Solving Electrochemistry Problems with Fick & Cottrell Laws

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Discussion Overview

The discussion revolves around solving electrochemistry problems using Fick's and Cottrell's laws, particularly focusing on the behavior of current density in relation to concentration of electroactive species. Participants explore the mathematical expressions for diffusion in both planar and spherical coordinates, as well as the derivation of Cottrell's law from Fick's law.

Discussion Character

  • Technical explanation
  • Mathematical reasoning
  • Debate/contested

Main Points Raised

  • One participant states that the current density is proportional to the concentration of electroactive species, leading to a question about the derivation of Cottrell's law from Fick's law.
  • Another participant challenges the initial claim, suggesting that current density should be proportional to the concentration gradient instead.
  • A participant acknowledges a mistake regarding the expression of current density and provides a solution for planar diffusion, referencing a chemistry book.
  • There is a request for the expression of concentration in spherical coordinates and the corresponding Cottrell law for radial diffusion.
  • One participant suggests that the problem resembles a 3D generalization of the 1D diffusion problem, proposing a potential form for the radial concentration gradient.
  • A suggestion is made to seek further assistance in the math section for solving the differential equation related to diffusion.

Areas of Agreement / Disagreement

Participants express differing views on the relationship between current density and concentration, with some agreeing on the need for clarification on the mathematical derivations involved. The discussion remains unresolved regarding the exact expressions for spherical coordinates and the corresponding Cottrell law.

Contextual Notes

Limitations include assumptions about initial conditions and boundary conditions for diffusion problems, which are not fully explored in the discussion.

Chris-jap
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Hello everybody
I have got an electrochemistry probleme
In the case of a planar electrode (one dimension) the current density is proportinnal to the concentration of electroactive species: i=-nFkC C depending of time
From Fick law dC/dt=Dd2C/d2x we can found Cottrell law: i=-nFAC0(D/PIt)1/2

Do tou know How?

And my second question is
What is the fick lack for spherical coordinate and what are the expression of C(t, spheric coordinate)
And also what is the new expression of Cottrell law?

Thank You for your attention and I apologize for my bad english.
Christophe
 
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With respect to Fick's Law - see http://en.wikipedia.org/wiki/Fick's_law_of_diffusion

As for spherical coordinates, see -
http://en.wikipedia.org/wiki/Nabla_in_cylindrical_and_spherical_coordinates

For a purely radial dependency, use only the \frac{\partial^2}{\partial{r^2}} term.

With regard to this question -
From Fick law dC/dt=Dd2C/d2x we can found Cottrell law: i=-nFAC0(D/PIt)1/2

Do tou know How?
Please clarify what one is asking. "Do you know how . . . ?"
 
Last edited:
Chris-jap said:
Hello everybody
I have got an electrochemistry probleme
In the case of a planar electrode (one dimension) the current density is proportinnal to the concentration of electroactive species: i=-nFkC C depending of time
Are you sure about this ?

I thought the current density was proportional to the concentration gradient dC(x,t)/dx
 
Last edited:
Thank you for your help
Your answer solve one part of my problem.
I made a mistake for the expression of current density, Goku you are right.

Thanks to you I solve one part of my problem

I found this solution for planar diffusion (not me, in a chemistry book)
C(x,t)=C0erf(x/(Dt)1/2)
and dC(x,t)/dx=C0/(PiDt)1/2 for x=0 replacing this term in the expression of current we found Cottrell law.

Now I try to found the expression of C(r,t) for a purely radial dependence and dC(r,t)/dr for r=R (R is the radius of the sphere, particles are inside the sphere and diffuse for the center to the border of the the sphere)

Do you have any other suggestion?

Chris
 
Chris-jap said:
Thank you for your help
Your answer solve one part of my problem.
I made a mistake for the expression of current density, Goku you are right.

Thanks to you I solve one part of my problem

I found this solution for planar diffusion (not me, in a chemistry book)
C(x,t)=C0erf(x/(Dt)1/2)
and dC(x,t)/dx=C0/(PiDt)1/2 for x=0 replacing this term in the expression of current we found Cottrell law.
Correct (if your initial condition is C(x,t=0) = C0 ).

Now I try to found the expression of C(r,t) for a purely radial dependence and dC(r,t)/dr for r=R (R is the radius of the sphere, particles are inside the sphere and diffuse for the center to the border of the the sphere)
This just looks like the 3D generalization of the previous 1D problem (with boundary conditions that require spherical symmetry). (ie : you are looking at 3D diffusion from a point source)

Perhaps the solution would look like dC(r,t)/dr = Kr2exp(r2/Pi*D*t) ?

You should probably ask a question in the math section (Calc and beyond) on methods for solving the differential equation for diffusion. They will be able to help better.
 

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