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Chem 151

FINAL EXAMINATION
December 18, 2007

Chem 151 Final Exam Grade Distribution (Fall 2007)

50

45

40

Median = 72.0 Average = 71.7

35

30

25

20

15

10

0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150

Name (Last, First)

1. (8 pts.) Classify each of the following reactions into one of the 4 categories listed below. Enter the number of category in the box following each reaction equation. Category I Ion-exchange reaction Category II Redox reaction Category III Ligand substitution reaction Category IV None of the above a. b. c. d. Cu(OH)2 (s) CuO (s) + H2O (l) 2 KClO3 (s) 2 KCl (s) + 3 O2 (g) IV II

[Fe(CN)6]4 (aq) + [Mo(CN)8]3 (aq) [Fe(CN)6]3 (aq) + [Mo(CN)8]4 (aq) [Co(NH3)6]I3 (aq) + 3AgNO3 (aq) [Co(NH3)6](NO3)3 (aq) + 3AgI (s)

II I

2. (6 pts.) Enter the systematic names of the two products in the last reaction of Question 1. Hexaamminecobalt(III) nitrate Silver iodide

3. (8 pts.) In the box below, write a balanced reaction equation to illustrate the disproportionation of bromine fluoride to form bromine trifluoride and bromine. 3 BrF BrF3 + Br2

Under suitable experimental condition, would bromine disproportionate? Circle your response. (YES/ NO) Bromine trifluoride has appreciable electrical conductance. It is postulated due to the following equilibrium: 2 BrF3 BrF2+ + BrF4 Is this a redox reaction? Circle your response (YES/ NO).

Name (Last, First)

4. A small amount of CuSO45H2O crystals are dissolved in four different solvents in separated containers. The absorption spectra of each solution is scanned using a Genesys 5 spectrophotometer and are shown below:

A.

CuSO45H2O dissolved in de-ionized water

B.

CuSO45H2O dissolved in 2 M H2SO4

C.

CuSO45H2O dissolved in 6 M HCl

D. CuSO45H2O dissolved in 6 M NaOH

a) (4 pts.) Enter the chemical formula of the major complex ion in solution A in the box. Cu(H2O)62+ b) (4 pts.) Enter the systematic name of the major complex ion in solution D in the box. Diaquatetrahydroxocuprate(II) or Triaquatrihydroxocuprate(II) c) (2 pts.) What is the color of solution B? Enter your answer in the box. Blue-green

d) (2 pts.) Which solution contains more than one kind of complex ions of appreciable concentrations? C e) (4 pts.) Solution C is green. What is the color of the [Cu(H2O)2Cl4]2 complex? Enter your answer in the box. Yellow Blue mixing with yellow makes the solution look green. f) (2 pts.) Based on the given information, does sulfate ion form stable complexes with Cu2+? Circle your response. YES/ NO 3

Name (Last, First)

5. To study the ligand substitution reaction of copper(II) complexes, Megan performs the following steps and scans the absorption spectrum of the solution in every step using a Genesys 5 spectrophotometer with 1.00 cm path-length. 810.0
0.587

Step 1 Megan dissolves CuSO45H2O crystals in de-ionized water to make a 0.14 M solution and obtains spectrum A.

Step 2 She mixes 1.0 mL of solution in Step 1 with 1.0 mL of 15 M aqueous NH3 and obtains spectrum B.

633.0 3.137

726.0 1.098

Step 3 She mixes 1.0 mL of solution in Step 2 with 1.0 mL of 0.20 M ethylenediaminetetraacetate solution (abbreviated as EDTA) and obtains spectrum C.

726.0 0.566

Step 4 She mixes 1.0 mL of solution in Step 3 with 1.0 mL of 15 M aqueous NH3 and obtains spectrum D.

a)

(4 pts.) Based on the given information, rank the affinities of Cu2+ for the ligands: EDTA, H2O, and NH3. EDTA NH3 H2O > >

b) (8 pts.) Calculate the extinction coefficient of the Copper-EDTA complex at the wavelength of maximum absorbance (max). Show your work in the space below and enter your answer with appropriate unit and correct number of significant figures in the box. 31 cm-1M-1 (2SF) A = and c = (0.14M)()() = 0.035 M bc 1.098 = = 31 cm-1M-1 (1.00)(0.035) 4

Name (Last, First)

6. On the right is the structural formula of EDTA, ethylenediaminetetraacetate. a) (4 pts.) Would EDTA function better as a ligand in an acidic medium or in a basic medium? Circle your response.

O
-

O CH2 N H 2C N H 2C C O OC O-

H2 C

H2 C

C O

C H2

b) (4 pts.) Enter the systematic name of a cobalt(III)-EDTA complex in the box below. DO NOT use abbreviation. Ethylenediaminetetraacetatocobaltate(III) 7. Tetraamminedichlorocobalt(III) chloride, [Co(NH3)4Cl2]Cl, is synthesized by a two-step procedure as illustrated by the two equations below: 4 Co(NO3)26H2O + 2 H2O2 + 4 (NH4)2CO3 + 16 NH3 4 [Co(NH3)5CO3]NO3 + 4 NH4NO3 + 28 H2O [Co(NH3)5CO3]NO3 + 3 HCl [Co(NH3)4Cl2]ClH2O + CO2 + NH4NO3 (Step 1) (Step 2)

a) (4 pts.) Write a balanced equation to show H2O2 acting as oxidizing agent in a basic medium. H2O2 + 2 e- 2 OH b) (6 pts.) If both steps go to completeness with 100.0% yield, calculate the grams of cobalt(II) nitrate hexahydrate, Co(NO3)26H2O (MW 291.00 g/mol) required in order to prepare 10.00 g of the product, [Co(NH3)4Cl2]ClH2O (MW 251.42 g/mol). Show your work in the space below and enter your answer in the box. 11.57 g.

10.0 g [Co(NH 3 ) 4 Cl 2 ]Cl H 2 O 1mol Co(NO 3 ) 2 6H 2 O 291.00 g )( )( ) 251.42 g/mol 1 mol [Co(NH 3 ) 4 Cl 2 ]Cl H 2 O 1mol Co(NO 3 ) 2 6H 2 O

= 11.57 g

c) (6 pts.) If the percentage yield of the first step is 75% and of the second step is 48%, calculate the grams of cobalt(II) nitrate hexahydrate, Co(NO3)26H2O needed in order to prepare 10.00 g of the product, [Co(NH3)4Cl2]ClH2O. Show your work in the space below and enter your answer with correct number of significant figures in the box. 32 g. (2 SF)
Overall percentage yield = (75%)(48%) = 36%

100 ) = 32 g Co(NO3)26H2O needed = (11.57 g )( 36

Name (Last, First)

8. To determine the total iron content in ferritin, Dan follows the procedure in Exp 7. First, he dispensed 1.00 mL of a ferritin stock solution into a 10-mL volumetric flask. Then, he added 1 mL of 2 M H2SO4, 1 mL of dihydroxyfumarate (abbreviated as DHF) and waits 30 minutes. Next, he added 2 mL of 2.5 M sodium acetate, 2 mL of ferrizine2- solution and waits another 30 minutes. Dan adds water to fill the volumetric flask to the calibration mark, caps the flask and mixes the solution thoroughly. Then, he transferred a portion of the solution to a cuvette and measured the absorbance of the solution (using an appropriate blank solution) at max= 561 nm and path-length 1.00 cm to obtain absorbance = 0.334. a) (4 pts.) In the box below, write the balanced oxidation half-reaction equation for the reaction of DHF and the iron core in ferritin.
O HO C O C C O O C OH
-

OH O C O C C OH

O C O-

Fumaric acid

Dihydroxyfumarate (DHF)

DHF fumaric acid + 2 e

b) (4 pts.) In the space below, briefly describe how Dan should make a blank solution for measuring the absorbance of his sample solution.
Dan should follow the procedure as described in the question except skipping the addition of ferritin stock solution and the waiting time.

c)

(10 pts.) When Sloppy Joe performs this experiment, he makes some mistakes. Listed below are the possible outcomes of the experiment when a certain mistake is made. Enter the number(s) of the outcomes associated with each mistake in the appropriate boxes. I) The obtained absorbance would be higher than 0.334. II) The obtained absorbance would be lower than 0.334. III) The solution in the volumetric flask would remain colorless. IV) The experimental outcome would be same as Dan. Joe forgets to add sulfuric acid Joe forgets to add ferrizine Joe forgets to add sodium acetate
II III & II III & II II I IV

Joe measures the absorbance at 700 nm instead of at 561 nm Joe aligns the 0.50 cm path-length of the blank curvette with the light beam Instead of waiting 30 minutes, Joe waits 60 minutes after the addition of reagents

Name (Last, First)

9. Carl set up the apparatus as shown to the right and performed an experiment to obtain the gas constant R. He weighed a test tube with dry MnO2. Then he added some KClO3 solid and took the mass again. He filled the Erlenmeyer flask with water, opened the pinch clamp, and heated the mixture in the test tube. Upon heating, oxygen gas was produced and displaced water from the flask into the beaker. Carl did not realize that he had over-heated the sample and both MnO2 and KClO3 had decomposed completely. He allowed the apparatus to cool down to room temperature, equalized the water levels of the beaker and the flask, and closed the pinch clamp. Below are Carls experimental data:
Room temperature, T = 26.0C Atmospheric Pressure, Patm = 700.0 torr Mass of test tube + MnO2 Mass of test tube + MnO2 + KClO3 Mass of test tube + residue after heating Mass of empty beaker Mass of beaker with displaced water

Rubber Stopper

Glass Tubing Rubber Tube (siphon)

Test Tube

Rubber Stopper Clamp

Pinch Clamp

Beaker

Flask

Figure 1

Density of water at this temperature, H2O= 0.99678 g/mL Sat. water vapor pressure at 26.0C, PH2O = 25.21 torr mi = 14.5678 g m0 = 14.7294 g m1 = 14.6622 g mb = 65.4 g mw = 123.5 g

For all the questions below, show your calculation steps in the space provided and enter your answers with correct number of significant figures in the appropriate boxes. a. (4 pts.) What was the volume of water displaced into the beaker? 1mL (123.5 g 65.4 g )( ) = 58.3 mL 0.99678 g
0.0583 L (3 SF)

b.

(4 pts.) How many moles of oxygen gas were produced? 1 mol (14.7294 g 14.6622 g )( ) = 0.00210 mol 31.998 g

0.00210 mol (3 SF)

c.

(10 pts.) If MnO2 (MW = 86.938 g/mol) and KClO3 (MW = 122.55 g/mol) decompose according to the equations below, calculate the mass of MnO2 in the test tube. 2 KClO3 (s) 2 KCl (s) + 3 O2 (g) 4 MnO2 (s) 2 Mn2O3 (s) + O2 (g)
0.042 g (2 SF)

1mol moles of KClO3 before heating = (14.7294 g 14.5678 g )( ) = 0.001319 mol 122.55 g 3 mol O2 moles of O2 produced by KClO3 = (0.001319 mol )( ) = 0.001978 mol 2 mol KClO3 moles of O2 produced by MnO2 = 0.00210 0.001978 = 0.00012 mol
Mass of MnO2 in test tube = (0.00012 mol O2 )(

4 mol MnO2 86.938 g )( ) = 0.042 g 1 mol O2 1mol MnO2

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Name (Last, First)

d.

(2 pts.) How would Carls mistake affect the experimental value of R? Circle the correct response.
Carls experimental value of R would be (higher/ lower/ same as) the true value.

10. Below is the structural formula and absorption spectrum of the molecule all-trans-1,3,5,7Octatetraene in solution.
H C H C H H C C H H C C H H C C H H

a.

(8 pts.) From the information obtained form the absorption spectrum, calculate the energy difference between the ground state and the first excited state of the octatetraene molecule. Enter your answer in the box and show your work below. 6.53 x 10-19 Joule
From spectrum max of ground state first excited state = 304 nm c 2.998 108 E = h = (6.626 10 34 )( ) = 6.53 10 19 9 304 10

b.

(8 pts.) Apply the simple model of a particle in a one-dimensional box to calculate the average C-C bond length in the octatetraene molecule. Show your work clearly in the space below, including the equations and parameters used in your calculation. Enter your answer in the box. 1.30 x 10-10 m 2 2
From En =

nh 8mL2

We have E =

h2 h2 Where N = number of -electrons (n 2 ni2 ) = ( N + 1) f in the conjugate system 8mL2 8mL2

h h2 ( N + 1) h = ( N + 1) to give L2 = 8mc 8mL2

c
(6.626 10 34 J s )(304 10 9 m) L = (8 + 1) = 8.30 10 19 m 2 31 8 8(9.11 10 kg )(2.998 10 m / s )
2

L = 9.11 x 10-10 m

9.11 10 10 m = 1.30 10 10 m Average bond length = 7

8

Name (Last, First)

11. (4 pts.) The oxygen-rich blood is red while the oxygen-poor blood is blue. The oxygen content of the blood is also related to the coordination number of iron in the heme group. Circle the correct response in each of the following questions. a) Which type of blood has a longer max in its absorption spectrum?
oxygen-rich blood oxygen-rich blood or or or oxygen-poor blood oxygen-poor blood oxygen-poor blood

b) Which type of blood in which the iron in the heme group is six coordinated? c) Which type of blood absorbs electromagnetic wave of higher energy?
oxygen-rich blood

12. (6 pts.) Alanine is an amino acid with a methyl group (CH3) as its side chain. Draw the structure of alanine in the space below.
H H2N C CH3 C OH O
+

O C O-

H3 N

C CH3

or

13. (10 pts.) From the two lists below, circle all the chemicals in an automobile airbag, a) before it deploys (Na3N, NaN3, KNO3, KOH, SiO2, N2, sodium silicate, silicon) (Na3N, NaN3, KNO3, KOH, SiO2, N2, sodium silicate, silicon)

b) after it deploys

There should be un-reacted KNO3 and SiO2 in the airbag because to ensure that all the hazardous substances (such as the alkali metals and their oxides) are all reacted, the other reagents (KNO3 and SiO2) that react with them should be in excess. 4 bonus points will be awarded to having both KNO3 and SiO2 circled.

If you need more space to present an answer, indicate the question number and write your answer inside the box below.

Useful Information:

1 atm = 760 torr K = C + 273.15 1 nm = 1 x 10-9 m Gas Constant = 8.314 Joule/molK = 0.08206 atmL/molK Speed of light, c = 2.998 x 108 m/s Plancks Constant, h = 6.626 x 10-34 J.s Mass of electron, me = 9.11 x 10-31 kg The allowed energies (En) of a particle of mass m in a one-dimensional box of length L is:

n2h2 En = 8mL2

Relations between Electronic Transition Energy and Color

Transition energy (kJ/mol) <165 166 176 196 206 214 226 239 249 279 292 >299 Wavelength (nm) >720 720 680 610 580 560 530 500 480 430 410 <400 Spectral color absorbed Infrared Red Red Orange Yellow Yellow-green Green Blue-green Blue Indigo Violet Ultraviolet Complementary color Colorless Green Blue-green Blue Indigo Violet Purple Red Orange Yellow Lemon yellow Colorless

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1 IA 1 H 1.0079 3 Li 2 IIA 4 Be

Periodic Table of the Elements

13 IIIA 5 B 14 IVA 6 C 15 VA 7 N 16 VIA 8 O

18 VIIIA 2 He 17 VIIA 4.0026 9 10 F Ne

6.941 9.0122 11 12 Na Mg 3 22.990 24.305 IIIB 19 20 21 K Ca Sc 4 IVB 22 Ti 5 VB 23 V 6 VIB 24 Cr 7 VIIB 25 Mn 8 6 26 Fe 9 VIIIB 27 Co 10 8 28 Ni 11 IB 29 Cu

10.811 12.01 14.007 15.999 18.998 20.180 13 14 15 16 17 18 Al Si P S Cl Ar 12 IIB 26.982 28.09 30.974 32.066 35.453 39.948 30 31 32 33 34 35 36 Zn Ga Ge As Se Br Kr

39.098 40.078 44.956 47.88 50.942 51.996 54.938 55.847 58.933 58.69 63.546 65.39 69.723 72.61 74.922 78.96 79.904 83.80 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 85.468 87.62 88.906 91.22 92.906 95.94 55 56 71 72 73 74 Cs Ba Lu Hf Ta W (98) 101.07 102.91 106.42 107.87 112.41 114.82 118.7 121.75 127.60 126.90 131.29 75 76 77 78 79 80 81 82 83 84 85 86 Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn (222) 118 Uuo

132.91 137.33 174.9 178.5 180.95 183.85 186.2 190.2 192.22 195.08 196.97 200.59 204.38 207.2 208.98 (209) (210) 87 88 103 104 105 106 107 108 109 110 111 112 113 114 116 Uun Uuu Fr Ra Lr Rf Db Sg Bh Hs Mt Uub Uut Uuq Uuh (223) (226) (260) (261) (262) (263) (262) (265) (266) (269) (272)

57 La Lanthanides 138.9 89 Ac Actinides (227)

58 Ce 140.1 90 Th 232.04

59 Pr 140.9 91 Pa 231.04

60 Nd 144.2 92 U 238.03

61 Pm (145) 93 Np (237)

62 Sm 150.4 94 Pu (244)

63 Eu 152.0 95 Am (243)

64 Gd 157.3 96 Cm (247)

65 Tb 158.9 97 Bk (247)

66 Dy 162.5 98 Cf (251)

67 Ho 164.9 99 Es (252)

68 Er 167.3 100 Fm (257)

69 Tm 168.9 101 Md (258)

70 Yb 173.0 102 No (259)

~The End~ Happy Holidays!!

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