3104 Assignment 1

Total marks 45

Question 1

[4+4+4]

1. A 3.96 x 10-4 M solution of compound A exhibited an absorbance of 0.624 at 238 nm in a 1.000-cm cuvet; a blank solution containing only solvent had an absorbance of 0.029 at the same wavelength. Find the molar absorptivity of compound A. 2. The absorbance of an unknown solution of compound A in the same solvent and cuvet was 0.375 at 238 nm. Find the concentration of A in the unknown. 3. A concentrated solution of compound A in the same solvent was diluted from an initial volume of 2.00 mL to a final volume of 25.00 mL and then had an absorbance of 0.733. What is the concentration of A in the concentrated solution?

Question 2

[4+4+4]

Cu+ reacts with neocuproine to form the colored complex (neocuproine)2Cu+, with an absorption maximum at 454 nm. Neocuproine is particularly useful because it reacts with few other metals. The copper complex is soluble in 3-methyl-1-butanol (isoamyl alcohol), an organic solvent that does not dissolve appreciably in water. In other words, when isoamyl alcohol is added to water, a two-layered mixture is formed, with the denser water layer at the bottom. If (neocuproine)2Cu+ is present, virtually all of it goes into the organic phase. For the purpose of this problem, assume that the isoamyl alcohol does not dissolve in the water at all and that all of the colored complex will be in the organic phase. Suppose that the following procedure is carried out: 1. A rock containing copper is pulverized, and all metals are extracted from it with strong acid. The acidic solution is neutralized with base and made up to 250.0 mL in flask A. 2. Next, 10.00 mL of the solution are transferred to flask B and treated with 10.00 mL of reducing agent to convert Cu2+ to Cu+. Then 10.00 mL of buffer are added so that the pH is suitable for complex formation with neocuproine.

3. 15.00 mL of this solution are withdrawn and placed in flask C. To the flask are added 10.00 mL of an aqueous solution containing neocuproine and 20.00 mL of isoamyl alcohol. After the mixture has been shaken well and the phases allowed to separate, all (neocuproine)2Cu+ is in the organic phase. 4. A few milliliters of the upper layer are withdrawn, and the absorbance at 454 nm is measured in a 1.00-cm cell. A blank carried through the same procedure gives an absorbance of 0.056. (a) Suppose that the rock contained 1.00 mg of Cu. What will be the concentration of Cu (mol/L) in the isoamyl alcohol phase? (b) If the molar absorptivity of (neocuproine)2Cu+ is 7.90 x 103 M-1 cm-1, what will be the observed absorbance? Remember that a blank carried through the same procedure gave an absorbance of 0.056. (c) A rock is analyzed and found to give a final absorbance of 0.874 (uncorrected for the blank). How many milligrams of Cu are in the rock?

The figure below represents the process explained above

Question 3

[2]

1. What color would you expect to observe for a solution of Fe(ferrozine)34- , which has a visible absorbance maximum at 562 nm?

Question 4

[3+3+3]

A compound with molecular mass 292.16 g/mol was dissolved in a 5-mL volumetric flask. A 1.00-mL aliquot was withdrawn, placed in a 10-mL volumetric flask, and diluted to the mark. The absorbance at 340 nm was 0.427 in a 1.000-cm cuvet. The molar absorptivity at 340 nm is 340 = 6 130 M-1 cm-1 . (a) Calculate the concentration of compound in the cuvet. (b) What was the concentration of compound in the 5-mL flask? (c) How many milligrams of compound were used to make the 5-mL solution?

Question 5

[2]

If a sample for spectrophotometric analysis is placed in a 10-cm cell, the absorbance will be 10 times greater than the absorbance in a 1-cm cell. Will the absorbance of the reagent-blank solution also be increased by a factor of 10?

Question 6
In formaldehyde, the transition n * , T1 occurs at 397 nm, and the n

[3]
* S1 transition

comes at 355 nm. What is the difference in energy (kJ/mol) between the S1 and T1 states? This difference is due to the different electron spins in the two states.

Question 7
What is the difference between fluorescence and phosphorescence?

[3]

Question 8
What is the difference between luminescence and chemiluminescence?

[2]