How to make Bromine

First off let me mention that bromine is nasty stuff. I'm not even going to make pure bromine, and the fumes can still hurt you a lot. I've accidentally filled parts of my house with it in gaseous form, and it wasn't fun at all, I had to ventilate it heavily in order to get the smell away.

Before you even consider this experiment, decide how important having bromine is to you, and IF you decide to proceed, do so outside on a slightly breezy day, or in a fume hood.

Chemical Equations:

The bromine in this experiment comes from sodium bromine, NaBr, which is a faily basic alkali-halide compound, and is a fairly harmless white powder much like salt. It should be fairly simply to use a different alkali halide, like potassium bromide, but sodium is generally the easiest to get.

In order to convince the bromine to leave it's beloved sodium, you need to find something more reactive to steal the sodium, leaving the bromine in fairly pure form. In this experiment, I use chlorine, yet another corrosive nasty gas you shouldn't even think about messing with.

In order to make chlorine, I need a chlorine doner, because it is expensive/difficult to get a canister of chlorine, buying pure bromine would be cheaper. My chlorine doner in this experiment will be calcium hypochlorite, Ca(ClO)2, and to get it to free it's chlorine, I'm going to treat it with hydrochloric acid, HCl.

The entire experiment should go something like this: HCl + Ca(ClO)2 = CaCl + H2O + Cl2, being calcium chloride, water, and chlorine, once the chlorine is there, NaBr + Cl = NaCl + Br, so you end up with a solution of calcium chloride, sodium chloride (table salt), and bromine, in water.

Note: Bromine vaporizes of VERY easily, even with bromine in water it will most likely make a small cloud of orange gas if left for too long. I would advise you figure out what you're going to do with it BEFORE you make it.

Experiment Construction:

The experiment really couldn't be more simple, because the ratios of the ingredients don't matter all that much, and it'll work under almost any conditions.

To start you need the following:

About 60ml of water, distilled will make your process cleaner but is by no means required, a small quantity of sodium bromide(available from my store), a small quantity of calcium hypochlorite(also available), and some hydrochloric acid. You'll also need a pippette (or eye-dropper) to handle the acid, a glass rod to stir (although the pippette would work), and although not shown here, gloves are a good idea.

These chemicals are fairly easily available being that sodium bromide and calcium hypochlorite are pool chemicals, the calcium hypochlorite can even be replaced by sodium hypochlorite, which is used in common bleach, more on this later, but the hydrochloric acid can be tricky. Odd as it may seem, it is a fairly common chemical for use in cleaning and concrete etching, if you go into most hardware stores they will have it as "muriatic" acid, which is simply an older name for the same thing. It is used in some drain cleaners and could be called "hydrogen chloride".

WARNING: Hydrochloric acid is NASTY stuff. A small breath of fumes will do perminant damage to lungs and throat, a spill on your skin will leave a burn in 20 seconds. DO THESE EXPERIMENTS SOMEPLACE WELL VENTILATED, PREFERABLY OUTSIDE. Also, wear enough clothing to cover all skin near the acid, and as I said, big gloves are a good idea.

First step, disolve calcium hypochlorite in water, you probably won't even need a gram of it but it's good to be sure you have enough, the last thing you want is to waste sodium bromide because you didn't have enough chlorine. It should turn this pretty yellow-green color once stirred up a bit.

Note: If you want to use bleach, simply pour out 80 ml of that, and skip the water entirely. It already has sodium hypochlorite disolved in it so you don't have to do the stirring.

Once you have this hypochlorite mixture (bleach or not), it's time to add the sodium bromide. If you used calcium hypochlorite, I'd say maybe twice as much sodium bromide should be added, if not, stick with about 2 grams. Stir until disolved, the solution shouldn't change visibly.

Once you have this solution, all you have to do is SLOWLY add the hydrochloric acid, freeing the chlorine from the hypochlorite, and thusly freeing the bromine from the sodium bromide.

If all is going well, it should immediately start to fade to orange, and if you're anywhere near above the beaker your nose should sting violently, therefor you SHOULD NOT BE ABOVE THE BEAKER! This step involves creating chlorine gas, some of it will be lost from the reaction and waft out of the beaker, you do NOT want to be anywhere near it. Also at this point there is bromine present, which will also slowly vaporize out of the beaker, and is also not something you want to breath.

As for how much acid to add, it is a tricky thing to decide, generally I simply add tiny bits at a time (like a pippette full) and stir gently, then I repeat these steps until it gets transparent(and bright orange). If you don't add enough you will have small amounts of hypochlorite left in your solution, if you add too much, you'll obviously enough have acid in solution. Neither of these are particularly a problem if the amounts are fairly small, and the bromine will be so nasty you won't notice the smell of bleach or acid. Once you're finished with this step, you should have a nice beaker of beautiful bright orange fuming solution of bromine!

Right about now, if you're as crazy as I was when I made this, you'll start wondering what the heck you're going to do with this stuff... What I did was I sealed some in a glass tube for my periodic table collection (although not pure it is a beautiful example), but then since I had a little extra, I thought I'd try to distill it and see if I could get PURE bromine... Basically all you have to do for this is gently heat the solution until bromine starts vaporizing out (as you can tel this isn't very hot), then force the vapors through a tube into the BOTTOM of a test tube submerged in an ice bath. This is not a very good scientific method, but I'm somewhat lacking in proper equipment, and it did technically work, I ended up with just enough to make this ampoule. Sadly I tried to show this distilling method here, but my apparatus cracked from the heat, and I had to clean it all up before I actually got any bromine.. Maybe another day.

Once again I cannot possibly put enough emphasis on the fact that THIS STUFF IS DANGEROUS! Even with my ventilation I still managed to inhale a tiny bit, and it wasn't a nice experience. You can clearly see in the picture below that it is actively vaporizing into orange smoke just by stirring it lightly, that's how volatile it is. A friend of a friend supposedly inhaled quite a bit of this and his lungs shrunk in half perminently, which is a harsh medical condition to live with.

If you want to dispose of it, I'd suggest you water it down with something like a ten-to-one water-to-bromine ratio, then let it sit someplace outside to let what bromine there is evaporate for a day, then you can safely dump it, but still be careful. If you get it on your hands, wash them very thoroughly with more water then you normally would.