Chemistry of Environmental Toxins

CE 480 /580
Winter Term 2020

Assigned: January 29
Due: February 12
Homework No. 2

1. As part of your environmental engineering consulting work, you have detected PCDDs and
PCDFs in your client’s soil. (A) How many congeners for each of these compound groups are
there? (B) Draw the general structure for each of these compound groups (you will have two (2)
general structures drawn for your solution). (C) Are you concerned about the detection of these
organic compounds in your client’s soil? In other words, will you advise your client to remediate
those soils for these toxins?

2. In your own words, how does the a) –OH, the b) -FH group, and the c) -NH group affect an
organic compound’s behavior in water? Provide some structural images to support your
statements (for example, one of your images (all should be hand drawn) should illustrate an
organic compound with an -OH residing in an aqueous solution).

3. Consider a di-halogenated aromatic. How do you expect (a) the melting point temperature to
trend for the ortho- structure versus the para- structure of this organic molecule? and (b) the
aqueous solubility?

4. Without looking it up, how would you expect the aqueous solubility of phenol versus n-
butylbenzene to vary and why?

5. You have been given a NAPL mixture of phenol and biphenyl composed of 30% by volume
phenol and the balance biphenyl. (a) What is the mole fraction of each organic compound in the
NAPL? (b) What is the mole fraction of each organic compound in the vapor phase if this liquid
solution is in equilibrium with its vapor phase? HINT: Begin part (b) using a fugacity box and
clearly state all assumptions.

6. We have seen Raoult’s Law written in terms of a compound’s vapor pressure (specifically, in
Figure 4.2 (d) in your textbook). Another form of Raoult’s Law we will often see applied in the
field of environmental chemistry is as follows:

1
𝑥 = 𝑥
𝛾
where the subscript w denotes the aqueous (water) phase, N denotes the separate liquid phase
(i.e., NAPL), and i denotes the constituent of interest (in equilibrium between these two phases),
and all other variables are as described in your lecture notes and/or textbook. Beginning with the
definition of equilibrium (in terms of the chemical potential, µ, and incorporating our fugacity
boxes), derive the above expression for Raoult’s Law. Show all of your steps and clearly state all
assumptions.