madscientist
National Hazard
Posts: 962
Registered: 19-5-2002
Location: American Midwest
Member Is Offline
Mood: pyrophoric
|
|
Elemental bromine isolation
I was thinking of several methods of isolating elemental bromine without distillation. This is the idea I tested:
2KMnO4 + 10NaBr + 16H2SO4 ----> 2KHSO4*H2O + 2Mn(HSO4)2*H2O +
10NaHSO4*H2O + 5Br2
I mixed 3.2g of granulated KMnO4 with 10.3g granulated NaBr. I then proceded to add 9.5mL of concentrated sulfuric acid. There was slight
bubbling, then the mix turned brown, and suddenly began spewing bromine gas. After a few more seconds, it began crackling, and I saw red flashes
within the reaction beaker. After about two minutes, visible quantities of bromine were no longer visible. I looked at the remaining solid, and noted
that it was slightly purplish (likely because sulfuric acid was participating in the oxidation of HBr, causing not all of the KMnO4 to be
used). I was hoping that the reaction would be a tad less violent, meaning that the reaction would have yielded liquid bromine instead of gaseous
bromine.
This is what I plan to try next:
2NaNO3 + 10NaBr + 12H2SO4 ----> 6NaHSO4 + 6NaHSO4*H2O + 5Br2 +
N2
That reaction should be much less violent. Hopefully, I'll just be able to pour off the bromine.
I weep at the sight of flaming acetic anhydride.
|
|
|
a_bab
Hazard to Others
Posts: 458
Registered: 15-9-2002
Member Is Offline
Mood: Angry !!!!!111111...2?!
|
|
I see no point in your desire to obtain directly liquid bromine. The byproducts will impurify your bromine and there is no way to filter it in the
usual, way, as is VERY volatile. You can distill it by the simple means of two testubes and a glass tube: one as reactor vessel and one testube to
collect and condense the bromine vapors. The second testube should be ofcourse kept in some cold bath. It's much simpler and there will be no nasty
stinks.
I have played quite a lot with bromine and it's a nasty stuff. I got burned (it was horrible), and the vapors are very irritable too...Not talking
about the things you can get with it: bromacetone, benzyl bromide, etc.
|
|
|
fluffy bunny
Harmless
Posts: 25
Registered: 17-10-2002
Location: Australia
Member Is Offline
Mood: No Mood
|
|
Madscientist, you do realise sulphuric acid reacts with KMnO4 to produce manganese septoxide don't you!! No wonder you had a very violent reaction,
manganese septoxide is some nasty shit, it spontaneously ignites, with almost any organic material.
I strongly reccomend you don't have any mixture with KMnO4 and H2SO4 in it together.
I've made very small amounts of this stuff and its really nasty.
Once a tiny drop landed on the bench without me noticing. There was a lighter there and, and it ate straight through the plastic causing it to
explode!
|
|
|
Nick F
Hazard to Others
Posts: 439
Registered: 7-9-2002
Member Is Offline
Mood: No Mood
|
|
I'd just bubble chlorine through a strong NaBr solution. I think there'd be less chance of any side reactions, you'd get some bromine chlorides but
the amounts of these would be insignificant unless you used a massive excess of chlorine.
NaOCl could probably be used too, like when preparing iodine from that tincture you can get in pharmacies. There'd be less chance of getting chlorides
with this.
Or, melt it down and electrolyse it. Condense the bromine and collect the sodium! Ahh, if only it was that simple eh?
|
|
|
madscientist
National Hazard
Posts: 962
Registered: 19-5-2002
Location: American Midwest
Member Is Offline
Mood: pyrophoric
|
|
I think that passing dry chlorine over NaBr should yield dry bromine without the bromine chlorides - if the temperature is kept over 10C (BrCl
decomposes with evolution of Cl2 at 10C).
I wasn't worried about Mn2O7 (yes, I have worked with it before) because it was created and destroyed in small amounts (due to
there being only small grains of KMnO4 in a mix of NaBr).
With the second process I suggested in the first post of this thread, it should be easy enough to separate the bromine with a separation funnel,
considering that the density of liquid Br2 is 3.1g/cm3, while the density of NaHSO4 is 2.74g/cm3, the
density of NaNO3 is 2.27g/cm3, and the density of H2SO4 is 1.84g/cm3. Everything that's not
bromine that's left after the reaction should float on it. The main problem that potentially could plague the reaction would be HBr gas escaping
before it's oxidized.
I weep at the sight of flaming acetic anhydride.
|
|
|
Darkfire
Hazard to Others
Posts: 292
Registered: 3-1-2003
Location: California
Member Is Offline
Mood: Wondering
|
|
Try my method
I think the safest and best way would be to use NaBr MnO2 and H2SO4.
CTR
|
|
|
I am a fish
undersea enforcer
Posts: 600
Registered: 16-1-2003
Location: Bath, United Kingdom
Member Is Offline
Mood: Ichthyoidal
|
|
Nick, how do you get the bromine out of the resulting mixture?
Do you extract it with a non-polar solvent? If so what?
Chris
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
Bromine? Oxidation!
Any oxidiser does the trick. H2O2 might be the most easy to get.
H2O2 + 2NaBr -> 2NaOH + Br2
H2O2 in diluted (10%) HCl. Purification by sublimation. (I hope this counts as "without distillation")
Every oxidising agent in acidic solution should do the job, bleach, chromiumsalts, MnO2.......
ORG
|
|
|
trinitrotoluene
Hazard to Others
Posts: 142
Registered: 17-10-2002
Location: California
Member Is Offline
Mood: paranoid
|
|
Yesterday I added some NaBr into water until it dissolved. Then added some HCl. After that precipitated it with 30% H2O2. The Br2 is in the soloution
it must be distilled to be isolated. Also distillation will also yield O2 as the H2O2 decomposes. I heated it to 60*C and visiable amount of Br2 gas
is given off. I had a 20" fan blowing the fumes to my backyard neighbors yard .
TNT
|
|
|
Organikum
resurrected
Posts: 2329
Registered: 12-10-2002
Location: Europe
Member Is Offline
Mood: busy and in love
|
|
this is just a quickshot, I haven´t looked it up (my MERCK index refuses to work).
Freezing? Will Br2 precipate by cooling it down? Perhaps it will be necessary to add something (ethylene glycol?) to lower the freezing point of the
solvent...
And sublimation seems possible. Decomposing the H2O2 with a drop of blood  and
sublimation over a few days.....
ORG
|
|
|
trinitrotoluene
Hazard to Others
Posts: 142
Registered: 17-10-2002
Location: California
Member Is Offline
Mood: paranoid
|
|
I was wondering if anyone had tried to isolate bromine using this method.
2 KBr+ 2 HNO3= 2 KNO3+ Br2
TNT
|
|
|
Mumbles
Hazard to Others
Posts: 436
Registered: 12-3-2003
Location: US
Member Is Offline
Mood: Procrastinating
|
|
trinitrotoluene, I think that procedure would yield 2HBr. You seem to have forgotten about the Hydrogens from the nitric acid.
Theres a proceedure for creating elemental Br in my chemistry book. I'll type it up as soon as I can find the book and proceedure.
|
|
|
Polverone
Now celebrating 21 years of madness
Posts: 3186
Registered: 19-5-2002
Location: The Sunny Pacific Northwest
Member Is Offline
Mood: Waiting for spring
|
|
HBr isn't that hard to oxidize. That is why you can't prepare HBr just by mixing H2SO4 and NaBr/KBr: the H2SO4 will oxidize at least a
portion of the HBr to elemental bromine. The nitric acid method is worth trying, at least.
|
|
|
madscientist
National Hazard
Posts: 962
Registered: 19-5-2002
Location: American Midwest
Member Is Offline
Mood: pyrophoric
|
|
Oops, I just realized that I forgot to post about the results of my second plan (the one involving nitrate) for preparing elemental bromine. The
reaction was violent, evolving considerable amounts of bromine gas, but wasn't quite as exothermic as the first attempt involving permanganate.
I weep at the sight of flaming acetic anhydride.
|
|
|
Cat Wrangler
Harmless
Posts: 1
Registered: 12-5-2003
Location: A remote, inactive volcano
Member Is Offline
Mood: No Mood
|
|
the nitrate method
I tried NaBr + KNO3 + H2SO4. When mixed together at room temperature, there was little activity from these three materials. Adding a little water soon
had Br2 pouring from the flask, but adding a large quantity of water stopped it. Oddly, when quenched with a large quantity of water the solution was
a light red, not the deep red-brown that I would have expected of Br2 in water.
Is there some way H2O might participate in the oxidation reaction, or is likely just the heating provided by H2O + H2SO4 that caused the Br2 evolution
to start?
chick diamagnet
|
|
|
sirius_cm
Harmless
Posts: 25
Registered: 17-5-2003
Location: Mid Florida
Member Is Offline
Mood: Tetrahedral
|
|
How bout the good ole activity series? I mean take some NaBr and add some Cl2, then all you have is Salt on the Bromine. Filter it, and bingo, its all
good 
Alpha Canis Major
\"The Enemy Gate is Down\"
|
|
|
alchemie
Harmless
Posts: 36
Registered: 4-6-2003
Member Is Offline
Mood: variational
|
|
liquid bromine
An interesting trick I read about in an old(1850´s) chemistry book is to distill the bromine from the flask where it is being generated, into another
flask containing concentrated H2SO4.
The purpose of the H2SO4 is to dry the bromine while, at the same time, keep it from evaporating, as it forms a layer beneath the lighter acid.
If the Br2 is introduced through a tube(glass, preferably) into the H2SO4 and the flask is chilled with an ice-bath, the Br2 losses should be greatly
diminished.
|
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
Dry KBr and conc sulfuric acid produces Br2 quite violently and in copious amounts. The sulfuric acid is reduced to SO2. Same goes for KI.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
Scorpion
Harmless
Posts: 4
Registered: 29-5-2003
Member Is Offline
Mood: No Mood
|
|
But what if the KBr is in a solution with water and not so concentrated. I would also think that in this way some HBr could be formed as an impurity
along with elemental Bromine...!!
|
|
|
vulture
Forum Gatekeeper
Posts: 3330
Registered: 25-5-2002
Location: France
Member Is Offline
Mood: No Mood
|
|
If the KBr is dissolved, nothing will happen because it's too diluted to keep the redox reaction going and secondly, HBr is a too strong acid to
be formed form sulfuric acid in solution.
I also doubt HBr will be formed during the dry reaction.
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
|
|
|
madscientist
National Hazard
Posts: 962
Registered: 19-5-2002
Location: American Midwest
Member Is Offline
Mood: pyrophoric
|
|
NaBr will react with H<sub>2</sub>SO<sub>4</sub> to liberate substantial quantities of elemental bromine, but also significant
amounts of HBr (HBr is the initial product; the reason for Br<sub>2</sub> being formed is HBr being oxidized by
H<sub>2</sub>SO<sub>4</sub>.) MnO<sub>2</sub> is typically used to help reduce the amount of HBr liberated.
[Edited on 6-6-2003 by madscientist]
I weep at the sight of flaming acetic anhydride.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
