Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
 Pages:  1  2    4  ..  9
Author: Subject: Chlorine
Nick F
National Hazard
****




Posts: 439
Registered: 7-9-2002
Member Is Offline

Mood: No Mood

[*] posted on 14-4-2004 at 03:49


FeCl3 is available cheaply for etching PCB's, do you think this might have a use? Maybe heat would work?



View user's profile View All Posts By User
Proteios
Hazard to Others
***




Posts: 109
Registered: 7-3-2004
Member Is Offline

Mood: No Mood

[*] posted on 14-4-2004 at 06:35


Lol.... so the test for purity is stench and colour....

as for your inability to get it to work..... well it worked 10 years ago when i was playin with this stuff, and working well. I would suggest tired old bleach but the fact that its gone brown suggest some reaction, but from memory this works best with adding a little bleach to a lot of FeSO4 (i seem to remember you get the most out at about a 1:1 ratio)

As for the FeII FeIII oxidation.... well yeah, like i said, i never really figured out what was goin on.... true alchemiy :)

Plus a suggestion... if you wanna make serious amount of Cl... dont do it in a test tube.... 5L bottles with 1/2 kg of FeSO4 work pretty well.

Im not shittin ya. It works big time.

[Edited on 14-4-2004 by Proteios]
View user's profile View All Posts By User This user has MSN Messenger
Proteios
Hazard to Others
***




Posts: 109
Registered: 7-3-2004
Member Is Offline

Mood: No Mood

[*] posted on 14-4-2004 at 06:45


Quote:
Originally posted by Organikum
Dear Proteios, only teenagers call others "lightweights" and speak like "before I went professional" - those real in the know dont have to show off like this.



meh... the words were spoken in jest.....

Before gettin a degree in chem. and before gettin a phd in chem. I was really into this... 'what can i make from household chemicals stuff'..... really into it....that why i like this forum.....
:):)!!mega-nostaligia!!:):)
View user's profile View All Posts By User This user has MSN Messenger
Nick F
National Hazard
****




Posts: 439
Registered: 7-9-2002
Member Is Offline

Mood: No Mood

[*] posted on 14-4-2004 at 07:50


"Before gettin a degree in chem. and before gettin a phd in chem."

Haha, there he goes again...
You've got a chemistry PhD and can't work out what's going on in that reaction?




View user's profile View All Posts By User
Proteios
Hazard to Others
***




Posts: 109
Registered: 7-3-2004
Member Is Offline

Mood: No Mood

[*] posted on 14-4-2004 at 08:27


Quote:
Originally posted by Nick F

Haha, there he goes again...
You've got a chemistry PhD and can't work out what's going on in that reaction?


nope.... but i dont hold my manhood weak until someone else does! :D


The first response to the reaction was

'FeSO4 + bleach is nonsense'

it then improved to..... 'a poor Cl generator'.... im sure eventually we will get back to the only practical way to quickly make large controlable amounts of Cl from domestic products.

:cool:!Happy huniting!:cool:

[Edited on 14-4-2004 by Proteios]
View user's profile View All Posts By User This user has MSN Messenger
Nick F
National Hazard
****




Posts: 439
Registered: 7-9-2002
Member Is Offline

Mood: No Mood

[*] posted on 14-4-2004 at 09:13


Edit: Arrghhh, just ignore that, spent too much time thinking about copper...

[Edited on 15-4-2004 by Nick F]




View user's profile View All Posts By User
Z-Row
Harmless
*




Posts: 11
Registered: 23-3-2004
Location: United States
Member Is Offline

Mood: Bemused

[*] posted on 14-4-2004 at 12:58


Perhaps the sodium ion is grabing the sulfate ion so you have a iron(II) ion floating around which grabs an oxygen and the rest is liberated as gas.

4NaOCl + 2FeSO4 --> 2Cl2 + 2Na2SO4 + 2FeO + O2

but I'm such an amateur!

[Edit: where'd the sodium hydroxide come from?]

[Edited on 14-4-2004 by Z-Row]
View user's profile View All Posts By User
Geomancer
Hazard to Others
***




Posts: 228
Registered: 21-12-2003
Member Is Offline

Mood: No Mood

[*] posted on 14-4-2004 at 13:21


Proteios: I don't have a good feeling about your proposed method. Liquid bleach is a lousy chlorine source. Solid hypochlorite should do better. You suggest a 1:1 ratio. 1:1 what?
I suspect the effect you observed was acid disproportionation of the hypochlorite combined with oxidation of the Fe(II) to Fe(III). Organikum wasn't testing for purity with his eyes and nose, just for the presence of chlorine gas. Any reaction producing the amounts of clorine you describe would produce a green cloud.

Organikum: I find it interesting that NaCl and ZnCl<sub>2</sub> should give different products. Any reason for this? Also, are you sure that hypochlorite gives O<sub>2</sub> or H<sub>2</sub>? I can see H<sub>2</sub>O and CO<sub>2</sub>, but these are more easily removed. Chlorine suitable for producing SnCl<sub>4</sub> can allegedly be produced by oxidizing HCl with KMnO<sub>4</sub> and drying the gas with H<sub>2</sub>SO<sub>4</sub>. MnO<sub>2</sub> may work too.
View user's profile View All Posts By User
Proteios
Hazard to Others
***




Posts: 109
Registered: 7-3-2004
Member Is Offline

Mood: No Mood

[*] posted on 14-4-2004 at 15:38


Quote:
Originally posted by Geomancer
Proteios: I don't have a good feeling about your proposed method. Liquid bleach is a lousy chlorine source. Solid hypochlorite should do better. You suggest a 1:1 ratio. 1:1 what?


This isnt jedi nite school......your feelings really dont enter into it..... it is demonstrable.

As for the ratios..... anything u choose....mass, volume....the principal point that i was making is that you dont have catalytic amount of FeSO4 and drown it in bleach.... from memory the reaction goes best when the FeSO4/ bleach mix is a thick goopy brown mess.

As for bleach being a lousy source of Cl....well yes n no. Yes in terms of avail. Cl per mass..... no in terms of available Cl per dollar freely available at the hardware store. Plus i think bleach is one of the purer chemical available as a domestic product.

Compared to electrolysis the current method is king. Electrolysis has a propensity to eat the electrodes in Aq. Electrolysisin molten salts is a pain in the ass. Speed of generation from electrolysis is a joke, plus the gas is tricky to collect.



ok.... this is my hack at the chemistry.....

on the left of the eqn. you know u have FeSO4 n NaOCl..... the brown stuff you get is a hydrate of one of the higher Iron oxides, or im no judge....The Na and SO4 ion remain in solution start to finish and do nothing.
FeII => FeIII +e
HOCl + e => OH- +0.5 Cl2

NaOCl ~ HOCl + NaOH

QED (?)

[Edited on 14-4-2004 by Proteios]
View user's profile View All Posts By User This user has MSN Messenger
t_Pyro
Hazard to Others
***




Posts: 120
Registered: 7-2-2004
Location: India
Member Is Offline

Mood: Volatile

[*] posted on 14-4-2004 at 19:11


Electrolysis of an aqueous solution of <i>any</i> ionic chloride would result in the formation of chlorine at the anode, provided the solution is concentated, and the anode inert. The evolution of O<sub>2</sub> is due to two reasons: The decomposition of HOCl <i>in situ</i>, and due to a competing de-electronation of OH<sup>-</sup> ions. The former can be counteracted by using a high current density so that the chlorine evolved has little time to react with the water, and also the % evolution of O<sub>2</sub> is less. The latter can be counteracted by ensuring that the chloride ion has a much higher concentration than the hydroxyl ions- in short, make sure that the solution is concentrated.

As for the FeSO<sub>4</sub> HOCl bit:
Fe<sup>2+</sup> -> Fe<sup>3+</sup> E<sup>o</sup> = -0.77V
2HOCl + 2e -> Cl<sub>2</sub> E<sup>o</sup>=+1.63V
Hence, the oxidation of ferrous to ferric, along with the reduction of chlorine should be a feasible reaction, at least on pen and paper.
View user's profile View All Posts By User
Organikum
resurrected
*****




Posts: 2261
Registered: 12-10-2002
Location: Europe
Member Is Offline

Mood: lonely

[*] posted on 15-4-2004 at 09:15


First I apologize for my mistake in believing that FeSO4 + bleach wont work at all.

Here I want to show some simple calculations:
- 100ml saturated ZnCl2/H2O solution contain about 235gram chlorine
- 100ml bleach 10% contain about 5gram chlorine.

So if the electrolytic cell runs down to a concentration of 50% - whats no problem at all without getting serious amounts of oxygen, the cell will produce 100gram+ chlorine. (I took into calculation some chlorine going into solution - all this is done for a worst case electrolysis) For producing 100gram chlorine from bleach 10% and FeSO4 you will need at least 2 liters of bleach - but stop - dont forget the chlorine which goes into solution in the masses of water here! So either you use much more bleach - more water - no sense, or you boil the aqueous solution and get wet wet wet chlorine which you wont dry with ease or some CaCl2.

- Carbon rods from batteries are free.
- Electricity - oh my....
- Old computer PS´s are free and everywhere.
- The zincoxide which I use is asscheap and if I would like to some HCl would be all whats needed to make new ZnCl2 from the zinc gained.
- An assembly of five jugs produces a steady stream of chlorine - all over all 1kg chlorine - from five jugs a 200ml. Absolute minimum.
- And it is fast. I will post the exact amount of chlorine per timeunit and cell after the weekend.

4,5 liters of 10% bleach equal 100ml ZnCl2 in H2O (saturated solution) - ever thought on this? :cool:

Could a moderator be so nice and edit my stupid dyslexic typo in the first post of this thread?
CHLORINE
not chloride of course.
thanks.
ORG




Irgendwas is ja immer
View user's profile View All Posts By User
Proteios
Hazard to Others
***




Posts: 109
Registered: 7-3-2004
Member Is Offline

Mood: No Mood

[*] posted on 15-4-2004 at 09:58


Quote:
Originally posted by Organikum
Here I want to show some simple calculations:
- 100ml saturated ZnCl2/H2O solution contain about 235gram chlorine
- 100ml bleach 10% contain about 5gram chlorine.

ORG


1L about 50g of Cl2... about 20L of gas. Gurgling a L of bleach onto FeSO4 alsmost instantly gets you 15L of Cl..... thats enough the make most rooms intolerable. To gereate 20L of gas by electrolysis would take ..... time. As for the Cl being wet.... the water content is essentially that of the vapour pressure of water (ca 20 mg/L)....I think youll find the biggerst prob. is the redisollution of the Cl2 into the water from the bleach, which i would guess will rob you of 1/4 of your yield.
The kit i used was a 5L bottle, adding maybe as much as 2-3L bleach.....making maybe 50 L Cl2 (by these nos.).... thats by most reckonings a pretty fearsome Cl generator.

I dont doubt a reasonable electrolysis kit could be rigged... all the electrolysis kits i ever rigged worked but were impractical.... they just never made the Cl quick enough to be useful (like i say... i was a teeny at the time)

chemical Cl2 react with water... once thats happened you cant get it back by distillation. However....it dissolves in water 2 give HCl n HOCL.... the latter will react again with FeSO4. I think the best guess of a 25 % loss to the water/FeSO4/NaOCl soln is as good as any. Bleach is cheap. FeSO4 is cheap. For me... even when poor, the losses were acceptable

[Edited on 15-4-2004 by Proteios]

[Edited on 15-4-2004 by Proteios]
View user's profile View All Posts By User This user has MSN Messenger
Organikum
resurrected
*****




Posts: 2261
Registered: 12-10-2002
Location: Europe
Member Is Offline

Mood: lonely

[*] posted on 15-4-2004 at 10:11


I guess you just dont take in account the planned use of the chlorine. I by no way plan to create a wargas which makes rooms inhabitable, but I want to produce an reagent for organic and inorganic reactions. Therefor I count my chlorine in gram not in liters as it are grams to count (moles would be more correct) which are going to react. Liters is no useful unit for me here. Also I want an steady and clean stream of chlorine over a longer time.

You might read the first posts in this thread to understand what this is about - no offense we are just talking about different things I believe and this might help to clear this up.

Example. For making 250gram SnCl4 I need at least 150gram chlorine and 250gram SnCl4 is not so much at all - Friedel-Crafts reactions require rather huge amounts of metalchlorides to work. (just an example - not more)




Irgendwas is ja immer
View user's profile View All Posts By User
Organikum
resurrected
*****




Posts: 2261
Registered: 12-10-2002
Location: Europe
Member Is Offline

Mood: lonely

[*] posted on 15-4-2004 at 10:30


The solubility of chlorine in water is about 0,1mole per liter at 25°C so roughly 3,5 gram per liter water - basic conditions boost the solubility though.

The production of oxygen in metalchloride electrolysis is dependant on the ph - under acidic conditions almost no oxygen will be formed not so under neutral or basic conditions. Thats why NaCl isnt favorable as I believe - because of the NaOh formation raising the ph.
The presence of oxygen is not problematic for the Sn to SnCl4 reaction but it is for the toluene chlorination. ZnCl2 was choosen because of the availability of zincoxide and because I have uses for the electrolytic pure zinc lateron. I will probably also try ironchloride another day for the electrolytic iron. It is just always nice in my eyes to have double features.... :)




Irgendwas is ja immer
View user's profile View All Posts By User
Proteios
Hazard to Others
***




Posts: 109
Registered: 7-3-2004
Member Is Offline

Mood: No Mood

[*] posted on 15-4-2004 at 10:33


Quote:
Originally posted by Organikum
Dont say I am nuts, but I searched and found no thread dedicated to this useful compound.

Lets open the competition:
We want chlorine - dry - clean - and in serious amounts from all over the world freely available starting chemicals.



sure np Organikum.... I reckon u r right bout the cross purpose thing.. but from the first post FeSO4 is certainly an obscure an effective way of producing large cheap fast amoutns of Cl... V obscure!

As for war gases.... gas attacks (WW1)typically consisted of tons..... the quatities we r talking here arnt even close 2 war gas amounts.....

As for units.... g/L moles/ (bar) are all sensible units used by chemist who regularly deal with gases.

I guess if you just want small amounts of cheap, controllable, pure Cl... the simplest answer is: buy a cylinder.
View user's profile View All Posts By User This user has MSN Messenger
Organikum
resurrected
*****




Posts: 2261
Registered: 12-10-2002
Location: Europe
Member Is Offline

Mood: lonely

[*] posted on 15-4-2004 at 11:47


Looking in the catalog of big chemical suppliers I see that I "can" buy everything there I ever thought of and much more. Not regarding the fact that this is of course plain hypothetical as here where I live it is at least "not easy" to buy such things, it is against what I am after. I am after to produce what I want from scratch - scratch here in the meaning of common OTC compounds - just for to do it. It gives me a good feeling and makes the police stay away from kicking in my door and asking unfriendly questions. I had this already - I dont need this anymore rest assured.

No cylinder. Ok?

Btw. could you Proteios try to write some more understandable english - this is an very international board and it is not so easy to understand what you are wanting to express. It´s not like you are talking to your favorite drugdealer at the corner of your ghetto ya know? :)
View user's profile View All Posts By User
Proteios
Hazard to Others
***




Posts: 109
Registered: 7-3-2004
Member Is Offline

Mood: No Mood

[*] posted on 15-4-2004 at 16:24


when i was a teeny doin this stuff, I got pally with a pharmasist.....he was kinda happy to order the stuff from the mainstream chem. suppliers....albeit...nothing too lethal or illegal....10% profit. Just a thought.....

Still one of my happier memories is making metalic bismuth from BiCO3.... which the pharmasist had loads of as some sort of stomach settling thing/antisceptic.

Good luck with the synthesis :)
View user's profile View All Posts By User This user has MSN Messenger
bogus poster
Harmless
*




Posts: 7
Registered: 13-1-2004
Location: locus
Member Is Offline

Mood: bogus

[*] posted on 16-4-2004 at 00:06


Might oven drying the FeSO4 (dehydrating) be helpful if one wants to make Cl2 from bleach and FeSO4. Also can the bleach be concentrated by distilling some water out - the bleach of commerce available here is only 5% concentrated?
And finally: How pure is the Cl2 produced this way? It will contain water - that was told before, but if - what else?
View user's profile View All Posts By User
t_Pyro
Hazard to Others
***




Posts: 120
Registered: 7-2-2004
Location: India
Member Is Offline

Mood: Volatile

[*] posted on 16-4-2004 at 09:29


Organikum, I didn't understand what you meant by "metachlorides" in relation to Friedel-crafts reactions. Were you talking about the alkylation and acylation reactions using organic chlorides?

The impurities in Chlorine made from bleach will primarily be due to oxygen, as stated previously.

I see now why zinc chloride would be prefered. The decrease in ph of the solution would be counteracted by the precipitation of the zinc hydroxide, hence preventing the de-electronation of the hydroxyl ions. Sodium hydroxide, however, is highly soluble, and would therefore cause oxygen impurities. Just a thought, but does chlorine react with alkaline pyrogallol?

[Edited on 16-4-2004 by t_Pyro]
View user's profile View All Posts By User
Organikum
resurrected
*****




Posts: 2261
Registered: 12-10-2002
Location: Europe
Member Is Offline

Mood: lonely

[*] posted on 16-4-2004 at 10:34


Sorry - it was a typo - it should read "metal-chlorides" referring to AlCl3/SnCl4/FeCl3 to name some of the Lewis-acids commonly used in Friedel-Crafts alkylations.

The use of FeSO4 seems to me on a second thought not so bad at all - not with bleach alone but as suggested with calciumhypochlorite aka Pool-Shock and FeSO4 - this would solve the problem of the masses of bleach needed - worth a try.

Proteois: To make you happy, I was wrong. So I have to thank you for a astonishing easy and at least to me new way to produce chlorine.
Thanks.
(this new way is much more valuable as the damage done to my poor ego - I blame it on vulture and thats it for me :))

A thought: Might the addition of an acid - HCl or H2SO4 suppress the the oxygen formation at least in parts? Hm.



Somehow I really lack this "golden touch" these days.....
...nevermind.

[Edited on 16-4-2004 by Organikum]
View user's profile View All Posts By User
Proteios
Hazard to Others
***




Posts: 109
Registered: 7-3-2004
Member Is Offline

Mood: No Mood

[*] posted on 16-4-2004 at 21:39


Quote:
Originally posted by Organikum
The use of FeSO4 seems to me on a second thought not so bad at all - not with bleach alone but as suggested with calciumhypochlorite aka Pool-Shock and FeSO4 - this would solve the problem of the masses of bleach needed - worth a try.



no problem :)

just happy to pass on the knowledge :) :)

on the above idea with the bleach powder..... looks reasonable, but may run into problems with solubiltiy/transport/mixing issues.

Ca(OCl)2 20g/100ml
CaSO4, low sol. CaOH2, v. low sol.
Fe2O3 insol.

300g FeSO4, should produce 70g Cl2. 24L.
This will produce an awful lot of insoluble stuff.... I hope that doesnt affect things too much 4 you!

Good luck n Happy Huntin!

[Edited on 17-4-2004 by Proteios]
View user's profile View All Posts By User This user has MSN Messenger
Organikum
resurrected
*****




Posts: 2261
Registered: 12-10-2002
Location: Europe
Member Is Offline

Mood: lonely

[*] posted on 17-4-2004 at 12:52


here we go....



FeSO4 straight from the box admixed with some dishwasher NaCl for to prevent clogging. It was filled into a special reaction vessel made from NYLON which was produced in my secret underground laboratories after my specifications...... ;)
(yeah - looks like a Coke-PET bottle I know... thats just a coverup... ehem..)




This is the complete setup for production of Cl2 - without drying up to now, which will be tried first by CaCl2 - if thus isnt satisfying I will go for conc. H2SO4 shudder

The also in my underground labs produced "pressure bleach injector" (looks like a bug sprayer I know...) will be filled with bleach, pressurized and will inject the bleach into the high-tekk reactor vessel where it is supposed to produce chlorine there.

First try is straight after the book - as Proteios suggested - next try will be made with adding some calcium hypochlorite to the FeSO4 to spice the reaction a little up.


Ok.
Some last wishes before I gonna kill myself/go to jail/get lynched by my neighbors ?

:P




Irgendwas is ja immer
View user's profile View All Posts By User
The_Davster
A pnictogen
*******




Posts: 2861
Registered: 18-11-2003
Member Is Offline

Mood: .

[*] posted on 17-4-2004 at 13:14


Why not just add some calcium hypochlorite straight into the bleach to increase the hypochlorite concentration, instead of adding it into the iron sulfate. If you add the solid calcium hypochlorite to the solid iron sulfate, and if there is any water present in either reactant or the coke bo...erm...nylon reactant vessel you will have chlorine produced without you being able to controll the rate.
View user's profile View All Posts By User
Organikum
resurrected
*****




Posts: 2261
Registered: 12-10-2002
Location: Europe
Member Is Offline

Mood: lonely

[*] posted on 17-4-2004 at 14:07


I will make a test before by mixing some hypochlorite with FeSO4 in a testtube to see what happens - or better how fast and violent this is going to happen. :)
View user's profile View All Posts By User
Saerynide
International Hazard
*****




Posts: 954
Registered: 17-11-2003
Location: The Void
Member Is Offline

Mood: Ionic

[*] posted on 18-4-2004 at 04:28


Quote:
Originally posted by Organikum
Ok.
Some last wishes before I gonna kill myself/go to jail/get lynched by my neighbors ?

:P

If you go to jail, be sure to tell us how the food is :D




"Microsoft reserves the right at all times to monitor communications on the Service and disclose any information Microsoft deems necessary to... satisfy any applicable law, regulation or legal process"
View user's profile View All Posts By User
 Pages:  1  2    4  ..  9

  Go To Top