INSTITUTE OF CHEMISTRY CHEM 17 LAB MIDTERM PROBLEM SET

University of the Philippines Diliman AY 2018-2019 Second Semester

I. Multiple Choice. Write the best answer from the following choices

1. Why is the total volume of the solution phase consistently set at a fixed volume throughout
the experiment?
 So that Ccal does not change during the determination of ΔHrxn.
 So that the concentration of the reactants does not change during the reaction.
 So that the temperature of the reaction is changing at a regular rate
 So that the calculations of ΔH is done at constant volume conditions

2. Complete the statement: When the reaction is ________ the predominant interactions in the
solution are __________.
 Endothermic; solute-solvent
 Endothermic; solute-solute
 Exothermic; solute-solute
 Exothermic; solvent-solvent

3. Which of the following statements will result to slower reaction rate of the iodine clock
reaction?
I. Increasing the Iodide concentration
II. Putting the reaction on an ice bath
III. Using wet beakers (beakers A and B)
IV. Addition of copper (II) nitrate
 I and II
 I and IV
 II and IV
 II and III

4. Consider the following statements

I. Reaction rate increases as temperature increases
II. Rate constant is directly proportional to the concentration of iodide
III. Arrhenius constant was calculated using the slope of the ln k vs 1/T plot
Which of the above statements is/are FALSE?
 II only
 I and III
 II and III
 III only

5. Given that the forward reaction is endothermic, which of the following would shift the
equilibrium to the formation of the blue complex?
2+ - 2-
Co(aq) +4Cl(aq) ↔[CoCl4 ](aq)
I. Addition of HCl
II. Doubling the volume of the solvent
III. Placing the reaction in boiling water
IV. Placing the reaction in ice bath
 I and II
 I and III
 I and IV
 I, II and III

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 INSTITUTE OF CHEMISTRY CHEM 17 LAB MIDTERM PROBLEM SET
University of the Philippines Diliman AY 2018-2019 Second Semester

6. Which of the following is TRUE about the equilibrium below? Assume that the initial system is
an orange solution
Fe3+(aq) + SCN-(aq) ↔ [FeSCN]2+(aq)
I. Addition of Fe(NO3)3 increases the intensity of orange solution.
II. Addition of KSCN decreases the intensity of orange solution.
III. Addition of HCl shifts the equilibrium to the right.
IV. Addition of KOH shifts the equilibrium to the left.
 I
 I and II
 I and IV
 I, III, and IV

7. In the determination of Keq of the iron(II)-thiocyanate complex, the following techniques were
performed to prevent interference of species other than the analyte EXCEPT:
 Preparation of lower KSCN concentrations in the unknown solutions
 Use of 0.1 M HCl as diluent for both standard and unknown solutions
 Separate preparation of unknown and standard blank solutions
 Baseline correction in spectral mode

8. Which of the following best represents the equilibrium system, A ↔ B, with a Keq value of
10.0? (A = black circles, B = green/grey circles)

9. A series of standard solutions of an unknown weak base was prepared from a 10 M stock
solution. The pH of each was measured as follows. Determine the base dissociation
constant of B.
[B]initial pH
0.10 11.25
0.25 11.36
0.40 11.50
0.55 11.62
0.70 11.73

 3.59 x 10-4
 3.01 x 10-6
 5.76 x 10 -3
 3.32 x 10-5
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 INSTITUTE OF CHEMISTRY CHEM 17 LAB MIDTERM PROBLEM SET
University of the Philippines Diliman AY 2018-2019 Second Semester

10. The Ka of a weak acid HA was determined by pH measurements. The best fit line was found
to be y = 0.6338 – 0.556 x (r2 = 0.988). Identify HA from the given below
Ka Acid
1.0 x 103 H2SO4
5.4 x 10-2 H2C2O4
7.1 x 10-3 H3PO4
4.4 x 10-7 H2CO3

 H2SO4
 H2C2O4
 H3PO4
 H2CO3
11. Which of the following correctly represent the Henderson-Hasselbalch equation?
[A− ]
 𝑝H = 𝑝K 𝑎 + ln
[HA]
[B]
 𝑝OH = 𝑝K 𝑏 + log +
[HB ]
[A− ]
 𝑝OH = 𝑝K 𝑏 − log
[HA]
𝑛 −
 𝑝H = 𝑝K 𝑎 + log A
𝑛HA

12. Which among the following buffer solutions would have the largest buffer capacity to resist
acids? (For NH3, pKb = 4.74)
 0.100 M NH3–NH4+ buffer (pH = 9.10)
 0.100 M NH3–NH4+ buffer (pH = 9.40)
 0.500 M NH3–NH4+ buffer (pH = 9.10)
 0.500 M NH3–NH4+ buffer (pH = 9.40)

II. Modified True or False. Write TRUE if the statement is true. Otherwise, change the underlined
word/s to make the statement true.
1. Precipitation reactions are always exothermic.
2. The pH of a 0.72 M NH3 solution (Kb=1.8x10-5) is
3. For any acid-conjugate base pair, pKa + pKb = pKw.
4. In the kinetics experiment, the over-all rate order is equal to two.
5. The entire experiment is under adiabatic and isothermal conditions.
6. In the kinetics experiment, copper (I) sulfate catalyzes the iodine clock reaction.
7. Addition of an acid to a dichromate solution turns its color from yellow to orange.
8. In the chromate – dichromate system, CrO72-, an orange complex, is stable in basic medium.
9. For a system in dynamic equilibrium, the rate of the forward and the backward reactions are
equal.
10. The pH of a buffer solution can be calculated using the Henderson-Hasselbalch equation.
11. Buffer preparation using a salt of a weak base and a strong acid is an example of partial
neutralization.
12. The UV-Vis spectrophotometer uses the photometric mode to determine the analytical
wavelength of a certain analyte.

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 INSTITUTE OF CHEMISTRY CHEM 17 LAB MIDTERM PROBLEM SET
University of the Philippines Diliman AY 2018-2019 Second Semester

III. Problem Solving. Show complete solutions for each problem below. Box the final answers.
[41 points]

1. [12 points] Determination of the enthalpy of dissolution of the salt MX(s) was done using a
coffee-cup calorimeter. During the experiment, too much salt was added to 10.00 mL of water.
It was observed that the temperature decreased from 25.00 oC to 14.62 oC.

Prior to this, the calorimeter was calibrated using 2.00 mL of 2.00 M HCl and 8.00 mL of 1.00
M NaOH and the temperature increased from 25.00 oC to 29.20 oC. Assume that the volume
from the calibration and sample system were the same.

Constants:
H+(aq) + OH-(aq) -> H2O(l) ΔHrxn= -55.85 kJ/mol
cMX = 864 J/g oC solubility: 36g/100g H2O ρwater = 1.00g/mL

A. What is the limiting reactant during the calibration process? [2]

B. Calculate the value of Ccal. [2]
C. How much, in grams, of MX was undissolved? [3]
D. Calculate the value of Ccal, corr [2]
E. Determine the ΔHrxn, in kJ, for the dissolution of MX. [3]

2. [10 points] Reduction of Cr(V) to Cr(III) is environmentally favorable as the latter is less toxic
to most organisms. It was found that ferrous ion is a possible reductant even under
oxygenated conditions. The kinetics of this reaction was probed using method of initial
rates.

Run [Cr5+] [O2] [Fe2+] Rate (x

10-5)
1 0.05 0.05 0.05 1.34
2 0.05 0.10 0.15 4.04
3 0.10 0.05 0.05 2.70
4 0.20 0.05 0.05 5.38
5 0.05 0.10 0.25 6.71
6 0.05 0.10 0.05 1.32
7 0.05 0.15 0.05 1.35

From the data above, determine:

A. Rate orders of the reaction with respect to (i) Cr 5+, (ii) Fe2+ and (iii) O2 using
graphical analysis (indicate corresponding equations of the best fit lines) [6]
B. Overall rate order [1]
C. Experimental rate law of the reaction [1]
D. Average rate constant of the reaction [2]

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 INSTITUTE OF CHEMISTRY CHEM 17 LAB MIDTERM PROBLEM SET
University of the Philippines Diliman AY 2018-2019 Second Semester

3. [10 points] Copper(II) forms a complex with 4-(2’-benzothiazolylazo)-salicylic acid in the

following way:
𝐶𝑢2+ + 2𝐵𝑇𝐴𝑆 ⇌ [𝐶𝑢(𝐵𝑇𝐴𝑆)2 ]2+ ,
The [Cu(BTAS)2]2+ complex absorbs maximally at 485 nm. In preparing standard solutions for
these complexes, appropriate volumes of 0.80 M Cu were mixed with a known excess volume
of 3.2 M BTAS, which were then diluted to 100 mL in the following way:

Volume of 0.8 M Cu(II), mL Volume of 3.2 M BTAS, mL A485

0.0 25 0.002
2.5 25 0.160
5.0 25 0.390
10.0 25 0.630
15.0 25 0.950
20.0 25 1.260
25.0 25 1.580

Samples of each were added to the cuvette and had absorbances measured at 485 nm.

A. Write out the equilibrium expression for [Cu(BTAS)2]2+? [1]

B. What is the equation relating the absorbance and concentration of [Cu(BTAS)2]2+?
Assume that all the Cu2+ has been converted to [Cu(BTAS)2]2+. Give the R2 of the
equation. [3]
C. What is the molar absorptivity of the complex? [2]
D. The table below shows the initial concentrations of Cu(II) and BTAS, with the
corresponding absorbances. What is the average Keq of the complex formation? [4]
[Cu(II)], M [BTAS], M A485
0.00 0.40 0.004
0.09 0.40 0.355
0.25 0.40 0.947
0.34 0.40 1.196

4. [9 points] You wish to prepare a 500 mL 0.10 M buffer solution of pH = 5.0. The only
available reagents are: (i) solid potassium citrate (MW: 306.395), (ii) 1.0 M NaOH, and (iii)
1.0 M HCl. Describe how would you prepare the desired buffer. The pKb values for citrate
(C6H5O73-) are pKb,1 = 7.6, pKb,2 = 9.24 and pKb,3 = 10.87.
A. Calculate the total number of buffer molecules in the solution [1]
B. State which pair of species (H3C6H5O7; H2C6H5O7-; HC6H5O72-; or C6H5O73-) are
present in the buffer solution [2]
C. Calculate the number of moles of the two species [4]
D. Calculate the amounts of potassium citrate, and the amount of HCl or NaOH needed
to make the buffer [2]

--- END OF PROBLEM SET (89/89) ---

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