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ChE391 LabManual F15
ChE391 LabManual F15
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
PRELAB REPORT QUESTIONS: ...........................................................................................46
REPORT QUESTIONS: ...........................................................................................................46
EXPERIMENT 4: Corrosion Studies .......................................................................................48
PRELAB REPORT QUESTIONS: ...........................................................................................63
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:
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:
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.
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.
All hazardous wastes must be emptied into the appropriate waste containers. Read waste
labels before disposing into any receptacle. Check compatibility first.
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.
Clean up work area. Remove lab gloves and wash hands before leaving.
Fire extinguisher
Safety shower
Fire alarm
Telephone
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:
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.
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)
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)
4)
5)
6)
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
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:
Title Page
Group number and names all the members of the group contributing to the report.
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)
Significance of the data obtained to Chemical Engineering (i.e. current and future
applications).
Theoretical Principles
This section should include:
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
6)
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)
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.
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
s
n
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
N 2
S yy
yi2
yi 2
N
10
Use the following equation to find the standard deviation of the slope, sm:
sm sr / S xx
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.
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:
Bacillus subtilis
2.500
Streptococcus faecalis
2.000
1.500
1.000
0.500
0.000
0
100
200
300
400
500
600
12
7)
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.
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.
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.
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:
Sample calculations
Material essential for understanding the report must remain in the body of the report.
15
1 page
Introduction
1-2 pages
Theoretical principles
1-2 pages
Experimental
1 page
Observation of results
1-2 pages
2-3 pages
1 page
References
page
Appendices
2+ pages
16
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)
(1-1)
(1-2)
(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.
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)
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)
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)
(1-8)
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
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:
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.
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
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
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
where
(2-4)
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
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
LAB 2: Voltammetry
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)
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.
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
ED 1101 rotator with a 2mm diameter platinum disk working electrode at the tip of
the rotator.
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
LAB 2: Voltammetry
34
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
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.
38
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)
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
39
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)
40
Voltage
OCV
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).
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)
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.
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
Motorized Fan
Flow Controller
Electrical circuit
To Exhaust
Knock Out
Drum
Gas Lines
43
MODE
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.
44
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
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%?
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
47
/ =
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)
for an alloy.
(4-3)
) = 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
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)
(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
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)
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:
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
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:
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
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
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
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.
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
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
Time
Needed
5 min
Left-side
15 min
Left-side
25-30 min
Benchtop
PRE-PART C:
15-20 min
Either
potentiostat
10-20 min
Right-side
10-15 min
Either
potentiostat
35-45 min
Either
potentiostat
benchtop
Station to Use
NOTES
20 min
62
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,
64
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
65