MT 202: Homework 9

Sai Gautam Gopalakrishnan

“Clapeyron-Clausius”

1. The throttling process can be modified to cool down liquids as well as gases. In one such
experiment, some amount of liquid CO2 is cooled from a temperature of 293 K to a
temperature of 194.5 K, while the pressure drops from an initial 5.7 MPa to a final 1 atm.
Given the 𝑝 − 𝑇 diagram of CO2 below, what do you think is the final state of CO2 after
the throttling process? Explain.

a. If gaseous CO2 forms during the throttling process, what fraction of the final
product is gas? The enthalpy of liquid CO2 under the initial temperature and
pressure is 24.2 kJ/mol, while the enthalpy of solid CO2 under the final conditions
is 6.75 kJ/mol. At 194.5 K and 1 atm, the enthalpy of sublimation is 25,100 J/mol.

2. Show that the total entropy of a pure component going through a first-order phase transition
is a linear function of the total volume of the pure component.
! "# $
a. Prove Δ𝑈 = Δ𝐻 (1 − ! "# %* for any first-order phase transition

3. For ice skating to be fun, i.e., for the skaters to move freely on ice, there has to be a layer
of water formed on the ice surface to reduce friction between the skating blades and the ice
layer, which allows for smooth transport across the skating rink. Most ice skating rinks are
kept at a temperature of -7oC so that the underlying ice layer is thick enough to support
several people on the rink.
There is a popular theory that the water layer on the ice surface is created due to the pressure
exerted by the weight of a skater. Given that the latent heat of melting of ice is fairly
invariant with temperature and has a value of 3.34×105 J/kg and volume change of melting
is 9.05×10-5 m3/kg (remember that ice contracts on melting), do you think is how the water
layer is created on a typical skating rink? You can assume a maximum weight of a skater
to be 100 kg and the skater being able to balance on a small area of ~10-3 m2 when tip-
toeing on their skater blades.
4. Ice is initially at 270 K and 1 atm pressure and is isentropically compressed until it starts
melting. What is the melting point of ice that is reached during this process? Assume a
!%
constant slope of the melting curve of ice, i.e., !$ |&'()*+, = −1.35 ×107 Pa/K. Other
useful properties of ice are 𝑐% =2.01×103 kJ/kg/K, 𝑣 =1.09 dm3/kg, and 𝛼- =1.58×10-4 K-
!%
1
. (Hint: evaluate (!$ * for ice and find the temperature, pressure combination at which it
.
!%
intersects the melting curve. Assume any temperature-dependence of (!$* can be
.
neglected for any integration.)

5. The standard boiling point of Li is 1620 K. What will be the vapor pressure of liquid lithium
at 1000 K if the enthalpy of vaporization of Li is 156×103 J/mol?
a. If the vapor pressure of solid lithium is given by the following equation (𝑝, 𝑇 in
atm, K),
19314
ln 𝑝 = 13.049 −
𝑇
what is the standard melting point of Li? Note that both liquid and solid phases will
exert the same vapor pressure during melting.

6. 100g of pure silver is placed in an evacuated chamber at 1500 K, whose volume is 1 m3.
What is the state of Ag in this chamber? If there are multiple phases of Ag in this chamber,
specify the fraction of each phase. Useful data: Standard melting point of Ag = 1235 K.
/0123
Silver expands upon melting. Vapor pressure of liquid Ag is given by ln 𝑝 = − $ +
12.5, where 𝑝 is in atm and 𝑇 in K. Enthalpy of melting of silver is 11.3 kJ/mol. Assume
gaseous silver behaves ideally.