Diachrynic
Hazard to Others
Posts: 226
Registered: 23-9-2017
Location: western spiral arm of the galaxy
Member Is Offline
Mood: zenosyne
|
|
Yield 136% while making Fe2O3 by electrolysis
So I made some Fe2O3 but the yield was way to high.
I did wash it, so I can't figure out the reason.
Following setup:
Two sources of iron (steel I suppose) were used as kathode and anode in a solution of 175 g NaCl in 1.3 l H2O for 320 minutes with a
starting power of 2.8 V / 2 A which had risen to 5.1 V / 2 A when I stopped it. Bubbles at the kathode, no bubbles at the anode.
The anode lost 11.08 g of material.
Reactions:
Kathode (-)
2 H2O + 2 e- → H2 + 2 OH-
Anode (+)
Fe → Fe2+ + 2 e-
The iron undergoes more reactions.
Fe2+ + 2 OH- → Fe(OH)2
4 Fe(OH)2 + O2 → 4 FeO(OH) + 2 H2O
I washed the stuff that settled to the bottom via repeated dilution and decantation, 5 l each, 2 times (and with a smaller volume a third time).
All that settled on the bottom was first boiled to dryness and then heated with a blowtorch.
2 FeO(OH) → Fe2O3 + H2O
Fe(OH)2 → FeO + H2O
4 FeO + O2 → 2 Fe2O3
21.61 g of a lovely rusty coloured powder was obtained.
Now, some calculations.
Assuming 11.08 g pure iron being converted, Faraday's first law tells us our efficiency:
F * n * z = η * I * t
η = F * n * z / (I * t)
Now, we have
F = 26.8 Ah / mol
n = m / M = 11.08 g / (55.85 g / mol) = 0.198 mol
z = 2
I = 2 A
t = 5.33 h
and we get
η = 99.557%
Bit high, but seems fine.
Now, yield.
Overall reaction:
4 Fe + O2 → 2 Fe2O3
So,
nIron / nIron(III)-oxide = 2 / 1
nIron(III)-oxide = 0.5 * nIron
mIron(III)-oxide = 0.5 * nIron * MIron(III)-oxide
and with
nIron = 0.198 mol
MIron(III)-oxide = 159.697 g / mol
we get
mIron(III)-oxide = 15.81 g
Now, remember we obtained 21.61 g! This would make 136% yield - impossible. I had some losses anyway.
So, something went wrong.
I repeated the experiment, but I filtered off the precipitate after the second decantation (gravity).
I thought, maybe there was some salt left in the water.
That time, 11.27 g of weight were lost at the anode.
η was 98.33%. While 16.13 g were expected, 21.12 g were obtained after boiling and blowtorching. The losses were bigger due to the filter paper.
Still, 131% yield.
Can someone help me? What is wrong here?
[Edited on 7-2-2018 by Diachrynic]
we apologize for the inconvenience
|
|
|
JJay
International Hazard
Posts: 3440
Registered: 15-10-2015
Member Is Offline
|
|
You probably have a hydrate or some form of iron(III) oxide-hydroxide. I think you can dehydrate it in a crucible to obtain more predictable results.
|
|
|
Diachrynic
Hazard to Others
Posts: 226
Registered: 23-9-2017
Location: western spiral arm of the galaxy
Member Is Offline
Mood: zenosyne
|
|
Okay, I'll repeat the experiment a third time and heat it longer and hotter. Will take some time.
Thanks for the advice!
we apologize for the inconvenience
|
|
|
Pumukli
National Hazard
Posts: 705
Registered: 2-3-2014
Location: EU
Member Is Offline
Mood: No Mood
|
|
"and we get
η = 99.557%
Bit high, but seems fine."
:-)
I admit that I never done this reaction before, but my gut-feeling is that 99.557% yield in an electrolysis reaction is more than suspect. So no, it's
not fine. :-)
May I ask you what kind of water was used for both the dissolution of NaCl and later for the washings?
You did not explicitely write distilled water so it might as well be tap water. Which could lead to co-precipitation of Ca and Mg
carbonates/hydroxides/whatnot with the Fe-compounds. It may have caused a 5-15% mass difference.
The proper desiccation (dehydration) of the FexOy(OH)z requires fairly high temperature I think. It may contribute to
another 15-25% error.
How did you measure the current? What kind of power source did you use?
If you used distilled water and the powder was red hot in the dryer, then I may have to reevaluate my world view. :-)
Anyway, interesting problem.
|
|
|
wg48
National Hazard
Posts: 821
Registered: 21-11-2015
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by Diachrynic  |
That time, 11.27 g of weight were lost at the anode.
η was 98.33%. While 16.13 g were expected, 21.12 g were obtained after boiling and blowtorching. The losses were bigger due to the filter paper.
Still, 131% yield.
Can someone help me? What is wrong here? |
Your doing the calculation incorrectly. Normally the theoretical yield is the ratio of the actual product to the theoretical maximum possible amount
of product.
The theoretical max product of Fe2O3 is 143% wrt iron dissolved, which means your yield is 131/143 = 92% wrt to the theoretical maximum possible
Fe2O3 from a given amout of Fe. Percentages are by weight.
Obviously Fe203 is heavy than the iron it contains. When you read this type of stuff or do such calculation its a good idea to always think "wrt what"
Oops: sorry guys, the above is BS, please ignore
[Edited on 7-2-2018 by wg48]
|
|
|
Diachrynic
Hazard to Others
Posts: 226
Registered: 23-9-2017
Location: western spiral arm of the galaxy
Member Is Offline
Mood: zenosyne
|
|
| Quote: Originally posted by wg48 | | Quote: Originally posted by Diachrynic |
That time, 11.27 g of weight were lost at the anode.
η was 98.33%. While 16.13 g were expected, 21.12 g were obtained after boiling and blowtorching. The losses were bigger due to the filter paper.
Still, 131% yield.
Can someone help me? What is wrong here? |
Your doing the calculation incorrectly. Normally the theoretical yield is the ratio of the actual product to the theoretical maximum possible amount
of product.
[Edited on 7-2-2018 by wg48] |
21.12 g (obtained mass of oxide) / 16.13 g (theoretical maximum mass of oxide) = 131%
| Quote: Originally posted by Pumukli |
I admit that I never done this reaction before, but my gut-feeling is that 99.557% yield in an electrolysis reaction is more than suspect. So no, it's
not fine. :-)
|
Yeah, it is kind of suspicious...
| Quote: Originally posted by Pumukli |
May I ask you what kind of water was used for both the dissolution of NaCl and later for the washings?
You did not explicitely write distilled water so it might as well be tap water. Which could lead to co-precipitation of Ca and Mg
carbonates/hydroxides/whatnot with the Fe-compounds. It may have caused a 5-15% mass difference.
|
Tap water for the dissolution, tap water for the first washing, destilled water for the second one.
I think the water here is soft, but I don't know. At least the toilet almost never has carbonates blocking the way ;D
| Quote: Originally posted by Pumukli |
The proper desiccation (dehydration) of the FexOy(OH)z requires fairly high temperature I think. It may contribute to
another 15-25% error.
|
Did it in a small ceramic bowl from an old chemistry building kit. Ethanol burner. Was kind of slow, so additional heating was done with a small
blowtorch (has a nice blue conical flame).
Used a DC power supply. Range 0-30 V / 0-5 A.
I used the number straight out of the dial. Probably a multimeter would have been better.
| Quote: Originally posted by Pumukli |
If you used distilled water and the powder was red hot in the dryer, then I may have to reevaluate my world view. :-)
Anyway, interesting problem.
|
Not quite red hot. It is funny, how the color changes and gets this lovely rusty red. If you blowtorch it, it actually gets darker, but returns to a
fuller red after it cools down.
we apologize for the inconvenience
|
|
|
wg48
National Hazard
Posts: 821
Registered: 21-11-2015
Member Is Offline
Mood: No Mood
|
|
Oops: sorry guys, my post was BS, please ignore.
My only excuse apart from being half brain dead is I was in a rush as my dog was nagging me for her walk.
|
|
|
JJay
International Hazard
Posts: 3440
Registered: 15-10-2015
Member Is Offline
|
|
| Quote: Originally posted by wg48 | Oops: sorry guys, my post was BS, please ignore.
My only excuse apart from being half brain dead is I was in a rush as my dog was nagging me for her walk.
|
Ok, I'll let it slide this time 
|
|
|
wg48
National Hazard
Posts: 821
Registered: 21-11-2015
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by JJay | | Quote: Originally posted by wg48 | Oops: sorry guys, my post was BS, please ignore.
My only excuse apart from being half brain dead is I was in a rush as my dog was nagging me for her walk.
|
Ok, I'll let it slide this time |
Oh thankyou JJ your so understanding.
Here is my BS but accurate maths LOL
|
|
|
AJKOER
Radically Dubious
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
If I am understanding correctly, you employed 175 g NaCl in 1.3 liters of H2O.
With this amount of aqueous NaCl, you create at the electrodes respectively, NaOH (aq) and Cl2 (aq).
Cl2 + H2O = H+ + Cl- + HOCl
The action of HOCl with Fe (electrode) forms eventually FeCl3 (reddish brown).
The action of NaOH on FeCl3:
3 NaOH + FeCl3 = 3 NaCl + Fe(OH)3
2 Fe(OH)3 is best thought of as hydrated ferric oxide, Fe2O3.3H2O .
------------------------------------------------
More detail, the action of Fe and HOCl is likely a fenton-type reaction with hypochlorous acid proceeding as follows:
Fe + 2 HOCl --> Fe(ll) + 2 .OH + 2 Cl-
Fe(ll) + HOCl --> Fe(lll) + .OH + Cl-
.OH + Cl- = OH- + .Cl
.Cl + .Cl --> Cl2
.Cl + Cl- = .Cl2-
.OH + .OH --> H2O2
Fe(ll) + H2O2 --> Fe(lll) + .OH + OH- (limited reaction until pH drops)
Formation of a basic iron chloride is also possible. Interaction with NaOH introduces Fe(OH)2 and Fe(OH)3 products.
Bottom line, not a pure product.
[Edited on 8-2-2018 by AJKOER]
|
|
|
DraconicAcid
International Hazard
Posts: 4333
Registered: 1-2-2013
Location: The tiniest college campus ever....
Member Is Offline
Mood: Semi-victorious.
|
|
| Quote: Originally posted by AJKOER | If I am understanding correctly, you employed 175 g NaCl in 1.3 liters of H2O.
With this amount of aqueous NaCl, you create at the electrodes respectively, NaOH (aq) and Cl2 (aq).
Cl2 + H2O = H+ + Cl- + HOCl
The action of HOCl with Fe (electrode) forms eventually FeCl3 (reddish brown).
The action of NaOH on FeCl3:
3 NaOH + FeCl3 = 3 NaCl + Fe(OH)3
2 Fe(OH)3 is best thought of as hydrated ferric oxide, Fe2O3.3H2O .
|
You are not going to oxidize chloride ion to chlorine at an iron electrode, when the iron is much more easily oxidized.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
|
|
|
AJKOER
Radically Dubious
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
With stainless steel, you will observe some chlorine even with 6 V battery. See https://forum.cosmoquest.org/showthread.php?96445-Electrolys...
|
|
|
Diachrynic
Hazard to Others
Posts: 226
Registered: 23-9-2017
Location: western spiral arm of the galaxy
Member Is Offline
Mood: zenosyne
|
|
I did some experiments with stainless steel, I observed no chlorine smell though. In any case, non-stainless steel probably wont generate chlorine due
to the potential of E = + 1.31 V IIRC. (And iron having - 0.41 V I think).
Anyway, blew a fuse on my multimeter while measuring the current. Going to take even more time than I tought.
we apologize for the inconvenience
|
|
|
Diachrynic
Hazard to Others
Posts: 226
Registered: 23-9-2017
Location: western spiral arm of the galaxy
Member Is Offline
Mood: zenosyne
|
|
Seems like my multimeter is broken in the 20 A range. Could only measure up to 400 mA. Anyway, in that range we get about 330 mA if we set 300 on the
dial. Assuming this tend continues up to 2 A, with 10% more we get 2.2 A, which translates to η = 90.5%. Is that more realistic?
we apologize for the inconvenience
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
