Suggested Answers to CHEM2400 Assignment 4

1. il
Z

E1/2

Figure 1A

Figure 1B

(a) The points of il and E1/2 are shown in Figure 1A. The limiting current is the constant current beyond the steep rise (point Z). Half-wave potential (point W) is the applied potential at which the current is equal to one half of the limiting current. (b) The limiting current occurs when concentration polarization occurs. At this point, the transfer of analyte to the working electrode surface is limited. Limiting current provides quantitative information about the concentration (c), by il=kc, where k is a constant. (c) If the answer is not reliable: The phenomenon shown in Figure 1B is caused by the reduction of O2 dissolved in solution. In order to obtain a reliable result, we should sparge the solution to remove the dissolved O2 first. If the answer is reliable: When the solution contains two or more metal ions and no dissolved oxygen, they may be reduced during the range of applied potential shown in Figure 1B, and thus the result in this voltammogram is reasonable and reliable. If the answer is can not be determined: Because we have no idea whether water or other metal ions reduction occurs in this voltammogram, the information is not enough to determine the reliability of this result. 2. (a) Based on the following formula, (you can read textbook to see how to derive this formula)

E appl = E1 / 2

i 0.0592 log n id i

Substituting Eappl = -0.512 V, i = 2.0 mA; Eappl = -0.535 V, i = 4.0 mA into the above formula, we can obtain equations (1) and (2). (You can substitute any two sets data of Eappl and i into the formula) 0.0592 2.0 0.512 = E1 / 2 log (1) n 10.0 2.0

0.535 = E1 / 2

0.0592 4.0 log n 10.0 4.0

(2)
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n=1, E1/2=-0.547 V. (The result will be different, depending on the data you substituted) (b) No. According to the Ilkovic equation:

(id ) max = 708nD 1 / 2 m 2 / 3 t 1 / 6 c

Stirring the solution will affect the drop time of Hg drop and therefore the value of t in the Ilkovic equation is no longer constant, and the concentration determined is not reliable. 3. (a) According to Beers Law, A = bc = 2.3103 L mol-1 cm-12.50-cm2.410-6 M = 1.3810-2 (b) P T % = 100% P0 A = log (P0/P) = -logT, T = 10-A =10-0.0138 = 0.9687, Therefore, T% = 96.87%. (c) A= -log (0.50.9687) = 0.3148 (d) He can dilute the solution by x folds, and then measure the absorbance. If the absorbance was near to 1.15/x, his result of A=1.15 is reliable. But if the result was far away from the linear relationship between concentration and absorbance, he might get an unreliable result. 4. (a) The maximum absorption wavelength would remain unchanged, and the absorbance will be reduced by about half. (b) The color of transition metal compounds will be complementary to the color of radiation that they absorbed. The cooper ammine complex absorbs yellow light, which is the complementary color of blue. (c) Usually, the energy of infrared is not sufficiently high to induce electronic transitions, but it can induce vibrational transitions. The molecule absorbs IR if any one of the vibrational modes causes a change in the dipole moment of the molecule. (d) Chromatography is used to separate mixed components based on the differences in the rates at which the components are carried through a fixed or stationary phase by a gaseous or liquid mobile phase, while extraction is based on the differences in solubility of the components in two immiscible liquids. 5. (a) Three vibrational modes of water molecule:

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All of the three vibrational modes are IR-active, because all of them can lead to a change in the dipole moment. (b) This question doesnt have a unique answer. As long as you can correctly state the principles of the method you choose or other reason that can justify your choice, the answer will be OK. This question aims at making you have a clear understanding of different separation methods learned in this chapter. Here are two suggested choices: Gas Chromatography (GC): pesticides can usually be converted to the gas phase easily and GC offers high sensitivity and efficiency for the analysis. High-Performance Liquid Chromatography (HPLC): in case there is a difficulty in converting the pesticide into a volatile species, it may be easier to analyze it in the solution form and HPLC is also a sensitive and feasible analytical method.

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