Chem 22 – Analytical Chemistry 2 Fourth Long Exam 08 Mar 2009

General Instructions:
1. No borrowing of test materials, including calculators and periodic tables. Observe complete silence.
2. STRICTLY NO ERASURE ON THE OBJECTIVE PART; otherwise it will be marked wrong.
3. WRITE YOUR SOLUTIONS COMPREHENSIVELY. Demerits will be given to unorganized solutions. Good luck!

I. Objective (2 pts each)

1. The half reaction that involves the loss of electron.
a) reduction c) redox
b) oxidation d) disproportionation
2. The type of redox reaction wherein a species is simultaneously oxidized and reduced.
a) combination c) disproportionation
b) decomposition d) oxidation
3. In superoxides, the oxidation number of oxygen is
a) –2 c) –½
b) –1 d) +5
4. What is the reductant used in the Jones redactor?
a) potassium permanganate c) granulated zinc metal
b) amalgamated zinc d) granulated metallic silver
5. If you want to convert Fe2+ to Fe3+, which of the ff. can be used?
a) Jones reductor c) Ag2O3
b) Walden reductor d) NaBiO3
6. Excess NaBiO3 after using can be removed by
a) boiling c) filtration
b) treatment of acid d) digestion
7. Mohr’s salt, the compound that Fe2+ is ordinarily prepared from, is
a) iron (II) ammonium sulfate
b) iron (III) ammonium sulfate
c) iron (II) ethylene diamine sulfate
d) iron (III) ethylene diamine sulfate
8. The indicator used in the thiosulfate process.
a) self-indicating c) 1,10-phenanthroline
b) starch indicator d) diphenylamine sulfonic acid
9. To prevent unwanted effect of the degradation of starch solution, what should be done?
a) store indicator in sterile conditions
b) adding a bacteriostat
c) just prepare fresh solution
d) all of the above
10. Which of the ff. is not a reason why permanganate process is often used than ceric process?
a) KMnO4 is available in modest cost
b) KMnO4 has available primary standard for solution preparation
c) the cerium (IV) solution has tendency to form basic salts in solutions that are less than 0.1 M of strong acid
d) none of the above
11. Which of the ff. is often used in standardizing KMnO 4 solutions?
a) Na2S2O3 c) As2O3
b) FeSO4 d) H2C2O4
12. How many electrons lost using the oxidation of iron metal?
a) 1 c) 3
b) 2 d) 0
13. In the treatment of ferrous ion with the dichromate ion, what should be the factor used in calculating the %Fe 2+?
a) 2/5 c) 1/6
b) 5/2 d) 6/1
14. The method of analysis that is based on the amount of radiation produced or absorbed of the atom/molecule/ ions of interest.
a) spectrophotometric or spectrochemical method c) spectroscopy
b) Potentiometry d) photometry
15. What is the law that is used in spectrophotometric method of analysis?
a) Gulberg-Waage Law c) Stokes-Einstein Law
b) Classius-Clapeyron Law d) Beer-Lambert Law
16. The negative logarithm of transmittance.
a) inverse transmittance c) intensity
b) absorbance d) frequency
17. The absorbance of the species is ________ the concentration of that species.
a) inversely proportional to c) equal to
b) directly proportional to d) the negative logarithm of
Po
18. The term log P refers to
a) Transmittance c) Absorbance
b) absorptivity d) Beer’s constant
19. What is the symbol of absorptivity?
a) a c) ε
b) A d) Po
 20. The method wherein different volume of a standard solution were added to the aliquots of the sample to determine its
concentration through spectrophotometric method.
a) spectrochemical method c) standard addition method
b) potentiometry d) indirect method

II. Problem Solving

1. The tetraethyl lead [Pb(C2H5)4] in a 25-mL of aviation gasoline was shaken with 15.00 mL of 0.02095 M I 2. The reaction is
Pb(C2H5)4 + I2 → Pb(C2H5)3I + C2H5I
After reaction was complete, the unused I2 was titrated with 6.09 mL of 0.03465 M Na2S2O3. Calculate the weight in milligrams of
Pb(C2H5)4 in each milliter of sample.(15 pts)
2 I2 1 Pb ( C2 H 5 )4
wtPb ( C 2 H 5 )4
=
[ 15 ( 0.02095 ) −6.09 ( 0.03465 )
( 2 N a2 S 2 O3
I2
)] (
1I2
323.2
)( )1
=1.3346
mL 25 mL
2. A 24.7 L sample of air drawn from vicinity of coking oven was passed over iodine pentoxide at 150 oC, where CO was converted
to CO2 and a chemically equivalent quantity of I2 was produced:
I2O5(s) + 5CO(g) → 5CO2(g) + I2(g)
The I2 distilled at this temperature was collected in a solution of KI. The I 3- produced was titrated with 7.76 mL of 0.00221 M
Na2S2O3. Calculate ppm CO. (15 pts)
4 I2 5CO

ppmCO=
7.76 ( 0.0021 ) N a2 S 2 O3 ( 2 N a2 S2 O3 )( 1I2 () 281COmg ) (10 )=105 , 914
6

g
(
24.7 L 0.830557
L )( 10001 gmg )
APAT PALA THIOSULFATE KC UNG EQUATION AY −¿ ¿
2−¿+2e ¿

2 S 2 O 2−¿→ S O ¿ 4 6
3
PM 1 atm ( 28.84 ) g
ρ= = =0.830557
RT 0.08206 (150+273.15) L
3. The spectrophotometric method of analysis was used for the analysis of chromium content in a water sample. Two groups of
experimenters analyze a water sample near a mining plant.
Data for Group A
Calibration:
concentration, ppm 0 10 20 40 60 80 100
Absorbance 0.002 0.053 0.143 0.284 0.425 0.568 0.697
Sample data (Spike: 2 mL of 500 ppm; Dilution is 30/50, volume of sample is 50 mL)
Sample 1a 1b 1c
Absorbance 0.262  0.258   0.404
r 2=0.999117216
0.262+ 0.258 50 50
c x=
2
( ^x )
30 ( )
=37.175
30 ( )
=61.96 ppm

0.262+ 0.258
%rec of spike=
0.404− ( 2
( x^ ) )
(100 )=103.86 %
2
500
50 ( )
Data for Group B (Standard addition Method)
Sample Volume: Five (5) 20-mL aliquots in 50 mL volumetric flask
Concentration of standard solution to be added: 15 ppm
Results
Volume added, mL 0 5 10 15 20
Absorbance  a  B c   d  e
20 0
[ 50 50 ]
a= 61.96 ( ) +15 ( ) ( ^y )=0.172

[ 2050 505 ]
b= 61.96 ( ) +15 ( ) ( ^y )=0.183

20 10
[ 50 50 ]
c= 61.96 ( ) +15 ( ) ( ^y )=0.194

[ 2050 1550 ]
d= 61.96 ( ) +15 ( ) ( ^y )=0.204

[ 2050 2050 ]
e= 61.96 ( ) +15 ( ) ( ^y ) =0.215

m=0.00214
 b=0.1722
b cs 0.1722 ( 15 )
c x= = =60.35
m V x 0.00214 ( 20 )
60.35−61.96
%dev = 100=−2.6 %
61.96
a. Determine the results (based on the average concentration 1a and 1b) of Group A, and determine the %recovery of spike.
b. Using the data of Group A, predict the absorbances of Group B. Recompute the concentration of the sample based on these
computed value and determine the %deviation of the results, if we consider the results of Group A as the true value.
4. A solution containing 5 ppm KMnO4 has a transmittance of 0.581 in a 1.0-cm cell at 520 nm wavelength. Find the concentration
of an unknown solution having an absorbance of 0.735 in a 3-cm cell. (10 pts)
−log 0.581=εbc=ε (1.0 )( 5 ) ; ε =0.0471645
0.735=0.0471645 (3 )( c ) ; c=5.19 ppm