I have silver working electrode and Ag/AgCl/KCl electrode. Will it be any problem if I am using potential from -0.6 V to 1.2 V vs Ag/AgCl/KCl. Will it be of any problem?
You don't say if there is a counter electrode in your system. If this is a two-electrode system, my answer would be different from my answer for a three-electrode system where the reference electrode is isolated from the bulk solution. If a two-electrode system is used, there must be chloride in the solution to poise the reference electrode and current densities must not perturb the reference electrode equilibrium. So before I can attempt an answer I need to know more about your setup.
Hello Khantesh Agrawal ,
If you are only considering electrochemical processes, using a silver/silver chloride reference electrode, provided with a frit, along with a silver working electrode, and some counter electrode, it should not be a problem at all.
However, you may need to consider other chemical reactions (not the ones driven by a potential) just to make sure that you are not going to observe a non-electrochemical reaction at the two silver electrodes.
Best regards,
Marie B.
Edit : Just seen the answer from @Richard A Durst, yes, more information would be great.
Dear All,
Yes, it is 3 electrode system with following components
Working electrode: Silver
Referece: Ag/AgCl/KCl(1M)
Counter: Pt wire
Electrolyte: K2PtCl4 (3mM)+ NaCl(0.5M)
Kindly give your comments
At the higher positive potentials you are planning to use, the silver electrode will be oxidized and introduce silver ions into the solution (although in the presence of your supporting electrolyte, silver chloride will form on the silver electrode). Also, silver ions will be reduced at the more negative potentials. These reactions will produce a Faradaic current that might mask other reactions that you are interested in. Since you don't describe what experiments you are planning, it's hard to predict what problems you might encounter. Is there some reason for the choice of a silver working electrode?
@ Prof Richard,
Thank you for your reply. The major reason why we are using Ag/AgCl is because mercury used in SCE is toxic and we would like to avoid it. Moreover, we already had Ag/AgCl in our lab, so it was handy to use it.
Please see the link below for more details regarding the problems we are facing:
https://www.researchgate.net/post/Is_Ag_AgCl_KCl1M_reference_electrode_in_a_3_electrode_system_a_stable_one_while_doing_CV_in_pH1_medium_between_0_V_and_13V_vs_SHE
I didn't realize that your purpose of the experiment was to platinize the silver electrode. My only experience was in the platinization of platinum for use in a hydrogen gas electrode. In this case, a very small amount of lead acetate was added to the electrodeposition solution to produce platinum black on the surface of the platinum which increases its catalytic activity for use as a hydrogen electrode in pH measurements. If you consult Roger Bates book: "Determination of pH — Theory and Practice", on pages 291-292 in the 1973 second edition, you will find details on this process. It also includes another reference to a method for platinization without the use of lead, but I have not had experience with this method.
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