.51 = 0.00151 mol mol To solve for the pressure in which the melting temperature decreases by 4K, use the Clapeyron equation. Hf us dP = dT T V m
Pf

dP =
Po

Hf us Vm

Tf To

1 dT T

(Pf Po ) = Pf = Po +

Tf Hf us ln( ) Vm To

Hf us Tf ln( ) V m To

In this part of the problem, Po = 1 bar, Hf us = 6010J/mol, Vm = -0.00151 L/mol, Tf = 269K, and To = 273K. Plugging all these values in and converting units, you get that the pressure to change the melting temperature of ice to 269K is 588bars.
orce For part B, the pressure exerted by the ice skater is P = F Area . The force exerted by the skater is the normal force against the ice, and the area is the area of the skate worn by the skater. Using this information, the pressure exterted is m 78kg 9.81 s 2 = 224bars 19 105 m 18 102 m

P =

At 224 bars, the melting temperature of the ice can be solved with the following. Pf = Po + Hf us Tf ln( ) V m To

Tf = To e

(Pf Po )Vm Hf us

Plugging in the values as state in part a and Pf = 224 bars, we get that the melting temperature at 224 bars is 271.5K. If the melting temperature is 269K, then the person that is gliding across the ice from the description described will not cause the ice to melt. 4. At the triple point, the coexistance line between the solid and gas, and the coexistance line between the liquid and gas converge to one point. This means that the vapor pressure of the solid and the vapor pressure of the liquid are equal to each other. To solve for the triple point temperature, 13.795 28893K 28266K = 12.374 TT P TT P 28893K 28266K 1.421 = TT P TT P 627K 1.421 = TT P TT P 1 = 1.421 627K 441K = TT P

To solve for the triple point pressure, just simply plug the triple point temperature into one of the vapor pressure equation and solve for PT P ln( PT P 28266K ) = 12.374 atm 441K = 51.72 PT P = 3.449 1023 atm To solve for the enthalpy of sublimation, consider it as a solid turning into gas. Since the molar volume of a gas is much, much bigger than a solid, we can consider the change in molar volume as Vm = Vm,gas Vm,solid Vm,gas = RT P . Using the Clausius-Clapeyron equation, we can set it up as the following: dP Hsub Hsub P Hsub = = = dT T V m T Vm,gas RT 2 28893K 13.79728893K/T P Hsub e = 2 T RT 2 Hsub 28893K = R J 28893K (8.314 ) = Hsub molK kJ Hsub = 240 mol

5. A rough sketch of the P-T diagram for NH3 , based on the information given. The points of interest are also labeled on the graph with A, B, C, D, and E.

6. The standard boiling temperature is the boiling temperature at 1 bar = 100,000 Pa. Plugging it into the vapor pressure equation, we can solve for Tb . ln(100, 000) = 23.593 3679.1 Tb 31.317 3679.1 11.513 = 23.593 Tb 31.317 3679.1 12.080 = Tb 31.317 Tb = 335.88K

To solve for the enthalpy of vaporization at the standard boiling temperature and 298K, use the Clausius-Clapeyron equation for the ideal gas behavior. Hvap P dP = dT RT 2
3679.1 Hvap P 3679.1 e23.593 T 31.317 = 2 (T 31.317) RT 2

Hvap 3679.1 = (T 31.317)2 RT 2 Hvap = RT 2 3679.1 (T 31.317)2

Plugging in the standard boiling temperature and 298K, we get that the enthalpy of vaporizations are 37.2kJ/mol and 38.2kJ/mol, respectively. A good question to ask yourself is: does this make sense? Why is the enthalpy of vaporization at 298K higher than at standard boiling point?

7. Solve for the standard enthalpy and entropy of fusion. To do that, lets rst solve for V m . Vm = Vm,liq Vm,sol 122.5g ml 122.5g ml )( ) =( 1.012g mol 1.075g mol ml L = 7.097 = 0.007097 mol mol To solve for the standard entropy of fusion, use the Clapeyron equation in the following fashion: Sf us dP = dT Vm dP =
Pf

Sf us dT V m Sf us V m
Tf

dP =
Po

dT
To

(Pf Po ) = Sf us =

Sf us (Tf To ) V m

(Pf Po )Vm (Tf To )

Plugging in the values and converting units, we get that Sf us = 38.4 j/molK. To solve for the enthalpy of fusion, Pf Hf us Tf 1 dP = dT Vm To T Po (Pf Po ) = Hf us = Hf us Tf ln( ) Vm To ln( Tf ) o
T

(Pf Po )Vm

As with the entropy of fusion, plugging in all the values and converting units, you get that Hf us = 16.44kJ/mol. 8. All three of the given equations are variations of the Clapeyron Equation, with equation a being the primary equation. For equation b, this is dealing with the transition from solid or liquid to gas, or vice versa. The approximation in this equation is that since the volume of the gas phase is much greater than the liquid or solid phase, Vm = Vm,gas Vm,liq Vm.gas . The assumption is this equation is that the gas acts ideal, where Vm,gas = RT P . For equation c, it is the integrated version of equation b. You can use each of these equations to solve for several variables, such as the enthalpy and entropy of transition, or the vapor pressure of a substance at a specc temperature. However, the primary use of these equations are for substances undergoing a phase change, such as from liquid to solid, or gas to solid.