Chemistry 59-141 Midterm Test Winter Term

Time: 40 minutes 9 February 2018

A
Name: _______ANSWER KEY_____ Lab Sec.& Time :_____________

Student ID#: ___________________ Name of TA: _________________

THE DATA PAGES AT THE END OF THE EXAMINATION PAPER CAN

BE REMOVED IF YOU WISH.

YOU MAY ATTEMPT THE QUESTIONS IN ANY ORDER

IF YOU REQUIRE MORE SPACE, YOU MAY WRITE ON THE BACK OF

THE QUESTION SHEET BUT INDICATE THIS CLEARLY IN THE
ANSWER SPACE.
This examination must be written in non-erasable INK

Marking Scheme

Question Value Mark

1 18

2 10

Total 28

% Grade 100%

Write legibly! Show all your working (marks will not be given if reasoning is not
shown). Give numerical answers to the appropriate number of significant digits
with correct units.

1
1. The peroxydisulfate anion, S2O82-, reacts with iodine according to the equation:

S2O82-(aq) + 2 I- (aq) 2 SO42- (aq) + I2 (aq)

Use the experimental data to determine (i) the rate equation for the reaction; (ii)
(a)
the overall order of the reaction and (iii) the rate constant for the reaction,
expressing it in the correct units.
[6 marks]
2- - -1
Expt Initial [S2O8 ] (M) Initial [I ] (M) Initial rate (M·s )
.
#1 0.350 0.210 1.470
#2 0.350 0.420 2.941
#3 0.700 0.420 5.880

Compare expt #1 and #2: [S2O82-] constant, double I- double rate: first order [I-] [1]
Compare expt #2 and expt #3: [I-] constant, double [S2O82-], double rate:
first order in [S2O82-] [1]
Rate = k[S2O82-][I-] [1]
Overall order = 1 + 1 = 2. [1]

Take any one experiment, e.g. #1

1.470 Ms-1 = k(0.35)(0.21) M2
k = 1.470/(0.35 x 0.21) = 20.0 M-1s-1 [2]
NB one mark for k, one for units.

Q1 continues/…

2
(b) A proposed mechanism for the reaction between S2O82- and I- is shown below.

S2O82- + I- SO42- + SO4I- (SLOW)

SO4I- + I- SO42- + I2 (FAST)

S2O82- + 2I-  2 SO42- + I2 Overall

(i) Show that the proposed two step mechanism corresponds to the overall
reaction.
[1 mark]
Add two steps together and show it is equal to the overall reaction from part (a)
(ii) Determine the intermediate(s) in this reaction.

SO4I- [1 mark]

(iii) If the first step is slow, determine the expected rate law for this reaction.
Does it agree with the experimentally determined rate law found in part (a)?
[2 marks]

If step 1 is RDS: Rate = k1[S2O82-][I-] [1]

This is consistent with the experimentally observed rate law. [1]

(iv) If the overall reaction is exothermic, sketch a diagram showing the energy
changes associated with the reaction. You should label your axes, starting
materials, products, intermediates, activation energies and transition states.
[8 marks]

3
2.
(a) An aqueous solution of SO2 was prepared by placing 1.00 L of water under a
pressure of 0.5 atm of SO2. Determine the concentration of SO2 in this solution
(mol·L-1).
[1 mark]

SSO2 = kHPSO2 = 1.20 mol.L-1atm-1 x 0.5 atm = 0.60 mol.L-1 [1]

[Information kH = 1.20 mol·L-1·atm-1]

(b) Assuming this system behaves as an ideal solution, calculate the total pressure
above the solution [PoH2O = 21.1 Torr, PoSO2 = 2520 Torr]
[5 marks]
MW(H2O) = (16.00 + (2 x 1.008)) = 18.016 g/mol [1]
1 litre water = 1000 g = 1000g/18.016 g/mol = 55.506 mol [1]
SO2 present in 1 litre = 0.60 mol (from part a)
H2O = 55.506/(55.506+0.600) = 0.989, SO2 = 0.60/(55.506 + 0.600) = 0.011 [2]
Ptot = (0.989 x 21.1) + (2520 x 0.011) = 48.6 Torr [1]

(c) The
observed pressure above the solution was found to be 27.7 Torr. What can
you determine about the strength of the solvent-solute interactions?
[1 mark]
Since the observed pressure is less than that expected based on ideal behavior then
solvent-solute interactions > solvent-solvent and solute-solute interactions

Question 2 continues/…

4
(d) For the aqueous solution of SO2 prepared in part (a) of this question, predict its
expected freezing point.
[3 marks]

i = 1, m = 0.60 mol/kg [1]

Tf = imKf = (1)(0.60)(1.86) = 1.12 oC [1]

New freezing point is -1.12 oC [1]

[For water Kf = 1.86 oC kg/mol]

[END OF EXAMINATION PAPER]

5
6
Useful Equations and Constants

Conversion Factors and Standard Units

Temperature: 0 K = 273.15 oC
Pressure: 1 atm = 101325 Pa = 760 Torr
1 bar = 105 Pa
Volume: 1 L = 1 dm3 = 1000 cm3
1 mL = 1 cm3
Mass: 1 kg = 1000 g

Fundamental Constants
Avogadro’s Number, NA 6.02214179 x 1023 mol-1
Boltzmann constant, k 1.38065032 x 10-23 JK-1
Gas constant, R 0.0831447215 L bar mol-1 K-1
8.31447215 J mol-1 K-1

Selected Key Equations

Chapter 12 – Colligative Properties

Raoults’ Law: Ptot = APoA + BPoB + …
Henry’s Law: Sgas = kHPgas
Depression of freezing point: Tf = imKf
Elevation of boiling point: Tb = imKb
Osmotic Pressure (Morse Equation):  = iMRT

Chapter 13 – Kinetics
Order of the Reaction Integrated Rate Law Half Life
[ A ]o
0 [ A ] t =[ A ] o−kt t ½=
2k
ln [ A ]t=ln [ A ] o−kt
ln ( 2 ) 0.693
1
ln
( )
[ A ]t
[ A ]o
=−kt
t ½=
k
=
k

1 1 1
2 = +kt t ½=
[ A ]t [ A ]o k [ A ]o
−E a −Ea
Arrhenius Equation: k=Ae RT ln k = + ln A
RT

( )
Two-Point Arrhenius k 2 −Ea 1 1
ln = −
Equation: k1 R T 2 T1