Plenty popping and crackling and spitting and hissing last night. I had a wonderful night, busily hovering around my new electrically heated molten metal bath, housing, a bunch of lead, with some tin in it, to lower the melting point, and some solder thrown in to do so further for convenience, and that, bathing a steel 'tin' containing a mixture of caustic soda, a small amount of salt, which I initially tried but wouldn't form a melt of its own, on its own (I'm hoping an induction heater and carbon crucibles will serve for electrolysis of molten salt. Give me time whilst it arrives (my old man is buying it, but will let me use it, he kind of more or less just wants to experiment and play about with it, IMO I'll end up using it more than he does
) to think about what to do with the chlorine gas liberated by such electrolysis. I'll be a scheming and a plotting for experiments or procedures that involve elemental Cl2. Making bromine, by passing it into an aqueous, strong solution of an alkali metal bromide, IMO preferably, for me, potassium bromide, because that way the byproduct would be potassium chloride, and whilst I can of course get all the salt I want as long as I have enough money to buy a given quantity and shops to stock it, if for example I wanted to spend a thousand pounds on table salt (and I really, really don't. A grand to me means lots and lots of plenty much more interesting and useful chemicals and the labware to react them in) I do not have pure potassium chloride, although a mix is available as 'lo-salt' for low sodium diets and salting food. The more reactive Cl2 displaces iodine from iodides and bromine from bromides, so it IS a convenient way to store Br2 and I2 (both are volatile, despite iodine being a solid, almost metallic looking element, it sublimes, and if left out in the open air, will fairly quickly (in storage terms) just evaporate (if actually heated, in a closed container it goes directly from solid to liquid under atmospheric pressure, bypassing a liquid, molten stage, this is called sublimation) and Br2 is a bugger to store, needing ideally sealing in glass ampoules until desired for use. So generally the best thing to do is either if the reaction suits the conditions, generate it in-situ for immediate reaction in the same vessel as something one might wish to brominate, or generate it, purify and distill, dry it etc. as and when your going to need it. It creeps through many plastics, and creeps through seals with ground glass so storing it in stoppered flasks is a no-no too. Also it viciously attacks the likes of rubber tubing and stoppers (and god help you if you spill it on you, I never have, but I know of someone who has, and they have been in and out of hospital. Its not especially toxic as such, but whilst Cl2 is a gas, and although more reactive than bromine and iodine, contact with Cl2 is unlikely to burn, liquid condensed chlorine would be another matter, and you can actually pick up a nugget of solid I2 in your fingers as long as you keep moving it about like you would say, a steel ball bearing at just such a temperature as to be uncomfortable but not to outright burn flesh, or a hot buttery crumpet (although needless to say, biting into a hot, buttery lump of iodine isn't the best idea:P) bromine is in between chlorine and iodine in terms of reactivity but unlike the gaseous chlorine and the solid iodine its a liquid and can soak into and penetrate the skin easily causing severe and reportedly very painful burns, causing a third degree burn in a matter of moments if enough be present.
So its a shitter of an element to store, one of the worst of the lot, ignoring radioactivity from gamma ray sources, to have to store. So perhaps if I think more along the lines of say, bromobenzene or alpha-bromotoluene which would be more useful, or N-bromosaccharin, N-bromosuccinimide, useful non-volatile brominating agents, and I can then experiment also with iodine mono- and tribromide as well as bromine monochloride, iodine mono- and tribromides and tne other nonfluorinated interhalogens (semicovalent compounds composed of only halogen atoms, such as for example the ones I have thus far prepared being iodine monochloride (a dark, volatile liquid which hydrolyzes on exposure to H2O or moisture in the air, fumes and with an unpleasan odour, similar in appearance to Br2 although easily distinguished from elemental bromine by means of its weight, being a liquid, a given volume is easily precisely measured, and due to differing density the weight will differ between Br2 and iodine monochloride and of course boiling point, plus although I haven't characterized the compound sufficiently to determine how to produce either, apparently a solid alpha- and beta form are also extant. And it is formed, as a distillable liquid by passing chlorine gas not in excess through a tube packed with solid iodine and condensing the result, if the Cl2 be not in excess then the monochloride of iodine is formed, if this be treated with further chlorine gas, or if excess Cl2 is used then a green crystalline solid, iodine trichloride is formed. That was a fun experiment I did a while back, although ruined by the fucking dirty pig filth when they opened the stoppered boro glass flask I had it contained in 'to take samples' (which they then left without, so obviously just came to trash the lab). I think, having more iodine than I know what to do with, aside from making some methyl and isopropyl iodides which are useful electrophilic alkylating agents, and in one particular reaction, the Appel, can be substituted for carbon tetrachloride to prepare the intermediate triphenylphosphonium halide with triphenylphosphine (which I have quite a lot of, a kg should last me a long time, especially since the usual byproduct of reactions involving PPh3 is triphenylphosphine oxide, and it can be recycled or used for other purposes) in this case alkyl halides, at least methyl iodide, can serve as a source of nucleophilic iodine, and used for preparing alkyl iodides, carbon tetrachloride is the more well known halogen source although unusually, acting as a reactant rather than solvent, although if the alcohol will dissolve in C-tet then of course it would play both roles) seems quite unfussy about its halogen source, even elemental Br2 apparently works for preparation of alkyl bromides from alcohols. This reaction is for halogenating alcohols. Quite a useful one from the looks of it too since triphenylphosphine is not highly watched (not that I'd let THAT stop me, I don't deal in unobtanium much
being, somewhat privileged in what I can and cannot obtain if I choose to pay for a reagent rather than make it, dig it out of the ground and smelt it, extract it et cetera or draw it from the air in the literal sense. I'm lucky, in that I have good sources and don't have to rely solely on OTCs, but many, if not most hobby chemists have to, with a lesser or greater degree of access to things you can't buy from a hardware store or make from what you can, but for them the Appel would be extremely useful, since the usual halogenating agents, such as thionyl chloride, PCl3, PCl5, POCl3, SO2Cl2 (sulfuryl chloride, not to be confused with SOCl2 which is thionyl chloride) are exceedingly difficult to make in the case of the sulfur oxychlorides although its doable with much effort, and the phosphorus halides involve, of course, phosphorus, and elemental phosphorus itself either red (especially watched due to its use in methamphetamine synthesisis, although its doubtful with the pills drying up as a source for pseudoephedrine/ephedrine in the US that US cooks are even using that red phosphorus/iodine reaction much, its just reputation mostly thats making it hard for the rest of us, at least, especially in the US, its right up there on the watched list) And winning it from readily available phosphate salts is difficult, and if one were to carefully (extremely carefully for it is lethally toxic) decompose the phosphine and diphosphine released from mole smokes containing metal phosphides (plus whilst afaik PH3, the phosphorus analog of ammonia, where P stands in place of nitrogen, is just plain toxic, P2H4 is both toxic AND pyrophoric, spontaneously igniting on contact with air) But that would be a relatively low yielding, and exceedingly dangerous route IMO, and not worth it as a source of phosphorus for all but the most desperately hard-up cook or chemist) it would however, if thermally decomposed, and the exit gases also burnt after passage through ice cold water to destroy any residual escaping phosphine, provide elemental phosphorus, probably in its white allotrope.
But bugger that for a lark, wouldn't even attempt it. One bubble of the stuff could be enough to kill you. Phosphine gas is in the 'deadly toxic' category. DeadliEST? certainly not but its the sort of thing you'd class along with cyanide gas or hydrogen azide gas (hydrazoic acid gas), hydrogen sulfide, hydrogen selenide (which is actually more toxic than cyanide gas and stinks like all hell condensed onto the head of a pin, each and every rotting stinking maggot, yanked wriggling from the pus-filled buboes of its pestilent carcasses from each and every sinner ever to rot in hell. Including the paedophiles and those maggots that are waiting for george bush and tony bliar as well as theresa may, when they kick the bucket. Satan probably having a big bucket of plague fleas ready and even ordering extra maggots from hell's local lava-lake fishing tackle store, he'd have to, to get just a few, desperate and starving maggots who have extremely low standards for maggots infesting pus-slobbering abscesses bursting forth in the noxious cadaver-waste of hell's vilest. The ones that would even eat paedophile-corpses and jeremy kyle. By choice.
