Chemistry 2311, Fall 2008

Student Name ______________________________ Quiz #1A (75 pts) 1.

Last Name of TA _______________

Waste Handling - Specifically describe how to handle each of the following waste materials generated during an experiment in lab. 8 pts (+ 2 each) a. a used chromatography column containing silica gel and solvent flush the column dry with air to remove all solvent. (The solvent would be place in organic hazardous waste or halogenated organic waste). The dry silica gel in nonhazardous solid waste.

b.

10 mL of unused 10% aqueous KOH solution

neutralize with aq 10 % HCl and flush down the drain with plenty of water.

c.

a clean but broken Erlenmeyer flask

(blue) broken glass trash can at end of bench

d.

The organic liquid residue left in the distilling flask after distillation dissolve in acetone and transfer to liquid organic hazardous waste

2.

Consider the reaction below that is sometimes performed in organic teaching labs to teach the principles of TLC, column chromatography, and melting points. The reaction produces a mixture of starting material (fluorene) and product (fluorenone) which can be easily separated by column chromatography.

Na2Cr2O7 CH3CO2H Fluorene, mp 114 oC, MW 166.2 O Fluorenone, mp 83 oC, MW 180.21

a.

If the reaction produced approximately 8 g of crude product to be purified by column chromatography, how much silica gel would be appropriate for the separation? 10-20 X +3 pts i. 8 g ii. 20 g iii. 120 g iv. 1200 g

b.

Unlike ferrocene and acetylferrocene, fluorene and fluroenone are both colorless, white solids. How would progress of the column chromatography be followed since no colored bands would be visible? +4 pts Collect fractions and TLC each fraction. Use some means to visualize the spots. Iodine or UV light work work. (Students could suggest others).

_____ 15 pts
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Chemistry 2311, Fall 2008

Na 2Cr2O7 Fluorene, mp 114 oC, MW 166.2 CH 3CO2H O Fluorenone, mp 83 oC, MW 180.21

c.

If 8.0 g of fluorene was used in the reaction as the limiting reagent and after chromatographic separation, 4.7 g of fluorenone was isolated, what was the % yield of the reaction? Show all calculations. 6 pts 8.0 g fluorene/166.2 g/mol fluorene = 0.048 mol +2 0.048 mol x 180.21 g/mol fluorenone = 8.7 g theoretical yield of fluorenone +2 (can be combined with above) 4.7 g/8.7 x 100 = 54% yield +2

d.

Which compound would most likely elute from the column first? Circle one. 2 pts Fluorene Fluorenone

e.

Consider the 8 cm TLC plate below where fractions 4-11 were combined for spot A, fractions 1215 were combined for spot B, and fractions 16-25 were combined for spot C. Label the following on the TLC plate: pure fluorene, pure fluorenone. Calculate the Rf value for spot A using the given numbers (note the baseline starts at 0.6 cm not 0 cm) 8 pts

8.0 cm
7.5 cm
3.7-0.6 = 0.45 +4

5.9 cm 3.7 cm
+2 +2

Rf of Spot A =

7.5-0.6

A fluorene

C fluorenone

0.6 cm 0.0 cm

f.

A solid was isolated from spot B (fractions 12-15) and its melting point determined. Based on the TLC and given mpts of fluorene and fluorenone as 114 oC and 83 oC, respectively, which melting pt range below would most likely be observed (assume A is less than 50% of the sample B)? 3 pts a. 196-197 oC b. 90-95 oC c. 70-80 oC d. 82-83 oC
cant be higher than both or sum cant be higher than B if mostly B this is best guess since B can not be sharp if mixture

g.

Which compound would have a singlet at 3.889 in the 1H NMR spectrum? Identify the Hs on the structure. 3 pts
Fluorene H H both benzylic so shifted downfield O Fluorenone no Hs not in 7-8 region

_____ 22 pts
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Chemistry 2311, Fall 2008

3.

Simple Distillation - Briefly answer the following questions concerning a proper distillation. 12 pts a. Use the diagram of a distillation head below to show the proper positioning of the thermometer bulb for an accurate boiling point. +3
+3

b.

How is the size of the distilling flask chosen? not more t han 1/ 2 f ull of liquid t o be distilled What is the purpose of the boiling stones? +3

c.

prevent bumping - pr ov ide a surf ace f or escape of v apors prevent super heating ( all OK ) d. Why should a distillation be stopped bef ore it reaches dryness? f ormation of explosive peroxides or other materials may +3 be concentrated or discomposed residue left in glassware

4.

a.

Draw structures for each of the solvents below that you have used in lab. Circle the solvent that is the most polar. 8 pts ethyl acetate methylene chloride diethyl ether

CH 3CO2CH 2CH 3

CH 2Cl2

CH 3CH2OCH2CH3

5.

Extraction. During a separatory funnel extraction using diethyl ether and water, in which layer would you find the majority of each of the following compounds. Put O for organic layer, and A for aqueous layer. 5 pts
O A O A K O Cl O hexane O

NaHCO3

6.

Fischer Esterification Reaction After performing the banana oil synthesis in 2311 lab, a student was so enthused that she wanted to use the Fischer Esterification reaction to synthesize isobutyl propionate A, which has the flavor of rum. Give the starting materials and reagent(s) the student would need to perform this synthesis. 5 pts
+1 O CH 3CH2 C OH +2 +

HO CH 2CH(CH3)2 +2

H 2SO4
or any acid CH3CH 2 (catalyst)

O C O A

CH 3 CH 2CH CH 3

_____ 30 pts
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Chemistry 2311, Fall 2008

7.

Standard Lab Techniques - In succinct words explain why 8 pts (+2 each) a. A heating mantle is not placed directly on the bench top during reflux.

So that the heat source can be quickly removed if necessary b. Pipetting directly from a reagent bottle is poor technique.

Contamination of the reagent can occur c. It is important to know the density of organic liquids before performing an extraction with water.

So that the top and bottom layer can be identified

d.

It is important to understand the mechanism of a reaction before performing it in lab.

So that by-products can be anticipated. Knowing if any gases are formed or physical properties of any by-products that would need to be separated or observed during purification such as distillation (TAs use your judgement on a good answer)

The End Please sign. I agree that discussing this quiz with any other student in the 2311 lab course will be detrimental to my grade. Therefore I promise to keep the contents and format of this quiz confidential until the TA has graded and returned the quiz. Signature _____________________________________

2 Bonus Points: Observe that the melting point of fluorene in problem 2 is HIGHER than the mpt of fluorenone, even though fluorenone is higher in polarity and molecular weight. What principle of melting point theory can account for this observation? Symmetry of crystal packing has a large influence on mpt. (Tightness of crystal lattice) Fluorene is more symmetrical than fluorenone.

_____ 8 + 2 Bonus points

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