Thermodynamics (CHE 330)

Winter 2016
HW #10
Due: Monday, April 4 2016 by the start of class
Guidelines:
1. On the first page, in the upper right hand corner, write:
Your Name
Your Discussion Section Number and GSI Name
Problem Set and Due Date (format the date using the ISO 8601 convention of
YYYY-MM-DD, e.g., 1776-07-04 for the 4thof July, 1776)
Students you have studied with while working on this assignment
2. Use 8.5 11 inch paper with straight edges (not paper torn from a spiral bound
notebook). You are welcome to format your solutions digitally; however, this is not
mandatory.
3. Number all pages (e.g., 1/5, 2/5, etc.), put your name on each page, and staple the pages
together do not paper clip or fold the corners.
4. Use a ruler (or computer application) when making sketches and drawings.
5. Please be neat and write legibly. If your work is illegible, the graders are instructed to
assume that it is incorrect.
Problem 1

You are separating an equimolar binary mixture of n-hexane (component 1) and ethanol (component
2) in a flash drum. The flash is performed at 0.1 bar.

The n-hexane mole fraction in the liquid phase (x1) must be equal to 0.3.

a. Assuming ideal behavior in the liquid and vapor phases, what is the temperature in the flash
separator? What are the values of y1, L, and V (total number of moles in the liquid and
vapor phases, respectively)?

b. Assuming ideal behavior in the vapor phase, but non-ideal behavior in the liquid phase,
repeat part a. Calculate: T, y1, L, and V. The activity coefficients for n-hexane and ethanol
can be described according to the van Laar equation with = 1.57 and = 2.58.

Additional material properties for parts a and b:

B
log 10 P vap ( in bar ) = A
T ( in K ) + C

Compound A B C
n-hexane 4.00266 1171.530 -48.784
ethanol 5.24677 1598.673 -46.424

c. If you want to increase L, should you increase or decrease the operating pressure of the flash
drum described in part b? Why?
Problem 2

Liquid-liquid equilibrium (LLE) data for a binary mixture of ethanol and dodecane is tabulated
below. Phase I is the ethanol-rich phase and phase II is the dodecane-rich phase.

Temperature (K) Mole fraction of ethanol in II Mole fraction of ethanol in I

273 0.310 0.863
282 0.421 0.826

a. Using the above data, sketch a T-x-x phase diagram in the relevant temperature range
representing the two-phase region and tie-lines.

b. Assuming that this binary mixture can be described by a van Laar model, compute the
parameters and for each of the two temperatures.

Ex
c. At each temperature, create a plot of G versus composition, making sure to include the
entire range of molar compositions, even the two-phase range.
Ex Ex
d. Derive a relationship to relate H and i for each species. Assume H doesnt change
Ex
very much with temperature. Using this relationship, plot H versus composition at a
temperature of 277 K. You may use the finite difference approximation.
Ex Ex
e. Plot S versus composition at 277 K. To estimate G at 277 K, use linear interpolation.

f. Do you think the one-constant Margules model could be used to describe this system
between the given temperatures? Why or why not?
Problem 3

You can use the Antoine equation for calculating Psat in all parts of this problem.

a. You make 400 ml of a 40 mol% ethanol solution in diethyl ether (density = 1.0 g/ml) to use
in a reaction at the oil-water interface. Something urgent makes you leave and you store the
mixture in a glass container initially under vacuum and close its cap. Assuming you have an
ideal mixture and constant temperature of 25C in the laboratory, calculate the final pressure
inside the glass container and composition of both phases?

b. When you come back, you take the liquid solution in part a and emulsify it in 800 ml of
water under a hood with dimensions of 0.511 m3. By knowing that the hood is turned
off to avoid losing the ethanol and assuming to have an ideal mixture, calculate the mass of
ethanol in each phase.

c. Repeat your calculations of part b by knowing that activity coefficients can be modeled by
van Laar equations.