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CHEM 367
Instrumental Analysis 1
Professors:
Joan Power
Eric Salin
Janine Mauzeroll

About this class

CHEM 367 DATA

3 credits
2 hours of lecture
4 hours of lab
Prerequisite: Chemistry 287, 297 or permission
from instructor

CHEM 367 is an introduction to analytical instrumentation.

COURSE INSTRUCTORS:
Professor Joan Power
Office: O.M. 222
Phone 398-3637
e-mail: Joan.Power@McGill.CA
Office hours any time by appointment.
Professor Eric Salin
Office: O.M. 212A
Phone 398-6236
e-mail: eric.salin@mcgill.ca
Office hours any time by appointment.
Professor Janine Mauzeroll
Office: P.P. 109C
Phone 398-3898
e-mail: Janine.Mauzeroll@mcgill.ca
Office hours any time by appointment.
Dr. Sam Sewall
Lecturer.
Responsible for overall operation of the laboratory.
e-mail samuel.sewall@mcgill.ca

Course Outline

2015 CHEM367



Date
Lecture Topic
Instructor
1 04-Sep Intro Lecture
J9
H
oliday


07-Sep
2 09-Sep Op Amps (PracIce Pblms)
J9
3 14-Sep Echem 1
J9
4 16-Sep Echem 2
J9
5 21-Sep Echem 3
J9
6 23-Sep Buer (PracIce Pblms)
J9
7 28-Sep Intro Matlab 1
Joan
8 30-Sep Intro Matlab 2
Joan
9 05-Oct Applied StaIsIcs 1
Joan
10 07-Oct Applied StaIsIcs 2
Joan

12-Oct Holiday

11 14-Oct Buer (PracIce Pblms)
Joan
Review & Midterm 1

12 19-Oct -Op Amps J9
-Echem
13 21-Oct GC 1
Eric
14 26-Oct GC 2
Eric
15 28-Oct HPLC 1
Eric
16 02-Nov HPLC 2
Eric
17 04-Nov MS
Alex
18 09-Nov MS
Alex
19 11-Nov MS
Alex
Review & Midterm 1
-GC
16-Nov
Eric
-HPLC
-MS
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21 18-Nov Capillary Electrophoresis 1
J9
22 23-Nov Capillary Electrophoresis 2
J9
23 25-Nov In Class Problem
J9
24 30-Nov Spectro prep for CHEM377 1
J9
25 02-Dec Spectro prep for CHEM377 2
J9
26 07-Dec Quiz (mostly CE)
J9

 SCHEDULED LECTURE PERIODS:

Monday Wed 12:30 -13:30 / Room OM 217
COURSE TEXT:
- Required: Principles of Instrumental Analysis, Skoog, and Leary, Sixth
edition
- Supplemental :
Spectrochemical analysis, Ingle and Crouch (In PSEAL or whatever the
latest name is)
Electrochemical Methods, 2nd Ed. A. J. Bard
CLASS NOTES:
On MyCourses.
ASSIGNED READING:
You are expected to have read the assigned reading material before
lecture.

 Students are expected to keep themselves informed of

goings on. You will be held responsible for material
presented in the following ways:
a. Verbally during lectures.
b. Written on the board during lectures.
c. As above in lab or tutorial from either a Demonstrator
or the Senior Demonstrator.
d. On the class bulletin board outside the lab.
e. Any handouts.
f. Electronic mail
g. My Courses Postings
8

GRADING
The course material is relatively easy.
Most theory has been covered in CHEM 287/297.
The difficulty lies in the amount of material that has to
be learned and then finally integrating this material
into a useful body of knowledge from which one can
select analytical techniques to solve a given problem.
The students usually do quite well. Each year roughly
70% of the class gets A's and B's. Usually everyone
passes; however, as many as 4 people (10%) have
failed in other years.
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Grading Scheme
Grading Scheme

Midterm 1
Midterm 2
Lab
Joan Assignment
Quiz

HOMEWORK:
To be discussed with Dr. Power

20%
25%
40%
10%
5%

We may use a variable weighting scheme this year to provide the student with the
highest possible score. It will probably be similar to the one used above. You are
guaranteed that the 25%-25% scheme will be available. The second option will be
decided later.
Note: There will be no makeup midterms. If you miss an exam you must have a
certified medical excuse.

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Examinations
EXAM PREPARATION:
The exams will test both problem solving and general knowledge. For
example, you should be able to draw in great detail any system or subsystem
studied and to explain its operation. In general, you should know how things
work, their advantages, disadvantages and their limitations. In addition, you
should be able to critically evaluate a technique and be able to chose a
method (methodology also) to solve a particular problem.
MIDTERM EXAMS
For 2015: There will be 2 midterms and they are 19 Oct, 16 Nov.
Be certain to let your other instructors know now what your schedule
is so as to avoid conflicts.
Midterm exams will start at 18:00.

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Laboratory
You must pass the lab to pass the course
Most laboratories will be graded by an oral
examination.
Your data should be worked up and turned in one
week after the experiment is done.
Your defense may be scheduled at that time and
any time thereafter.
This means that you must learn how to use the
equipment, even though you work with a partner!
Remember, your partner won't be taking the oral
examination for you!
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Professional Conduct

1. SAFETY: standard safety procedures are to be learned and followed. Students are
expected to know these procedures, be competent in their execution and adhere to them.

Eye safety is critical. Students in repeated violation of any safety policy will not be allowed to
work in the laboratory and consequently will not finish the course.

2. LABORATORY: students are expected to have read the experiment before coming to the
lab. We are very limited with respect to certain equipment and failure to come to the lab
prepared may result in failure to complete the experiment in the scheduled time. This
may result in no credit for this experiment due to the tight scheduling requirements. Preexperiment exams may be given (oral or written). If you fail the exam the demonstrator
may require you to leave and return only when you have prepared adequately. This may
mean the loss of a laboratory period and consequent failure to complete an experiment.
Please note that you must pass the lab in order to pass the course!

3. Plagiarism of all kinds must be avoided. You absolutely must do your own work. If
you present work as yours and you do not quote sources or you can not defend it (e.g.,
present computer code that you can not clearly explain) then you can be considered to
have committed plagiarism. This has unpleasant consequences, to say the least, minimally
including a visit to the Dean of Students. Go directly to Dean (not Chair), do not collect
$200! Note that every year at least one person has been sent up to the Dean.

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Method of Operation
In addition to the traditional lecture mode some of
the available class time will be used as tutorial/
discussion time (Socratic Method).
In turn, it it important to (1) read material before
class, and (2) expect to be called upon.

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Method of Operation
1. Lab write-ups have been reduced significantly. In
turn, students are expected to demonstrate knowledge
during the laboratory practical exam and during class,
both orally and hands-on.
2. Homework is collected although additional
problems may be recommend in preparation for
midterms. You are expected to be able to work
numeric problemscalibration, etc. Anything
covered in the book is fair game unless explicitly
excluded. The emphasis will be on material covered
in lecture.
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Method of Operation
3. Learning Matlab.
Lab and lecture are highly integrated in many
respects. You will be learning Matlab in order to
work with data from one of your experiments and
apply statistics. You will have homework and
laboratories that will help and guide you to learn to
use this tool. This knowledge is important in
subsequent CHEM 377 analytical classes.

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Method of Operation
4. Case Studies
In discussing mass spectrometry and other
techniques, we will be preparing you for the Case
Study type questions that will be incorporated in
both midterms. The difficulty of these questions
lies in the fact that you have to pool your entire
chemistry knowledge in order to select analytical
techniques to solve a given problem. Most students
(80%) do extremely well in these questions.
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Introduction

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Instrumental Methods
Instrumental Methods of Analyses
Conductivity
Electrode Potential
Light absorption or emission
Mass-to-charge ratio
Fluorescence
Separations
Chromatographic
Electrophoretic

Growth of modern instrumental methods of analysis

has paralleled the development of the electronics and
computer industries
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20

Chemical and Physical Properties

Most of these require a source of energy to stimulate a measurable

response from the analyte
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Analytical Chemistry Taster

22

Janine Mauzeroll

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Electric vehicle development

Intrinsically tied to:
Improved Battery Performance
Vehicle Weight Reduction

Green Electric Vehicles

Weight reduction implies a
transition from
MS
Al Alloys

Mg Alloys
Slight problem of the
Galvanic Series Position

Mg Alloy Corrosion Resistance Quite

Poor!
!Corrosion Chemistry

!
!

phase: Mg rich phase (anode)

phase: Mg17Al12 (cathode)

Mg Alloy Corrosion Observed

Side View Optical Micrograph - 48 hours
exposure to a 1.6 wt.% NaCl solution

Steel

Mg

4 m

!
!

phase: Mg rich phase (anode)

phase: Mg17Al12 (cathode)

Sample A- with the dome of

corrosion products still attached.

Surface Analytical Methods Applied to Mg Corrosion

Artwork created by Franois Ducharme

Anal. Chem. (2015), In Press

29

Car Components Made of Mg Alloys

Cradle

Door Inner
Module

Lift Gate

Anal. Chem. (2015), In Press

30

Surface Analytical Methods Applied to Magnesium Corrosion

Scanning vibrating electrode technique (SVET)

Local electrochemical impedance spectroscopy
(LEIS)
Scanning droplet cell (SDC)
Scanning Kelvin probe force microscopy
(SKPFM)
Scanning electrochemical microscopy (SECM)

31

Surface Analytical Methods Applied to Magnesium Corrosion

Scanning vibrating electrode technique (SVET)

A) SVET setup schematic
representation;
B) SVET experiment for
AE44AA6063 galvanic
couple Corr. Sci., 52,
3514-3522, (2010);
C) Schema of the 3D
simulation domain;
D) Experimental SVET &
model ( Anal. Chem., 84,
9899-9906, (2012).

Anal. Chem. (2015), In Press

32

Surface Analytical Methods Applied to Magnesium Corrosion

Scanning droplet cell (SDC)

A) SDC schematic representation;
B) Optical micrograph of an AZ91 Mg alloy
following surface etching where sites of local
potentiodynamic polarization curves have been
highlighted (1-5);
C) Local polarisation curves recorded at 16.6 mV/s
using a 10 mm diameter capillary filled with an
electrolyte solution of 0.1M NaClO4. Corr. Sci.,
53, 3108-3113, (2011).

Anal. Chem. (2015) In Press

33

Use of SECM to investigate Magnesium Alloys Corrosion

Generation/Collection Mode

Potentiometric Mode

Ion-Selective Mg2+ sensor

Pt microelectrode
! Measures dissolution
! Track the
of the alloys
evolution of
hydrogen
! 2.72 mg/cm2/d
! Identify cathodic
! Depends on how the
sites
material is casted
Mg

Feedback Mode

Micropipet
! Determine local corrosion rate
! 263 mm y-1 when galvanically
coupled

Constant Distance Mode

Pt or C microelectrodes
! Monitor film formation
! Quantify apparent
kinetics

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Challenges to Achieve Quantitative

SECM Data

Use of microelectrode having controlled geometry

Keeping track of topography effect
Working around or with gas evolution
Establishing a library of usable mediators for feedback
mode
Apply knowledge gained from bare alloys to coated
car components.
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Microelectrode having controlled geometry

Table 1. RG of Experimental Disk UMEs

Anal. Chem. (2015), 87, 25652569 36

Working around gas evolution

JEAC 2014, 720721 (0), 121-127.

37

Working around gas evolution: ii) Model convection contributions

Anal. Chem (2015), submitted

Working around gas evolution: iii) Use Glycol as an electrolyte

a)

b)

Corr. Sci (2015) 93, 70-79.

2

pA

100 m

Feedback Mode of Scanning Electrochemical Microscopy

What is needed for a feedback measurement
1) Microelectrode
2) Biased/Unbiased sample of interest
3) Additive (redox mediator) exhibiting fast and reversible electron transfer upon
oxidation/reduction

Normalized Current

2.5

e-

2.0
-

e
e

1.5

Fc
Fc

Fc
+
Fc

1.0

0.5
0

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Quantify the regeneration

rate of the redox mediator

Normalized Distance
39

Feedback Mode of SECM to Monitor Mg Alloys Corrosion

FcMeOH FcMeOH+ + e2H2O + 2e- 2OH- + H2

Eo = 0.25 V
Eo = 0 V

40

Local Surface Reactivity Quantification

Unpublished

41

 Commercial Coating
Cracks in E-coat

SEM cross section of sample coated Mg

Cracks in conversion coating
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Future Directions
1) Develop multifunctional probes capable of
tracking simultaneously topography and specific
electrochemical fluxes;
2) Understand and predict coating failure of Mg
car components.
3) Propose industrial viable additives to promote
coating self-healing & improve corrosion
resistance.
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Next Time:
The wonderful world of operational
amplifiers.

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