ChE391 LabManual F15

CHE 391
CHEMICAL ENGINEERING LABORATORY 4
DEPARTMENT OF CHEMICAL ENGINEERING

Edition: Fall 2015
TABLE OF CONTENTS
INTRODUCTION .......................................................................................................................1
ACADEMIC OFFENCES UW Policy #71 .................................................................................2
LABORATORY SAFETY..........................................................................................................3
GENERAL INSTRUCTIONS ....................................................................................................4
LABORATORY REPORTS .......................................................................................................5
A. Preliminary Reports ................................................................................................................5
B. Memo reports .........................................................................................................................6
Evaluating Errors .........................................................................................................................9
Propagation of Error Equations .................................................................................................10
Error in Linear Regression Analysis .........................................................................................10
Assessing Quality of Fitted Data ...............................................................................................11
Tables and Figures.....................................................................................................................11
EXPERIMENT 1: Electrowinning of Zinc from Zinc Sulphate Solution...............................17
PRELAB REPORT QUESTIONS ............................................................................................22
REPORT QUESTIONS ............................................................................................................23
EXPERIMENT 2: Potential-Controlled Analysis of Redox Couple........................................25
PRELAB REPORT QUESTIONS: ...........................................................................................35
DATA ANALYSIS: ..................................................................................................................35
EXPERIMENT 3: Analysis of Fuel Cell Performance Curves ................................................38
REPORT QUESTIONS: ...........................................................................................................46
EXPERIMENT 4: Corrosion Studies .......................................................................................48
DATA ANALYSIS: ..................................................................................................................63
EXPERIMENTS 5 and 6: COMSOL Tutorials .......................................................................65
INTRODUCTION
Progress in the field of science or technology depends not only on a clear grasp of relevant
theoretical principles, but also on the quality of experimental investigations carried out in that
field. Solutions to many complex problems of interest to chemical engineers can be approached
by a carefully designed and properly executed experimental program.
Laboratory courses allow the student to study numerous experimental arrangements, equipment
details, and measuring devices which cannot be covered adequately in a lecture course. An
appreciation is also gained of the difficulties involved in obtaining accurate data under properly
controlled conditions.
Basically, the three main course objectives of this laboratory course are:
To assist in the understanding of some basic principles of chemical engineering through

actual observations of the behaviour of electrochemical systems.
To help develop skills in experimentation, data analysis and interpretation of results.
To practice in the art of writing effective engineering reports.
General Lab Info
ACADEMIC OFFENCES
EXCERPTS FROM THE UNIVERSITY OF WATERLOO POLICY #71
"STUDENT ACADEMIC DISCIPLINE POLICY"
Original text available at:
http://www.adm.uwaterloo.ca/infosec/Policies/policy71.htm
"A university is a community of scholars in which knowledge is generated and disseminated
through scholarship and teaching. All members of the community - faculty, students and staff
are bound to conduct themselves with honesty, integrity, fairness and concern for others. Any
action which unnecessarily impedes the scholarly activities of members of the University is an
offence punishable by appropriate disciplinary action."
Some of the academic offences outlined by the University include:
Infringing unreasonably on the work of other members of the University community

(disrupting classes or examinations; harassing, intimidating or threatening others).
Cheating on examinations, assignments, work-term reports, or any other work used to

judge student performance. Cheating includes copying from another student's work
or allowing another student to copy from one's own work, submitting another person's
work as one's own, fabrication of data, consultation with an unauthorized person
during an examination or test, and use of unauthorized aids.
Plagiarism, which is the act of presenting the ideas, words or other intellectual
property of another as one's own. The use of other people's work must be properly
acknowledged and referenced in all written material such as take-home examinations,
essays, laboratory reports, work-term reports, design projects, statistical data,
computer programs and research results.
Submitting an essay, report, or assignment when a major portion has been previously
submitted or is being submitted for another course without the express permission of
all instructors involved.
Please note that Improper Collaboration or Inappropriate Collaboration is an academic offence.

While the lab experiment is a collaborative effort, lab reports must be written independently, to
do otherwise, is an academic offence.
If unsure of what the limits are, ASK!
General Lab Info
LABORATORY SAFETY
It is essential that engineers develop a habit of safety in all experimental work. Dealing with
flammable corrosive liquids, spattering reagents, violent chemical reactions, or the escape of
steam can be quite dangerous in the absence of sensible protective measures or devices.
All students are required to have completed a WHMIS course. If you have any doubts
about a procedure, ask the TA for assistance.
Safety goggles and lab coats must be worn inside the lab. Closed-toe shoes and long
pants are required. Contact lenses must NOT be worn in lab.
Read the Material Safety Data Sheets (MSDS) prior to experiment.
All hazardous wastes must be emptied into the appropriate waste containers. Read waste
labels before disposing into any receptacle. Check compatibility first.
Keep chemical bottles closed tightly when not in use.
Immediately inform your Teaching Assistant of any injuries or spills. For cuts, burns and
if a chemical comes in contacts with your skin, eyes or mouth, flush immediately with
water at the sink or safety station. You must file an accident report with the department.
In the event of a serious injury, inform the TA that you wish to go to Health Services.
The TA will send someone to accompany you.
Dispose of any broken glass in the bucket labelled Broken Glass.
Clean up work area. Remove lab gloves and wash hands before leaving.
Make sure to know the location of the following:
Fire extinguisher
Safety shower
First aid kit
Fire alarm
Telephone
FOOD and BEVERAGES ARE STRICTLY PROHIBITED FROM THE LAB
General Lab Info
GENERAL INSTRUCTIONS
Most of the experiments require several students working together in order to manipulate the
equipment, take readings, and record the data. Accordingly, students are assigned to groups of
three.
Before commencing an experiment, all members of a group should have a thorough
understanding of:
Theoretical principles involved in the experiment.
Type and amount of data to be recorded.
Expected results.
Whenever the foregoing requirements are met, the experiment can become a true learning
experience which will immeasurably assist in understanding the underlying principles;
otherwise, the exercise becomes merely one of manipulation of equipment and the reading of
various instruments.
Every member of a lab group is expected to actively participate in the lab. The
pre-assigning of duties to each member of the group is strongly advised in order
for the experiment to be performed effectively and quickly.
PROFESSIONAL CONDUCT: Although you are going to work as a group, some marks are
allocated for individual professional conduct. Marks will be deducted for horse-play and lack of
participation in the experiment.
ATTENDANCE: Marks are reduced for latecomers to the lab. If you need to miss part of a lab
session for a co-op interview, you must inform the TA in advance to ensure that you fulfil your
lab requirements. Refer to course outline for details.
In the event of a lab missed due to an illness, contact the TA or lab instructor
within 2 days to make arrangements to make-up missed session. You must
provide the chemical engineering undergraduate secretary with a Verification of
Illness form completed by a doctor. Forms may be downloaded from:
http://uwaterloo.ca/health-services/student-medical-clinic/services/verification-illness.
General Lab Info
LABORATORY REPORTS
Two types of laboratory reports are required for each lab in this course. The requirements for
each type of report are outlined below:
A. Preliminary Reports
The purpose of a Preliminary Report is to prepare for the experiment. Each group prepares one
Preliminary Report for each experiment (excluding computer tutorials). The marks for these
reports count toward the course mark of each group member. This report should be submitted to
the online dropbox by noon of the day before your lab session. It will be checked to see that the
group is not pursuing some erroneous task and graded. Your TA will address any concerns at the
start of the lab session.
The report should contain the following:
1)
Statement of the objective.
2)
General summary of the experimental design in your own words (i.e. number of runs and
range over which the experiment, equipment used, diagram of experimental set-up, etc.).
3)
Equations to be used in calculation of results.
4)
Possible hazards to be encountered in the experiment and safety precautions to be taken.
5)
Blank datasheet with appropriate headings (bring a copy to lab).
6)
Answers to Prelab Report Questions from lab manual.
SAFETY ASSESSMENT CHECKLIST

When evaluating the safety hazards involved in an experiment, consider the follow hazard categories:
Chemical Hazards (e.g. exposure, toxicity, incompatibilities, waste handling,
by-products formed)
Electrical shock
Burn/scald potential or risk of fire
Radiation exposure
Pinch points or Rotating parts
Cuts or Stabs potential
Pressurized lines (explosions), vacuum systems (implosions)
Potential Projectiles
Suffocation hazard or low O2 level potential
Trips/falls
Overhead hazards (falling objects, low-clearance zones)
Continued on next page
General Lab Info
Also consider the precautions that must be taken to ensure your personal safety and that of the people
working nearby.
o
o
o
o
o
o
Proper handling of chemicals

Proper operation of equipment
Personal Protection Equipment (PPE) required
Protective devices needed on equipment (i.e. Guarding on rotating parts)
Preventative behavior (i.e. securing loose clothing and hair, not wearing contact lenses when
working with chemicals, checking integrity of PPE, etc.)
Emergency response (avoiding injuries or contamination from hazardous incidents: what to do if
there is a spill of chemical, basic first aid, etc.)
B. Memo reports
A Memo Report is a complete record of your experiment. When required, a memo report is
prepared and submitted by each group. It describes:
Why the experiment was performed.
What data were obtained, and
Your interpretation of the data

A scientific report is not merely a list of facts or observations; it must provide an
interpretation of the findings and show their significance. A good engineering
report is organized logically and the wording chosen carefully so that the reader
knows exactly what you mean and where to find the evidence that supports your
conclusions.
The Memo Report should include the following:

1)
Title Page
Name of the University and Department.
Course number and name.
Experiment number and title
Group number and names all the members of the group contributing to the report.
Date experiment was performed.
To whom and the date that the report was submitted.
General Lab Info
2)
Table of Contents
List the divisions of the report with page numbers opposite. Lengthy divisions should be
subdivided into appropriate headings.
3)
Introduction
The purpose of the Introduction is to guide the reader to consider the importance of the topic
being presented. It should include:
4)
General background information relating to the experiment.
Significance of the data obtained to Chemical Engineering (i.e. current and future
applications).
Brief statement of the objective.
Theoretical Principles
This section should include:
Overview of the theoretical foundation of the experiment.
Include all necessary equations to be used in the calculations. Label each with a unique
id. Define variables. Derivations of equations go in the Appendix. Remember to state
any assumptions associated with the derivation of the equation.
Conclude with a brief statement indicating how the objectives will be met using the
theoretical principles involved.
The Introduction and Theoretical Principles must be written in your own words. Do not
copy from the Lab Manual. Research your topic. Use library resources.
5)
Experimental
In this section:
Summarize, in your own words, what was done during the laboratory based on
procedures given in the Laboratory Manual
Identify how equation(s) from theory section will be applied.
Include a labeled sketch or schematic of the experimental set-up.
State all modifications made to the procedure.
General Lab Info
6)
Observations and Results

In this section, you should present your qualitative and quantitative observations. Guide the
reader through the manipulation of the data in fitting it to the theoretical model.
Qualitative Observations
a)
Describe the experimental observations and, if required, refer to the appendix which
contains your original measurements.
b)
Report any irregularities in the experimental procedure that might explain outlying
data points.
Original datasheet should go in an appendix
Quantitative Results
c)
Present results which were calculated based on the data recorded during the
experiment. Remember to add reference to which equation from theoretical
principles section was used. Place sample calculations in the appendix but refer to
them here.
d)
Use tables or figures to clearly demonstrate trends in data (Refer to Tables and
Figures section below).
e)
List the estimated precision of your measurements, as well as, any other
observations which may help to explain the results. Refer to the Evaluating Error
section.
f)
Use significant digits. Remember to include units.
Always maintain significant figures when reporting measured or calculated values. The
number of digits used to express a value is extremely important as it indicates the precision
of the value. The last significant digit is considered to vary by 10 % unless the error is
specified. It is incorrect and misleading to report values to higher precision than possible
from the equipment used in the experiment. Refer to Chapter 11 section 6.2 in Introduction
to Professional Engineering in Canada by Andrews et. al. (2003) for more information on
determining significant figures through algebraic operations.
General Lab Info
Evaluating Errors
Unless one is counting individual objects, there is error inherent in all measurements. Two types
of errors occur: Systemic (or determinate) and Random errors.
Systemic errors are constant or proportional biases in a measurement occurring due to the
investigators habits or poor calibration or drift of the analytical equipment. For example, the
ruler was misread by +0.5 mm each time, or the pressure gauge was zeroed when the system
pressure was actually 10 psi. Large differences between experimentally-derived results and
commonly-accepted or cited values of a parameter are likely due to the occurrence of systemic
errors. Fortunately, systemic errors may be identified and correction factors used to compensate
for them if they can be quantified. Systemic errors can also be minimized by regular
recalibration of analytical equipment and by standardizing experimental procedures.
Random errors, on the other hand, are inevitable and vary from reading to reading. It is an
estimate of these random errors which must be included when reporting any measurement or
derived experimental value. Unlike systemic errors, random errors cannot be quantified exactly
but they can be approximated. For example, you measure the length of your pen to be 16.0 cm
using a ruler with gradations to the nearest 0.5 cm. Those markings are thick and imprecise so
you might assume that you can read precisely to, say, the nearest 0.1 cm. This is the external
error of this measurement. You would report the length as 16.0 0.1 cm. Depending on the
size of the scale of measurement, the human eye can differentiate up to 1/10 of the interval
between markings. For digital displays, the precision is to the manufacturers specifications, if
given or half of one decimal place below the last stable digit. Use your judgment in assessing
the precision of the measurements made during the experiments.
Random errors tend to offset each other so, for any given parameter the average of several
repeated measurements will be more precise than any single measurement. You can estimate
this higher precision by calculating the average value ( x ) and the standard deviation (s) of n
repeats. Your measurement would be reported as x SE where the standard error SE can be
approximated by:
SE
General Lab Info
s
n
Propagation of Error Equations

If the precision of individual measurements are known, the overall precision of any value derived
from these measured values can be approximated using the equations shown below:
y k k1a k 2b k3c ...
Addition and Subtraction
Multiplication and Division
k1a2 k2b2 k3c2 ...
kab
cd
2
y
a b c d

y
a b c d
Exponential
y bn
In General
y n b
y
b
y f ( x)
y x
dy
dx
Where: k, n are constants, a, b, c, d, x and y are measured variables, x is the standard deviation
of x which can be approximated by the standard error of a repeated measurement or the estimated
precision or external error of a single measurement.
Error in Linear Regression Analysis
Linear regression uses the Method of Least Squares to determine the line which best fits N
experimental data points. The relationship is plotted as: y = mx + b. Generally in the 290
experiments, the values of interest from a regression line are the intercept, b or the slope of line,
m. Unless the data fit perfectly to a straight (i.e. R2=1), then some error is inherent in these
regressed values and this error must be reported.
Generally in linear regression, the known value is plotted on the x-axis while the measured value
which has some error associated with it is plotted on the y-axis. Linear regression attempts to
determine the error in the y-value associated with a given x-value.
To simplify the calculations, some key quantities need first be defined:
S xx
Sr
xi2
xi 2
S yy m2 S xx
General Lab Info
N 2
S yy
yi2
yi 2
N
where (xi,yi) are the individual data points.
10
Use the following equation to find the standard deviation of the slope, sm:
sm sr / S xx
The standard deviation of the y-intercept, sb, is given by:
Sb S r
xi
N
xi2
The standard deviation, sc, of any point taken from the regressed line ( =
+ )
based on an average of M replicate measurements, is found using:
S
Sc r
m
1 1 yc y 2

M N
m2 S xx
The line over y indicates the mean (average) of all measured values of yi (where i = 1.N)
used to determine the regression line.
Assessing Quality of Fitted Data

When regressing data, it is assumed that the random deviations from the model are
independent, normally distributed, and have a constant variance. For any modeling of fitted
data, you should assess the quality of the fit of the model using the coefficient of
determination and residual plots. Outliers should be identified and justification provided if
they are removed from the evaluation of the data.
Tables and Figures

Any tables and figures must be explicitly mentioned (cited) in the text and should be
inserted in the report as closely after they have been cited as possible. All figures and tables
must have titles and they must give units for all data presented. Identify tables using Roman
numerals (i.e. Table I).
Tables must contain enough information to stand alone. The reader should not have to refer
to the report to understand it. An example of a table is shown below.
The experimental conditions and the measurement results are shown in Table .
General Lab Info
11
TABLE I: pH of the reaction product in the titration of 1.0 mmol/L Copper perchlorate using
0.04 wt % Ethylenediamine [en] solution (298 K).
[en] in Cu solution
mmol/L
0.00
1.46
2.93
4.41
pH
2.80
2.89
3.05
3.05
Figures should be prepared by computer. Label all figures with Arabic numerals (i.e. Figure
1, Figure 2, etc.) and a relevant title. As with tables, be sure to include all information that is
necessary for the reader to interpret or identify the image (i.e. reaction temperature, pressure,
etc.) in the title or in a caption.
For graphs:
Label each axis with a scale and title. Remember to include units.
If several sets of data being plotted, use a legend to identify the different symbols.
Depict observed data as discrete points.
Plot trendlines or fitted models using lines.
Sign and date all the figures in ink.
Figure 1:
Microbial Growth Curves

(grown at 37C in Tryptose Phosphate broth
with 2.5 g/L dextrose added)
3.000
Bacillus subtilis
2.500
Optical Density (ABS)
Streptococcus faecalis
2.000
1.500
1.000
0.500
0.000
0
100
200
300
400
500
600
Incubation Time (min)
General Lab Info
12
7)
Discussion of Results and Error Analysis

This is the most important part of the report. Many students have trouble knowing what
to discuss. A good guideline is to think of the experiment not merely as a school exercise but
as an experiment being performed as engineering research. Indicate which observations or
calculated results would be useful to other engineers who might read your report. Guide the
reader through your analysis of the observed results. Explain any discrepancies with the
theory and what may have occurred to cause the discrepancy?
Discuss the quality of your experimental data. Are there any data points which may be
unreliable? State the reasons for the unreliability. Consider the purity of the reagents
used, quality of measurements made, etc.
All the equations should be presented in the theoretical principles section and
referred here in the discussion section only by equation number.
Note that you must support your ideas and this will usually require finding and
reading reference material.
Discuss your calculated results. It may be necessary to review briefly any key
assumption made in the derivation of the equation used in the calculations and how they
might affect the result obtained. Mention any assumptions made in the calculations, such
as, values assigned as constants or data points that were excluded from the calculations.
Relate your results to the theory. Do your results agree with values presented in
literature? Include references. Check overall error relative to error propagation results.
Are your values reasonable? If not, try to explain the course of the discrepancy.
Discuss the error analysis. Include a discussion of the individual measurement errors that
contributed to the overall error in the calculated results. Which measurement error had
the largest effect on the results? Could the results be improved by taking replicate
measurements, by using different equipment, or by taking measurements under different
conditions? Is the precision in your results comparable to experiments in the literature?
Discuss the significance of your results, and any new information that has been learned.
8)
Conclusions
This section should include a summary statement of the relation between the results and the
objectives of the experiment.
What are the principal results of the experiment? They can be listed in point form stating
the most important ones first.
Summarize the significance of the results obtained as they relate to applications in
engineering.
General Lab Info
13
9)
Recommendations
Recommendations to improve the experiment should be included here.
Most important recommendation should be made first.
Make sure your recommendations are feasible from a practical point of view.
If possible, give estimates of the costs involved when making such modifications.
Approximate the % improvement in the quality of the results that could be obtained.
10) Nomenclature
Define all the symbols used in the report in alphabetical order.
11) References
For journals, give complete information, including names of all the authors, title of the
article, name of the journal, volume, page number(s) and the year of publication. For
example:
1.
Reilly, P.M., B.M.E. van der Hoff, and M. Ziogas, Statistical study of the application
of the Huggins equation to measure intrinsic viscocity, J. Appl. Polym. Sci., 24, 20872100 (1979)
For references to books give author(s), Title, edition, publisher, place and (year of
publication), and the page number(s).
2.
Laidler, K.J. and Meisner, J.H., "Physical Chemistry", Benjamin/Cummings Publ. Co.
Inc., Menlo Park, California (1982), p. 789.
For websites give the authors name, Title of section used, URL, (date accessed)
3.
Shuzon Ohe, Distillation Computation, http://www.s-ohe.com/McCabe-Thiele.html

(accessed Jan. 19, 2005).
The abbreviation et al. should not be used in the reference list. List the names of all authors.
Do not repeat references. If the next reference refers to the same article or book write:
4.
Ibid., p.238.
If referring to a reference already listed, refer to its reference number and give page number:
5.
Ref. 2, p. 237.
General Lab Info
14
12) Appendices
The purpose of putting extraneous material, such as, experimental data into the appendix is to
prevent disruption of the coherence of the report by long derivations or large columns of
numbers. Materials that should be in the appendix include:
Long tables of original observations.
Lengthy derivations of equations
Sample calculations
Answers to Report questions.
Material essential for understanding the report must remain in the body of the report.
General Lab Info
15
LENGTH of MEMO REPORTS for ChE391

To reduce the time spent in writing memo reports, the following guidelines have been
established regarding the length of Memo Reports for the CHE-391 course.
Title or cover page

Table of contents
1 page
Introduction
1-2 pages
Theoretical principles
1-2 pages
Experimental
1 page
Observation of results
1-2 pages
Discussion of results and Error Analysis
2-3 pages
Conclusions and Recommendations
1 page
References
page
Appendices
2+ pages
Your reports should be as straightforward and concise as possible.

Note that Figures and Tables are not included in the guidelines above.
General Lab Info
16
EXPERIMENT 1: Electrowinning of Zinc from Zinc Sulphate Solution
INTRODUCTION:
Extractive Metallurgy of Zinc
The principal minerals that contain zinc are sphalerite, zinc blende (ZnS) and marmatite
(ZnFeS). Zincite (ZnO) and smithsonite (ZnCO3) are of less importance. Over 50% of zinc is
produced from mixed ZnPb ores. Canadian mines produced ~7% of the worlds zinc in 2006
(approximately 710 000 tonnes) and was ranked fifth in worldwide zinc below that of USA [774
000 tonnes] and Peru [1 233 000 tonnes] (1).
The processing of zinc sulphide ores initially involves the physical separation of the desired
mineral from waste rock to produce a concentrate. ZnS is the primary component of this
concentrate, however, minor amounts of other minerals that contain copper, cadmium, cobalt,
nickel, silver, etc are also extracted. The concentrate is treated to chemically extract and
ultimately recover zinc in a pure metallic form for subsequent fabrication. Over the last 50+ years
the predominant approach in the zinc industry has been to use hydrometallurgical methods for
chemical treatment. These methods employ aqueous chemistry to extract the desired species.
Most zinc hydrometallurgical processes involve dissolving (or leaching) metals from the
concentrate into a sulphuric acid solution. This step is usually done by one of two methods:
i)
roasting (high temperature oxidation) of dry concentrate to convert ZnS to ZnO

ZnS + 3/2 O2 ZnO + SO2
(1-1)
followed by leaching out of Zn2+ in a concentrated H2SO4 solution

ZnO + 2 H+ Zn2+ + H2O
ii)
(1-2)
direct oxidative leaching of ZnS in a concentrated H2SO4 solution containing O2 at high

temperature and pressure
ZnS + 2 H+ + O2 Zn2+ + S0 + H2O
(1-3)
Once leaching is complete, the solution goes through a series of purification steps to remove
other metal ions (e.g., Cu2+, Co2+, Ni2+, Cd2+) leached from the ore before being charged to the
electrowinning cells. These valuable metals are recovered but more importantly, the Zn
electrowinning process is enhanced. Zn2+ is the most difficult transition metal to reduce in
aqueous solutions. Consequently, any other transition metals present in solution will
preferentially deposit during electrowinning. For this reason, control of the solution chemistry
during zinc processing is particularly important.
LAB 1: Electrowinning of Zinc
17
Zinc Electrowinning
Zinc electrowinning is carried out in electrolytes containing concentrated ZnSO4 (typically 50-60
g/L Zn2+) and H2SO4 (150-200 g/L H2SO4). Zinc deposition occurs at the cathode via equation
1-4 which is typically made of aluminum or titanium.
Zn2+(aq) + 2 e- Zn(s)
E0 = - 0.76 V
(1-4)
Zinc is rather electronegative relative to hydrogen, however, substantial hydrogen evolution is

avoided (fortunately!) owing to the high hydrogen overpotential at a zinc surface. Still, some
hydrogen evolution does occur according to the process:
2 H+(aq) + 2 e- H2(g)
E0 = 0 V
(1-5)
At the anode (usually Pb), the oxidation of H2O occurs via eqn 1-6:
H2O O2 + 2 H+ + 2 e-
(1-6)
evolving O2 gas and H+ ions.
One of the obvious aims of operators is to minimize H2 evolution since it consumes current that
would otherwise be used to produce the desired Zn metal product. Under proper conditions, the
rate of hydrogen evolution is slow and Zn deposition has relatively fast kinetics. A low working
temperature (about 35C) and high current density (about 600 A/m2) successfully keep hydrogen
evolution at a low rate.
A number of quantities are useful in characterizing the performance of electrowinning processes.
The current efficiency (CE) is defined as:
= / 100%
where:
(1-7)
IZn = current used for Zn deposition

I = total applied current
IZn is related to the mass of Zn deposited by Faradays Law:

= ( )/( )
where :
(1-8)
n = number of electrons transferred per mol of Zn plated

F = Faraday constant (96485 C/mol or 26.8 Ah/mol)
m = mass of Zn deposited (g)
MZn = atomic mass of zinc (65.37 g/mol)
t = duration of electrolysis
18
A measure of the electrical energy required to produce a specific mass of deposit is given by the
specific energy consumption, SEC. It is related to the cell voltage V and the current efficiency,
CE as follows:
(1-9)
100

100

Specific Energy Consumption is usually expressed in units of kWh/tonne. The minimization of

SEC is a prime factor in optimizing process performance.
Another quantity of importance is the Decomposition Voltage that is defined as the minimum
cell voltage required to initiate metal deposition. It is most easily determined by measuring the
cell voltage as a function of applied current (or vice versa) and extrapolating the resulting I-V
plot to I = 0. The decomposition voltage is generally close in magnitude to the cell potential (but
in contrast to cell potential, it has no theoretical significance).
Effect of Additives on Zinc Electrowinning

Electrolyte composition generally has a significant effect on the behaviour and efficiency of
metal electrowinning. It is particularly critical in Zn-electrowinning because of the sensitivity of
both Zn deposition and H2 evolution on the electrolyte composition. As with other
electrodeposition processes, small amounts of organic compounds such as glue and gelatin are
added to the plating solution. In amounts up to approx 50 ppm, these additives enhance the
morphology of the zinc deposits by improving their smoothness and compactness and reducing
their grain size. However, the trade-off for this improvement is that the organics tend to decrease
the current efficiency for Zn deposition. To counteract this, operators have learned through
experience to add other components in small amounts. One such additive is antimony (Sb) in the
+3 oxidation state.
As mentioned previously, the presence of other metal ions in the electrolyte can have a
significant effect on the effectiveness of the process. A particularly remarkable example is the
extreme sensitivity of the current efficiency for Zn deposition to the Sb(III) concentration and to
the complexity of its influence [see Table 1-1 (ref 3)]. With no other additives in solution, the
presence of Sb(III) at concentrations under 0.1 ppm has been found to decrease the current
efficiency by 50 % (4)!! Also, a significant change in the morphology of the deposits occurs. It
appears that Sb(III) is playing some catalytic role, although the details are still poorly
understood. However, when a similar amount of Sb(III) is added along with 20-50 ppm glue or
gelatin, the effect is entirely opposite. The current efficiency of the zinc deposits actually
increases over that observed without additives present. Furthermore, the adherence of the zinc
19
deposit to the aluminum substrate is reduced, facilitating its removal at the end of electrolysis.
For these reasons, operators routinely add small amounts of both glue and antimony to the
electrowinning cells but, very close control of their concentrations is essential. Note the dramatic
improvement in CE when [Sb] = 0.08 mg/L and the glue concentration is increased from zero to
60 mg/L, or even as low as 5 mg/L.
Table 1-1:
The combined effect of antimony and glue on current efficiency [after Mackinnon
et al.; for full set of data, consult ref.3]
Current efficiency, CE per cent
0.04
[Sb] mg/L
0
Glue mg/L
0
91.0
85.6
5
90.1
85.5
10
88.8
86.9
30
86.8
90.2
60
85.9
90.6
Note: Re-dissolution of some Zn deposit has also been observed.
0.08
29.0
68.4
75.7
85.8
91.3
EQUIPMENT:
D.C power supply
Multimeter
Switch box
Aluminum cathodes
Lead anodes
Electrolytic cells
Drying oven
Analytical balance
Zinc Sulfate Solutions
PROCEDURE:
Following the demonstration of the operation of the electrowinning cells, continue with the
procedure outlined below. Each lab group will be assigned different applied current (0.4-0.7
A) and volume of Sb(III) solution to add (50-200 L) to each cell in Part C.
Take note of the various electrolyte solutions and information provided to you.
20
PART A:
Effect of Zinc Concentration
1. Label and weigh each aluminum cathode. Record the weight. Measure the diameter of the
electrowinning cells.
2. Assemble all four cells with spacers in between and enclose each cell with one aluminum
plate and one lead plate positioned in an alternating pattern. The equipment is designed in
such a way to keep the electrode distance uniform and constant. Measure the spacing
between each anode (lead) and cathode (aluminum).
3. Tighten the assembly firmly to seal each cell against the electrodes. Check that the edges of
the cells are on the plate surfaces.
4. Over the sink, fill each cell with water using the squeeze bottle. Ensure there are no leaks. If
leaking, check position of plates. Otherwise, try tightening further (but not excessively as
this can damage the assembly). If leak persists, disassemble and replace cell.
5. Pour out the water and fill each cell with 50mL of the designated electrolyte solution.
Warning, these solutions are prepared with 1 M sulphuric acid solution. Wear gloves. Keep
a record of the solution concentration in each cell.
6. Connect all the cells in series using the short wires with alligator clips.
7. Connect the lead electrode (anode) to the positive terminal of the D.C power supply and the
aluminum electrode (cathode) to the negative terminal.
8. Connect the switch box to the electrodes. Position 1 in the switch box should be connected
to cell 1, position 2 to cell 2 and so on.
9. Connect the switch box to the multimeter. Turn on the power supply and turn the voltage
control knob in the clockwise direction all the way.
10. Turn the current control knob to acquire about 0.6 amperes or any other value instructed by
your TA.
11. Measure the voltage across the electrodes in each cell by switching to the appropriate
positions on the switch box. Also check the temperature of each cell. Record temp and
voltage of each cell every five minutes until a steady-state is reached (~30 min).
12. At the end of the experiment, switch everything off and disconnect all the wires. Discard the
electrolytes in the appropriate waste container and rinse the cells with deionized water.
13. Remove all the four cathodes and place them in the oven to dry at 110C. After about 20
minutes remove the cathodes from the oven and allow them to cool to room temperature.
Reweigh each cathode and record the values.
21
PART B:
Effect of Acidity
Repeat procedure as outlined in Part A using a different set of electrolytes in which the acidity
is varied and the zinc concentration is kept constant.
14. Record the acid and zinc concentrations in the solutions.
PART C:
Effect of Additives
Follow the procedure outlined in Part A using electrolytes containing trace amounts of Sb(III)
or other additive.
15. Add 50 mL of electrolyte with the same composition of acid, Zn2+ and gelatin to each cell.
16. Using a micropipette, add an equal volume of each antimony solution to its respective cell.
The TA will inform you of the volume of additive solution to use specifically for your tests
(volume added ranges from 60-140 uL).
17. Once you have completed the electrolysis and determined the change in mass of the cathodes
(dry), examine the deposits relative to each other and to those from parts A and B. Note
texture and any features of each deposit. Make a sketch of what you see. Note any trends
you observe with respect to the variation in Sb(III) level.
PRELAB REPORT QUESTIONS

1. The electrowinning cells are assembled in series with equal spacing between places. What is
the purpose of this configuration?
2. What is the purpose of the electrolyte in the electroplating cell?
3. What effect might the electrolyte conductivity have on the plating performance? How does
solution temperature affect its conductivity?
4. The voltage drop measured across a cell includes potential differences due to energy losses.
Which overpotentials might contribute to the inefficiencies in an electrowinning cell? Can
they be quantified?
22
REPORT QUESTIONS
1. Scott et al. (4) have obtained the following empirical expression for the conductivity of
ZnSO4 H2SO4 solutions:
= 32.0 + 0.27[2 4 ]( 35) + 19.6([2 4 ] 1.12) 11.1([2+ ] 1.25)
where = conductivity (S/m)
T = temperature (C)
[H2SO4] = H2SO4 concentration in electrolyte (mol/L)
[Zn2+] = Zn2+ concentration in electrolyte (mol/L)
(a) Estimate the IR drop at the beginning of each experiment in Parts A and B.
(b) Estimate the IR drop at the end of each experiment in Parts A and B assuming the
current efficiency remains constant throughout electrolysis.
(c) For each case, determine the percentage of the cell voltage represented by the IR
drop.
2. Looking at your results from Question 1 above, explain why the cell voltage varies with time
during electrolysis?
3. The cell voltage changes more rapidly during the initial stages of electrolysis than in the later
stages. Explain the behaviour observed in the initial stages.
4. How is the current efficiency in each of the experiments in Parts A and B affected by the
[Zn2+]/[H+] ratio? Comment on the relationship between CE and this ratio. (Note: the initial
[H+] is not necessarily the same as concentration of H2SO4 initially added to the
electrolyte.)
5. Scott et al. (4) provide the following data for electrowinning of Zn in a 55 g/L Zn ; 110 g/L
H2SO4 solution at 35 oC and a current density of 500 A/m2 :
time (h)
CE (%)
SEC (kWh/tonne)
8
95.9
2861
24
96.2
2835
42
96.0
2820
56
96.2
2855
72
96.2
2855
It would appear from theory that the product of current efficiency and specific energy
consumption should be a constant. Show the relationship between the SEC and CE in your
data.
23
6. In a zinc electroplating process the specific rate of mass deposited in a continuous operation
is 433 g Zn/m2h . The process operates at 540 A/m2 .
(a) What is the cathodic current efficiency?
(b) If the current efficiency were improved by 10%, what would be the specific rate of mass
deposition under otherwise identical conditions?
REFERENCES:
(1) http://www.zinc.org/Documents/Communications/Publications/ZincGuide2004.pdf
(accessed November 24, 2009)
(2) D.J. Mackinnon, R.M. Morrison, J.E. Mouland and P.E. Warren, J.Appl.Electrochem. 20
728 736 (1990)
(3) A.R. Ault and E.J. Frazer, J. Appl. Electrochem. 18 583 589 (1988)
(4) A.C. Scott, R.M. Pitblado, G.W. Barton and A.R. Ault, J.Appl.Electrochem. 18 120 127
(1988)
24
EXPERIMENT 2: Potential-Controlled Analysis of Redox Couple

(Reminder: Each group should bring a USB flash drive to the lab to copy your observed data)
INTRODUCTION:
In industrial processes, electrochemical cells are operated with 2 electrodes anode and cathode.
Under these conditions, one can control or monitor what is happening throughout the cell as a
whole. For example, the cell voltage that can be applied or monitored includes several
components voltage drops at both electrode surfaces, ohmic drop across the electrolyte, voltage
drops at contact points, etc. However, such a 2-electrode set-up is not useful to study or control
events occurring at a single electrode. For this purpose, a 3-electrode configuration is required.
As shown in Figure 2-1, a 3-electrode cell is made up of a working electrode, a reference
electrode and an auxiliary (or counter) electrode. The working electrode provides the surface on
which the reaction of interest can be studied or controlled. Most commonly, the potential drop at
the working electrode surface is controlled or monitored using an instrument called a
potentiostat.
Figure 2-1: Typical 3-electrode cell for potential-controlled experiments
LAB 2: Voltammetry
25
The ability of the potentiostat to measure or control the potential drop at the working electrode
surface in a 3-electrode cell is due to the role of the reference electrode. During cell operation,
the potential drop between the working electrode and the reference electrode is continually
monitored. The device within a potentiostat that measures this potential drop has very high
impedance so that the circuit branch between the working and reference electrodes draws very
little current. Typically, standard reference electrodes (e.g., calomel, silver chloride, etc.) with
very stable properties are used so that the half cell potential of the reference electrode (relative to
SHE) is known and the potential of the working electrode can determined.
Although no current flows between the working and reference electrodes during operation, the
current generated by the working electrode must still flow through some part of the cell. This is
where the auxiliary (or counter) electrode comes into play. As current is generated, it flows
through the circuit branch linking the working and auxiliary electrodes. In fact, the sole purpose
of the auxiliary electrode is to complete the flow of current through the cell. It can be any
electrode as long as its electrochemical properties do not affect the behaviour of the working
electrode. In practice, it is desirable during operation for the auxiliary electrode not to produce
substances that can cause interfering reactions at the working electrode.
In this experiment, data will be obtained using different potentiodynamic electrochemical
techniques: (1) cyclic voltammetry in a stirred and unstirred solution; (2) linear sweep
voltammetry in a solution in which the working electrode is rotated at high speed and (3)
chronoamperometry. The redox reaction between the ferricyanide(III) ion Fe(CN)63- and the
ferrocyanide(II) ion Fe(CN)64- in electrolyte solution is:
Fe(CN)63- (aq) + e- Fe(CN)64- (aq)
(2-1)
In such solutions where the concentration of the reacting species (i.e., ferricyanide(III) or
hexachloroiridate(IV)) is much lower than the background electrolyte (i.e., KCl or KNO3), the
contribution of migration to the transport of the reacting species is negligible. Migration is only
significant for the transport of the background electrolyte under these conditions. (Note: Refer to
pages 5.5-5.8 of your ChE 331 course notes for more discussion of this matter).
Before describing the experimental procedure, it will be useful to provide brief background on
the three electrochemical methods to be used in these experiments.
LAB 2: Voltammetry
26
Cyclic Voltammetry in Unstirred Solution

In Cyclic Voltammetry, the working electrode potential is varied linearly in one direction and
then reversed back in the opposite direction. The change in the electrode potential over time
follows a pattern similar to the triangular waveform shown in Figure 2-2. This process of
sweeping the potential first in one direction and then reversing in the opposite direction can be
repeated over many cycles, if desired. The current generated over the cycle is measured and
plotted versus the electrode potential on a diagram called a voltammogram. A sudden change in
current on such a plot usually signifies the occurrence of an electrode reaction.
Figure 2-2: Potential-time waveform for cyclic voltammetry
If the electrode reaction under consideration is reversible, then the reaction will proceed
cathodically, i.e.,
O + ne e- R
(2-2)
during the portion of the cycle when the electrode potential is being varied in the negative
direction and the electrode potential becomes sufficiently negative. When the scan direction is
reversed and the electrode potential becomes sufficiently positive, the above reaction can reverse
itself and proceed anodically, i.e.,
R O + ne e-
(2-3)
The resulting voltammogram will reflect the onset of both the cathodic and anodic reactions by
displaying cathodic and anodic current rises during the corresponding portions of the cycle. In
the situation where the solution is unstirred and the working electrode is stationary, these current
rises will appear as distinct cathodic and anodic peaks, as shown in Figure 2-3. In the example
shown, the electrode potential is scanned first in the negative direction and the electrolyte
contains only species O at the start of the experiment.
LAB 2: Voltammetry
27
IP
Figure 2-3: Typical voltammogram for a reversible redox process O + ne e- R in

an unstirred solution.
Image courtesy of S Koshy
When the solution is quiescent, the current reaches a peak value Ip during a cycle when the
concentration of the reactant during that portion of the cycle reaches zero at the electrode surface
(i.e., reaction becomes mass transfer-limiting). For a planar electrode surface, the magnitude of
this peak current is related to the operating conditions of the scan and the conditions within the
solution by the Randles-Sevcik equation. For the general cathodic reaction (2-2), this equation is:
| | = 0.4463
where
1/2 1/2 1/2

(
)
(2-4)
v = electrode potential sweep rate (V s-1)

R = gas constant (8.314 J mol-1 K-1)
T = solution temperature (K)
ne = number of electrons transferred for each reactant O consumed
A = area of working electrode surface (m2)
F = Faraday constant (96,485.31 C mol-1)
D = diffusion coefficient of reactant O (m2 s-1)
C = concentration of reactant O in the bulk solution (mol m-3)
The Randles-Sevcik equation applies to the situation when the contribution of migration to the
transport of the reactant can be neglected. Since the Randles-Sevcik equation is applicable only
when the solution is unstirred, transport of the reactant is assumed to occur by diffusion alone.
LAB 2: Voltammetry
28
Linear Sweep Voltammetry of a Rotated Disk Electrode

In this technique, the working electrode potential is varied linearly with time in one direction
(i.e., towards more positive or more negative electrode potential) as shown in Figure 2-4. The
resulting current is measured and plotted versus the electrode potential. A rise in current
signifies the occurrence of an electrode reaction. The shape of the voltammogram is often
affected by whether the solution is being agitated during the linear sweep and the extent to which
the solution is agitated. A typical voltammogram obtained when a solution is being agitated is
shown in Figure 2-5. Typically, the linear sweep voltammogram is a sigmoidal-shaped curve,
with the current leveling off to a plateau when the electrode potential is swept to a sufficiently
negative or positive value. When the current reaches this plateau, the reaction has reached mass
transport-limiting conditions where the concentration of the reactant at the electrode surface has
reached zero. The value of the current at this plateau is called the limiting current Il (see pages
5.9-5.13 in your course notes).
Figure 2-4: Potential-time waveform for

linear sweep voltammetry
Figure 2-5: Typical linear sweep voltammogram

obtained when solution is agitated
The most common method of agitation is to mount the working electrode onto a rotating disk
electrode (RDE) apparatus. In this set-up, the working electrode is a small disk imbedded in an
insulator and vertically mounted in the shaft of a synchronous controllable-speed motor. During
an experiment, the shaft is rotated with constant angular velocity about an axis perpendicular to
the plane disk surface (Figure 2-6). This is a particularly popular method of agitation since it
provides well-defined hydrodynamic conditions and is one of the few agitated electrode systems
for which analytical solutions to the convective-diffusion transport equations have been obtained.
Thus, it makes analysis of experimental data relatively straightforward.
LAB 2: Voltammetry
29
Side View
Bottom View
Figure 2-6: Rotating disk electrode assembly
LAB 2: Voltammetry
Images courtesy of S Koshy
30
Consider the general electron transfer reaction for the conversion of species O to species R
O + nee- R
(2-5)
Under conditions where transport of the reactant O in the vicinity of the working electrode
surface occurs by diffusion and convection (this corresponds to the conditions of these
experiments where the concentration of the reacting species is small compared to that of the
background electrolyte), it can be shown that the transport-limiting current Il for a reversible
reaction (such as that considered in this experiment) is given by the Levich equation:
= 0.620 2/3 1/2 1/6
where :
(2-6)
= angular rotational velocity of working electrode (rad s-1)

2
=
f
60
f = rotational speed of working electrode (rpm)
= kinematic viscosity of solution (m2 s-1)
ne, F, A, C and D have the same meanings as in equation (2-1) above
Chronoamperometry
The chronoamperometry technique involves making a step change in the working electrode
potential from a value where no electrode reaction occurs to a value where a reaction occurs and
monitoring the resulting current as a function of time (Figure 2-7). If the working electrode is
stationary, the solution is unstirred and the concentration of the reactant is small compared to that
of the background electrolyte, then diffusion is the primary mode of transport of the reacting
species in the vicinity of the working electrode during the electrode reaction.
Figure 2-7: Chronoamperometry experiment. (A) Potential-time waveform.

(B) Typical current-time electrode response obtained when solution is unstirred.
LAB 2: Voltammetry
31
The technique usually involves stepping the electrode potential to a value where the electrode
reaction proceeds quickly enough that the concentration of the reactant at the electrode surface
almost instantaneously approaches zero (i.e., diffusion-limiting conditions). Under these
conditions, the variation of the current I with time t can be shown to follow the Cottrell equation:
(2-7)
ne F A C D1/2
I(t)=
1/2 t1/2
where ne, F, A, C and D have been defined previously.
Deviations in the electrode response from the behaviour predicted by the Cottrell equation often
occur at long times (usually t 100 s) due to effects of natural convection within the cell.
Natural convection arises from concentration differences produced by the electrode reaction in
the vicinity of the working electrode.
EQUIPMENT:
Voltalab 21 Potentiostat
CTV 101 speed control unit
ED 1101 rotator with a 2mm diameter platinum disk working electrode at the tip of
the rotator.
XR 110 calomel reference electrode
XM 110 platinum auxiliary electrode
A30T970 thermostated electrochemical cell
REAGENTS:
The TA will provide a solution to be analyzed by the three electrochemical techniques during
these experiments. This solution contains the electroactive species (Fe(CN)63-) dissolved in the
background electrolyte (0.1 - 1 M KCl). Each lab group will be given a different solution so
please take note of the composition of your solutions.
After each experiment, export and save the data to an Excel file. Transfer files to your USB
flash drive. Make note of all parameters for each experiment (i.e., scan rate, rotational speed,
potential range, working area of electrode, etc.).
LAB 2: Voltammetry
32
PROCEDURE:
Detailed instructions for the operation of the equipment and proper instrument settings will be
provided by the TA.
Electrochemical Analysis Using Solution Containing Redox Couple
Cyclic voltammetry, linear sweep voltammetry and chronoamperometry will be conducted on the
solution containing Fe(CN)63-. Take note of the exact concentration of the solution.
Allow the TA to fill the cleaned cell with the solution and install the three electrodes (working,
reference and the auxiliary) in the cell.
BEFORE EACH ANALYSIS, purge the cell with a low but, steady flow of N2 for 30 s. The
line pressure regulator for N2 is on the back-bench on opposite side of the computer.
From Voltmaster4 software (password is password):
a. Create a new sequence from FILE.
b. Then, from SEQUENCE dropdown, choose Sequence Edition and ADD appropriate
voltammetry test from the list. Note Chronoamperometry is found under PULSE icon.
c. Highlight added test and press EDIT. Enter the appropriate parameters as specified in the
procedure then press Green Arrow . Create a file folder, type in filename and press
ENTER to begin scan.
Part A: Cyclic Voltammetry in Unstirred Solution
1.
Make sure the working electrode is not rotated during the cyclic voltammetry
experiments. Wait until the solution is quiescent before beginning the scan.
The first cyclic potential scan will cover the range +0.5 V -0.5 V for 1 cycle at a scan
rate of 10 mV/s. Carry out the scan.
2. Open the .CRV file that was generated and from the CURVE dropdown menu select Export
Data to generate an Excel file. Alternatively, the CRV file can be imported directly to Excel
but headings/units will be missing (this data is given in SI units of volts, amperes and
seconds). NOTE, a datafile must be downloaded for each scan performed in this experiment.
3. Repeat the above cyclic potential scan for 8, 6, 5 and 4 mV/s sweep rates. Note: Turn on the
rotator for a few seconds and purge with N2 after each experiment at a given sweep rate to
re-mix the solution. However, make sure that the rotator is turned off and the solution has
become quiescent before beginning the scan at the next sweep rate.
LAB 2: Voltammetry
33
Part B: Cyclic Voltammetry in Stirred Solution

4. Set the rotation speed to 4000 rpm and repeat the scan described above in Step 1.
5. Maintaining the rotation speed at 4000 rpm, repeat using a potential scan rate of 5 mV/s
Part C: Linear Sweep Voltammetry of a Rotating Disk Electrode

6. The potential will be scanned from +0.5 V to 0.5 V at a scan rate of 10 mV/s and electrode
rotation speed of 4000 rpm. Carry out the scan.
7. Repeat the above scan for each of the following electrode rotation speeds: 3200, 2100, 1600
and 900 rpm.
Part D: Chronoamperometry in Unstirred Solution

8. The first experiment will be a potential step from +0.5 V to -0.5 V in unstirred solution.
Set E1 = 500 mV, t1 = 1 sec, E2 = -500 mV, t2 = 10 sec and measure period = 0.6 sec.
Make sure the working electrode is not rotated during this analysis. Wait until the
solution has become quiescent before beginning the experiment.
9. Apply the potential step and monitor the resulting current over time.
Part E: Chronoamperometry in Stirred Solution

10. The remaining experiments will be a potential step from +0.5 V to -0.5 V in stirred solution
at each of the following electrode rotation speeds: 4000, 2100, and 900 rpm. Set E1 = 500
mV, t1 = 1 sec, E2 = -500 mV, t2 = 10 sec and measure period = 0.6 sec.
When the last experiment is complete, inform the TA. Be sure to copy your datafiles from the
computer.
LAB 2: Voltammetry
34
PRELAB REPORT QUESTIONS:

1. The reference electrode used in this lab is a Standard Calomel Electrode filled with saturated
KCl. What is the standard potential for this electrode? What function does it serve in the 3electrode test cell?
2. Why is KCl(aq) added to the K3Fe(CN)6 solution being tested in this experiment?
3. You will be testing a solution containing less than 0.15 M K3Fe(CN)6 in 0.1 M KCl or 1 M
KCl. Find an estimate for the kinematic viscosity of this solution and for the diffusion
coefficient of Fe(CN)63- ion in KCl from literature.
4. List and define the three types of mass transport that can occur in an electrochemical cell.
Which type dominates when cell is stirred?
5. The same range of potentials is proposed to be tested in the cyclic voltammetry (CV), linear
sweep voltammetry (LSV) and Chronoamperometry runs. What effects will cause the
voltammagrams to differ between tests (refer to images in Introduction section)?
6. What does the area under the cathodic and anodic waves in a cyclic voltammagram
represent?
DATA ANALYSIS:
Cyclic Voltammetry
1. Compare the cyclic voltammograms obtained under unstirred conditions at the different scan
rates on the same plot. Based on the shape and trends observed in the voltammagrams, what
can be inferred about the redox reaction taking place (e.g. regarding kinetic rate or number of
electrons transferred or effect of scan rate, etc.)?
2. Use the cathodic peak currents from the series of cyclic voltammograms acquired at various
sweep rates under unstirred conditions in the solution containing the redox couple to estimate
the diffusion coefficient of the Fe(CN)63- ion from the Randles-Sevcik equation. Pay close
attention to units. The diffusion coefficient should be reported in units of m2s-1.
3. Cyclic voltammograms in the solution containing the redox couple were obtained under
stirred conditions (4000 rpm) at scan rates of 10 mV/s and 5 mV/s. What effect, if any, did
the scan rate have on your voltammograms? Explain.
4. Why does the anodic current peak disappear from the cyclic voltammogram when the
solution is agitated?
LAB 2: Voltammetry
35
Chronoamperometry
1. Fit the observed chronoamperogram to the Cottrell equation. Perform a linear least square
regression of the data to find the equation of the best straight line that fits the data. It is
important to keep in mind that this best straight line should pass through the origin in order
to be compatible with the Cottrell equation. To obtain the best results, you will not use all of
your transient I(t) data. At the very start of the experiment, certain effects occur that are not
accounted for by the Cottrell equation, so you may need to exclude the first two data points
corresponding to t = 0.6 s and 1.2 s.
2. Do the data points obtained near the end of the scan deviate from straight-line behaviour?
Which data points might be removed from the analysis? Justify this in terms of the
phenomena occurring during the electrode reaction then make an estimate of the diffusion
coefficient of Fe(CN)63- ion from the Cottrell equation. Pay close attention to the units.
3. Chronoamperometry experiments were conducted under stirred solutions. Each of the
resulting curves obtained in the solution containing the redox couple shows that, given
sufficient time, the current reaches a constant value. Compare the constant current value
obtained to the IL value measured with the linear sweep voltammetry experiments at equal
electrode rotational speeds. Are they the same? Comment.
Linear Sweep Voltammetry of a Rotating Disk Electrode
1. Compare the linear sweep voltammograms obtained under different rotational speeds at a
sweep rate of 10 mV/sec. Comment on the effect of rotation speed on the voltammograms.
2. Use the limiting currents IL obtained from the series of linear sweep voltammograms
obtained in the solution containing the redox couple to estimate the diffusion coefficient of
the Fe(CN)63- ion from the Levich equation. Note that rotation velocities should be
converted to rads-1.
General Overview of Results
1. The three voltammetric techniques used in this experiment provide varying estimates of the
diffusion coefficient of ferricyanide ion. Compare each technique on the basis of providing
an accurate estimate of the diffusion coefficient of a solute. Which method(s) do you think
is(are) more reliable? Why? Provide evidence from your data to support your conclusions.
2. Consider that you are conducting a cyclic voltammetry experiment in an unstirred solution on
a reversible redox couple that has slow reaction kinetics. What effect do you think this will
have on the position and the separation of the cathodic and anodic current peaks in the
resulting voltammogram?
3. Measure the areas under each wave in your cyclic voltammograms obtained at various
potential scan rates in an unstirred solution. What trend is observed? Explain why the area
under the cathodic wave is generally larger than that of the corresponding anodic wave?
LAB 2: Voltammetry
36
REFERENCES:
1. A.J. Bard and L.R. Faulkner, "Electrochemical Methods: Fundamentals and Applications, 2nd
Edn., Wiley & Sons, 2001.
2. A.J. Bard and L.R. Faulkner, "Electrochemical Methods: Fundamentals and Applications, 1st
Edn., Wiley & Sons, 1980.
3. J. Wang, "Analytical Electrochemistry", VCH, 1994.
4. R.G. Compton and C.E. Banks, "Understanding Voltammetry", Hackensack, NJ : World Scientific,
2007
LAB 2: Voltammetry
37
EXPERIMENT 3: Analysis of Fuel Cell Performance Curves
INTRODUCTION:
The global use of energy derived mostly from the combustion of fossil fuels is considered to be
the leading cause of the release of global warming compounds such as CO2 into the atmosphere.
Today, hydrogen fuel cells are considered to be one of the most promising renewable energy
technologies for the future with applications ranging from cell phones to automobiles (Thomas,
1999).
Similar to a battery, a fuel cell operates as a galvanic cell, i.e., a device that uses an
electrochemical reaction to generate electricity. Since it functions as an electrochemical cell, a
fuel cell contains the same basic components as does a battery anode, cathode and electrolyte.
Unlike batteries, however, fuel cells are fed a continuous supply of reactants and therefore can
produce power for as long as the reactants are available. Fuel cells have higher theoretical
efficiencies than thermal combustion engines because they are not restricted by the Carnot cycle
and instead directly convert fuel into useable electricity. There are many different types of fuel
cells, e.g., hydrogen polymer electrolyte fuel cells (PEMFC), solid oxide fuel cells (SOFC),
direct methanol fuel cell (DMFC). This laboratory experiment is concerned with a PEMFC
which uses hydrogen and oxygen gases as reactants and contains a very thin solid polymer
membrane as the electrolyte, as shown in Figure 3-1. This membrane must be an ionic conductor
to ensure that H+ ions can move from the anode to the cathode.
Figure 3-1: Schematic of a hydrogen polymer electrolyte membrane fuel cell
LAB 3: Fuel cell
38
Electrochemistry of a Hydrogen Fuel Cell

One of the electrochemical reactions in a PEM fuel cell can be described simply as the
dissociation of hydrogen gas to hydrogen ions and electrons at the anode, as shown in (3-1):
H2 2H+ + 2e-
E025C = 0V
(3-1)
where E0 is its half-cell equilibrium electrode potential measured against a standard hydrogen
electrode. The electrons then flow through the external circuit to a load connected to the cell,
thereby providing the electrical energy to operate the load. The electrons flow through the load
and then back into the fuel cell external circuit to the cathode. Meanwhile, the H+ ions released
by reaction (3-1) are conducted through the electrolyte to the cathode. Both the electrons and
hydrogen ions recombine exothermically with oxygen on the cathode to produce heat and water
via electrochemical reaction (3-2):
2H+ + O2 + 2e- H2O
E025C = 1.229V
(3-2)
Eo25C = 1.229V
(3-3)
The overall reaction is given in (3-3):

H2 + O2 H2O
These reactions are made to occur on small catalyst particles (usually platinum-based) attached
to a conductive electrode backing material such as graphite or carbon fibres. This ensures that the
reactions can proceed rapidly and the active surface area for the reactions is as large as possible.
From the overall reaction, the maximum theoretical voltage that a fuel cell can generate is 1.229
V at room temperature and gas pressures of 1 atmosphere using pure gas streams. The half-cell
potentials above depend on several factors such as temperature, pressure, and the mole fractions
of the reactants in the gas streams. The relationship that relates the cell potential E to these
variables is the Nernst equation:
E E 0
RT aH2O
ln
nF aH2 aO2 1 / 2
(3-4)
where E0 is the standard cell potential, R is the gas constant, T is the temperature in Kelvin, n is
the number of electrons transferred in the reaction (i.e., 2 in this case), F is Faradays constant,
and aH2O, aH2 and aO2 are the activities of water, hydrogen, and oxygen, respectively. It is
important to emphasize that the value of E determined from Eq (3-4) is the theoretical voltage
generated when no current is flowing and is termed the Open Circuit Cell Voltage. In practice,
however, the highest achievable open circuit voltage is lower than the theoretical value and
usually lies between 0.95 and 1.0 V due to inefficiencies in the cell, e.g., leakage of H 2 from the
anode compartment to the cathode compartment. Of course, the function of an operating fuel cell
is to generate current. When current is actually flowing, the cell voltage will be lower than the
open circuit value due to losses associated with current flow, i.e, ohmic resistance through the
electrolyte, electrodes and external connections, kinetic limitations of the electrode reactions and
LAB 3: Fuel cell
39
mass transfer limitations of reactants at the electrode surfaces.

Voltage and Power
In order to achieve voltages necessary for different fuel cell applications, many cells are
combined in series in what are called fuel cell stacks. The stack voltage VStack and average cell
voltage Vaverage are given in (3-5) and (3-6):
n
VStack Vi
(3-5)
i 1
Vaverage
V
i 1
(3-6)
where Vi is the voltage generated by the ith cell in a stack and n is the total number of cells in the
stack.
Stack power PStack and average cell power Paverage are given by (3-7) and (3-8):
PStack VstackI Vi I
i 1
Paverage
(3-7)
PStack
n
(3-8)
Fuel Cell Performance Characterization

The main measure of fuel cell performance is the polarization curve. A polarization curve is a
plot of the fuel cell current density (i.e., current through one cell per active anode or cathode area
of a cell) versus the average fuel cell voltage. The curve can be segmented into four regions
characterized by the major source of overpotential (or loss) in each of the sections, as shown in
Figure 3-2.
The first region is, in fact, a point and indicates the cell voltage when no current is flowing. This
corresponds to the open circuit potential discussed previously and is denoted as OCV in the
figure. Although the OCV should be equal to the Nernst potential, it is typically 0.1 0.2 V
lower due to non-ideal conditions and mixed potentials caused by gas crossover from the anode
to the cathode.
LAB 3: Fuel cell
40
Ideal Voltage (1.23V)
Voltage
OCV
Cathode and Anode

Activation Overpotential
Overpotentia
l
Concentration
Overpotentia
Overpotential
l
Voltage
Ohmic
Overpotential
Current Density
Figure 3-2: Regions of a typical PEMFC polarization curve
At low current densities, activation polarization is the dominant source of energy losses in an
operating fuel cell. Activation polarization arises due to limitations associated with the kinetics
of the electrode reactions. It becomes an important factor when the electrochemical reaction is
controlled by sluggish electrode kinetics. Of the two electrode reactions in a fuel cell, oxygen
reduction at the cathode is usually the rate limiting reaction and therefore contributes the most to
activation polarization (USDOE, 2000). Due to its relationship to reaction rates, the activation
polarization is also affected by the total active surface area of the catalyst surface. Losses of the
active catalyst surface area during operation due to phenomena such as particles falling off the
electrode backing material or the buildup of solid reaction products on the catalyst particles are
registered as activation polarization
At intermediate current densities, the major sources of energy loss come from the ohmic
resistances through the cell. These losses arise due to the resistance to ion flow through the
electrolyte membrane and the resistance to electron flow through the gas diffusion layer (GDL).
As shown in Figure 3-1, the GDL is a thin layer of carbon fibres or paper between each fuel
channel and electrode that serves to better distribute the reactant gases to the catalyst sites on
each electrode. Other factors contributing to the cell ohmic losses include contact resistances
between the different components and electronic resistance through the bipolar plate. Resistance
to proton flow through the membrane is the largest individual contributor to the ohmic losses
(USDOE, 2000).
LAB 3: Fuel cell
41
The final region in the polarization curve is dominated by losses due to concentration
polarization, or diffusion limited operation, at high current densities. Under such high currents,
the kinetics of the electrode reactions are so high that the transport of the reactants to the active
catalyst sites limits the rate at which the fuel cell can operate. The problems of mass transfer can
be further accentuated due to phenomena such as slow diffusion caused by nitrogen
accumulating near the cathode or the presence of water in the pores of the electrode. The term
flooding of the fuel cell is used to describe a situation when water completely fills the electrode
and significantly blocks reactants from reaching reaction sites.
Stoichiometry
In order to achieve a specific current in a fuel cell, the correct amount of reactants must be
delivered to the cell. Generally stated, the volumetric flow rate of a gaseous reactant required by
the fuel cell (converted to STP conditions for convenience) for a specific current output is given
by Faradays law (3-9) as follows:
Q
where:
I VSTP N c
F ne
(3-9)
Q is the volumetric flow rate (L/s) of reactant into the

stack/product out of the stack,
I is the total current (A) flowing through the stack,
Nc is the number of cells in the stack
ne is the moles of electrons transferred per mole of reactant r
consumed based on the electrode reaction stoichiometry,
VSTP is the volume an ideal gas occupies at STP (22.4 L/mol)
In general, a fuel cell is supplied with excess reactants in order to achieve the best possible
performance. The ratio of the actual inlet volumetric flow rate to the amount required from
Faradays law is typically referred to as the stoichiometry S and is given by (3-10):
Fin Fout Q
Q
Q
(3-10)
where Fin and Fout are the inlet and outlet flow rates, respectively. Systems where no unreacted
gas is discharged from the cell are called dead-ended.
LAB 3: Fuel cell
42
EQUIPMENT:
A schematic of the fuel cell demonstration station is provided in Figure 3-3. The fuel cell used
in this experiment is a 5-cell stack with each cell having 10 cm2 active area. Hydrogen is
supplied via a compressed gas cylinder and air is forced through the cell by a fan. A series of
resistors are used to create a load for the fuel cell. The total resistance of the load depends on the
position of the port to which the fuel cell is connected. The range of resistances is sufficient to
generate a polarization curve that depicts the three main overpotential regions. Labview
software is used to display measurements of the fuel cell voltage, current flowing through the
circuit, H2 inlet pressure and outlet flowrate. The flowrate of H2 out of the fuel cell can be
controlled using the software.
PROCEDURE:
A polarization curve is obtained by varying the resistance of the load and measuring the current
and cell voltage output. Higher resistances lead to lower currents and vice versa. All polarization
curves in this experiment will be obtained by decreasing load resistance from high to low. Six
different configurations of the fuel cell system are to be tested. Each run will use the procedure
outline in Part A with the modification specified.
*NOTE* Minute fluctuation in voltage and current reading will occur even after the system is
allowed to stabilize. An average between the lowest and the highest value of the fluctuations
should be taken to increase the accuracy of the experimental data**
Pressure
Regulator
Flowmeter
Solenoid
Valve
P
Shunt
Fuel Cell Stack

Resistor
Board
Motorized Fan
Flow Controller
Electrical circuit
To Exhaust
Knock Out
Drum
Gas Lines
Figure 3-3: Schematic of the Fuel Cell Demonstration Station in DWE1518
LAB 3: Fuel cell
43
Part A: Fuel Cell Warm-up

NOTE: Part A will be done for you before lab session begins but procedure should be reviewed
so that you are familiar with test station operation.
1. Ensure that breaker switch on fuel cell circuit is off.
2. Open LabView and start the data collection program by pressing white at top left.
3. Turn on air fan located below fuel cell stack to its low speed setting.
4. Open the N2 and H2 cylinders and slowly increase the delivery line pressure to ~5 psig.
Check that delivery line valve is open.
Check the STOP icon on bottom of Labview display. This is the safety switch that
operates a solenoid valve that controls the type of gas delivered to the fuel cell stack.
Refer to table below. Ensure that system is active with H2 supplied to the cell stack.
BUTTON
COLOUR
MODE
TYPE OF GAS FLOWING TO

FUEL CELL STACK
Grey with green

light nearby
SAFE
N2
Burgundy (grey
light nearby)
ACTIVE
H2
IN THE EVENT OF A FIRE set button to grey Safe Mode to stop flow of H2 to
cell stack then inform TA and evacuate the immediate area.
5. Set H2 outflow from the fuel cell test station in Labview window to 20 mL/min.
6. Using the pressure reading display in LabView, adjust the anode pressure of the cell
stack using the pressure control dial on the backboard to between 1.5 - 2 psig.
* CAUTION * DO NOT EXCEED AN ANODE PRESSURE OF 2 PSIG as
this can lead to H2 leakage from the cell stack.
Clockwise turn increases pressure. Note that when backing off pressure, system
response is slow but can be sped up by increasing outflow rate to 50 mL/min.
7. Wait for cell stack to reach OPEN CIRCUIT VOLTAGE (OCV: the voltage at zero
current). It takes a few minutes for cell stack to fill with H2 and initiate reaction.
8. Apply a load on the circuit by insert the plug into resistor #8 and switching breaker to
complete circuit. Let system run for ~15 minutes to warm-up cell stack.
LAB 3: Fuel cell
44
Part B: Baseline operation

Start experiment from this point.
1. Switch off circuit breaker and remove plug from resistor board. Fuel cell should now
be warmed up.
2. Allow system to stabilize at its OCV for approximately 2 minutes then record the
following values from the Labview display:
Current (A)
Voltage (V)
Average H2 inlet flowrate (sccpm or mL/min)
Average actual outlet flowrate and set-point (sccpm or mL/min)
Anode pressure (psig)
3. Insert the free wire from the fuel cell into resistor slot #1 (the highest resistance) and
close switch to complete the circuit with a load. A decrease in voltage and a small
increase in current should be observed.
4. Adjust pressure control dial (clockwise to increase) to maintain the anode pressure
recorded in Step B2.
5. Allow the readings to stabilize (approximately 1 minute) then record the values for the
parameters listed in Step B2.
6. Turn off the main switch then move to next resistor slot and repeat from Step B3 until
readings for all 10 resistor slots have been obtained. This baseline data will be used as
a point of comparison for subsequent runs.
7. At end, switch off the circuit, remove the resistor plug, increase the air fan to the
maximum setting and allow air to flow through the cell stack for at least 1 minute
before starting the test on the next operational parameter.
Part C: Reduced pressure operation
Repeat the procedure in part B, however, reduce and maintain the anode pressure at 0.5 psi.
Part D: Dead-end anode operation
Repeat the procedure in part B, however, set the outlet flow rate to zero cc/min.
Part E1: Operation at increased air flow rate
Repeat the procedure in part B, however, turn fan onto the high speed setting.
Part E2: Operation at zero air flow rate
Repeat the procedure for part B, however, turn fan off.
LAB 3: Fuel cell
45

1. Visit the fuel cell test station in the SW corner of DWE 1518. How many cells are in the fuel
cell stack? Label the reactant sources on a copy of Fig 3-3.
2. Describe the theoretical principle behind thermal mass flow meters?
3. Determine the Nerst potential of a single fuel cell operating at 21C supplied with 1.5 psig
pure H2 and air from the room (ambient conditions are 1 ATM, 50% rel. hum.).
4. List some properties and operating conditions that influence the performance of a fuel cell.
5. A 10-cell PEMFC stack operating at 20C under 1 atm with an inlet air flowrate of 55 ml/min
and inlet H2 flowrate of 55 ml/min produces a current density of 280 A/m2 at 9.3 V.
Determine the oxygen and hydrogen stoichiometries at these operating conditions. The active
area of each cell is 15 cm2.
6. Describe the type of materials typically used in each of the following components of a fuel
cell and the functions of each component:
a. Endplates
b. Bipolar plate
c. Gas diffusion layer
d. Anode catalyst
e. Cathode catalyst
f. Electrolyte
REPORT QUESTIONS:
1. Using the baseline polarization curve collected in part B, propose a design for a fuel cell
stack to power a full-size sedan. The vehicle must be able to achieve a maximum power of
90kW. The electric motor and other high voltage power electronics on the vehicle cannot
operate below 240V, so the fuel cell must maintain a voltage of at least 240V.
a) Specify the number of cells, cell area, and stack OCV. On the baseline polarization curve,
identify the location of peak power.
b) Assuming each bipolar plate is 0.3 cm thick, calculate the power density (power per
volume) of your fuel cell stack. Some automotive stacks have attained a power density of
2.5kW/L
(Nissans
claim
for
its
next-generation
fuel
cell
http://www.sae.org/mags/SVE/10329). What thickness would your bipolar plates need to
be to achieve this power density? The thickness of all other components may be
neglected.
2. When driving in an urban area, the fuel cell vehicle in Question 1 attains an average speed of
50 km/h and an average power consumption of 8.5kW. If the vehicle can store 4.3 kg of
hydrogen, how far can the vehicle travel, assuming a fuel cell efficiency of 70%?
LAB 3: Fuel cell
46
3. Many green technologies are being adapted for the automobile industry. What are some of
the factors that have limited the widespread commercialization of fuel cells? Compare the
advantages and disadvantages of fuel cells relative to other emerging mobile energy options.
REFERENCES:
Carette, L, Friedrich, K.A., Stimming, U., Fuel Cells, 1 (2001), 5-39.
Thomas, S., Zalbowitz, M., Fuel Cells Green Power, Los Alamos National Laboratory, New
Mexico (1999), http://www.lanl.gov/orgs/mpa/mpa11/Green%20Power.pdf
U.S. Department of Energy (US DOE), Fuel Cell Handbook
http://www.ansaldofuelcells.com/files/fuel_cells_handbook.pdf
LAB 3: Fuel cell
EG&G Services (2000),
47
EXPERIMENT 4: Corrosion Studies

Special thanks to Dr. J. Vazquez-Arenas for his contributions and guidance
INTRODUCTION:
Based on the IUPAC definition, corrosion is an irreversible interfacial reaction of a material
(metal, ceramic, polymer) with its environment which results in consumption of the material or
its dissolution into the material of a component of the environment. From pieces of airplanes
falling from the sky to leaking oil pipelines and nuclear reactors and the tragic gas explosion at
Union Carbide in Bhopal, India 1984, corrosion has been a prime factor in many commercial and
industrial accidents (Roberge, 2012). A study in the USA alone showed that the
replacement/repair of deteriorating infrastructure and equipment damaged by the effects of
metallic corrosion had overall costs of approximately $276 billion in 1998 which represented
~3.1% of the annual US GDP that year (Jacobsen, 2003). NACE, the Corrosion Society believes
that 25-30% of this cost could have been recovered if appropriate corrosion management
practices had been implemented (Jacobsen, 2003). It is a natural process that some materials,
particularly metals, will corrode upon exposure to air and moisture. However, proper selection
of construction materials for given environments, the application of corrosion control techniques
and regular inspection and maintenance can avert some of the devastating consequences of this
natural degradation and extend the lifespan of infrastructure and equipment.
Traditionally, corrosion testing was performed using immersion tests or in atmosphere-controlled
spray chambers over extended periods of time to simulate naturally occurring conditions. With
the development of electrochemical techniques, estimates of the corrosion rates of materials can
be made within hours instead of days, month or years allowing for more rapid development of
new corrosion resistant alloys, protective coatings, and corrosion abatement techniques.
Corrosion maintenance/replacement costs can be minimized as electrochemical corrosion tests
can provide timely data on the compatibility and stability of materials during the design stages
before materials are purchased or construction on projects begins.
Estimating the Corrosion Rate
From ASTM G31-72, the average corrosion rate of a specimen in terms of penetration rate (i.e.
depth lost per unit time) can be estimated from measurements of the mass lost over a given
period of immersion in a test medium using the following equation:
(4-1)
/ =
Where: K = conversion factor based on desired corrosion rate units

(8.76x104 for mm/y (metric) 3.45x106 for mpy (imperial)
W = mass loss in g, to nearest 1 mg
A = exposed surface area in cm2, to nearest 0.01 cm2
t = time of exposure in hours, to nearest 0.01 h
= Density in g/cm3
LAB 4: Corrosion Studies
48
Electrochemical corrosion testing techniques can also provide estimates of corrosion rates based
on observed estimates of the corrosion current density, icorr and Faradays Law:
( /) = 3.27 103
(4-2)
Where: is measured corrosion current in A/cm2

is the density of the material tested in g/cm3
is the equivalent weight of the sample material
EW is the mass that a component loses per equivalent of charge transferred. For alloys, only
species exceeding 1 mass percent of the total alloy weight are included in the calculation of this
value:
=
for an alloy.
(4-3)
Where: fi is the mass fraction of element i in an alloy,

ni is the valence of the i
Wi is the atomic weight of element i.
The corrosion rate may also be expressed in terms of a mass loss rate:
(
) = 8.954 103
2
(4-4)
There are various electrochemical techniques available for estimating icorr. In this experiment,
you will be performing EIS, Tafel, and LPR scans.
Electrochemical Corrosion Testing Techniques
EIS
Electrochemical Impedance Spectroscopy (EIS) is a relatively modern corrosion testing
technique in which the response of an electrochemical system (i.e. current output) to a small AC
signal (i.e. a voltage cosine or sine wave) applied across the cell is monitored for shifts in their
relative amplitude and phase angle. The following conversions transform the sinusoidal
response into rotational vector representation with the in-phase portion of the current defined as
the real component and the out-of-phase portion defined as the imaginary component of the
rotating vector.
or I = || cos()
(4-5)
or jI" = || sin()
||2 = | |2 + | |
(4-6)
(4-7)
Figure 4-1 demonstrates the conversion of the frequency input and current output into a vector.
49
Imaginary
|I|
t
E
I
Real
Time, t
Phase
Shift,
Imaginary
|Z| = E/I
Real
Adapted from ASTM G106-89 (2010)
Figure 4-1: Conversion of Current and Voltage Output obtained from Electrochemical
Impedance Spectroscopy to Rotational Vector Representation and EIS Impedance Vector
|| with Phase Shift, .
In EIS, the current response || is monitored relative to the voltage input signal || over a range
of voltage switching frequencies (i). The parameters of interest are the impedance = / and
the shift in the phase angle between the input and output, , as shown in the figure above. For
ease in mathematical manipulations, the defining equations become:
= ( "") + "( "") =
tan =
+"
(4-8)
+"
"
(4-9)
||2 = |Z|2 + |Z"|2
(4-10)
In DC systems, = 0 and the rate of the kinetic electrochemical reaction can be modeled similar
to a resistor in an electrical circuit. In AC systems, phenomenon such as film formation,
adsorption and diffusion cause capacitance and inductance to occur leading to a shift in the phase
angle between the voltage input and the current output. The current through a capacitor is
always = 90 out-of-phase relative to the voltage across it. A capacitor behaves as a short
circuit at high frequencies and an open circuit at low frequencies. Inductors act in the opposite
manner. The current through an inductor always lags the voltage across the inductor by 90 and
they behave as open circuits at low frequencies and as large impedances at high frequencies
(PAR App. Note AC-1). Based on the data collected in an EIS scan, the electrochemical system
can be modeled as a circuit consisting of a combination of resistors, capacitors and inductors
configured in series and/or parallel. The simplest configuration for impedance measurements is
called a Randles cell and is shown in Figure 4-2.
50
CDL
CDLd = double layer capacitance
dl
R = uncompensated resistance
RP = polarization resistance
RP
Figure 4-2 Randles Cell or Equivalent Circuit for a Single Electrochemical Cell (adapted from
PAR AppNote AC-1)
At high frequencies, the impedance of the double layer capacitance CDL diminishes below RP and
acts as a short circuit. The current flows through CDL instead of RP and so the measured
impedance is mainly due to R.
At low frequency, the impedance of CDL becomes very high and the current takes the route
through R and RP. In the absence of capacitance and inductance, the Imaginary Impedance
Zimaginary value goes to zero and only the Real Impedance Zreal is observed. A plot of Zimaginary
versus Zreal or Nyquist Plot from the EIS scan takes the form of Figure 4-3.
Imaginary Impedance, Z
Decreasing frequency, f = /(2)
maxZ = 1/(CDL RP)
max
Real Impedance, Z
R + RP
RP = 2Ztan
Figure 4-3: Nyquist plot for Randles cell (adapted from PAR App Note AC-1).
As the electrochemical system becomes more complex, such as, when (1) other chemical
reactions take place in the corrosion cell, (2) diffusion limitations occur, or (3) when non-porous
coatings are present on the test sample, the EIS output deviates from the half circle plot and the
51
configuration of the equivalent circuit becomes more involved. Refer to PAR Application Note
AC-1 for more information on this.
EIS data may also be plotted in a Bode plot which exhibits the relationship between the absolute
impedance || or the phase shift of impedance and the frequency.
|Z|=1/CDL
90
Log |Z|
Phase Shift,
max
RP+R
R
0
Log
Figure 4-4: Bode Plot of EIS data from a Randles Cell (adapted from PAR App Notes AC-1)
Ohmic (or uncompensated) resistance dominates the Impedance at high frequency and R can
then be read from the horizontal plateau at high frequencies. At low frequencies, RP also
contributes to impedance. If R is known, RP can be calculated from the plateau at low
freqencies. At intermediate frequencies, the CDL controls the total impedance of the Randles cell
with the slope of the straight line that fits the impedance vs log data equaling -1. At the yintercept where log =0, the total impedance is equal to the inverse of CDL as shown in the figure
above. Note that slopes of - or - can indicate diffusion control in the cell.
The CDL of the system can be estimated from the frequency at the maximum phase shift
using the following equation:
1
= (
) (1 +
(4-11)
If estimates of Tafel beta constants are known, the Rp value can be used to estimate Icorr from the
following equation:
=
= 2.303( + )
(4-12)
@
52
Tafel Plots
The Tafel equation (4-13) can be used to model the behavior of one isolated electrochemical
reaction. An electrochemical reaction under kinetic control obeys the Tafel Equation:
= 0 exp[2.3 ( )/]
Where:
(4-13)
I = the measured current

I0 = a reaction dependent constant called the Exchange Current
E = measured electrode potential
Eo = equilibrium potential when I=0
= Tafel Constant (volts/decade).
In a corrosion system, there are two opposing reactions occurring: the anodic corrosion reaction
and a cathodic reaction such as the reduction of O2 or H+. The Tafel equations for both the
anodic and cathodic reactions in a corrosion system can be combined to generate the ButlerVolmer Equation:
= + = ([2.3 ( corr )/ ] [2.3 ( corr )/ ])
Where:
Ecorr = the corrosion potential in volts

a = the anodic Beta Tafel or Stern-Geary Constant volts/decade
c = the cathodic Beta Tafel or Stern-Geary Constant in volts/decade
Potential
At highly anodic currents (accelerated corrosion rate), the contribution from cathodic current
becomes negligible and the measured current is essentially just anodic current. Vice versa occurs
at highly cathodic currents. This can be clearly seen in the Tafel plot which shows the
relationship between potential and the log of the current density. Beta constants can be estimated
from the slopes of the curves at potentials far away from Ecorr. The current density at the point
where the anodic and cathodic currents intersect with Ecorr is the corrosion current density, icorr.
This value can be used to estimate the corrosion rate of the specimen as outlined in equation 4-2.
Cathodic
Current
Ecorr
Anodic
Current
Icorr
Log Current Density

Figure 4-5: Tafel Plot
adapted from Gamry Application Note: Getting Started with Electrochemical Corrosion Testing
53
LPR
The Linear Polarization Resistance (LPR) test allows for a quick estimation of the Resistance
Polarization, Rp by scanning a small range of potential differences across the corrosion potential,
Ecorr and finding the slope of the potential vs current density plot at the point of zero current.
This Rp value can then be used to give an estimate of icorr via equation 4-12.
OBJECTIVE:
The objective of this experiment is to compare estimates of the corrosion rate for various metals
under various environmental conditions by immersion and electrochemical corrosion testing
techniques.
EQUIPMENT:
PAR VersaStat3-400 Potentiostat w/(2A max.) and Frequency Response Analyzer (FRA)
Versastudio corrosion software
1L Ametek Corrosion Test Cell (Princeton model K47) inc. 1 Saturated calomel reference
electrode filled with saturated KCl, 2 graphite counter electrodes, a Teflon sealed working
electrode sample holder, salt bridge tube and gas sparger.
2 clean metal (mild steel, stainless steel, aluminium, copper and brass) cylindrical coupons
(9.2 mm dia. 12 mm approx with #3-48 tap)
2 clean metal rectangular coupons (mild steel, stainless steel, aluminium, and copper)
Paraffin wax and paint
250 mL sample bottles and fishing wire
Incubators (room temp up to 60C)
REAGENTS:
0.1 - 1 M NaCl(aq), HCl(aq), NaOH(aq), or H3PO4(aq)

0-0.5 M H2SO4(aq)
PROCEDURE:
Samples will be cleaned in advance of the lab according to procedure outlined in Part A. One
group will study the effect of a coating on the corrosion of a sample in a given media while the
other group will test for the effect of the corrosion media. Data will be shared between groups
within a given session. Both groups should decide upon test conditions at the start of the lab
session. One or two members from each group will begin with Part B (plating the Co-Zn
coating) on the left-side station. The other members will start with Part Ci EIS of plain steel in
the chosen test media on the right-side station. Electrochemical testing is done via procedure
outline in Part C. NOTE: the EIS test is only available on the right-side station but LPR and
Tafel tests can be done using either potentiostat. Refer to Table 4-2 for a summary of time
required for each part of this experiment.
*IMPORTANT* Wear lab gloves when handling steel coupons as contamination by
skin oils can impede the corrosion process.
54
PART A: Preparation of Sample Coupons (cylindrical, wire or plate coupons)

Preparation of the coupons is a critical step in corrosion studies as the samples should be clean of
oils and grease and the surface should be uniform. Cleaning follows the procedure
recommended in ASTM G1-03 (2011):
1. Clean in a pre-degassed ultra-sonicating bath containing distilled water for 30 minutes
2. Rinse thoroughly with distilled water and sand with 600 grit paper to smooth surface. Then
rinse sample with methanol or acetone to remove any remnant grease.
3. Rinse thoroughly with distilled water and allow to air dry. Do not use paper or cloth to dry
as lint can affect observed corrosion rate. Place in oven to accelerate drying and transfer to
dessicator to cool.
OPTIONAL PART B: Pulse-Plating of a Cobalt-Zinc Coating

Those that start with Part B will perform the plating procedure listed below on the left-side
station and leave their plated sample submerged in the chosen test media while continuing with
corrosion testing (Part C) of a non-plated sample. When finished, corrosion testing can then be
performed on the plated sample.
1. The TA will attach a cylindrical sample coupon to the test assembly headpiece. Measure and
record the diameter of a cleaned mild steel cylindrical coupon using the calipers. Ask TA or
instructor for help in reading the scale properly.
*NOTE* Be gentle but firm if tightening the assembly. It should seal
snuggly but be aware that the glass tube on the headpiece will crack
easily under too much compression.
2. Wrap a thin strip of paraffin wax film around the cylindrical coupons to cover all except the
bottom flat face. Be sure to seal around the sample attachment point with paraffin wax.
3. Insert the sample into a beaker containing Co-Zn solution. Insert two graphite electrodes and
the reference electrode. Ensure that the opening on the side of the reference is open.
Position the reference electrode close to but not touching the sample. Double-check that the
electrodes are not in contact with each other.
Electroplate a coating onto cylindrical sample coupon using the following procedure:
4. Make the following connections to the VersaStat potentiostat: Connect counter electrodes
together using wire with alligator clips and then attach RED lead from Versastat to one clip.
Attach GREEN lead to working electrode. Attach WHITE lead to reference electrode.
BLACK lead is not used DO NOT CONNECT TO CELL. Confirm connections with
TA/instructor before initiating the potentiostat.
5. Ensure potentiostat is turned on (switch is on back top right side of box) and open the
Versastudio software, if not already done.
55
6. Under Tools menu, click on select instrument and select the appropriate model# (refer to
front of potentiostat). Instrument title bar is light blue when selected.
7. Under Experiment menu choose New and create a cyclic voltammetry (single) test. Create
a group folder and save file. Experiment Properties window appears.
8. Under the COMMON tab, update the reference electrode type (i.e. SCE w/sat KCl),
working electrode type (solid), working electrode area (calculate from measured diameters),
density of material and the equivalent weight of material (values needed from literature).
Enter any comments or notes about the experiment in the Comments box.
9. Next, click on Cyclic Voltammetry to enter the test conditions. Initial Potential is the OC
voltage. Set Vertex Potential to 2 V w.r.t SCE reference and the Final Potential to - 0.2 V
w.r.t. SCE reference with No Hold at vertex. Set scan rate to 10 mV/s. Save the file.
10. Press the green GO arrow on menu bar to begin the scan. Two windows open: (1) Current vs
Potential plot; and (2) Dataview showing datapoints for Potential (V), Current (A) and
Elapsed Time (s). Stop scan if current goes increasingly anodic (e.g. >100 mA, refer to
Figure 4-6 below).
11. Create an EXCEL file and transfer plot data to a new worksheet using Versastat Data menu
Copy and selecting relevant parameters from the pop-up list. Click Copy button.
Graphs can be generated from this data or copied directly from Versastudio by using the
Copy icon in the graphic window: select Copy Data as Image from dropdown. Other
figures can be generated using the View menus Add Graph feature.
12. Review cyclic voltammetry scan to find high and low potentials for cyclic plating operation
(refer to arrows on voltammagram below).
Current
High setting
for Zn removal
Co plating begins
first at less
negative potential
Anodic region
= corrosion
Potential
Low setting for

Co and Zn plating
together
Figure 4-6: Cyclic voltammetry for determination of plating limits.
56
13. Remove the Cyclic Voltammetry and Insert a new scan. From the Advanced Actions
tab, choose Loop in the Sequence Actions list and press OK. Then click on Loop#1 and
add a Chronoamperometry action from the Voltammetry list. Repeat to add a second
Chronoamperometry action in the same loop. It is important that these first two
chronoamperometry runs are subdirectories of the loop within Common. Check that the
Common parameters are still valid.
14. Click on Loop#1 and enter the number of cycles for the electroplating (between 5-30).
15. Click on the first Chronoamperometry and enter the LOW (i.e. more negative) Potential
setting for a Duration of 4.5 s. Click on the second Chronoamperometry and enter the
HIGH (less negative) Potential setting for a Duration of 0.5 s. *NOTE* Time per Point
must be equal to or lower than the Duration. The lower the Time per Point, the more
points plotted in the output. Add one more Chronoamperometry scan to the main directory
outside of LOOP#1 to ensure that the process ends on at the lower plating potential.
16. Save to a new filename and run the scan. A current vs potential will appear showing the
cyclic plating activity. Once the scan is finished, turn off the potentiostat and remove the
lead from the working electrode. NOTE: the plating solution may generate a small amount
of chlorine gas. Remove headpiece from solution and check for plating BUT DO NOT
REMOVE the wax film.
17. Rinse the plated sample thoroughly with deionized water and then place in 1 L corrosion cell
containing test medium to equilibrate.
18. Fill a salt bridge with some test solution taking care to remove any air bubbles from the
bottom of tube. Attach to corrosion cell and make sure that the bridge tube tip is positioned
within a few mms of (but not touching) the sample coupon. For image of assembled
corrosion test cell refer to http://www.princetonappliedresearch.com/Our-Products/Accessories/CorrosionCell-Kit.aspx.
19. Purge the cell with a low flow of N2 for two intervals of 10 min. separated by a 5 min. break
and then let rest for ~1 hour while you perform corrosion tests (Part C) on plain steel coupon.
57
PART C: Electrochemical Corrosion Testing (EIS, Tafel, and LPR)

Refer to Table 4-2 for approximate lengths of the various electrochemical tests.
If testing different media (i.e. you are not preparing the plated coating) then the first two tests to
perform should be EIS on a sample in the chosen corrosion test media (i.e. NaCl, HCl, H2SO4,
H3PO4, NaOH, etc.). Discuss choice of media with instructor during prelab sample preparation
during week before scheduled session.
Ci) Electrochemcial Impedance Spectroscopy (EIS)
*NOTE* EIS tests must be the first

corrosion test run for samples but the corrosion rate calculation from EIS will depend on Tafel
Constants found in part Ciii. Refer to Step 13.
1. Insert or create a new scan called a Potentiostatic EIS from the Technique Actions:
Impedance list. *NOTE* EIS function is only available on Potentiostat # 12095465 which
has an FRA (Frequency Response Analyzer). EIS test takes just a few minutes to complete.
2. Make the following connections to the VersaStat potentiostat: Connect counter electrodes
together using wire with alligator clips and then attach RED lead from Versastat to one clip.
Attach GREEN lead to working electrode. Attach WHITE lead to reference electrode.
BLACK lead is not used DO NOT CONNECT TO CELL. Confirm connections with
TA/instructor before initiating the potentiostat.
3. Under the COMMON tab, update the reference electrode type (i.e. SCE w/sat KCl),
working electrode type (solid), working electrode area (calculate from measured diameter),
density of mild steel and the equivalent weight of mild steel (values needed from literature).
Enter any comments or notes about the experiment in the Comments box.
4. Open the virtual potentiostat window from Tools, click External Cell and record the approx
OCV for the cell, which has been resting for at least 45 min to equilibrate.
5. Click on Potentiostatic EIS and enter the following parameters:
Start Frequency: 10000 Hz
End Frequency: 0.05 Hz
Amplitude: 10 mV
Potential: enter Ecorr value (i.e. value at OCV)
NOTE for plated samples, use the same Ecorr as the non-plated steel in the test medium.
6. Three windows appear showing: (1) the magnitude of the impedance versus frequency or
Bode Plot (2) the imaginary component of impedance against the real component of
impedance or Nyquist Plot and (3) the dataview table which shows the data being collected.
7. Use the software to fit the data to find Rs and Rs+Rp. If fitting is not good or if curve is
incomplete, estimate the endpoint, use the fitting feature in the Versastat software or ask your
TA for an EIS-fitting MATLAB code. Note: EIS corrosion rate calculation requires the input
of Tafel Constants (see part Ciii).
58
8. Create an EXCEL file and transfer plot data to a new worksheet using Versastat Data menu
Copy and selecting relevant parameters from the pop-up list. Click Copy button.
Graphs can be generated from this data or copied directly from Versastudio by using the
Copy icon in the graphic window: select Copy Data as Image from dropdown. Other
figures can be generated using the View menus Add Graph feature.
Cii) Linear Polarization Resistance
*NOTE* LPR must be the second corrosion test run for any sample but the LPR corrosion rate
estimate will depend on Tafel Constants found in part Ciii. Refer to Step 13.
9. Create a new Linear Polarization Resistance scan from the Corrosion tests listing. Enter setup data in COMMON Window. LPR test parameters are set by default. Run scan.
10. Use the RP Fit feature (see icons above plot) to find the slope of the Potential vs Current
output at Ecorr.
Ciii) Tafel Plots
11. Create a new Tafel scan from the Corrosion tests listing and enter set-up data. Narrow the
scan range to 0.2 to -0.2 V vs OCV. Run scan.
12. On the plot of Potential vs log Current, use the Tafel Fit feature to determine the Tafel
Cathodic and Anodic Beta values, Ecorr and Icorr.
13. Go to Tools menu Options and enter the Corrosion Properties: Cathodic and Anodic Beta
values and then return to EIS and LPR data to perform corrosion calculations. You should
provide support of the calculated values using theoretical electrochemistry equations.
PART D: Immersion Corrosion Testing

There will be sufficient time to complete Part D while awaiting the Tafel scan to finish.
However, Part D may be performed at any point during the lab session.
** The first part of Part D is to be completed at least 3 days prior to attend Lab 4. Contact
lab instructor to arrange a time to prepare your samples**
Before the lab session:
1. Remove mild steel or galvanized steel coupon from desiccator.
2. Select the test media and label the sample bottles on the wall and lid.
59
3. Choose a condition to test such as: composition of specimen; effect of galvanic coatings or
other corrosion control measures; duration of exposure; corrosion solution composition and
concentration; temperature; pH; partially versus fully submerged; aerated vs deaerated;
fluid velocity; shape of specimen; or sample pretreatments/coating. Other conditions may be
tested if resources are available in the lab; discuss your ideas with the instructor. Table 4-1
gives some examples of possible test conditions.
4. Each group will prepare two samples to compare one condition or can co-ordinate samples
with other group scheduled for same session to make more comparisons.
5. Use fishing line to suspend sample from vial cap so that coupon will be submerged in the
corrosive test solution inside the jar. For quantitative studies (i.e. corrosion rate
determination) sample must be fully submerged in the media or suspended completely above
the corrosion media without touching the bottom or sides of the container. Partial
submergence is used for qualitative observation of the effect of the air-liquid interface on the
corrosion mechanism.
6. Remember to label your samples with group ID, date, time, test conditions. Make sure that
lid is fully labeled as sample will remain with lid after removed from jar.
7. Once samples are assembled, place container inside the incubator(s) at test temperature(s)
until your scheduled lab session.
During the lab:
1. Observe corroded coupon. Note the physical appearance of the coupon such as localized
pitting, discoloration, or surface film. Also, note if the test media has changed colour or has
solids suspended.
2. Record the date and time of submergence and initial sample mass, as well as, the current date
and time.
3. Remove sample from container, rinse with DI H2O and place in the drying oven for 30
minutes or until sample is completely dry. Try not to dislodge any corrosion product when
washing. Record weight and compare to its initial mass prior to submergence. Observe
surface under stereomicroscope on second bench in DWE 1518 and record observations.
4. Scour sample surface with cleaning pad to remove corrosion product taking care not to
remove the base metal. Rinse with deionized water and return to oven to dry. Reweigh
cleaned dry coupon and again compare to initial mass.
5. Determine weight lost over time due to corrosion for each sample.
60
Table 4-1: Preselected Corrosion Conditions to Test in Part D Immersion Tests

Coupons are suspended using fishing line in 250 mL sample bottles filled with the test media.
Jar #
Sample Coupon
Material
Solution Composition
and Concentration
Temperature
Full
or
Submerged
Half
N2 purged?
Mild
0.5 M HCl
25
Fully Submerged
No
Galvanized
0.5 M HCl
25
Fully Submerged
No
Mild
0.5 M NaCl
25
Fully Submerged
No
Galvanized
0.5 M HCl
25
Fully Submerged
No
Mild
0.5 M NaOH
25
Fully Submerged
No
Galvanized
0.5 M NaOH
25
Fully Submerged
No
Mild
0.5 M HCl
40
Fully Submerged
Yes
Galvanized
0.5 M NaCl
40
Fully Submerged
Yes
Mild
0.5 M HCl
40
Half-submerged
No
10
Mild
0.5 M NaCl
40
Half-submerged
No
11
Mild
0.1 M HCl
40
Fully Submerged
No
12
Mild
0.5 M HCl
40
Fully Submerged
No
13
Mild
0.1 M NaCl
40
Fully Submerged
No
14
Mild
0.5 M NaCl
40
Fully Submerged
No
15
Mild
0.1 M NaOH
40
Fully Submerged
No
16
Mild
0.5 M NaOH
40
Fully Submerged
No
17
Galvanized
0.1 M HCl
40
Fully Submerged
No
18
Galvanized
0.5 M HCl
40
Fully Submerged
No
19
Galvanized
0.1 M NaCl
40
Fully Submerged
No
20
Galvanized
0.5 M NaCl
40
Fully Submerged
No
21
Galvanized
0.1 M NaOH
40
Fully Submerged
No
22
Galvanized
0.5 M NaOH
40
Fully Submerged
No
Other options for test conditions include using Basic Media (NaOH or NH4OH), other Acidic
media (diluted H2SO4, H3PO4), Simulated media (e.g. bioreactor mixture, dilute acetic acid,
etc.), painted coatings or wax coatings.
Other metals available to test include: copper, stainless steel, and aluminium.
61
Table 4-2: Approximate times for Electrochemical Corrosion Tests

Procedure
Time
Needed
SAMPLE PREP: Measuring and waxing sample

couple for plating
5 min
Left-side
Part B: CoZn coating

Cyclic voltammetry scan & Co-Zn plating of mild
steel using chronoamperometry
15 min
Left-side
PRE-PART C: N2 purging before corrosion testing
25-30 min
Benchtop
PRE-PART C:
15-20 min
Either
potentiostat
PART C: EIS must be done before LPR on a

sample
Set-up and running of an EIS scan with .65
potentiostat with FRA function
10-20 min
Right-side
PART C: LPR must be done before Tafel test

on a sample
10-15 min
Either
potentiostat
35-45 min
Either
potentiostat
Consider to do Part D while

waiting
benchtop
Can be done while awaiting results

of electrochemical tests
Equilibration of sample in corrosion media
Station to Use
NOTES
Remove sample from plating

solution and rinse with DI H2O.
Place in 1L beaker of solution with
carbon electrodes & reference.
Start inert gas purge (2 sets of 10
min) then leave sitting until
finished corrosion test on plain
steel. Continue with Part C.
Set-up and running of an LPR scan

PART C: Tafel last corrosion test to perform on
a given sample
Set-up and running of a Tafel scan
PART D: Immersion Tests
20 min
62

1. Show the red-ox reactions occurring for the corrosion of your samples in your chosen test
media.
2. Prove that equations 4-2 and 4-4 are derived from Faradays Law.
3. What is the equivalent weight and density of the material to be tested (i.e. material chosen for
Part D: mild steel, copper, aluminum, stainless steel or galvanized (i.e. zn-coated) steel)?
4. Find a reference for the corrosion rate of your test material(s) in the chosen test media (or
similar) between 20-40 C (HINT: many journal articles related to the testing of corrosion
protection strategies will compare to corrosion rate of an untreated metal)?
5. What is passivation in the corrosion process and how does it affect the corrosion rate?
6. Describe the types of corrosion that can occur and the environmental conditions that lead to
their occurrence. Can these phenomena be quantified by electrochemical testing techniques?
7. Give an example of how corrosion can affect a chemical engineering industry.
8. Briefly describe two corrosion control techniques used in a chemical engineering field.
DATA ANALYSIS:
9. Estimate the corrosion rate of your samples in your test media from the Rp values given by
EIS and LPR techniques and the icorr values from Tafel plots.
10. Determine the corrosion rate of the immersed samples (in non-scoured and scoured forms).
Compare and discuss factor tested.
11. Compare your measured corrosion rates to values found in literature. Which analytical
technique used in Lab 4 most closely matches the literature value? What factors might make
this technique better than the others tested?
12. Describe the types of corrosion (e.g. general, pitting, crevice, etc) that can occur and the
environmental conditions that lead to their occurrence. Can these phenomena be quantified
by electrochemical testing techniques? Is the immersion testing technique sufficient to
quantify their contribution to corrosion rates?
13. Describe the potential cost of corrosion to a chemical engineering industry.
14. Briefly describe three corrosion control techniques used.
63
REFERENCES:
ASTM G1-03, Standard Practice for Preparing , Cleaning, and Evaluating Corrosion Test
Specimens, Pennsylvania:ASTM International (2011), pp9.
ASTM G3-89, Standard Practice for Conventions Applicable to Electrochemical Measurements
in Corrosion Testing, Pennsylvania:ASTM International (2010), pp9.
ASTM G31-72, Standard Practice for Laboratory Immersion Corrosion Testing of Metals,
Pennsylvania:ASTM International (2004), pp9.
ASTM G102-89, Standard Practice for Laboratory Calculation of Corrosion Rates and Related
Information from Electrochemical Measurements, Pennsylvania:ASTM Intl (2010), pp7.
ASTM G106-89, Standard Practice for Verification of Algorithm and Equipment for
Electrochemical Impedance Measurements, Pennsylvania:ASTM International (2010), pp11.
Baboian, R., Electrochemical Techniques for Corrosion Engineering, Houston:NACE (1986)
Fontana, M.G., Corrosion Engineering, New York:McGraw-Hill Book Company (1986).
Gamry Application Notes: Getting Started with Electrochemical Corrosion Measurement,
http://www.gamry.com/assets/Application-Notes/Getting-Started-with-ElectrochemicalCorrosion-Measurement.pdf (accessed Sept 21, 2012).
Guthrie, J., Battat, B. and Grethlein, C. Material Ease: Accelerated Corrosion Testing The
AMPTIAC Quarterly 6(3) p 11-15.
Jacobson,
G.A.
Corrosion
http://www.nace.org/Corrosion-101/
(accessed Sept 20, 2012).
A
Natural
but
Controllable
Process
NACE International The Corrosion Society 2003,
Kruger, Jerome, Encyclopedia of Electrochemistry, http://electrochem.cwru.edu/encycl/ The

Johns Hopkins University:Baltimore, MD 21218, USA April, 2001 (accessed Sept 15, 2012.)
Materials Evaluation and Engineering, Inc., Handbook of Analytical Methods for Materials:
Electrochemical Corrosion Testing, http://mee-inc.com/esca.html (accessed June 27, 2012).
Noor, E.A. and Al-Moubaraki, A.H., Corrosion behaviour of mild steel in hydrochloric acid
solutions, Int J Electrochem Sci 3(2008) pp 806-818.
Princeton Applied Research, Application Note AC-1: Basics of Electrochemical Impedance
Spectroscopy
Roberge,
Pierre
R.,
PhD,
P.Eng.,
Corrosion
Dcotors
http://corrosiondoctors.org/Pollution/bhopal.htm Kingston Technical Software:2012 (accessed Sept 15, 2012).
Vazquez-Arenas, J and Pritzker, M, Steady-State model for anomalous Co-Ni electrodeposition
in sulfate solutions in Electrochemica Acta 66 (2012) pp139-150.
64
EXPERIMENTS 5 and 6: COMSOL Tutorials
Labs ci, 5 and 6 are computer-based tutorials on COMSOL. Refer to materials posted in Lab 5
and Lab 6 folder on LEARN. Read over assignment and prepare any background material
needed before coming to the tutorial. The TA will inform you of the submission due date.
Contact your TA for further information.
COMSOL
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CHE 391

CHEMICAL ENGINEERING LABORATORY 4

DEPARTMENT OF CHEMICAL ENGINEERING

To assist in the understanding of some basic principles of chemical engineering through

To help develop skills in experimentation, data analysis and interpretation of results.

To practice in the art of writing effective engineering reports.

General Lab Info

Infringing unreasonably on the work of other members of the University community

Cheating on examinations, assignments, work-term reports, or any other work used to

Please note that Improper Collaboration or Inappropriate Collaboration is an academic offence.

General Lab Info

Read the Material Safety Data Sheets (MSDS) prior to experiment.

Keep chemical bottles closed tightly when not in use.

Dispose of any broken glass in the bucket labelled Broken Glass.

Make sure to know the location of the following:

First aid kit

FOOD and BEVERAGES ARE STRICTLY PROHIBITED FROM THE LAB

General Lab Info

Theoretical principles involved in the experiment.

Type and amount of data to be recorded.

General Lab Info

Statement of the objective.

Equations to be used in calculation of results.

Possible hazards to be encountered in the experiment and safety precautions to be taken.

Blank datasheet with appropriate headings (bring a copy to lab).

Answers to Prelab Report Questions from lab manual.

SAFETY ASSESSMENT CHECKLIST

General Lab Info

Proper handling of chemicals

Why the experiment was performed.

What data were obtained, and

Your interpretation of the data

The Memo Report should include the following:

Name of the University and Department.

Course number and name.

Experiment number and title

Date experiment was performed.

To whom and the date that the report was submitted.

General Lab Info

General background information relating to the experiment.

Brief statement of the objective.

Overview of the theoretical foundation of the experiment.

Identify how equation(s) from theory section will be applied.

Include a labeled sketch or schematic of the experimental set-up.

State all modifications made to the procedure.

General Lab Info

Observations and Results

Use significant digits. Remember to include units.

General Lab Info

General Lab Info

Propagation of Error Equations

y k k1a k 2b k3c ...

Addition and Subtraction

Multiplication and Division

k1a2 k2b2 k3c2 ...

General Lab Info

where (xi,yi) are the individual data points.

The standard deviation of the y-intercept, sb, is given by:

Assessing Quality of Fitted Data

Tables and Figures

General Lab Info

Microbial Growth Curves

Optical Density (ABS)