Name ______________________________ Purdue University School of Civil Engineering Exam #1 9 February 2012, 8-9 PM, Lilly 1105 1.

Short Answer Questions. For each of the questions on this page, you should be able to provide complete, correct answers in a few sentences, sometimes less! Write neatly. Illegible answers will be counted incorrect. a) (4 pts.) Rachel Carson published a book in 1962 that addressed the environmental fate of a number of industrial chemicals, including DDT. What was the title of that book? Silent Spring b) Recent predictions suggest that the global population could expand by 2-3 billion people by the end of the 21st century. Where is the majority of this population growth expected to take place: i. (2 pts.) Developed countries or developing countries? Developing countries CE 350, Spring 2012 E.R. Blatchley III

ii.

(2 pts.) Urban or rural areas? Urban areas

c) (4 pts.) You are given a contaminant in water that is present at a concentration of 10 ppm. What is its concentration in mg/L? The units ppm and mg/L are essentially identical for aqueous solutions. Therefore, 10 ppm = 10 mg/L. d) (2 pts.) In response to the question Is Sustainable Development Compatible with Human Welfare?, Jeremy Rifkin compares philosophies in the U.S. and Europe with respect to several issues. Which geographic area is described by Rifkin as being more willing to take risk, when it comes to the inventions and their possible effects on the environment? United States or Europe? United States e) (2 pts.) What was the primary argument in favor of exempting the US military from environmental regulations? Exemptions are required to maintain military readiness. f) (4 pts.) What is the partial pressure of oxygen in air when the total atmospheric pressure is 1.2 atm and the temperature is 25C? Express your answer in atm. ( ) ( ) ( )

2. Hydrocyanic acid (aka, hydrogen cyanide, Prussic Acid, or HCN) is a weak acid. aqueous solution, HCN can lose a proton to yield the cyanide ion (CN-):

In

The pKa value for this reaction is 9.2. HCN is extremely volatile and highly toxic. CN- is essentially non-volatile (like all ions), much less toxic, and forms complexes with many metal ions in solution. Therefore, knowledge of its acid/base behavior is important with respect to its behavior in the environment. a. (10 pts.) You are given an aqueous solution that contains some Cyanide (a term that is used to describe the sum of the concentrations of HCN and CN-). The pH of this solution is initially 11.0. What form of Cyanide will predominate under these conditions? Use appropriate calculations to justify your answer. For this reaction, as developed in class, ([
[
-

] ]

). Therefore, when pH > pKa,

the left-hand side of the equation is positive. Therefore, [CN ] > [HCN], and most of the cyanide will exist in solution as the conjugate base, CN-.

b. (10 pts.) A strong acid is added to the solution to reduce the pH to 6.0. What form of cyanide will predominate under these conditions? Use appropriate calculations to justify your answer. By similar logic to above, when pH < pKa, most of the cyanide will be in the form of HCN.

3a. (10 pts.) Reduced iron (Fe2+) can cause problems in water supplies. Many common oxidants in water can promote oxidation to Fe3+, with subsequent precipitation of Fe(OH)3. Among the oxidants that can promote this reaction is molecular oxygen (O2). The stoichiometry of iron oxidation by dissolved oxygen (DO) is defined as:
4 Fe 2 O2 10 H 2 O 4 Fe(OH ) 3 8 H

You are given a water supply containing 5 mg/L of reduced iron (as Fe). How much DO (expressed as concentration, in units of mg/L) is required to completely oxidize the iron in the water?

b. (10 pts.) What mass of Fe(OH)3 will be produced per 1000 L of water as a result of this reaction? Express your answer in grams.

) (

( )

4. Sodium chloride (NaCl) is commonly used in regeneration of household water softeners. In this process, solid NaCl is placed in a tank of water to create a brine solution. Periodically, the brine solution is pumped into the water softener to accomplish regeneration, by a process we will discuss later in the semester called ion exchange. A schematic of this system is presented below. The schematic is intended to illustrate the condition of the brine tank at the beginning (left) and end (right) of a typical month of operation. Specifically, at the beginning of the month, solid NaCl pellets are added to the system. By the end of the month, most of the salt pellets have dissolved, but some solid NaCl remains in the brine tank. The solubility product for NaCl at room temperature is roughly 36 M2.

Beginning of Month

End of Month

a. (10 pts.) Based on this description of the system, what concentration of Na+ ions do you expect to find in this system at the beginning of the month? Express your answer in molar units and in units of g/L. Assume no Na+ or Cl- are present in the water. NaCl will dissociate as follows:

Therefore, for every mole of NaCl that dissolves, we get one mole of Na+ and one mole of Cl-. [ ] , or Therefore, the molar concentrations of Na+ and Cl- will be equal. Therefore, [ ] , or [ ]

b. (5 pts.) How do you expect the concentration of Na+ ions in the brine at the end of the month to compare with the concentration that was found at the beginning of the month: higher, lower, or the same? Briefly explain your answer. It will be the same. In both cases, the liquid will be in equilibrium with the solid NaCl. Therefore, the composition will be the same at the beginning and end of the month. c. (5 pts.) HCl, a strong acid, is added to the system such that the pH of the solution is dropped and the chloride ion concentration [Cl-] is raised to 8 M. If we wait for the system to reach equilibrium, what value of [Na+] do you expect to find? Express your answer in molar units only.

5. Activated carbon is commonly used to remove contaminants from water and air by sorption. Equilibrium partitioning between activated carbon and water has been quantified for many contaminants, including MTBE (methyl tert-butyl ether). MTBE is an oxygenate compound that was developed to improve the octane rating of petroleum fuels, and to improve combustion of these fuels in car engines, thereby improving air quality. Unfortunately, large quantities of MTBE-containing fuel have leaked from underground storage tanks, resulting in contamination of groundwater sources. As it turns out, some forms of activated carbon are effective for removal of MTBE from water. The Freundlich isotherm, as defined in class and in the book takes the form:

For MTBE at room temperature, reported values1 of the Freundlich isotherm parameters are: K = 0.218 (mg/g)(L/g)1/n 1/n = 0.479 (dimensionless)

a. (10 pts.) Imagine that a single piece of activated carbon is dropped into a large tank of water, such that the concentration of MTBE in the tank is unchanged by the addition of the carbon. If the concentration of MTBE in the tank is 20 g/L, what concentration (in mg/g) of MTBE would you expect in the carbon if you allowed it to come to equilibrium with the water?

b. (10 pts.) On the axes below, sketch the shape of the sorption isotherm that you would expect for these values of K and 1/n. Your sketch should clearly indicate the trend of qe as a function of Ce down to the limit of extremely low concentration (i.e., Ce 0). Correctly label both axes to conform the standard method used for illustration of sorption isotherms.

qe

0 0 Ce

T.F. Speth and R.J. Miltner (1990) Adsorption capacity of GAC for synthetic organics, Journal, American Water Works Association, 90, 4, 171-174.

Equations: Law or Relationship Ideal Gas Law Chemical Equilibrium Acid/Base Equilibrium Precip/Dissol Equilibrium Gas/Liquid Equilibrium (Henrys Law) Sorption/Desorption (Freundlich Isotherm) Octanol/Water Partitioning

Process

Governing Equation PV = nRT [ ] [ ] [ ] [ ] [ ][ ] [ ] [ ] [ ]

[ ] [ ]