Table of contents 1

Table of contents
TABLE OF CONTENTS......................................................................................................................................1
1. PRINCIPLES OF OPERATION...................................................................................................................5
1.1 PREFACE............................................................................................................................................................... 5
1.2 THE CONCEPT...................................................................................................................................................... 6
2. GETTING STARTED WITH GPES ............................................................................................................9
2.1 RECORDING A CYCLIC VOLTAMMOGRAM WITH THE DUMMY CELL........................................................... 10
2.2 THE USE OF THE MANUAL CONTROL WINDOW............................................................................................. 13
2.3 DATA MANIPULATION OF A CYCLIC VOLTAMMOGRAM............................................................................... 14
2.4 CALCULATION OF A CORROSION RATE. ......................................................................................................... 17
2.5 NOISE REDUCTION............................................................................................................................................ 19
2.6 DATA ANALYSIS WITH CHRONO-AMPEROMETRY. ....................................................................................... 20
2.7 DATA ANALYSIS WITH DIFFERENTIAL PULSE VOLTAMMETRY. .................................................................. 21
2.8 ANALYSIS OF ELECTRO CHEMICAL NOISE.................................................................................................... 22
2.9 IR-COMPENSATION........................................................................................................................................... 23
2.10 DETECTION OF NOISE PROBLEMS.................................................................................................................. 24
3. THE GPES WINDOWS.................................................................................................................................27
3.1 GPES MANAGER WINDOW ............................................................................................................................. 27
File menu .............................................................................................................................................................27
Method .................................................................................................................................................................32
Utilities.................................................................................................................................................................32
Project ..................................................................................................................................................................43
Options.................................................................................................................................................................51
Window.................................................................................................................................................................52
Help.......................................................................................................................................................................52
Tool bar................................................................................................................................................................52
3.2 STATUS BAR....................................................................................................................................................... 53
3.3 MANUAL CONTROL WINDOW.......................................................................................................................... 53
Current range .....................................................................................................................................................54
Settings.................................................................................................................................................................54
Potential...............................................................................................................................................................55
Noise meters ........................................................................................................................................................55
iR-compensation .................................................................................................................................................55
Integrator.............................................................................................................................................................56
Filter panel ..........................................................................................................................................................56
3.4 DATA PRESENTATION WINDOW ...................................................................................................................... 56
File........................................................................................................................................................................57
Copy......................................................................................................................................................................58
Plot........................................................................................................................................................................58
Analysis................................................................................................................................................................60
Edit data...............................................................................................................................................................60
Work scan ............................................................................................................................................................60
Work potential ....................................................................................................................................................60
Editing graphical items and viewing data .....................................................................................................60
3.5 EDIT PROCEDURE WINDOW............................................................................................................................. 63
3.6 ANALYSIS RESULTS WINDOW.......................................................................................................................... 64
4. ANALYSIS OF MEASURED DATA..........................................................................................................65
4.1 PEAK SEARCH.................................................................................................................................................... 65
4.2 CHRONOAMPEROMETRIC PLOT ....................................................................................................................... 68
4.3 CHRONOCOULOMETRIC PLOT ......................................................................................................................... 69
4.4 LINEAR REGRESSION......................................................................................................................................... 69
4.5 INTEGRATE BETWEEN MARKERS..................................................................................................................... 70
2 User Manual GPES for Windows Version 4.9
4.6 WAVE LOG ANALYSIS....................................................................................................................................... 70
4.7 TAFEL SLOPE ANALYSIS................................................................................................................................... 71
4.8 CORROSION RATE............................................................................................................................................. 71
4.9 SPECTRAL NOISE ANALYSIS............................................................................................................................. 73
4.10 FIND MINIMUM AND MAXIMUM.................................................................................................................... 74
4.11 INTERPOLATE.................................................................................................................................................. 74
4.12 TRANSITION TIME ANALYSIS......................................................................................................................... 74
4.13 FIT AND SIMULATION..................................................................................................................................... 74
The simulation method ......................................................................................................................................75
The fitting method ..............................................................................................................................................75
Elements of the Fit and Simulation Window.................................................................................................76
Fitting and simulation step by step .................................................................................................................76
Fitting in more detail .........................................................................................................................................81
Fit and simulation error messages..................................................................................................................84
Descriptions of the models................................................................................................................................85
4.14 CURRENT DENSITY......................................................................................................................................... 95
4.15 WE2 VERSUS WE PLOT................................................................................................................................. 95
4.16 ENDPOINT COULOMETRIC TITRATION......................................................................................................... 95
5. EDITING OF MEASURED DATA.............................................................................................................97
5.1 SMOOTH............................................................................................................................................................. 97
5.2 CHANGE ALL POINTS........................................................................................................................................ 98
5.3 DELETE POINTS................................................................................................................................................. 98
5.4 BASELINE CORRECTION ................................................................................................................................... 98
5.5 SUBTRACT DISK FILE........................................................................................................................................ 99
5.6 SUBTRACTION OF SECOND SIGNAL FROM FIRST SIGNAL. ............................................................................ 99
5.7 DERIVATIVE....................................................................................................................................................... 99
5.8 INTEGRATE........................................................................................................................................................ 99
5.9 FOURIER TRANSFORM....................................................................................................................................100
5.10 CONVOLUTION TECHNIQUES.......................................................................................................................100
Detection of overlapping peaks.................................................................................................................... 102
Determination of formal potential and the number of electrons involved ............................................ 104
Irreversible homogeneous reaction consuming the product of the electrode process ........................ 105
Investigations of factors controlling the transport to the electrode....................................................... 106
Algorithms for convolution............................................................................................................................ 108
5.11 CONVOLUTION IN PRACTICE .......................................................................................................................109
5.12 IR DROP CORRECTION..................................................................................................................................110
APPENDIX I GPES DATA FILES............................................................................................................... 111
APPENDIX II DEFINITION OF PROCEDURE PARAMETERS..................................................... 113
APPENDIX III COMBINATION OF GPES AND FRA........................................................................ 127
APPENDIX IV MULTICHANNEL CONTROL...................................................................................... 129
Installation and test ........................................................................................................................................ 129
Program operation.......................................................................................................................................... 130
APPENDIX V TECHNICAL SPECIFICATIONS................................................................................... 133
Interface for mercury electrodes (IME, IME 303 and IME663)............................................................. 134
Burettes ............................................................................................................................................................. 134
Hardware specifications of optional modules............................................................................................ 134
SCAN-GEN: analog scan generator module.............................................................................................. 134
ADC750: dual channel fast ADC module ................................................................................................... 135
ECD: low current amplifier module ............................................................................................................ 135
ARRAY and BIPOT: (bipotentiostat) module............................................................................................. 135
FI20: filter and integrator module............................................................................................................... 135
BSTR10A: current booster for PGSTAT20 potentiostat/galvanostat..................................................... 135
Table of contents 3
INDEX................................................................................................................................................................... 137
Chapter 1 Principles of operation 5
1. Principles of operation
1.1 Preface
Autolab and the General Purpose Electrochemical System software (GPES) provide a
fully computer controlled electrochemical measurement system.
It can be used for different purposes, i.e.:
• general electrochemical research
• polarographic analysis in conjunction with a dropping or static mercury drop
electrode
• voltammetric analysis with solid electrodes, such as glassy carbon or rotating disk
electrodes
• research of electrochemical processes like plating, deposition and etching
• electrochemical corrosion measurements
• electrochemical detection in Flow Injection Analysis (FIA) and High Performance
Liquid Chromatography (HPLC).

The instrument is controlled by a personal computer equipped with an IBM/PC or AT
I/O expansion bus. All the Autolab configurations are supported by GPES:
• µAutolab or µAutolab Type II, the compact version of a standard Autolab with
potentiostat
• Autolab with potentiostat/galvanostat PGSTAT10/12/20/30/100 and other,
optional, modules.
The GPES combines the measurement of data and its subsequent analysis. GPES runs
under MS-Windows 95, 98 and NT. Its installation is described in the "Installation
and Diagnostics" guide.
The user should be familiar with MS-Windows.
The GPES program consists of two distinct parts i.e.:
• The user-interface, graphics and data-analysis software.
• The routines which perform all the communication with the Autolab instrument.
Both parts communicate via shared memory. The measurement tasks run with the
highest priority. All the spare time is left for MS-Windows applications.

Familiarisation with GPES is best obtained by experimenting. Most of the required
help which might be necessary to perform the measurements and the data analysis is
provided for by the on-line help within the program.

This manual concentrates more on explaining the general concepts and backgrounds
than on guiding the user through the program. Moreover, this manual tries to explain
the possibilities of GPES. The "Installation and Diagnostics" guide explains the
hardware aspects, the computer requirements and the installation.
6 User Manual GPES for Windows Version 4.9

1.2 The concept
The design of GPES Windows has been based on the following ideas:
• GPES should incorporate the facilities electrochemists need.
• The user should have full and easy control over the Autolab instrument via the
computer.
• 'How to perform experiments' should be easy and clear.
• Actions should require only a few clicks.
• The introduction learning period should be short.
• All important electrochemical techniques should be available.
• GPES should be a full and standard Windows application.
• Series of unattended experiments, using different techniques and/or procedures,
should be possible.
The GPES screen consists of several windows: one for manual control over the
potentiostat/galvanostat, one for data presentation and manipulation, one for entering
the experiment parameters and one for collecting results of data analysis. Surrounding
windows, menu options and tool bars give extra facilities like cell-diagnosis,
accessory control, Autolab configuration, access and data transfer to programs like
Excel and MS-Word.

The MS-Windows related terminology used in this manual is in agreement with the
standard as described in the book "The GUI Guide - international terminology for
Windows Interface" (Microsoft Press, Washington ISBN 1-55615-538-7). It is a good
book to become acquainted with the Windows vocabulary.

The following mouse conventions are used:
• Quickly pressing and releasing the mouse button is called "clicking". A click of
the left mouse button on a menu option, a button, an input item on the screen,
etceteras will result in an action.
• Clicking and holding down the left mouse button is called "dragging" and is used
for several purposes. You can focus on an item on the screen without an action,
you can drag a window when the mouse pointer is in its title bar. It can be used to
shrink or to enlarge a window when the mouse pointer is on the border of a
window. Finally, you can drag a scroll bar, a slider or a zoom-panel.
• A double-click of the left mouse button is used to perform particular actions.
Except for the standard uses in window actions, it is used to edit the graph in the
Data presentation window.
• A click of the right mouse button is used to open a zoom panel in the Data
presentation window or to shrink or enlarge the Graphics panel in the Setup
Template option in the Print menu window, which appears after selecting Print
from the File option in the GPES Manager window.
Chapter 1 Principles of operation 7
The following keyboard functions are supported:
• RETURN/ENTER key:
jump to next data input field;
select menu option; or
click button with focus.
• left and right arrow key:
move cursor in data input field.
• up and down arrow:
move up and down in potential/current level input in chronomethods; or
move up and down in a menu.
• ALT:
puts focus on the menu bar of the window with the focus;
typing a subsequent underlined character will move the cursor to the
corresponding menu item, a RETURN/ENTER will select the menu item.
• ESC: aborts the execution of the measurement procedure.
• F1: access Help.
• F4: plot rescale.
• F5: starts the execution of the measurement procedure.
• F6 and shift F6: change focus to the next window.

This manual does not describe the background of the electrochemical methods. We
would like to refer to the ‘Electrochemical methods’-manual and some excellent
textbooks:

• C.M.A. Brett and A.M.O. Oliveira Brett,
Electrochemistry
Oxford science publications ISBN 0-19-855388-9

• Allen J. Bard and Larry R. Faulkner,
Electrochemical Methods: Fundamentals and Applications
J. Wiley & Sons ISBN 0-471-05542-5

• R. Greef, R. Peat, L.M. Peter, D. Pletcher and J. Robinson,
Instrumental Methods in Electrochemistry
Ellis Horwood Limited ISBN 0-13-472093-8.
Chapter 2 Getting started with GPES 9
2. Getting started with GPES
In this chapter some basic examples are given to become familiar with GPES. The
possibilities and the options of the software are described. Some of the examples
contain a measurement with the Autolab dummy cell, so before you start with the first
example, please connect the dummy cell box to the cell cable by putting the banana
plug connector into the matching colour connector on the dummy cell. The red banana
plug should be connected to WE(a).
As soon as you start GPES, by clicking the icon in the Autolab application window,
you will see the standard layout of the GPES software, which consists of three
windows and two bars.
The two bars are:
• The GPES manager bar, with the menus and the tool buttons.
• The Status bar at the bottom of the screen, which contains the start and stop
buttons for measurement and displays the system messages.
Fig. 1 Default layout of GPES windows
10 User Manual GPES for Windows Version 4.9
The three windows are:
• The Edit procedure window, which specifies all the experimental parameters.
Changed parameters are automatically saved when leaving the software and will
appear as default parameters on the next occasion. For most of the techniques, this
window will consist of two pages.
• The Manual control window, which manually controls the settings of the
potentiostat/galvanostat.
• The Data presentation window, which gives a graphical display of the measured
data, and allows you to do data analysis and/or modification.
The options and possibilities of these three windows will be explained in detail in the
next chapter.
2.1 Recording a cyclic voltammogram with the dummy cell
1. Before starting with this (and with the other examples) please check the hardware
configuration of your system. You can do this by executing the hardware
configuration program. In the Autolab hardware configuration window, you can check
if all the modules in your instrument are also selected in the software, if so, you can
close this window by clicking ‘OK’. See also the Installation and diagnostics manual.
2. From the Method menu of the GPES manager bar, please select ‘Cyclic
voltammetry (staircase) Normal’.
3. Select ‘Open procedure’ from the File menu, and open the ‘testcv.icw’ from the
\autolab\testdata directory.
Fig. 2 The Open procedure window
Chapter 2 Getting started with GPES 11
4. In the Edit procedure window, you will now find all the measurement parameters.
By clicking ‘Start’ the program will start the dummy cell measurement. During the
measurement you can automatically rescale the curve in the Data presentation window
by typing F4 on your keyboard.
5. After the measurement is done, the curve should look like the curve in figure
‘Results of procedure TESTCV’, i.e. a straight line, if not, please consult the
“Installation and Diagnostics” guide in this manual.
6. In the Edit procedure window, please select ‘Number of scans’ and change the
value from 1 to 100. If you now press start again, the program will start to do 100
scans. You can always stop the measurement by using ‘Esc’ on your keyboard, or by
clicking the Abort button. Please do so after a few scans. After stopping, the Data
presentation window will show you the last scan. You can also select one of the
previous scans by using the Work scan option.
7. You are able to change some measurement parameters during the measurement by
using the Send option in the Edit procedure window. Please (re)start a measurement
with 100 scans and during the measurement change the ‘Scan rate’ from 0.1 V/s to 1
V/s. After clicking ‘Send’ the speed of the measurement will increase. You can again
stop the measurement by using the ‘Esc’ button.
Fig. 3 Results of procedure TESTCV
12 User Manual GPES for Windows Version 4.9
Fig. 4 Edit procedure window
Chapter 2 Getting started with GPES 13
8. After finishing a measurement, the program allows you to save more than one scan
by selecting ‘Save scan’ and then selecting a scan that you would like to save. For the
following scans you want to save, please select ‘Save scan as’. The ‘Save data buffer’
option saves all the scans that the PC has in its memory.
2.2 The use of the Manual control window
The Manual control window allows you to control the potentiostat manually, instead
of via a measurement procedure. With the dummy cell still connected to the cell
cable, and the procedure “testcv” loaded, you can try the following:
1. Clicking the highest current range (10 mA for a PGSTAT10/µAutolab, 100 mA for
a PGSTAT12/100 and 1 A for a PGSTAT20/30) results in the selection of all current
ranges except the 100nA range. This allows automatic current ranging using all the
‘checked’ ranges, during the execution of a measurement procedure. The green circle
indicates which current range is active. Check this by clicking on one of the circles
and see what happens on the front panel of the potentiostat.
2. The cell can be switched on and off manually, please click the cell on/off button,
and check the result on the potentiostat.
3. By using the slider below ‘Potential’ it is possible to set a potential value. Make
sure that the cell is ‘on’ and use the slider to set a potential of 1 V. In the Manual
control window the current and the potential are given. By clicking the Clock on/off
button the program will start making a graph of the current versus time. Switch the
clock off again, and use the window below the slider to set a potential of 0 V. Switch
the cell off again.
Fig. 5 Manual control window: the appearance depends on the Autolab configuration
14 User Manual GPES for Windows Version 4.9
2.3 Data manipulation of a cyclic voltammogram.
1. Choose ‘File’ and ‘Load scan’ and load the datafile ‘democv01’ in the
\autolab\testdata directory. Enlarge the graph by clicking the maximise button on the
Data presentation window.
2. Double click the curve in the Data presentation window. A plot parameter window
appears, in which you can change the colour of the curve, or change from a ‘line’
display to a ‘scattered’ display.
Please try this by changing the colour and the style of the line. Select the settings that
you feel are the most suitable for this curve.
3. With the peak search option, the software allows you to determine all peak
parameters of the CV. Choose ‘Analysis’ and ‘Peak search’. When the Peak search
window appears, click the Options>> button, the program now allows you to set a
number of options. Start by selecting ‘Curve cursor’ and ‘Lin. front baseline’, click
close and press the search button in the Peak search window. You are now asked to
set two markers for a baseline in front of the peak, please do so and press OK. The
program shows the result of the peak search in the ‘Peak search results window’ and
shows the peak in the curve.
4. Please repeat the above after selecting ‘Automatic’ and ‘Linear baseline’ in the
Options>> window. Click search, and have a look at the results.
5. Close the Peak search results window and choose ‘Window’ and ‘Analysis results’
from the GPES manager bar. In this window all the data analysis results are kept as
long as you do not exit the GPES software. Please check under ‘File’ that you are able
to ‘Save’, ‘Print’ or ‘Clear’ the results. Close the Analysis results window.
6. Under ‘Edit data’ choose the option ‘Subtract disk file’. Select the same file that
has been loaded: ‘democv01’. Note that, as might be expected, the result is a
horizontal line at I=0. By selecting ‘Plot’ and ‘Resume’ the original curve is retrieved.
This option always allows you to get back to the original curve after editing or
analysing the data.
7. Under ‘Edit data’ choose the option ‘Baseline correction’. Select ‘Linear baseline’
at the settings, and press ‘Set markers’. You are now asked to set two markers for the
baseline you want to correct. Set the markers on the horizontal part of the forward
curve before the peak and press ‘OK’. Note that the Data presentation window now
shows you both the original and the corrected curve (in black). By clicking OK you
accept the corrected curve and the original is removed from the window. Using the
‘Resume’ option, however, gives you back the original.
8. The option ‘Wave Log analysis’ under ‘Analysis’ allows you to determine the half-
wave potential and the number of electrons for S-shaped voltammogram, for example
a Normal pulse voltammogram. The file ‘democv01’ may be transferred to an S-
shaped curve by choosing ‘Edit data’, ‘Convolution’ and ‘Time semi-integral’. For
more details on the convolution techniques, please read the relevant chapter in this
manual.
Chapter 2 Getting started with GPES 15
After selecting ‘Wave log analysis’, you are asked to set markers for the baseline and
the limiting current line for the forward (or black) curve. Please set two markers for
the baseline and press OK and do the same for the limiting line. Now the Wave log
analysis window gives you a value for the half-wave potential and the height of the
curve. By clicking ‘Continue’ the curve transforms and you are again asked to set two
markers. After doing this and clicking OK, you get the results for the analysis in the
Wave log analysis window.
Close this window and choose ‘Plot’ and ‘Resume’.
Fig. 6 Results of time semi-integral convolution
16 User Manual GPES for Windows Version 4.9
9. From the GPES manager bar, choose ‘File’ and ‘Print’, the Print menu allows you
to print the measured data, one or more of the windows, and a Template. Select
‘Template’ and ‘Set-up template’. With this option you can print a measured curve
together with the most important measurement parameters on one sheet. With ‘Insert’
and ‘Field’ you can add or remove fields with parameters from the template. You can
also drag fields around to put them on another place on the sheet. By clicking ‘File’
and ‘Print preview’ the values for the parameters and the curve are shown. The size of
the curve may be changed by clicking it with the right mouse button and then moving
your mouse (without pressing a button!). The way in which the parameters are
displayed may be changed by double clicking a field and choosing for example
‘scientific’ and then setting a precision. (Precision -1, means that the value is printed
with the format used in the Edit procedure window). Close the Template window.
Fig. 7 Wave log analysis option
Chapter 2 Getting started with GPES 17
2.4 Calculation of a corrosion rate.
Before you start, make sure that the method is still Cyclic Voltammetry, Normal.
1. Load the datafile ‘democv02’ from the \autolab\testdata directory.
2. In the Data presentation window, double click the vertical axis. The vertical axis
window appears.
Fig. 8 Results of printing of the template
18 User Manual GPES for Windows Version 4.9
3. Change the scale from the axis from linear to Lg, i.e. 10log. Please note that you
are also able to change the range of the axis and the position of the intercept of the
axis in this window. Close the window, and note the change of the curve.
4. From the Analysis menu, choose ‘Corrosion rate’. The Corrosion rate window
appears.
Fig. 8a Vertical axis window
Chapter 2 Getting started with GPES 19
In this window the program shows a first value for the corrosion potential, as well as
for the polarisation resistance. Furthermore you can specify values for the surface
area, the equivalent weight and the density of the material you are using. For this
example you can set these values to 1. Click the Tafel slopes button. You are asked to
set markers on the anodic branch and on the cathodic branch. After you have done so,
the Corrosion rate window appears, with a list of parameters, among which the
corrosion rate in mm/year. By clicking the Start fit button, the software will adjust the
parameters until a best fit of the original curve is found. This fitted curve is shown in
black, and the final values for the parameters are given.
Click close and transform the vertical axis of the curve back to linear.
2.5 Noise reduction
Make sure that the method is Cyclic voltammetry (staircase), normal.
1. Load the datafile ‘democv04’ from the \autolab\testdata directory.
2. From the Edit data menu, choose the Smooth option. The Smooth window appears,
and gives you the possibility to choose from different smoothing methods. Choose
FFT (Fast Fourier Transform) with linear graph. Click the Smooth button, the curve is
now transformed to the frequency spectrum and a marker window appears. You are
asked to set one marker for the cut-off frequency: set this marker at ca 7 Hz and press
OK. All frequencies above 7 Hz will now be filtered out. Please note that the 7 Hz is
Fig. 9 Corrosion rate analysis
20 User Manual GPES for Windows Version 4.9
not the frequency of the potential or current noise. The scaling is arbitrary. Note the
smoothed curve in black, with OK you accept the curve, and the noisy original will
disappear.
2.6 Data analysis with Chrono-amperometry.
From the Method menu on the GPES manager bar, choose Chrono-amperometry
(interval time < 0.1 s).
1. Load the datafile ‘democx01’ from the \autolab\testdata directory.
2. The curve shown is the result of a double potential step experiment. To do data
analysis it is more convenient to choose just one of both potential levels at a time. To
do so, from the Plot menu in the Data presentation window, choose select potential,
and select the -0.7 V level. The data shown now are the result of the selected potential
step.
3. In Chrono-amperometry the current is proportional to 1/Square root of time. In
order to visualise this, please double click the horizontal axis and change the scale to
1/square root. The curve is now linear. From the Analysis menu, choose ‘Linear
regression’ and set two markers for the beginning and the end of the linear regression.
The Linear regression window now gives you the results. From the slope of this line,
it is possible to calculate for example the diffusion coefficient.
Fig. 10 Data smoothing using FFT
Chapter 2 Getting started with GPES 21
4. From the Plot menu choose ‘Resume’ and the original curve will reappear.
2.7 Data analysis with differential pulse voltammetry.
From the Method menu, choose voltammetric analysis and then Differential Pulse.
1. Load the datafile ‘demoea01’ from the \autolab\testdata directory.
2. From the Analysis menu choose Peak Search. Under the options, choose the
automatic search, close the Options window and press the search button. The Peak
search results window will now show parameters for four peaks. For the first three the
results are reasonable, but for the peak at the highest potential the linear baseline is
not the best option.
3. With the Set window option under the Plot menu, you are able to extract the last
peak from the curve. Set the markers so that only the last peak is visible. Now there
are two options (please start each option after setting the window around the last
peak):
a. From the Edit data menu choose ‘baseline correction’ and select the polynomial
basecurve. Click the set markers button and set the markers for the baseline (one on
each side of the peak). After ‘OK’, the corrected (black) curve is shown with a more
horizontal baseline. You can now use the automatic peak search option to find the
peak parameters. Please do so and check the difference with the automatic search on
the non-corrected curve by opening the Analysis results window.
Fig. 11 Transition time analysis
22 User Manual GPES for Windows Version 4.9
b. From the Analysis menu, choose the Peak search option. Under options, choose
‘curve cursor’ with a polynomial baseline. After pressing the Search button you are
asked to set two markers for the baseline, please do so. Now the Peak search results
window will give you the parameters of this search. Please open the Analysis results
window to compare this option with the result of option a. As should be expected, the
results of these two options are very similar. Close the Analysis results window.
2.8 Analysis of Electro Chemical Noise
From the Method menu, choose Electrochemical noise and then Transient.
1. Load the datafile ‘demoecn1’ from the \autolab\testdata folder.
2. From the Analysis menu choose Spectral noise analysis.
3. Choose a Hanning Window, check subtract offset, and the Result type: E(f) and
I(f).
4. By clicking OK, a spectral analysis is performed on the Potential and the Current
components of the noise signal.
Fig. 12 Example of polynomial baseline correction
Chapter 2 Getting started with GPES 23
2.9 iR-compensation
When your Autolab is equipped with a PGSTAT12/20/30/100, you are able to
measure the uncompensated resistance in your electrochemical cell and to compensate
for this resistance. The GPES software provides two methods to do this: iR Interrupt
and Positive feedback (see Chapter 3 for more details). This example is meant to
make you more familiar with both options. Before starting, please connect the WE
connector of the cell cable to WE(c) on the dummy cell.
I-interrupt
a. Under the Utilities option in the GPES window, please choose I-interrupt, the iR-
compensation window will appear. In the manual control window please type 1.0 V in
the potential panel, and check the 1 mA Current range checkbox. You can now switch
the cell on, by clicking the button in manual control.
b. In the iR-compensation window, please give the following values: Duration of
interrupt =0.001 s; First marker =1; Second marker =2. The current will now be
interrupted for 0.001 s, and the decay of the potential in time is measured. Please click
the Measure button. After a short time, in the result panel a value of about 100 should
appear. When you want to compensate for 90% of this value (Never use 100% of the
measured value!), you can do this by typing the value in the iR-compensation panel in
the Manual Control window. After clicking the iR-compensation button the program
will automatically compensate the measurements for the value given.
Fig.13 Example Electrochemical Noise analysis
24 User Manual GPES for Windows Version 4.9
Positive feedback
With positive feedback you can give in values for the resistance yourself, and you can
see when the current starts to oscillate, i.e. when you have overcompensated the
resistance.
a. Please choose the Positive feedback option in the Utilities menu, an iR-
compensation will appear in which you can type the following values:
Potential pulse = 0.1 V; Duration = 0.01 s. Connect dummy cell (C) and put the
current range to 1 mA. After pressing ‘start’ the program will start applying potential
pulses. By giving different values in the iR-compensation panel and watching the
change in the i-t curve you can check how high the uncompensated resistance is.
Please check the change after typing a value of “95”. Now do the same after typing
“130”, you will see oscillations appearing, you have now done overcompensation.
Please note that if you reach a value where the current starts to oscillate, you should
use 90% of this value during your measurements.
2.10 Detection of noise problems
In the GPES software an option is available to detect noise problems. Since noise is
encountered frequently in electrochemical research, it is useful to become familiar
with the detection of problems caused by noise. In GPES, the Check Cell option under
the Utilities menu, provides the option to detect noise.
Fig. 14 Effect of overcompensation of the iR-drop
Chapter 2 Getting started with GPES 25
Please connect the red banana plug to the WE(c) connection on the dummy cell. In
order to generate some noise, please connect an unshielded cable between the blue
banana plug and the RE connector on the dummy cell, and place part of this
unshielded cable over the monitor of your computer. In manual control please check
the 100 nA Current range checkbox.
After selecting the Check Cell option, the Check Cell window appears. After pressing
the measure button, the program will start checking the electrode connections, and
will then measure the noise level. With the unshielded cable over the monitor, you
will see the current levels in red and the software will give you a warning that the
noise level is too high. Please redo the measurement without the unshielded cable.
You will now see the current levels in black indicating that the noise level is
acceptable.
Please use this option if you have doubts about the noise level in your system.
Chapter 3 The GPES windows 27
3. The GPES windows
3.1 GPES Manager window
The title bar of the GPES Manager window contains several options i.e. File, Method,
Utilities, Project, Window, Help.
File menu
This menu contains options which are usually present in Windows programs.
Open procedure
A procedure is a file containing all the experimental parameters. It contains
measurement parameters, potentiostat/galvanostat settings, and graphics display
values. The extension of the file which is mentioned in the "File name" field should
not be changed.
The directory in which the procedure file is stored is called the procedure directory.
When the directory in the Open procedure window is changed and a procedure file is
Fig. 15 The File menu
28 User Manual GPES for Windows Version 4.9
successfully loaded from this new directory, this new directory becomes the new
default procedure directory.
Normally only files with the current method are shown in the load window. By
selecting Show all GPES files in File dialog box (Utility menu), all procedures are
displayed and can be selected.
It is also possible to load procedure files from the DOS version GPES 3. If this is
required, click the "List Files of Type" drop down button and select the proper option.
It is also possible to load a procedure from other methods/techniques than the current
one. The program will change automatically to the method described in the selected
procedure. See the Dropdown menu called "List Files of Type".
Save procedure
This option will save a procedure under its current name in the procedure directory.
Save procedure as
Allows to store a procedure on disk in the procedure directory with a different name
as the current one. Please use the default file extension as mentioned in "File name"
field or omit the extension. In the latter case the correct extension will be added.
Print
The Print menu window appears after selecting this option. The Print select panel
allows to choose between the print-out of the measured data, a dump of a window,
and the print of a template consisting of a user-defined set of measurement parameters
and a copy that can be scaled of the current graph.
The Setup template option allows to edit the template. The parameters on the template
can be selected using the Insert menu option.
The parameter position can be dragged over the screen with the mouse. The comment
text as well as the attribute of the item with focus can be edited by double clicking on
it. If you have changed the template according to your requirements, please do not
forget to save it (see corresponding File option).
The rectangle in the template is the Graph frame. The focus is on the frame after a
click in the frame. If the left hand mouse button is pressed down within this frame it
can be dragged.
If the right hand button is clicked, the lower right corner of the frame jumps to the
mouse cursor and is subsequently attached to the mouse cursor. This allows you to
adjust the frame size. After a click with the left hand mouse button the attachment is
broken. The appearance of the graph in the print out of the template depends on the
actual size and shape of the Data presentation window.
The print of the template will cover half a page if printed in ‘portrait’ and a full page
if printed in ‘landscape’. See print setup. On the print-out the parameter values also
appear. The print-out can also be previewed (see corresponding File option).
Load data (sometimes called Load scan)
Allows to load previously measured data from disk.
It is also possible to load data files from the DOS version GPES3 or data files of other
methods or techniques than the current one. If this is required, click the "List Files of
Type" drop down button and select the proper option. You can select multiple files at
a time by using <Shift> or <Control>, combined with the mouse action. This allows
Chapter 3 The GPES windows 29
you to load the work data as well as 10 overlay files. After this action it is possible to
exchange the work data by clicking ‘Work scan’ on the Data presentation window.
Save data
Store the most recent measured data under the current procedure name on disk. In
case of cyclic and linear sweep voltammetry the user is asked to select a scan number
first. The data are stored in the so-called data directory, together with the
corresponding procedure parameters.
When more than one scan is recorded in Cyclic voltammetry, it is possible to save the
previously measured scan while the measurement is going on. This option is available
at the File menu on the Data presentation window. The option is called ‘Quick save of
previous scan’. This option can also be activated by typing ‘SAVE’ on the keyboard.
The path and the name of the file can be specified on page two of the Edit procedure
window (‘Direct output filename’). The last five characters of the file name will be
used as the scan number.
Please note: These files can be overwritten during another measurement session with
the same procedure.
Save scan as
This options allows to save a scan in Cyclic and Linear sweep voltammetry.
First, if more than one scan is recorded, a menu is shown from which the user can
select the number of the scan to be saved.
Save data as
Similar as the previous option but the name of the file name containing the data can
be specified. For cyclic and linear sweep voltammetry a submenu is presented from
which the required data format can be selected.
Save data buffer as
This option can only be selected for cyclic and linear sweep voltammetry. The whole
data memory is dumped on disk in binary format in the data directory under a user
specified procedure name, together with the corresponding procedure parameters.
This is the only save option which stores all relevant data. If a buffer is reloaded, all
data treatment and save option are open for use.
30 User Manual GPES for Windows Version 4.9
Export to scanno. vs Q+,Q- file
When a cyclic voltammogram is observed with more than one scan it is possible to
save the observed cathodic and anodic charge data against the scan number. The file,
with the extension .Q&Q, has the following layout:
ScanNr Q+ (C) Q-(C)
1 1.697E-07 -2.351E-07
2 1.670E-07 -2.365E-07
3 1.671E-07 -2.363E-07
4 1.672E-07 -2.357E-07
5 1.674E-07 -2.356E-07
6 1.675E-07 -2.361E-07
7 1.669E-07 -2.356E-07
8 1.667E-07 -2.358E-07
9 1.674E-07 -2.364E-07
10 1.675E-07 -2.355E-07
.
.
Export Chrono data
This option is only available for cyclic voltammetry. It allows to store the chrono-
amperometric data which are recorded at the vertex potential. See the input
parameters under the heading "Chrono-amperometry" in the Edit procedure window
Export to BAS-DigiSim data
This option is only available for cyclic voltammetry. Save the current active in such a
format that it can be read by the program DigiSim. This is an ASCII-file with the
default extension .TXT.
Export data buffer to text file
This option can only be selected for cyclic and linear sweep voltammetry. As in the
previous option the whole data memory is stored on disk, but in this case in a readable
ASCII-format. The file consists of several columns. The first column is the potential
(or current in galvanostat mode) and the other columns are the measured currents for
subsequent scans (potentials in galvanostat mode). The first row indicates the scan
number. The separator c.q. delimiter between two columns is a TAB character. The
default extension of the file is .TXT. They are meant to be read by MS-Excel, they
cannot be read by GPES. In order to create a nice and properly columned file, each
scan should have the same number of points. This means that the Reverse button
should not have been clicked. Also an interruption of a scan by pressing ESC should
be avoided.
Chapter 3 The GPES windows 31
The layout of the text file saved with the ‘Export data buffer to text file’ also contains
some important procedure parameters:
Date: 26-May-97
Time: 14:12:17
Exp. Conditions:
Linear sweep voltammetry
Begin potential (V) = .0000
End potential (V) = 1.0000
Step potential (V) = .02441
Scan rate (V/s) = .99992
Equilibration time (s) = 10
Number of Data Points = 42
Potential Scan 1 Scan 2
0.024414 -1.191406E-07 -1.232910E-07
.
.
Load data buffer
This option can only be selected for data from cyclic and linear sweep voltammetry.
Allows to load the complete set of scans (see Save data buffer). This is only possible
if in the start-up menu "Autolab applications" has been chosen.
Delete files
This option allows to delete procedures and measured data files. The File window
shows only the procedure files. A selected procedure will be deleted from disk
together with corresponding data files. A delete action can not be undone.
Exit
The GPES window will be closed and the program is exited. The program settings are
stored on disk.
32 User Manual GPES for Windows Version 4.9
Method
The required electrochemical technique can be selected with the Method menu The
type of experiment parameters in the Edit procedure window will change depending
on the selected technique.
For more information see the manual section on “Electrochemical methods”.
The settings in the File menu and the data analysis also depend on the type of
technique. More details about the available methods can be found in a separate
chapter.
Utilities
The Utilities window allows to select electrode control, burette control, I-interrupt,
positive feedback, hardware, check cell, plate, sleep mode, set colour defaults, and
options.
Fig. 16 The Method menu
Chapter 3 The GPES windows 33
Electrode control
The Electrode control option allows to operate a static mercury drop electrode which
is connected via an IME-interface to the Autolab. The stirrer can be switched on and
off, the purge valve can be opened and closed, and a mercury drop can be created.
The Reset button will reset the digital I/O port of the Autolab instrument. The Purge
and Stirrer will be switched off. This option is not accessible when no static mercury
drop electrode is connected to the Autolab.
Fig. 17 The Utilities menu
34 User Manual GPES for Windows Version 4.9
Fig. 18 The Electrode control
window
Burette control
The burette control option allows to control motorburettes connected to Autolab via
the DIO48 module. Consult the "Installation and Diagnostics" guide about the type of
burettes that can be connected. First click the Setup button. Then select the burette.
The displayed Burette setup window allows to define the connected burette. Please
consult the manual of your burette for the parameters.
Fig. 19 The Burette control window
Chapter 3 The GPES windows 35
The ‘Maximum time to check for Ready’ is the maximum wait time for the software
to receive a "ready" signal from the burette.
The DIO port used is shown on your Autolab front.
The Dose button will dose the amount specified above. The dosed volume is
displayed.
The Dose on button will dose with the speed displayed above.
The Reset button will give a ‘reset’-command to the burette and sets the dosed
volume to zero.
RDE-control
In order to control an external Rotating Disk Electrode (RDE), an option is available
in the Utilities menu of the GPES manager. In Hardware configuration, an external
RDE should be specified. After selecting the RDE control item the following window
appears:
With the scroll bar it is possible to control the rotation speed of the RDE. You can
also enter the number of rotations per minute by changing the r.p.m. edit field or enter
the rotation speed in radials per second in the rad/s edit field.
After pressing the Setup button the RDE setup window appears:
Fig. 20 The RDE control window
36 User Manual GPES for Windows Version 4.9
In this screen you can configure the RDE.
MUX control
The channel number of the SCNR16A, SCNR8A or MULTI4 module can be selected
manually by the operator before starting the measurement procedure:
1. Open the MUX control dialog by selecting MUX control from the Utility menu.
The dialog screen shown in the figure below will pop up.
2. Enable the checkbox “Use Multiplexer Module”.
3. Choose the desired channel.
4. Pressing <Apply> or closing the dialog screen will set the selected channel.
5. The active channel number will be indicated in the Manual control window.
Fig. 21 The RDE setup window
Fig. 21a The MUX control window
Chapter 3 The GPES windows 37
If you want to return to direct connections, you can disable the “Use Multiplexer
Module” checkbox.
I-interrupt
The I-interrupt option provides a method to determine the Ohmic resistance of the
cell. This option is only available when the Autolab is equipped with a
PGSTAT12/20/30/100 potentiostat/galvanostat. The technique involves switching off
the current and measuring the potential-time curve. As soon as the current is switched
off, the potential difference across the Ohmic resistance is zero and the charged
double layer is discharged. By extrapolating the curve following a straight line to the
beginning (time is zero), the iR-drop is calculated. Since the current is measured just
before switching off the cell, the uncompensated resistance is calculated.
It will be clear that for a proper calculation of the uncompensated Ohmic resistance
Ru, the current must be known very precisely. Proper measurement must be done at a
potential where the current is high enough to be measured and the applied current
range must be adequate to measure the current. For proper measurements, the current
must be at least in the order of 1 mA.
Also make sure that the current at the applied potential, before the current
interruption, can be measured sufficiently accurate. Therefore select a proper current
range, which means that the current should be in the order of the selected current
range.
It is recommended to switch off the iR-compensation, see Manual control window.
In order to get an accurate value for the uncompensated Ohmic-drop, the I-interrupt
measurements should be done at the highest possible speed. If an ADC750 module is
present in the Autolab system it is possible to use this module, in order to speed up the
measurements to 750 kHz.
Before measuring you need to specify the potential range at which the I-interrupt is
performed. If the potential is within the limit of -1V to 1V, specify 1 V range. If the
potential is outside this range, specify 10 V range.
On the iR-compensation window that appears, several parameters need to be
specified.
Duration of the interrupt: The interruption period; a reasonable value is .001 to .01.
The shorter the better.
First/second marker: The data point numbers between which a straight line is fitted.
In total 20 points are measured.
After the parameters have been specified, the Measure button can be clicked. The
measured data are subsequently plotted and the straight line is drawn. The calculated
uncompensated resistance is printed in the Result panel.
Now the Set marker button is available. When clicked you can change the First and
Second marker value by clicking two data points on the measured curve.
38 User Manual GPES for Windows Version 4.9
The calculated uncompensated resistance can be used as an estimated start value to be
used in the Positive feedback option. See next section.
WARNING: Too high Ohmic drop compensation can cause oscillation of the
potentiostat, which may cause damage to the working electrode.
An example of the use of I-interrupt is given in the chapter 'Getting started with
GPES'.
Positive feedback
The Positive feedback option provides an interactive method for determination and
compensation of the Ohmic resistance of the cell. This option is available only when
the Autolab is equipped with a PGSTAT12/20/30 or 100 potentiostat/galvanostat. The
technique of measurements is based on measuring the current response after applying
a potential pulse. The current response is displayed on the screen. The current
response depends on the actual values of the Ohmic resistance and the doublelayer
capacitance. Compensation of the Ohmic resistance results in a faster decaying of the
charging current. When the compensation is near 100%, the measured current
response will show damped oscillation.
Three parameters need to be specified.
Potential range: Can be either 10 Volt or 1 Volt. If the expected measured potential is
< 1 Volt or > -1 V, select the 1 Volt range. Otherwise select 10 V range.
Potential pulse: The height of the applied potential pulse. A reasonable value is 0.1V.
Duration: The period during which the current versus time data are measured. This is
twice the duration of the pulse. A reasonable value is 0.01 s.
Fig. 22 Example of the results of a current-interrupt measurement
Chapter 3 The GPES windows 39
When the Start button is clicked, current versus time measurements are done
repeatedly and the iR-compensation of the potentiostat is switched on. Now the
compensated resistance can be varied with the iR-compensation slider on the Manual
control window.
When "Switch iR-compensation off at current overload" is checked, the cell will be
switched off when the current exceeds about 8 times the current range value. This
normally occurs when the potentiostat oscillates because the compensated resistance
is too high.
WARNING: Too high Ohmic drop compensation can cause oscillation of the
potentiostat, which may cause damage of the working electrode.
Calibrate pH-Electrode
This window allows to calibrate pH electrodes. It is possible to specify two buffer
solutions and the calibration temperature. Measuring the pH as a 2
nd
Signal gives the
possibility to specify a measurement temperature. The pH is corrected for
temperature.
fig 22a. Effect of overcompensation of the iR-drop
40 User Manual GPES for Windows Version 4.9
When the value for a pH buffer is Ok press the Accept button. The OK button will
actuate the calibration for the measurement.
Check cell
The Check cell option allows to check the electrode connections and the noise level.
When selecting this option an empty window appears with a Cancel and a Measure
button. First apply a proper electrode potential and current range on the Manual
control menu. Subsequently click the Measure button. The window will subsequently
give information about the Electrode connections by comparing the applied and
measured electrode potential.
Also during 0.100 second the current is sampled at the highest rate possible.
Fig. 23 The Check cell window
Fig. 22b The Calibrate pH-Electrode window
Chapter 3 The GPES windows 41
The next figure shows a noisy signal displayed after pressing Measure. The plot
clearly shows periodic noise with a frequency of 50 Hz. After optimising the cell
simply by removing the unshielded cable of the reference electrode, the same
measurement shows a better signal-to-noise ratio.
The measured current and the five average values over one power cycle, normally
0.020 second, are plotted in the Measure window. The obtained five average values
Fig. 24a A noisy signal
Fig 24b A better signal-to-noise ratio
42 User Manual GPES for Windows Version 4.9
and their standard deviations are given in the Check cell window. A judgement about
the noise level and the selected current range are given. See also Chapter 16 of the
"Installation and Diagnostics" guide. It is possible, after an improvement of e.g. the
cell configuration, to re-Measure. By pressing Cancel the Check cell window
disappears.
Plate
The Plate option will display a window in which three plating potentials, a 'cell off'
wait time and a final potential can be specified.
Fig. 25 The Plate window
The three plating potentials are alternated with the 'cell off' time. Subsequently the
'final' potential is applied.
Sleep mode
When the Sleep mode option is clicked, newly measured data will no longer be
displayed in the Manual control window and the Data presentation window. This
option is useful when during slow but time consuming measurements a spreadsheet
program or word processor is activated. The Sleep mode will minimise the time
required by GPES. During the sleep mode, the measuring part of GPES will stay
active. In this way data are measured but not displayed.
Chapter 3 The GPES windows 43
Project
The Project option allows to execute a large number of electrochemical experiments
unattended. A project encompasses a number of tasks which have to be executed
sequentially. Sometimes this is called batch mode processing. A measurement
procedure is normally activated by clicking the Start button in the lower left corner. It
is also possible to start a procedure by creating and subsequently executing a project.
A project can be created by selecting the Project edit option. First you have to indicate
whether a new project should be made (New option) or an existing project file should
be opened (Open option). An example of a project is delivered with the GPES4
program in the testdata directory.
After editing a Project it can be stored on disk under its current name (Save option) or
under a new name (Save as option).
When Edit is selected the Edit project window appears with two options on the main
menu bar. The Check option checks whether there are syntax errors in the project
commands. The Edit option provides the standard Cut, Copy and Paste option.
Below you will find the Project script language definitions and rules.
Project command rules
• Both upper and lower case characters can be used in command lines.
• Space characters are ignored.
• If during the execution an error occurs the project continues with the next line.
• An error message will be printed in the Results window.
• One line per command.

• The following commands are allowed:
; <string>
rem <string> : comment
Procedure!Method = <method id> : define the electrochemical method
Procedure!Open("<filename>") : open a procedure file
Procedure!SaveAs("<filename>") : save the procedure file
Procedure!Start : start the execution of the procedure
Procedure!AddToStandby(<real>) : Add a value to the standby potential.
Only available for Chrono-Ampero-
and Chrono-Coulometry experiments.
Procedure!AddToPotlevel(<real>) : Add a value to all specified potential
levels. Only available for Chrono-
Ampero- and Chrono-Coulometry
experiments.
Procedure!AddToPotlevelEx
(<n>,<real>) : Add a value to a specific potential
level (n). Only available for Chrono-
Ampero- and Chrono-Coulometry
experiments.

44 User Manual GPES for Windows Version 4.9
Procedure!AddToCurlevelEx
(<n>,<real>) : Add a value to a specific current
level (n). Only available for Chrono-
Potentiometry experiments.

Dataset!Open("<filename>") : open a previously measured data file
Dataset!SaveAs("<filename>") : save the measured data
Dataset!AutoNum = <n> : enable auto-numbered files names,
starting with number <n>
Dataset!AutoReplace ("<string>") : specify the string which should be
replaced by a number in the
<filename> for auto-numbered files.
Example (see below)
;Start file numbering with number 5
DataSet!AutoNum = 5
;Replace string xxx
DataSet!AutoReplace("xxx")
;Save Automatic number file
DataSet!SaveAs("c:\autolab\data\filexxx")
;The first file is now saved as
c:\autolab\data\file005.ocw

Please note:
When a FRA-project is started from GPES and the FRA-project and both projects
contain the command 'DataSet!AutoNum = <n>', then the number of the FRA-project
is overruled by the number in the GPES-project.

Dataset!PeakSearch : perform automatic peaksearch with
baseline correction
Dataset!Selectscan = <scanno> : select a recorded scan number in
cyclic or linear sweep voltammetry
for further processing
Dataset!MinMax : find the minimum and maximum
value in a dataset
Dataset!Smooth = <smooth level> : smooth the data using the Savitsky
and Golay algorithm. The smooth
level can be an integer number
between 0 and 4. Note that after the
execution of the project the smoothed
data are replaced by the originally
measure data
Dataset!SaveQ&Q(“<filename>“) : store the anodic and cathodic charge
versus scan number (Q&Q files) for
cyclic voltammetry data. The filename
must be specified without an
extension.

Chapter 3 The GPES windows 45
Dataset!SaveImpedance
(“<filename>“) : project command to store impedance
data measured for AC-voltammetry.
The extension is .IMP. The filename
must be specified without an
extension.
Dataset!Subtract("<filename1>",
<filename2>","<filename3>") : subtract files and save the result in
another file. <filename3> =
<filename1> - <filename2>
Utility!SetRDERPM = <rpm> : set the Rotating Disk Electrode to a
specific rotation speed. The set-up of
the RDE is made in the RDE control
option under Utilities.

Results!Clear : clear the Results window
Results!SaveAs : save the Results window

System!Run("<filename>") : execute another program and wait
until it terminates.
The System!Run command search for
the program file with the next
sequence:
.PIF
.EXE
.COM
.BAT

System!Beep : give a beep
Print!Template : print a hardcopy according to the
template
Print!Plot : print a hardcopy of the Plot window
Print!Procedure : print a hardcopy of the measurement
procedure
Print!Results : print a hardcopy of the Results
window
FRA!Start("<filename>") : start a FRA project file from GPES
"<filename>" should be a FRA
project file

Utility!Channel = <n> : sets the active channel to <n>. The
MUX will be automatically enabled
when necessary.
Utility!NextChannel : increase the active channel number
with one. If the channel is not
available, the active channel number
is set to 1.
46 User Manual GPES for Windows Version 4.9
Please note:
The last 2 commands are available in the GPES and FRA programs. However, for
FRA projects that are called from within GPES projects, all channel switching
commands in the FRA project scripts are ignored. In such cases, the GPES project
will have exclusive control over the channel selection.
Utility!Delay = <n> : hold the project for <n> seconds.

Repeat(<n>)
EndRepeat : with the Repeat and EndRepeat
commands it is possible to repeat a
part of the project <n> times. You can
nest these commands maximal 5
times.

ForAllChannels("<filename>") : executes the active measurement
procedure for all available MUX-
channels and store the results in the
<filename> adding 3 characters to the
filename as channel number counter,
for example: fname001, fname002,
etc. .

DIO!SetMode("<Connector>",
"<Port>","<Mode>") : set the mode of a port of the DIO.
DIO!SetBit("<Connector>","<Port>",
"<n>","<Bit>") : set a single pin of the DIO on or off.
DIO!SetByte("<Connector>","<Port>"
,"<n>") : set a port of the DIO to the specified
value.
DIO!WaitBit("<Connector>","<Port>",
"<n>","<Bit>") : wait until a single pin of the DIO is
set on or off.
DIO!WaitByte("<Connector>","<Port>",
"<n>") : wait until a port of the DIO is set to
the specified value.

Burette!DoseVolume (<Burette number>
,<Dose volume>) : dose a specified volume to the
specified burette.
Burette!Fill (<Burette number>) : Fill the burette.
Burette!Flush (<Burette number>
,<Number of flushes>) : flush the burette.
Burette!Reset (<Burette number>) : Will give a 'reset'-command to the
burette.

Chapter 3 The GPES windows 47
• The <method id> can be:
VA : voltammetric analysis
CV : cyclic or linear sweep voltammetry
CM : one of the chronomethods
ECD : multi mode electrochemical detection
ECN : electrochemical noise
SAS : steps and sweeps
PSA : potentiometric stripping analysis
<string> : line of text
<filename> : a filename without extension, but including a directory name
<scanno> : the number of a recorded scan
<rpm> : rotations per minute
The FRA project file can only be executed if the FRA-program is already running.
For more information about the combination of GPES and FRA, see Appendix III in
the GPES manual.

A special case occurs when the measurement should start at the open circuit potential.
Normally the user is asked to click the Continue button, but in automatic mode the
program continues by itself after 1 second.
When no scan number is selected in cyclic or linear sweep voltammetry, the program
uses the last recorded scan as default.
Examples of projects can be found in the files ‘Demo01.mac’ and ‘Demo02.mac’
present in the \AUTOLAB\TESTDATA folder.
Project wizard
The Project wizard provides an easy way of editing and/or defining a project. This
option allows the user to pick project command lines from a list of all commands,
insert them in a project and define the parameters. The window below gives a project
Wizard overview.
48 User Manual GPES for Windows Version 4.9
Every project command can be inserted in the project, deleted or moved to another
place. A short description of the command is given in the information and syntax
box. Using the parameter button one can define the parameters that belong to that
specific command.
Project examples
Example 1: Cyclic voltammetry on MUX channel 2 and 4
The following example of a GPES project will perform the "c:\autolab\testdata\testcv"
procedure on channels 2 and 4, and stores the results in “c:\autolab\data\test channel
1” and in ”c:\autolab\data\test channel 4” :
Procedure!Method = CV
Procedure!Open("c:\autolab\testdata\testcv")
Utility!Channel = 2
Procedure!Start
Dataset!SaveAs("c:\autolab\data\test channel 1")
Utility!Channel = 4
Procedure!Start
Dataset!SaveAs("c:\autolab\data\test channel 4")
Example 2: Chrono amperometry on consecutive MUX channels
Fig 26. An example of a project inside the Project wizard
Chapter 3 The GPES windows 49
The following example will perform the "c:\autolab\testdata\testca" procedure on
channels 1 to 4, and stores their results using automatic filename numbering. The
result will be stored as “test scanner with cm 001”, “test scanner with cm 002”, “test
scanner with cm 003” and “test scanner with cm 004” with the number corresponding
to the channel:
Procedure!Method = CM
Procedure!Open("c:\autolab\testdata\testca")
Dataset!Autonum = 1
Dataset!Autoreplace("xxx")
Utility!Channel = 1
Repeat(4)
Procedure!Start
Dataset!SaveAs("c:\autolab\data\ test scanner with cm xxx")
Utility!NextChannel
Endrepeat
Example 3: Provide or receive trigger signals to or from DIO ports
These are the commands to set any of the pins on a DIO port of the Autolab
instrument. They can for example be used to control a Metrohm 730 Sample Changer.
Any of the pins can be set from low to high or the other way around, and can also be
used to receive an input trigger. With the SetMode command, one specifies whether
one wants to send or receive a trigger. SetBit allows to set one of the pins to on or off.
SetByte can be used to set multiple pins to on or off.
50 User Manual GPES for Windows Version 4.9
DIO!SetMode("P1", "A", "OUT")
;On connector P1, port A, the mode is set to OUT, so ready to
send a trigger.
DIO!SetBit("P1", "A", "4", "ON")
;On connector P1, port A, Pin number 5 (pin number 1 has value 0)
is set ON (i.e. sends a trigger).
DIO!SetBit("P1", "A", "4", "OFF")
;On connector P1, port A, Pin number 5 is set OFF again.
DIO!SetMode("P1", "A", "IN")
;On connector P1, port A, the mode is set to IN, so ready to
receive a trigger.
DIO!WaitBit("P1", "A", "2", "ON")
;The project will wait for an input trigger on P1, port A, Pin
number 3.
DIO!SetMode("P1", "A", "OUT")
;On connector P1, port A, the mode is set to OUT, so ready to
send a trigger.
DIO!SetByte("P1", "A", "3")
;On P1, port A, both pin 1 (2^0) and 2 (2^1) are set ON. In case
one wants to set Pin 3 and 5, one needs to set the value 40
(=2^3+2^5) instead of 3.
DIO!SetMode("P1", "A", "IN")
;On connector P1, port A, the mode is set to IN, so ready to
receive a trigger.
DIO!WaitByte("P1", "A", "3")
;On P1, port A, the project is waiting for an input trigger on
both pin 1 and 2 .
;In case one wants to receive the trigger on Pin 4 and 6, one
needs to set the value 80 (=2^4+2^6) instead of 3.
Fig. 26a Schematic overview of both DIO ports with PIN numbering for the different
sections. Pin 25 is always the digital ground.
Port1 Port 2
Section A
Section B
Section C UPPER
dgnd
Section C LOWER
1
2
3
4
5
6
7
8
1
2
3
4
1
2
3
4
5
6
7
8
2
3
4
1
25
Section C LOWER
Chapter 3 The GPES windows 51
Options
The Options menu encompasses the following items.
Trigger
Under this item the option Trigger is present. After selecting this option the following
window appears. In this window the trigger pulse can be configured.
After enabling the trigger pulse option, the 'Start' button has to be clicked. The
program will go through pretreatment and equilibration and will then wait for the
trigger-signal.
Fig. 27 The Trigger option window
52 User Manual GPES for Windows Version 4.9
pretreatment…. equilibration measurement end of measurement
Rescale after measurement.
Enable or disable automatic rescaling directly after the measurement of a
voltammogram.
Rescale during measurement
When this option is activated, the graph in the Data presentation window is rescaled
when a measured data point is outside the boundaries of the plot.
Procedure name in Data presentation Window
With this option it is possible to print the procedure file name on the Data presentation
window. This is useful to identify the graph when it is dumped on a printer.
Show all GPES files in File dialog box
If this option is activated, all files of all techniques are shown in the File dialog boxes
of the File menu. The program will switch automatically to the appropriate method.
Window
The Window option allows the selection of windows which should be shown on the
screen. The Tile option gives the default partitioning of the screen.
The Close all option will delete all the GPES windows except for the status bar and
the GPES Manager window.
Help
The Help option is the top entry point in the help structure. For most topics on the
screen Help is available. By pressing F1 the specific information about the part of the
screen on which has been focused is given.
Tool bar
The tool bar contains a list of buttons, the current electrochemical method, and the
name of the current measurement procedure.
The buttons give short cuts to various menu options which are frequently used. Place
the mouse pointer on top of a button. Its meaning will appear in yellow, if pressing the
button is allowed.
low
high
Chapter 3 The GPES windows 53
3.2 Status bar
The lowest part of the screen is reserved for the status bar. The Start button starts the
execution of a measurement procedure. After clicking this button, other buttons
appear which allow to advance to a next stage or to abort a measurement procedure.
The Status and Message panel give important control information.
After the Start button is clicked, the cell is switched on and the measurement starts
with a pre-treatment.
If an automatic mercury drop electrode is connected to Autolab, the following control
sequence is executed: the solution is purged, if the purge time exceeds 0 s.
Subsequently a new drop will be created. Then the cell will be switched on and the
pre-treatment potentials are applied when their duration is not zero. During these
periods, the stirrer will be on. Before the measurement starts, the stirrer is switched
off and the initial or standby potential is applied and the equilibration period starts in
order to stop convection of the solution.
During the pre-treatment period, the measured dc-current is printed in the Manual
control window.
3.3 Manual control window
The Manual control window gives full control over the potentiostat/galvanostat of the
Autolab instrument, including the optional modules:
• the low current module ECD
• the bipotentiostat module BIPOT
• the 10 A current booster BSTR10A
• the integrator/filter module FI20 for the PGSTAT12/20/30/100.
Fig. 28 Manual control window
54 User Manual GPES for Windows Version 4.9
It is also possible to perform potential/current/charge measurements as a function of
time. Note that some of the Autolab settings are part of the measurement procedure.
The Manual control window consists of several panels.
Current range
In the Current range panel the green 'LED' indicates the actual current range. A mark
in the neighbouring check box indicates whether the current range can be selected.
Only a joined column of selectable current ranges is allowed. The software always
checks whether the row is closed. If a range separated from another range is checked,
the intermediate ranges are checked automatically. When a check box is clicked
again, the check disappears. The allowed current ranges are stored on disk as part of
the procedure. Sometimes a current range annotation is coloured red. This means that
it is advised not to select this current range during execution of the current procedure.
The response times of this current range is too high for the specified measurement
procedure.
Settings
In the Settings panel, the mode of operation can be defined.The text on the button
represents the current situation. The following buttons might appear (depending on
the type of potentiostat/galvanostat):
Cell on/off: allows to switch cell on or off. In the ‘off’ position the connection of the
potentiostat with the potentiostat/galvanostat is broken, so no current can flow
between the counter and working electrode.
High Sens off/on: it indicates whether the gain 100 of the amplifier of the AD-
converter is used. If "off" only gain 1 and 10 are used.
The current resolution is improved by a factor of 10. The disadvantage of the high
sensitivity "on" is that the measurements are somewhat slower and that they are more
susceptible to overloads. It is recommended to switch the high sensitivity "on" only
when the limits of the digital resolution show. For example, at the current range
100nA the current resolution is improved from 3pA to 0.3 pA, when high sensitivity
is switched on. See also the chapter about the digital base of Autolab in the
"Installation and Diagnostics" guide.
High Stability/High Speed: The potentiostats/galvanostats can be used in either the
high speed, with high bandwidth, mode or the high stability, with low bandwidth,
mode. The bandwidth at high stability is about 10 kHz. Some electrochemical cells
may cause stability problems with the instrument in high speed mode. Especially cells
with high capacity and low resistance may cause oscillations. Using the instrument in
high stability mode may prevent oscillations. It is advised to use high stability in all
experiments, except when high bandwidth is needed. High speed or high bandwidth is
needed when frequencies higher than 10 kHz or sampling or interval times below 100
µs are used.
Potentiostat/Galvanostat: allows switching from potentiostatic to galvanostatic mode.
It is highly recommended to switch the cell off before the mode change. In case of
potentiostatic control, the output of the DAC module corresponds to an applied
potential level. In case of galvanostatic control, the output of the DAC module
corresponds to an applied current.
Chapter 3 The GPES windows 55
iR-comp. on/off: switches iR-compensation’ on’ or ’off’. A more elaborate description
is found in the dedicated paragraph in this chapter (only available with a
PGSTAT12/20/30/100).
Potential
The Potential panel contains a slider and a text box. With these tools the applied
potential can be specified. The slider box can be dragged to change the value. A click
on the arrows and slider bar changes the value by a distinct increment. The increment
is different for the arrows and for the bar.
In the two panels below the measured current, potential and/or time can be displayed,
depending on the option button selected.
The option button "2nd Sig." appears, in case a chronomethod or the method cyclic or
linear sweep voltammetry is selected and the Record second signal option is checked
on page 2 of the procedure parameter list.
The Clock off/on button in the lowest of the two panels starts the timer, and displays
the measured data from the panel above in the Data presentation window. This makes
it possible to display graphically what is going on. These measured data can be
replotted, printed, and the graph can be stored. However, the data can neither be
saved, analysed, nor edited.
Noise meters
The noise levels for current and potential signals are visualised by 2 noise meters at
the signal panels. When these VU-meters are active, the first green LED or a grey
background is shown.
The VU-meter for the current signal is only active when the cell is switched on. The
VU-meter for the potential signal is also active when the cell is switched off i.e. no
current can flow. During the execution of the procedure (except for pre-treatment
stage) the VU-meters are inactive.
In case more than 4 LED's of the VU-meter are on, it is advised to take precautions.
You can select a higher current range or minimise the noise of your electrochemical
cell. High potential noise levels are often caused by the reference electrode.
iR-compensation
The iR-compensation panel appears only when the Autolab is equipped with a
PGSTAT12/20/30/100 potentiostat/galvanostat. In order to perform iR-compensation
the iR-compensation button on the Settings panel should be switched to "iR-comp.
on". Subsequently the Ohmic resistance can be specified using the slider or by typing
in the textbox. Note that when the iR-compensation is switched on, automatic current
ranging is no longer possible. The checked current range box becomes the actual
current range.
In case of a manual change of the current range, the compensated resistance will be
kept as constant as possible. Because internally the compensation is proportional to
the current range, the value for the compensation needs to be recalculated when the
current range is changed. With a change of current range the resolution of the
compensation will alter. The maximum compensation of a current range equals two
times the measurement resistance. This means that for the 1 A range the maximum
56 User Manual GPES for Windows Version 4.9
compensated resistance is 2 Ohm and for the 1 µA range it is 2 MOhm. The resolution
is always 0.05% of the measurement resistance.
Integrator
The Integrator panel appears only when the Autolab is equipped with an analog
integrator. This is not the case with a PGSTAT12/20/30/100 potentiostat/galvanostat
unless the Autolab is equipped with a FI20-module. For further use, see the section
about chronocoulometry.
Filter panel
The Filter panel appears when the Autolab is equipped with an ECD or an FI20
module. The following option buttons can be clicked "Off", "5s", "1s", ".1s". The
effect of a filter constant of e.g. 5s is that 5 seconds after a potential perturbation has
been applied, the current response can be measured correctly.
The “Remote led” indicates when it is possible to edit the parameters in Manual
Control. In cases where it is red, it is not possible to edit the parameters in this
window.
3.4 Data presentation window
The Data presentation window serves several functions:
• display of data
• data analysis
• data manipulation
• communication with other programs like Paintbrush, Excel or MS-Word.
The window consists of a menu bar, a graphical display, and a message line.
As mentioned earlier the measured data are kept in a shared data memory block with
the data acquisition software. During the measurement the measured data points are
also copied to the memory block of the Data presentation window. After the
measurements the data in this memory block can be modified by options in the Data
presentation window. However, it is always possible to resume the measured data.
Note that the save options of the File menu of the GPES Manager window always
save the measured data. Also note that for cyclic and linear sweep voltammetry,
during the execution of a procedure, the measured data are plotted, but after the
measurements only the last measured scan is visible. The data, which can be modified
in the Data presentation window, are called work data and can be stored from the File
menu of the Data presentation window in a work data file. This file cannot be
distinguished from the files with measured data. Both types of files have the same
format and layout. Some care should be taken with saving the work data. For
example, as is described further on, the display of the current values can be changed
to a square root of the current. If the work data are then saved, not the current values
but the square root of the current is saved.
Chapter 3 The GPES windows 57
On the message line at the bottom of the graphical display important text about the
required user actions during analysis of editing data appears. If no message is
displayed, the currently measured potential and current are displayed.
File
The file option allows to create data files based op on data presented in the Data
presentation window. It allows to save the so-called work data file as discussed
above. The following options are available.
Save work file
This option was discussed above.
Save I(forward) and Save I(backward)
The Electrochemical techniques Square wave, Differential pulse and Differential
Normal pulse provides the forward and backward current data. These curves can be
plotted but not analysed. The separate curves can be stored, and retrieved with ‘File’,
‘Load data’ from the Gpes manager window to do analysis.
Save impedance data
When an AC voltammetry measurement is done, the impedance data for each data
point can be saved to disk. This option is present in the File menu of the Data
presentation window. The file, with the extension .IMP, has the following layout:
Date: 02-May-97
Time: 13:24:39
Frequency (Hz) : 252.020
Amplitude (Vrms): .001
Phase sensitive : Yes
Phase (degree) : 20.000
E/V i(ac)/A Z/ohm phi/deg Rs/ohm Cs/F
.
.
.
NOTE: These data are additional data and can only be obtained after the
measurement, NOT after loading a data file.
Quick save of previous scan
When a Cyclic or Linear sweep voltammetry measurement with more than one scan is
going on it is possible to save the previous measured scan. This option can also be
activated by typing 'SAVE' on the keyboard. This option work similar to the
procedure parameter ‘Save every nth cycle’.
Save as Chrono data
Save a Step segment of Steps and Sweeps as Chrono methods data. This data file can
be read in Chrono methods in order to perform data analysis.
Save as Linear sweep data
Save a Sweep segment of Steps and Sweeps as Linear sweep data. This data file can
be read in the Linear sweep method in order to perform data analysis.
58 User Manual GPES for Windows Version 4.9
Copy
The Copy option allows to copy the graph to clipboard or to dump the graph in a
bitmap file (.BMP). These files can be read by programs like Paintbrush, Excel or
MS-Word. These programs allow editing of the graphs. The best result is obtained by
doing this from a maximised Data presentation window. By default GPES only draws
dots. It is sometimes better to draw lines. This can be achieved by double-clicking the
data points in the graph. For further information, see the paragraph on Editing
graphical items.
Plot
The Plot option contains all kind of possibilities to manipulate the graph like plot
refresh, automatic scaling, zooming, setting a Data window, display of a previously
measured signal. Sometimes, not all options are selectable because they are not
applicable or intervene with current active data analysis options. Also when the
execution of a procedure is going on, not all options are selectable.
New plot
The New plot option removes objects, such as lines and markers, from the screen.
During measuring a cv, this option removes the previous measured data points from
the screen.
Fig. 29 The Plot menu
Chapter 3 The GPES windows 59
Some sub-options require explanation.
Automatic
This option automatically rescales the data during a measurement.
Resume
The Resume option makes a fresh copy of the measured data into the Data
presentation window. This allows you to get back to the original data after doing data
analysis.
Zoom
Clicking the Zoom option has the same effect as pressing the right mouse button.
When this option is activated a magnifying glass appears. When subsequently the left
mouse button is clicked and held down a Zoom window can be created.
Set window
The Set window option allows to define a part of the data set. Any further data
manipulation and display will be applied to this part of the data. With Chrono
methods the x-values will be normalised to 0, so the x-axis always starts at t=0.
First- and Second signal
The First, and Second signal options are selectable, when, next to the current or
potential signal, a second signal is recorded. A marker in front of these options means
that they are displayed. When both are displayed no further data analysis is possible.
E vs t plot and dt/dE vs E plot
These options appear only when the method is Potentiometric stripping analysis. It
allows switching between these types of plots. The E vs t plot can be used to do
Transition time analysis (see the chapter on the analysis of measured data) in order to
analyse the kinetics and reversibility of the electrode process. The dt/dE vs E plot can
be used for electroanalytical purposes.
Show I (forward)
This option shows for the techniques square wave and differential pulse voltammetry
only. With square wave voltammetry it allows to toggle the display of the current
measured in the pulse which is applied in the scan direction. With differential pulse
voltammetry it allows to toggle the display of the current before applying the pulse.
Show I (backward)
This option shows for the techniques square wave and differential pulse voltammetry
only. With square wave voltammetry it allows to toggle the display of the current
measured in the pulse which is applied in the opposite of the scan direction. With
differential pulse voltammetry it allows to toggle the display of the current measured
in the pulse.
60 User Manual GPES for Windows Version 4.9
Load overlay file
This option allows the making of a graphical overlay of one or more data sets. A
maximum of 10 overlays can be made. You can select multiple files at a time by using
<Shift> or <Control>, combined with the mouse action.
The overlay legends shown in the Data presentation window, will also be visible in a
print-out. After clicking the New plot option or the Resume option, the overlays will
disappear. It is possible to load overlays together with the main data (see Load
data/scan option of the File menu)
Reverse axes
This option will reverse the direction of the horizontal as well as the vertical axis. It
allows peaks always to be displayed upwards.
Enter text
When this option is clicked the text "Text field" appears in the left top corner of the
graph. This text can be dragged over the graph. After double-clicking the text field,
the text itself, and the format can be modified. The first text line of the Paste buffer
can be inserted on the text field as well. Thus a line of text from the Analysis results
window can be copied to the Paste buffer and subsequently inserted there. Please note,
that the text cannot be stored.
Analysis
The Analysis option contains an elaborate set of methods to extract essential
parameters from the measured data. The background is described in the special
chapter about this subject. The available data analysis options depend on the selected
electrochemical method.
Edit data
The Edit data option gives the opportunity to modify the presented data. The
backgrounds are explained in the special chapter about this subject.
Work scan
The Work scan option, which is only present for cyclic and linear sweep voltammetry,
allows the selection of a scan for further data analysis.
Work potential
The Work potential option, which is only present for multi mode electrochemical
detection, allows the selection of a potential for further data analysis and peak search.
Editing graphical items and viewing data
Except for the available options, items of the graph can be edited by double-clicking
them. The following items can be double-clicked:
• the axis annotation
• the axis itself


Chapter 3 The GPES windows 61

Fig. 30 Horizontal axis window



• the axis description
• the plot title and subtitle
• the data.
Colours, sizes, marker types, text, formats, axis position: all these things can be
changed. Please take some care with changes in Colours. E.g. do not make the data
colour the same as its background colour.
62 User Manual GPES for Windows Version 4.9
Fig. 31 Plot parameter window
By double-clicking the data points a window appears, which among the standard
graphical operations also gives the possibility to view the data values itself and to edit
them. Moreover the data can be copied to clipboard and subsequently be entered into
e.g. a spreadsheet program.
Fig. 32 Graph parameter window
Double-clicking the axis itself allows scaling and positioning of the axis and selection
of the axis function. Data can be displayed, among others, as linear inverse,
10
log,
natural log, square root, inverse square root. Except for the linear and
10
log, the value
Chapter 3 The GPES windows 63
of the presented data is modified in real. So all subsequent operations are really
performed on e.g. the square root of the data.
In case of the
10
log, not the values but the axis is changed to a logarithmic axis.
When the button "| 1 |" in the upper right corner is clicked, the Graph parameter
window appears. This window allows modification of the relative scale parameters of
the so called graph and plotting area, and their background colours.
All the changes made to colour and sizes are stored in the default graphics display
file. The other changes are kept in the procedure file.
3.5 Edit procedure window
The Edit procedure window consists of 2 pages. In Page 1 the most common
parameters can be specified. Page 2 contains the other parameters. The meaning of
each parameter is clarified by the Help program.
A list of parameter descriptions is given in the appendix about this subject.
In the option bar, the Send option is displayed. This option can only be clicked during
the execution of a measurement procedure. It is relevant when a parameter is changed.
The Send option activates the modified value. The modified value is accepted when a
beep sounds.
The layout and setup of the Edit procedure window is more or less the same for all
electrochemical methods.
For most methods on Page 1, the following type of parameters can be specified:
• the first pre-treatment and subsequent equilibration
• the definition of the type of measurement
• the potential or current level parameters
• the title and subtitle.

The items on page 2 depend on the method.

For voltammetric analysis the following extra items are available:
• number of voltammetric scans which will be recorded subsequently and averaged
• a number of comment lines.

For cyclic and linear sweep voltammetry the following items are extra available:
• extra pre-treatment stages
• special measurement conditions
• special display option to swap x- and y-axis (Tafel plot)
• a number of comment lines
• current boundaries for reversing the scan direction
• optional chronoamperometric measurement conditions at the vertices
• optional recording of an external signal.

For the chronomethods the following extra items are available:
• extra pre-treatment stages
• special measurement conditions
64 User Manual GPES for Windows Version 4.9
• optional recording of an extra signal
• a number of comment lines.

For electrochemical detection the following extra items are available:
• extra pre-treatment stages
• a number of comment lines
• differential pulse condition (if applicable).

For potentiometric stripping analysis the following extra items are available:
• smooth level during differentiation of potential versus time data
• a number of comment lines.
A full list of input parameters is given in appendix II.
3.6 Analysis results window
The Analysis option of the Data presentation window allows the making of an
analysis of the data. In some cases the results are displayed in a special window which
differs per analysis technique. In all cases a report of analysis is printed in the
Analysis results window.
The Analysis results window contains all the results of the analysis of the data. Only
when the GPES Manager window is closed, the Analysis results window is cleared.
The File option of this window allows the user to clear, save or print the content of the
window. The Edit option allows the user to remove (Cut) the selected part of the text.
Text can be selected by keeping the left mouse button pressed and moving it over the
window. The Copy option copies the content of the window to the paste buffer
including a so called DDE link. For example, MS-Word can, via Paste special option
makes a Paste Link. This means that any change to the content of the window will
automatically be copied to the MS-Word document until the link is broken via the
Links... option of MS-Word.
The Paste option will include text from the paste buffer.
It is possible to copy results of Analysis into the graph of the Data presentation
window. This is useful if you want to have a complete printout of the graph. You can
include the Analysis text as follows:
• You can select (a part of) the text,
• Under the option Edit click the option Copy (or Cut). Now the text is present in
the paste buffer,
• Now select the Copy menu on the Data presentation window,
• Select Paste text.
The text will be included into the graph.
Please note:
In the Data presentation, you can drag the text to the position you want. The text in
Data presentation can not be changed, but can be cleared by double clicking and
typing in a space in the Text field. You can also change the text style in the window.
For a proper outlined text a change to the font ‘Courier’ is sometimes required.
Chapter 4 Analysis of measured data 65
4. Analysis of measured data
Under the Analysis option on the Data presentation menu there are a number of
facilities to analyse measured data. Some analysis techniques are specific for an
electrochemical method.
The results of the analysis are sometimes displayed in a specific window. In all cases
the results are printed in the Analysis results window. This window can be made
visible from the Window option on GPES Manager menu bar.
In most cases not all options are selectable. This may have the following causes:
• The option is not relevant for the electrochemical method.
• The execution of a measurement procedure is in progress.
• Another conflicting option is already selected.
• Just after the recording of more than one cyclic or linear sweep voltammogram, a
selection of the scan to be analysed can be made. See Work scan option on the
Data presentation window. By default the last measured full scan is displayed.
• When a second signal has been recorded concurrent, first a selection has to be
made which signal should be analysed. See Plot menu on the Data presentation
window.
• The option is not relevant or cannot activated because an ambiguous situation is
present, i.e. it is not clear on what data the analysis should be done.
4.1 Peak search
When the Peak search option is selected, the Peak search window appears. If the
curve shows distinct peaks, you can often simply click the Search button in the right
panel and the results are shown in an appearing Results panel. The number of digits is
the same as the precision of the axis.
The Clear button will erase the Results window and will refresh the plot. The Close
button closes the Peak search window. The Show results button will show the Results
window.
The Peak search options window gives several options to search for peaks in a
voltammogram. It opens when the Option button is clicked. If Automatic option
button is 'checked', the peak search algorithm needs two input parameters to be
specified: the minimum peak height and the peak width. Otherwise only a value for
the minimum peak height is required. These parameters have to be specified in the
Minimum panel. Peaks with a height below the minimum peak height will be omitted.
The peak width parameter determines the width of the window which moves through
the data set. Peaks with a width (at half peak height) which are smaller than the
specified peak width might not be found.
It is possible to find peaks that are present as shoulders on a steep base curve.
For this purpose the Peak search option contains an Include shoulders option. The
option is found at the Peak search options window and can be selected only in
automatic search mode.
When this option is clicked on, the Peak search is performed after a basecurve
correction on the background, according to the moving average baseline correction
66 User Manual GPES for Windows Version 4.9
method. This method can also be performed separately. See Baseline correction
option in the Edit data menu.
Fig. 42 Peak search window
Fig. 44 Set results format window
Fig. 43 Peak search options window
Fig. 45 Peak search results window
Chapter 4 Analysis of measured data 67
Peaks are normally searched in the scan direction. If this is not required, the Reverse
option in the upper right corner of the window should be checked.
In the Baseline panel it can be 'checked' whether or not the peaks found will be
corrected for the baseline. This baseline is determined by means of the tangent fit
method.
The tangent is drawn from the left side to the right side of a peak if ‘linear baseline is
checked’. In cyclic and linear sweeps it may be better to use only the front of the peak
to construct the tangent. This is done when ‘Lin. front baseline’ is checked.
If the automatic peak search method fails, the Automatic search should be switched
off. Two alternatives are present: curve cursor and free cursor. In both modes two
points need to be marked; the beginning and the end point of the peak. In curve cursor
mode the markers are automatically put on the voltammogram. In free cursor mode
the marks can be put everywhere on the graph. In curve cursor mode the two markers
several types of basecurves can be drawn: linear, 3rd order polynomial, or
exponential. Moreover, in case of double peaks, only peakheight of the front peak, the
rear peak, or highest in the whole selected peak area can be determined.
Furthermore it is also possible to draw a linear baseline in case only the front part or
only the rear part of the baseline is known. The options Lin. front baseline or Lin. rear
baseline on the Baseline panel should then be ‘checked’. Now two points on the front
part respectively rear part of the peak should be marked. In free cursor mode only a
linear baseline can be drawn.
When the options 'Curve cursor, linear baseline' and 'Free cursor' are selected,
baselines can be constructed manually. After the first point of the baseline has been
marked, a line connected to this point will be dragged until a second marker is
clicked.
The Set format button can be clicked to adjust the formats in the Set results format
window. The defaults in this window are the formats of the axis-labels.
Fig. 46 Example of polynomial basecurve in peak
68 User Manual GPES for Windows Version 4.9
The results of the peak search are:
Position : potential at which the current with respect to the baseline has a
maximum.
Height : maximum current with respect to baseline.
Peak area : area of the peak corrected for the baseline. For data from
cyclic linear sweep voltammetry the area is expressed in
Coulombs. This means that the area is divided by the scanrate.
Derivative : the sum of the absolute values of the maximum and the
minimum in the derivative of peak.
Ep - Ep/2 : the difference between peak potential and the potential at half
height. This value is only printed for data from cyclic and
linear sweep voltammetry. It is useful to derive kinetic
parameters. See the book of C.M.A. Brett and A.M.O.
Oliveira Brett, Electrochemistry Oxford science publications
ISBN 0-19-855388-9.
In quantitative voltammetric practice the peak height is the most widely used
parameter to determine concentrations. The peak area is less sensitive to noise, but if
the peak is not completely isolated from another peak, the error in the peak area will
be high. The sum of the derivatives of the peak is less sensitive to peak overlap.
However, derivation of an experimental curve will increase noise. For more details
see Ref.: J. Tacussel, P. Lectere and J.J. Fombon, J. Electroanal. Chem.,214 (1986)
79-94.
4.2 Chronoamperometric plot
The Chronoamperometric plot option produces a special plot for two sequential
potential steps in a chronoamperometric experiment. The first step should be the
forward potential step and the second the reverse potential step in a (quasi-)reversible
Fig. 47 Example of a linear front baseline
Chapter 4 Analysis of measured data 69
electrode reaction. The book of A.J. Bard and L.J. Faulkner, Electrochemical
Methods, Fundamentals and Applications, Chapter 5 (ISBN 0-471-05542-5) gives
more details.
If data for more than two potential steps are present, a selection of the first (forward)
potential step can be made. This option is only active if it is applicable.
4.3 Chronocoulometric plot
The Chronocoulometric plot option produces a special plot for two sequential
potential steps in a chronocoulometric experiment. The first step should be the
forward potential step and the second the reverse potential step in a (quasi-) reversible
electrode reaction. The book of A.J. Bard and L.J. Faulkner, Electrochemical
Methods, Fundamentals and Applications, Chapter 5 (ISBN 0-471-05542-5) gives
more details. If data for more than two potential steps are present, a selection of the
first (forward) potential step can be made. This option is only active if it is applicable.
The charge flown since the beginning of the potential step is plotted versus
the square root of the time since the start of the step.
The kinetic parameters can be obtained by selecting the Linear regression option (see
below). A line should be fitted for the forward as well as for the reverse plot. The fit
parameters appear in the Analysis results window as well as in the results panel.
4.4 Linear regression
The Linear regression option allows to fit a straight line through a part of the
measured curve.
When the option has been selected, two windows appear. One is the Linear regression
window and the other is the Markers window. When the user has marked the begin
and end point of the line on the measured curve and has clicked the OK button, a line
is drawn so that the sum of squares of the differences between measured and
calculated value is minimum.
Fig. 48 Linear regression window
70 User Manual GPES for Windows Version 4.9
The slope of the line (dY/dX), its inverse, the intercept (the value at X = 0), the
number of points between begin and end point, the standard deviations and the
correlation coefficient are displayed in the Linear regression window. More lines can
be fitted when the Set line button is clicked.
4.5 Integrate between markers
This operation will determine the area under the curve between two selected points.
With cyclic voltammetry, the area is expressed as charge (C). Thus the calculated area
is divided by scanrate.
4.6 Wave log analysis
The Wave log analysis option is active for voltammetric analysis and cyclic and linear
sweep voltammetry.
The half wave potential E
½
can be determined and Tafel slope analysis can be done
for a S-shaped cyclic voltammograms or convoluted voltammograms (see
Convolution option). After having selected this option, the user is asked to define a
base line and a limiting line. Subsequently E
½
is calculated from the crossing between
the average line of the base line and the limiting line with the measured curve. The
limiting current at E
½
is calculated as two times the current at E
½
with respect to the
base current.
After pressing the Continue button on the Wave log analysis window, a Tafel line
analysis can be done from the plot of ln {(id - i )/i} versus the potential, where "i"
stands for current, "id" for limiting current and "ln" for natural logarithm. If a cyclic
voltammogram has been deconvoluted the "i" is replaced by "m". The markers for the
line should be selected not too far from zero on the Y-axis.
The intercept is at E = 0. The parameter Alpha * n (αn) has been calculated from the
slope:
Chapter 4 Analysis of measured data 71
slope = αnF/RT F = Faraday constant = 96484.6 C/mol
R = Gas constant = 8.31441 J/mol/K
T = temperature = 298.15 at 25°C
n = no. of transferred electrons
α = 1 for reversible reactions
α = transfer coefficient for irreversible reactions.
An example of wave log analysis is described in Chapter ‘Getting started with GPES’.
4.7 Tafel slope analysis
This option is only available for Cyclic and Linear sweep voltammetry. When the
option is selected, the current is plotted on a logarithmic scale. The user is asked to set
markers for the anodic and cathodic branch on the curve. In principle this option
works similar to Corrosion rate analysis without the fitting part.
4.8 Corrosion rate
This option allows the determination of the corrosion rate and the polarisation
resistance.
If the current versus the potential curve passes the zero current line more than once,
the user is asked to define a window of interest around the point where the anodic
current balances the cathodic current. Before doing this, it might be useful to draw the
horizontal axis through the origin of the vertical axis. This can be done by double-
clicking the horizontal axis and subsequently selecting the "Origin" in the Intercept
position panel.
If the curve passes the zero current line only once, the whole curve is used for the
analysis.
Subsequently the graph is transformed in a logarithmic scaled current versus potential
plot and the Corrosion rate window appears. This window shows the corrosion
potential and the polarisation resistance at the corrosion potential.
In this window the surface area (SA), equivalent weight (EW), and the density (D) of
the electrode material can be specified. These data are used to calculate the corrosion
rate in terms of current density (I
corrosion
) and millimetres/year (CR):
I
corrosion
= i
corrosion
/SA A/cm2
and
CR = 3272*i
corr
*EW/(SA * D)
The polarisation resistance Rp is determined by taking the reciprocal value of the
derivative di/dE. The derivative is obtained from a 2nd order polynomial fit through
the corrosion potential and its neighbours. From this Rp value the corrosion rate can
be obtained:
72 User Manual GPES for Windows Version 4.9
i
corrosion
= B/Rp where B is normally an empirical constant.
B can also be obtained from the Tafel slopes (M. Stern and A.L. Geary, J.
electrochem. Soc. 1957, 104, 56).
After clicking the Tafel slope button, the Marker window appears. Now the Tafel line
for cathodic branch has to be defined by marking two points. After the OK-button on
Marker window has been clicked, the same has to be done for the anodic branch.
After the Tafel lines have been set, a second Corrosion window appears with the
results:
1. The corrosion current, corrosion current density and the corrosion rate.
2. The Tafel slopes b
a
and b
c
.
3. The corrosion potential at zero current and the corrosion potential as calculated
from cross-point of the two Tafel lines.
4. The Polarisation resistance Rp obtained from the equation:
1 | 1 1 `
Rp = B/i
corrosion
where B = ÷÷ and S = 2.303 * ÷÷ + ÷÷
S . b
a
b
c
,
Fig. 49 Corrosion rate analysis
Chapter 4 Analysis of measured data 73
The corrosion rate is determined on the basis of the equation:
¹ ] ] ¹
i = i
corrosion
' exp s1(E - E
corr
) ] - exp -s2(E - E
corr
) ] '
¹ ] ] ¹
where s1 = slope of the anodic branch = 2.303/b
a
s2 = slope of the cathodic branch = 2.303/b
c
E
eq
= the equivalence or corrosion potential
i
corrosion
= the corrosion rate or exchange current in Ampere
When the Start fit button is clicked, a fit is performed on the slopes and the corrosion
current. The observed corrosion potential, i.e. the potential where i = 0, is taken as the
corrosion potential E
corr
.
The fitting is performed according to the non-linear least square fit method of
Levenberg/Marquardt. The values obtained from the Tafel lines are used as start
parameters. After some iterations the fit results are presented on the screen. Also the
number of iterations and the goodness of fit parameter chi-square are given. Chi-
square is the sum of the squares of the differences between measured and calculated
data. The fitted slopes are s1 and s2. The fitting procedure can be interrupted by
clicking the Stop button.
The comparison between the observed and the calculated curve is shown.
The Tafel slope parameter α can be obtained from the slopes:
b = 2.303 RT/3αnF F = Faraday constant = 96484.6 C/mol
R = Gas constant = 8.31441 J/mol/K
T = temperature = 298.15 at 25°C
n = no. of transferred electrons
2.303 = ln (10)
It is sometimes possible to improve the fit by clicking the Restart button.
4.9 Spectral noise analysis
After recording current- and potential- noise transients, it is commonly desired to
perform a statistical or frequency analysis on the results. The GPES software enables
the calculation of a frequency spectrum for current and potential or impedance. It can
be activated in the Analysis menu of the Data presentation window.
The frequency spectrum is calculated by means of a FFT algorithm. Since it requires
the dataset to be a power of 2, the number of datapoints is automatically extended
when necessary. In case of an interrupted measurement (<Abort> was pressed), the
dataset is padded with zeros.
In principle, the Fourier method should only be used on datasets that are periodical
and “fit” exactly in the time duration of the recorded scan. For noise signals, this is of
course not true. Therefore for some cases, it would be advisable to apply a so-called
74 User Manual GPES for Windows Version 4.9
“Window function”. These operations will counteract the effects that were mentioned
above. A total of 5 functions are available:
none/Bartlett/Hanning/Hamming/Blackman.
A range of literature is available on the theoretical background of signal processing.
See: “Numerical Recipes”, W.H.Press et al., Cambridge University Press,
Cambridge 1997
4.10 Find minimum and maximum
The Find minimum and maximum option shows the minimum and maximum Y-value
with their corresponding X-values.
4.11 Interpolate
The Interpolate option allows the user to calculate one or more X-values or Y-values
which corresponds to a given value on the other axis. A linear interpolation is used to
calculate intermediate values.
4.12 Transition time analysis
The Transition time analysis option only appears for chronopotentiometric data or
data from Potentiometric stripping analysis. The background of this analysis is fully
described in the book of C.M.A. Brett and A.M.O. Oliveira Brett, Electrochemistry
Oxford science publications ISBN 0-19-855388-9.
After selecting this option, a graph of the time versus potential is presented and the
user is asked to specify two marker points for subsequently the baseline, the transition
line, and the limiting line.
The time difference between the crosspoints of the transition line and the base line
respectively the limiting line is defined as the quantity 'tau'. The crosspoint of the
transition line with the baseline is called t-base of 'tau'. Finally also the quantity E3/4 -
E1/4 is given. This is the difference in potential at three quarters of 'tau' and at one
quarter of 'tau'.
Subsequently the plot can be transformed dependent on whether the measured system
is thought to be reversible or irreversible. Finally a linear regression can be done to
extract the kinetic parameters from fitting a straight line. An example of transition
time analysis is given in the chapter ‘Getting started with GPES’.
4.13 Fit and simulation
The Fit and simulation option is located in the Analysis menu of the Data Presentation
window. It provides the method to determine parameters of electrochemical
processes, like formal redox potential, heterogeneous rate constant, transfer
coefficient α etc., as well as to simulate theoretical current-potential curves. The table
Chapter 4 Analysis of measured data 75
below summarises the models (i.e. combinations of experimental techniques and
reaction mechanisms) for which fitting and simulation are currently available.
The models available for fitting and simulation are extended with the mechanisms in
which two parallel reactions are involved. The models are called 'two-component'
models and are available for the cyclic voltammetry technique.
In all the above models it has been assumed that the experiment is carried out on a
stationary electrode in an unstirred solution. The fit and simulation works only with
staircase voltammograms but not with linear scans. Moreover, in cyclic voltammetry,
the current measured during a potential step depends on the “history” of the scan, i.e.,
on the number, height and duration of all preceding steps. This means that for the sake
of speed, the number of potential steps should in the scan should be kept small.
The simulation method
Digital simulation of current-potential curves is based on finite difference method.
Equations of the transport of electroactive substances to the electrode surface are
solved by Crank-Nicolson technique, a method widely used by electrochemists and
renowned for its accuracy and stability. The time-dependent concentration profiles
obtained from these equations are used for the calculation of the current.
The advantage of digital simulation is its versatility. This feature is easily visible
when the simulation method is compared with analytical equations describing current-
potential curves, which have a number of restrictions on their validity.
The fitting method
Fitting is carried out using Marquardt nonlinear least-squares method. The model
functions are either calculated from analytical equations (wherever possible) or
obtained by digital simulation of the electrode processes. The convergence criteria are
based on the value of χ
2
, Σ(Y-Y
fit
)
2
, and its change during the last iteration, as well as
on the requested precision of the fitted parameters.
Table 2 Models available for fitting and simulation.
staircase cyclic
voltammetry
differential pulse
voltammetry
normal pulse
voltammetry
square wave
voltammetry
reversible reversible reversible reversible
quasi-reversible quasi-reversible quasi-reversible quasi-
reversible
irreversible irreversible irreversible irreversible
ErCi (irreversible
chemical reaction)
two-component
ErCi (irreversible
chemical reaction)
ErCi (irreversible
chemical reaction)
ErCi
(irreversible
chemical
reaction)
76 User Manual GPES for Windows Version 4.9
Elements of the Fit and Simulation Window
In the upper part of the Fit and simulation window there is the drop-down menu with
a list of available models, five action buttons, and two option buttons to switch
between the fit and the simulation mode of the program. The list of models that can be
used depends on the experimental technique chosen.
The middle part of the window contains three display fields. 'Init. Guess' button starts
the calculation of the initial guesses of fitable parameters. Fast Fit performs a fit on a
reduced data set. See the chapter ‘Fitting in more detail’ about the data reduction and
other fast fit parameters. The Full Fit button starts a fit of the model on all data points.
This button is replaced by the Simulate button in case the simulation option is chosen.
The Stop Fit button will interrupt a running fit procedure. Fields show the status of
calculations, the value of χ
2
and the elapsed time.
The lower part of the fit and simulation window displays the parameters. Normally,
only fitable parameters are shown (it is possible to display all parameters by choosing
the Extended setup option from the Option menu). Each line contains the name of the
parameter, its value and a checkbox to indicate whether the parameter should be fitted
or not. In extended setup, in each line there are additional fields for the value and the
type (absolute, relative or disabled) of the convergence criterion.
Fitting and simulation step by step
Fitting
1 Load a cyclic voltammogram file,
C:\AUTOLAB\TESTDATA\DEMOCVO3.0CW.
2 From Analysis menu (Data presentation window) select Fit and Simulation.
3 Select the model 'reversible' from the drop-down menu in the top part of the
appearing window.
Fig. 50 Fit and simulation window
Chapter 4 Analysis of measured data 77
4 Make sure the switch right to the model name is set to Fit.
5 Get the initial guesses for the parameters either by clicking Init. guess button,
pressing Alt-G or by choosing Initial guess from the Option menu.
6 Check whether the number of exchanged electrons is correct.
7 Select parameters to fit by checking the boxes next to parameter names. If
necessary, adjust the starting value of parameters by clicking it with the mouse
pointer and entering the new value (make sure that the number of electrons is set
to 2).
8 If necessary, switch to extended setup (Option menu, or Ctrl-E) to edit other
parameters or to change parameter’s convergence criteria. Parameters that are
visible in the extended setup but invisible in the standard setup are not fitable, i.e.,
their values are not changed during the fit process (see "Fitting: choosing
parameters to fit" and "Fitting: convergence criteria" for more detailed
information).
9 Select Full Fit control parameters from the Option menu and adjust their values
(see "Fitting: advanced options" for details).
10 Click Fast Fit button on a reduced number of data points.
11 The fitting proceeds until the convergence criteria are satisfied or the maximal
number of iterations is reached, whatever comes first. It is possible to stop fitting
at any moment by clicking Stop fit button. It is possible, that the program will
need a few seconds to complete the iteration before stopping.
12 During the fit, the field Status shows the number of the iteration, field Chi-square
shows the χ
2
value and field Elapsed time shows time elapsed from the start of the
fit.
13 If convergence is reached, the Status field contains information "ready" and the
number of iterations.
14 If the maximal number of iterations has been carried out without reaching the
demanded convergence criteria values, the status field displays information
"stopped" and the number of iterations.
15 If fit has been stopped by Stop fit button, the status field displays information
"interrupted".
16 Pressing Full Fit starts the new cycle of fitting, taking all data into account, with
as start values the values visible on the screen. The number of iterations and the
elapsed time counter are reset.
17 Fit parameters can be saved using option Save fit parameters and reloaded using
the option Load fit parameters (both options from File menu).
18 To replace the work data by the fitted curve use Make work data option from the
File menu.
19 To quit the fit window click the Close button, press Alt-C or select Close from the
File menu.
During fitting the results of each iteration are shown in the Data Presentation window
together with the original data set. It is possible, that some iterations will go in the
wrong direction delivering worse approximations than the previous one. In this case
the fitting procedure steps back and tries to obtain another, better approximation. The
process of stepping back can take few iterations, during which curves observed on the
screen may differ severely with the analysed data. However, this is not a reason to
worry, as the fitting procedure finally comes with a better approximation.
78 User Manual GPES for Windows Version 4.9
Simulation
1 Load the differential pulse voltammogram C:\autolab\testdata\demoea01.
2 Set a window (see Plot menu on Data presentation window) between -1.150 and -
0.850.
3 From Analysis menu (Data presentation window) select Fit and Simulation.
4 Select the model reversible from the drop-down menu in the top part of the
appearing window and set the simulation mode by activating radio-button
Simulation.
5 Switch on extended setup (option Extended setup in the Option menu or Ctrl-E).
6 Set values of parameters.
7 Check whether the type of the process (oxidation/reduction) is set correctly.
8 Each parameter has its allowed range. If a value is entered that exceeds this range,
it is automatically adjusted to fit within it.
9 If necessary, adjust simulation options (Fit control parameters in the Options
menu). For details on these options see "Simulation: advanced options".
10 The Init. guess button can be used all the time to obtain estimates of parameters
for the work data.
11 Press Simulation button or Alt-S to start calculations.
12 When simulation is completed, the status field shows message "simulation ready".
The χ
2
field displays the sum of squares of datapoints values, y
i
i
2

.
13 The comparison can be improved by switching to ‘Fit’ and selecting ‘Full Fit’.
To make simulation results permanent, select the Make work data option from the File
menu. Close the fit and simulation window (Close button or Alt-C or Close option
from the File menu), or switch to fitting (by pressing Fit button close to the model
name), or select another model. In the last case a new list of parameters appears with
their default values.
Chapter 4 Analysis of measured data 79
Fitting: advanced options
It is possible to fine-tune the fitting process. Parameters influencing the fit can be set
by choosing Fit control parameters (Option menu) or by pressing Ctrl-P. The
following parameters appear on the screen:
Fit control parameters
Maximum change of chi-square (scaled):
The convergence is reached when the last change in χ
2
is not larger than the given
fraction of χ
2
value.
Maximum fitting time:
The time limit of fit procedure. If it is set to 0 (default) no checking of the time is
done. Change default value of this parameter only if there is a clear reason to do so.
Maximum number of iterations:
The limit for the number of iteration (fitting stops earlier if all convergence criteria
are satisfied).
Fig. 51 The Fit control parameters
80 User Manual GPES for Windows Version 4.9
Number of iterations per fitting step:
Indicates how many iterations are carried out before a signal to break from the user
can be processed and the data on the screen is updated.
Extended parameter setup allows to change default settings of individual convergence
criteria for fitted parameters. A convergence criterion is satisfied when the change in
the parameter value does not exceed the predefined level. Convergence criteria may
be absolute or relative (type of the criterion is indicated by the buttons visible in the
extended setup). Selecting No button for any parameter disables its convergence
criterion (numerical value of previous setting remains visible).
Simulation control parameters
Most of the simulation options are set automatically by the program. In the choice of
their values the program assumes that the parameters of the electrode process have
moderate values and tries to find a reasonable compromise between results precision
and the calculation time. However, when extreme values of parameters (or extreme
combinations of values) are set, or when very high accuracy is desired, automatic
settings may be insufficient.
The simulation options are set by choosing Fit control parameters from the Option
menu. The middle part of the appearing window contains parameters that control the
way the calculations are carried out. These parameters are presented below:
Minimal number of simulation steps per potential value:
The minimal number of simulations cycles carried out for each value of the potential.
If this value is set to N, then each potential step time is divided into N subintervals and
the simulation is carried out for each of these subintervals with time step equal to 1/N
fraction of the step time. The default value is 4.
Maximal number of simulation steps per potential value:
The upper limit for the previous parameter.
Number of points in concentration gradient calculation:
The value of the current is calculated from the derivative of the reactant concentration
at the electrode surface. In digital simulation, the values of concentrations are discrete
and defined only in grid points, and in calculations of concentration gradient the
specified number of points is used. Use of many points usually gives a better precision
of the calculated current. On the other hand, the increase of number of the datapoints
significantly increases the execution time. The default value for this parameter is 2.
Parameter A in space transformation y=ln(1+Ax):
To speed up the calculations, the space grid exponentially expands with the distance
from the electrode surface. This is obtained by transforming the space in such a way,
that the increasing distances in the real space correspond to equally spaced distances
in the transformed space. The program uses Feldberg’s function y=ln(1+Ax) for space
transformation and the rate of expansion, thus also the number of points in
concentration profile, is controlled by parameter A. This parameter should be in the
range 2...3, and its default setting is 2.
Chapter 4 Analysis of measured data 81
Use LU decomposition for boundary condition:
This is the option to provide an alternative way to solve the matrix representing
boundary condition at the electrode surface. The matrix is highly sparse and it is
usually solved by direct method. However, it can happen that the LU (=Lower/Upper)
decomposition method gives better results in some cases, but it is significantly slower
when the number of points used to calculate concentration gradient increases. Default
setting is not to use LU method.
Fast Fit parameters
See "Fitting in more detail, Full and Fast fit".
Data reduction factor:
Allows to carry out fast fit with a data set reduced by this factor (in the reduced data
set points are evenly spaced). The actual value of this factor depends also on the
minimal number of points for fast fit (For more information consult "Fitting: Fast and
Full fit").
Minimum number of points for Fast Fit:
This is the limit for the data reduction factor. The data set used for fast fitting cannot
have fewer points than set by this parameter.
Maximum number of iterations for Fast Fit:
The limit for the iteration number. After reaching it, the fitting procedure switches to
regular fit with all data points.
Fitting in more detail
Fast and Full fit
When working with larger data sets (over 200 points), often obtained in cyclic
voltammetry, it may be attractive to speed up fitting by getting raw values of
parameters with a reduced data set and then to refine them using full set. For this
purpose one can use the reduced data set fitting feature of the fit and simulation
program.
In the reduced data set only every N-th point is used in the fitting. The number N is
called Data reduction factor. Certainly, this factor cannot be very high because fitting
with very few points is likely to deliver parameter values that are not much better than
the initial guesses the program can make. Therefore the user can define the minimal
number of points that the reduced data set must contain. The actual reduction factor is
the smaller number from the data reduction value set and the (total
datapoints)/(minimal datapoints) ratio. Data reduction factor equal to 1 means that no
Fast Fit is performed.
Parameters to control Fast Fit can be set in a window activated by option “Fit control
parameters” from Option menu. In the lower part of this window the data reduction
factor, minimal number of points in the reduced data set and the maximal number of
Fast Fit iterations can be set. Using Fast Fit can be particularly useful when initial
guesses do not deliver good estimates of the parameters, or when fitting process tends
to oscillate.
82 User Manual GPES for Windows Version 4.9
Choosing parameters to fit
Each model is defined by a number of parameters. These parameters are measurement
parameters (e.g., start potential, scan rate), general parameters (e.g., temperature) and
specific parameters (e.g., diffusion coefficient, standard redox potential etc.).
From these parameters only some can be fitted and they are called fitable parameters.
The general rule is that only specific parameters can be fitted. From them, parameters
that can acquire only certain values (for example: the number of electrons involved in
the process) are not fitable.
It is only possible to fit successfully parameters that are independent on each other,
i.e., change in the model due to variation of a certain parameter cannot be obtained by
combination of variations of other parameters. Although models are built in such a
way that interdependent parameters are avoided, it can happen that the particular data
set renders two parameters dependent or partially dependent. An example of such
situation is a data set obtained in cyclic voltammetry with a quasi-reversible system: if
scan potentials are chosen so that only one peak (cathodic or anodic) is visible, it is
impossible to determine both the heterogeneous reaction rate k
s
and the formal
potential E
o
of the redox couple.
How to detect dependence of parameters is explained in "Finding interdependence of
fitted parameters".
Initial guesses
The program provides initial guesses for most of the fitable parameters. The exact list
of parameters for which initial guesses are calculated is available in the description of
the models.
To calculate initial guesses of the parameters, click the button Init. guess, select
option “Initial guesses” from the Option menu or press Alt-I. Initial guesses will
appear on the screen. Also the type of the process (reduction or oxidation) is set to the
default value: reduction for scans going toward negative potentials, and oxidation for
scans going toward positive potentials. The type of the process is an extended setup
parameter, that can be inspected and modified when extended parameter mode is on
(Ctrl-E or the Extended setup option from the Options menu).
To check the correctness of initial guesses before starting the actual fit, switch the
mode to simulation (option button near the model name) and then click the Simulate
button. A curve will be simulated with the current parameter settings, and displayed in
Data Presentation window. If initial guesses are satisfactory, switch back to fit mode
and proceed with fitting. Special care in checking is required for the number of
Exchanged electrons and the Dimensionless electrode radius.
Adjust step size
The fit and simulation option for CV automatically searches for the potential step in
the CV-data. However the data can sometimes have an non-equidistant step in the
potential data (i.e. if measured with ADC750). The fit and simulation software
assumes an equidistant step in the potential. Therefor the fit can give error messages.
In order to get rid of these error messages, an option to adjust the step to the step
potential from the procedure is available. The button is visible on the Fit and
simulation window when the ‘Extended setup’ is activated. Please note that the kinetic
parameters, as a result of this fit, are not reliable anymore.
Chapter 4 Analysis of measured data 83
Convergence criteria
Fitting process is carried out until convergence criteria are satisfied or either the
iteration limit or time limit is reached. There are two types of convergence criteria:
based on χ
2
and related to the parameter value change.
Criteria based on χ
2
demand that:
1. change of χ
2
in the last iteration step must be negative (χ
2
decreases)
2. value of χ
2
(weighted with σ
0
) should be less than 1 (or less than y
i
i
2

for
unweighted data)
3. the last change in χ
2
is so small, that it can be neglected. The value that can be
neglected is defined by the user as the maximal relative in χ
2
(Option menu, “Fit
control parameters”). The default maximal change is 0.01 (=1%) of χ
2
value.
Criteria related to fitted parameters value require, that the change to the parameter
value in the last iteration should not exceed a certain value. This value can be defined
as an absolute, or as a relative one (a fraction of the parameter’s value). In the
extended setup (Option menu) it is possible to define the value and the type
(absolute/relative) of the convergence criterion for each fitable parameters. The
Fig. 52 Convergence criteria
84 User Manual GPES for Windows Version 4.9
Convergence field contains the criterial value, and the buttons right to the value field
can be used to select the absolute type of the criterion, the relative one or to disable
the criterion for this parameter. The fitting process finishes when all the convergence
criteria are satisfied. If the convergence is not reached in spite of many interactions
done, this can be due to the following reasons:
1. Demanded precision of the parameters is unrealistic. The level of noise in the data,
or precision of the measured variable (usually current) may keep the variation of
the parameter of interest above the demanded level.
2. The type of the criterion is not appropriate. For example, in datasets where the
background is very small it is better to use the absolute criterion than the relative
one for background value, and relate it to the measured peak or wave current.
The model is not applicable. In this situation the value of χ
2
is usually larger than 1
(or larger than y
i
i
2

for unweighted data) while all other criteria can be met. It is then
advisable to either change the model, of re-examine settings for non-fitable
parameters, like the number of electrons involved in the electrode reaction.
Finding interdependence of fitted parameters
Dependence of parameters can be detected by inspection of the covariance matrix
(Covariance matrix in the Option menu or Ctrl-M). The diagonal terms are unity. If a
term corresponding to a pair of parameters is significant, there is a serious chance that
these two parameters are interdependent.
Problems can arise if two or more parameters are interdependent. The matrices used
during fit can become singular and an error occurs. Also, the fitted values of
interdependent parameters are meaningless, or the program oscillates and it cannot
deliver the final values. Finally, the computational time unnecessary increases,
because fitting of each parameter requires the calculation of the derivative of the fitted
curve with respect to this parameter. Some derivatives can be calculated analytically,
but some not, and in the latter case the derivative must be obtained numerically. This
requires an additional simulation per iteration step.
Fit and simulation error messages
error -1: “xxxxxxx”:
Internal error of the fit and simulation program. String “xxxxxxx” contains specific
information about the problem. Please report circumstances under which this error
appeared.
error 1: Not enough memory:
There is not enough memory available to carry out the simulation. Try to free some
memory by closing other applications.
error 10: Technique not supported:
An operation has been requested that is not supported for the currently selected
technique. Please report circumstances under which this error appeared.
error 11: Mechanism not supported:
An operation has been requested that is not supported for this electrode reaction
mechanism. Please report circumstances under which this error appeared.
Chapter 4 Analysis of measured data 85
error 12: Model not supported:
An operation has been requested that is not supported for the model chosen. Please
report circumstances under which this error appeared.
error 20: Negative reactant concentration obtained:
Negative concentration of the reactant at the electrode surface has been obtained
during the simulation of concentration profiles. This is usually due to the extreme
value of the potential, at which the ratio of reactant to product concentration is either
very small or very large. The general remedy is to shorten the potential range used. If
it is not possible, try to use another settings for advanced simulation parameters. If
this doesn’t help, please report the problem.
error 21: Negative product concentration obtained:
Negative concentration of the product at the electrode surface has been obtained
during the simulation of concentration profiles. This is usually due to the extreme
value of the potential, at which the ratio of reactant to product concentration is either
very small or very large. The general remedy is to shorten the potential range used. If
it is not possible, try to use another settings for advanced simulation parameters. If
this doesn’t help, please report the problem.
error 51: GAUSSJ: Singular Matrix-1:
Two or more parameters in the model are dependent or nearly dependent.
error 52: GAUSSJ: Singular Matrix-2:
Two or more parameters in the model are dependent or nearly dependent.
Descriptions of the models
General remarks
All models of electrode reactions assume diffusion to an electrode with finite
dimensions. The size of the electrode is characterised by the dimensionless electrode
radius
r r D
d e R
· / τ
where r
e
is the radius in meters, D
R
is the diffusion coefficient of the reactant in m
2
/s
and τ is the characteristic time parameter of the technique. The time parameter τ is
equal to RT/nFV (in staircase and cyclic voltammetry, V=scan rate), to pulse time (in
normal pulse voltammetry and chrono techniques), to modulation time (in differential
pulse techniques) and to inverse of frequency (in square wave voltammetry).
If the electrode is large or the τ parameter is small (fast experiments), i.e., only linear
diffusion takes place, the dimensionless electrode radius should be set to zero. This
value indicates that the radius of the electrode is irrelevant. All electron transfer rates
are normalised according to equation
k k D
R
· τ
86 User Manual GPES for Windows Version 4.9
and all homogeneous (chemical) reaction rates are normalised by multiplication by τ
k k
c h e m c h e m
· τ
Use of normalised constants allows carrying out fitting without the knowledge of
diffusion coefficients.
In all equations in the description of the models the log() function refers to 10-based
logarithm, and ln() function to natural (e-based) logarithm.
Cyclic voltammetry: reversible electrode process
Reaction equation: R P
ne

← → ÷÷
Fitable parameters:
redox potential E
0
(V)
normalised current I
norm
(I = I
norm
*χ(at)) (A)
constant background current (A)
Initial guesses available for: number of exchanged electrons, E
0
, I
norm
, background
current
Comments: According to the theory, the peak current is equal to
nFAc
bulk
(πaD)
1/2
*
χ(at), where the first term is equal to the fitable parameter I
norm
and
the function χ(at), a=nFV/RT, V being scan rate, represents the shape of the
voltammetric peak. The peak value of this function is 0.4463 for linear sweep
voltammetry, while for voltammetry utilising the staircase voltage ramp the exact
value depends on the step height, step time and the current sampling parameter α.
Details regarding the function χ(at) can be found in literature
1
.
Cyclic voltammetry: quasi-reversible electrode process
Reaction equation: R P
ne k
s

← → ÷÷
,
Fitable parameters:
redox potential E
0
(V)
Log (normalised electron transfer rate), ( ) log k
s
transfer coefficient α
normalised current I
norm
(I = I
norm
*χ(bt)) (A)
constant background current (A)
Initial guesses available for: number of exchanged electrons, log(k
s
), E
0
, I
norm
,
background current
Comments: The parameter ( ) log k
s
is a 10-base logarithm of the electron transfer rate,
normalised with respect to the time scale of the experiment k k R T nFV D
s s
· ,
where V is the scan rate and k
s
is the electron transfer rate used in Butler-Volmer
equation

1
R. S. Nicholson and I. Shain, Anal. Chem., vol. 36, 1964, page 706.
Chapter 4 Analysis of measured data 87
( ) ( )
( ) ( ) ( ) ( ) I k c n F R T E E c n F R T E E
s R P
· − − + − − e xp e xp α α
0 0
1
According to the theory, the peak current is equal to nFAc
bulk
(πbD)
1/2
*
χ(bt), where the
first term is equal to the fitable parameter I
norm
and the function χ(bt), b=αnFV/RT,
represents the shape of the voltammetric peak. The peak value of this function
depends on the electron transfer rate k
s
, the transfer coefficient α, the step height, step
time and the current sampling parameter α.
Cyclic voltammetry: irreversible electrode process
Reaction equation: R P
ne k
s

÷ → ÷÷
,
Fitable parameters:
Log(Normalised electron transfer rate at E
0
=0), ( ) log k
f h
0
(exchanged electrons)*(transfer coefficient) αn
normalised current I
norm
(I = I
norm
*χ(bt)) (A)
constant background current (A)
Initial guesses available for: E
0
, αn, I
norm
, background current
Comments: The parameter ( ) log k
f h
0
is a 10-base logarithm of the electron transfer rate,
normalised with respect to the time scale of the experiment k k R T n F V D
f h f h
0 0
· ,
where V is the scan rate and k
0
fh
is the electron transfer rate at E=0, used in reduced
Butler-Volmer equation
( ) ( ) ( )( ) ( ) I k c n F R T E k c n F R T E E
f h R s R
· − · − −
0 0
e xp e xp α α
According to the theory, the peak current is equal to nFAc
bulk
(πbD)
1/2
*
χ(bt), where the
first term is equal to the fitable parameter I
norm
and the function χ(bt), b=αnFV/RT,
represents the shape of the voltammetric peak. The peak value of this function is equal
to 0.4958 for linear sweep voltammetry, and for staircase voltammetry it depends on
the electron transfer rate k
s
, the transfer coefficient α, the step height, step time and
the current sampling parameter α. Details regarding the function χ(bt) can be found in
literature.
There is no need to set the number of exchanged electrons, because the term αn is
fitted as a whole.
Cyclic voltammetry: reversible electrode process followed by irreversible
chemical reaction (ECi)
Reaction equation: R P B
ne
k
cf

← → ÷÷ ÷ → ÷
Fitable parameters:
redox potential E
0
(V)
forward chemical reaction rate kc(foll)-> (norm.) = k
cf
normalised current I
norm
(I = I
norm
*χ(bt)) (A)
constant background current (A)
Initial guesses available for: number of exchanged electrons, E
0
, I
norm
, background
current
88 User Manual GPES for Windows Version 4.9
Comments: The forward chemical reaction rate is normalised with respect to the time
scale of the voltammetric experiment, ( ) k k R T n F V
c f c f
· . Similarly to previous cases,
the voltammetric peak current is expressed as a product of the peak shape function
χ(bt) and the term including the electrode area, concentration, diffusion coefficient
and the number of exchanged electrons. Details regarding this mechanism can be
found in literature.
Cyclic voltammetry: two-component models
Two-component models represent the situation when two electroactive species are
reduced or oxidised at the electrode independently from each other. In such situations
their peaks can overlap, what hinders the extraction of relevant parameters for
separate reactions.
There is a number of two-component models available, differing in the degree of
reversibility of each electron transfer (reversible, quasi-reversible or irreversible
mechanism). The parameters are denoted with numbers 1 and 2 to indicate to which
component they correspond.
Reaction equations for single component:
R P
i
n e
i

← → ÷ (reversible process)
R P
i
n e k
i
s

← → ÷÷
,
(quasi-reversible process)
R P
i
n e k
i
s

÷ → ÷÷
,
(irreversible process)
Fitable parameters
• reversible case:
redox potential E
0
(V)
normalised current I
norm
(I = I
norm
*χ(at)) (A)
• quasi-reversible case:
redox potential E
0
(V)
Log(normalised electron transfer rate), ( ) log k
s
)
transfer coefficient α
normalised current I
norm
(I = I
norm
*χ(bt)) (A)
• irreversible case:
Log(Normalised electron transfer rate at E
0
=0), ( ) log k
f h
0
(exchanged electrons)*(transfer coefficient) αn
normalised current I
norm
(I = I
norm
*χ(bt)) (A)
• common parameter:
constant background current (A)
Initial guesses available for:
Comments: According to the theory, the peak current is equal to
nFAc
bulk
(πaD)
1/2
*
χ(at) (reversible processes) or nFAc
bulk
(πbD)
1/2
*
χ(bt) (irreversible
processes), where the first term is equal to the fitable parameter I
norm
and the functions
χ(at) and χ(bt) represent the shape of the voltammetric peak. The parameters a and b
are respectively a=nFV/RT, b=αnFV/RT, V being the scan rate. The peak values of
these function are 0.4463 (reversible) and 0.4958 (irreversible) for linear sweep
voltammetry. If voltammetry with staircase voltage ramp is used, the exact value
Chapter 4 Analysis of measured data 89
depends on the step height, step time and the current sampling parameter α. Details
regarding the function χ(at) and χ(bt)can be found in literature.
The electron transfer rates k
s
and k
f h
0
are defined as follows:
k k R T n F V D
f h f h
0 0
· and k k R T nFV D
s s
·
while the Butler-Volmer equations for respectively quasi-reversible and irreversible
processes are
( ) ( )
( ) ( ) ( ) ( ) I k c n F R T E E c n F R T E E
s R P
· − − + − − e xp e xp α α
0 0
1 (quasi-
reversible)
( ) ( ) ( )( ) ( ) I k c n F R T E k c n F R T E E
f h R s R
· − · − −
0 0
e xp e xp α α (irreversible)
Due to the possible complication of two-component voltammograms, it can happen
that the initial guesses are inferior to those obtained in simpler models. However, it is
always possible to select datapoints (by setting the window in such a way that only
one peak is covered), do initial guesses for one-component model and transfer the
results to two-component model.
When electron transfer processes are different, for example Er+Ei, all parameters
marked with (1) refer to electron transfer Er, while all marked with (2) - to electron
transfer Ei. The initial guess procedure can have problems with appropriate
assignment of peaks to the components. This assignment can be changed by swapping
the values referring to the first component and to the second component. In case of
irreversible electron transfer it is necessary, however, to adjust the value of k
f h
0
using
the relationship ∆ ∆ k n F E R T e
f h p
0
· α log .
Normal pulse voltammetry: reversible electrode process
Reaction equation: R P
ne

← → ÷÷
Fitable parameters:
halfwave potential E
1/2
(V)
limiting current I
lim
(A)
constant background current (A)
Initial guesses available for: number of exchanged electrons, E
1/2
, I
lim
, background
current
Comments: The theoretical expression for the limiting current at a large flat electrode
is I
lim
=nFAc
bulk
(D
R
/πt
p
)
1/2
, where t
p
is the pulse time. The halfwave potential should be
equal to polarographic halfwave potential.
Normal pulse voltammetry: quasi-reversible electrode process
Reaction equation: R P
ne k
s

← → ÷÷
,
Fitable parameters:
redox potential E
0
(V)
Log(normalised electron transfer rate), ( ) log k
s
transfer coefficient α
limiting current I
lim
(A)
constant background current (A)
90 User Manual GPES for Windows Version 4.9
Initial guesses available for: number of exchanged electrons, E
0
, I
norm
, background
current
Comments: The parameter ( ) log k
s
is a 10-base logarithm of the electron transfer rate,
normalised with respect to the time scale of the experiment k k t D
s s p
· , where t
p
is
the pulse time and k
s
is the electron transfer rate used in Butler-Volmer equation
( ) ( )
( ) ( ) ( ) ( ) I k c n F R T E E c n F R T E E
s R P
· − − + − − e xp e xp α α
0 0
1
The theoretical expression for the limiting current at a large flat electrode is
I
lim
=nFAc
bulk
(D/πt
p
)
1/2
.
Normal pulse voltammetry: irreversible electrode process
Reaction equation: R P
ne k
s

÷ → ÷÷
,
Fitable parameters:
Characteristic potential E
*
(V)
Log(Normalised electron transfer rate at E
0
=0), ( ) log k
f h
0
(exchanged electrons)*(transfer coefficient) αn
limiting current I
lim
(A)
constant background current (A)
Initial guesses available for: ( ) log k
f h
0
, αn, E
*
E, I
norm
, background current
Comments: There is no need to set the number of exchanged electrons, because the
term αn is fitted as a whole. The theoretical expression for the limiting current at a
large flat electrode is I
lim
=nFAc
bulk
(D/πt
p
)
1/2
, where t
p
is the pulse time. The
characteristic potential E
*
is defined as ( ) ( ) E RT nF k E RT nF k
fh s
*
ln ln · · + α α
0 0
,
where k k t D
f h f h p
0 0
· and k k t D
s s p
· . k
s
and k
0
fh
are the electron transfer rates
used in Butler-Volmer equation
( ) ( ) ( )( ) ( ) I k c n F R T E k c n F R T E E
f h R s R
· − · − −
0 0
e xp e xp α α
Normal pulse voltammetry: reversible electrode process followed by
irreversible chemical reaction (ECi)
Reaction equation: R P B
ne
k
cf

← → ÷÷ ÷ → ÷
Fitable parameters:
redox potential E
0
(V)
forward chemical reaction rate kc(foll)-> (norm.) k
c f
limiting current I
lim
(A)
constant background current (A)
Initial guesses available for: number of exchanged electrons, E
0
, I
norm
, background
current
Chapter 4 Analysis of measured data 91
Comments: The theoretical expression for the limiting current at a large flat electrode
is I
lim
=nFAc
bulk
(D/πt
p
)
1/2
, where t
p
is the pulse time. The forward chemical reaction
rate is normalised with respect to the time scale of the experiment, k k t
c f c f P
· .
Normal pulse voltammetry: reversible electrode process (analytical), quasi-
reversible electrode process (analytical) and irreversible electrode process
(analytical)
These models differ from the previous only by the fact, that each point of the normal
pulse voltammogram is calculated from analytical expressions for
chronoamperometry under the following assumptions:
• the current is measured at the end of the potential pulse
• before each potential pulse concentrations of the species at the electrode surface
are the same as in the bulk of the solution
The latter means that no significant electrode reaction occurs at the base potential, and
that the interval time is long enough to restore the initial concentrations (or the
dropping mercury electrode is used). In addition to this, it is assumed in the reversible
model that the product of the electrode reaction is initially absent in the solution.
Thanks to analytical expressions the speed of calculations is much higher than in the
regular model based on finite-difference simulation. Therefore, if the mentioned
assumptions are valid, this model should be preferred.
Differential pulse voltammetry: reversible electrode process
Reaction equation: R P
ne

← → ÷÷
Fitable parameters:
peak potential E
p
(V)
peak current I
p
(A)
constant background current (A)
Initial guesses available for: number of exchanged electrons, E
p
, I
p
, background
current
Comments: The approximate expression for the peak height, valid under linear
diffusion conditions, is
I
p
= nFAc
bulk
(D/πt
m
)tanh(nF∆E/4RT)
where t
m
is the modulation time and ∆E is the modulation amplitude.
Differential pulse voltammetry: quasi-reversible electrode process
Reaction equation: R P
ne k
s

← → ÷÷
,
Fitable parameters:
peak potential E
p
(V)
Log(normalised electron transfer rate), ( ) log k
s
transfer coefficient α
peak current I
p
(A)
constant background current (A)
92 User Manual GPES for Windows Version 4.9
Initial guesses available for: number of exchanged electrons, E
p
, ( ) log k
s
, α, I
p
,
background current
Comments: The parameter ( ) log k
s
is a 10-base logarithm of the electron transfer rate,
normalised with respect to the time scale of the experiment, k k t D
s s m R
· , where V
is the scan rate and k
s
is the electron transfer rate used in Butler-Volmer equation
( ) ( )
( ) ( ) ( ) ( ) I k c n F R T E E c n F R T E E
s R P
· − − + − − e xp e xp α α
0 0
1
The general expression for the peak height does not exist, expressions for particular
situations are complicated.
Differential pulse voltammetry: irreversible electrode process
Reaction equation: R P
ne k
s

÷ → ÷÷
,
Fitable parameters:
Characteristic potential E
*
(V)
Log(Normalised electron transfer rate at E
0
=0), ( ) log k
f h
0
(exchanged electrons)*(transfer coefficient) αn
peak current I
p
(A)
constant background current (A)
Initial guesses available for: number of exchanged electrons, E
p
, ( ) log k
f h
0
, αn, I
p
,
background current
Comments:
There is no need to set the number of exchanged electrons, because the term αn is
fitted as a whole.
The characteristic potential E
*
is defined as
( ) ( ) E RT nF k E RT nF k
fh s
*
ln ln · · + α α
0 0
, where k k t D
f h f h m R
0 0
· and
k k t D
s s m R
· . k
s
and k
0
fh
are the electron transfer rates used in Butler-Volmer
equation
( ) ( ) ( )( ) ( ) I k c n F R T E k c n F R T E E
f h R s R
· − · − −
0 0
e xp e xp α α
Differential pulse voltammetry: reversible electrode process followed by
irreversible chemical reaction (ECi)
Reaction equation: R P B
ne
k
cf

← → ÷÷ ÷ → ÷
Fitable parameters:
redox potential E
0
(V)
normalised forward chemical reaction rate kc(foll)-> (norm.), k
c f
peak current I
p
(A)
constant background current (A)
Initial guesses available for: E
p
, I
p
, background current
Chapter 4 Analysis of measured data 93
Comments: The forward chemical reaction rate is normalised with respect to the time
scale of the voltammetric experiment, k k t
c f c f m
· . No simple expression is available
for the peak height.
Square wave voltammetry: reversible electrode process
Reaction equation: R P
ne

← → ÷÷
Fitable parameters:
formal potential E
0
(V)
peak current I
p
(A)
constant background current (A)
Initial guesses available for: E
p
, I
p
, background current (fitting on net current)
E
pf
, I
pf
, background current (fitting on
forward/backward current)
Comments: There is no simple expression for the net peak current. The interpretation
of the value of I
p
depends whether fitting takes place on the net current or on
forward/backward currents: in the first case Ip corresponds to the height of the net
current, in the second - to the height of the forward peak. Switching between net
current and forward/backward current will therefore result in the difference in peak
heights.
The potential of the peak is very close to the polarographic halfwave potential.
Square wave voltammetry: quasi-reversible electrode process
Reaction equation: R P
ne k
s

← → ÷÷
,
Fitable parameters:
formal potential E
0

(V)
Log( normalised electron transfer rate), ( ) log k
s
transfer coefficient α
peak current I
p
(A)
constant background current (A)
Initial guesses available for: E
p
, I
p
, background current
Comments: The parameter ( ) log k
s
is a 10-base logarithm of the electron transfer rate,
normalised with respect to the time scale of the experiment k k f D
s s R
· , where f is
the frequency and k
s
is the electron transfer rate used in Butler-Volmer equation
( ) ( )
( ) ( ) ( ) ( ) I k c n F R T E E c n F R T E E
s R P
· − − + − − e xp e xp α α
0 0
1
There is no simple expression for the net peak current. The interpretation of the value
of I
p
depends whether fitting takes place on the net current or on forward/backward
currents: in the first case Ip corresponds to the height of the net current, in the second
- to the height of the forward peak. Switching between net current and
forward/backward current will therefore result in the difference in peak heights.
Square wave voltammetry: irreversible electrode process
Reaction equation: R P
ne k
s

÷ → ÷÷
,
Fitable parameters:
94 User Manual GPES for Windows Version 4.9
Characteristic potential E
*
(V)
Log( normalised electron transfer rate at E0=0), ( ) log k
f h
0
(exchanged electrons)*(transfer coefficient) αn
peak current I
p
(A)
constant background current (A)
Initial guesses available for: E
*
,I
p
, background current
Comments: There is no need to set the number of exchanged electrons, because the
term αn is fitted as a whole.
The characteristic potential E
*
is defined as
( ) ( ) E RT nF k E RT nF k
fh s
*
ln ln · · + α α
0 0
, where ( ) k k f D
f h f h R
0 0
· and
( ) k k f D
s s R
·
( ) k k R T n F V D
s s
·
. where f is the frequency and k
s
and k
0
fh
are the
electron transfer rates used in simplified Butler-Volmer equation
( ) ( ) ( )( ) ( ) I k c n F R T E k c n F R T E E
f h R s R
· − · − −
0 0
e xp e xp α α
There is no simple expression for the net peak current. The interpretation of the value
of I
p
depends whether fitting takes place on the net current or on forward/backward
currents: in the first case Ip corresponds to the height of the net current, in the second
- to the height of the forward peak. Switching between net current and
forward/backward current will therefore result in the difference in peak heights.
Square wave voltammetry: reversible electrode process followed by
irreversible chemical reaction (ECi)
Reaction equation: R P B
ne
k
cf

← → ÷÷ ÷ → ÷
Fitable parameters:
redox potential E
0
(V)
normalised forward chemical reaction rate kc(foll)-> (norm.) k
c f
peak current I
p
(A)
constant background current (A)
Initial guesses available for: E
p
, I
p
, background current
Comments: The forward chemical reaction rate is normalised with respect to the time
scale of the experiment, k k f
c f c f
· , where f is the frequency.
There is no simple expression for the net peak current. The interpretation of the value
of I
p
depends whether fitting takes place on the net current or on forward/backward
currents: in the first case Ip corresponds to the height of the net current, in the second
- to the height of the forward peak. Switching between net current and
forward/backward current will therefore result in the difference in peak heights.
Chapter 4 Analysis of measured data 95
4.14 Current density
The current density is calculated with the surface area, using the surface area on page
2 of the procedure window.
4.15 WE2 versus WE plot
When a BIPOT is present, Iring versus Idisk plots can be constructed with this option.
4.16 Endpoint Coulometric titration
After performing a coulometric titration experiment (Chrono method (>0.1s)
potentiometry (galvanostatic) with pX/pH signal) this option can be chosen.
The experiment time is converted into charge (the current applied is given from the
procedure) and only the pX/pH signal is shown on the y-axes. Furthermore the
‘Endpoint Coulometric titration’ window is opened, to find the endpoint. If you
follow the instructions the turning point will be shown as endpoint.
• The endpoint is obtained from the zero crossing(s) in the 2
nd
derivative. The 2
nd
derivative and endpoint are calculated using the last applied level. If only one
level is defined all calculations are done on this particular level.
• The 2
nd
derivative values are normalised so do not pay attention to the absolute
values. The 2
nd
derivative plot is used for indicative purposes only.
• The show 2
nd
derivative button is active after the Find endpoint button has been
pressed.
• The ‘Show last level’ button appears only if more then one level is measured.
• If the amount of measured point is poor the indicated end point in the curve can be
slightly different from the actual zero crossing in the 2
nd
derivative. The pointer
can only be set on a real data-point and not on an interpolated point in between.
96 User Manual GPES for Windows Version 4.9
Parameters:
Filter for derivative: Filter factor to reduce noise on the 2
nd
derivative.
1%: no filtering – 25%: heavy filtering.
Window for zero crossings: Defines when a zero crossing should be noticed as a real
zero crossing. This window defines the amount of points
with different sign before and after the zero crossing.
Due to Faraday’s law the equivalent of generated titrant is proportional to the charge
and the equivalent of the analyte can be calculated (see also Application note
“Coulometric titration”, and “Installation and Diagnostics Guide: pX-module).
Fig 52a. Coulometric titration plot
Chapter 5 Editing of measured data 97
5. Editing of measured data
5.1 Smooth
Every measurement is disturbed by noise. In many cases the noise level will be low,
but especially at low current levels the amount of noise can be severe. In order to
enhance the signal to noise ratio of experimental data sets, a Smooth option is
supplied. The data files can be smoothed using either the Savitsky-Golay algorithm or
a FFT-algorithm.
Smoothing can be performed on the whole curve or a part of it. When only a part of
the curve should be smoothed, click the Smooth window button and select a part of
the curve. The remainder will not be smoothed. This option is only available for
Savitzky and Golay smoothing.
The popular Savitzky and Golay method is described in Anal. Chem.,36,1627 (1964).
Their method presumes that a number of points can be fitted to a polynomial so that
the best curve will pass through the experimental points. This method is also called
weighted moving averaging. Before the smooth routine of Savitzky and Golay is
applied to the data set, spikes in the set of data are removed.
The Smooth option in all programs first asks which smooth level has to be applied.
Valid levels are 0 to 4.
These levels are :
0- spike rejection only
1- spike rejection and a 5-point weighed moving average
2- spike rejection and a 9-point weighed moving average
3- spike rejection and a 15-point weighed moving average
4- spike rejection and a 23-point weighed moving average
The applicable smooth level heavily depends on the number of points of the data set.
The more points within the curve, the higher the smooth level can be without
modifying the curve too much.
Having selected the FFT option, a logarithmic or linear frequency domain plot is
displayed. Now a cutoff frequency has to be supplied, which should be less than the
dominant noise frequency. The FFT-smoothing algorithm assumes that the signal is
composed of n/2 sine waves of different frequencies, where n is the number of
measured data points, filled up to a power of 2 (512, 1024, etc.). The added data
points get a value of zero. A cut-off frequency of for instance 20 means that the
amplitudes of the 20 sine waves with the lowest frequencies are kept, all other
amplitudes are set to zero. After a back-transformation, both the original curve and the
smoothed curve are displayed and the question is posed whether the original data
should be replaced. The FFT-algorithm is very effective in removing noise originating
from the power-source. The FFT-algorithm is explained in the book "Numerical
Recipes", W.H. Press et al., Cambridge University Press, ISBN 0 521 30811 9. FFT-
smoothing should not be used in data files with spikes or discontinuities. It works best
98 User Manual GPES for Windows Version 4.9
if the noise only consists of a periodic disturbance with a higher frequency than the
real signal. The real signal should not change much within one period of this periodic
disturbance.
Please note that the presented frequency in the frequency domain plot is not the
frequency of the noise in the current or potential signal. The frequency is presented in
an arbitrary unit.
5.2 Change all points
This option allows to add a constant value to all data points or to multiply all
datapoints with a constant value.
5.3 Delete points
It is possible to remove points from the plot. You can specify up to 20 points.
This option can be used to remove spikes from the measured data. With resume (Data
presentation, Plot) the original data set will be loaded again. The Save work data
(Data presentation, File) can be used to save the adjusted data-set.
5.4 Baseline correction
Four types of baselines can be specified.
The first is the linear baseline. Two markers on the measured curve can be specified,
which then define a line. After acceptation of the markers, the corrected curve is also
drawn. By clicking either the Cancel or the OK button on the Baseline correction
window, the correction can be either ignored or accepted.
It is also possible to subtract a polynomial baseline. After selecting this option the
user is asked to mark between two and five data points as contact points between
baseline and curve. After accepting the markers the program will calculate a 3rd order
polynomial through the markers.
The third type calculates a connecting exponential curve through the specified begin
and end point. The whole curve is subsequently corrected for this baseline.
Finally, there is the so-called ‘Moving average baseline’. This is an automatic
baseline correction. This method is very effective when peaks show as shoulders on
steep flanks. After a baseline correction real peaks will show. The number of data
points is reduced by calculating the average within a step window. The step window is
the minimum peak width which can be specified on the Baseline correction window.
The baseline is subsequently calculated by comparing each point with the mean value
of its two neighbours. If the absolute mean value is lower, it replaces the current
value. This operation is repeated again and again until no data point is replaced
anymore. If more than 1000 iterations are required, a message is given and the process
stops. As a default minimum peakwidth a value of 30 mV or less is advised in most
cases. The process can be hindered by anomalies in the voltammogram. Please note
that this technique cannot be applied for Cyclic and Linear sweep voltammograms.
Chapter 5 Editing of measured data 99
5.5 Subtract disk file
This option allows to subtract a previously measured data set from the current one. In
case the spacing between the two data sets is different a linear interpolation method is
used.
5.6 Subtraction of second signal from first signal.
This option allows to subtract a simultaneously measured second signal using either
of the free ADC-channels from the current or potential signal (first signal). In case the
spacing between the two data sets is different a linear interpolation method is used.
The option is only enabled when a second signal is really available.
5.7 Derivative
First the data points are smoothed according to the Savitsky-Golay algorithm (see
above) using smooth factor 2. Subsequently the derivative is determined by the simple
algorithm:
y(n) - y(n-1) ] y(n+1) - y(n) ]
dy/dx (n) = 0.5* ÷÷÷÷÷ ] + 0.5* ÷÷÷÷÷− ]
x(n) - x(n-1) ] x(n+1) - x(n) ]
For cyclic and linear voltammetry the time derivative is given, i.e. x is the time since
the start of the scan instead of the potential.
5.8 Integrate
The integral is determined using the trapezium rule, which assumes a straight line
between two data points.
For cyclic and linear voltammetry the time integral is given, i.e. x is the time since the
start of the scan instead of the potential.
Fig 52b: Baseline correction window
100 User Manual GPES for Windows Version 4.9
5.9 Fourier transform
The frequency spectrum is determined by means of a Fast Fourier method (FFT). The
real frequency is displayed on the x-axis.
5.10 Convolution techniques
Convolution voltammetry consists essentially of a voltammetric,
chronoamperometric, or chronocoulometric experiment followed by a mathematical
transformation - convolution. The technique delivers quantities directly related to the
concentration of electroactive species at the electrode surface (instead of the flux of a
compound, as in the case of the original techniques) and it is rather insensitive to iR-
drop.
In a number of electroanalytical techniques, the current measured displays
proportionality to a t


function. The popularity of this type of dependence originates
from the solution of Fick's law in the case of semi-infinite linear diffusion, the most
common type of the transport of the reagent to the electrode. According to this
solution, the gradient of the concentration of a substance, consumed in the electrode
process, decreases with the square root of the electrolysis time and so does the current
which is proportional to this gradient. Such a dependence can be easily observed in
chronocoulometry, chronoamperometry, and in voltammetry (in this latter case in the
descending branch of the peak).
Fig. 53 Convolution menu
Chapter 5 Editing of measured data 101
Using a convolution method, the effect of the decrease of the concentration gradient
can be eliminated from the total response of the electrode. The surface concentration
of the product of an electrode reaction during the experiment can be obtained using
equation

.
c
s
(t) = i(t)*g(t)/(nFAD
½
) (eq. 1)
where i(t)*g(t) is a convolution operation defined as
x x
⌠ ⌠
f
1
(x)*f
2
(x) = 1 f
1
(u)f
2
(x-u)du = 1 f
1
(x-u)f
2
(u)du (eq. 2)
⌡ ⌡
0 0
The function g(t) depends on the transport conditions and the electrode geometry,
being in the simplest case (πt)
½
. The convolution of a voltammogram results in an S-
shaped curve, where voltammetric peaks are replaced by waves, very similar to
polarographic ones. In the case of a fast and uncomplicated electron transfer, the wave
can be described using the equation
E = E
½
+ (RT/nF)ln[(m
d
-m)/m] (eq. 3)
where m denotes current convolution (for approximate description of kinetic-
controlled processes the RT/nF value should be replaced by RT/αnF). The height of
the plateau is given by the formula
m
d
= nFAD
½
C (eq. 4)
It can be shown that such a result is independent of the scan rate used and that the
height of the wave is insensitive to iR-drop.
Convolution of voltammetric data with a t

function results in a curve equivalent to
the derivative of the previous one (up to a normalisation factor). Valuable features of
this new curve can be noted: symmetric, narrow peaks which are much better resolved
compared to asymmetric, "tailing" voltammetric ones. The obtained t

convolution
peak follows the function


) K.B. Oldham, Anal. Chem. 58 (1986) 2296, J.C. Myland, K.B. Oldham, C.G.
Zoski, J. Electroanal. Chem. 193 (1985) 3.
102 User Manual GPES for Windows Version 4.9
e = nFAD
½
Ccosh
-2
[nF/2RT(E-E°')] (eq. 5)
in case of a fast, reversible electron transfer.
It is also possible to use other convolution functions e.g. to separate the spherical
diffusion effect, the kinetic effect of the preceding homogeneous reaction etc

.
In chronoamperometry, convolution of current with t
½
function results in a horizontal
line at the height equal to
e = nFAD
½
C (eq. 6)
if the transport to the electrode follows semi-infinite linear diffusion. For
chronocoulometry, convolution with a t

function leads exactly to the same result.
It is profitable to distinguish a class of convolutions with a g(t) function in the form
g(t)=t
-u
(u is a real number): such a convolution can be considered as a generalised
differentiation/integration (differintegration) operation with respect to the variable t.
In this approach, the value of the exponent denotes the order of integration (if
positive) or differentiation (if negative) and thanks to the convolution definition, the
value of u need not be integer. Differintegration is cumulative, i.e. d
½
/dt
½
(d
½
i/dt
½
) =
di/dt or d

/dt

(di/dt) = d
½
i/dt
½
. From the practical point of view, two forms of
convolution, with t
½
and t

, deserve special attention. They can be considered as,
respectively, semi-integration and semi-differentiation.
Another reason for mentioning differintegration is that there are special algorithms
allowing this operation to be performed rapidly. For more information please refer to
K.B. Oldham, J. Spanier, "The Fractional Calculus", Academic Press, N.Y., 1974.
As mentioned before, in case of semi-infinite linear diffusion the results of
convolution with the function t
±½
(semi-integration and semi-differentiation) are well-
defined and quite simple. This suggests that these methods can be used for the
investigation of variations of product concentration on the electrode surface as well as
detection and studies of phenomena, resulting in deviations from linear diffusion
transport. Other practical applications are the resolution of overlapping voltammetric
peaks, the determination of the formal potentials and numbers of electrons involved in
the reaction step, detection of the adsorption on the electrode as well as of the
irreversible homogeneous reaction consuming the product generated by the electron
transfer step.
Detection of overlapping peaks
The nature of the voltammetric peak causes overlap in case of complex
voltammograms. While the ascending branch of the peak rises rapidly and the
beginning of the rise can easily be found, the descending branch follows a t

function
and is characterised with a slow decrease. Even far away from the top of the peak, the


) F.E. Woodard, R.D. Goodin, P.J. Kinlen, Anal. Chem. 56 (1984) 1920, J.H.
Carney, Anal. Chem. 47 (1975) 2267.
Chapter 5 Editing of measured data 103
value of the current differs significantly from zero. Due to this feature, all following
voltammetric peaks rise from the "tail" of the previous one.
If the separation of two voltammetric peaks is large enough, they can be detected
without any problems. The situation is difficult when the distance between peaks gets
smaller: below a certain distance, the first peak is reduced to a shoulder on the rising
part of the next peak. The extreme situation is shown in fig. 56 C, where the overlap is
very strong, so that only one peak can be observed and there is no indication for the
presence of more of them.
In most situations, except in those of extreme overlap, semi-derivative peaks are
clearly visible and their number can easily be found. There are, however, three
important limitations to this method. First, voltammograms that are to be semi-
differentiated, should be background-corrected: semi-differentiation changes a
constant or a linear background into complicated forms in the semi-derivative domain.
Fig. 54 Overlapping linear voltammetric peaks and their semi-derivatives
104 User Manual GPES for Windows Version 4.9
Secondly, semi-derivative peak artefacts have to be recognised: consider the case of
an uncomplicated slow electron transfer leading to the voltammogram presented in the
appropriate figure.
The curve in the above-mentioned figure is the result of semi-differentiation, where
two peaks appear, one in the forward and one in the backward branch. The second
semi-derivative peak does not represent any hidden voltammetric peak, but is an
artefact resulting from semi-differentiation of a wave-like current decay. Such a peak
can only appear in the backward branch of semi-derivative voltammograms and has
characteristic features: in the potential range, where such a peak appears, (i) there is
no backward voltammetric peak, (ii) there is a forward peak and (iii) the sign of SCV
current values is the same in both branches. All peaks that satisfy these criteria, are
probably artefacts.
The third limitation of the method stems from the fact that results presented in the
above-mentioned figure concern an uncomplicated electron transfer under semi-
infinite linear diffusion conditions. The form of the peak is different when the
mechanism of the reaction and the transport type change: usually peaks become less
symmetric and broader, resulting in a decrease in separation capability and, in certain
situations, leading to deformations of neighbouring semi-derivative peaks.
Determination of formal potential and the number of electrons involved
The equation 5 describes the form of a semi-derivative voltammetric peak in a case of
uncomplicated fast electron transfer under semi-infinite linear diffusion transport. It is
clear that the peak potential is equal to the formal potential of the reacting system and,
for cyclic voltammetry, that both anodic and cathodic peaks appear at the same
potential. This feature can be used as a simple and rapid test for reversibility of the
reaction. This test is superior to the well-known test based on the difference of
potentials of voltammetric peaks, as it does not require knowledge about the number
of electrons involved.
If the rate of electrode reaction is limited by the diffusion or by kinetics of the
electron transfer, the number of electrons involved can be determined from the half-
width of the semi-derivative peak. This half-width should be
Fig. 55 Peak artefacts in semi-derivative voltammetry
Chapter 5 Editing of measured data 105
w = 3.53RT/nF (eq. 7)
for a diffusion-controlled process and
w = 2.94RT/αnF (eq. 8)
for a rate-controlled process.
Irreversible homogeneous reaction consuming the product of the
electrode process
The criterion for the absence of an irreversible homogeneous reaction is restoration of
the initial state at the electrode surface after a cyclic change of electrode potential. If
such a reaction does not occur, the surface concentration of all species after the
experiment should be exactly the same as before.
As the convolution of the voltammetric current with a t
½
function (semi-integration)
produces a value proportional to the surface concentration of the product of the
reaction, the convoluted value should return exactly to zero after completion of the
cycle, which means that the product of the reaction has been entirely converted back
to the substrate

. If it does not return to zero, the consumption of the initially present
substance is suggested.
It should be stressed, however, that this method requires diffusion to be semi-infinite
and linear. In situations where this is not the case, corrections have to be made. Such a
correction is available (S.O. Engblom, K.B. Oldham, Anal. Chem. 62(1990)625) for


) F.E. Woodard, R.D. Goodin, P.J. Kinlen, Anal. Chem. 56 (1984) 1920, I.D.
Dobson, N. Taylor, L.R.H. Tipping in "Electrochemistry, Sensors and Analysis"
(M.R. Smyth, J.G. Vos, eds.), Elsevier, Amsterdam, 1986.
Fig. 56 Semi-integration of voltammograms in case of the absence (A) and the
presence (B) of an irreversible homogenous reaction. Thin line - voltammogram,
thick line - semi-integral
106 User Manual GPES for Windows Version 4.9
spherical electrodes (mercury drops) under the name of spherical convolution it
requires the values of electrode radius and of diffusion coefficient, delivering the
concentration of the reaction product on the surface of a spherical electrode.
If the presence of an irreversible homogeneous reaction is detected, its rate can be
measured. For this purpose a so-called kinetic convolution can be used. In this
transformation the effect of consumption of the product by the reaction with the rate k
can be eliminated; by means of inserting different values of k one can obtain the result
in which a convoluted current at the end of the cycle approaches the same value as on
the beginning of the cycle.
Some problems can be expected if the substrate or the product of the reaction is
accumulated on (or in) the electrode by adsorption, deposition, or amalgamation. In
this case, the initial value of the surface concentration is not restored after the
completion of the voltammetric cycle and convoluted voltammograms will not deliver
proper results.
Investigations of factors controlling the transport to the electrode
Theoretically the most simple and quite commonly encountered transport type is
semi-infinite linear diffusion: the substance diffuses from the bulk of the solution,
where the concentration is constant, to the planar electrode, where it is consumed. The
flux of the substance depends on the gradient of the concentration at the electrode
surface; this gradient decreases with the rate proportional to the square root of the
electrolysis time.
Linear diffusion leads to the simplest description, but unfortunately its conditions are
rarely realised in the experimental setups used in electrochemistry. In case of mercury
electrodes, the surface of the electrode is not planar, and the diffusion can be
approximated using a linear model over a short period of time only. In case of solid
electrodes a so-called edge effect occurs: the contribution of spherical diffusion
appears. Apart from the geometry of electrodes, chemical processes taking place in
the solution can disturb the concentration profiles developed during the electrolysis,
for instance when electroactive species are produced by a homogeneous chemical
process; another example of deviations from the linear model may be caused by the
adsorption of the compound on the electrode surface.
It can be useful to consider different types of transport as deviations from the semi-
infinite linear diffusion case. These deviations can then be classified into two groups:
deviations, causing an increase of the transport to the electrode and those causing a
decrease. In the first group, spherical diffusion and different kinetic effects are
included; the second group covers effects such as limited diffusion and reaction from
the adsorbed state.
Spherical diffusion enhances the transport because the spherical expansion of the
diffusion zone increases its volume faster than in the semi-infinite linear case. The
increased volume results in a larger amount of the substance that diffuses to the
electrode.
Kinetic effects occur when the electroactive compound is involved in a chemical
equilibrium. The local decrease of its concentration within the diffusion layer disturbs
the equilibrium and in consequence leads to the production of the compound in a
chemical process. This extra amount increases the flux of the substance to the
electrode surface. Such conditions can be called mixed linear diffusion - kinetic
effects. For a long electrolysis time, the kinetic increase of the flux can entirely
Chapter 5 Editing of measured data 107
compensate the decrease of the concentration gradient and may lead to steady-state
conditions provided that the amount of compound involved in reagent production is
present in large excess.
Another type of effect can be observed when the solution is present in the form of a
thin layer. Electrolysis under such circumstances first leads to the depletion of this
layer and then to the exhaustion of the entire solution volume. This effect can
relatively easily be observed in case of the dissolution of metals from a small
amalgam drop or from amalgam film electrodes: the process is initially controlled by
linear diffusion, but after some time the drop is depleted and the flux of the substance
through the electrode surface drops more rapidly than t

. This is called limited
diffusion.
An extreme case of this situation is the reaction of a substance adsorbed on the
electrode or forming a monolayer on its surface. In such a case no transport is needed
and the whole amount of substance reacts within a very short time. The measured
current drops sharply to zero after exhaustion of the compound.
Cyclic chronoamperometry and chronocoulometry
If an electroactive compound reaches the electrode by means of semi-infinite linear
diffusion, and the potential of the electrode is such that the surface concentration of
the compound is kept zero, the current can be described using Cottrell's equation
i = nFAD
½


t

(eq. 9)
where n is the number of electrons involved, F - Faraday's constant, A - electrode
area, D and C the diffusion coefficient and the bulk concentration of the compound,
respectively, and t - time from the beginning of electrolysis. Integration of this
equation leads to the expression for the charge
i = nFAD
½


t
½
(eq. 10)
Semi-integration of eq. 9 or semi-differentiation of eq. 10 leads to the formula
m = nFAD
½
C (eq. 11)
In case of additional contributions enhancing the transport due to, for instance,
spherical diffusion or a kinetic effect, the semi-charge is greater than predicted from
the purely linear model and the line displays positive bias. The inverse effect appears
when the transport is slower than for limited diffusion or if the reagent is strongly
adsorbed on the electrode.
There are a number of experimental problems, that should be mentioned here. First,
the data used for studies of transport phenomena should be corrected for the
background otherwise deviations from linearity of the graphs can have other reasons.
In case of kinetic control of the process, the time scale of the experiment also
108 User Manual GPES for Windows Version 4.9
determines the range of reaction rates and equilibrium constants that can be detected.
The quantitative discussion of influences of different experimental factors on the
convolution curve can be found in Goto M, Oldham KB, Anal. Chem. 46(1974)1522.
Linear and staircase voltammetry
The convolution techniques facilitate the interpretation of voltammograms,
particularly the information included in the peak shape. As already said, this shape
can be considered as produced by the convolution of two functions: function I,
describing the surface concentration of the reaction product, and function II,
representing the flux of the reaction substrate, depending on the geometry of the
measuring system.
In the simplest case of semi-infinite linear diffusion and fast electron transfer,
function I has the form of an S-shaped wave and function II is a t

decay. The
character of function I is well-reflected in the ascending branch of the voltammetric
peak; function II is responsible for the t

- proportional decay of the descending
branch of the peak. Semi-integration (convolution of the SCV peak with a t
½
function)
should therefore give a wave with a horizontal plateau.
When the transport to the electrode is enhanced or diminished compared to semi-
infinite linear diffusion, the descending branch of the SCV peak can be approximated
using a t
u
function, where u>-0.5 for faster transport (slower decay) and u<-0.5 for
slower transport (faster decay). Changes in transport result in semi-integrated waves
with a biased plateau (negative for slower transport, positive for a faster one).
Algorithms for convolution
As mentioned before, there are special algorithms for differintegration as well as for
other convolution. Below, four algorithms used for differintegration and convolution
are described in short.
G0 algorithm (Grünwald-0)
This algorithm can be used to carry out differintegration to any order. The data must
be acquired in constant intervals. For the order = 1 the operation is equivalent to
differentiation, for -1 - to integration using rectangle method. For +½ the
G0 algorithm is the same as semi-differentiation. For -½ the G0 algorithm is the same
as semi-integration. Error in results increases with the length of the interval and
accumulates, i.e. error in latter points is larger than in earlier ones. Important
advantage is that this algorithm does not require the value of the function for t=0,
which makes it very well suited for transformation of chronoamperometric data
(where i(t=0)->∞. The disadvantage of the algorithm is that the total number of
operations is proportional to the square of the number of data points, so calculation
time grows fast with the length of the data set. The fundamentals of this algorithm are
described in Oldham KB, J. Electroanal. Chem. 121(1981) 431.
FRLT algorithm (Fast Riemann-Liouville Transform)
This is a fast, approximate algorithm based on a recursive digital filter. It is best suited
for differintegration in the range of 0.0...-0.5 (up to semi-integration). It is less precise
than G0 algorithm, but the number of operations is linearly related to the number of
Chapter 5 Editing of measured data 109
data points. For details refer to Pajkossy T, Nyikos L, J. Electroanal. Chem.
179(1984) 65.
Spherical convolution
The algorithm is used to carry out convolution of the data measured using a spherical
electrode and staircase potential waveform. Values of the diffusion coefficient, the
electrode radius as well as the delay between begin of the potential step and the
current sampling moment are necessary. The number of operations is proportional to
the square of data points. Details of the algorithm can be found in S.O. Engblom, K.B.
Oldham, Anal. Chem. 62(1990)625.
Kinetic convolution
This algorithm carries out kinetic convolution according to F.E. Woodard, R.D.
Goodin, P.J. Kinlen, Anal. Chem. 56 (1984) 1920. The number of operations is
approximately proportional to the square of the number of points. This convolution
requires the value of the rate constant of irreversible homogeneous follow-up reaction
(ECi mechanism).
5.11 Convolution in practice
The Convolution option can be selected for data measured with cyclic and linear
sweep voltammetry. This convolution menu offers a number of transformations of the
data set, like differentiation, integration, and convolutions.
There are three principal types of convolution available: differintegration (convolution
with t
-u
function, equivalent to fractional differentiation or integration, depending on
u), using G0 or FRLT algorithm, spherical convolution, and kinetic convolution. The
difference between G0 and FRLT algorithm is that G0 is more exact, while FRLT is
faster with large data sets. Two items: semi-integration and semi-differentiation
denote differintegrations using FRLT with the u value equal to -0.5 and 0.5,
respectively.
It is possible to carry out more transformations in succession. Because
differintegration is an operation that can be cumulated, double semi-differentiation is
equivalent to differentiation and the integration followed by semi-differentiation is
equal to semi-integration. Please note that some combinations, especially those
involving differentiation are not equivalent: differentiation+integration is not the same
as integration+differentiation.
In all convolutions the scale on the Y axis represents c
s
(t)nFAD
½
, where c
s
(t) is the
concentration of the product of the electron transfer step on the surface of the
electrode.
110 User Manual GPES for Windows Version 4.9
It is also possible to perform the convolution on part of the voltammogram (See Set
window option of the Plot menu).
It is recommended that the cyclic voltammogram starts at zero current. This can be
achieved by performing a baseline correction.
5.12 iR drop correction
iR drop correction allows for software correction of the potential data for the Ohmic
drop in the solution. This option can be used for data from cyclic and linear sweep
voltammetry.
After supplying a value for the solution resistance, the measured and corrected curve
are shown. The question appears whether the data are corrected.
Fig. 57 Example of a convoluted voltammogram
Appendix I GPES data files 111
Appendix I GPES data files
The following types of files are used by GPES
Graphical display settings for:
• cyclic and linear sweep voltammetry *.ici
• chronomethods *.ixi
• voltammetric analysis *.iei
• multi mode electrochemical detection *.idi
• potentiometric stripping analysis *.ipi
• steps and sweeps *.ifi
• electrochemical noise *.ini
These data files are in ASCII-format and are stored in the procedure directory and in
the data directory.

Experiment parameter settings for:
• cyclic and linear sweep voltammetry *.icw
• chronomethods *.ixw
• voltammetric analysis *.iew
• multi mode electrochemical detection *.idw
• potentiometric stripping analysis *.ipw
• steps and sweeps *.ifw
• electrochemical noise *.inw
These data files are in ASCII-format and are stored in the procedure directory and in
the data directory.

Measured data files for:
• cyclic and linear sweep voltammetry *.ocw
• chronomethods *.oxw
• voltammetric analysis *.oew
• multi mode electrochemical detection *.odw
• potentiometric stripping analysis *.opw
• steps and sweeps *.ofw
• electrochemical noise *.onw
These data files are in ASCII-format and are stored in the data directory.

Data memory buffer in binary format for:
• cyclic and linear sweep voltammetry *.bcw
• *.cv1
• *.cv2
• *.cv3
These data files are in binary format and are stored in the data directory.

Data memory buffer in ASCII-format and BAS Digisim file for:
• cyclic and linear sweep voltammetry *.txt
These data files are in ASCII-format and are stored in the data directory.

112 User Manual GPES for Windows Version 4.9
Project files containing command lines for automatic processing of measurement
procedures and data analysis: *.mac
These data files are in ASCII format and are stored in the data directory.

Print template files: *.def
These data files are in ASCII format and are stored in the Autolab directory.

File containing anodic and cathodic charges
in cyclic voltammetry: *.q&q
These data files are in ASCII format and are stored in the data directory.

The GPES executable file: gpes4.exe
The GPES binary help file: gpes40.hlp

The system parameter file, ASCII-format: sysdef40.inp
Description file of sysdef40.inp, ASCII-format: sysdef40.txt

Fit & simulation parameter files: *.efs
Appendix II Definition of procedure parameters 113

Appendix II definition of procedure parameters

CM : Chronomethods
CV : Cyclic and linear sweep voltammetry
ECD : Electrochemical detection
ECN : Electro Chemical Noise
PSA : Potentiometric stripping analysis
SAS : Steps and Sweeps
VA : Voltammetric analysis

ADC channel number: (Second signal, CV, CM)
The channel number which should be used for recording the output from an external
source.

Amplitude: (VA ac voltammetry)
The root-mean-square value of the applied potential sine wave perturbation.
Amplitude: (VA square wave)
Half of the peak to peak value in the squared wave perturbation.

Base potential: (VA normal pulse, differential normal pulse)
The base potential level. The pulse will be superimposed on this potential level.

Begin potential: (CV linear sweep)
The potential at which the ramp starts.

Cell off after measurement: (All)
If not 'checked' the cell switch will be left in the 'on' position after the measurement
procedure has been completed. The applied potential is the "stand-by potential".

Comment : (All)
A panel to type in several lines of text.

Conditioning potential: (VA)
This is the first potential applied after the start of the procedure. This potential is
normally applied to clean the electrode surface. This potential is not applied when its
duration is set to zero.
Correct iR-drop during dyn. iR: (CV, CM with dynamic iR compensation)
If ‘checked’ the potential will be corrected for the ohmic drop. If ‘not checked’ the
value of the ohmic drop is determined only.

Current range: (bipotentiostat, CV, CM)
The input parameter only appears when the Autolab is equipped with the
bipotentiostat module. The maximum range is 10 mA, the minimum range is 100 nA.
114 User Manual GPES for Windows Version 4.9

Cutoff on charge: (CM interval time > .1 s)
If checked, in chrono-amperometry or -coulometry, the specified cutoff value is
charge, otherwise it is current. This feature allows to specify a cutoff value for the
charge in chrono-amperometry.

Cutoff value: (CM interval time > .1 s)
If the specified value is exceeded, the measurements will proceed with the next
potential level or, if it is the last potential level in the sequence, the measurements will
stop.
Cutoff value for 2
nd
signal >(V’): (CV and CM interval time > .1s)
This value is the upper limit for the 2
nd
signal, as soon as this limit is reached, the
experiment will stop.
Cutoff value for 2
nd
signal <(V’): (CV and CM interval time > .1s)
This value is the lower limit for the 2
nd
signal, as soon as the limit is reached, the
experiment will stop.

Cutoff value for time >: (CM interval time > .1s)
The measurement is aborted when the time exceeds the specified value. It is only
active when the option ‘Specify time limit’ is checked.

Define potential w.r.t. OCP: (CM)
If 'checked', the stand-by potential and the specified potential levels are
applied with respect to the open circuit potential (OCP). Before the equilibration
starts, the OCP is recorded. If sufficiently stationary, a button can be pressed to
continue.

Define start potential w.r.t. OCP: (CV)
If this item is checked the measurement starts with measuring the OCP. After
acceptance the Start potential will be corrected for the OCP (Start potential + OCP). If
you want to start at the OCP.

Define vertex potential w.r.t. OCP: (CV)
If ‘checked’, the vertex and start potentials are specified with respect to the open
circuit potential (OCP). Before the equilibration starts, the OCP is recorded. If
sufficiently stationary, a button can be pressed to continue.

Deposition potential: (VA)
This is the second potential applied after the start of the procedure. This potential is
normally applied to deposit the components to be analysed on the electrode. This
potential is not applied when its duration is set to zero.

Direct output filename: (CM interval time > .1 s)
If a file name (without extension) is specified, the measured data are directly written
to a data file with the extension ".oxw". This option may be useful for long duration
measurements. It prevents loss of data due to a failure in the power supply.
Appendix II Definition of procedure parameters 115

If the number of measured data points exceeds the allowed maximum (default
10,000), the program will continue to store the data points on disk, although the data
points are no longer plotted on the screen and stored in the computer memory. Also
the data file becomes too long to be loaded by the GPES program.

Direct Output filename: (CV)
The path and the name of the file. The last five characters of the file name will be
used as the scan number. This filename will be used for the Save every nth Cycle
option.

Duration of Measurement: (ECN)
The total duration of the Measurement. It will be rounded to the next nearest power of
2 times the Interval time.

Dynamic iR amplitude: (CV, CM interval times > .1s)
The amplitude of the square wave in Dynamic iR compensation.

End potential

: (CV linear sweep, SAS)
The potential at which the ramp stops.

Equilibrate with potential pulses: (ECD)
If 'checked', the specified potential pulses are applied without recording data,
otherwise the stand-by potential is applied.

Equilibration time: (All)
The time to equilibrate the electrode at the start potential (CV, VA) or the stand-by
potential (CM, ECD, PSA).

Equilibration threshold level: (VA, CV, CM, ECD)
If enabled, the Equilibration stage will be aborted after reaching this specified current.
The measurements will start as soon as this threshold value is exceeded. This option is
not available for galvanostatic measurements.

Final rotation speed (rpm): (LSV staircase hydrodynamic)
The rotation speed applied during the last scan.

First conditioning potential

: (CV, CM, ECD)
The first potential which is applied after the Start button has been pressed. If the
corresponding "Duration" is zero, the potential is not applied.
First potential boundary: (CV)
Used, in combination with ‘Second potential boundary’, for automatic calculation of
the total positive and total negative charge. Only active when ‘Use boundaries for
Q+/Q- calc.’ is ‘checked’.




) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry
'potential' should be read as 'current' and vice versa.

116 User Manual GPES for Windows Version 4.9
First vertex potential

: (CV cyclic)
The potential goes from the start potential to the first vertex potential where it turns
around to go to the second vertex potential.

Frequency: (VA)
The number of times the square wave or sine wave perturbation is applied per second
in respectively square wave voltammetry and ac voltammetry.

Highest current range: (bipotentiostat, CV, CM)
The input parameter only appears when the Autolab is equipped with the bi-
potentiostat module. The maximum range is 10 mA, the minimum range is 100 nA.
The actual current range for the bi-potentiostat module will be automatically set
between the specified ‘highest’ and ‘lowest’ current range.

Initial rotation speed (rpm): (LSV staircase hydrodynamic)
The rotation speed applied during the first scan.

Interval time: (CM interval time > .1 s)
Normally the time between two recorded data points. If a maximum dE, di, or dQ
value is specified, the actual interval time can be less. For more information see the
chapter on the methods.

Interval time: (ECD)
The time between two current measurements in dc-amperometry.

Interval time: (ECN)
The time between two recorded current and potential samples. It should be >=
0.002 s.

Interval time: (VA)
Time between two measurements.

Linear(1) or square root(2) distr.: (LSV staircase hydrodynamic)
The rotation speed table is calculated with a Linear distribution (1) or with a square
root distribution (2). A linear distribution means that, when the initial speed is e.g.
100 and the final speed is e.g. 1000 with 10 scans, the subsequent rotation speeds will
be 100, 200, 300, ..... 1000.

Lowest current range: (bipotentiostat, CV, CM)
The input parameter only appears when the Autolab is equipped with the bi-
potentiostat module. The maximum range is 10 mA, the minimum range is 100 nA.
The actual current range for the bi-potentiostat module will be automatically set
between the specified ‘highest’ and ‘lowest’ current range.

Maximum dE, di, or dQ: (CM interval time > .1 s)
In case the box "Specify maximum dE, di, or dQ" is 'checked' and if the change in
current, charge, or potential exceeds the specified value, a data point will be recorded.


Appendix II Definition of procedure parameters 117


Maximum time interval: (CV, stationary current)
After this period the current is supposed to be stationary.

Maximum time of measurements: (PSA)
The measurements will stop when duration of the measurement exceeds the specified
time.

Measurement temperature: (CV, CM with pH as second signal)
Temperature for pH correction with respect to the calibration temperature.

Minimum abs(di/i) per second: (CV, stationary current)
Every second the relative current change is determined. If during three seconds this
relative change is less than the specified value the current is supposed to be stationary.
The next potential is applied.

Minimum abs(di) per second: (CV, stationary current)
Every second the absolute current change is determined. If during three seconds this
relative change is less than the specified value the current is supposed to be stationary.
Minimum variation: (CM)
Value at which the experiment is stopped or the next step in the experiment will be
applied. This value is only active if the ‘Specify minimum variation’ is ‘checked’.

Modulation amplitude: (VA differential pulse)
The height of the potential pulse. The pulse direction is the same as the scan direction
when the specified amplitude is positive. If a negative amplitude is specified, the
pulse direction is reversed with respect to the scan direction.

Modulation amplitude: (VA differential normal pulse)
Potential superimposed on the sum of base potential and pulse amplitude.

Modulation time: (VA)
Time during which the modulation amplitude(differential pulse, differential normal
pulse) or the sine wave(ac voltammetry) is applied. A convenient value is 0.07 s for
differential pulse and differential normal pulse. For ac-voltammetry 0.5 s is
convenient.

Number of cycles: (CM interval times < .1 s)
The number of times the sequence of potential levels as specified in the potential level
table are applied. After the measurements only the last cycle is in the computer
memory. All the measured data of the previous cycles are lost. In most cases the
number of cycles will be one, but for e.g. pulse plating experiments a higher number
can be specified.

Number of cycles: (CM interval times > .1 s)
The number of cycles you want to measure. A cycle includes the pre-treatment. The
old data (previous scan) will be overwritten by the new one. The direct output file
(when specified) is appended with every scan. The time parameter also adds up.
118 User Manual GPES for Windows Version 4.9
Between two scans the interval time is recorded by the computer clock and this time is
also added to the time parameter. After reaching the maximum number of points in
memory (=10000) the on-line plot option will stop. The actual data-points however,
will be in memory and are plotted after the ‘number of cycles’ has been reached or
after pressing ‘Abort’.

Number of equilibration scans: (CV Scan averaging)
Number of cycles of linear sweeps to reach an equilibrium. The averaging starts after
the specified number of scans. The equilibration scans are not kept in memory.

Number of potential steps: (CM)
During the measurements the potential steps from the stand-by potential to a number
of potential levels. These levels can be specified under header 'Potentials'

Number of pulses: (ECD)
The number potential levels which should be applied in multiple pulse or differential
pulse mode.

Number of scans: (CV)
The number of cycles or linear sweeps to be measured.
Number of scans: (LSV staircase hydrodynamic)
The number of scans with a different rotation speed.
Number of scans: (VA)
The number of times a voltammogram is recorded. The presented voltammogram is
the average of all recorded voltammograms.

Phase: (VA ac voltammetry)
If "Phase sensitive" field above is ‘checked’, the supplied value will be the phase shift
with respect to the applied ac potential at which the ac current is obtained.

Phase sensitive: (VA ac voltammetry)
If 'checked' a value for the phase should be supplied.

Potential: (bipotentiostat, CV, CM)
The input parameter only appears when the Autolab is equipped with the
bipotentiostat module. The constant potential which should be applied to the second
working electrode.

Potential limit: (PSA)
The measurements will stop when the potential passes the specified potential limit.

Potential shift: (CV)
The specified amount will be added to the recorded potentials of the voltammogram.
In this way it is possible to record potential versus present reference electrode, but
display them with respect to another.
Appendix II Definition of procedure parameters 119


Potentials

: (CM)
A table of potential levels can be specified. The number of rows is equal to
the ‘number of potential levels’ specified on the field above. During a measurement
sequence, the potential steps from the stand-by potential to each of the specified
levels, The following columns can be specified in the potential table:
Potential: the required potential level
Duration: the time the potential level is applied
Sample time: the time between two current samples. This column is only present for
the chronomethod with interval times < .1s. See description of the methods.

Potentials table: (ECD)
In this table the potential levels to be applied, and their duration can be specified in
multiple pulse or differential pulse mode. The number of rows is equal to the
"Number of pulses". In multiple pulse mode, in a third column, it can be specified
whether the current should be recorded or not. In differential pulse mode the two
levels, specified on page 2, are recorded.

Pulse time: (VA Normal pulse)
Time during which the potential pulse is applied.

Purge time: (All)
The time the gas valve is positioned to flow the gas through the cell. This parameter
only appears when an automatic electrode is present (see Hardware configuration
program).

Quick save of previous scan: (CV)
When more then one scan is recorded in Cyclic voltammetry, it is possible to save the
previously measured scan. This option can also be activated by typing 'SAVE' on the
keyboard. The path and the name of the file can be specified as the ‘Direct output
filename’. The last five characters of the file name will be used as the scan number.

Record Bipotentiostat signal: (bipotentiostat, CV, CM)
The input parameter only appears when the Autolab is equipped with the
bipotentiostat module.

Record second signal: (CV, CM)
The primary signal, current or potential, is sampled via one of the channels of the
ADC164 or ADC124 analog to digital converter module.
If "Record second signal" is 'checked', the voltage level of an additional channel of the
ADC164 or ADC124 module is sampled as well. The channel number can be
specified.
The ADC164 or ADC124 module has 16 input channels which can be recorded. An
internal multiplexer allows switching from one channel to another. Four of them have
an external BNC-plug. Normally, input number three and four are free channels, i.e.
not used by GPES. They can be used to record the output of another instrument.



) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry
'potential' should be read as 'current' and vice versa.
120 User Manual GPES for Windows Version 4.9
The input parameters, related to the second signal, do not appear when the Autolab is
equipped with a bipotentiostat module.

Reverse scan for i> : (CV)
If "Specify current boundaries" is 'checked', the scan direction will be reversed if the
current exceeds the specified value.

Reverse scan for i< : (CV)
If "Specify current boundaries" is 'checked', the scan direction will be reversed if the
current becomes lower than the specified value.

Run time: (ECD)
The duration of the measurement.

Save every nth Cycle: (CV)
When more then one scan is to be recorded in Cyclic voltammetry, it is possible to
save scan at regular intervals during the measurements. If this parameter is zero, no
scans will be saved during the measurements, otherwise every nth scan will be stored
on disk. If, e.g. '5' is specified, scan 1, 5, 10, 15 are saved. The path and the name of
the file can be specified on page two of the Edit procedure window ('Direct output
filename'). The last five characters of the file name will be used as the scan number.
Please note: These files can be overwritten during another measurement session with
the same procedure.

Scan rate

: (CV Staircase)
The required speed of potential change. The lowest scan rate is 0.00001. The highest
acceptable depends on the speed of the AD-converter, the computer, and the step
potential. The essential number for the highest scan rate is the number of potential
steps per second i.e. (scan rate)/(step potential). The maximum value is 4,800 with
normal CV (2400 with Bipot or 2
nd
Signal). With Fast scan CV the maximum value is
45,000. The specified value is adjusted by the program, so that the number of steps
per second becomes equal to one of the discrete values of the Autolab hardware timer.
The maximum values might vary in combination with advanced options like “Specify
current boundaries”, “High sensitivity”, “alpha (different from 1)” and
“Chronoamperometry at vertexes”.

Scan rate: (CV Linear scan)
The required speed of potential change. The lowest scan rate is 0.001. This is a
hardware limitation of the SCAN-GEN module.
The highest scan rate is 10,000 V/s for the SCAN-GEN module. As stated above, no
more than about 4,800 samples per second can be taken in combination with the
ADC164 or ADC124 module. This limits the measurable scan rate to about 10 V/s.
Higher scan rates can be measured with ADC750 module, which allows to measure
750,000 samples per second.

Second conditioning potential

: (CV, CM, ECD)



) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry
'potential' should be read as 'current' and vice versa.
Appendix II Definition of procedure parameters 121

The second potential which is applied after the Start button has been pressed. If the
corresponding "Duration" is zero, the potential is not applied.
Second potential boundary: (CV)
Used, in combination with ‘First potential boundary’, for automatic calculation of the
total positive and total negative charge. Only active when ‘Use boundaries for Q+/Q-
calc.’ is ‘checked’.
Second vertex potential: (CV cyclic)
The potential goes from the start potential to the first vertex potential where it turns
around to go to the second vertex potential.
Show noise around zero Volt : (ECN, with ECN-module selected)
If ‘checked’ the potential noise will be plotted around zero volt in stead of around the
DC-potential.

Signal multiplier: (Second signal, CV, CM)
The recorded "second signal" is measured in Volts. It can be multiplied by a factor to
convert it into another unit.

Signal offset: (Second signal, CV, CM)
The recorded "second signal" is measured in Volts. An offset can be supplied to
convert it into another unit.

Smooth level: (PSA)
The potential - time data are recorded. Subsequently the data are smoothed using the
Savitsky-Golay algorithm and the derivative dt/dE is calculated.
See for further details the section on "smoothing".

Specify cutoff value for 2
nd
signal: (CV, CM interval times > .1s)
If ‘checked’, the 2
nd
signal will be checked on the ‘Cutoff value for 2
nd
signal >(V’)’
and ‘Cutoff value for 2
nd
signal <(V’)’. The measurement will stop (CV) or proceed
with the next potential level or stop if it is the last potential level in the sequence
(CM).
Specify current boundaries: (CV, normal, or stationary current mode)
If 'checked', the scan direction will be reversed, if the current exceeds one of the
values specified below. In case of linear sweep voltammetry, the recording of the scan
will be terminated.

Specify cutoff value: (CM interval time > .1s)
If 'checked' and the specified cutoff value is exceeded, the measurements will proceed
with the next potential level or, if it is the last potential level in the sequence, the
measurements will stop.


122 User Manual GPES for Windows Version 4.9

Specify maximum dE, di, or dQ: (CM interval time > .1s)
If 'checked', a data point will not only be recorded after the specified interval time, but
also if the change in current, charge, or potential exceeds the specified value.

Specify minimum variation: (CM)
If ‘checked’, this parameter can be used to stop a chrono-amperometry or chrono-
potentiometry experiment as soon as the change in, respectively, current or potential
is less than the ‘Minimum variation’ value. In other words, as soon as the measured
signal has reached the ‘Minimum variation’, the experiment is stopped or the next
step in the experiment is applied.

Specify Time limit: (CM interval time > .1s)
If this option is checked, the measurement will stop when the time exceeds the value
specified for ‘Cutoff value for time >’. This option might be of use when a large
number of cycles is specified.

Stand-by potential

: (All)
The potential which is applied after the measurement in case of ‘cell on after
measurement’. Sometimes (CM, ECD) it is also the 'start' potential before a
measurement.

Start potential

: (CV, VA)
The potential at which the measurement, after the pre-treatment, begins.

Step potential

: (CV)
The potential increment between two successive current measurements. The specified
value is adjusted by the program, so that it becomes equal to the closest 16 bit
(DAC164) or 12 bit (DAC124) value and the number of steps per second becomes
equal to the closest value of the Autolab hardware timer. See also "Scan rate".



) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry
'potential' should be read as 'current' and vice versa.



) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry
'potential' should be read as 'current' and vice versa.


Appendix II Definition of procedure parameters 123

Steps and sweeps table: (SAS)
A table in which up to 10 potential level or sweeps can be defined. The following
items can be specified.
Segment type:
Not used This level will not be included in the measurement
Step One potential can be applied during a given time. The current is
sampled with the specified interval time.
Staircase sweep The potential sweeps from the previous applied potential to the
End potential with the specified scan rate. The current is
sampled at the end of every potential step. If the segment type
of the first level is specified as a sweep, the start potential
equals the Standby potential.
Linear sweep Equal to Staircase sweep but performed with SCAN-GEN
module. If the SCANGEN module is present, it is only possible
to select Linear sweep segment (Staircase sweep is disabled).

Potential (V) (Step segment)

Sample time (s) (Step segment) (the lowest possible value is 0.0002 s)

Total time(s) (Step segment)

End potential (V) (Sweep segment)

Scan rate (V/s) (Sweep segment) (the highest possible value is 5000 times the
step potential value)

Step potential (V) (Sweep segment)

The parameters for the Step segments are similar to the chrono-methods with short
interval times (see items ‘Potentials’ in the appendix). The parameters for the Sweep
segment are similar to the parameters for Linear sweep voltammetry.

Stirrer off during conditioning: (VA)
Switch off the stirrer of the Automatic electrode during the conditioning stage.

Stirrer off during deposition: (VA)
Switch off the stirrer of the Automatic electrode during the deposition stage.

Stop Equilibrium at threshold: (VA, CV, CM, ECD)
Enable the option to abort the equilibration stage when the Equilibration threshold
level is reached.

Stop scan: (CV, linear sweep)
The recording of the sweep will be terminated if the current exceeds the upper or
lower specified limit.
124 User Manual GPES for Windows Version 4.9
Surface area / cm^2: (CV & CM)
Surface area of the working electrode, with which the Current density can be
calculated in the Analysis menu of the Data presentation window.

Switch cell off when i=0 A:(CM interval time < .1 s)
If this option is checked the cell will be switched off during levels specified with a
current equals 0 A. This feature assures zero current. If this option is not checked, the
current is set to zero with the cell switch ‘on’. This means that a small offset current
of maximum 0.2% of the selected current range can flow.

Tafel plot: (CV)
If checked, the x-axis becomes the 10Log-axis of the measured current and the y-axis
becomes the potential axis. This option has been added to allow presentation of
traditional Tafel plots. It does not give any functional contribution. Unless required, it
is recommended to use this option. Normally recorded voltammograms can always be
converted to corrosion plots:
Load previously measured data; check corrosion plot; save the data again; reload the
data. Now the data should be presented as a corrosion plot.

Third conditioning potential

: (CV, CM, ECD)
The third potential which is applied after the Start button has been clicked. If the
corresponding "Duration" is zero, the potential is not applied.

Time to wait for OCP: (CV, CM)
The time you want to wait for acceptance of the Open Circuit Potential. If this time
has expired the program will continue using the OCP measured at that time. If this
parameter is 0(zero), the program will not continue unless the 'Accept' button is
pressed. If 0(zero) is specified in a procedure that is used in a project, the program
will wait for 2 seconds at the OCP and will use the OCP measured at that moment.

Title and subtitle: (All)
Text lines to describe the experiment.
These lines are the same as the ones displayed above the plot.

Type of signal: (CV, CM)
Aux signal - Signal measured on selected ADC-channel
Charge - Calculated charge
Potential - Measured potential
Current - Measured current
ESPR - Measured response from ESPR device
pH - Measured response of the pX module (converted to pH, see Utilities
menu, Calibrate pH-electrode)
pX - Measured response of the pX module




) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry
'potential' should be read as 'current' and vice versa.


Appendix II Definition of procedure parameters 125

Use ADC750: (CV, CM)
When the ADC750 module for fast AD conversions is present in the Autolab
instrument, it can be used for fast CV or chrono measurements if an interval time is
smaller than 100 µs.
Use boundaries for Q+/Q- calc.: (CV)
If ‘checked’ this option enables the user to set potential boundaries for automatic
charge calculation. Between the first and second potential boundary the total positive
and total negative charge will be calculated automatically. Charge values are
displayed in the status bar, at the bottom of the screen. The option is mainly used for
Cyclic Voltammetric Stripping in electroplating research. If this option is not checked,
the ‘First and Second vertex potential’ are used as potential boundaries.

Use dynamic iR-compensation : (CV, CM interval times > .1s)
This options offers the possibility to measure and compensate for the Ohmic Drop
during the measurement. This is useful in systems where the Ohmic Drop changes
during the experiment. At every potential level, either a step in staircase cyclic
voltammetry or a step in chronoamperometry, a small amplitude (Dynamic iR
amplitude) high frequency square wave signal is added. By measuring the resulting
current responses, the Ohmic Drop is calculated.
Please keep in mind that the following limitations apply to this technique:
• The sweep rate in cyclic voltammetry is limited.
• The method cannot be used in combination with a Rotating Disk Electrode, an
ARRAY, ADC750, BIPOT, pX or ECD module or any other device (EQCM,
ESPR, etc.) that will result in an external signal.
• Hardware adjustments are necessary for this option, so the option cannot be used
on an older instrument with new software only.
• The method only works in High Speed mode.
Use ECN module: (ECN)
Use the ECN module to perform the noise measurements.

Use high ADC resolution:(CV staircase fast scan)
Fast scan measurements are done at a fixed gain. If this option is checked the
measurement are done at gain 10 of the ADC-module, otherwise gain 1 is used.

Use lowest possible interval time: (CM interval times < .1s)
If this option is checked, the sample time per level will disappear from the table at
page one. It is not possible to specify a sample time anymore. The sample time is
calculated just after the measurement and depends on the speed of the PC that is used
and on the type of AD converter included in the Autolab system. In general it is
possible to get an interval time of approximately 19 µs.
126 User Manual GPES for Windows Version 4.9
Value of alpha: (CV staircase)
Fraction of the time interval, between two potential steps, at which the current is
sampled. It should normally be 1. Only in cases where linear sweep voltammetry
should be compared with staircase voltammetry, this number should be different. The
number should be at least 0.25. Linear sweep voltammetry equals staircase
voltammetry for reversible systems when α = 0.25.
Ref.: M. Saralthan, R.A. Osteryoung, J. Electroanal. Chem. 222, 69 (1987).

Wait after first vertex: (CV, staircase cyclic voltammetry, normal or stationary current
mode)
If ‘checked’, scanning will stop at the first vertex potential and a chronoamperogram
will be recorded, with duration and sample time as specified. The chronoamperogram
is not displayed on the screen, but the data are stored in memory and can be saved on
disk using the File option on the Data presentation window.

Wait after second vertex: (CV, staircase cyclic voltammetry, normal or stationary
current mode)
If ‘checked’, scanning will stop at the second vertex potential and a
chronoamperogram will be recorded, with duration and sample time as specified. The
chronoamperogram is not displayed on the screen, but the data are stored in memory
and can be saved on disk using the File option on the Data presentation window.
Appendix III Combination of GPES and FRA 127

Appendix III Combination of GPES and FRA

The FRA and GPES programs can be used at the same time. Moreover a FRA project
file can be executed from GPES. The command FRA!Start(<"filename">) is available
for this purpose.
However, in general it is important to note that both programs share the Autolab
instrument and the graphics part of the software. Moreover, both programs require a
considerable amount of the system resources. This means that when both programs
are active, hardly any system resources are left. The amount of free system resources
can be seen in option ‘About program manager’ in the Help menu of the Program
manager window.

Practical rules are:
• The computer should be equipped with at least 32 MB RAM
• It is not possible that both programs are measuring and controlling the Autolab
instrument
• Before the FRA program starts measuring, the ‘sleep mode’ in GPES is
automatically switched on. This means that the GPES screen is no longer updated.
• Do not use function keys when both programs are active, because they will cause
actions in both programs.
• When a measurement procedure is being executed, user interaction with the
programs should be avoided.
• Apart from GPES and FRA no other program/window should be active.
Appendix IV Multichannel control 129
Appendix IV Multichannel control
It is possible to control the multichannel potentiostat with GPES. Activate the
multichannel option by starting GPES with the shortcut "Multichannel GPES". The
multichannel software is similar to the GPES software, however, some options are
different or not available. The differences are explained in this paragraph.
Installation and test
The Hardware Setup program contains a button for Multichannel setup. After pressing
this button the following screen appears:
The items above are factory settings and should normally not be changed. The test of
the software is similar to the test of GPES. The procedure TESTCV6 can be used for
more than one potentiostat.
If the multichannel system is equipped with ARRAY modules, one dummy cell is
available. After loading the procedure TESTCV6 from the \AUTOLAB\TESTDATA-
directory, the Multi channel control window shows that PGSTAT and ARRAY-2 are
“active”. Now connect the dummy cell. The lead from ARRAY-2 should be
connected to WE(b). After starting the execution of the procedure, the normal dummy
cell response should appear and the current response should be the same for both
channels. In a subsequent measurement ARRAY-3 can be connected to the dummy
cell in stead of ARRAY-2. After ARRAY-2 has been made inactive and ARRAY-3
active, the same current response is expected. In this way all channels can be checked.
In case of a multi-PGSTAT10 set-up two dummy cells should be available. The
PGSTAT10-2 should be connected to the second dummy cell. Then the same
procedure should be followed as for the multi-ARRAY set-up as described above.
The DIAGNOST test is available, but does not work properly. The “zero-test” of the
ADC does not work properly because the test-channel is used for one of the extra
channels.
Fig. 59 Multichannel configuration
130 User Manual GPES for Windows Version 4.9
Program operation
After starting the program an extra Window appears :
When this window is behind other windows on the screen it can be shown with the
Window option from the GPES manager. The last item is Multichannel. After clicking
this item the multichannel window will be shown. Depending on the configuration,
this screen will be adjusted. The base potential for all arrays, including the PGSTAT,
can be set in the PGSTAT panel. If offset DAC’s are present, a specified offset
potential can be given.
With ‘Dependent current ranging’ the current range of all channels will be the same.
Changing the current range of ‘Array 4’ will lead to a current range change of all
channels. The Active-option button allows to select the channels that should be
measured. Note that the potential will always be applied to all channels.
The number of items on the Manual control window is considerably reduced
compared to normal GPES.
On the Data presentation window two additional items are present.
1. The Signal menu allows to select the signal from which channel is the active work
signal. All Edit and Analysis operation will be performed on this signal. The
currently selected signal is shown between brackets.
2. The Plot overlay signal option in the Plot menu allows to overlay several signals.
It operates similarly to the other overlay options.
The following methods are available in the multichannel mode:
Voltammetric analysis
• Differential pulse
• Square wave
• Sampled DC
• Normal pulse

Fig. 60 Multi channel control window
Appendix IV Multichannel control 131
Cyclic voltammetry
• Normal

Linear sweep voltammetry
• Normal

Chronomethods
• Amperometry
• Potentiometry
During the measurements, the sampling duration is the same as in the normal GPES.
This is described in the chapter about the Methods. However in the multichannel
mode all six possible channels sampled one after an other. So the number of samples
per channel from which the average registered current c.q. potential value is, one sixth
of the normal GPES. If a channel is specified as 'active', it only means that the
measured current c.q. potential is registered.
The minimum sampling time is equal to 6 ranged AD-conversion and this is 6 times as
long as in normal GPES. This has a consequence for the minimum interval time in
Chronomethods with short interval times. The minimum time is now about 800
microseconds (see also the information about the manual control window).
Specifications of the instrument are almost similar to those of the PGSTAT10
potentiostat.
Appendix V Technical specifications 133
Appendix V Technical specifications
µAutolab
type II
Autolab with
PGSTAT12
Autolab with
PGSTAT30
Autolab with
PGSTAT100
maximum output current ± 80 mA ± 250 A ± 1 A ± 250 mA
maximum output voltage ± 12 V ± 12 V ± 30 V ± 100 V
potentiostat yes yes yes yes
galvanostat yes yes yes yes
potential range ± 5 V ± 10 V ± 10 V ± 10 V
applied potential accuracy ± 0.2% of setting
2 mV
± 0.2% of setting
2 mV
± 0.2% of setting
2 mV
± 0.2% of setting
2 mV
applied potential resolution 150 µV 150 µV 150 µV 150 µV
measured potential resolution 300, 150 or 30 µV 300, 150 or 30 µV 300, 150 or 30 µV 300, 150 or 30 µV
current ranges 10 nA to 10 mA in
seven ranges
10 nA to 100 mA
in eight ranges
10 nA to 1 A
in nine ranges
10 nA to 100 mA
in eight ranges
applied and measured
current accuracy ± 0.2% of current
and ± 0.2% of
current range
± 0.2% of current
and ± 0.2% of
current range
± 0.2% of current
and ± 0.2% of
current range
± 0.2% of current
and ± 0.2% of
current range
applied current resolution 0.03% of current
range
0.03% of current
range
0.03% of current
range
0.03% of current
range
measured current
resolution
0.0003% of current
range
0.0003% of current
range
0.0003% of current
range
0.0003% of current
range
- at current range
of 10 nA 30 fA 30 fA 30 fA 30 fA
potentiostat bandwidth (1) 500 kHz 500 kHz >1 MHz 500 kHz
- potentiostat risetime/falltime
(1 V step, 10-90%) (1) 1 µs < 250 ns < 250 ns < 500 ns
potentiostat modes high speed/
high stability
high speed/
high stability
high speed/
high stability
high speed/
high stability
input impedance of
electrometer
> 100 GΩ//< 8 pF > 100 GΩ//< 8 pF > 100 GΩ//< 8 pF > 100 GΩ//< 8 pF
input bias current @25°C < 1 pA < 1 pA < 1 pA < 1 pA
bandwidth of electrometer > 4 Mhz > 4 Mhz > 4 Mhz > 4 Mhz
IR-compensation n.a. depending on selected
range: 0Ω-200Ω at
100 mA range to 0Ω-
200 MΩ at 10 nA
range, current
interrupt and positive
feedback available
depending on selected
range: 0Ω-20Ω at 1 A
range to 0Ω-200 MΩ
at 10 nA range,
current interrupt and
positive feedback
available
depending on selected
range: 0Ω-200Ω at
100 mA range to 0Ω-
200 MΩ at 10 nA
range, current
interrupt and positive
feedback available
- resolution n.a. 0.025% 0.025% 0.025%
four electrode control no yes yes yes
front panel meter no potential and current potential and current potential and current
Analog outputs (BNC
connector)
potential and
current
potential, current and
optionally charge
potential, current and
optionally charge
potential, current and
optionally charge
control voltage input no yes yes yes
multichannel option no no no no
134 User Manual GPES for Windows Version 4.9
µAutolab
type II
Autolab with
PGSTAT12
Autolab with
PGSTAT30
Autolab with
PGSTAT100
booster option no yes yes on request
analog integrator yes optionally available optionally available optionally available
- time constants 10 and 100 ms,
1 and 10 s
10 and 100 ms,
1 and 10 s
10 and 100 ms,
1 and 10 s
10 and 100 ms,
1 and 10 s
interfacing parallel ISA card parallel ISA card parallel ISA card parallel ISA card
A/D converter 16-bit with software
programmable gains
of 1, 10 and 100
16-bit with software
programmable gains
of 1, 10 and 100
16-bit with software
programmable gains
of 1, 10 and 100
16-bit with software
programmable gains
of 1, 10 and 100
auxiliary input channels 1 2 2 2
D/A converter 16-bit
three channels
16-bit, four channels
(optionally eight)
16-bit, four channels
(optionally eight)
16-bit, four channels
(optionally eight)
auxiliary output channel 1 1 1 1
digital I/O lines 48 48 48 48
(W x D x H) 26 x 26 x 9 cm³ 52 x 42 x 17 cm³ 52 x 42 x 17 cm³ 52 x 42 x 17 cm³
weight 3.2 kg 22 kg 25 kg 25 kg
power requirements 30 W
100-240 V, 50/60 Hz
170 W
100-240 V, 50/60 Hz
170 W
100-240 V, 50/60 Hz
170 W
100-240 V, 50/60 Hz
Notes: (1) Measured at 1 mA current range, 1 kOhm impedance, high speed mode when applicable.
Interface for mercury electrodes (IME, IME 303 and IME663)
Supported electrodes
• Metrohm VA Stand 663
• EG&G PAR303(A)
• dropping mercury electrodes with knock-off hammer
Control lines
• new drop
• purge on/off
• stirrer on/off
Burettes
• Metrohm Dosimat 665/765
• Schott T90 and T100
Hardware specifications of optional modules
SCAN-GEN: analog scan generator module
• scan range t 5 V relative to initial potential
• vertex potentials 2.5 mV resolution and 5 mV accuracy
• output offset t 1 mV maximum
• ranges of scan rates 100 mV/s to 10 kV/s full scale (six ranges)
• scan rate 1 in 4096 resolution,
accuracy t (0.2% full scale + 500 µV/s)
temperature dependence < 0.04%/K
• hold mode available
• maximum number of scans 32767
• monitor output (BNC) scan signal
Appendix V Technical specifications 135
ADC750: dual channel fast ADC module
• number of ADCs 2, each with four input channels
• maximum conversion rate 750 kHz
• maximum integration time 5.5 ms (mean of 4096 AD conversions)
• basic resolution 1 in 4096 (12 bit)
• resolution of measurements - potential 5 mV at range 10 V
2 mV at range 4 V
1 mV at range 2 V
- current 0.5%, 0.05% and 0.005% of full
scale
• memory 128000 samples per channel
(optionally 512000 samples)
ECD: low current amplifier module
• current ranges 100 pA to 100 µA full scale (seven ranges)
1 pA and 10 pA with selectable-gain amplifier
• current measurement t 0.5% accuracy
• type of filter third order Sallen-Key
• filter time constants RC-times 0 s, 10 ms, 100 ms and 500 ms
• compensation of current offset t 10 µA maximum
• monitor output (BNC) current
ARRAY and BIPOT: (bipotentiostat) module
• current ranges 100 nA to 10 mA full scale (six ranges)
1 nA and 10 nA with selectable-gain amplifier
• current measurement t 0.2% accuracy
• maximum current output t 35 mA
• potential range t 5 V
• potential accuracy t (0.2% + 2 mV)
• monitor output (BNC) current
• external input potential control
FI20: filter and integrator module
• filter section
- type of filter third order Sallen-Key
- filter time constants RC-times 0 s, 10 ms, 100 ms and 500 ms
- output offset t 2 mV
- monitor output (BNC) filter output
• integrator section
- ranges 10 ms, 100 ms, 1 s and 10 s
- charge measurement 0.2% accuracy
- temperature dependence < 0.04%/K
- monitor output (BNC) charge output
BSTR10A: current booster for PGSTAT30 or PGSTAT100
• maximum output voltage t 20 V
• maximum output current t 10 A
• maximum output power 200 W
• bandwidth 4 kHz full power
• current measurement 10 A full scale t 0.5% accuracy
• dimensions (W x D x H) 37 x 36 x 15.5 cm
• weight approx. 9 kg.
Note: Specifications subject to change without notice.
Index 137
Index
A
ac voltammetry ........................................................................................................................... 113, 116, 117, 118
Analysis results ....................................................................................................................................................... 64
Automatic ................................................................................................................................................................. 59
axis annotation ..................................................................................................................................................58, 60
B
BAS-DigiSim........................................................................................................................................................... 30
basecurve.................................................................................................................................................................. 67
baseline..................................................................................................................................44, 67, 68, 74, 98, 110
Batch mode .............................................................................................................................................................. 43
Burette control......................................................................................................................................................... 34
C
Calibrate pH-Electrode .......................................................................................................................................... 39
Check cell...........................................................................................................................................................40, 42
Chronoamperometric plot...................................................................................................................................... 69
chronoamperometry ............................................................................................................................ 100, 102, 107
Chronocoulometric plot ......................................................................................................................................... 69
chronocoulometry .........................................................................................................................56, 100, 102, 107
chronomethods .............................................................................................................................................7, 47, 63
colours ................................................................................................................................................................61, 63
Computer..................................................................................................................................... 5, 6, 115, 117, 120
configuration................................................................................................................................................... 5, 6, 42
convolution............................................................................................................................................................108
Convolution .................................................................................................................................................... 70, 100
Copy.............................................................................................................................................................43, 58, 64
corrosion.........................................................................................................................................5, 71, 72, 73, 125
corrosion rate....................................................................................................................................... 19, 71, 72, 73
Coulometric titration .............................................................................................................................................. 95
Crank-Nicolson....................................................................................................................................................... 75
Current density........................................................................................................................................................ 95
current range......................................................................................................................................37, 54, 55, 113
curve cursor ............................................................................................................................................................. 67
cyclic voltammetry ......................................................................................................................................104, 127
D
Data buffer................................................................................................................................................................ 31
Delete files ............................................................................................................................................................... 31
derivative...........................................................................................................68, 69, 71, 99, 101, 103, 104, 121
differential pulse............................................................................................................................................ 64, 117
DIO ports.................................................................................................................................................................. 49
dt/dE vs E plot ......................................................................................................................................................... 59
E
E vs t plot.................................................................................................................................................................. 59
Edit procedure ...................................................................................................................................................32, 63
electrochemical detection...........................................................................................................................5, 47, 60
Electrode control..................................................................................................................................................... 33
Enter text ................................................................................................................................................................... 60
Exit............................................................................................................................................................................. 31
Export Chrono data ................................................................................................................................................ 30
Export data buffer................................................................................................................................................... 30
Export to BAS-DigiSim data ................................................................................................................................ 30
138 User Manual GPES for Windows Version 4.9
F
FFT......................................................................................................................................................................73, 97
Filter for derivative................................................................................................................................................. 96
First- and Second signal ........................................................................................................................................ 59
Fit ............................................................................................................................................................................... 74
free cursor...........................................................................................................................................................67, 68
frequency spectrum................................................................................................................................................. 73
G
galvanostat ...................................................................................................................................................... 5, 6, 30
GPES 3 files............................................................................................................................................................. 28
GPES3 files .............................................................................................................................................................. 28
graphics .....................................................................................................................................................5, 6, 27, 63
H
help....................................................................................................................................................5, 7, 52, 63, 112
High sensitivity ....................................................................................................................................................... 54
I
Idisk........................................................................................................................................................................... 95
I-interrupt ................................................................................................................................................................. 37
integrate.................................................................................................................................................................... 99
integrator............................................................................................................................................................53, 56
Interpolate ................................................................................................................................................................ 74
iR drop ....................................................................................................................................................................110
iR-compensation........................................................................................................................................37, 39, 55
Iring........................................................................................................................................................................... 95
L
linear regression.........................................................................................................................................69, 70, 74
linear sweep voltammetry................................................................................................................29, 47, 63, 127
Load data............................................................................................................................................................28, 31
Load scan ................................................................................................................................................................. 28
M
manual control..............................................................................................................................................6, 37, 53
Marquardt................................................................................................................................................................. 75
Mercury drop electrode.......................................................................................................................................... 53
Method menu........................................................................................................................................................... 32
Metrohm 730 Sample Changer............................................................................................................................. 49
mouse....................................................................................................................................................................6, 28
MS-Windows.........................................................................................................................................................5, 6
MS-Word................................................................................................................................................ 6, 56, 58, 64
MULTI4.................................................................................................................................................................... 36
MUX control............................................................................................................................................................ 36
N
New plot ................................................................................................................................................................... 58
noise................................................................................................................................................40, 42, 69, 97, 98
normal pulse..................................................................................................................................................113, 119
O
Open procedure ....................................................................................................................................................... 27
overlay ...................................................................................................................................................................... 60
P
peak search........................................................................................................................................... 60, 65, 67, 68
pH buffer................................................................................................................................................................... 40
Index 139
pH electrodes ........................................................................................................................................................... 39
Plate........................................................................................................................................................................... 42
plot title ..................................................................................................................................................................... 61
polarisation resistance......................................................................................................................................71, 72
Positive feedback.................................................................................................................................................... 38
potentiometric stripping analysis ...................................................................................................................59, 64
potentiostat .........................................................................................................................................5, 6, 27, 38, 39
Print ..............................................................................................................................................................6, 28, 112
Procedure name in Data presentation Window................................................................................................. 52
Project .............................................................................................................................................................. 43, 112
Project command rules........................................................................................................................................... 43
Project examples ..................................................................................................................................................... 48
Project wizard .......................................................................................................................................................... 47
pX/pH........................................................................................................................................................................ 95
Q
Quick save................................................................................................................................................................ 57
R
RDE-control............................................................................................................................................................. 35
Rescale after measurement .................................................................................................................................... 52
Rescale during measurement ................................................................................................................................ 52
Resume................................................................................................................................................................59, 60
Reverse axes ............................................................................................................................................................ 60
S
Save data .....................................................................................................................................................29, 30, 57
Save procedure ........................................................................................................................................................ 28
Save procedure as ................................................................................................................................................... 28
Save scan.................................................................................................................................................................. 29
Scan averaging ......................................................................................................................................................118
SCNR16A................................................................................................................................................................. 36
SCNR8A................................................................................................................................................................... 36
second signal ................................................................................................................... 55, 59, 65, 113, 119, 121
Set window...................................................................................................................................................... 59, 110
Show all GPES files in File dialog box............................................................................................................... 52
Show I (backward).................................................................................................................................................. 59
Show I (forward)..................................................................................................................................................... 59
simulation................................................................................................................................................................. 74
Sleep mode............................................................................................................................................................... 42
smooth .........................................................................................................................................................44, 97, 99
Smooth....................................................................................................................................................................121
Spectral noise analysis ........................................................................................................................................... 73
square wave...................................................................................................................................................113, 116
Start button .............................................................................................................................................................. 53
stationary current ................................................................................................................................ 117, 121, 127
Status bar.................................................................................................................................................................. 53
surface area .............................................................................................................................................................. 95
T
Tafel slope............................................................................................................................................ 70, 71, 72, 73
tool bar..................................................................................................................................................................6, 52
transition time ....................................................................................................................................................59, 74
trigger..................................................................................................................................................................49, 51
V
viewing data............................................................................................................................................................. 60
voltammetric analysis .................................................................................................................................5, 63, 70
140 User Manual GPES for Windows Version 4.9
W
Wave log ............................................................................................................................................................16, 70
WE2 versus WE plot .............................................................................................................................................. 95
Window for zero crossings ................................................................................................................................... 96
Window function .................................................................................................................................................... 74
Work potential......................................................................................................................................................... 60
Work scan ..........................................................................................................................................................60, 65
Z
zoom......................................................................................................................................................................6, 59

2

User Manual

GPES for Windows

Version 4.9

4.6 W AVE LOG ANALYSIS....................................................................................................................................... 70 4.7 TAFEL SLOPE ANALYSIS ................................................................................................................................... 71 4.8 CORROSION RATE ............................................................................................................................................. 71 4.9 SPECTRAL NOISE ANALYSIS............................................................................................................................. 73 4.10 FIND MINIMUM AND MAXIMUM .................................................................................................................... 74 4.11 INTERPOLATE .................................................................................................................................................. 74 4.12 TRANSITION TIME ANALYSIS......................................................................................................................... 74 4.13 FIT AND SIMULATION ..................................................................................................................................... 74 The simulation method ......................................................................................................................................75 The fitting method ..............................................................................................................................................75 Elements of the Fit and Simulation Window .................................................................................................76 Fitting and simulation step by step .................................................................................................................76 Fitting in more detail .........................................................................................................................................81 Fit and simulation error messages..................................................................................................................84 Descriptions of the models................................................................................................................................85 4.14 CURRENT DENSITY......................................................................................................................................... 95 4.15 WE2 VERSUS WE PLOT ................................................................................................................................. 95 4.16 ENDPOINT COULOMETRIC TITRATION ......................................................................................................... 95 5. EDITING OF MEASURED DATA.............................................................................................................97 5.1 SMOOTH ............................................................................................................................................................. 97 5.2 CHANGE ALL POINTS........................................................................................................................................ 98 5.3 DELETE POINTS................................................................................................................................................. 98 5.4 BASELINE CORRECTION ................................................................................................................................... 98 5.5 SUBTRACT DISK FILE ........................................................................................................................................ 99 5.6 SUBTRACTION OF SECOND SIGNAL FROM FIRST SIGNAL. ............................................................................ 99 5.7 DERIVATIVE ....................................................................................................................................................... 99 5.8 INTEGRATE ........................................................................................................................................................ 99 5.9 FOURIER TRANSFORM ....................................................................................................................................100 5.10 CONVOLUTION TECHNIQUES.......................................................................................................................100 Detection of overlapping peaks.................................................................................................................... 102 Determination of formal potential and the number of electrons involved ............................................ 104 Irreversible homogeneous reaction consuming the product of the electrode process ........................ 105 Investigations of factors controlling the transport to the electrode....................................................... 106 Algorithms for convolution............................................................................................................................ 108 5.11 CONVOLUTION IN PRACTICE .......................................................................................................................109 5.12 IR DROP CORRECTION ..................................................................................................................................110 APPENDIX I GPES DATA FILES............................................................................................................... 111 APPENDIX II DEFINITION OF PROCEDURE PARAMETERS..................................................... 113 APPENDIX III COMBINATION OF GPES AND FRA ........................................................................ 127 APPENDIX IV MULTICHANNEL CONTROL...................................................................................... 129 Installation and test ........................................................................................................................................ 129 Program operation.......................................................................................................................................... 130 APPENDIX V TECHNICAL SPECIFICATIONS................................................................................... 133 Interface for mercury electrodes (IME, IME 303 and IME663)............................................................. 134 Burettes ............................................................................................................................................................. 134 Hardware specifications of optional modules............................................................................................ 134 SCAN-GEN: analog scan generator module.............................................................................................. 134 ADC750: dual channel fast ADC module ................................................................................................... 135 ECD: low current amplifier module ............................................................................................................ 135 ARRAY and BIPOT: (bipotentiostat) module............................................................................................. 135 FI20: filter and integrator module............................................................................................................... 135 BSTR10A: current booster for PGSTAT20 potentiostat/galvanostat..................................................... 135

Table of contents

3

INDEX................................................................................................................................................................... 137

.

Familiarisation with GPES is best obtained by experimenting. The measurement tasks run with the highest priority. Moreover.e. • The routines which perform all the communication with the Autolab instrument.1 Preface Autolab and the General Purpose Electrochemical System software (GPES) provide a fully computer controlled electrochemical measurement system. Its installation is described in the "Installation and Diagnostics" guide. It can be used for different purposes. . The "Installation and Diagnostics" guide explains the hardware aspects. The GPES program consists of two distinct parts i. the compact version of a standard Autolab with potentiostat • Autolab with potentiostat/galvanostat PGSTAT10/12/20/30/100 and other. such as glassy carbon or rotating disk electrodes • research of electrochemical processes like plating. The user should be familiar with MS-Windows.: • general electrochemical research • polarographic analysis in conjunction with a dropping or static mercury drop electrode • voltammetric analysis with solid electrodes. modules. The instrument is controlled by a personal computer equipped with an IBM/PC or AT I/O expansion bus.Chapter 1 Principles of operation 5 1. All the spare time is left for MS-Windows applications.: • The user-interface. Both parts communicate via shared memory. the computer requirements and the installation. GPES runs under MS-Windows 95. Most of the required help which might be necessary to perform the measurements and the data analysis is provided for by the on-line help within the program. Principles of operation 1. i.e. The GPES combines the measurement of data and its subsequent analysis. 98 and NT. deposition and etching • electrochemical corrosion measurements • electrochemical detection in Flow Injection Analysis (FIA) and High Performance Liquid Chromatography (HPLC). optional. All the Autolab configurations are supported by GPES: • µAutolab or µAutolab Type II. graphics and data-analysis software. this manual tries to explain the possibilities of GPES. This manual concentrates more on explaining the general concepts and backgrounds than on guiding the user through the program.

• All important electrochemical techniques should be available.international terminology for Windows Interface" (Microsoft Press. • 'How to perform experiments' should be easy and clear.9 1. a slider or a zoom-panel. It is a good book to become acquainted with the Windows vocabulary. The GPES screen consists of several windows: one for manual control over the potentiostat/galvanostat. a button. you can drag a scroll bar. an input item on the screen. A click of the left mouse button on a menu option. it is used to edit the graph in the Data presentation window. one for data presentation and manipulation. The MS-Windows related terminology used in this manual is in agreement with the standard as described in the book "The GUI Guide . one for entering the experiment parameters and one for collecting results of data analysis. • The introduction learning period should be short. You can focus on an item on the screen without an action. Except for the standard uses in window actions. It can be used to shrink or to enlarge a window when the mouse pointer is on the border of a window. accessory control. you can drag a window when the mouse pointer is in its title bar. should be possible. access and data transfer to programs like Excel and MS-Word. Surrounding windows. • Series of unattended experiments. The following mouse conventions are used: • Quickly pressing and releasing the mouse button is called "clicking". which appears after selecting Print from the File option in the GPES Manager window. • The user should have full and easy control over the Autolab instrument via the computer. • Actions should require only a few clicks. using different techniques and/or procedures. • A double-click of the left mouse button is used to perform particular actions.2 The concept The design of GPES Windows has been based on the following ideas: • GPES should incorporate the facilities electrochemists need. menu options and tool bars give extra facilities like cell-diagnosis.6 User Manual GPES for Windows Version 4. etceteras will result in an action. • Clicking and holding down the left mouse button is called "dragging" and is used for several purposes. • A click of the right mouse button is used to open a zoom panel in the Data presentation window or to shrink or enlarge the Graphics panel in the Setup Template option in the Print menu window. Washington ISBN 1-55615-538-7). Autolab configuration. • GPES should be a full and standard Windows application. . Finally.

Wiley & Sons ISBN 0-471-05542-5 R. Peat. Brett and A. • F5: starts the execution of the measurement procedure. Instrumental Methods in Electrochemistry Ellis Horwood Limited ISBN 0-13-472093-8.M.O.Chapter 1 Principles of operation 7 The following keyboard functions are supported: • RETURN/ENTER key: jump to next data input field. • F4: plot rescale. We would like to refer to the ‘Electrochemical methods’-manual and some excellent textbooks: • C. R. select menu option. typing a subsequent underlined character will move the cursor to the corresponding menu item. • • . • ESC: aborts the execution of the measurement procedure.M. • F1: access Help.A. Oliveira Brett. Greef. • left and right arrow key: move cursor in data input field. Pletcher and J. D. or move up and down in a menu. • F6 and shift F6: change focus to the next window. • ALT: puts focus on the menu bar of the window with the focus. Peter. a RETURN/ENTER will select the menu item. This manual does not describe the background of the electrochemical methods. • up and down arrow: move up and down in potential/current level input in chronomethods. Bard and Larry R. Electrochemistry Oxford science publications ISBN 0-19-855388-9 Allen J. L. Electrochemical Methods: Fundamentals and Applications J. or click button with focus. Robinson. Faulkner.M.

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Chapter 2 Getting started with GPES 9 2. please connect the dummy cell box to the cell cable by putting the banana plug connector into the matching colour connector on the dummy cell. with the menus and the tool buttons. Fig. Getting started with GPES In this chapter some basic examples are given to become familiar with GPES. which consists of three windows and two bars. The red banana plug should be connected to WE(a). Some of the examples contain a measurement with the Autolab dummy cell. which contains the start and stop buttons for measurement and displays the system messages. by clicking the icon in the Autolab application window. you will see the standard layout of the GPES software. The possibilities and the options of the software are described. 1 Default layout of GPES windows The two bars are: • The GPES manager bar. As soon as you start GPES. so before you start with the first example. • The Status bar at the bottom of the screen. .

• The Data presentation window. For most of the techniques. Select ‘Open procedure’ from the File menu. In the Autolab hardware configuration window. please select ‘Cyclic voltammetry (staircase) Normal’. which specifies all the experimental parameters. The options and possibilities of these three windows will be explained in detail in the next chapter. • The Manual control window. and open the ‘testcv.1 Recording a cyclic voltammogram with the dummy cell 1. which manually controls the settings of the potentiostat/galvanostat. if so. Before starting with this (and with the other examples) please check the hardware configuration of your system. 3. which gives a graphical display of the measured data. You can do this by executing the hardware configuration program. 2.icw’ from the \autolab\testdata directory.9 The three windows are: • The Edit procedure window. you can check if all the modules in your instrument are also selected in the software. Changed parameters are automatically saved when leaving the software and will appear as default parameters on the next occasion. 2. From the Method menu of the GPES manager bar. Fig. 2 The Open procedure window . and allows you to do data analysis and/or modification. See also the Installation and diagnostics manual. you can close this window by clicking ‘OK’. this window will consist of two pages.10 User Manual GPES for Windows Version 4.

the program will start to do 100 scans. 6. Please do so after a few scans.1 V/s to 1 V/s. Fig. After stopping. please select ‘Number of scans’ and change the value from 1 to 100.e. In the Edit procedure window. 3 Results of procedure TESTCV 5. the curve should look like the curve in figure ‘Results of procedure TESTCV’. or by clicking the Abort button. After clicking ‘Send’ the speed of the measurement will increase. In the Edit procedure window. Please (re)start a measurement with 100 scans and during the measurement change the ‘Scan rate’ from 0. If you now press start again. After the measurement is done. You can again stop the measurement by using the ‘Esc’ button. . 7. the Data presentation window will show you the last scan. a straight line. By clicking ‘Start’ the program will start the dummy cell measurement. please consult the “Installation and Diagnostics” guide in this manual. You can always stop the measurement by using ‘Esc’ on your keyboard.Chapter 2 Getting started with GPES 11 4. You can also select one of the previous scans by using the Work scan option. You are able to change some measurement parameters during the measurement by using the Send option in the Edit procedure window. During the measurement you can automatically rescale the curve in the Data presentation window by typing F4 on your keyboard. you will now find all the measurement parameters. if not. i.

9 Fig.12 User Manual GPES for Windows Version 4. 4 Edit procedure window .

and the procedure “testcv” loaded. and check the result on the potentiostat. For the following scans you want to save. This allows automatic current ranging using all the ‘checked’ ranges.2 The use of the Manual control window Fig. please click the cell on/off button. instead of via a measurement procedure. By using the slider below ‘Potential’ it is possible to set a potential value. 3. Switch the clock off again. After finishing a measurement.Chapter 2 Getting started with GPES 13 8. In the Manual control window the current and the potential are given. 100 mA for a PGSTAT12/100 and 1 A for a PGSTAT20/30) results in the selection of all current ranges except the 100nA range. With the dummy cell still connected to the cell cable. Check this by clicking on one of the circles and see what happens on the front panel of the potentiostat. Switch the cell off again. The ‘Save data buffer’ option saves all the scans that the PC has in its memory. . and use the window below the slider to set a potential of 0 V. The cell can be switched on and off manually. 2. during the execution of a measurement procedure. you can try the following: 1. the program allows you to save more than one scan by selecting ‘Save scan’ and then selecting a scan that you would like to save. please select ‘Save scan as’. 5 Manual control window: the appearance depends on the Autolab configuration The Manual control window allows you to control the potentiostat manually. Make sure that the cell is ‘on’ and use the slider to set a potential of 1 V. 2. The green circle indicates which current range is active. Clicking the highest current range (10 mA for a PGSTAT10/µAutolab. By clicking the Clock on/off button the program will start making a graph of the current versus time.

You are now asked to set two markers for a baseline in front of the peak. Please repeat the above after selecting ‘Automatic’ and ‘Linear baseline’ in the Options>> window. A plot parameter window appears. The program shows the result of the peak search in the ‘Peak search results window’ and shows the peak in the curve. gives you back the original. The file ‘democv01’ may be transferred to an Sshaped curve by choosing ‘Edit data’. Close the Analysis results window. the program now allows you to set a number of options. Start by selecting ‘Curve cursor’ and ‘Lin. Double click the curve in the Data presentation window. ‘Convolution’ and ‘Time semi-integral’. Select the same file that has been loaded: ‘democv01’. Select the settings that you feel are the most suitable for this curve. Choose ‘Analysis’ and ‘Peak search’. 5. Please try this by changing the colour and the style of the line. Note that. When the Peak search window appears. 6.9 2. Under ‘Edit data’ choose the option ‘Baseline correction’. click close and press the search button in the Peak search window. front baseline’. You are now asked to set two markers for the baseline you want to correct. click the Options>> button. Choose ‘File’ and ‘Load scan’ and load the datafile ‘democv01’ in the \autolab\testdata directory. in which you can change the colour of the curve. 2. Please check under ‘File’ that you are able to ‘Save’. 3. By selecting ‘Plot’ and ‘Resume’ the original curve is retrieved. Enlarge the graph by clicking the maximise button on the Data presentation window. please do so and press OK. Select ‘Linear baseline’ at the settings. as might be expected. Under ‘Edit data’ choose the option ‘Subtract disk file’. This option always allows you to get back to the original curve after editing or analysing the data. and have a look at the results. or change from a ‘line’ display to a ‘scattered’ display. 1. however.14 User Manual GPES for Windows Version 4. Close the Peak search results window and choose ‘Window’ and ‘Analysis results’ from the GPES manager bar. With the peak search option. The option ‘Wave Log analysis’ under ‘Analysis’ allows you to determine the halfwave potential and the number of electrons for S-shaped voltammogram. In this window all the data analysis results are kept as long as you do not exit the GPES software.3 Data manipulation of a cyclic voltammogram. ‘Print’ or ‘Clear’ the results. for example a Normal pulse voltammogram. Click search. 4. 8. By clicking OK you accept the corrected curve and the original is removed from the window. Set the markers on the horizontal part of the forward curve before the peak and press ‘OK’. and press ‘Set markers’. . the software allows you to determine all peak parameters of the CV. 7. For more details on the convolution techniques. the result is a horizontal line at I=0. Note that the Data presentation window now shows you both the original and the corrected curve (in black). please read the relevant chapter in this manual. Using the ‘Resume’ option.

After doing this and clicking OK. 6 Results of time semi-integral convolution After selecting ‘Wave log analysis’. you are asked to set markers for the baseline and the limiting current line for the forward (or black) curve. Close this window and choose ‘Plot’ and ‘Resume’.Chapter 2 Getting started with GPES 15 Fig. . By clicking ‘Continue’ the curve transforms and you are again asked to set two markers. you get the results for the analysis in the Wave log analysis window. Now the Wave log analysis window gives you a value for the half-wave potential and the height of the curve. Please set two markers for the baseline and press OK and do the same for the limiting line.

The size of the curve may be changed by clicking it with the right mouse button and then moving your mouse (without pressing a button!). With ‘Insert’ and ‘Field’ you can add or remove fields with parameters from the template. With this option you can print a measured curve together with the most important measurement parameters on one sheet. By clicking ‘File’ and ‘Print preview’ the values for the parameters and the curve are shown.16 User Manual GPES for Windows Version 4. Select ‘Template’ and ‘Set-up template’. means that the value is printed with the format used in the Edit procedure window). (Precision -1.9 Fig. Close the Template window. 7 Wave log analysis option 9. one or more of the windows. choose ‘File’ and ‘Print’. The way in which the parameters are displayed may be changed by double clicking a field and choosing for example ‘scientific’ and then setting a precision. You can also drag fields around to put them on another place on the sheet. the Print menu allows you to print the measured data. . and a Template. From the GPES manager bar.

Before you start. make sure that the method is still Cyclic Voltammetry. 2. 1. In the Data presentation window. The vertical axis window appears.4 Calculation of a corrosion rate. Normal. double click the vertical axis. . Load the datafile ‘democv02’ from the \autolab\testdata directory.Chapter 2 Getting started with GPES 17 Fig. 8 Results of printing of the template 2.

4. Close the window. and note the change of the curve. 10log. choose ‘Corrosion rate’. Change the scale from the axis from linear to Lg.e. Please note that you are also able to change the range of the axis and the position of the intercept of the axis in this window. 8a Vertical axis window 3. The Corrosion rate window appears. i.9 Fig. From the Analysis menu. .18 User Manual GPES for Windows Version 4.

1. Click close and transform the vertical axis of the curve back to linear. For this example you can set these values to 1.Chapter 2 Getting started with GPES 19 Fig. This fitted curve is shown in black. Please note that the 7 Hz is . Load the datafile ‘democv04’ from the \autolab\testdata directory. Furthermore you can specify values for the surface area. You are asked to set one marker for the cut-off frequency: set this marker at ca 7 Hz and press OK. the software will adjust the parameters until a best fit of the original curve is found. 2. with a list of parameters. By clicking the Start fit button. as well as for the polarisation resistance. Click the Smooth button. normal. All frequencies above 7 Hz will now be filtered out. the curve is now transformed to the frequency spectrum and a marker window appears. and the final values for the parameters are given. From the Edit data menu. and gives you the possibility to choose from different smoothing methods. Click the Tafel slopes button. The Smooth window appears. After you have done so. among which the corrosion rate in mm/year. 9 Corrosion rate analysis In this window the program shows a first value for the corrosion potential. the equivalent weight and the density of the material you are using.5 Noise reduction Make sure that the method is Cyclic voltammetry (staircase). Choose FFT (Fast Fourier Transform) with linear graph. You are asked to set markers on the anodic branch and on the cathodic branch. 2. choose the Smooth option. the Corrosion rate window appears.

In order to visualise this. From the Analysis menu.9 not the frequency of the potential or current noise. please double click the horizontal axis and change the scale to 1/square root. The data shown now are the result of the selected potential step. choose Chrono-amperometry (interval time < 0. and the noisy original will disappear. 10 Data smoothing using FFT 2. from the Plot menu in the Data presentation window. From the slope of this line. choose select potential. with OK you accept the curve. it is possible to calculate for example the diffusion coefficient. 1. 2. The Linear regression window now gives you the results.6 Data analysis with Chrono-amperometry. The scaling is arbitrary. Note the smoothed curve in black.7 V level. In Chrono-amperometry the current is proportional to 1/Square root of time. The curve shown is the result of a double potential step experiment. choose ‘Linear regression’ and set two markers for the beginning and the end of the linear regression. To do data analysis it is more convenient to choose just one of both potential levels at a time. From the Method menu on the GPES manager bar.20 User Manual GPES for Windows Version 4. . Fig. 3. and select the -0. Load the datafile ‘democx01’ from the \autolab\testdata directory. The curve is now linear. To do so.1 s).

From the Method menu. From the Edit data menu choose ‘baseline correction’ and select the polynomial basecurve. close the Options window and press the search button. 11 Transition time analysis 4. Please do so and check the difference with the automatic search on the non-corrected curve by opening the Analysis results window. After ‘OK’.Chapter 2 Getting started with GPES 21 Fig. Click the set markers button and set the markers for the baseline (one on each side of the peak). 1. You can now use the automatic peak search option to find the peak parameters. From the Analysis menu choose Peak Search. choose the automatic search. Load the datafile ‘demoea01’ from the \autolab\testdata directory. you are able to extract the last peak from the curve. The Peak search results window will now show parameters for four peaks. the corrected (black) curve is shown with a more horizontal baseline. With the Set window option under the Plot menu. From the Plot menu choose ‘Resume’ and the original curve will reappear. 2. but for the peak at the highest potential the linear baseline is not the best option.7 Data analysis with differential pulse voltammetry. Now there are two options (please start each option after setting the window around the last peak): a. Set the markers so that only the last peak is visible. choose voltammetric analysis and then Differential Pulse. 3. For the first three the results are reasonable. . 2. Under the options.

. 1. please do so.9 b. and the Result type: E(f) and I(f). a spectral analysis is performed on the Potential and the Current components of the noise signal. 12 Example of polynomial baseline correction 2. choose Electrochemical noise and then Transient. choose ‘curve cursor’ with a polynomial baseline. Now the Peak search results window will give you the parameters of this search. 2.8 Analysis of Electro Chemical Noise From the Method menu. choose the Peak search option. As should be expected. From the Analysis menu choose Spectral noise analysis. Close the Analysis results window. Please open the Analysis results window to compare this option with the result of option a. Load the datafile ‘demoecn1’ from the \autolab\testdata folder. check subtract offset. 3. the results of these two options are very similar. Fig. Choose a Hanning Window. By clicking OK. 4.22 User Manual GPES for Windows Version 4. Under options. After pressing the Search button you are asked to set two markers for the baseline. From the Analysis menu.

in the result panel a value of about 100 should appear. Second marker =2. and the decay of the potential in time is measured. the iRcompensation window will appear. You can now switch the cell on. Before starting. The GPES software provides two methods to do this: iR Interrupt and Positive feedback (see Chapter 3 for more details). . In the manual control window please type 1. I-interrupt a.13 Example Electrochemical Noise analysis 2. b. please give the following values: Duration of interrupt =0. First marker =1.0 V in the potential panel. After clicking the iR-compensation button the program will automatically compensate the measurements for the value given. and check the 1 mA Current range checkbox.001 s. you are able to measure the uncompensated resistance in your electrochemical cell and to compensate for this resistance. please choose I-interrupt.9 iR-compensation When your Autolab is equipped with a PGSTAT12/20/30/100. by clicking the button in manual control. please connect the WE connector of the cell cable to WE(c) on the dummy cell. you can do this by typing the value in the iR-compensation panel in the Manual Control window. Please click the Measure button. The current will now be interrupted for 0. Under the Utilities option in the GPES window. When you want to compensate for 90% of this value (Never use 100% of the measured value!). In the iR-compensation window.001 s.Chapter 2 Getting started with GPES 23 Fig. After a short time. This example is meant to make you more familiar with both options.

and you can see when the current starts to oscillate.01 s. an iRcompensation will appear in which you can type the following values: Potential pulse = 0. you have now done overcompensation. Please note that if you reach a value where the current starts to oscillate. Since noise is encountered frequently in electrochemical research. it is useful to become familiar with the detection of problems caused by noise. provides the option to detect noise. when you have overcompensated the resistance. Now do the same after typing “130”. Please check the change after typing a value of “95”.e. . Connect dummy cell (C) and put the current range to 1 mA. you should use 90% of this value during your measurements.24 User Manual GPES for Windows Version 4. Please choose the Positive feedback option in the Utilities menu. 14 Effect of overcompensation of the iR-drop 2. Fig. In GPES.9 Positive feedback With positive feedback you can give in values for the resistance yourself. the Check Cell option under the Utilities menu. you will see oscillations appearing. a.1 V. i. After pressing ‘start’ the program will start applying potential pulses. Duration = 0.10 Detection of noise problems In the GPES software an option is available to detect noise problems. By giving different values in the iR-compensation panel and watching the change in the i-t curve you can check how high the uncompensated resistance is.

you will see the current levels in red and the software will give you a warning that the noise level is too high. Please redo the measurement without the unshielded cable. and will then measure the noise level. Please use this option if you have doubts about the noise level in your system. the program will start checking the electrode connections. please connect an unshielded cable between the blue banana plug and the RE connector on the dummy cell. After pressing the measure button. In manual control please check the 100 nA Current range checkbox. After selecting the Check Cell option. In order to generate some noise.Chapter 2 Getting started with GPES 25 Please connect the red banana plug to the WE(c) connection on the dummy cell. . and place part of this unshielded cable over the monitor of your computer. With the unshielded cable over the monitor. You will now see the current levels in black indicating that the noise level is acceptable. the Check Cell window appears.

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Help.Chapter 3 The GPES windows 27 3. Project. File. Fig. File menu This menu contains options which are usually present in Windows programs. Method. When the directory in the Open procedure window is changed and a procedure file is . The GPES windows 3. Window. 15 The File menu Open procedure A procedure is a file containing all the experimental parameters. The directory in which the procedure file is stored is called the procedure directory.1 GPES Manager window The title bar of the GPES Manager window contains several options i. potentiostat/galvanostat settings. and graphics display values.e. The extension of the file which is mentioned in the "File name" field should not be changed. It contains measurement parameters. Utilities.

The appearance of the graph in the print out of the template depends on the actual size and shape of the Data presentation window.28 User Manual GPES for Windows Version 4. By selecting Show all GPES files in File dialog box (Utility menu). See print setup. This allows . The focus is on the frame after a click in the frame. please do not forget to save it (see corresponding File option). Please use the default file extension as mentioned in "File name" field or omit the extension. The print-out can also be previewed (see corresponding File option). On the print-out the parameter values also appear. The rectangle in the template is the Graph frame. Normally only files with the current method are shown in the load window. The parameter position can be dragged over the screen with the mouse. and the print of a template consisting of a user-defined set of measurement parameters and a copy that can be scaled of the current graph. If this is required.9 successfully loaded from this new directory. This allows you to adjust the frame size. click the "List Files of Type" drop down button and select the proper option. It is also possible to load a procedure from other methods/techniques than the current one. It is also possible to load procedure files from the DOS version GPES 3. combined with the mouse action. See the Dropdown menu called "List Files of Type". If the right hand button is clicked. Print The Print menu window appears after selecting this option. the lower right corner of the frame jumps to the mouse cursor and is subsequently attached to the mouse cursor. The program will change automatically to the method described in the selected procedure. After a click with the left hand mouse button the attachment is broken. this new directory becomes the new default procedure directory. If you have changed the template according to your requirements. The Setup template option allows to edit the template. Load data (sometimes called Load scan) Allows to load previously measured data from disk. If the left hand mouse button is pressed down within this frame it can be dragged. click the "List Files of Type" drop down button and select the proper option. The print of the template will cover half a page if printed in ‘portrait’ and a full page if printed in ‘landscape’. Save procedure as Allows to store a procedure on disk in the procedure directory with a different name as the current one. If this is required. You can select multiple files at a time by using <Shift> or <Control>. It is also possible to load data files from the DOS version GPES3 or data files of other methods or techniques than the current one. Save procedure This option will save a procedure under its current name in the procedure directory. The parameters on the template can be selected using the Insert menu option. all procedures are displayed and can be selected. In the latter case the correct extension will be added. a dump of a window. The comment text as well as the attribute of the item with focus can be edited by double clicking on it. The Print select panel allows to choose between the print-out of the measured data.

For cyclic and linear sweep voltammetry a submenu is presented from which the required data format can be selected. Save scan as This options allows to save a scan in Cyclic and Linear sweep voltammetry. After this action it is possible to exchange the work data by clicking ‘Work scan’ on the Data presentation window. If a buffer is reloaded. The data are stored in the so-called data directory. Save data buffer as This option can only be selected for cyclic and linear sweep voltammetry. This is the only save option which stores all relevant data. The path and the name of the file can be specified on page two of the Edit procedure window (‘Direct output filename’). First. Please note: These files can be overwritten during another measurement session with the same procedure. This option can also be activated by typing ‘SAVE’ on the keyboard. if more than one scan is recorded. In case of cyclic and linear sweep voltammetry the user is asked to select a scan number first.Chapter 3 The GPES windows 29 you to load the work data as well as 10 overlay files. a menu is shown from which the user can select the number of the scan to be saved. The option is called ‘Quick save of previous scan’. The last five characters of the file name will be used as the scan number. all data treatment and save option are open for use. When more than one scan is recorded in Cyclic voltammetry. together with the corresponding procedure parameters. . This option is available at the File menu on the Data presentation window. Save data Store the most recent measured data under the current procedure name on disk. The whole data memory is dumped on disk in binary format in the data directory under a user specified procedure name. together with the corresponding procedure parameters. Save data as Similar as the previous option but the name of the file name containing the data can be specified. it is possible to save the previously measured scan while the measurement is going on.

356E-07 -2. has the following layout: ScanNr 1 2 3 4 5 6 7 8 9 10 .Q&Q. Q+ (C) 1.674E-07 1. The first column is the potential (or current in galvanostat mode) and the other columns are the measured currents for subsequent scans (potentials in galvanostat mode). The file consists of several columns.30 User Manual GPES for Windows Version 4. Export data buffer to text file This option can only be selected for cyclic and linear sweep voltammetry.355E-07 Export Chrono data This option is only available for cyclic voltammetry.TXT. This is an ASCII-file with the default extension . They are meant to be read by MS-Excel.674E-07 1. . The file.365E-07 -2.364E-07 -2.q.697E-07 1.672E-07 1.669E-07 1. each scan should have the same number of points.file When a cyclic voltammogram is observed with more than one scan it is possible to save the observed cathodic and anodic charge data against the scan number. vs Q+.363E-07 -2.675E-07 Q-(C) -2.TXT. See the input parameters under the heading "Chrono-amperometry" in the Edit procedure window Export to BAS-DigiSim data This option is only available for cyclic voltammetry.667E-07 1.Q.357E-07 -2. In order to create a nice and properly columned file. they cannot be read by GPES.671E-07 1.358E-07 -2. Save the current active in such a format that it can be read by the program DigiSim.675E-07 1. but in this case in a readable ASCII-format.670E-07 1. This means that the Reverse button should not have been clicked.351E-07 -2. The default extension of the file is . with the extension .9 Export to scanno.356E-07 -2. The first row indicates the scan number. The separator c. As in the previous option the whole data memory is stored on disk. Also an interruption of a scan by pressing ESC should be avoided. It allows to store the chronoamperometric data which are recorded at the vertex potential.361E-07 -2. . delimiter between two columns is a TAB character.

02441 Scan rate (V/s) = . Delete files This option allows to delete procedures and measured data files. A delete action can not be undone. . Conditions: Linear sweep voltammetry Begin potential (V) = . The program settings are stored on disk.0000 End potential (V) = 1. . This is only possible if in the start-up menu "Autolab applications" has been chosen. Allows to load the complete set of scans (see Save data buffer).0000 Step potential (V) = . A selected procedure will be deleted from disk together with corresponding data files.232910E-07 Load data buffer This option can only be selected for data from cyclic and linear sweep voltammetry.191406E-07 Scan 2 -1.99992 Equilibration time (s) = 10 Number of Data Points = 42 Potential 0.024414 . The File window shows only the procedure files. Exit The GPES window will be closed and the program is exited.Chapter 3 The GPES windows 31 The layout of the text file saved with the ‘Export data buffer to text file’ also contains some important procedure parameters: Date: 26-May-97 Time: 14:12:17 Exp. Scan 1 -1.

9 Method The required electrochemical technique can be selected with the Method menu The type of experiment parameters in the Edit procedure window will change depending on the selected technique. hardware. . sleep mode. positive feedback. burette control. 16 The Method menu The settings in the File menu and the data analysis also depend on the type of technique. check cell. plate. and options. I-interrupt. set colour defaults.32 User Manual GPES for Windows Version 4. More details about the available methods can be found in a separate chapter. Utilities The Utilities window allows to select electrode control. For more information see the manual section on “Electrochemical methods”. Fig.

the purge valve can be opened and closed. The Reset button will reset the digital I/O port of the Autolab instrument. and a mercury drop can be created. . The stirrer can be switched on and off. This option is not accessible when no static mercury drop electrode is connected to the Autolab. The Purge and Stirrer will be switched off. 17 The Utilities menu Electrode control The Electrode control option allows to operate a static mercury drop electrode which is connected via an IME-interface to the Autolab.Chapter 3 The GPES windows 33 Fig.

18 The Electrode control window Burette control The burette control option allows to control motorburettes connected to Autolab via the DIO48 module.34 User Manual GPES for Windows Version 4. Please consult the manual of your burette for the parameters. Consult the "Installation and Diagnostics" guide about the type of burettes that can be connected. Fig. First click the Setup button. 19 The Burette control window The displayed Burette setup window allows to define the connected burette. .9 Fig. Then select the burette.

The Dose on button will dose with the speed displayed above. The DIO port used is shown on your Autolab front. an option is available in the Utilities menu of the GPES manager. After selecting the RDE control item the following window appears: Fig. edit field or enter the rotation speed in radials per second in the rad/s edit field. The dosed volume is displayed. The Reset button will give a ‘reset’-command to the burette and sets the dosed volume to zero.p. 20 The RDE control window With the scroll bar it is possible to control the rotation speed of the RDE. The Dose button will dose the amount specified above.Chapter 3 The GPES windows 35 The ‘Maximum time to check for Ready’ is the maximum wait time for the software to receive a "ready" signal from the burette. an external RDE should be specified.m. In Hardware configuration. You can also enter the number of rotations per minute by changing the r. RDE-control In order to control an external Rotating Disk Electrode (RDE). After pressing the Setup button the RDE setup window appears: .

Open the MUX control dialog by selecting MUX control from the Utility menu. The dialog screen shown in the figure below will pop up. SCNR8A or MULTI4 module can be selected manually by the operator before starting the measurement procedure: 1. Fig. Enable the checkbox “Use Multiplexer Module”. Choose the desired channel. 21a The MUX control window . 2. The active channel number will be indicated in the Manual control window. 21 The RDE setup window In this screen you can configure the RDE.9 Fig. MUX control The channel number of the SCNR16A. 4. Pressing <Apply> or closing the dialog screen will set the selected channel. 3.36 User Manual GPES for Windows Version 4. 5.

The calculated uncompensated resistance is printed in the Result panel. Now the Set marker button is available. the uncompensated resistance is calculated. First/second marker: The data point numbers between which a straight line is fitted. specify 10 V range. the current must be known very precisely. the Measure button can be clicked. The measured data are subsequently plotted and the straight line is drawn. In total 20 points are measured. Also make sure that the current at the applied potential. For proper measurements. Before measuring you need to specify the potential range at which the I-interrupt is performed. It will be clear that for a proper calculation of the uncompensated Ohmic resistance Ru. If the potential is outside this range. I-interrupt The I-interrupt option provides a method to determine the Ohmic resistance of the cell. Since the current is measured just before switching off the cell. By extrapolating the curve following a straight line to the beginning (time is zero). . The technique involves switching off the current and measuring the potential-time curve. The shorter the better. If an ADC750 module is present in the Autolab system it is possible to use this module. Therefore select a proper current range. the I-interrupt measurements should be done at the highest possible speed. It is recommended to switch off the iR-compensation. In order to get an accurate value for the uncompensated Ohmic-drop. Proper measurement must be done at a potential where the current is high enough to be measured and the applied current range must be adequate to measure the current. a reasonable value is .001 to . the potential difference across the Ohmic resistance is zero and the charged double layer is discharged. which means that the current should be in the order of the selected current range. Duration of the interrupt: The interruption period. This option is only available when the Autolab is equipped with a PGSTAT12/20/30/100 potentiostat/galvanostat. can be measured sufficiently accurate. the iR-drop is calculated. before the current interruption.01. you can disable the “Use Multiplexer Module” checkbox. If the potential is within the limit of -1V to 1V. After the parameters have been specified. As soon as the current is switched off. see Manual control window. When clicked you can change the First and Second marker value by clicking two data points on the measured curve. the current must be at least in the order of 1 mA. several parameters need to be specified. On the iR-compensation window that appears. specify 1 V range.Chapter 3 The GPES windows 37 If you want to return to direct connections. in order to speed up the measurements to 750 kHz.

Three parameters need to be specified. See next section. 22 Example of the results of a current-interrupt measurement The calculated uncompensated resistance can be used as an estimated start value to be used in the Positive feedback option. This option is available only when the Autolab is equipped with a PGSTAT12/20/30 or 100 potentiostat/galvanostat. . A reasonable value is 0. Compensation of the Ohmic resistance results in a faster decaying of the charging current. If the expected measured potential is < 1 Volt or > -1 V. select the 1 Volt range.9 Fig. When the compensation is near 100%. Potential range: Can be either 10 Volt or 1 Volt. the measured current response will show damped oscillation. Positive feedback The Positive feedback option provides an interactive method for determination and compensation of the Ohmic resistance of the cell.1V. The current response depends on the actual values of the Ohmic resistance and the doublelayer capacitance. Otherwise select 10 V range. which may cause damage to the working electrode. Duration: The period during which the current versus time data are measured. Potential pulse: The height of the applied potential pulse. A reasonable value is 0. This is twice the duration of the pulse.01 s. An example of the use of I-interrupt is given in the chapter 'Getting started with GPES'.38 User Manual GPES for Windows Version 4. The current response is displayed on the screen. WARNING: Too high Ohmic drop compensation can cause oscillation of the potentiostat. The technique of measurements is based on measuring the current response after applying a potential pulse.

current versus time measurements are done repeatedly and the iR-compensation of the potentiostat is switched on. It is possible to specify two buffer solutions and the calibration temperature. . which may cause damage of the working electrode. WARNING: Too high Ohmic drop compensation can cause oscillation of the potentiostat.Chapter 3 The GPES windows 39 When the Start button is clicked. The pH is corrected for temperature. Effect of overcompensation of the iR-drop Calibrate pH-Electrode This window allows to calibrate pH electrodes. Now the compensated resistance can be varied with the iR-compensation slider on the Manual control window. Measuring the pH as a 2nd Signal gives the possibility to specify a measurement temperature. This normally occurs when the potentiostat oscillates because the compensated resistance is too high. the cell will be switched off when the current exceeds about 8 times the current range value. fig 22a. When "Switch iR-compensation off at current overload" is checked.

100 second the current is sampled at the highest rate possible. When selecting this option an empty window appears with a Cancel and a Measure button. Also during 0. First apply a proper electrode potential and current range on the Manual control menu. Check cell The Check cell option allows to check the electrode connections and the noise level.40 User Manual GPES for Windows Version 4. The window will subsequently give information about the Electrode connections by comparing the applied and measured electrode potential. Subsequently click the Measure button. 23 The Check cell window . Fig. The OK button will actuate the calibration for the measurement.9 Fig. 22b The Calibrate pH-Electrode window When the value for a pH buffer is Ok press the Accept button.

The plot clearly shows periodic noise with a frequency of 50 Hz. are plotted in the Measure window. After optimising the cell simply by removing the unshielded cable of the reference electrode. the same measurement shows a better signal-to-noise ratio.Chapter 3 The GPES windows 41 The next figure shows a noisy signal displayed after pressing Measure. 24a A noisy signal Fig 24b A better signal-to-noise ratio The measured current and the five average values over one power cycle. normally 0. The obtained five average values . Fig.020 second.

the cell configuration. newly measured data will no longer be displayed in the Manual control window and the Data presentation window. It is possible. to re-Measure.g. 25 The Plate window The three plating potentials are alternated with the 'cell off' time. A judgement about the noise level and the selected current range are given. Fig.42 User Manual GPES for Windows Version 4.9 and their standard deviations are given in the Check cell window. Plate The Plate option will display a window in which three plating potentials. a 'cell off' wait time and a final potential can be specified. after an improvement of e. . By pressing Cancel the Check cell window disappears. In this way data are measured but not displayed. Sleep mode When the Sleep mode option is clicked. This option is useful when during slow but time consuming measurements a spreadsheet program or word processor is activated. See also Chapter 16 of the "Installation and Diagnostics" guide. The Sleep mode will minimise the time required by GPES. During the sleep mode. Subsequently the 'final' potential is applied. the measuring part of GPES will stay active.

First you have to indicate whether a new project should be made (New option) or an existing project file should be opened (Open option).and Chrono-Coulometry experiments. Below you will find the Project script language definitions and rules. Only available for ChronoAmpero. The Edit option provides the standard Cut. <string> rem <string> Procedure!Method = <method id> Procedure!Open("<filename>") Procedure!SaveAs("<filename>") Procedure!Start Procedure!AddToStandby(<real>) • : : : : : : Procedure!AddToPotlevel(<real>) comment define the electrochemical method open a procedure file save the procedure file start the execution of the procedure Add a value to the standby potential.Chapter 3 The GPES windows 43 Project The Project option allows to execute a large number of electrochemical experiments unattended. It is also possible to start a procedure by creating and subsequently executing a project. : Add a value to a specific potential level (n). If during the execution an error occurs the project continues with the next line. Project command rules • • • • • Both upper and lower case characters can be used in command lines. An example of a project is delivered with the GPES4 program in the testdata directory.and Chrono-Coulometry experiments. A project can be created by selecting the Project edit option. When Edit is selected the Edit project window appears with two options on the main menu bar. Copy and Paste option. After editing a Project it can be stored on disk under its current name (Save option) or under a new name (Save as option). The Check option checks whether there are syntax errors in the project commands. Only available for Chrono-Amperoand Chrono-Coulometry experiments. Sometimes this is called batch mode processing. A measurement procedure is normally activated by clicking the Start button in the lower left corner. One line per command. The following commands are allowed: . Procedure!AddToPotlevelEx (<n>. A project encompasses a number of tasks which have to be executed sequentially. An error message will be printed in the Results window. : Add a value to all specified potential levels. Only available for ChronoAmpero. Space characters are ignored.<real>) .

Dataset!PeakSearch Dataset!Selectscan = <scanno> : perform automatic peaksearch with baseline correction : select a recorded scan number in cyclic or linear sweep voltammetry for further processing : find the minimum and maximum value in a dataset : smooth the data using the Savitsky and Golay algorithm. then the number of the FRA-project is overruled by the number in the GPES-project. starting with number <n> : specify the string which should be replaced by a number in the <filename> for auto-numbered files.44 User Manual GPES for Windows Version 4.ocw Please note: When a FRA-project is started from GPES and the FRA-project and both projects contain the command 'DataSet!AutoNum = <n>'. Dataset!Open("<filename>") Dataset!SaveAs("<filename>") Dataset!AutoNum = <n> Dataset!AutoReplace ("<string>") Example (see below) .Start file numbering with number 5 DataSet!AutoNum = 5 .<real>) : Add a value to a specific current level (n).Replace string xxx DataSet!AutoReplace("xxx") . Note that after the execution of the project the smoothed data are replaced by the originally measure data : store the anodic and cathodic charge versus scan number (Q&Q files) for cyclic voltammetry data.The first file is now saved as c:\autolab\data\file005. The filename must be specified without an extension. The smooth level can be an integer number between 0 and 4. Dataset!MinMax Dataset!Smooth = <smooth level> Dataset!SaveQ&Q(“<filename>“) .9 Procedure!AddToCurlevelEx (<n>. Only available for ChronoPotentiometry experiments.Save Automatic number file DataSet!SaveAs("c:\autolab\data\filexxx") . : open a previously measured data file : save the measured data : enable auto-numbered files names.

IMP. The filename must be specified without an extension. Dataset!Subtract("<filename1>".Chapter 3 The GPES windows 45 Dataset!SaveImpedance (“<filename>“) : project command to store impedance data measured for AC-voltammetry.<filename2> : set the Rotating Disk Electrode to a specific rotation speed. The MUX will be automatically enabled when necessary. The extension is . If the channel is not available. the active channel number is set to 1. <filename2>". The set-up of the RDE is made in the RDE control option under Utilities. : increase the active channel number with one. : subtract files and save the result in another file.COM ."<filename3>") Utility!SetRDERPM = <rpm> Results!Clear Results!SaveAs System!Run("<filename>") System!Beep Print!Templa te Print!Plot Print!Procedure Print!Results FRA!Start("<filename>") Utility!Channel = <n> Utility!NextChannel .BAT : give a beep : print a hardcopy according to the template : print a hardcopy of the Plot window : print a hardcopy of the measurement procedure : print a hardcopy of the Results window : start a FRA project file from GPES "<filename>" should be a FRA project file : sets the active channel to <n>. The System!Run command search for the program file with the next sequence: .EXE .PIF . <filename3> = <filename1> . : clear the Results window : save the Results window : execute another program and wait until it terminates.

In such cases. DIO!WaitByte("<Connector>". Utility!Delay = <n> Repeat(<n>) EndRepeat : hold the project for <n> seconds."<Port>" . .<Number of flushes>) : flush the burette. You can nest these commands maximal 5 times. etc."<Bit>") : wait until a single pin of the DIO is set on or off. all channel switching commands in the FRA project scripts are ignored. for FRA projects that are called from within GPES projects. Burette!Fill (<Burette number>) : Fill the burette. "<n>") : wait until a port of the DIO is set to the specified value. for example: fname001. Burette!DoseVolume (<Burette number> . Burette!Reset (<Burette number>) : Will give a 'reset'-command to the burette."<n>") : set a port of the DIO to the specified value. Burette!Flush (<Burette number> . "<n>". the GPES project will have exclusive control over the channel selection.<Dose volume>) : dose a specified volume to the specified burette. However. ForAllChannels("<filename>") DIO!SetMode("<Connector>". "<Port>"."<Port>"."<Bit>") : set a single pin of the DIO on or off.9 Please note: The last 2 commands are available in the GPES and FRA programs."<Mode>") : set the mode of a port of the DIO. ."<Port>". fname002. "<n>".46 User Manual GPES for Windows Version 4. DIO!WaitBit("<Connector>"."<Port>". DIO!SetBit("<Connector>". DIO!SetByte("<Connector>". : executes the active measurement procedure for all available MUXchannels and store the results in the <filename> adding 3 characters to the filename as channel number counter. : with the Repeat and EndRepeat commands it is possible to repeat a part of the project <n> times.

. This option allows the user to pick project command lines from a list of all commands. When no scan number is selected in cyclic or linear sweep voltammetry. insert them in a project and define the parameters. Normally the user is asked to click the Continue button.mac’ and ‘Demo02. see Appendix III in the GPES manual. A special case occurs when the measurement should start at the open circuit potential. but including a directory name <scanno> : the number of a recorded scan <rpm> : rotations per minute The FRA project file can only be executed if the FRA-program is already running.Chapter 3 The GPES windows 47 • The <method id> can be: VA : voltammetric analysis CV : cyclic or linear sweep voltammetry CM : one of the chronomethods ECD : multi mode electrochemical detection ECN : electrochemical noise SAS : steps and sweeps PSA : potentiometric stripping analysis <string> : line of text <filename> : a filename without extension. For more information about the combination of GPES and FRA. Project wizard The Project wizard provides an easy way of editing and/or defining a project. Examples of projects can be found in the files ‘Demo01. the program uses the last recorded scan as default. The window below gives a project Wizard overview.mac’ present in the \AUTOLAB\TESTDATA folder. but in automatic mode the program continues by itself after 1 second.

48 User Manual GPES for Windows Version 4. An example of a project inside the Project wizard Every project command can be inserted in the project. Using the parameter button one can define the parameters that belong to that specific command. A short description of the command is given in the information and syntax box. and stores the results in “c:\autolab\data\test channel 1” and in ”c:\autolab\data\test channel 4” : Procedure!Method = CV Procedure!Open("c:\autolab\testdata\testcv") Utility!Channel = 2 Procedure!Start Dataset!SaveAs("c:\autolab\data\test channel 1") Utility!Channel = 4 Procedure!Start Dataset!SaveAs("c:\autolab\data\test channel 4") Example 2: Chrono amperometry on consecutive MUX channels . Project examples Example 1: Cyclic voltammetry on MUX channel 2 and 4 The following example of a GPES project will perform the "c:\autolab\testdata\testcv" procedure on channels 2 and 4. deleted or moved to another place.9 Fig 26.

The result will be stored as “test scanner with cm 001”. one specifies whether one wants to send or receive a trigger. and can also be used to receive an input trigger. They can for example be used to control a Metrohm 730 Sample Changer. Any of the pins can be set from low to high or the other way around.Chapter 3 The GPES windows 49 The following example will perform the "c:\autolab\testdata\testca" procedure on channels 1 to 4. “test scanner with cm 003” and “test scanner with cm 004” with the number corresponding to the channel: Procedure!Method = CM Procedure!Open("c:\autolab\testdata\testca") Dataset!Autonum = 1 Dataset!Autoreplace("xxx") Utility!Channel = 1 Repeat(4) Procedure!Start Dataset!SaveAs("c:\autolab\data\ test scanner with cm xxx") Utility!NextChannel Endrepeat Example 3: Provide or receive trigger signals to or from DIO ports These are the commands to set any of the pins on a DIO port of the Autolab instrument. . and stores their results using automatic filename numbering. With the SetMode command. SetByte can be used to set multiple pins to on or off. SetBit allows to set one of the pins to on or off. “test scanner with cm 002”.

In case one wants to receive the trigger on Pin 4 and 6. so ready to send a trigger. DIO!SetMode("P1". Pin number 5 (pin number 1 has value 0) is set ON (i. one needs to set the value 40 (=2^3+2^5) instead of 3. so ready to send a trigger. Fig. "A".On connector P1. "A". DIO!WaitBit("P1".50 User Manual GPES for Windows Version 4.e. both pin 1 (2^0) and 2 (2^1) are set ON. "2".9 DIO!SetMode("P1". "A". "OUT") .On connector P1. "OUT") . DIO!SetMode("P1". "A". "A". port A.On P1. "3") .On connector P1. port A. the project is waiting for an input trigger on both pin 1 and 2 . "3") . 26a Schematic overview of both DIO ports with PIN numbering for the different sections. so ready to receive a trigger. port A.The project will wait for an input trigger on P1. one needs to set the value 80 (=2^4+2^6) instead of 3. "OFF") .On connector P1. Port1 1 2 3 4 Section A 5 6 7 8 1 2 Section C UPPER 3 4 1 2 Section C LOWER 3 4 1 2 3 4 Section B 5 6 7 8 25 dgnd Port 2 Section C LOWER .On P1. port A. "4". "4". DIO!SetByte("P1". DIO!SetMode("P1". . "ON") . port A. "ON") . DIO!SetBit("P1". Pin 25 is always the digital ground. "A". sends a trigger). "IN") . port A. In case one wants to set Pin 3 and 5. "IN") . the mode is set to OUT. "A". DIO!WaitByte("P1". the mode is set to IN. the mode is set to OUT. Pin number 3. Pin number 5 is set OFF again.On connector P1. "A". port A. port A. the mode is set to IN. "A". so ready to receive a trigger.On connector P1. port A. DIO!SetBit("P1".

the 'Start' button has to be clicked. After selecting this option the following window appears.Chapter 3 The GPES windows 51 Options The Options menu encompasses the following items. Trigger Under this item the option Trigger is present. The program will go through pretreatment and equilibration and will then wait for the trigger-signal. 27 The Trigger option window After enabling the trigger pulse option. . In this window the trigger pulse can be configured. Fig.

This is useful to identify the graph when it is dumped on a printer. . The buttons give short cuts to various menu options which are frequently used. and the name of the current measurement procedure. The Tile option gives the default partitioning of the screen. the current electrochemical method. Place the mouse pointer on top of a button. the graph in the Data presentation window is rescaled when a measured data point is outside the boundaries of the plot. For most topics on the screen Help is available. The Close all option will delete all the GPES windows except for the status bar and the GPES Manager window. Procedure name in Data presentation Window With this option it is possible to print the procedure file name on the Data presentation window. Enable or disable automatic rescaling directly after the measurement of a voltammogram.52 User Manual GPES for Windows Version 4. equilibration measurement end of measurement high low Rescale after measurement. all files of all techniques are shown in the File dialog boxes of the File menu. Rescale during measurement When this option is activated. Window The Window option allows the selection of windows which should be shown on the screen. Help The Help option is the top entry point in the help structure.9 pretreatment…. Its meaning will appear in yellow. By pressing F1 the specific information about the part of the screen on which has been focused is given. The program will switch automatically to the appropriate method. Show all GPES files in File dialog box If this option is activated. if pressing the button is allowed. Tool bar The tool bar contains a list of buttons.

28 Manual control window . The Status and Message panel give important control information. the following control sequence is executed: the solution is purged.3 Manual control window The Manual control window gives full control over the potentiostat/galvanostat of the Autolab instrument. other buttons appear which allow to advance to a next stage or to abort a measurement procedure. if the purge time exceeds 0 s. including the optional modules: • the low current module ECD • the bipotentiostat module BIPOT • the 10 A current booster BSTR10A • the integrator/filter module FI20 for the PGSTAT12/20/30/100. Before the measurement starts. Fig. After the Start button is clicked. If an automatic mercury drop electrode is connected to Autolab. the stirrer will be on. During the pre-treatment period. Subsequently a new drop will be created. the cell is switched on and the measurement starts with a pre-treatment. Then the cell will be switched on and the pre-treatment potentials are applied when their duration is not zero. During these periods. the stirrer is switched off and the initial or standby potential is applied and the equilibration period starts in order to stop convection of the solution.Chapter 3 The GPES windows 53 3. the measured dc-current is printed in the Manual control window.2 Status bar The lowest part of the screen is reserved for the status bar. After clicking this button. The Start button starts the execution of a measurement procedure. 3.

54 User Manual GPES for Windows Version 4. . In case of potentiostatic control. The Manual control window consists of several panels. Only a joined column of selectable current ranges is allowed. High Stability/High Speed: The potentiostats/galvanostats can be used in either the high speed. so no current can flow between the counter and working electrode. with low bandwidth. the mode of operation can be defined. Current range In the Current range panel the green 'LED' indicates the actual current range. If a range separated from another range is checked.The text on the button represents the current situation. The response times of this current range is too high for the specified measurement procedure.3 pA. the check disappears. For example. In the ‘off’ position the connection of the potentiostat with the potentiostat/galvanostat is broken. mode. Sometimes a current range annotation is coloured red. Using the instrument in high stability mode may prevent oscillations. The current resolution is improved by a factor of 10. This means that it is advised not to select this current range during execution of the current procedure. It is highly recommended to switch the cell off before the mode change.9 It is also possible to perform potential/current/charge measurements as a function of time. In case of galvanostatic control. High Sens off/on: it indicates whether the gain 100 of the amplifier of the ADconverter is used. at the current range 100nA the current resolution is improved from 3pA to 0. Settings In the Settings panel. Some electrochemical cells may cause stability problems with the instrument in high speed mode. The software always checks whether the row is closed. the output of the DAC module corresponds to an applied potential level. Especially cells with high capacity and low resistance may cause oscillations. mode or the high stability. with high bandwidth. Note that some of the Autolab settings are part of the measurement procedure. It is recommended to switch the high sensitivity "on" only when the limits of the digital resolution show. High speed or high bandwidth is needed when frequencies higher than 10 kHz or sampling or interval times below 100 µs are used. See also the chapter about the digital base of Autolab in the "Installation and Diagnostics" guide. except when high bandwidth is needed. Potentiostat/Galvanostat: allows switching from potentiostatic to galvanostatic mode. The bandwidth at high stability is about 10 kHz. The following buttons might appear (depending on the type of potentiostat/galvanostat): Cell on/off: allows to switch cell on or off. It is advised to use high stability in all experiments. the output of the DAC module corresponds to an applied current. the intermediate ranges are checked automatically. If "off" only gain 1 and 10 are used. The allowed current ranges are stored on disk as part of the procedure. when high sensitivity is switched on. When a check box is clicked again. A mark in the neighbouring check box indicates whether the current range can be selected. The disadvantage of the high sensitivity "on" is that the measurements are somewhat slower and that they are more susceptible to overloads.

When these VU-meters are active. The Clock off/on button in the lowest of the two panels starts the timer. depending on the option button selected. The VU-meter for the potential signal is also active when the cell is switched off i. on". and the graph can be stored. the compensated resistance will be kept as constant as possible. the first green LED or a grey background is shown. In case of a manual change of the current range. A click on the arrows and slider bar changes the value by a distinct increment. printed.e. In order to perform iR-compensation the iR-compensation button on the Settings panel should be switched to "iR-comp. During the execution of the procedure (except for pre-treatment stage) the VU-meters are inactive. automatic current ranging is no longer possible. nor edited. You can select a higher current range or minimise the noise of your electrochemical cell. With a change of current range the resolution of the compensation will alter. potential and/or time can be displayed. In case more than 4 LED's of the VU-meter are on. In the two panels below the measured current. The maximum compensation of a current range equals two times the measurement resistance. However. This makes it possible to display graphically what is going on. The checked current range box becomes the actual current range. the data can neither be saved. Note that when the iR-compensation is switched on. A more elaborate description is found in the dedicated paragraph in this chapter (only available with a PGSTAT12/20/30/100). and displays the measured data from the panel above in the Data presentation window. Subsequently the Ohmic resistance can be specified using the slider or by typing in the textbox. no current can flow. The slider box can be dragged to change the value. it is advised to take precautions. in case a chronomethod or the method cyclic or linear sweep voltammetry is selected and the Record second signal option is checked on page 2 of the procedure parameter list. The VU-meter for the current signal is only active when the cell is switched on.Chapter 3 The GPES windows 55 iR-comp. Noise meters The noise levels for current and potential signals are visualised by 2 noise meters at the signal panels. the value for the compensation needs to be recalculated when the current range is changed. iR-compensation The iR-compensation panel appears only when the Autolab is equipped with a PGSTAT12/20/30/100 potentiostat/galvanostat. High potential noise levels are often caused by the reference electrode." appears. With these tools the applied potential can be specified. These measured data can be replotted. analysed. The increment is different for the arrows and for the bar. The option button "2nd Sig. Potential The Potential panel contains a slider and a text box. Because internally the compensation is proportional to the current range. on/off: switches iR-compensation’ on’ or ’off’. This means that for the 1 A range the maximum .

9 compensated resistance is 2 Ohm and for the 1 µA range it is 2 MOhm. Some care should be taken with saving the work data.4 Data presentation window The Data presentation window serves several functions: • display of data • data analysis • data manipulation • communication with other programs like Paintbrush.1s". Also note that for cyclic and linear sweep voltammetry. which can be modified in the Data presentation window. ". the current response can be measured correctly. Filter panel The Filter panel appears when the Autolab is equipped with an ECD or an FI20 module. see the section about chronocoulometry. not the current values but the square root of the current is saved. The effect of a filter constant of e. are called work data and can be stored from the File menu of the Data presentation window in a work data file. The “Remote led” indicates when it is possible to edit the parameters in Manual Control. Excel or MS-Word.g. As mentioned earlier the measured data are kept in a shared data memory block with the data acquisition software. . as is described further on. it is always possible to resume the measured data. The following option buttons can be clicked "Off". However. During the measurement the measured data points are also copied to the memory block of the Data presentation window. If the work data are then saved. In cases where it is red. This file cannot be distinguished from the files with measured data. Both types of files have the same format and layout. For example. a graphical display.56 User Manual GPES for Windows Version 4. Integrator The Integrator panel appears only when the Autolab is equipped with an analog integrator. The data. the display of the current values can be changed to a square root of the current. it is not possible to edit the parameters in this window. The resolution is always 0.05% of the measurement resistance. For further use. but after the measurements only the last measured scan is visible. 5s is that 5 seconds after a potential perturbation has been applied. "1s". 3. The window consists of a menu bar. during the execution of a procedure. Note that the save options of the File menu of the GPES Manager window always save the measured data. After the measurements the data in this memory block can be modified by options in the Data presentation window. This is not the case with a PGSTAT12/20/30/100 potentiostat/galvanostat unless the Autolab is equipped with a FI20-module. and a message line. the measured data are plotted. "5s".

020 Amplitude (Vrms): . This option work similar to the procedure parameter ‘Save every nth cycle’. . with the extension .001 Phase sensitive : Yes Phase (degree) : 20. It allows to save the so-called work data file as discussed above.000 E/V i(ac)/A .Chapter 3 The GPES windows 57 On the message line at the bottom of the graphical display important text about the required user actions during analysis of editing data appears. File The file option allows to create data files based op on data presented in the Data presentation window. This option can also be activated by typing 'SAVE' on the keyboard. This option is present in the File menu of the Data presentation window. Quick save of previous scan When a Cyclic or Linear sweep voltammetry measurement with more than one scan is going on it is possible to save the previous measured scan. Z/ohm phi/deg Rs/ohm Cs/F NOTE: These data are additional data and can only be obtained after the measurement. The separate curves can be stored. Save I(forward) and Save I(backward) The Electrochemical techniques Square wave. Differential pulse and Differential Normal pulse provides the forward and backward current data. The following options are available. Save as Linear sweep data Save a Sweep segment of Steps and Sweeps as Linear sweep data.IMP. Save work file This option was discussed above. has the following layout: Date: 02-May-97 Time: 13:24:39 Frequency (Hz) : 252. These curves can be plotted but not analysed. the impedance data for each data point can be saved to disk. The file. the currently measured potential and current are displayed. Save impedance data When an AC voltammetry measurement is done. Save as Chrono data Save a Step segment of Steps and Sweeps as Chrono methods data. ‘Load data’ from the Gpes manager window to do analysis. If no message is displayed. NOT after loading a data file. . and retrieved with ‘File’. This data file can be read in Chrono methods in order to perform data analysis. . This data file can be read in the Linear sweep method in order to perform data analysis.

Plot The Plot option contains all kind of possibilities to manipulate the graph like plot refresh. setting a Data window. not all options are selectable because they are not applicable or intervene with current active data analysis options. Also when the execution of a procedure is going on. automatic scaling. These files can be read by programs like Paintbrush. from the screen. this option removes the previous measured data points from the screen. Fig. see the paragraph on Editing graphical items.9 Copy The Copy option allows to copy the graph to clipboard or to dump the graph in a bitmap file (. 29 The Plot menu . zooming. Sometimes. Excel or MS-Word.58 User Manual GPES for Windows Version 4. During measuring a cv. It is sometimes better to draw lines. New plot The New plot option removes objects. These programs allow editing of the graphs. display of a previously measured signal. This can be achieved by double-clicking the data points in the graph. By default GPES only draws dots. such as lines and markers. not all options are selectable. For further information. The best result is obtained by doing this from a maximised Data presentation window.BMP).

Any further data manipulation and display will be applied to this part of the data. Resume The Resume option makes a fresh copy of the measured data into the Data presentation window. With Chrono methods the x-values will be normalised to 0. With differential pulse voltammetry it allows to toggle the display of the current before applying the pulse. When subsequently the left mouse button is clicked and held down a Zoom window can be created. Show I (forward) This option shows for the techniques square wave and differential pulse voltammetry only. With square wave voltammetry it allows to toggle the display of the current measured in the pulse which is applied in the scan direction. Set window The Set window option allows to define a part of the data set. . When both are displayed no further data analysis is possible. next to the current or potential signal. when. Show I (backward) This option shows for the techniques square wave and differential pulse voltammetry only. With square wave voltammetry it allows to toggle the display of the current measured in the pulse which is applied in the opposite of the scan direction. The dt/dE vs E plot can be used for electroanalytical purposes. A marker in front of these options means that they are displayed.and Second signal The First. Automatic This option automatically rescales the data during a measurement. It allows switching between these types of plots. a second signal is recorded. First. When this option is activated a magnifying glass appears. E vs t plot and dt/dE vs E plot These options appear only when the method is Potentiometric stripping analysis. This allows you to get back to the original data after doing data analysis. so the x-axis always starts at t=0. With differential pulse voltammetry it allows to toggle the display of the current measured in the pulse. Zoom Clicking the Zoom option has the same effect as pressing the right mouse button.Chapter 3 The GPES windows 59 Some sub-options require explanation. The E vs t plot can be used to do Transition time analysis (see the chapter on the analysis of measured data) in order to analyse the kinetics and reversibility of the electrode process. and Second signal options are selectable.

The following items can be double-clicked: • the axis annotation • the axis itself . The backgrounds are explained in the special chapter about this subject. will also be visible in a print-out. After clicking the New plot option or the Resume option. You can select multiple files at a time by using <Shift> or <Control>. Thus a line of text from the Analysis results window can be copied to the Paste buffer and subsequently inserted there.9 Load overlay file This option allows the making of a graphical overlay of one or more data sets. items of the graph can be edited by double-clicking them. which is only present for multi mode electrochemical detection. Edit data The Edit data option gives the opportunity to modify the presented data. This text can be dragged over the graph. The background is described in the special chapter about this subject. the overlays will disappear. The overlay legends shown in the Data presentation window. and the format can be modified. which is only present for cyclic and linear sweep voltammetry. Editing graphical items and viewing data Except for the available options. A maximum of 10 overlays can be made. The first text line of the Paste buffer can be inserted on the text field as well. combined with the mouse action. allows the selection of a potential for further data analysis and peak search. Please note. It is possible to load overlays together with the main data (see Load data/scan option of the File menu) Reverse axes This option will reverse the direction of the horizontal as well as the vertical axis. It allows peaks always to be displayed upwards. the text itself. After double-clicking the text field. The available data analysis options depend on the selected electrochemical method. Enter text When this option is clicked the text "Text field" appears in the left top corner of the graph. allows the selection of a scan for further data analysis.60 User Manual GPES for Windows Version 4. that the text cannot be stored. Analysis The Analysis option contains an elaborate set of methods to extract essential parameters from the measured data. Work scan The Work scan option. Work potential The Work potential option.

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Fig. 30 Horizontal axis window

the axis description the plot title and subtitle • the data. Colours, sizes, marker types, text, formats, axis position: all these things can be changed. Please take some care with changes in Colours. E.g. do not make the data colour the same as its background colour.
• •

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Fig. 31 Plot parameter window

By double-clicking the data points a window appears, which among the standard graphical operations also gives the possibility to view the data values itself and to edit them. Moreover the data can be copied to clipboard and subsequently be entered into e.g. a spreadsheet program. Fig. 32 Graph parameter window

Double-clicking the axis itself allows scaling and positioning of the axis and selection of the axis function. Data can be displayed, among others, as linear inverse, 10 log, natural log, square root, inverse square root. Except for the linear and 10 log, the value

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of the presented data is modified in real. So all subsequent operations are really performed on e.g. the square root of the data. In case of the 10 log, not the values but the axis is changed to a logarithmic axis. When the button "| 1 |" in the upper right corner is clicked, the Graph parameter window appears. This window allows modification of the relative scale parameters of the so called graph and plotting area, and their background colours. All the changes made to colour and sizes are stored in the default graphics display file. The other changes are kept in the procedure file. 3.5 Edit procedure window The Edit procedure window consists of 2 pages. In Page 1 the most common parameters can be specified. Page 2 contains the other parameters. The meaning of each parameter is clarified by the Help program. A list of parameter descriptions is given in the appendix about this subject. In the option bar, the Send option is displayed. This option can only be clicked during the execution of a measurement procedure. It is relevant when a parameter is changed. The Send option activates the modified value. The modified value is accepted when a beep sounds. The layout and setup of the Edit procedure window is more or less the same for all electrochemical methods. For most methods on Page 1, the following type of parameters can be specified: • the first pre-treatment and subsequent equilibration • the definition of the type of measurement • the potential or current level parameters • the title and subtitle. The items on page 2 depend on the method. For voltammetric analysis the following extra items are available: • number of voltammetric scans which will be recorded subsequently and averaged • a number of comment lines. For cyclic and linear sweep voltammetry the following items are extra available: • extra pre-treatment stages • special measurement conditions • special display option to swap x- and y-axis (Tafel plot) • a number of comment lines • current boundaries for reversing the scan direction • optional chronoamperometric measurement conditions at the vertices • optional recording of an external signal. For the chronomethods the following extra items are available: • extra pre-treatment stages • special measurement conditions

You can also change the text style in the window.6 Analysis results window The Analysis option of the Data presentation window allows the making of an analysis of the data. • Select Paste text. • Now select the Copy menu on the Data presentation window. The Paste option will include text from the paste buffer.. The Analysis results window contains all the results of the analysis of the data. You can include the Analysis text as follows: • You can select (a part of) the text. via Paste special option makes a Paste Link. The text in Data presentation can not be changed. For example. . The Edit option allows the user to remove (Cut) the selected part of the text. save or print the content of the window. Text can be selected by keeping the left mouse button pressed and moving it over the window. • Under the option Edit click the option Copy (or Cut). This is useful if you want to have a complete printout of the graph. A full list of input parameters is given in appendix II.9 • • optional recording of an extra signal a number of comment lines. MS-Word can. the Analysis results window is cleared. For a proper outlined text a change to the font ‘Courier’ is sometimes required. It is possible to copy results of Analysis into the graph of the Data presentation window. In some cases the results are displayed in a special window which differs per analysis technique. The text will be included into the graph. you can drag the text to the position you want. Please note: In the Data presentation.64 User Manual GPES for Windows Version 4. 3. option of MS-Word. In all cases a report of analysis is printed in the Analysis results window.. The Copy option copies the content of the window to the paste buffer including a so called DDE link. The File option of this window allows the user to clear. For potentiometric stripping analysis the following extra items are available: • smooth level during differentiation of potential versus time data • a number of comment lines. This means that any change to the content of the window will automatically be copied to the MS-Word document until the link is broken via the Links. Only when the GPES Manager window is closed. Now the text is present in the paste buffer. For electrochemical detection the following extra items are available: • extra pre-treatment stages • a number of comment lines • differential pulse condition (if applicable). but can be cleared by double clicking and typing in a space in the Text field.

This window can be made visible from the Window option on GPES Manager menu bar. When this option is clicked on. the peak search algorithm needs two input parameters to be specified: the minimum peak height and the peak width. See Plot menu on the Data presentation window. The results of the analysis are sometimes displayed in a specific window. In all cases the results are printed in the Analysis results window. Analysis of measured data Under the Analysis option on the Data presentation menu there are a number of facilities to analyse measured data. Otherwise only a value for the minimum peak height is required.e. The peak width parameter determines the width of the window which moves through the data set. • Another conflicting option is already selected. • When a second signal has been recorded concurrent. This may have the following causes: • The option is not relevant for the electrochemical method. i. a selection of the scan to be analysed can be made. according to the moving average baseline correction . The number of digits is the same as the precision of the axis. it is not clear on what data the analysis should be done. The Peak search options window gives several options to search for peaks in a voltammogram. The Close button closes the Peak search window. • Just after the recording of more than one cyclic or linear sweep voltammogram. The Show results button will show the Results window. For this purpose the Peak search option contains an Include shoulders option. If the curve shows distinct peaks. the Peak search window appears. The Clear button will erase the Results window and will refresh the plot. • The option is not relevant or cannot activated because an ambiguous situation is present. Peaks with a width (at half peak height) which are smaller than the specified peak width might not be found. If Automatic option button is 'checked'. The option is found at the Peak search options window and can be selected only in automatic search mode. By default the last measured full scan is displayed. first a selection has to be made which signal should be analysed.Chapter 4 Analysis of measured data 65 4. It opens when the Option button is clicked. In most cases not all options are selectable. • The execution of a measurement procedure is in progress. It is possible to find peaks that are present as shoulders on a steep base curve. Peaks with a height below the minimum peak height will be omitted. the Peak search is performed after a basecurve correction on the background. See Work scan option on the Data presentation window. Some analysis techniques are specific for an electrochemical method. These parameters have to be specified in the Minimum panel.1 Peak search When the Peak search option is selected. you can often simply click the Search button in the right panel and the results are shown in an appearing Results panel. 4.

42 Peak search window Fig. This method can also be performed separately. 43 Peak search options window Fig. Fig.9 method. 45 Peak search results window . See Baseline correction option in the Edit data menu.66 User Manual GPES for Windows Version 4. 44 Set results format window Fig.

or highest in the whole selected peak area can be determined. If this is not required. In curve cursor mode the two markers several types of basecurve s can be drawn: linear. After the first point of the baseline has been marked. . In the Baseline panel it can be 'checked' whether or not the peaks found will be corrected for the baseline. The options Lin. the Reverse option in the upper right corner of the window should be checked. the Automatic search should be switched off. The tangent is drawn from the left side to the right side of a peak if ‘linear baseline is checked’. Now two points on the front part respectively rear part of the peak should be marked. front baseline’ is checked. This is done when ‘Lin. The defaults in this window are the formats of the axis-labels.Chapter 4 Analysis of measured data 67 Peaks are normally searched in the scan direction. the beginning and the end point of the peak. This baseline is determined by means of the tangent fit method. Two alternatives are present: curve cursor and free cursor. front baseline or Lin. only peakheight of the front peak. a line connected to this point will be dragged until a second marker is clicked. rear baseline on the Baseline panel should then be ‘checked’. Moreover. or exponential. In free cursor mode the marks can be put everywhere on the graph. When the options 'Curve cursor. linear baseline' and 'Free cursor' are selected. In free cursor mode only a linear baseline can be drawn. in case of double peaks. baselines can be constructed manually. In cyclic and linear sweeps it may be better to use only the front of the peak to construct the tangent. In curve cursor mode the markers are automatically put on the voltammogram. Fig. 3rd order polynomial. the rear peak. In both modes two points need to be marked. If the automatic peak search method fails. The Set format button can be clicked to adjust the formats in the Set results format window. 46 Example of polynomial basecurve in peak Furthermore it is also possible to draw a linear baseline in case only the front part or only the rear part of the baseline is known.

J. : the sum of the absolute values of the maximum and the minimum in the derivative of peak.M.J. Lectere and J. derivation of an experimental curve will increase noise. This value is only printed for data from cyclic and linear sweep voltammetry. : the difference between peak potential and the potential at half height. 4. 47 Example of a linear front baseline Peak area Derivative Ep . but if the peak is not completely isolated from another peak. It is useful to derive kinetic parameters.: J..A.M.9 The results of the peak search are: Position Height : potential at which the current with respect to the baseline has a maximum. Electroanal. This means that the area is divided by the scanrate.O. The first step should be the forward potential step and the second the reverse potential step in a (quasi-)reversible . For more details see Ref. Electrochemistry Oxford science publications ISBN 0-19-855388-9. : maximum current with respect to baseline. Chem. See the book of C. Fombon.2 Chronoamperometric plot The Chronoamperometric plot option produces a special plot for two sequential potential steps in a chronoamperometric experiment. Oliveira Brett. Tacussel. the error in the peak area will be high. Brett and A. Fig. P.68 User Manual GPES for Windows Version 4. However. In quantitative voltammetric practice the peak height is the most widely used parameter to determine concentrations. The sum of the derivatives of the peak is less sensitive to peak overlap. The peak area is less sensitive to noise.Ep/2 : area of the peak corrected for the baseline. For data from cyclic linear sweep voltammetry the area is expressed in Coulombs.214 (1986) 79-94.

Chapter 5 (ISBN 0-471-05542-5) gives more details. This option is only active if it is applicable. a line is drawn so that the sum of squares of the differences between measured and calculated value is minimum. The charge flown since the beginning of the potential step is plotted versus the square root of the time since the start of the step. Bard and L. The book of A.J.Chapter 4 Analysis of measured data 69 electrode reaction. Faulkner.J. If data for more than two potential steps are present. This option is only active if it is applicable. A line should be fitted for the forward as well as for the reverse plot.J.4 Linear regression The Linear regression option allows to fit a straight line through a part of the measured curve. two windows appear.J. a selection of the first (forward) potential step can be made. The book of A. If data for more than two potential steps are present. Electrochemical Methods. 4. Fig.3 Chronocoulometric plot The Chronocoulometric plot option produces a special plot for two sequential potential steps in a chronocoulometric experiment. Bard and L. Chapter 5 (ISBN 0-471-05542-5) gives more details. When the option has been selected. One is the Linear regression window and the other is the Markers window. When the user has marked the begin and end point of the line on the measured curve and has clicked the OK button. a selection of the first (forward) potential step can be made. Faulkner. Electrochemical Methods. Fundamentals and Applications. 4. The kinetic parameters can be obtained by selecting the Linear regression option (see below). The first step should be the forward potential step and the second the reverse potential step in a (quasi-) reversible electrode reaction. Fundamentals and Applications. 48 Linear regression window . The fit parameters appear in the Analysis results window as well as in the results panel.

the standard deviations and the correlation coefficient are displayed in the Linear regression window.9 The slope of the line (dY/dX). 4. its inverse. the area is expressed as charge (C). The limiting current at E½ is calculated as two times the current at E½ with respect to the base current.6 Wave log analysis The Wave log analysis option is active for voltammetric analysis and cyclic and linear sweep voltammetry. the intercept (the value at X = 0). the user is asked to define a base line and a limiting line. Subsequently E½ is calculated from the crossing between the average line of the base line and the limiting line with the measured curve. Thus the calculated area is divided by scanrate.5 Integrate between markers This operation will determine the area under the curve between two selected points. More lines can be fitted when the Set line button is clicked. The half wave potential E½ can be determined and Tafel slope analysis can be done for a S-shaped cyclic voltammograms or convoluted voltammograms (see Convolution option). The markers for the line should be selected not too far from zero on the Y-axis. "id" for limiting current and "ln" for natural logarithm. With cyclic voltammetry. If a cyclic voltammogram has been deconvoluted the "i" is replaced by "m". where "i" stands for current. a Tafel line analysis can be done from the plot of ln {(id . the number of points between begin and end point.70 User Manual GPES for Windows Version 4. After having selected this option.i )/i} versus the potential. 4. After pressing the Continue button on the Wave log analysis window. The parameter Alpha * n (αn) has been calculated from the slope: . The intercept is at E = 0.

This window shows the corrosion potential and the polarisation resistance at the corrosion potential. Subsequently the graph is transformed in a logarithmic scaled current versus potential plot and the Corrosion rate window appears. These data are used to calculate the corrosion rate in terms of current density (Icorrosion ) and millimetres/year (CR): Icorrosion = icorrosion /SA A/cm2 and CR = 3272*icorr*EW/(SA * D) The polarisation resistance Rp is determined by taking the reciprocal value of the derivative di/dE. and the density (D) of the electrode material can be specified. the whole curve is used for the analysis. 4. If the curve passes the zero current line only once. From this Rp value the corrosion rate can be obtained: .15 at 25°C n = no.Chapter 4 Analysis of measured data 71 slope = αnF/RT F = Faraday constant = 96484. If the current versus the potential curve passes the zero current line more than once. the user is asked to define a window of interest around the point where the anodic current balances the cathodic current. An example of wave log analysis is described in Chapter ‘Getting started with GPES’.31441 J/mol/K T = temperature = 298. The derivative is obtained from a 2nd order polynomial fit through the corrosion potential and its neighbours. of transferred electrons α = 1 for reversible reactions α = transfer coefficient for irreversible reactions.8 Corrosion rate This option allows the determination of the corrosion rate and the polarisation resistance. Before doing this. When the option is selected. The user is asked to set markers for the anodic and cathodic branch on the curve. the current is plotted on a logarithmic scale. In principle this option works similar to Corrosion rate analysis without the fitting part.6 C/mol R = Gas constant = 8. In this window the surface area (SA). 4. This can be done by doubleclicking the horizontal axis and subsequently selecting the "Origin" in the Intercept position panel. it might be useful to draw the horizontal axis through the origin of the vertical axis. equivalent weight (EW).7 Tafel slope analysis This option is only available for Cyclic and Linear sweep voltammetry.

The corrosion potential at zero current and the corrosion potential as calculated from cross-point of the two Tafel lines. B can also be obtained from the Tafel slopes (M. After the OK-button on Marker window has been clicked. the Marker window appears. J. 3. 4.72 User Manual GPES for Windows Version 4. Now the Tafel line for cathodic branch has to be defined by marking two points. a second Corrosion window appears with the results: 1. Geary. After clicking the Tafel slope button. 2. corrosion current density and the corrosion rate. the same has to be done for the anodic branch. 1957. 49 Corrosion rate analysis .303 * Fig. The Tafel slopes ba and bc.L. Soc. 56).9 icorrosion = B/Rp where B is normally an empirical constant. The Polarisation resistance Rp obtained from the equation: 1  S  1 1    +    ba bc  Rp = B/icorrosion where B = and S = 2. The corrosion current. electrochem. 104. After the Tafel lines have been set. Stern and A.

The observed corrosion potential. It can be activated in the Analysis menu of the Data presentation window. The Tafel slope parameter α can be obtained from the slopes: b = 2. the potential where i = 0. The values obtained from the Tafel lines are used as start parameters. The fitting is performed according to the non-linear least square fit method of Levenberg/Marquardt.6 C/mol = Gas constant = 8.303/bc = the equivalence or corrosion potential = the corrosion rate or exchange current in Ampere When the Start fit button is clicked. is taken as the corrosion potential Ecorr. The fitted slopes are s1 and s2. The frequency spectrum is calculated by means of a FFT algorithm.Ecorr)       s1 s2 Eeq icorrosion    i = icorrosion where = slope of the anodic branch = 2. Therefore for some cases. of transferred electrons = ln (10) It is sometimes possible to improve the fit by clicking the Restart button. The comparison between the observed and the calculated curve is shown. In principle. the number of datapoints is automatically extended when necessary.and potential.303/ba = slope of the cathodic branch = 2. i. the dataset is padded with zeros.15 at 25°C = no. In case of an interrupted measurement (<Abort> was pressed). For noise signals.31441 J/mol/K = temperature = 298.9 Spectral noise analysis After recording current.noise transients. Since it requires the dataset to be a power of 2. 4.303 RT/3αnF F R T n 2. it would be advisable to apply a so-called . it is commonly desired to perform a statistical or frequency analysis on the results. The GPES software enables the calculation of a frequency spectrum for current and potential or impedance. a fit is performed on the slopes and the corrosion current.303 = Faraday constant = 96484.Chapter 4 Analysis of measured data 73 The corrosion rate is determined on the basis of the equation:       exp s1(E .exp -s2(E . Also the number of iterations and the goodness of fit parameter chi-square are given. The fitting procedure can be interrupted by clicking the Stop button.Ecorr)  . this is of course not true. After some iterations the fit results are presented on the screen.e. the Fourier method should only be used on datasets that are periodical and “fit” exactly in the time duration of the recorded scan. Chisquare is the sum of the squares of the differences between measured and calculated data.

Brett and A. Oliveira Brett. 4. A range of literature is available on the theoretical background of signal processing. The background of this analysis is fully described in the book of C.M. An example of transition time analysis is given in the chapter ‘Getting started with GPES’. See: “Numerical Recipes”. 4. 4.12 Transition time analysis The Transition time analysis option only appears for chronopotentiometric data or data from Potentiometric stripping analysis. Electrochemistry Oxford science publications ISBN 0-19-855388-9. The crosspoint of the transition line with the baseline is called t-base of 'tau'. Finally a linear regression can be done to extract the kinetic parameters from fitting a straight line. as well as to simulate theoretical current-potential curves. the transition line. Cambridge 1997 4. Subsequently the plot can be transformed dependent on whether the measured system is thought to be reversible or irreversible. A linear interpolation is used to calculate intermediate values. a graph of the time versus potential is presented and the user is asked to specify two marker points for subsequently the baseline.. The table . The time difference between the crosspoints of the transition line and the base line respectively the limiting line is defined as the quantity 'tau'.H.Press et al. like formal redox potential.A. Cambridge University Press. W.M. It provides the method to determine parameters of electrochemical processes.O. and the limiting line. transfer coefficient α etc. Finally also the quantity E3/4 E1/4 is given. A total of 5 functions are available: none/Bartlett/Hanning/Hamming/Blackman.9 “Window function”.11 Interpolate The Interpolate option allows the user to calculate one or more X-values or Y-values which corresponds to a given value on the other axis. After selecting this option. These operations will counteract the effects that were mentioned above.10 Find minimum and maximum The Find minimum and maximum option shows the minimum and maximum Y-value with their corresponding X-values.13 Fit and simulation The Fit and simulation option is located in the Analysis menu of the Data Presentation window. heterogeneous rate constant.74 User Manual GPES for Windows Version 4.. This is the difference in potential at three quarters of 'tau' and at one quarter of 'tau'.

This means that for the sake of speed. which have a number of restrictions on their validity. combinations of experimental techniques and reaction mechanisms) for which fitting and simulation are currently available. The simulation method Digital simulation of current-potential curves is based on finite difference method. on the number. The time-dependent concentration profiles obtained from these equations are used for the calculation of the current. The convergence criteria are based on the value of χ2 . Σ(Y-Yfit )2 .e. staircase cyclic voltammetry reversible quasi-reversible irreversible ErCi (irreversible chemical reaction) differential pulse voltammetry reversible quasi-reversible irreversible ErCi (irreversible chemical reaction) normal pulse voltammetry reversible quasi-reversible irreversible ErCi (irreversible chemical reaction) square wave voltammetry reversible quasireversible irreversible ErCi (irreversible chemical reaction) two-component In all the above models it has been assumed that the experiment is carried out on a stationary electrode in an unstirred solution. height and duration of all preceding steps. The fitting method Fitting is carried out using Marquardt nonlinear least-squares method.. and its change during the last iteration. This feature is easily visible when the simulation method is compared with analytical equations describing currentpotential curves. in cyclic voltammetry.e. i. Moreover. Equations of the transport of electroactive substances to the electrode surface are solved by Crank-Nicolson technique. as well as on the requested precision of the fitted parameters. The advantage of digital simulation is its versatility.Chapter 4 Analysis of measured data 75 below summarises the models (i. a method widely used by electrochemists and renowned for its accuracy and stability. Table 2 Models available for fitting and simulation. the current measured during a potential step depends on the “history” of the scan. The model functions are either calculated from analytical equations (wherever possible) or obtained by digital simulation of the electrode processes. The fit and simulation works only with staircase voltammograms but not with linear scans. . the number of potential steps should in the scan should be kept small. The models are called 'two-component' models and are available for the cyclic voltammetry technique. The models available for fitting and simulation are extended with the mechanisms in which two parallel reactions are involved.

This button is replaced by the Simulate button in case the simulation option is chosen. and two option buttons to switch between the fit and the simulation mode of the program.76 User Manual GPES for Windows Version 4. Guess' button starts the calculation of the initial guesses of fitable parameters.9 Elements of the Fit and Simulation Window Fig. 'Init. In extended setup. five action buttons. Each line contains the name of the parameter. Fast Fit performs a fit on a reduced data set. its value and a checkbox to indicate whether the parameter should be fitted or not. only fitable parameters are shown (it is possible to display all parameters by choosing the Extended setup option from the Option menu). . the value of χ2 and the elapsed time. The Stop Fit button will interrupt a running fit procedure.0CW. Normally. 50 Fit and simulation window In the upper part of the Fit and simulation window there is the drop-down menu with a list of available models. See the chapter ‘Fitting in more detail’ about the data reduction and other fast fit parameters. The middle part of the window contains three display fields. The list of models that can be used depends on the experimental technique chosen. C:\AUTOLAB\TESTDATA\DEMOCVO3. Fields show the status of calculations. Fitting and simulation step by step Fitting 1 Load a cyclic voltammogram file. 2 From Analysis menu (Data presentation window) select Fit and Simulation. relative or disabled) of the convergence criterion. The Full Fit button starts a fit of the model on all data points. in each line there are additional fields for the value and the type (absolute. 3 Select the model 'reversible' from the drop-down menu in the top part of the appearing window. The lower part of the fit and simulation window displays the parameters.

taking all data into account. It is possible to stop fitting at any moment by clicking Stop fit button. The process of stepping back can take few iterations.Chapter 4 Analysis of measured data 77 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Make sure the switch right to the model name is set to Fit. their values are not changed during the fit process (see "Fitting: choosing parameters to fit" and "Fitting: convergence criteria" for more detailed information). In this case the fitting procedure steps back and tries to obtain another. It is possible. Parameters that are visible in the extended setup but invisible in the standard setup are not fitable. with as start values the values visible on the screen. If necessary. during which curves observed on the screen may differ severely with the analysed data. as the fitting procedure finally comes with a better approximation. better approximation.. pressing Alt-G or by choosing Initial guess from the Option menu. Select Full Fit control parameters from the Option menu and adjust their values (see "Fitting: advanced options" for details). the Status field contains information "ready" and the number of iterations. the field Status shows the number of the iteration. guess button. switch to extended setup (Option menu. the status field displays information "interrupted". this is not a reason to worry. It is possible. adjust the starting value of parameters by clicking it with the mouse pointer and entering the new value (make sure that the number of electrons is set to 2). Get the initial guesses for the parameters either by clicking Init. If the maximal number of iterations has been carried out without reaching the demanded convergence criteria values. Check whether the number of exchanged electrons is correct. that some iterations will go in the wrong direction delivering worse approximations than the previous one. During fitting the results of each iteration are shown in the Data Presentation window together with the original data set. whatever comes first. press Alt-C or select Close from the File menu. However. Select parameters to fit by checking the boxes next to parameter names. To replace the work data by the fitted curve use Make work data option from the File menu. Pressing Full Fit starts the new cycle of fitting. field Chi-square shows the χ2 value and field Elapsed time shows time elapsed from the start of the fit. During the fit. Click Fast Fit button on a reduced number of data points. If fit has been stopped by Stop fit button. or Ctrl-E) to edit other parameters or to change parameter’s convergence criteria. If convergence is reached. The fitting proceeds until the convergence criteria are satisfied or the maximal number of iterations is reached. If necessary. To quit the fit window click the Close button. Fit parameters can be saved using option Save fit parameters and reloaded using the option Load fit parameters (both options from File menu). The number of iterations and the elapsed time counter are reset.e. . i. the status field displays information "stopped" and the number of iterations. that the program will need a few seconds to complete the iteration before stopping.

i 13 The comparison can be improved by switching to ‘Fit’ and selecting ‘Full Fit’. The χ2 field displays the sum of squares of datapoints values. 3 From Analysis menu (Data presentation window) select Fit and Simulation. To make simulation results permanent. it is automatically adjusted to fit within it. 8 Each parameter has its allowed range. If a value is entered that exceeds this range. select the Make work data option from the File menu. Close the fit and simulation window (Close button or Alt-C or Close option from the File menu). or switch to fitting (by pressing Fit button close to the model name).78 User Manual GPES for Windows Version 4. 7 Check whether the type of the process (oxidation/reduction) is set correctly. 12 When simulation is completed.9 Simulation 1 Load the differential pulse voltammogram C:\autolab\testdata\demoea01. 11 Press Simulation button or Alt-S to start calculations. 2 Set a window (see Plot menu on Data presentation window) between -1. adjust simulation options (Fit control parameters in the Options menu). ∑ yi2 . For details on these options see "Simulation: advanced options". 4 Select the model reversible from the drop-down menu in the top part of the appearing window and set the simulation mode by activating radio-button Simulation. 9 If necessary. . the status field shows message "simulation ready". In the last case a new list of parameters appears with their default values.850. 10 The Init. 5 Switch on extended setup (option Extended setup in the Option menu or Ctrl-E).150 and 0. guess button can be used all the time to obtain estimates of parameters for the work data. 6 Set values of parameters. or select another model.

Maximum fitting time: The time limit of fit procedure.Chapter 4 Analysis of measured data 79 Fitting: advanced options Fig. Maximum number of iterations: The limit for the number of iteration (fitting stops earlier if all convergence criteria are satisfied). 51 The Fit control parameters It is possible to fine-tune the fitting process. Parameters influencing the fit can be set by choosing Fit control parameters (Option menu) or by pressing Ctrl-P. . Change default value of this parameter only if there is a clear reason to do so. The following parameters appear on the screen: Fit control parameters Maximum change of chi-square (scaled): The convergence is reached when the last change in χ2 is not larger than the given fraction of χ2 value. If it is set to 0 (default) no checking of the time is done.

. In digital simulation. These parameters are presented below: Minimal number of simulation steps per potential value: The minimal number of simulations cycles carried out for each value of the potential. This parameter should be in the range 2. then each potential step time is divided into N subintervals and the simulation is carried out for each of these subintervals with time step equal to 1/N fraction of the step time. A convergence criterion is satisfied when the change in the parameter value does not exceed the predefined level. the space grid exponentially expands with the distance from the electrode surface. This is obtained by transforming the space in such a way. is controlled by parameter A.80 User Manual GPES for Windows Version 4. . However. Extended parameter setup allows to change default settings of individual convergence criteria for fitted parameters. Use of many points usually gives a better precision of the calculated current. thus also the number of points in concentration profile.3. Parameter A in space transformation y=ln(1+Ax): To speed up the calculations. or when very high accuracy is desired. Selecting No button for any parameter disables its convergence criterion (numerical value of previous setting remains visible). The program uses Feldberg’s function y=ln(1+Ax) for space transformation and the rate of expansion.9 Number of iterations per fitting step: Indicates how many iterations are carried out before a signal to break from the user can be processed and the data on the screen is updated. If this value is set to N.. that the increasing distances in the real space correspond to equally spaced distances in the transformed space. the values of concentrations are discrete and defined only in grid points. In the choice of their values the program assumes that the parameters of the electrode process have moderate values and tries to find a reasonable compromise between results precision and the calculation time. and its default setting is 2. when extreme values of parameters (or extreme combinations of values) are set. Maximal number of simulation steps per potential value: The upper limit for the previous parameter. automatic settings may be insufficient. and in calculations of concentration gradient the specified number of points is used. On the other hand. Convergence criteria may be absolute or relative (type of the criterion is indicated by the buttons visible in the extended setup). The simulation options are set by choosing Fit control parameters from the Option menu. Number of points in concentration gradient calculation: The value of the current is calculated from the derivative of the reactant concentration at the electrode surface. The middle part of the appearing window contains parameters that control the way the calculations are carried out. Simulation control parameters Most of the simulation options are set automatically by the program. the increase of number of the datapoints significantly increases the execution time. The default value is 4. The default value for this parameter is 2.

Full and Fast fit". Data reduction factor equal to 1 means that no Fast Fit is performed. minimal number of points in the reduced data set and the maximal number of Fast Fit iterations can be set. For this purpose one can use the reduced data set fitting feature of the fit and simulation program. Maximum number of iterations for Fast Fit: The limit for the iteration number. However. Therefore the user can define the minimal number of points that the reduced data set must contain. it can happen that the LU (=Lower/Upper) decomposition method gives better results in some cases. The actual value of this factor depends also on the minimal number of points for fast fit (For more information consult "Fitting: Fast and Full fit"). it may be attractive to speed up fitting by getting raw values of parameters with a reduced data set and then to refine them using full set. this factor cannot be very high because fitting with very few points is likely to deliver parameter values that are not much better than the initial guesses the program can make. Fast Fit parameters See "Fitting in more detail. The actual reduction factor is the smaller number from the data reduction value set and the (total datapoints)/(minimal datapoints) ratio. In the lower part of this window the data reduction factor. Data reduction factor: Allows to carry out fast fit with a data set reduced by this factor (in the reduced data set points are evenly spaced). Default setting is not to use LU method. After reaching it. but it is significantly slower when the number of points used to calculate concentration gradient increases. the fitting procedure switches to regular fit with all data points. The data set used for fast fitting cannot have fewer points than set by this parameter. Fitting in more detail Fast and Full fit When working with larger data sets (over 200 points). The number N is called Data reduction factor. The matrix is highly sparse and it is usually solved by direct method. Certainly. often obtained in cyclic voltammetry. Minimum number of points for Fast Fit: This is the limit for the data reduction factor. Parameters to control Fast Fit can be set in a window activated by option “Fit control parameters” from Option menu.Chapter 4 Analysis of measured data 81 Use LU decomposition for boundary condition: This is the option to provide an alternative way to solve the matrix representing boundary condition at the electrode surface. . In the reduced data set only every N-th point is used in the fitting. or when fitting process tends to oscillate. Using Fast Fit can be particularly useful when initial guesses do not deliver good estimates of the parameters.

g.g. select option “Initial guesses” from the Option menu or press Alt-I. If initial guesses are satisfactory. To check the correctness of initial guesses before starting the actual fit. temperature) and specific parameters (e. Therefor the fit can give error messages. The general rule is that only specific parameters can be fitted. Adjust step size The fit and simulation option for CV automatically searches for the potential step in the CV-data. Also the type of the process (reduction or oxidation) is set to the default value: reduction for scans going toward negative potentials. These parameters are measurement parameters (e. In order to get rid of these error messages. Special care in checking is required for the number of Exchanged electrons and the Dimensionless electrode radius.. How to detect dependence of parameters is explained in "Finding interdependence of fitted parameters". Please note that the kinetic parameters. Initial guesses will appear on the screen.. click the button Init. that can be inspected and modified when extended parameter mode is on (Ctrl-E or the Extended setup option from the Options menu). an option to adjust the step to the step potential from the procedure is available.g. The button is visible on the Fit and simulation window when the ‘Extended setup’ is activated. it is impossible to determine both the heterogeneous reaction rate k s and the formal potential Eo of the redox couple. Initial guesses The program provides initial guesses for most of the fitable parameters. as a result of this fit. An example of such situation is a data set obtained in cyclic voltammetry with a quasi-reversible system: if scan potentials are chosen so that only one peak (cathodic or anodic) is visible. general parameters (e. However the data can sometimes have an non-equidistant step in the potential data (i. start potential. It is only possible to fit successfully parameters that are independent on each other.e. The type of the process is an extended setup parameter. scan rate). and displayed in Data Presentation window.. guess. diffusion coefficient. parameters that can acquire only certain values (for example: the number of electrons involved in the process) are not fitable.82 User Manual GPES for Windows Version 4. i.. . A curve will be simulated with the current parameter settings. Although models are built in such a way that interdependent parameters are avoided. To calculate initial guesses of the parameters. change in the model due to variation of a certain parameter cannot be obtained by combination of variations of other parameters. and oxidation for scans going toward positive potentials. switch the mode to simulation (option button near the model name) and then click the Simulate button. it can happen that the particular data set renders two parameters dependent or partially dependent. switch back to fit mode and proceed with fitting. From them. From these parameters only some can be fitted and they are called fitable parameters. standard redox potential etc.).e. The fit and simulation software assumes an equidistant step in the potential. are not reliable anymore. The exact list of parameters for which initial guesses are calculated is available in the description of the models. if measured with ADC750).9 Choosing parameters to fit Each model is defined by a number of parameters.

Criteria based on χ2 demand that: 1. In the extended setup (Option menu) it is possible to define the value and the type (absolute/relative) of the convergence criterion for each fitable parameters. The .01 (=1%) of χ2 value. “Fit control parameters”). 52 Convergence criteria Fitting process is carried out until convergence criteria are satisfied or either the iteration limit or time limit is reached.Chapter 4 Analysis of measured data 83 Convergence criteria Fig. value of χ2 (weighted with σ0 ) should be less than 1 (or less than ∑ yi2 for i unweighted data) 3. the last change in χ2 is so small. change of χ2 in the last iteration step must be negative (χ2 decreases) 2. This value can be defined as an absolute. that the change to the parameter value in the last iteration should not exceed a certain value. The value that can be neglected is defined by the user as the maximal relative in χ2 (Option menu. that it can be neglected. The default maximal change is 0. or as a relative one (a fraction of the parameter’s value). Criteria related to fitted parameters value require. There are two types of convergence criteria: based on χ2 and related to the parameter value change.

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Convergence field contains the criterial value, and the buttons right to the value field can be used to select the absolute type of the criterion, the relative one or to disable the criterion for this parameter. The fitting process finishes when all the convergence criteria are satisfied. If the convergence is not reached in spite of many interactions done, this can be due to the following reasons: 1. Demanded precision of the parameters is unrealistic. The level of noise in the data, or precision of the measured variable (usually current) may keep the variation of the parameter of interest above the demanded level. 2. The type of the criterion is not appropriate. For example, in datasets where the background is very small it is better to use the absolute criterion than the relative one for background value, and relate it to the measured peak or wave current. The model is not applicable. In this situation the value of χ2 is usually larger than 1 (or larger than ∑ yi2 for unweighted data) while all other criteria can be met. It is then
i

advisable to either change the model, of re-examine settings for non-fitable parameters, like the number of electrons involved in the electrode reaction. Finding interdependence of fitted parameters Dependence of parameters can be detected by inspection of the covariance matrix (Covariance matrix in the Option menu or Ctrl-M). The diagonal terms are unity. If a term corresponding to a pair of parameters is significant, there is a serious chance that these two parameters are interdependent. Problems can arise if two or more parameters are interdependent. The matrices used during fit can become singular and an error occurs. Also, the fitted values of interdependent parameters are meaningless, or the program oscillates and it cannot deliver the final values. Finally, the computational time unnecessary increases, because fitting of each parameter requires the calculation of the derivative of the fitted curve with respect to this parameter. Some derivatives can be calculated analytically, but some not, and in the latter case the derivative must be obtained numerically. This requires an additional simulation per iteration step. Fit and simulation error messages error -1: “xxxxxxx”: Internal error of the fit and simulation program. String “xxxxxxx” contains specific information about the problem. Please report circumstances under which this error appeared. error 1: Not enough memory: There is not enough memory available to carry out the simulation. Try to free some memory by closing other applications. error 10: Technique not supported: An operation has been requested that is not supported for the currently selected technique. Please report circumstances under which this error appeared. error 11: Mechanism not supported: An operation has been requested that is not supported for this electrode reaction mechanism. Please report circumstances under which this error appeared.

Chapter 4 Analysis of measured data

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error 12: Model not supported: An operation has been requested that is not supported for the model chosen. Please report circumstances under which this error appeared. error 20: Negative reactant concentration obtained: Negative concentration of the reactant at the electrode surface has been obtained during the simulation of concentration profiles. This is usually due to the extreme value of the potential, at which the ratio of reactant to product concentration is either very small or very large. The general remedy is to shorten the potential range used. If it is not possible, try to use another settings for advanced simulation parameters. If this doesn’t help, please report the problem. error 21: Negative product concentration obtained: Negative concentration of the product at the electrode surface has been obtained during the simulation of concentration profiles. This is usually due to the extreme value of the potential, at which the ratio of reactant to product concentration is either very small or very large. The general remedy is to shorten the potential range used. If it is not possible, try to use another settings for advanced simulation parameters. If this doesn’t help, please report the problem. error 51: GAUSSJ: Singular Matrix-1: Two or more parameters in the model are dependent or nearly dependent. error 52: GAUSSJ: Singular Matrix-2: Two or more parameters in the model are dependent or nearly dependent. Descriptions of the models General remarks All models of electrode reactions assume diffusion to an electrode with finite dimensions. The size of the electrode is characterised by the dimensionless electrode radius
rd = re / D R τ

where re is the radius in meters, DR is the diffusion coefficient of the reactant in m2 /s and τ is the characteristic time parameter of the technique. The time parameter τ is equal to RT/nFV (in staircase and cyclic voltammetry, V=scan rate), to pulse time (in normal pulse voltammetry and chrono techniques), to modulation time (in differential pulse techniques) and to inverse of frequency (in square wave voltammetry). If the electrode is large or the τ parameter is small (fast experiments), i.e., only linear diffusion takes place, the dimensionless electrode radius should be set to zero. This value indicates that the radius of the electrode is irrelevant. All electron transfer rates are normalised according to equation
k = k τ DR

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and all homogeneous (chemical) reaction rates are normalised by multiplication by τ
kc h e m = kc h e m τ

Use of normalised constants allows carrying out fitting without the knowledge of diffusion coefficients. In all equations in the description of the models the log() function refers to 10-based logarithm, and ln() function to natural (e-based) logarithm. Cyclic voltammetry: reversible electrode process Reaction equation: R ← → P  Fitable parameters: redox potential E0 (V) normalised current Inorm (I = Inorm *χ(at)) (A) constant background current (A) Initial guesses available for: number of exchanged electrons, E0 , Inorm , background current Comments: According to the theory, the peak current is equal to nFAcbulk (πaD)1/2 *χ(at), where the first term is equal to the fitable parameter Inorm and the function χ(at), a=nFV/RT, V being scan rate, represents the shape of the voltammetric peak. The peak value of this function is 0.4463 for linear sweep voltammetry, while for voltammetry utilising the staircase voltage ramp the exact value depends on the step height, step time and the current sampling parameter α. Details regarding the function χ(at) can be found in literature 1 . Cyclic voltammetry: quasi-reversible electrode process
s Reaction equation: R ←→ P Fitable parameters: redox potential E0 (V) Log (normalised electron transfer rate), log ( k s ) transfer coefficient α normalised current Inorm (I = Inorm *χ(bt)) (A) constant background current (A) Initial guesses available for: number of exchanged electrons, log(k s), E0 , Inorm , background current Comments: The parameter log ( k s ) is a 10-base logarithm of the electron transfer rate, normalised with respect to the time scale of the experiment k s = k s RT nFVD , where V is the scan rate and k s is the electron transfer rate used in Butler-Volmer equation

ne −

ne− ,k

1

R. S. Nicholson and I. Shain, Anal. Chem., vol. 36, 1964, page 706.

Inorm. the peak current is equal to nFAcbulk (πbD)1/2* χ(bt). Cyclic voltammetry: reversible electrode process followed by irreversible chemical reaction (ECi) Reaction equation: R ← → P → B  Fitable parameters: redox potential E0 (V) forward chemical reaction rate kc(foll)-> (norm. the step height. log k f0h (exchanged electrons)*(transfer coefficient) αn normalised current Inorm (I = Inorm *χ(bt)) (A) constant background current (A) Initial guesses available for: E0 . b=αnFV/RT. step time and the current sampling parameter α. There is no need to set the number of exchanged electrons. used in reduced Butler-Volmer equation I = k 0h c R e x p −αn F RT E = k s c f ( ) (( ) ) R e x p −αn F RT (( )( E − E )) 0 According to the theory.) = k cf normalised current Inorm (I = Inorm *χ(bt)) (A) constant background current (A) Initial guesses available for: number of exchanged electrons.Chapter 4 Analysis of measured data 87 I = ks c ( R e x p −αn F RT ( E − E 0 ) + c ( ) P e x p ( 1 − αn F ) RT ( E − E 0 ) ( )) According to the theory. normalised with respect to the time scale of the experiment k f0h = k 0h RT n F VD . the step height. and for staircase voltammetry it depends on the electron transfer rate k s. represents the shape of the voltammetric peak. the transfer coefficient α. the transfer coefficient α. Cyclic voltammetry: irreversible electrode process s Reaction equation: R → P Fitable parameters: Log(Normalised electron transfer rate at E0 =0). step time and the current sampling parameter α. The peak value of this function depends on the electron transfer rate k s. background current ne− kcf . where the first term is equal to the fitable parameter Inorm and the function χ(bt). background current ne− . Inorm . f where V is the scan rate and k 0 fh is the electron transfer rate at E=0. b=αnFV/RT. where the first term is equal to the fitable parameter Inorm and the function χ(bt). the peak current is equal to nFAcbulk (πbD)1/2* χ(bt). E0 . The peak value of this function is equal to 0. Details regarding the function χ(bt) can be found in literature. represents the shape of the voltammetric peak.4958 for linear sweep voltammetry. αn.k ( ) Comments: The parameter log k f0h is a 10-base logarithm of the electron transfer rate. because the term αn is fitted as a whole.

In such situations their peaks can overlap. Cyclic voltammetry: two-component models Two-component models represent the situation when two electroactive species are reduced or oxidised at the electrode independently from each other. log ( k s ) ) transfer coefficient α normalised current Inorm (I = Inorm *χ(bt)) (A) • irreversible case: Log(Normalised electron transfer rate at E0 =0). the peak current is equal to nFAcbulk (πaD)1/2 *χ(at) (reversible processes) or nFAcbulk (πbD)1/2 *χ(bt) (irreversible processes). Reaction equations for single component: ne− Ri ←→ P i (reversible process) Ri ← s → P i  n e − . The parameters are denoted with numbers 1 and 2 to indicate to which component they correspond. The peak values of these function are 0. what hinders the extraction of relevant parameters for separate reactions.9 Comments: The forward chemical reaction rate is normalised with respect to the time scale of the voltammetric experiment. There is a number of two-component models available.88 User Manual GPES for Windows Version 4. quasi-reversible or irreversible mechanism).4463 (reversible) and 0. k c f = k c f ( RT n F V ) . If voltammetry with staircase voltage ramp is used. V being the scan rate. Details regarding this mechanism can be found in literature. differing in the degree of reversibility of each electron transfer (reversible. the exact value ( ) .k (quasi-reversible process) Ri  → P i  (irreversible process) Fitable parameters • reversible case: redox potential E0 (V) normalised current Inorm (I = Inorm *χ(at)) (A) • quasi-reversible case: redox potential E0 (V) Log(normalised electron transfer rate). where the first term is equal to the fitable parameter Inorm and the functions χ(at) and χ(bt) represent the shape of the voltammetric peak.4958 (irreversible) for linear sweep voltammetry. diffusion coefficient and the number of exchanged electrons. log k f0h (exchanged electrons)*(transfer coefficient) αn normalised current Inorm (I = Inorm *χ(bt)) (A) • common parameter: constant background current (A) Initial guesses available for: Comments: According to the theory. the voltammetric peak current is expressed as a product of the peak shape function χ(bt) and the term including the electrode area. b=αnFV/RT. The parameters a and b are respectively a=nFV/RT. concentration. ks n e −. Similarly to previous cases.

while all marked with (2) . f ( ) ( ) ( ) Normal pulse voltammetry: reversible electrode process Reaction equation: R ← → P  Fitable parameters: halfwave potential E1/2 (V) limiting current Ilim (A) constant background current (A) Initial guesses available for: number of exchanged electrons. In case of irreversible electron transfer it is necessary. to adjust the value of k f0h using the relationship ∆k 0h = αn F ∆E p RT log e . The halfwave potential should be equal to polarographic halfwave potential. However. it is always possible to select datapoints (by setting the window in such a way that only one peak is covered). This assignment can be changed by swapping the values referring to the first component and to the second component. Ilim . do initial guesses for one-component model and transfer the results to two-component model. Normal pulse voltammetry: quasi-reversible electrode process s Reaction equation: R ←→ P Fitable parameters: redox potential E0 (V) Log(normalised electron transfer rate).to electron transfer Ei.Chapter 4 Analysis of measured data 89 depends on the step height.k . where t p is the pulse time. log ( k s ) transfer coefficient α limiting current Ilim (A) constant background current (A) ne − ne− . it can happen that the initial guesses are inferior to those obtained in simpler models. The electron transfer rates k s and k f0h are defined as follows: k f0h = k 0h f RT n F VD and k s = k s RT nFVD while the Butler-Volmer equations for respectively quasi-reversible and irreversible processes are I = k s c R e x p ( −αn F RT ( E − E 0 ) ) + c P e x p ( ( 1 − αn F ) RT ( E − E 0 ) ) (quasireversible) I = k 0h c R e x p ( −αn F RT ) E = k s c R e x p ( −αn F RT ) ( E − E 0 ) (irreversible) f Due to the possible complication of two-component voltammograms. for example Er+Ei. E1/2 . all parameters marked with (1) refer to electron transfer Er. background current Comments: The theoretical expression for the limiting current at a large flat electrode is Ilim =nFAcbulk (DR/πt p )1/2 . When electron transfer processes are different. step time and the current sampling parameter α. Details regarding the function χ(at) and χ(bt)can be found in literature. however. The initial guess procedure can have problems with appropriate assignment of peaks to the components.

Inorm . E* E. Normal pulse voltammetry: irreversible electrode process s Reaction equation: R → P Fitable parameters: Characteristic potential E* (V) ne− . because the term αn is fitted as a whole. normalised with respect to the time scale of the experiment k s = k s t p D . k s and k 0 fh are the electron transfer rates f f used in Butler-Volmer equation I = k 0h c R e x p −αn F RT E = k s c f (( ) ) R e x p −αn F RT (( )( E − E )) 0 Normal pulse voltammetry: reversible electrode process followed by irreversible chemical reaction (ECi) Reaction equation: R ← → P → B  Fitable parameters: redox potential E0 (V) forward chemical reaction rate kc(foll)-> (norm. log k f0h (exchanged electrons)*(transfer coefficient) αn limiting current Ilim (A) constant background current (A) Initial guesses available for: log k f0h .k Log(Normalised electron transfer rate at E0 =0). Inorm . background current Comments: There is no need to set the number of exchanged electrons. ( ) ( ) where k 0h = k 0h t p D and k s = k s t p D . E0 . The 0 characteristic potential E* is defined as E * = ( RT αnF ) ln k fh = E 0 + ( RT αnF ) ln k s .90 User Manual GPES for Windows Version 4. where t p is the pulse time.) k c f limiting current Ilim (A) constant background current (A) Initial guesses available for: number of exchanged electrons. background current ne− kcf . αn.9 Initial guesses available for: number of exchanged electrons. E0 . where t p is the pulse time and k s is the electron transfer rate used in Butler-Volmer equation I = ks c ( R e x p −αn F RT ( E − E 0 ) + c ( ) P e x p ( 1 − αn F ) RT ( E − E 0 ) ( )) The theoretical expression for the limiting current at a large flat electrode is Ilim =nFAcbulk (D/πtp )1/2 . The theoretical expression for the limiting current at a large flat electrode is Ilim =nFAcbulk (D/πt p )1/2 . Inorm . background current Comments: The parameter log ( k s ) is a 10-base logarithm of the electron transfer rate.

that each point of the normal pulse voltammogram is calculated from analytical expressions for chronoamperometry under the following assumptions: • the current is measured at the end of the potential pulse • before each potential pulse concentrations of the species at the electrode surface are the same as in the bulk of the solution The latter means that no significant electrode reaction occurs at the base potential. Thanks to analytical expressions the speed of calculations is much higher than in the regular model based on finite-difference simulation. In addition to this. and that the interval time is long enough to restore the initial concentrations (or the dropping mercury electrode is used). quasireversible electrode process (analytical) and irreversible electrode process (analytical) These models differ from the previous only by the fact. if the mentioned assumptions are valid. valid under linear diffusion conditions. The forward chemical reaction rate is normalised with respect to the time scale of the experiment. k c f = k c f t P . background current Comments: The approximate expression for the peak height.k . is Ip = nFAcbulk (D/πtm)tanh(nF∆E/4RT) where t m is the modulation time and ∆E is the modulation amplitude. Ep . it is assumed in the reversible model that the product of the electrode reaction is initially absent in the solution. Normal pulse voltammetry: reversible electrode process (analytical). Therefore. Differential pulse voltammetry: reversible electrode process Reaction equation: R ← → P  Fitable parameters: peak potential Ep (V) peak current Ip (A) constant background current (A) Initial guesses available for: number of exchanged electrons.Chapter 4 Analysis of measured data 91 Comments: The theoretical expression for the limiting current at a large flat electrode is Ilim =nFAcbulk (D/πt p )1/2 . this model should be preferred. Ip . where t p is the pulse time. log ( k s ) transfer coefficient α peak current Ip (A) constant background current (A) ne − ne− . Differential pulse voltammetry: quasi-reversible electrode process s Reaction equation: R ←→ P Fitable parameters: peak potential Ep (V) Log(normalised electron transfer rate).

Ip . where k f0h = k 0f h t m D R and ne− . log ( k s ) . log k f0h . αn.k ( ) ( ) k s = k s t m D R . expressions for particular situations are complicated. k c f peak current Ip (A) constant background current (A) Initial guesses available for: Ep . normalised with respect to the time scale of the experiment. α.92 User Manual GPES for Windows Version 4.). log k f0h (exchanged electrons)*(transfer coefficient) αn peak current Ip (A) constant background current (A) Initial guesses available for: number of exchanged electrons. because the term αn is fitted as a whole. Ep . Ip . background current Comments: There is no need to set the number of exchanged electrons. Ip .9 Initial guesses available for: number of exchanged electrons. background current ne− kcf . The characteristic potential E* is defined as 0 E * = ( RT αnF ) ln k fh = E 0 + ( RT αnF ) ln k s . where V is the scan rate and k s is the electron transfer rate used in Butler-Volmer equation I = ks c ( R e x p −αn F RT ( E − E 0 ) + c ( ) P e x p ( 1 − αn F ) RT ( E − E 0 ) ( )) The general expression for the peak height does not exist. Differential pulse voltammetry: irreversible electrode process s Reaction equation: R → P Fitable parameters: Characteristic potential E* (V) Log(Normalised electron transfer rate at E0 =0). k s and k 0fh are the electron transfer rates used in Butler-Volmer equation I = k 0h c R e x p −αn F RT E = k s c f (( ) ) R e x p −αn F RT (( )( E − E )) 0 Differential pulse voltammetry: reversible electrode process followed by irreversible chemical reaction (ECi) Reaction equation: R ← → P → B  Fitable parameters: redox potential E0 (V) normalised forward chemical reaction rate kc(foll)-> (norm. k s = k s t m D R . Ep . background current Comments: The parameter log ( k s ) is a 10-base logarithm of the electron transfer rate.

to the height of the forward peak. Ipf. normalised with respect to the time scale of the experiment k s = k s fD R . Square wave voltammetry: irreversible electrode process s Reaction equation: R → P Fitable parameters: ne− . Square wave voltammetry: quasi-reversible electrode process s Reaction equation: R ←→ P Fitable parameters: formal potential E0 (V) Log( normalised electron transfer rate). in the second . Ip . No simple expression is available for the peak height. in the second . Switching between net current and forward/backward current will therefore result in the difference in peak heights.Chapter 4 Analysis of measured data 93 Comments: The forward chemical reaction rate is normalised with respect to the time scale of the voltammetric experiment. background current (fitting on net current) Epf. Switching between net current and forward/backward current will therefore result in the difference in peak heights.k . k c f = k c f t m .k I = ks c ( R e x p −αn F RT ( E − E 0 ) + c ( ) P e x p ( 1 − αn F ) RT ( E − E 0 ) ( )) There is no simple expression for the net peak current. log ( k s ) transfer coefficient α peak current Ip (A) constant background current (A) Initial guesses available for: Ep . background current Comments: The parameter log ( k s ) is a 10-base logarithm of the electron transfer rate. background current (fitting on forward/backward current) Comments: There is no simple expression for the net peak current. The potential of the peak is very close to the polarographic halfwave potential. The interpretation of the value of Ip depends whether fitting takes place on the net current or on forward/backward currents: in the first case Ip corresponds to the height of the net current. where f is the frequency and k s is the electron transfer rate used in Butler-Volmer equation ne − ne− . Square wave voltammetry: reversible electrode process Reaction equation: R ← → P  Fitable parameters: formal potential E0 (V) peak current Ip (A) constant background current (A) Initial guesses available for: Ep . Ip .to the height of the forward peak. The interpretation of the value of Ip depends whether fitting takes place on the net current or on forward/backward currents: in the first case Ip corresponds to the height of the net current.

Ip . Switching between net current and forward/backward current will therefore result in the difference in peak heights. in the second . ne− kcf . The characteristic potential E* is defined as 0 E * = ( RT αnF ) ln k fh = E 0 + ( RT αnF ) ln k s . Switching between net current and forward/backward current will therefore result in the difference in peak heights. where k f0h = k 0h ( fD R ) and f . k c f = k c f f .94 User Manual GPES for Windows Version 4. background current Comments: The forward chemical reaction rate is normalised with respect to the time scale of the experiment. log k f0h (exchanged electrons)*(transfer coefficient) αn peak current Ip (A) constant background current (A) Initial guesses available for: E* . background current Comments: There is no need to set the number of exchanged electrons. where f is the frequency and k s and k 0 fh are the electron transfer rates used in simplified Butler-Volmer equation R s ( ) ks = ks ( fD ) k = ks ( RT n F V ) ) ) D I = k 0h c R e x p −αn F RT E = k s c f (( R e x p −αn F RT (( )( E − E )) 0 There is no simple expression for the net peak current. Square wave voltammetry: reversible electrode process followed by irreversible chemical reaction (ECi) Reaction equation: R ← → P → B  Fitable parameters: redox potential E0 (V) normalised forward chemical reaction rate kc(foll)-> (norm. Ip . The interpretation of the value of Ip depends whether fitting takes place on the net current or on forward/backward currents: in the first case Ip corresponds to the height of the net current. because the term αn is fitted as a whole.to the height of the forward peak. The interpretation of the value of Ip depends whether fitting takes place on the net current or on forward/backward currents: in the first case Ip corresponds to the height of the net current. in the second .to the height of the forward peak.) k c f peak current Ip (A) constant background current (A) Initial guesses available for: Ep .9 Characteristic potential E* (V) Log( normalised electron transfer rate at E0=0). There is no simple expression for the net peak current. where f is the frequency.

The experiment time is converted into charge (the current applied is given from the procedure) and only the pX/pH signal is shown on the y-axes. The ‘Show last level’ button appears only if more then one level is measured. The 2nd derivative values are normalised so do not pay attention to the absolute values. . • • • • • The endpoint is obtained from the zero crossing(s) in the 2nd derivative. If only one level is defined all calculations are done on this particular level. 4.Chapter 4 Analysis of measured data 95 4.15 WE2 versus WE plot When a BIPOT is present.14 Current density The current density is calculated with the surface area.1s) potentiometry (galvanostatic) with pX/pH signal) this option can be chosen. If you follow the instructions the turning point will be shown as endpoint. Furthermore the ‘Endpoint Coulometric titration’ window is opened. The 2nd derivative and endpoint are calculated using the last applied level. The pointer can only be set on a real data-point and not on an interpolated point in between.16 Endpoint Coulometric titration After performing a coulometric titration experiment (Chrono method (>0. to find the endpoint. If the amount of measured point is poor the indicated end point in the curve can be slightly different from the actual zero crossing in the 2nd derivative. 4. using the surface area on page 2 of the procedure window. The show 2nd derivative button is active after the Find endpoint button has been pressed. The 2nd derivative plot is used for indicative purposes only. Iring versus Idisk plots can be constructed with this option.

Coulometric titration plot Parameters: Filter for derivative : Filter factor to reduce noise on the 2nd derivative.96 User Manual GPES for Windows Version 4.9 Fig 52a. and “Installation and Diagnostics Guide: pX-module). 1%: no filtering – 25%: heavy filtering. Window for zero crossings: Defines when a zero crossing should be noticed as a real zero crossing. . Due to Faraday’s law the equivalent of generated titrant is proportional to the charge and the equivalent of the analyte can be calculated (see also Application note “Coulometric titration”. This window defines the amount of points with different sign before and after the zero crossing.

Valid levels are 0 to 4.spike rejection and a 9-point weighed moving average 3. After a back-transformation. both the original curve and the smoothed curve are displayed and the question is posed whether the original data should be replaced. Press et al. etc. When only a part of the curve should be smoothed.. The data files can be smoothed using either the Savitsky-Golay algorithm or a FFT-algorithm. a logarithmic or linear frequency domain plot is displayed. but especially at low current levels the amount of noise can be severe. where n is the number of measured data points.spike rejection only 1. Having selected the FFT option. which should be less than the dominant noise frequency. The FFT-smoothing algorithm assumes that the signal is composed of n/2 sine waves of different frequencies. The more points within the curve. The Smooth option in all programs first asks which smooth level has to be applied. This option is only available for Savitzky and Golay smoothing. It works best . Their method presumes that a number of points can be fitted to a polynomial so that the best curve will pass through the experimental points.). Before the smooth routine of Savitzky and Golay is applied to the data set. ISBN 0 521 30811 9. In many cases the noise level will be low. Now a cutoff frequency has to be supplied. The FFT-algorithm is very effective in removing noise originating from the power-source. a Smooth option is supplied. filled up to a power of 2 (512. Smoothing can be performed on the whole curve or a part of it. W. Chem.spike rejection and a 5-point weighed moving average 2. In order to enhance the signal to noise ratio of experimental data sets. The added data points get a value of zero.1 Smooth Every measurement is disturbed by noise. all other amplitudes are set to zero. This method is also called weighted moving averaging.Chapter 5 Editing of measured data 97 5.1627 (1964). 1024. These levels are : 0. The remainder will not be smoothed. click the Smooth window button and select a part of the curve.. A cut-off frequency of for instance 20 means that the amplitudes of the 20 sine waves with the lowest frequencies are kept.36. FFTsmoothing should not be used in data files with spikes or discontinuities.H. the higher the smooth level can be without modifying the curve too much. The popular Savitzky and Golay method is described in Anal.spike rejection and a 15-point weighed moving average 4.spike rejection and a 23-point weighed moving average The applicable smooth level heavily depends on the number of points of the data set. Editing of measured data 5. Cambridge University Press. The FFT-algorithm is explained in the book "Numerical Recipes". spikes in the set of data are removed.

As a default minimum peakwidth a value of 30 mV or less is advised in most cases. The number of data points is reduced by calculating the average within a step window.2 Change all points This option allows to add a constant value to all data points or to multiply all datapoints with a constant value. After a baseline correction real peaks will show. it replaces the current value. 5. Two markers on the measured curve can be specified.98 User Manual GPES for Windows Version 4. 5. It is also possible to subtract a polynomial baseline. After accepting the markers the program will calculate a 3rd order polynomial through the markers.9 if the noise only consists of a periodic disturbance with a higher frequency than the real signal. You can specify up to 20 points. The step window is the minimum peak width which can be specified on the Baseline correction window. File) can be used to save the adjusted data-set. The process can be hindered by anomalies in the voltammogram.3 Delete points It is possible to remove points from the plot. This option can be used to remove spikes from the measured data. The frequency is presented in an arbitrary unit. Please note that the presented frequency in the frequency domain plot is not the frequency of the noise in the current or potential signal. The third type calculates a connecting exponential curve through the specified begin and end point. The Save work data (Data presentation. If the absolute mean value is lower. a message is given and the process stops. the correction can be either ignored or accepted. With resume (Data presentation. The first is the linear baseline. there is the so-called ‘Moving average baseline’. the corrected curve is also drawn. This operation is repeated again and again until no data point is replaced anymore. If more than 1000 iterations are required. Finally. This is an automatic baseline correction. Plot) the original data set will be loaded again. By clicking either the Cancel or the OK button on the Baseline correction window. After selecting this option the user is asked to mark between two and five data points as contact points between baseline and curve. The whole curve is subsequently corrected for this baseline. After acceptation of the markers. which then define a line. The baseline is subsequently calculated by comparing each point with the mean value of its two neighbours. Please note that this technique cannot be applied for Cyclic and Linear sweep voltammograms. . 5. The real signal should not change much within one period of this periodic disturbance.4 Baseline correction Four types of baselines can be specified. This method is very effective when peaks show as shoulders on steep flanks.

x is the time since the start of the scan instead of the potential.8 Integrate The integral is determined using the trapezium rule.5* For cyclic and linear voltammetry the time derivative is given.e. Subsequently the derivative is determined by the simple algorithm:  y(n) . i.7 Derivative First the data points are smoothed according to the Savitsky-Golay algorithm (see above) using smooth factor 2. x is the time since the start of the scan instead of the potential. i. For cyclic and linear voltammetry the time integral is given.y(n)   −   x(n+1) .6 Subtraction of second signal from first signal. In case the spacing between the two data sets is different a linear interpolation method is used.5*  x(n) .x(n)  dy/dx (n) = 0. The option is only enabled when a second signal is really available. . In case the spacing between the two data sets is different a linear interpolation method is used.e.y(n-1)     + 0. 5. 5. 5.Chapter 5 Editing of measured data 99 Fig 52b: Baseline correction window 5.5 Subtract disk file This option allows to subtract a previously measured data set from the current one. which assumes a straight line between two data points. This option allows to subtract a simultaneously measured second signal using either of the free ADC-channels from the current or potential signal (first signal).x(n-1)   y(n+1) .

9 Fourier transform The frequency spectrum is determined by means of a Fast Fourier method (FFT). 5. The real frequency is displayed on the x-axis. and in voltammetry (in this latter case in the descending branch of the peak). decreases with the square root of the electrolysis time and so does the current which is proportional to this gradient. Such a dependence can be easily observed in chronocoulometry.convolution. chronoamperometric. consumed in the electrode process. the gradient of the concentration of a substance. as in the case of the original techniques) and it is rather insensitive to iRdrop.10 Convolution techniques Convolution voltammetry consists essentially of a voltammetric. According to this solution. 53 Convolution menu In a number of electroanalytical techniques. the current measured displays proportionality to a t -½ function.100 User Manual GPES for Windows Version 4. . The technique delivers quantities directly related to the concentration of electroactive species at the electrode surface (instead of the flux of a compound. chronoamperometry. or chronocoulometric experiment followed by a mathematical transformation . the most common type of the transport of the reagent to the electrode. Fig. The popularity of this type of dependence originates from the solution of Fick's law in the case of semi-infinite linear diffusion.9 5.

In the case of a fast and uncomplicated electron transfer. "tailing" voltammetric ones. Oldham. K. 2) The function g(t) depends on the transport conditions and the electrode geometry.C. very similar to polarographic ones. The height of the plateau is given by the formula md = nFAD½C (eq. C. 3) where m denotes current convolution (for approximate description of kineticcontrolled processes the RT/nF value should be replaced by RT/αnF). Anal. Convolution of voltammetric data with a t -½ function results in a curve equivalent to the derivative of the previous one (up to a normalisation factor). 4) It can be shown that such a result is independent of the scan rate used and that the height of the wave is insensitive to iR-drop. Oldham. narrow peaks which are much better resolved compared to asymmetric. Zoski.B. Chem. Myland.G. The convolution of a voltammogram results in an Sshaped curve. the wave can be described using the equation E = E½ + (RT/nF)ln[(md -m)/m] (eq. J. The surface concentration of the product of an electrode reaction during the experiment can be obtained using equation∗ . The obtained t -½ convolution peak follows the function ∗ ) K. 1) where i(t)*g(t) is a convolution operation defined as x ⌠  f1 (u)f2 (x-u)du = ⌡ 0 x ⌠  f1 (x-u)f2 (u)du ⌡ 0 f1 (x)*f2 (x) = (eq. 193 (1985) 3. .Chapter 5 Editing of measured data 101 Using a convolution method. Chem. being in the simplest case (πt)½.B. Electroanal. J. cs(t) = i(t)*g(t)/(nFAD½) (eq. where voltammetric peaks are replaced by waves. Valuable features of this new curve can be noted: symmetric. 58 (1986) 2296. the effect of the decrease of the concentration gradient can be eliminated from the total response of the electrode.

Differintegration is cumulative. R. Anal.D. In this approach. deserve special attention. detection of the adsorption on the electrode as well as of the irreversible homogeneous reaction consuming the product generated by the electron transfer step. Spanier. Detection of overlapping peaks The nature of the voltammetric peak causes overlap in case of complex voltammograms. Another reason for mentioning differintegration is that there are special algorithms allowing this operation to be performed rapidly. Anal. N. reversible electron transfer. 1974.H. . They can be considered as. Carney. respectively. P.102 User Manual GPES for Windows Version 4.9 e = nFAD½Ccosh-2 [nF/2RT(E-E°')] (eq. the descending branch follows a t -½ function and is characterised with a slow decrease. Even far away from the top of the peak. It is also possible to use other convolution functions e. two forms of convolution. Woodard.. convolution of current with t ½ function results in a horizontal line at the height equal to e = nFAD½C (eq. Academic Press. 6) if the transport to the electrode follows semi-infinite linear diffusion. the value of u need not be integer. the value of the exponent denotes the order of integration (if positive) or differentiation (if negative) and thanks to the convolution definition. This suggests that these methods can be used for the investigation of variations of product concentration on the electrode surface as well as detection and studies of phenomena. Goodin. the ∗ ) F.g. convolution with a t -½ function leads exactly to the same result. "The Fractional Calculus". resulting in deviations from linear diffusion transport. As mentioned before.J.B. Kinlen. the determination of the formal potentials and numbers of electrons involved in the reaction step. 5) in case of a fast. 47 (1975) 2267. From the practical point of view. semi-integration and semi-differentiation. with t ½ and t -½. For chronocoulometry. J. J. 56 (1984) 1920. Other practical applications are the resolution of overlapping voltammetric peaks. Oldham. d½ /dt ½ (d½i/dt ½) = di/dt or d-½/dt -½ (di/dt) = d½i/dt ½. Chem. to separate the spherical diffusion effect. Chem. While the ascending branch of the peak rises rapidly and the beginning of the rise can easily be found.e. in case of semi-infinite linear diffusion the results of convolution with the function t±½ (semi-integration and semi-differentiation) are welldefined and quite simple. It is profitable to distinguish a class of convolutions with a g(t) function in the form g(t)=t -u (u is a real number): such a convolution can be considered as a generalised differentiation/integration (differintegration) operation with respect to the variable t. For more information please refer to K. In chronoamperometry.E. i.Y. the kinetic effect of the preceding homogeneous reaction etc∗ .

First. If the separation of two voltammetric peaks is large enough. There are. The extreme situation is shown in fig. however. semi-derivative peaks are clearly visible and their number can easily be found. so that only one peak can be observed and there is no indication for the presence of more of them. 54 Overlapping linear voltammetric peaks and their semi-derivatives In most situations. they can be detected without any problems. Due to this feature. voltammograms that are to be semidifferentiated. the first peak is reduced to a shoulder on the rising part of the next peak.Chapter 5 Editing of measured data 103 value of the current differs significantly from zero. Fig. The situation is difficult when the distance between peaks gets smaller: below a certain distance. should be background-corrected: semi-differentiation changes a constant or a linear background into complicated forms in the semi-derivative domain. except in those of extreme overlap. . all following voltammetric peaks rise from the "tail" of the previous one. where the overlap is very strong. three important limitations to this method. 56 C.

This test is superior to the well-known test based on the difference of potentials of voltammetric peaks. The third limitation of the method stems from the fact that results presented in the above-mentioned figure concern an uncomplicated electron transfer under semiinfinite linear diffusion conditions. Such a peak can only appear in the backward branch of semi-derivative voltammograms and has characteristic features: in the potential range. as it does not require knowledge about the number of electrons involved. leading to deformations of neighbouring semi-derivative peaks. Fig. the number of electrons involved can be determined from the halfwidth of the semi-derivative peak. If the rate of electrode reaction is limited by the diffusion or by kinetics of the electron transfer. where such a peak appears.104 User Manual GPES for Windows Version 4. that both anodic and cathodic peaks appear at the same potential. in certain situations. semi-derivative peak artefacts have to be recognised: consider the case of an uncomplicated slow electron transfer leading to the voltammogram presented in the appropriate figure. Determination of formal potential and the number of electrons involved The equation 5 describes the form of a semi-derivative voltammetric peak in a case of uncomplicated fast electron transfer under semi-infinite linear diffusion transport. for cyclic voltammetry. where two peaks appear. All peaks that satisfy these criteria. The second semi-derivative peak does not represent any hidden voltammetric peak. (ii) there is a forward peak and (iii) the sign of SCV current values is the same in both branches. It is clear that the peak potential is equal to the formal potential of the reacting system and. This feature can be used as a simple and rapid test for reversibility of the reaction. (i) there is no backward voltammetric peak. 55 Peak artefacts in semi-derivative voltammetry The curve in the above-mentioned figure is the result of semi-differentiation. resulting in a decrease in separation capability and. are probably artefacts. but is an artefact resulting from semi-differentiation of a wave-like current decay. The form of the peak is different when the mechanism of the reaction and the transport type change: usually peaks become less symmetric and broader. This half-width should be . one in the forward and one in the backward branch.9 Secondly.

56 (1984) 1920. J.G. If it does not return to zero. the surface concentration of all species after the experiment should be exactly the same as before. I. Smyth.semi-integral As the convolution of the voltammetric current with a t ½ function (semi-integration) produces a value proportional to the surface concentration of the product of the reaction. that this method requires diffusion to be semi-infinite and linear. Elsevier. It should be stressed. Vos. which means that the product of the reaction has been entirely converted back to the substrate∗ . eds. Dobson. 56 Semi-integration of voltammograms in case of the absence (A) and the presence (B) of an irreversible homogenous reaction. P. L. If such a reaction does not occur. N. Chem. Anal. Oldham. 8) for a rate-controlled process. Tipping in "Electrochemistry. 7) for a diffusion-controlled process and w = 2. In situations where this is not the case.B.E. Anal. Kinlen.Chapter 5 Editing of measured data 105 w = 3. Taylor. K. however.J. Such a correction is available (S. Engblom. the convoluted value should return exactly to zero after completion of the cycle. thick line .D.).R. 1986. corrections have to be made.voltammogram.O. 62(1990)625) for ∗ ) F. Woodard.H.53RT/nF (eq. Goodin. Chem. Fig. the consumption of the initially present substance is suggested. Irreversible homogeneous reaction consuming the product of the electrode process The criterion for the absence of an irreversible homogeneous reaction is restoration of the initial state at the electrode surface after a cyclic change of electrode potential.R. R.94RT/αnF (eq.D. . Amsterdam. Thin line . Sensors and Analysis" (M.

Apart from the geometry of electrodes. Linear diffusion leads to the simplest description.kinetic effects. but unfortunately its conditions are rarely realised in the experimental setups used in electrochemistry. its rate can be measured. the kinetic increase of the flux can entirely . delivering the concentration of the reaction product on the surface of a spherical electrode. These deviations can then be classified into two groups: deviations. Kinetic effects occur when the electroactive compound is involved in a chemical equilibrium. Some problems can be expected if the substrate or the product of the reaction is accumulated on (or in) the electrode by adsorption. In case of solid electrodes a so-called edge effect occurs: the contribution of spherical diffusion appears. the initial value of the surface concentration is not restored after the completion of the voltammetric cycle and convoluted voltammograms will not deliver proper results. another example of deviations from the linear model may be caused by the adsorption of the compound on the electrode surface.9 spherical electrodes (mercury drops) under the name of spherical convolution it requires the values of electrode radius and of diffusion coefficient. or amalgamation. Such conditions can be called mixed linear diffusion . For a long electrolysis time. where the concentration is constant. Spherical diffusion enhances the transport because the spherical expansion of the diffusion zone increases its volume faster than in the semi-infinite linear case. If the presence of an irreversible homogeneous reaction is detected.106 User Manual GPES for Windows Version 4. causing an increase of the transport to the electrode and those causing a decrease. by means of inserting different values of k one can obtain the result in which a convoluted current at the end of the cycle approaches the same value as on the beginning of the cycle. deposition. for instance when electroactive species are produced by a homogeneous chemical process. It can be useful to consider different types of transport as deviations from the semiinfinite linear diffusion case. to the planar electrode. this gradient decreases with the rate proportional to the square root of the electrolysis time. Investigations of factors controlling the transport to the electrode Theoretically the most simple and quite commonly encountered transport type is semi-infinite linear diffusion: the substance diffuses from the bulk of the solution. The local decrease of its concentration within the diffusion layer disturbs the equilibrium and in consequence leads to the production of the compound in a chemical process. For this purpose a so-called kinetic convolution can be used. the second group covers effects such as limited diffusion and reaction from the adsorbed state. where it is consumed. chemical processes taking place in the solution can disturb the concentration profiles developed during the electrolysis. The increased volume results in a larger amount of the substance that diffuses to the electrode. and the diffusion can be approximated using a linear model over a short period of time only. In this transformation the effect of consumption of the product by the reaction with the rate k can be eliminated. In this case. In case of mercury electrodes. This extra amount increases the flux of the substance to the electrode surface. The flux of the substance depends on the gradient of the concentration at the electrode surface. In the first group. the surface of the electrode is not planar. spherical diffusion and different kinetic effects are included.

The measured current drops sharply to zero after exhaustion of the compound. In case of kinetic control of the process. The inverse effect appears when the transport is slower than for limited diffusion or if the reagent is strongly adsorbed on the electrode.Chapter 5 Editing of measured data 107 compensate the decrease of the concentration gradient and may lead to steady-state conditions provided that the amount of compound involved in reagent production is present in large excess. Another type of effect can be observed when the solution is present in the form of a thin layer. respectively. First. F . In such a case no transport is needed and the whole amount of substance reacts within a very short time. for instance. 10 leads to the formula m = nFAD½C (eq. and t . 11) In case of additional contributions enhancing the transport due to.Faraday's constant. the semi-charge is greater than predicted from the purely linear model and the line displays positive bias. Cyclic chronoamperometry and chronocoulometry If an electroactive compound reaches the electrode by means of semi-infinite linear diffusion.electrode area. This effect can relatively easily be observed in case of the dissolution of metals from a small amalgam drop or from amalgam film electrodes: the process is initially controlled by linear diffusion. 9) where n is the number of electrons involved. Electrolysis under such circumstances first leads to the depletion of this layer and then to the exhaustion of the entire solution volume. that should be mentioned here. 10) Semi-integration of eq. spherical diffusion or a kinetic effect. There are a number of experimental problems. the current can be described using Cottrell's equation i = nFAD½ Cπ-½ t-½ (eq. but after some time the drop is depleted and the flux of the substance through the electrode surface drops more rapidly than t -½. Integration of this equation leads to the expression for the charge i = nFAD½ Cπ-½ t ½ (eq. the data used for studies of transport phenomena should be corrected for the background otherwise deviations from linearity of the graphs can have other reasons. 9 or semi-differentiation of eq. and the potential of the electrode is such that the surface concentration of the compound is kept zero. the time scale of the experiment also . D and C the diffusion coefficient and the bulk concentration of the compound. An extreme case of this situation is the reaction of a substance adsorbed on the electrode or forming a monolayer on its surface.time from the beginning of electrolysis. This is called limited diffusion. A .

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determines the range of reaction rates and equilibrium constants that can be detected. The quantitative discussion of influences of different experimental factors on the convolution curve can be found in Goto M, Oldham KB, Anal. Chem. 46(1974)1522. Linear and staircase voltammetry The convolution techniques facilitate the interpretation of voltammograms, particularly the information included in the peak shape. As already said, this shape can be considered as produced by the convolution of two functions: function I, describing the surface concentration of the reaction product, and function II, representing the flux of the reaction substrate, depending on the geometry of the measuring system. In the simplest case of semi-infinite linear diffusion and fast electron transfer, function I has the form of an S-shaped wave and function II is a t -½decay. The character of function I is well-reflected in the ascending branch of the voltammetric peak; function II is responsible for the t -½ - proportional decay of the descending branch of the peak. Semi-integration (convolution of the SCV peak with a t ½ function) should therefore give a wave with a horizontal plateau. When the transport to the electrode is enhanced or diminished compared to semiinfinite linear diffusion, the descending branch of the SCV peak can be approximated using a t u function, where u>-0.5 for faster transport (slower decay) and u<-0.5 for slower transport (faster decay). Changes in transport result in semi-integrated waves with a biased plateau (negative for slower transport, positive for a faster one). Algorithms for convolution As mentioned before, there are special algorithms for differintegration as well as for other convolution. Below, four algorithms used for differintegration and convolution are described in short. G0 algorithm (Grünwald-0) This algorithm can be used to carry out differintegration to any order. The data must be acquired in constant intervals. For the order = 1 the operation is equivalent to differentiation, for -1 - to integration using rectangle method. For +½ the G0 algorithm is the same as semi-differentiation. For -½ the G0 algorithm is the same as semi-integration. Error in results increases with the length of the interval and accumulates, i.e. error in latter points is larger than in earlier ones. Important advantage is that this algorithm does not require the value of the function for t=0, which makes it very well suited for transformation of chronoamperometric data (where i(t=0)->∞. The disadvantage of the algorithm is that the total number of operations is proportional to the square of the number of data points, so calculation time grows fast with the length of the data set. The fundamentals of this algorithm are described in Oldham KB, J. Electroanal. Chem. 121(1981) 431. FRLT algorithm (Fast Riemann-Liouville Transform) This is a fast, approximate algorithm based on a recursive digital filter. It is best suited for differintegration in the range of 0.0...-0.5 (up to semi-integration). It is less precise than G0 algorithm, but the number of operations is linearly related to the number of

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data points. For details refer to Pajkossy T, Nyikos L, J. Electroanal. Chem. 179(1984) 65. Spherical convolution The algorithm is used to carry out convolution of the data measured using a spherical electrode and staircase potential waveform. Values of the diffusion coefficient, the electrode radius as well as the delay between begin of the potential step and the current sampling moment are necessary. The number of operations is proportional to the square of data points. Details of the algorithm can be found in S.O. Engblom, K.B. Oldham, Anal. Chem. 62(1990)625. Kinetic convolution This algorithm carries out kinetic convolution according to F.E. Woodard, R.D. Goodin, P.J. Kinlen, Anal. Chem. 56 (1984) 1920. The number of operations is approximately proportional to the square of the number of points. This convolution requires the value of the rate constant of irreversible homogeneous follow-up reaction (ECi mechanism). 5.11 Convolution in practice The Convolution option can be selected for data measured with cyclic and linear sweep voltammetry. This convolution menu offers a number of transformations of the data set, like differentiation, integration, and convolutions. There are three principal types of convolution available: differintegration (convolution with t -u function, equivalent to fractional differentiation or integration, depending on u), using G0 or FRLT algorithm, spherical convolution, and kinetic convolution. The difference between G0 and FRLT algorithm is that G0 is more exact, while FRLT is faster with large data sets. Two items: semi-integration and semi-differentiation denote differintegrations using FRLT with the u value equal to -0.5 and 0.5, respectively. It is possible to carry out more transformations in succession. Because differintegration is an operation that can be cumulated, double semi-differentiation is equivalent to differentiation and the integration followed by semi-differentiation is equal to semi-integration. Please note that some combinations, especially those involving differentiation are not equivalent: differentiation+integration is not the same as integration+differentiation. In all convolutions the scale on the Y axis represents cs(t)nFAD½, where cs (t) is the concentration of the product of the electron transfer step on the surface of the electrode.

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Fig. 57 Example of a convoluted voltammogram

It is also possible to perform the convolution on part of the voltammogram (See Set window option of the Plot menu). It is recommended that the cyclic voltammogram starts at zero current. This can be achieved by performing a baseline correction. 5.12 iR drop correction iR drop correction allows for software correction of the potential data for the Ohmic drop in the solution. This option can be used for data from cyclic and linear sweep voltammetry. After supplying a value for the solution resistance, the measured and corrected curve are shown. The question appears whether the data are corrected.

ici • chronomethods *. Data memory buffer in ASCII-format and BAS Digisim file for: • cyclic and linear sweep voltammetry *.ocw • chronomethods *.opw • steps and sweeps *.txt These data files are in ASCII-format and are stored in the data directory.idi • potentiometric stripping analysis *.cv1 • *.cv3 These data files are in binary format and are stored in the data directory.icw • chronomethods *. Experiment parameter settings for: • cyclic and linear sweep voltammetry *.oew • multi mode electrochemical detection *.ini These data files are in ASCII-format and are stored in the procedure directory and in the data directory.onw These data files are in ASCII-format and are stored in the data directory.iei • multi mode electrochemical detection *.ixi • voltammetric analysis *.ofw • electrochemical noise *.iew • multi mode electrochemical detection *.inw These data files are in ASCII-format and are stored in the procedure directory and in the data directory.idw • potentiometric stripping analysis *.ixw • voltammetric analysis *.odw • potentiometric stripping analysis *. Measured data files for: • cyclic and linear sweep voltammetry *. . Data memory buffer in binary format for: • cyclic and linear sweep voltammetry • *.ifw • electrochemical noise *.ipw • steps and sweeps *.ifi • electrochemical noise *.bcw *.oxw • voltammetric analysis *.cv2 • *.ipi • steps and sweeps *.Appendix I GPES data files 111 Appendix I GPES data files The following types of files are used by GPES Graphical display settings for: • cyclic and linear sweep voltammetry *.

txt *.efs .mac These data files are in ASCII format and are stored in the data directory.inp sysdef40.9 Project files containing command lines for automatic processing of measurement procedures and data analysis: *. Print template files: *.inp. ASCII-format: Description file of sysdef40.hlp sysdef40. The GPES executable file: The GPES binary help file: The system parameter file.def These data files are in ASCII format and are stored in the Autolab directory.q&q These data files are in ASCII format and are stored in the data directory. File containing anodic and cathodic charges in cyclic voltammetry: *.112 User Manual GPES for Windows Version 4. ASCII-format: Fit & simulation parameter files: gpes4.exe gpes40.

. Current range: (bipotentiostat. This potential is normally applied to clean the electrode surface. Begin potential: (CV linear sweep) The potential at which the ramp starts.Appendix II Definition of procedure parameters 113 Appendix II definition of procedure parameters CM CV ECD ECN PSA SAS VA : Chronomethods : Cyclic and linear sweep voltammetry : Electrochemical detection : Electro Chemical Noise : Potentiometric stripping analysis : Steps and Sweeps : Voltammetric analysis ADC channel number: (Second signal. Correct iR-drop during dyn. CV. Conditioning potential: (VA) This is the first potential applied after the start of the procedure. CM) The channel number which should be used for recording the output from an external source. The applied potential is the "stand-by potential". Amplitude: (VA square wave ) Half of the peak to peak value in the squared wave perturbation. The maximum range is 10 mA. iR: (CV. Cell off after measurement: (All) If not 'checked' the cell switch will be left in the 'on' position after the measurement procedure has been completed. Comment : (All) A panel to type in several lines of text. The pulse will be superimposed on this potential level. CM) The input parameter only appears when the Autolab is equipped with the bipotentiostat module. This potential is not applied when its duration is set to zero. Base potential: (VA normal pulse. the minimum range is 100 nA. If ‘not checked’ the value of the ohmic drop is determined only. CM with dynamic iR compensation) If ‘checked’ the potential will be corrected for the ohmic drop. Amplitude: (VA ac voltammetry) The root-mean-square value of the applied potential sine wave perturbation. differential normal pulse) The base potential level. CV.

1s) This value is the upper limit for the 2nd signal. OCP: (CM) If 'checked'.9 Cutoff on charge: (CM interval time > . . as soon as the limit is reached. Cutoff value for time >: (CM interval time > . OCP: (CV) If ‘checked’. a button can be pressed to continue. If sufficiently stationary.t. the OCP is recorded. Define potential w. the experiment will stop. the stand-by potential and the specified potential levels are applied with respect to the open circuit potential (OCP). This potential is normally applied to deposit the components to be analysed on the electrode. the measured data are directly written to a data file with the extension ". Cutoff value for 2nd signal <(V’): (CV and CM interval time > .114 User Manual GPES for Windows Version 4. This potential is not applied when its duration is set to zero. the specified cutoff value is charge.r. It prevents loss of data due to a failure in the power supply. This option may be useful for long duration measurements. Define vertex potential w.r.t.oxw". the vertex and start potentials are specified with respect to the open circuit potential (OCP). if it is the last potential level in the sequence. the measurements will proceed with the next potential level or. a button can be pressed to continue.1 s) If checked.1s) The measurement is aborted when the time exceeds the specified value. otherwise it is current. Define start potential w. It is only active when the option ‘Specify time limit’ is checked. This feature allows to specify a cutoff value for the charge in chrono-amperometry. the experiment will stop.1s) This value is the lower limit for the 2nd signal. After acceptance the Start potential will be corrected for the OCP (Start potential + OCP). in chrono-amperometry or -coulometry. If sufficiently stationary.1 s) If a file name (without extension) is specified.r. Cutoff value: (CM interval time > . OCP: (CV) If this item is checked the measurement starts with measuring the OCP.t.1 s) If the specified value is exceeded. the OCP is recorded. Before the equilibration starts. the measurements will stop. Direct output filename: (CM interval time > . Cutoff value for 2nd signal >(V’): (CV and CM interval time > . as soon as this limit is reached. Deposition potential: (VA) This is the second potential applied after the start of the procedure. If you want to start at the OCP. Before the equilibration starts.

Dynamic iR amplitude: (CV. CM interval times > . Equilibrate with potential pulses: (ECD) If 'checked'. First conditioning potential∗ : (CV. although the data points are no longer plotted on the screen and stored in the computer memory. VA) or the stand-by potential (CM. PSA). First potential boundary: (CV) Used. Duration of Measurement: (ECN) The total duration of the Measurement.Appendix II Definition of procedure parameters 115 If the number of measured data points exceeds the allowed maximum (default 10. the Equilibration stage will be aborted after reaching this specified current. It will be rounded to the next nearest power of 2 times the Interval time. This filename will be used for the Save every nth Cycle option. ECD) If enabled. Direct Output filename: (CV) The path and the name of the file.’ is ‘checked’. Also the data file becomes too long to be loaded by the GPES program. . CM. CV. Equilibration threshold level: (VA.1s) The amplitude of the square wave in Dynamic iR compensation. the specified potential pulses are applied without recording data. Final rotation speed (rpm): (LSV staircase hydrodynamic) The rotation speed applied during the last scan. ECD. the potential is not applied.calc. for automatic calculation of the total positive and total negative charge. This option is not available for galvanostatic measurements. ∗ ) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry 'potential' should be read as 'current' and vice versa. The measurements will start as soon as this threshold value is exceeded. SAS) The potential at which the ramp stops. Equilibration time: (All) The time to equilibrate the electrode at the start potential (CV.000). in combination with ‘Second potential boundary’. CM. otherwise the stand-by potential is applied. If the corresponding "Duration" is zero. Only active when ‘Use boundaries for Q+/Q. the program will continue to store the data points on disk. The last five characters of the file name will be used as the scan number. ECD) The first potential which is applied after the Start button has been pressed. End potential∗ : (CV linear sweep.

002 s. di. CV. The maximum range is 10 mA. The actual current range for the bi-potentiostat module will be automatically set between the specified ‘highest’ and ‘lowest’ current range. or dQ" is 'checked' and if the change in current. or dQ: (CM interval time > . Interval time: (CM interval time > . Frequency: (VA) The number of times the square wave or sine wave perturbation is applied per second in respectively square wave voltammetry and ac voltammetry.. 1000. The maximum range is 10 mA. charge.9 First vertex potential∗ : (CV cyclic) The potential goes from the start potential to the first vertex potential where it turns around to go to the second vertex potential. the minimum range is 100 nA. or potential exceeds the specified value.1 s) Normally the time between two recorded data points. the subsequent rotation speeds will be 100. A linear distribution means that. the actual interval time can be less.. di. Interval time: (VA) Time between two measurements. Interval time: (ECD) The time between two current measurements in dc-amperometry. Linear(1) or square root(2) distr. or dQ value is specified. Maximum dE. CM) The input parameter only appears when the Autolab is equipped with the bipotentiostat module.116 User Manual GPES for Windows Version 4. CV. when the initial speed is e.1 s) In case the box "Specify maximum dE.. Highest current range: (bipotentiostat. di. Initial rotation speed (rpm): (LSV staircase hydrodynamic) The rotation speed applied during the first scan. Interval time: (ECN) The time between two recorded current and potential samples. For more information see the chapter on the methods.g. the minimum range is 100 nA. .: (LSV staircase hydrodynamic) The rotation speed table is calculated with a Linear distribution (1) or with a square root distribution (2). CM) The input parameter only appears when the Autolab is equipped with the bipotentiostat module. The actual current range for the bi-potentiostat module will be automatically set between the specified ‘highest’ and ‘lowest’ current range. 200. Lowest current range: (bipotentiostat. 100 and the final speed is e.. 1000 with 10 scans. It should be >= 0. If a maximum dE. 300. a data point will be recorded. .g.

Measurement temperature: (CV. Modulation amplitude: (VA differential pulse) The height of the potential pulse. stationary current) Every second the absolute current change is determined. Maximum time of measurements: (PSA) The measurements will stop when duration of the measurement exceeds the specified time. Number of cycles: (CM interval times > .g. Number of cycles: (CM interval times < . differential normal pulse) or the sine wave(ac voltammetry) is applied. If during three seconds this relative change is less than the specified value the current is supposed to be stationary. stationary current) Every second the relative current change is determined. Modulation amplitude: (VA differential normal pulse) Potential superimposed on the sum of base potential and pulse amplitude.5 s is convenient. the pulse direction is reversed with respect to the scan direction.1 s) The number of cycles you want to measure. Minimum abs(di/i) per second: (CV. All the measured data of the previous cycles are lost. Minimum abs(di) per second: (CV. This value is only active if the ‘Specify minimum variation’ is ‘checked’. If a negative amplitude is specified. The pulse direction is the same as the scan direction when the specified amplitude is positive. Modulation time: (VA) Time during which the modulation amplitude(differential pulse. A convenient value is 0. The next potential is applied. Minimum variation: (CM) Value at which the experiment is stopped or the next step in the experiment will be applied. pulse plating experiments a higher number can be specified. The direct output file (when specified) is appended with every scan. stationary current) After this period the current is supposed to be stationary.1 s) The number of times the sequence of potential levels as specified in the potential level table are applied. The old data (previous scan) will be overwritten by the new one. CM with pH as second signal) Temperature for pH correction with respect to the calibration temperature. but for e.07 s for differential pulse and differential normal pulse. After the measurements only the last cycle is in the computer memory. . For ac-voltammetry 0. The time parameter also adds up. A cycle includes the pre-treatment.Appendix II Definition of procedure parameters 117 Maximum time interval: (CV. In most cases the number of cycles will be one. If during three seconds this relative change is less than the specified value the current is supposed to be stationary.

The constant potential which should be applied to the second working electrode. CV. will be in memory and are plotted after the ‘number of cycles’ has been reached or after pressing ‘Abort’. Potential: (bipotentiostat. Potential limit: (PSA) The measurements will stop when the potential passes the specified potential limit. The averaging starts after the specified number of scans. The equilibration scans are not kept in memory. but display them with respect to another. These levels can be specified under header 'Potentials' Number of pulses: (ECD) The number potential levels which should be applied in multiple pulse or differential pulse mode. Potential shift: (CV) The specified amount will be added to the recorded potentials of the voltammogram.118 User Manual GPES for Windows Version 4. Number of scans: (LSV staircase hydrodynamic) The number of scans with a different rotation speed. the supplied value will be the phase shift with respect to the applied ac potential at which the ac current is obtained. Number of scans: (VA) The number of times a voltammogram is recorded. . Phase: (VA ac voltammetry) If "Phase sensitive" field above is ‘checked’. Number of scans: (CV) The number of cycles or linear sweeps to be measured. Number of potential steps: (CM) During the measurements the potential steps from the stand-by potential to a number of potential levels. Number of equilibration scans: (CV Scan averaging) Number of cycles of linear sweeps to reach an equilibrium. After reaching the maximum number of points in memory (=10000) the on-line plot option will stop. CM) The input parameter only appears when the Autolab is equipped with the bipotentiostat module. In this way it is possible to record potential versus present reference electrode. Phase sensitive: (VA ac voltammetry) If 'checked' a value for the phase should be supplied. The presented voltammogram is the average of all recorded voltammograms. The actual data-points however.9 Between two scans the interval time is recorded by the computer clock and this time is also added to the time parameter.

Quick save of previous scan: (CV) When more then one scan is recorded in Cyclic voltammetry. If "Record second signal" is 'checked'. They can be used to record the output of another instrument. CV. Normally. current or potential. During a measurement sequence. In differential pulse mode the two levels. The ADC164 or ADC124 module has 16 input channels which can be recorded. ∗ ) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry 'potential' should be read as 'current' and vice versa. Record second signal: (CV. in a third column.Appendix II Definition of procedure parameters 119 Potentials∗ : (CM) A table of potential levels can be specified. The number of rows is equal to the ‘number of potential levels’ specified on the field above. the potential steps from the stand-by potential to each of the specified levels. This column is only present for the chronomethod with interval times < . is sampled via one of the channels of the ADC164 or ADC124 analog to digital converter module. Potentials table: (ECD) In this table the potential levels to be applied. the voltage level of an additional channel of the ADC164 or ADC124 module is sampled as well. The channel number can be specified. This option can also be activated by typing 'SAVE' on the keyboard. . it can be specified whether the current should be recorded or not. An internal multiplexer allows switching from one channel to another.1s. CM) The primary signal. Record Bipotentiostat signal: (bipotentiostat. Purge time: (All) The time the gas valve is positioned to flow the gas through the cell. are recorded. specified on page 2. Four of them have an external BNC-plug. and their duration can be specified in multiple pulse or differential pulse mode. The last five characters of the file name will be used as the scan number. In multiple pulse mode. i. it is possible to save the previously measured scan. CM) The input parameter only appears when the Autolab is equipped with the bipotentiostat module. input number three and four are free channels. See description of the methods. not used by GPES. Pulse time: (VA Normal pulse) Time during which the potential pulse is applied.e. The following columns can be specified in the potential table: Potential: the required potential level Duration: the time the potential level is applied Sample time: the time between two current samples. This parameter only appears when an automatic electrode is present (see Hardware configuration program). The path and the name of the file can be specified as the ‘Direct output filename’. The number of rows is equal to the "Number of pulses".

Please note: These files can be overwritten during another measurement session with the same procedure. The specified value is adjusted by the program. Save every nth Cycle: (CV) When more then one scan is to be recorded in Cyclic voltammetry. and the step potential.00001. Scan rate: (CV Linear scan) The required speed of potential change. Scan rate∗ : (CV Staircase) The required speed of potential change. 5. 10. This limits the measurable scan rate to about 10 V/s. the computer. If.800 with normal CV (2400 with Bipot or 2nd Signal).000.120 User Manual GPES for Windows Version 4.g. CM. The lowest scan rate is 0.000 V/s for the SCAN-GEN module. 15 are saved. With Fast scan CV the maximum value is 45.000 samples per second. so that the number of steps per second becomes equal to one of the discrete values of the Autolab hardware timer. Reverse scan for i< : (CV) If "Specify current boundaries" is 'checked'. the scan direction will be reversed if the current exceeds the specified value. related to the second signal. The essential number for the highest scan rate is the number of potential steps per second i. the scan direction will be reversed if the current becomes lower than the specified value. '5' is specified. This is a hardware limitation of the SCAN-GEN module. “alpha (different from 1)” and “Chronoamperometry at vertexes”. (scan rate)/(step potential). Second conditioning potential∗: (CV. Reverse scan for i> : (CV) If "Specify current boundaries" is 'checked'. As stated above. The last five characters of the file name will be used as the scan number. The highest acceptable depends on the speed of the AD-converter. The maximum values might vary in combination with advanced options like “Specify current boundaries”. do not appear when the Autolab is equipped with a bipotentiostat module. e. Run time: (ECD) The duration of the measurement. ECD) ∗ ) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry 'potential' should be read as 'current' and vice versa. otherwise every nth scan will be stored on disk. Higher scan rates can be measured with ADC750 module.001.800 samples per second can be taken in combination with the ADC164 or ADC124 module. The maximum value is 4. scan 1. The lowest scan rate is 0. no more than about 4. . which allows to measure 750. The highest scan rate is 10. “High sensitivity”. The path and the name of the file can be specified on page two of the Edit procedure window ('Direct output filename').e. no scans will be saved during the measurements. it is possible to save scan at regular intervals during the measurements. If this parameter is zero.9 The input parameters.

Show noise around zero Volt : (ECN.1s) If 'checked' and the specified cutoff value is exceeded. It can be multiplied by a factor to convert it into another unit. or stationary current mode) If 'checked'. the recording of the scan will be terminated. See for further details the section on "smoothing". Subsequently the data are smoothed using the Savitsky-Golay algorithm and the derivative dt/dE is calculated. In case of linear sweep voltammetry. Specify cutoff value: (CM interval time > . normal. the 2nd signal will be checked on the ‘Cutoff value for 2nd signal >(V’)’ and ‘Cutoff value for 2nd signal <(V’)’. Signal offset: (Second signal.1s) If ‘checked’.Appendix II Definition of procedure parameters 121 The second potential which is applied after the Start button has been pressed. An offset can be supplied to convert it into another unit. the measurements will stop. CM) The recorded "second signal" is measured in Volts.time data are recorded. . Signal multiplier: (Second signal. Smooth level: (PSA) The potential . if it is the last potential level in the sequence. Second potential boundary: (CV) Used. the scan direction will be reversed. CV. Specify cutoff value for 2nd signal: (CV.’ is ‘checked’. If the corresponding "Duration" is zero. CV. CM) The recorded "second signal" is measured in Volts. Second vertex potential: (CV cyclic) The potential goes from the start potential to the first vertex potential where it turns around to go to the second vertex potential. the measurements will proceed with the next potential level or. the potential is not applied. with ECN-module selected) If ‘checked’ the potential noise will be plotted around zero volt in stead of around the DC-potential. The measurement will stop (CV) or proceed with the next potential level or stop if it is the last potential level in the sequence (CM). if the current exceeds one of the values specified below. Only active when ‘Use boundaries for Q+/Qcalc. CM interval times > . Specify current boundaries: (CV. in combination with ‘First potential boundary’. for automatic calculation of the total positive and total negative charge.

122 User Manual GPES for Windows Version 4. Sometimes (CM. ECD) it is also the 'start' potential before a measurement. This option might be of use when a large number of cycles is specified. this parameter can be used to stop a chrono-amperometry or chronopotentiometry experiment as soon as the change in.1s) If 'checked'.9 Specify maximum dE. See also "Scan rate". Stand-by potential∗ : (All) The potential which is applied after the measurement in case of ‘cell on after measurement’. The specified value is adjusted by the program.1s) If this option is checked. but also if the change in current. begins. ∗ ) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry 'potential' should be read as 'current' and vice versa. so that it becomes equal to the closest 16 bit (DAC164) or 12 bit (DAC124) value and the number of steps per second becomes equal to the closest value of the Autolab hardware timer. as soon as the measured signal has reached the ‘Minimum variation’. VA) The potential at which the measurement. or potential exceeds the specified value. a data point will not only be recorded after the specified interval time. Specify Time limit: (CM interval time > . after the pre-treatment. current or potential is less than the ‘Minimum variation’ value. the experiment is stopped or the next step in the experiment is applied. Specify minimum variation: (CM) If ‘checked’. ∗ ) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry 'potential' should be read as 'current' and vice versa. the measurement will stop when the time exceeds the value specified for ‘Cutoff value for time >’. Step potential∗ : (CV) The potential increment between two successive current measurements. charge. In other words. di. respectively. Start potential∗ : (CV. or dQ: (CM interval time > . .

Staircase sweep The potential sweeps from the previous applied potential to the End potential with the specified scan rate. Stop scan: (CV. CM. ECD) Enable the option to abort the equilibration stage when the Equilibration threshold level is reached. The parameters for the Sweep segment are similar to the parameters for Linear sweep voltammetry. . Stirrer off during conditioning: (VA) Switch off the stirrer of the Automatic electrode during the conditioning stage. If the segment type of the first level is specified as a sweep. Segment type: Not used This level will not be included in the measurement Step One potential can be applied during a given time. If the SCANGEN module is present. Potential (V) (Step segment) Sample time (s) (Step segment) Total time(s) (Step segment) End potential (V) (Sweep segment) Scan rate (V/s) (Sweep segment) (the highest possible value is 5000 times the step potential value) (the lowest possible value is 0. linear sweep) The recording of the sweep will be terminated if the current exceeds the upper or lower specified limit. it is only possible to select Linear sweep segment (Staircase sweep is disabled).Appendix II Definition of procedure parameters 123 Steps and sweeps table: (SAS) A table in which up to 10 potential level or sweeps can be defined. The current is sampled with the specified interval time. Stirrer off during deposition: (VA) Switch off the stirrer of the Automatic electrode during the deposition stage. Stop Equilibrium at threshold: (VA. CV. the start potential equals the Standby potential. Linear sweep Equal to Staircase sweep but performed with SCAN-GEN module.0002 s) Step potential (V) (Sweep segment) The parameters for the Step segments are similar to the chrono-methods with short interval times (see items ‘Potentials’ in the appendix). The following items can be specified. The current is sampled at the end of every potential step.

the program will not continue unless the 'Accept' button is pressed. Title and subtitle: (All) Text lines to describe the experiment. Third conditioning potential∗ : (CV.Measured response from ESPR device pH . the program will wait for 2 seconds at the OCP and will use the OCP measured at that moment.Signal measured on selected ADC-channel Charge . Time to wait for OCP: (CV. Now the data should be presented as a corrosion plot. . If this parameter is 0(zero). It does not give any functional contribution. This feature assures zero current.9 Surface area / cm^2: (CV & CM) Surface area of the working electrode. save the data again. If 0(zero) is specified in a procedure that is used in a project. it is recommended to use this option. If this option is not checked. Normally recorded voltammograms can always be converted to corrosion plots: Load previously measured data. These lines are the same as the ones displayed above the plot. CM) The time you want to wait for acceptance of the Open Circuit Potential. ECD) The third potential which is applied after the Start button has been clicked. This means that a small offset current of maximum 0.Measured response of the pX module (converted to pH.Measured current ESPR . CM) Aux signal . Unless required. Calibrate pH-electrode) pX . check corrosion plot. If the corresponding "Duration" is zero. CM. reload the data.Measured response of the pX module ∗ ) In galvanostatic cyclic voltammetry or galvanostatic chronopotentiometry 'potential' should be read as 'current' and vice versa. This option has been added to allow presentation of traditional Tafel plots. Type of signal: (CV. the x-axis becomes the 10Log-axis of the measured current and the y-axis becomes the potential axis. see Utilities menu.124 User Manual GPES for Windows Version 4. the potential is not applied. the current is set to zero with the cell switch ‘on’. If this time has expired the program will continue using the OCP measured at that time. Switch cell off when i=0 A:(CM interval time < . with which the Current density can be calculated in the Analysis menu of the Data presentation window.2% of the selected current range can flow.Calculated charge Potential .1 s) If this option is checked the cell will be switched off during levels specified with a current equals 0 A. Tafel plot: (CV) If checked.Measured potential Current .

• Hardware adjustments are necessary for this option. This is useful in systems where the Ohmic Drop changes during the experiment. either a step in staircase cyclic voltammetry or a step in chronoamperometry. pX or ECD module or any other device (EQCM.Appendix II Definition of procedure parameters 125 Use ADC750: (CV. Please keep in mind that the following limitations apply to this technique: • The sweep rate in cyclic voltammetry is limited. Use high ADC resolution:(CV staircase fast scan) Fast scan measurements are done at a fixed gain. it can be used for fast CV or chrono measurements if an interval time is smaller than 100 µs. Use dynamic iR-compensation : (CV. ESPR. an ARRAY. so the option cannot be used on an older instrument with new software only. If this option is not checked. ADC750. If this option is checked the measurement are done at gain 10 of the ADC-module. otherwise gain 1 is used. CM) When the ADC750 module for fast AD conversions is present in the Autolab instrument. a small amplitude (Dynamic iR amplitude) high frequency square wave signal is added.calc. At every potential level. By measuring the resulting current responses.1s) If this option is checked. Use lowest possible interval time: (CM interval times < . Use ECN module: (ECN) Use the ECN module to perform the noise measurements. Between the first and second potential boundary the total positive and total negative charge will be calculated automatically. the sample time per level will disappear from the table at page one. at the bottom of the screen. BIPOT. The sample time is calculated just after the measurement and depends on the speed of the PC that is used and on the type of AD converter included in the Autolab system. etc. the Ohmic Drop is calculated. It is not possible to specify a sample time anymore. In general it is possible to get an interval time of approximately 19 µs. • The method only works in High Speed mode.) that will result in an external signal.: (CV) If ‘checked’ this option enables the user to set potential boundaries for automatic charge calculation. Charge values are displayed in the status bar. . the ‘First and Second vertex potential’ are used as potential boundaries. The option is mainly used for Cyclic Voltammetric Stripping in electroplating research. Use boundaries for Q+/Q. • The method cannot be used in combination with a Rotating Disk Electrode.1s) This options offers the possibility to measure and compensate for the Ohmic Drop during the measurement. CM interval times > .

but the data are stored in memory and can be saved on disk using the File option on the Data presentation window.A. Saralthan. Electroanal.25. 222. The chronoamperogram is not displayed on the screen. normal or stationary current mode) If ‘checked’. but the data are stored in memory and can be saved on disk using the File option on the Data presentation window.25. staircase cyclic voltammetry. with duration and sample time as specified.9 Value of alpha: (CV staircase) Fraction of the time interval. with duration and sample time as specified. Wait after first vertex : (CV. Chem. scanning will stop at the second vertex potential and a chronoamperogram will be recorded. The number should be at least 0.: M. It should normally be 1. R. between two potential steps.126 User Manual GPES for Windows Version 4. Wait after second vertex : (CV. J. Osteryoung. 69 (1987). . Only in cases where linear sweep voltammetry should be compared with staircase voltammetry. this number should be different. The chronoamperogram is not displayed on the screen. staircase cyclic voltammetry. at which the current is sampled. scanning will stop at the first vertex potential and a chronoamperogram will be recorded. Ref. normal or stationary current mode) If ‘checked’. Linear sweep voltammetry equals staircase voltammetry for reversible systems when α = 0.

because they will cause actions in both programs. Practical rules are: • The computer should be equipped with at least 32 MB RAM • It is not possible that both programs are measuring and controlling the Autolab instrument • Before the FRA program starts measuring. The command FRA!Start(<"filename">) is available for this purpose. . • Apart from GPES and FRA no other program/window should be active. in general it is important to note that both programs share the Autolab instrument and the graphics part of the software. the ‘sleep mode’ in GPES is automatically switched on. • Do not use function keys when both programs are active. However. • When a measurement procedure is being executed. This means that when both programs are active.Appendix III Combination of GPES and FRA 127 Appendix III Combination of GPES and FRA The FRA and GPES programs can be used at the same time. Moreover. Moreover a FRA project file can be executed from GPES. hardly any system resources are left. The amount of free system resources can be seen in option ‘About program manager’ in the Help menu of the Program manager window. This means that the GPES screen is no longer updated. user interaction with the programs should be avoided. both programs require a considerable amount of the system resources.

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Now connect the dummy cell. however. one dummy cell is available. The PGSTAT10-2 should be connected to the second dummy cell. The DIAGNOST test is available. Activate the multichannel option by starting GPES with the shortcut "Multichannel GPES". The multichannel software is similar to the GPES software. In a subsequent measurement ARRAY-3 can be connected to the dummy cell in stead of ARRAY-2. The differences are explained in this paragraph. In case of a multi-PGSTAT10 set-up two dummy cells should be available. . the normal dummy cell response should appear and the current response should be the same for both channels. but does not work properly. The procedure TESTCV6 can be used for more than one potentiostat. the same current response is expected. After ARRAY-2 has been made inactive and ARRAY-3 active. 59 Multichannel configuration The items above are factory settings and should normally not be changed.Appendix IV Multichannel control 129 Appendix IV Multichannel control It is possible to control the multichannel potentiostat with GPES. Installation and test The Hardware Setup program contains a button for Multichannel setup. In this way all channels can be checked. some options are different or not available. After loading the procedure TESTCV6 from the \AUTOLAB\TESTDATAdirectory. After pressing this button the following screen appears: Fig. The test of the software is similar to the test of GPES. the Multi channel control window shows that PGSTAT and ARRAY-2 are “active”. After starting the execution of the procedure. The lead from ARRAY-2 should be connected to WE(b). Then the same procedure should be followed as for the multi-ARRAY set-up as described above. The “zero-test” of the ADC does not work properly because the test-channel is used for one of the extra channels. If the multichannel system is equipped with ARRAY modules.

Changing the current range of ‘Array 4’ will lead to a current range change of all channels. The last item is Multichannel. including the PGSTAT. The Plot overlay signal option in the Plot menu allows to overlay several signals. 60 Multi channel control window When this window is behind other windows on the screen it can be shown with the Window option from the GPES manager. Depending on the configuration. 2. The following methods are available in the multichannel mode: Voltammetric analysis • Differential pulse • Square wave • Sampled DC • Normal pulse . this screen will be adjusted. On the Data presentation window two additional items are present. With ‘Dependent current ranging’ the current range of all channels will be the same. The Active-option button allows to select the channels that should be measured. It operates similarly to the other overlay options. The number of items on the Manual control window is considerably reduced compared to normal GPES. All Edit and Analysis operation will be performed on this signal.130 User Manual GPES for Windows Version 4. The base potential for all arrays. After clicking this item the multichannel window will be shown. 1. The currently selected signal is shown between brackets. a specified offset potential can be given. Note that the potential will always be applied to all channels. If offset DAC’s are present. The Signal menu allows to select the signal from which channel is the active work signal. can be set in the PGSTAT panel.9 Program operation After starting the program an extra Window appears : Fig.

potential value is. However in the multichannel mode all six possible channels sampled one after an other. The minimum time is now about 800 microseconds (see also the information about the manual control window). potential is registered. it only means that the measured current c. This is described in the chapter about the Methods. So the number of samples per channel from which the average registered current c. . one sixth of the normal GPES. This has a consequence for the minimum interval time in Chronomethods with short interval times. the sampling duration is the same as in the normal GPES. Specifications of the instrument are almost similar to those of the PGSTAT10 potentiostat.Appendix IV Multichannel control 131 Cyclic voltammetry • Normal Linear sweep voltammetry • Normal Chronomethods • Amperometry • Potentiometry During the measurements.q. If a channel is specified as 'active'.q. The minimum sampling time is equal to 6 ranged AD-conversion and this is 6 times as long as in normal GPES.

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0003% of current range 30 fA >1 MHz < 250 ns high speed/ high stability > 100 GΩ//< 8 pF < 1 pA > 4 Mhz depending on selected range: 0Ω-20Ω at 1 A range to 0Ω-200 MΩ at 10 nA range.potentiostat risetime/falltime (1 V step.2% of setting 2 mV 150 µV 300.2% of current range 0. current and optionally charge yes no Autolab with PGSTAT30 ±1A ± 30 V yes yes ± 10 V ± 0.0003% of current range 30 fA 500 kHz < 500 ns high speed/ high stability > 100 GΩ//< 8 pF < 1 pA > 4 Mhz depending on selected range: 0Ω-200Ω at 100 mA range to 0Ω200 MΩ at 10 nA range.0003% of current range 30 fA 500 kHz 1 µs high speed/ high stability > 100 GΩ//< 8 pF < 1 pA > 4 Mhz n.Appendix V Technical specifications 133 Appendix V Technical specifications µAutolab type II maximum output current maximum output voltage potentiostat galvanostat potential range applied potential accuracy applied potential resolution measured potential resolution current ranges applied and measured current accuracy ± 80 mA ± 12 V yes yes ±5V ± 0. current and optionally charge yes no Autolab with PGSTAT100 ± 250 mA ± 100 V yes yes ± 10 V ± 0.025% yes potential and current potential.0003% of current range 30 fA 500 kHz < 250 ns high speed/ high stability > 100 GΩ//< 8 pF < 1 pA > 4 Mhz depending on selected range: 0Ω-200Ω at 100 mA range to 0Ω200 MΩ at 10 nA range.resolution four electrode control front panel meter Analog outputs (BNC connector) control voltage input multichannel option n. 150 or 30 µV 10 nA to 100 mA in eight ranges ± 0.03% of current range 0. 10-90%) (1) potentiostat modes input impedance of electrometer input bias current @25°C bandwidth of electrometer IR-compensation .025% yes potential and current potential.025% yes potential and current potential.03% of current range 0.2% of setting 2 mV 150 µV 300. current interrupt and positive feedback available 0. Autolab with PGSTAT12 ± 250 A ± 12 V yes yes ± 10 V ± 0.2% of current range 0.2% of current and ± 0.03% of current range 0.2% of current range 0. current interrupt and positive feedback available 0.2% of current range 0.2% of current and ± 0.a. 150 or 30 µV 10 nA to 1 A in nine ranges ± 0. 150 or 30 µV 10 nA to 10 mA in seven ranges ± 0.2% of current and ± 0.2% of current and ± 0. current interrupt and positive feedback available 0.2% of setting 2 mV 150 µV 300.2% of setting 2 mV 150 µV 300. 150 or 30 µV 10 nA to 100 mA in eight ranges ± 0.a.03% of current range 0. current and optionally charge yes no applied current resolution measured current resolution .at current range of 10 nA potentiostat bandwidth (1) . no no potential and current no no .

2% full scale + 500 µV/s) temperature dependence < 0. four channels (optionally eight) 1 48 52 x 42 x 17 cm³ 25 kg 170 W 100-240 V. 50/60 Hz interfacing A/D converter auxiliary input channels D/A converter auxiliary output channel digital I/O lines (W x D x H) weight power requirements Notes: (1) Measured at 1 mA current range.2 kg 30 W 100-240 V.04%/K available 32767 scan signal . 1 and 10 s parallel ISA card 16-bit with software programmable gains of 1. 10 and 100 2 16-bit. 50/60 Hz Autolab with PGSTAT30 yes optionally available 10 and 100 ms. Interface for mercury electrodes (IME. four channels (optionally eight) 1 48 52 x 42 x 17 cm³ 25 kg 170 W 100-240 V. 1 and 10 s parallel ISA card 16-bit with software programmable gains of 1. four channels (optionally eight) 1 48 52 x 42 x 17 cm³ 22 kg 170 W 100-240 V. 1 kOhm impedance. 10 and 100 2 16-bit.9 µAutolab type II booster option analog integrator . 1 and 10 s parallel ISA card 16-bit with software programmable gains of 1. 1 and 10 s parallel ISA card 16-bit with software programmable gains of 1.time constants no yes 10 and 100 ms. 50/60 Hz Autolab with PGSTAT100 on request optionally available 10 and 100 ms. 10 and 100 1 16-bit three channels 1 48 26 x 26 x 9 cm³ 3.5 mV resolution and 5 mV accuracy ± 1 mV maximum 100 mV/s to 10 kV/s full scale (six ranges) 1 in 4096 resolution. 50/60 Hz Autolab with PGSTAT12 yes optionally available 10 and 100 ms.134 User Manual GPES for Windows Version 4. accuracy ± (0. IME 303 and IME663) Supported electrodes • Metrohm VA Stand 663 • EG&G PAR303(A) • dropping mercury electrodes with knock-off hammer Control lines • new drop • purge on/off • stirrer on/off Burettes • Metrohm Dosimat 665/765 • Schott T90 and T100 Hardware specifications of optional modules SCAN-GEN: analog scan generator module • • • • • scan range vertex potentials output offset ranges of scan rates scan rate • • • hold mode maximum number of scans monitor output (BNC) ± 5 V relative to initial potential 2. 10 and 100 2 16-bit. high speed mode when applicable.

monitor output (BNC) third order Sallen-Key RC-times 0 s.005% of full scale 128000 samples per channel (optionally 512000 samples) ECD: low current amplifier module • current ranges current measurement type of filter filter time constants compensation of current offset monitor output (BNC) • • • • • 100 pA to 100 µA full scale (seven ranges) 1 pA and 10 pA with selectable-gain amplifier ± 0.5% accuracy third order Sallen-Key RC-times 0 s.type of filter .current 0.5 ms (mean of 4096 AD conversions) 1 in 4096 (12 bit) . Note: Specifications subject to change without notice.temperature dependence . 100 ms. 100 ms and 500 ms ± 10 µA maximum current ARRAY and BIPOT: (bipotentiostat) module • current ranges 100 nA to 10 mA full scale (six ranges) 1 nA and 10 nA with selectable-gain amplifier • current measurement ± 0.2% accuracy < 0.Appendix V Technical specifications 135 ADC750: dual channel fast ADC module • number of ADCs • maximum conversion rate • maximum integration time • basic resolution • resolution of measurements • memory 2.monitor output (BNC) integrator section .output offset .04%/K charge output BSTR10A: current booster for PGSTAT30 or PGSTAT100 • • • • • • • maximum output voltage maximum output current maximum output power bandwidth current measurement dimensions (W x D x H) weight ± 20 V ± 10 A 200 W 4 kHz full power 10 A full scale ± 0.charge measurement . .5 cm approx. 10 ms. 0.2% + 2 mV) • monitor output (BNC) current • external input potential control FI20: filter and integrator module • • filter section . 10 ms. 1 s and 10 s 0.potential 5 mV at range 10 V 2 mV at range 4 V 1 mV at range 2 V . each with four input channels 750 kHz 5.ranges .05% and 0. 9 kg.5%.2% accuracy • maximum current output ± 35 mA • potential range ±5V • potential accuracy ± (0.5% accuracy 37 x 36 x 15. 100 ms and 500 ms ± 2 mV filter output 10 ms.filter time constants .

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............................ 107 Chronocoulometric plot ......Index 137 Index A ac voltammetry ............................. 73...................................................................................................................................... 6............................................................................................... 43 Burette control........................ 54................................................ 113....................... 30 Export to BAS-DigiSim data ................. 30 ................................................................................................................................... 117........................................................................................................................................................... 67 baseline..........................................5.......................................................... 47................. 127 D Data buffer....................................................................... 6........................................................................................................................................................................................................................................................................................................ 98.......... 42 convolution............................................................37.............40............ 107 chronomethods .................... 49 dt/dE vs E plot ............ 60 Electrode control................................................................................................ 31 Delete files .................................................................................................................................................................................................................................56........................................................................................................................... 5................................. 100 Copy.................. 63 colours .................................................................................... 39 Check cell................................................ 71............................................................ 63 electrochemical detection......................................................58............................................................................................................................................ 71.................. 103.............. 115..................................... 100......................................................... 120 configuration.......................................................................................................................................................................................... 102.......... 71....................................................................................................... 95 Crank-Nicolson....... 64...........................68.............. 60 B BAS-DigiSim...........................................................................................................................................................7........108 Convolution .............................................................................................................................................................................................................................. 95 current range.............................................................................. 75 Current density...................................................................... 72.. 19............... 118 Analysis results ............................. 69 chronoamperometry ............ 59 axis annotation ...........................................................104.................................................................................................................................................................................................................................................................................................................................................................................................................................................. 68.......................................... 59 E E vs t plot................. 101.................................................................................................................................................................................................................................................................. 100......................................................................................................................................................................................................... 30 Export data buffer................. 30 basecurve................................. 42 Chronoamperometric plot...................................................... 31 derivative........................................... 67......................................................................................................................................................................... 67 cyclic voltammetry ............................................ 60 Exit................................................................ 116...... 104.......44....... 69 chronocoulometry .................................................................................................... 69..................... 117 DIO ports........................................ 113 curve cursor ....... 73 Coulometric titration .................................... 102.................................................................................. 121 differential pulse.................32........... 58.......................................................................................................................................................................................................................................................................................... 63 Computer................. 117...........43....... 125 corrosion rate............................................................................................................................................................... 110 Batch mode ......................... 31 Export Chrono data ......5............................................................................... 72................61....................................................................................... 5........................................ 64 Automatic ...................................................................................................................................................... 64 corrosion............................... 74........................................................................................................................................................................................................ 55......... 59 Edit procedure ............................................................................................ 47......................................................................................................................................... 34 C Calibrate pH-Electrode .......................................................................................................................................................................... 33 Enter text .. 99....... 70.........................................................

............................................................. 63 H help .........................................................................................................................................................................................................................5....................................................................... 68 pH buffer................................................................... 54 I Idisk.............. 28 MS-Windows........................................................................................... 27........................................53............................138 User Manual GPES for Windows Version 4.......................................73.......................................................................................................................................................................................................................... 127 Load data......................................... 74 free cursor............................................................... 37 integrate.............................................................................. 32 Metrohm 730 Sample Changer.........................................................6....................................................................................5...................................................................................................................... 75 Mercury drop electrode........................................................ 30 GPES 3 files.................................. 96 First................................................................................................................... 63......... 47.................................................................................................................. 6................. 69................................................................................................................................................................................................................................................................................................... 39.............................................................................. 56 Interpolate ... 53 Marquardt.......................................... 95 L linear regression.......................... 74 linear sweep voltammetry...............................................................and Second signal.............................................................................110 iR-compensation................................................ 67.............................. 58 noise............................................................................................................... 49 mouse........................................................................................... 70............. 56......................................................................................................... 28 M manual control....................... 63....6........................................................................................................................................................................ 36 MUX control.................................................... 60................ 59 Fit ......................................................................................................... 28 graphics ............................................................ 65............................................................................................................................... 95 I-interrupt .......................... 98 normal pulse..............................................................................................................................................................113....... 36 N New plot ............ 55 Iring.......................................................... 6...........................................................................5................................................................................................................................................................................................................................................................................................................................ 27 overlay ................................................................................................................................................................................... 97............................................. 42.......................... 73 G galvanostat.............................40................................................... 37.......................................37.............................. 7.............................................................................................................................................................................................................................................................. 28 GPES3 files ........... 52........................................................ 74 iR drop .............................................................................................................. 119 O Open procedure ............................................................................................................................... 40 .......... 6.....................67.....................................................69.................................................................... 99 integrator......................................................................................................................................................................................................................29........................................................... 112 High sensitivity ............................................................................................................................................ 5................................................................................................................. 6 MS-Word............................. 53 Method menu.................................................. 60 P peak search........9 F FFT ...............................................................................................................................................................28.............. 64 MULTI4....................................................................................... 68 frequency spectrum............................................................................................................................................... 97 Filter for derivative........................................................................................................................................................................................................................................................................................................................... 31 Load scan ..................... 58..............

....... 57 Save procedure ......... 53 surface area ....................................................................................................................................................................................Index 139 pH electrodes .......................... 52 transition time ............................................................................................................. 127 Status bar....................................................................................................................................................6. 43 Project examples ................................................................................................................................................................ 117.......................... 119.................. 27..... 121 Set window.............................................................................................................................................................................. 72.................................................. 65.......... 95 T Tafel slope................................. 28 Save procedure as .......................................................................................118 SCNR16A......................................................................................................................... 73 tool bar..................................................................................................................... 116 Start button .............................................. 30........................................... 60 S Save data ... 97......................................................... 60 voltammetric analysis ............................................................................................................................................................................................................................................................................................................................................................................................................................................... 36 second signal ..................................................................................................................................................... 59................................................. 38.......................................................... 64 potentiostat.......................... 113........................... 55.....................................................5............................................................................ 121.. 36 SCNR8A................................ 52 Rescale during measurement ...................... 53 stationary current ........................................................ 71................... 112 Procedure name in Data presentation Window.................................... 99 Smooth................... 28.................................................................................................. 110 Show all GPES files in File dialog box.........................................113........................................................................ 42 plot title ....................................................................................................................... 38 potentiometric stripping analysis .................................................................................................................................................................................................................................................................................................................................29..........71................................................................................................................................................................... 95 Q Quick save.................................. 112 Project command rules...................... 73 square wave...........59...................................................................................................................................................................................................................................... 59 Show I (forward)....................................................................................................................................................................................................................................................................................... 6......59............................................................................................. 47 pX/pH.......................................... 48 Project wizard .................... 72 Positive feedback........................................................................................................................................................... 52 Resume............................................................................................................................. 63....................................... 70.............................................................................................................................................................................. 43..................................5..............................................................44...............121 Spectral noise analysis .................................................................................................................................................... 61 polarisation resistance................................................................................................................................... 52 Show I (backward).....................................................................................................................................................................6.........................................................................................................................................49. 59 simulation................................................................................................................................... 60 Reverse axes ..................................................................................................................................................................................................................................................................................................................................................................................................59............................................................................................. 42 smooth ...... 59............................................................................................................................................................................................................................................................................ 35 Rescale after measurement...................................................... 29 Scan averaging ................................................................................................................................................................................................................................................................................................................. 39 Print............................................................ 70 ........ 57 R RDE-control.................................................................................................................... 74 Sleep mode........................................................................... 51 V viewing data............................................................................................................................................ 28 Save scan................................................................................................. 74 trigger................................................................................................ 52 Project ...................................... 39 Plate..................................................

.......................................................60......................... 65 Z zoom........................................................................................................................................................................... 60 Work scan ................................................................................................................... 96 Window function ................................................................................................................................................................. 59 ............6..........................16........................................................................... 95 Window for zero crossings ................140 User Manual GPES for Windows Version 4.................................................... 70 WE2 versus WE plot.................................................................................................................................................................................9 W Wave log ................................................................................... 74 Work potential.......................................................................................

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