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Specialty Chemistry Forums => Citizen Chemist => Topic started by: Jango on November 23, 2010, 11:58:51 AM

Title: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Jango on November 23, 2010, 11:58:51 AM
Hi,

I'm interested in doing various experiments, including electrolysis of various solutions. I'm searching for DC power supplies, and have found some good ones on eBay. I want the electrolysis to be done as fast as possible (i.e: larger amounts of chemical to be formed at each electrode per second).

Should I look for a DC power supply that has a higher voltage and a lower current (e.g: 20V 2A)? Or should I look for one with a lower voltage and a higher current (e.g: 13.8V 15A)?

I can't afford the ones that have a massive voltage and current, and I only want to electrolyse relatively small amounts at once (e.g: 100-200ml of a 1M solution).
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Grundalizer on November 23, 2010, 01:06:45 PM
current is the driving force in electrolysis, because the amount of charge (current) that flows between the electrodes means more electrons are changing places which means more things are being reduced/oxidized.  I'd just get a 9V D cell battery for $5
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Jango on November 23, 2010, 01:31:44 PM
Ok, thanks for your reply. :)

So I should look at getting the 13.8V 15A DC power supply? I can get one from eBay for £35.

I've tried using 9V batteries in the past, but they run out, so I only get an hour or so of full-power electrolysis from that. I've been looking for something that has a constant, reliable supply so that I can leave it running so that the electrolysis finishes relatively quickly (also why I am only electrolysing small quantities).

I don't know exactly what you mean by a '9V D cell battery', or where to get them from.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Jango on November 23, 2010, 01:38:22 PM
Sorry, accidental double post.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Jango on November 23, 2010, 01:47:40 PM
Sorry again, not used to this forum layout. I'll get used to it. Won't happen again. :)
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Grundalizer on November 23, 2010, 03:45:46 PM
Yeah, that power supply sounds fine.  Remember that if you look at the redox potentials of whatever metals you are trying to electrolyze...say Copper and Zinc, I think it's a max voltage production of 1.5 V or something.  So you really only need 1.5V battery to run it in reverse, but the more current the better.  I'm not sure if a higher voltage allows it to run faster, or if it's a waste.

Sorry, this is what I meant by D cell.

http://en.wikipedia.org/wiki/Lantern_battery
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Grundalizer on November 23, 2010, 03:47:29 PM
Also, as much as I love chemical forums for general questions, for serious at home chemistry I also check out sciencemadness.org which I know a lot of people on here also use.

http://www.sciencemadness.org/talk/

They are a little more hardcore DIY at home chemists who have some really detailed posts along the lines of what you are asking.  I'd check with them.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: FreeTheBee on November 23, 2010, 04:59:07 PM
Make sure to stir properly and use large surface area electrodes if you want things to go fast. The kinetically limited current increases exponentially with the overpotential, so it is quite easy to run into mass transport limitations.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: billnotgatez on November 23, 2010, 07:52:35 PM
i vaguely remember CRC Handbook of Chemistry & Physics had various measurements involving electrolysis.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Zerm on November 23, 2010, 08:15:01 PM
Voltage determines which reactions are being driven by redox potential but current determines the rate.  A derivative of Ohm's law holds Voltage = Current * Resistance.  The resistance of your cell depends on electrode surface area, distance between electrodes, electrolyte concentration, temperature, and charge carrier mobility.  The resistance will be whatever it is during the procedure and will likely change dramatically over the course of the reaction.  Considering the resistance as fixed (that is we can do nothing to affect it), a change in voltage will yield a change in current.  It is largely a question of what undesirable side reactions may be driven at higher voltage potentials.

What ever power supply you choose should best have precision tunable voltage regulation and be rated for high power. 
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: FreeTheBee on November 24, 2010, 03:02:17 AM
A Faradaic process does not follow Ohm's law. There is an ohmic resistance in the cell of course, due to contacts, concentrations and so on.. but that's only part of the story. The rate of the electrochemical reactions at the surface determines the current and the rate depends exponentially on the potential. You can look up Butler-Volmer to get a description.
However, the reactions can only proceed if there are electroactive species available at the electrode surface. So, if you push the reaction faster than material can be brought to the surface, you will get a mass transport limited current.
Sorry, to go a little of-topic.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Grundalizer on November 24, 2010, 10:14:27 AM
It's always great to go in depth--thanks for the explenation
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Jango on November 26, 2010, 09:43:51 AM
Thanks for all of your explanations everyone. :)

Voltage determines which reactions are being driven by redox potential but current determines the rate.  A derivative of Ohm's law holds Voltage = Current * Resistance.  The resistance of your cell depends on electrode surface area, distance between electrodes, electrolyte concentration, temperature, and charge carrier mobility.  The resistance will be whatever it is during the procedure and will likely change dramatically over the course of the reaction.  Considering the resistance as fixed (that is we can do nothing to affect it), a change in voltage will yield a change in current.  It is largely a question of what undesirable side reactions may be driven at higher voltage potentials.

What ever power supply you choose should best have precision tunable voltage regulation and be rated for high power. 

So, basically, I need a power supply where I can change the voltage, has a high current (eg: 10-20A), and that also has a high wattage, am I right?
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: billnotgatez on November 26, 2010, 10:21:22 AM
an interesting experiment you can post here is

vary the voltage and see the change of output

hypothesis may be

a curve with a peak
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Jango on November 26, 2010, 10:31:17 AM
It would be interesting, yes.

But can you answer my question? :)
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Zerm on November 26, 2010, 07:23:37 PM
Yes, that is what you need.  (Also Voltage * Current = Wattage)  Of course, you can afford a smaller power rating if you have a smaller electrolytic cell.  However, by FreeTheBee's thinking, it will probably be very difficult to quantitatively figure how much power you need without experimentation.  I say just get the highest power that you're willing to pay for and go from there.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Jango on November 27, 2010, 06:21:13 AM
Yes, that is what you need.  (Also Voltage * Current = Wattage)  Of course, you can afford a smaller power rating if you have a smaller electrolytic cell.  However, by FreeTheBee's thinking, it will probably be very difficult to quantitatively figure how much power you need without experimentation.  I say just get the highest power that you're willing to pay for and go from there.

Great, thank you very much guys. :)

I may start off with a few lantern batteries first before buying the power supply, just to see how well they work.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Zerm on November 27, 2010, 01:05:53 PM
Good luck and let us know how it works please!
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: FreeTheBee on November 27, 2010, 01:11:47 PM
Note that a high voltage will lead to side reactions, such as reduction or oxidation of you're solvent. A high potential will than give you large currents, but if those electrons are used to form hydrogen and not copper or zinc it isn't much use.

I should have used the term current density instead of current in my earlier post. If you looked up the Butler Volmer equation, you might have noticed the A in there. Increasing overpotential leads to a higher current density and thus to a higher current. But, using a larger electrode at the same potential also increases current since the current equals current density times surface area.

That's why I pointed out that it is good to use large electrodes, since then you can maintain high currents at a relatively low current density. This way you don't need as high overpotential, which reduces problems with side reactions.

Good luck with the experiments.
Title: Re: Does a higher voltage used in electrolysis increase the rate of electrolysis?
Post by: Jango on November 27, 2010, 02:52:04 PM
Note that a high voltage will lead to side reactions, such as reduction or oxidation of you're solvent. A high potential will than give you large currents, but if those electrons are used to form hydrogen and not copper or zinc it isn't much use.

I should have used the term current density instead of current in my earlier post. If you looked up the Butler Volmer equation, you might have noticed the A in there. Increasing overpotential leads to a higher current density and thus to a higher current. But, using a larger electrode at the same potential also increases current since the current equals current density times surface area.

That's why I pointed out that it is good to use large electrodes, since then you can maintain high currents at a relatively low current density. This way you don't need as high overpotential, which reduces problems with side reactions.

Good luck with the experiments.


Thanks, I'll bear that in mind and make sure that my electrodes are as big as possible.

I once tried to electrolyse copper sulphate using two 9V batteries, and I got hydrogen at the cathode as well as copper, that explains why! At first I had no idea what was going on. :)