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Write the FIRST

UBC CHEM 325/345 Practise Final Exam LETTER of your
LAST NAME in
April 26th , 2016 this box
Complete the following information in ink:

Family (last) name _______________________ First name __________________________

***Please print neatly!*** ***Please print neatly!****
This sample exam is meant to provide you an example
of the style and format of your upcoming exam.
Signature: ______________________________
The experiments tested in this exam differ from the UBC student number _________________
experiments on which you'll be tested!

You have 150 minutes to complete this exam. Check that this exam paper consists of 15 PAGES PRINTED ON
BOTH SIDES. Write all answers on this examination paper. The only calculator permitted is the Sharp EL-510. All
other calculators/electronic devices will be confiscated.
RULES GOVERNING FORMAL EXAMINATIONS
1. Each examination candidate must be prepared to produce, upon the request of the invigilator or examiner, his or
her UBC card for identification.
2. Examination candidates are not permitted to ask questions of the examiners or invigilators, except in cases of
supposed errors or ambiguities in examination questions, illegible or missing material, or the like.
3. No examination candidate shall be permitted to enter the examination room after the expiration of one-half hour
from the scheduled starting time, or to leave during the first half hour of the examination. Should the examination
run forty-five (45) minutes or less, no examination candidate shall be permitted to enter the examination room once
the examination has begun.
4. Examination candidates must conduct themselves honestly and in accordance with established rules for a given
examination, which will be articulated by the examiner or invigilator prior to the examination commencing. Should
dishonest behaviour be observed by the examiner(s) or invigilator(s), pleas of accident or forgetfulness shall not be
received.
5. Examination candidates suspected of any of the following, or any other similar practices, may be immediately
dismissed from the examination by the examiner/invigilator, and may be subject to disciplinary action:
 speaking or communicating with other examination candidates, unless otherwise authorized;
 purposely exposing written papers to the view of other examination candidates or imaging devices;
 purposely viewing the written papers of other examination candidates;
 using or having visible at the place of writing any books, papers or other memory aid devices other than
those authorized by the examiner(s); and,
 using or operating electronic devices, including but not limited to telephones, calculators, computers, or
similar devices other than those authorized by the examiner(s)—(electronic devices other than those
authorized by the examiner(s) must be completely powered down if present at the place of writing).
6. Examination candidates must not destroy or damage any examination material, must hand in all examination
papers, and must not take any examination material from the examination room without permission of the examiner
or invigilator.
7. Notwithstanding the above, for any mode of examination that does not fall into the traditional, paper-based method,
examination candidates shall adhere to any special rules for conduct as established and articulated by the examiner.
8. Examination candidates must follow any additional examination rules or directions communicated by the
examiner(s) or invigilator(s).

Maximum
Section Question Marks % Grade
marks
Analytical A1-A5 XX / 20%
Inorganic I1 10 / 20%
Organic O1-O4 10 / 20%
Physical P1-P4 XX / 20%
Interdisciplinary F1-F2 17 / 20%
Total XX / 100%
 
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A-0013: Determination of Nitrate and Nitrite by Ion Chromatography

In this experiment, you used a calibration curve approach to determine concentrations of both nitrate and nitrite
anions in the E-6 g/ml range. You compared use of peak area and peak height as your analytical signal. The
instrument used featured an anion exchange column, carbonate:bicarbonate buffer as eluent, chemical
suppression system and conductivity detector.
The A-13 experiment covered here is not the current mandatory experiment for either CHEM 325 or 345.

A.1. Considering only an ideal case (e.g. ignoring experimental error), would a solution of equal nitrate
and nitrite concentrations give two equal area peaks? Explain why or why not. [2 marks]

A.2. Instrument settings will affect the chromatogram you record. Match the following changes in
instrument parameters with their outcomes: [1 mark each]
You are not obligated to use all available outcomes and you may use an outcome more than once.

Change
Decreased eluent pressure
Double the concentration of
both carbonate and bicarbonate
in the eluent
Eluent pH increased by one
unit
Double the bicarbonate
concentration without
changing carbonate
concentration
Triple the nitrate and nitrite
concentrations in the sample
Resulting
outcome
List of outcomes to select from:
A Decreased retention time for all
species
B Increased retention time for all
species
C Increased retention time for
nitrate only
D Decreased baseline conductivity
E Increased baseline conductivity
Decreased peak tailing
F
G Increased peak tailing
H Increased column temperature

The figure below shows ion chromatograms of a single sample, recorded with and without chemical
suppression used. The sample is nitrite and nitrate of unequal concentrations in the E-6 g/ml range, as
was typical in your experiment.
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A.3. In the chemical suppression system, what is being suppressed? Choose the best answer. [1 mark]

a. The size of the peaks

b. The conductivity due to the nitrate species
c. The conductivity due to the nitrate species
d. The interference from cations present in the sample
e. The concentrations of carbonate and bicarbonate

A.4. Write the balanced chemical reaction(s) involved in the suppression process [2 marks]

A.5. Using the figure above as a guide, briefly describe the advantages of using a chemical suppression
system in anion chromatography. [2 marks]

A.6. Making use of the chromatogram above for reference, give the approximate retention times at which
the following species would elute: [1 mark each]
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(a) a cationic species such as Na+ Retention time:__________________

(b) a neutral species such as methanol Retention time:__________________
(c) a divalent anion such as thiosulfate (S2O32-) Retention time:__________________

I-0006: Preparation and Magnetism of Chromium (II) Acetate

In this experiment, you synthesized a binuclear Cr(II) complex with acetate as the ligand. The redox reaction
involves potassium dichromate, zinc and sodium acetate. The resulting product was a dark brown, crystalline
product. Answer the following questions based on this experiment.

I.1. In the synthesized binuclear chromium(II) complex, acetate is: [1 mark]

a. A monodentate, anionic ligand.
b. A bidentate, neutral ligand.
c. A bidentate, anionic ligand
d. A bridging, anionic ligand.
e. A bridging, neutral ligand.

I.2. The final product was characterized by magnetic susceptibility measurements. Through a discussion
of the structure and bonding in the product, explain what type of magnetism is exhibited by the desired
product and why? [3 marks]

I.3. Provide one other analytical techniques could you use to characterize the final product. Briefly explain
how the technique could be used. [2 marks]

I.4. A Chem 345 student measures the magnetic susceptibility for their synthesized chromium complex and
calculates the magnetic moment to be a small value (~0.794 B.M.). Based on this value, can you predict
the number of unpaired electrons on each Chromium center? Explain the source for this small
paramagnetic behaviour. [4 marks]
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O-0006: Synthesis of N,N-Diethyl-m-Toluamide (DEET)

In this experiment, m-toluic acid was converted to the corresponding acid chloride by heating with thionyl
chloride in the presence of catalytic pyridine. After removing excess thionyl chloride by distillation, the
residue was treated with an ethereal solution of diethylamine to produce N,N-diethyl-m-toluamide.

O.1. a) Draw the structural formula of thionyl chloride. [1 mark]

b) Write the equation for the reaction of water with thionyl chloride. NOTE: A mechanism is not required, just
the balanced reaction! [1 mark]

c) Describe the precautions that must be taken to safely handle thionyl chloride while working outside of a
fume hood. [2 marks]

O.2. The following question deals with interpretation of proton NMR spectra as related to experiment O-0006. This
method was used to assess both the composition and purity of the product isolated.

a) On the blank diagram provided below, sketch the 1H NMR spectrum for diethylamine. Clearly indicate the expected
chemical shift and the signal multiplicity for each set of chemically-inequivalent hydrogens in the molecule,
assuming that the sample was measured as a solution in chloroform-d1 on a 300 MHz NMR spectrometer with added
TMS as the reference. [4 marks]

Chemical shift (ppm)
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b) In practice, the 1H NMR spectrum of DEET (shown below) has an unusual appearance.

Peak table for 1H NMR spectrum of N,N‐diethyl‐m‐toluamide 

(0.05 mL DEET in 0.5 mL CDCl3) 

1.09 ppm 

1.23 ppm 

2.352 ppm 

3.24 ppm 

3.53 ppm 

1.139 ppm  ‐CH3 
‐CH2‐ 
7.18 ppm 

7.251 ppm 

Chemical shift (ppm)
Explain why the signals from the ethyl group appear broad, while the aromatic proton signals are sharp and well-defined.
The use of structural formulae will be helpful additions to your answer! [3 marks]

O.3. Under certain conditions, the symmetrical anhydride 1 shown is produced as a major by-product.

a) Based on the reaction conditions used to prepare DEET, explain how this compound may be formed by providing
the structure of the key compounds that would need to be present in the reaction mixture. [2 marks]

b) Describe two characterization techniques that could detect the presence of anhydride 1 in the product mixture
isolated. Include specific features about what would be observed if the anhydride were present in addition to the
desired product. [2 marks]
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P-0007: Rotational-Vibrational Spectroscopy of HCl

Experiment Summary

A chemistry student reacted sulfuric acid (H2SO4) with sodium chloride (NaCl). A gas was formed and the
student collected the following spectra:

 
 
Answer the following questions based on the spectrum provided.

P.1. (a) Write the balanced chemical reaction for the formation of the gas: [ marks]

(b) Assign each spectrum to the corresponding molecule: H35Cl or H37Cl [ marks]

High intensity spectrum (X) ____________________

Low intensity spectrum (Y) ____________________

(c) Both infrared spectra show multiple sharp lines. What gives rise to this observed structure?

(i) Vibrations [ marks]

(ii) Rotations
(iii) Electronic Transitions
(iv) Spin Transitions
(v) Translations
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P.2. Two different methods can be used to assign the spectra to H35Cl or H37Cl . Describe each method. [
marks]

i. _________________________________________________________________________________
_________________________________________________________________________________
ii. _________________________________________________________________________________
_________________________________________________________________________________

P.3. Using the hydrogen chloride spectra above and the relationship, , approximate

where the deuterium chloride molecule infrared spectra should be centered in wavenumbers. Show
your work. [ marks]. (Hint: the mass of deuterium is approximately twice the mass of hydrogen)

P.4. The fine structure observed in the spectra of HCl (X and Y) is dependent on the constant Be. Be is
approximately equal to half the average distance between two peaks in the spectra.
a) Estimate Be from the spectra above: _______________________________________
b) What is the name of the constant Be? _______________________________________

P.5. From gas phase spectra it is also possible to measure the bond length of the molecule (re) using the
following equation: . Estimate Be for the DCl molecule. Show your work.
[marks] (Hint: the bond length of HCl can be considered equal to the bond length of DCl)

 
 
 
 
 
Bonus: Name another experimental method to measure a bond length: _____________________
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Interdisciplinary Section (F)

The following section combines topics from both inorganic (Part A) and analytical (Part B) chemistry. The
purpose of this section is to probe your ability to use the knowledge and experience gained from the course to
answer questions about an experiment that you have not run in the labs.

Introduction:
A copper(II) metal complex is prepared in a third year lab, ammonium tetrachlorocuprate(II)
{[(CH3CH2)2NH2]2CuCl4}. When heated, this yellow solid turns to a red-purple complex having the same
chemical formula. The complex is characterized by FTIR and UV-Vis spectroscopy. Answer the following
questions…. 

Part A: Inorganic
1. What is the d-electron configuration for Cu(II)? Draw the possible splitting of the d-orbitals and
show the distribution of electrons for a tetrahedral structure.
2. a. What could cause the color change on heating?
b. The max for the yellow complex is at 450 nm whereas that for the red-purple complex is at 550 nm.
Comment on the energies of these transitions and what could be causing these transitions?
3. In the IR spectra, a peak is seen at ~3100 cm-1 for the green complex but disappears in the yellow
one. What structural feature may be changing as the complex is heated?
 

Part B
Thermochromic compounds can find use as robust, low-cost thermometers.

Consider the absorbance spectra for two states of the thermochromic ammonium tetrachlorocuprate (II)
compound as shown below.

One could monitor the absorbance at 550 nm, and knowing the temperatures at which the compound is
in all yellow and all red-purple states, one could use the measured absorbance to determine a
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temperature between these two limits. Suppose that you have collected the set of calibration data shown
below. You note that the graph is non-linear at either end (data in orange circles) and linear in the
middle (data in black diamonds).

The data point at (60.5,0.61) appears to be an outlier. This might be due to random error in the measurement
(either of temperature or absorbance), or systematic error in the measurement (either of temperature or
absorbance).
a) Describe how you could assess whether the cause of the outlier is a random error or a systematic
error. [2 marks]
.

b) If the cause of the outlier was systematic error, how could you assess whether the error is due to bias
in the temperature measurement or bias in the absorbance measurement? [2 marks]

c) Why does the trend become non-linear at higher temperatures? [1 mark]

d) In the box below, sketch the absorbance at 487 nm as a function of temperature that would be
observed upon heating this compound. [1 mark]
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