Cyclic voltammetry (CV) simulator written in Microsoft Excel

File uploaded by Jay Brown on Nov 19, 2015Last modified by Jay Brown on May 21, 2019
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Description

 

The attached file is an updated version of a simple, easy-to-use cyclic voltammetry (CV) simulator written in Microsoft Excel.1 The spreadsheet supports up to four chemical species that are each undergoing up to four redox couples. Experimental CVs with up to 10,000 data points in text format can be copied/pasted into the spreadsheet for comparison to the simulation. The spreadsheet can be operated in protected mode or unprotected and modified as needed. The spreadsheet is provided with no guarantee and it may not be suitable for all applications. System requirements: Microsoft Windows 8.1 Office software or later. New version (v_14) uploaded to website on 5/18/19.

 

Important notes

 

You must list your potential values in the proper order for your simulations to work. List your formal redox potential (Eo') values in decreasing order if reduction occurs during the forward sweep. Reverse this order if oxidation occurs during the forward sweep. You can then coalesce two adjacent peaks by exchanging their Eo' values. Set the Eo' values of unused peaks beyond the switching potential (E2) in the proper order noted above to exclude them from the model. Set the starting potential (E1) value greater than the switching potential (E2) if reduction occurs during the forward sweep. Reverse this order if oxidation occurs during the forward sweep.

 

Software updates

 

Added intervening and removal rate constants for Species 1 on 5/18/19. The spreadsheet no longer assumes the first process is a charge transfer. Placed diffusion, intervening, and removal calculations into separate grids to simplify the equations. The spreadsheet is now using the Sequential method to calculate homogeneous reactions.2

 

Incorporated the Saul’yev RL variant to simulate Fick’s Second Law of Diffusion on 1/8/17. This method can calculate thinner reaction layers than the combined Taylor series that was used previously.1-3 Reducing the variable xscale reduces the length of the diffusion grids and places the concentration points closer to the working electrode surface. However, using diffusion grids that are too short or long will distort your simulations, so adjust this parameter only as needed.

 

Separated the equations involving the number of electrons in the rate-determining step from the total number of electrons transferred on 12/22/16. The number of electrons in the rate-determining step (na) now controls the peak width. The total number of electrons transferred (n) now controls the total current.4

 

Added first-order intervening rate constants (kI1) between electron transfers on 12/20/16. The smaller you make a kI1 value, the slower the corresponding species is populated. Symbols kR1 and kR2 are now used to indicate first- and second-order apparent forward homogeneous rate constants that remove a corresponding species from the cycle.4

 

Spreadsheet variables

 

Several variables from the original spreadsheet were renamed to incorporate new features. The following table describes the variables that are used in the newest version of the spreadsheet.

 

Variable

Definition

Value and/or unit(s)

Gain

Amplification factor for experimental background

Unitless multiplier

Offset

Constant added to the experimental current

A

Eoˊ

Formal potential for a redox couple

V

n

Total number of electrons transferred per species (controls total peak area)

Unitless

na

Number of electrons transferred in the rate determining step (controls peak width)

Unitless

D

Common diffusion coefficient

 ≈ 1 x 10-5 cm2/s

ko

Standard heterogeneous rate constant for an electron transfer

cm/s

a

Transfer coefficient for a redox couple

≈ 0.5 (unitless)

Cbulk

Bulk concentration of the analyte

mol/cm3

E1

Starting potential of the CV experiment

V

E2

Switching potential of the CV experiment

V

v

Scan rate used during the CV experiment

V/s

A

Surface area of the working electrode

cm2

T

Temperature of the sample during experiment

K

xscale

Compress or expand x-axes of diffusion grids

Percentage (%)

kI1

Rate constant for first-order intervening homogenous reaction between electron transfers

s-1

kR1

Rate constant for a first-order homogeneous reaction that removes a species from electron transfer cycle

s-1

kR2

Rate constant for second-order homogeneous reaction that removes a species from electron transfer cycle

cm3/mol•s

 

Bug report

 

Bug in the removal grids was corrected on 5/19/19. Minor bug in the stacked plot corrected on 12/11/18. Bug in the intervening homogeneous reaction calculations was corrected on 1/12/17. Bug in the data selection process was corrected on 4/25/16. Bug in the Import data page graphics corrected on 12/31/15. Bug in the concentration calculations of the 4th redox couple oxidized form corrected on 12/8/15. Bug in the time increment calculations was corrected on 11/16/15.

 

References cited

 

1. J. H. Brown, J. Chem. Educ., 2016, 93 (7), 1326–1329. DOI: 10.1021/acs.jchemed.6b00052.

 

2. D. Britz, Digital Simulation in Electrochemistry 3ed ed., Springer: Berlin, 2010, ISBN: 978-3-642-06307-7.

 

3. D. K. Gosser, Cyclic Voltammetry: Simulation and Analysis of Reaction Mechanisms, VCH Publishers: New York, 1993, ISBN: 1-56081-026-2.

 

4. A. J. Bard, L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, Wiley: New York, 1980, ISBN: 0-471-05542-5.

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