UP Academic League of Chemical Engineering Students (UP ALCHEMES)

Academics Affairs Committee Review and Tutorials Program, AY 2013-2014

Chem 17 Second Exam (SAMPLE EXAM)

I. Modified True or False: Write TRUE if the statement is correct. Otherwise, changed the underlined word to make the
sentence correct.
1. Precipitation would occur if the reaction quotient is greater than the solubility product constant.
2. The following solutions are ranked in increasing solubility of Ca(OH)2: 0.3 M KCl < 0.3 M Na2SO4 = 0.3 M CaCl2
< 1.0 M NaOH < 1.5 M NaCl.
3. Addition of zinc dust to a saturated copper(II) oxalate solution will shift the precipitation of the solid forward.
4. In Expt. 5, the solutions were acidified in order to prevent the formation of Fe(OH)3.
5. The violet solution obtained after adding HCl to Co
2+
solution was due to the formation of CoCl4
2-
.
6. [Cu(NH3)4]
2+
is a complex that mostly absorbs blue light.
7. Precipitation would not occur if a 0.05 M solution of ammonia was to be mixed with 0.1 M solution of MgCl2. Kb
ammonia is 1.8 x 10
-5
, Ksp MgCl2 is 1.810
-11
.
8. A buffer can be prepared by adding 10.0 mol of benzoic acid (pKa = 4.19) and 15.0 mol NaOH in 100 mL water.
9. Change in absorbance over change in wavelength is maximum at the max.
10. Ammonium hypochlorite solution at 25 C will give a pOH higher than 7 (Kb of NH3 = 1.810
-5
, Kb of ClO
-
=
2.910
-7
).
II. Multiple Choice
1. Given the redox reaction
3 2 2 2
( aq) 2( aq) ( aq) ( aq)
Fe Hg Fe Hg
+ + + +
+ + , with Keq = 9.1410
-6
at 25 C, what is the equilibrium
concentration of ferrous ion if the initial concentrations are as follows:
3 2
( aq) 2( aq)
Fe Hg 0.500 M,
+ +
( ( = =

2 2
( aq) ( aq)
Fe Hg 0.0300 M
+ +
( (

= = ?
A. 0.497 M B. 0.499 M C. 0.0326 M D. 0.00192 M
2. A certain indicator has an indicator pH range of 1.88 3.88. It has an acid color of red and a base color of yellow.
What will be the color of a solution if 3 drops of this indicator is placed in a 30 mL 0.10 M CH3COOH solution?
A. Red B. Yellow C. Orange D. Clear
3. Which of the following will happen to the molar solubility of Ca(OH)2 if it was suspended in 0.20 M MgSO4 instead
of 0.50 M KCl?
A. It will increase
B. It will decrease
C. It will remain the same
D. The effect cannot be determined
4. Which of the following buffer systems will have the strongest buffer capacity?
A. 0.0010 M CH3COOH + 0.0020 M Na(CH3COO)
B. 0.100 M CH3COOH + 0.200 M Na(CH3COO)
C. 0.100 M Na2HPO4 + 0.200 M H3PO4
D. 0.200 M NaH2PO4 + 0.300 M Na3PO4
5. Which of the following will happen to Q of the reaction Fe
3+
+ 4Cl
-
FeCl4
-
when AgNO3 is added to a solution
containing FeCl4
-
?
A. It will increase
B. It will decrease
C. It will remain the same
D. The effect on Q cannot be determined
6. 50.00 mL of 0.0500 M H3PO4 is titrated with 0.100 M NaOH. What is the volume of the base added when the pH
of the solution is equal to pKa2?
A. 25.0 mL B. 75.0 mL C. 50.0 mL D. 37.5 mL
7. Which of the following buffer systems is the best to use to prepare a buffer of pH 7.00?
A. H2CO3/NaHCO3 (Ka1 = 4.210
-7
)
B. NaH2PO4/Na2HPO4 (Kb2 = 1.6110
-7
)
C. HCOOH/Na(HCOO) (Ka = 1.810
-4
)
D. NH/NHCl (Kb = 1.810
-5
)
8. When a solution of K2CrO4 is mixed with NaOH, the color of the resulting solution is ________.
A. Yellow B. Orange C. Blood red D. Colorless
9. The homogenous gas reaction
2( g) 2( g) (g) 2 ( g)
CO H CO H O + + is known as the water gas reaction. The enthalpy
and entropy of the reaction at 1000 K are as follows:
o
1000
H 35.04 kJ/mol, A =
o
1000
S 32.11 J/(mol K) A = . What
is the Kc of the water gas reaction at 1000K?
A. 1.000 B. 2930 C. 2.930 D. 0.7029
10. What is the molar solubility of a zinc phosphate solution? (Ksp = 9x10
-33
)
A. 3.9x10
-7
B. 6.3x10
-12
C. 2.1x10
-11
D. 1.5x10
-7

11. What is the Keq of the following reaction
2(s) 3 4( aq) 3 2(s) 2 ( l )
Ba(OH) H PO Ba (PO4) H O + + given the following
constants at 25 C: Ksp: Ba(OH)2 = 510
-3
, Ba3(PO4)2 = 3.410
-23
, phosphoric acid: pKa1 = 2.149, pKa2 = 7.201,
pKa3 = 12.347, and Kw = 110
-14
?
A. 1.4910
76
B. 1.4910
56
C. 6.7110
-57
D. 6.7110
-77

12. Which of the following will happen to the measured absorbance if air bubbles were present in one of the standard
solutions?
A. It will increase
B. It will decrease
C. It will remain the same
D. The effect cannot be determined
13. Ethylenediamine, en, is a difunctional weak base with dissociation constants as follows: pKb1 = 4.071, pKb2 =
7.149. What is the concentration of H2(en)
2+
in a 0.070 M solution of ethylenediamine?
A. 7.1010
-8
M
B. 2.4010
-3
M
C. 4.17410
-12
M
D. 2.4510
-6
M
14. What is the pH of a 1.010
-5.4
M solution of HCl at 100 C?
A. 5.40 B. 5.00 C. 5.56 D. 5.27
15. Which of the following will increase when the concentration of the [Fe(SCN)]
2+
complex is decreased?
A. Molar absorptivity
B. max
C. % Transmittance
D. Absorbance
III. Problem Solving:
1. The percent purity of sodium arsenate hemihydrate (SAH) and its dissociation constants were quantitatively
determined by generating a titration curve. A 5.000 g sample containing SAH and inert contents was dissolved in
50 mL distilled water and was titrated by standardized 1.00 M HCl. The titration curve of SAH is shown below:



a. Find and label (1
st
, 2
nd
, etc.) the endpoints of the titration curve.
b. Find and label (1
st
, 2
nd
, etc.) the half endpoints of the titration curve.
c. Calculate pKb1, pKb2, and pKb3 of SAH.
d. Calculate the pH of the system at the final endpoint.
e. Calculate the pH of the system 2.00 mL of titrant after the final endpoint.
f. Using the first endpoint, calculate the percent purity of the SAH sample. (MW = 216.89 g/mol)
g. What indicators should you use for the endpoints of the titration? Check the table below for a list of
indicators and their corresponding pKa:

Indicator pKa Indicator pKa
Thymol blue 1.65 Bromothymol blue 7.10
Methyl orange 3.46 Cresol red 8.32
Bromocresol green 4.66 Thymolphthalein 9.90
Methyl red 5.00 Alizarin yellow GG 11.0

2. You wish to prepare a 0.100 M 200 mL buffer of pH 4.00, 6.00, and 10.00 for a protein digestion experiment.
Unfortunately, the only information you have are the osmotic pressure (at 25 C) of 0.009 M solutions of the
dicarboxylic (diprotic) acids, and the pH of their 0.100 M ampholytes:
Acid Osmotic pressure, atm pH of 0.100 M ampholyte MW of Na2A, g/mol
Aminomalonic 0.2655 6.575 163.04
Citraconic 0.3355 4.220 174.07
Diethylmalonic 0.3420 4.750 204.13
Iminodipropionic 0.2397 6.860 205.12
Maleic 0.3673 4.075 160.03
It was found out that the concentration of fully deprotonated species (A
2-
) of each acid is very small.
11.4
9.085
4.58
0
2
4
6
8
10
12
14
0 10 20 30 40 50 60 70 80
pH
Volume titrant, mL

A
B
C
D
E
F
G

a. Find pKa1 and pKa2 of each acid.
b. Find the concentration of maleic acid (H2A), hydrogen maleate (HA
-
) and maleate (A
2-
) in 0.001 M of sodium
maleate and its pH.
c. You only have salts of the acids fully deprotonated form (Na2A), and 1.50 M HCl. Which salts will you
choose for the preparation of the buffers?
d. How many mL of acid and grams of salt you need to prepare the three buffers? The molecular weight (g/mol)
of each salt can be found in the table.

3. You wish to separate the following cations in a 50 mL solution: Ag
+
, Tl
+
Fe
3+
, Pb
2+
, and Co
2+
. In a solution,
2 2 3
Ag Tl 0.025 M, Pb 0.04 M, Co Fe 0.02 M
+ + + + +
( ( ( ( ( = = = = =

. You have the following reagents for
separation: 0.1 M of NaCl, 0.5 M of NaI and Na2SO4, 3.0 M of NH3 (Kb = 1.7510
-5
) and 1.0 M Na4EDTA.

The following Kf and Ksp at 25 C are also given:

Formula Keq Formula Keq
AgCl 1.810
-10
Fe(OH)3 410
-38

AgI 8.510
-17
TlCl 1.710
-4

PbCl2 1.610
-5
TlI 6.510
-4

PbI2 7.110
-9
[Fe(EDTA)]
-
1.710
24

PbSO4 1.610
-8
[Co(EDTA)]
2-
2.010
16


You started adding NaI reagent to the solution. Assume volume changes are negligible during precipitation.
a. How much mL of NaI you must add right before another cation precipitates?
b. Is the precipitation of the first cation complete (< 0.1%)?
The solution was then decanted. Assume negligible volume changes during decantation. You then started adding
NaCl reagent to the solution.
c. How much mL of NaCl you must add right before another cation precipitates?
d. Is the precipitation of the second cation complete (< 0.1%)?
After decantation, you started adding Na2SO4 again to precipitate the third cation.
e. How much mL of Na
2
SO
4
you must add to ensure complete precipitation of the third cation?
After decantation, you added 1 mL Na4EDTA to the solution. Then, you added 15 mL of NH3 reagent.
f. Will the fourth cation undergo complete precipitation?

4. Methane (CH4) can be converted to dimethyl ether (CH3OCH3) at high temperatures by the overall reaction:
+ + +
4( g) 2( g) 2( g) 3 3( g) 2 ( g)
CH CO 2H CH OCH H O
The following data at 25 C are also given:

Reaction H, kJ/mol S, J/(mol K)
+ +
( g) 2 ( g) 2( g) 2( g)
CO H O CO H
-41 -74.1
+ +
( g) 2( g) 2 ( g) 4( g)
CO 3H H O CH
-206 -230.7
+ +
2( g) 2( g) 3 ( g) 2 ( g)
CO 3H CH OH H O
-49.1 -161.2
+
3 3( g) 2 ( g) 3 ( g)
CH OCH H O 2CH OH
37 23.8

a. Calculate Kc of the overall reaction at 25 C.
b. At 3500 K, The reaction was allowed to reach equilibrium with the following initial mole fractions:
4 2 2 3 3 2
CH CO H CH OCH H O
0.33, 4 X = X = X = X = X . If the initial total molarity of the reaction vessel is 8.00 M,
find the equilibrium concentration of each reactant and product.
c. The reaction vessel was then allowed to expand by adding 5.00 kg of CH4, 8.00 kg CO2, 1.00 kg H2, and 1.00
kg argon. After expansion the reaction was allowed to reach equilibrium with the volume of the vessel kept
constant. If the original volume of the vessel is 10.0 L, find the final pressure (in atm) of dimethyl ether at
equilibrium. (MW in g/mol: CH4 = 16.04, CO2 = 44.01, H2 = 2.02, Ar = 39.95)


5. The formation constants of [Fe(CN)6]
4-
and [Ni(CN)4]
2-
was quantitatively determined by spectrophotometry. The
Fe
3+
and Ni
2+
standard solutions were prepared by taking a 10.00 mL aliquot from their 0.01 M stock solution and
diluting it to 100 mL. Varying amounts of the stock solution and KCN were mixed together to form the complex:

Solution mL of cation mL of 0.05 M KCN mL of d. H2O
blank 0.00 10.00 10.00
1 1.00 10.00 9.00
2 2.00 10.00 8.00
3 4.00 10.00 6.00
4 8.00 10.00 2.00
The following data were obtained after analyzing each solution in a spectrophotometer (in their respective max):

[Fe(CN)6]
3-
Absorbance [Ni(CN)4]
2-
Absorbance
1 0.5115 1 1.7810
2 1.0240 2 3.5610
3 2.0460 3 7.1200
4 4.0920 4 14.2400
max = 480 nm max = 400 nm

20 mL aliquot of 0.05 M KCN solution was then taken and diluted to 100 mL. This serves as the diluted KCN
solution for Fe
3+
, but for Ni
2+
a 10 mL aliquot was taken from Fes diluted KCN and diluted to 100 mL. The
same standard cation solution was used for Ni
2+
, but for Fe
3+
the 0.01 M stock solution was used instead:

Solution mL of cation mL of diluted KCN mL of d. H2O
blank 0.00 0.00 20.00
1 4.00 4.00 12.00
2 6.00 6.00 8.00
3 7.50 7.50 5.00
The following data were obtained after analyzing each solution in a spectrophotometer (in their respective max):

[Fe(CN)6]
3-
Absorbance [Ni(CN)4]
2-
Absorbance
1 3.40994 1 1.78083
2 5.11474 2 2.67075
3 6.39334 3 3.33819

a. What is the color of [Fe(CN)6]
3-
and [Ni(CN)4]
2-
? (Violet: 400 nm 440 nm, Blue: 440 nm 490 nm)
b. Give the equations of the calibration curves.
c. Calculate the molar absorptivity constant (in M
-1
cm
-1
) of [Fe(CN)6]
3-
and [Ni(CN)4]
2-
if the path length of
the cuvette is 100 mm.
d. Calculate the average formation constant of [Fe(CN)6]
3-
and [Ni(CN)4]
2-
.
e. Given the displacement reaction ( ) ( )
2 3
3 2
( aq) ( aq)
4 6
( aq) ( aq)
Ni CN Fe Fe CN Ni

+ +
( ( + +

, calculate its
equilibrium constant.

6. The solubility of barium(II) hydroxide octahydrate, Ba(OH)2 8H2O was investigated by acid-base titration. Solid
Ba(OH)2 was dissolved in five different media. After filtration of the turbid solution, the saturated solution was
then titrated. A 20 mL aliquot was taken then added with phenolphthalein and titrated with standardized 0.200 M
HNO3:

Medium Temperature, C Volume of titrant, mL
distilled water 25 8.43
distilled water 35 10.86
distilled water 50 15.42
90 mL d. H2O + 10 mL 0.1 M NaOH 25 ???
75 mL d. H2O + 25 mL 0.1 M Ba(NO3)2 25 ???

a. Calculate the molar solubility of Ba(OH)2 8H2O at 25 C.
b. Calculate Ksp of Ba(OH)2 8H2O at 25 C.
c. Calculate the missing data in the table. What is the effect induced on adding NaOH or Ba(NO3)2?
d. Calculate the enthalpy (in kJ/mol) and entropy (in J/(mol K)) of precipitation of Ba(OH)2 8H2O.
e. Which of the following 0.1 M reagents when added with distilled water will induce diverse-ion effect on
the solubility of Ba(OH)2 8H2O?
- KCl
- NaCl
- MgSO4
- Na2SO4
- BaCl2
- Mg(NO3)2
- Ca(NO3)2
- NaNO3