My attempt to prepare useful bismuth compounds from "pink bismuth" has yielded a fair volume of bismuth sulfate solution of unknown concentration, a small quantity of solid basic bismuth sulfate, an even smaller quantity of bismuth oxychloride, and this weird stuff:

I was hoping to get ammonium bismuth sulfate tetrahydrate, Bi(NH₄)(SO₄)₂·4H₂O, by dissolving bismuth carbonate in sulfamic acid with a little H₂SO₄ and heating in the double boiler. Ammonium bismuth sulfate should have formed well-defined crystals. Instead there appeared a large quantity of little glittering scales, like flakes of mica, while the solution became yellow and viscous. Whatever it is, it seems to be more soluble in cold water than in hot; a quantity of the solution, if evaporated until the micaceous flakes appear and then refrigerated, redissolves them. The solution also reacts with filter paper so, when I attempted to collect the substance, the liquid ate a hole in the paper on the first try. What you see here firmly glued itself to the paper as it dried and can't be collected.

I've searched for any description of a material like this and found nothing. Information on bismuth compounds in general, apart from the common ones, is unbelievably scanty. I'm tempted to investigate further but I'm getting way off the track. All I wanted to do at the start was prepare some bismuth sulfate for use in qualitative tests for Na and K, not get sidetracked by (literally) every bright, shiny object that comes my way.

I hate having to buy dry ice for an experiment because the smallest chunk I can get is about eight pounds and most goes to waste. I figured I'd try using it to cool my soda pop. It'll cool the whole liquid, I thought, because it'll sink, unlike ice which floats at the top and waters it down. Right? It actually doesn't work so hot. You have to wait for the violent bubbling to die down, and the heat transfer between a chunk of dry ice and the soda is actually quite poor, so it actually takes longer to cool the soda. The dry ice is blanketed by a layer of CO₂ gas that insulates it pretty well. Eventually, though, enough soda freezes around the dry ice that it starts acting like an ordinary ice cube with a core of carbon dioxide.

I'm going to try cooling cream with it, since I have some on hand. I've heard of instant ice cream with liquid nitrogen; could crushed dry ice do the same?

Incidentally, I got the stuff in hopes of purifying crude K₂CO₃ by gassing a concentrated solution of the "pearl ash" with CO₂, precipitating KHCO₃. Looking into the matter, I've found that preparing good quality potash has always been trickier than preparing good sodium carbonate. The Solvay soda process, that marvel of chemical engineering that made Na₂CO₃ one of the cheapest substances on earth, only works for potassium if you substitute horrible volatile amines like trimethylamine for the ammonia used for Solvay soda. Thumbs down.

I've been coming to depend on it as a kind of indelible notebook to keep track of the progress of my hobby projects. It's no substitute for a real lab notebook but at the very least I can write myself short notes to keep track of all the different things I'm doing at once. It just so happens that others can see the notebook too. Anyway, if you want to see what I've been doing, just go to https://twitter.com/monoceros4 and marvel. Or shudder.

I did remember to bring a camera to Anthrocon and even remembered to use it now and again. Too bad I didn't remember to use it for a group photo. Also, I remain shy about asking fursuiters to stop and pose. I know some of them just lap it up, but I don't like feeling like a pushy tourist.

Hardly any of my fursuit parade pictures came out. Flash photography seemed like a bad idea for a couple of reasons. First, in a situation where you're trying to take photos of something at medium distance amidst a crowd, using the flash often gets you brilliant illumination of your foreground, e.g. the backs of other watchers' heads, while the thing you want photographed is dark. Second, our camera is crummy and takes ten seconds at least to recharge between shots, during which time half the parade has gone by. So I tried taking all the parade pictures with the flash off, so almost all of them are ruined by motion blur. There were a few photographs better than the average, but nothing very good. Anyway, behind the link up above I've put up a Flickr gallery of twelve pictures from the parade. There were a lot of good suits on display, to be sure, and not just the usual tigers, wolves, and foxes.

I commissioned a lot of badges and one sketch this year. As I said in a previous post, I felt like I was making up for all the other times I'd chickened out on asking, or asked too late. I've put up some scans of the pieces--small and low-detailed enough, I hope, to be consistent with fair usage.

I got this from HollyAnn. Next time I think I'll ask for a sketch; what caught my notice about the work I'd seen online from her was more about theme than style, and needs a larger canvas than a con badge.


Kamilya Storme had at her table a couple examples of paired badges and I just had to get one. So here is me with my cute kitty. *melts*


I've already bought a few small pieces from Diana Harlan Stein and, while I'd never seen any drawing of hers with a horsie in it, I took the chance because I love her style. It's a beautiful bit of work.


I'd been neglecting the Artists' Alley by concentrating on the Dealers' Den list but after a few words with Misha I realized I should see what I could find. You see a lot of the same in the Artists' Alley, to be sure, but occasionally something unusual too. The work of Rukis Croax caught my eye and I asked for a commission and got a huge and beautiful badge that, frankly, makes me feel a bit unworthy. Damn...if only I looked that handsome in real life.


Finally I went to Caribou Ink for my first sketchbook sketch. I had been toying with the idea of asking for something, well, a bit beyond PG-rated, since I saw from her online work that she had considerable talent for drawing truly ahem stimulating drawings of that sort. But I couldn't go through it with such a request and ended up requesting something simpler and more wholesome. She told me later that she'd tried extra hard, seeing that it was to be the first sketch in the book. I love it.


On the last full day Misha, net-cat, Procyon and I went up the Monongahela Incline, a short cable car line that runs up the steep bluffs overlooking the Monongahela River south of downtown Pittsburgh. We'd seen it last year when we went to Station Square but this time we took the trip. We didn't spend a lot of time up there but enough to breathe in some fresh evening air and take in some beautiful views of the city and the river. Also there was a Catholic church not far from the cable car station, which I've since identified as the parish church of Saint Mary on the Mount. You know, every year at AC I wonder why I don't take the time to attend Mass; it's not like there's much to miss on Sunday mornings. I figure that everyone else would think I was weird or stuffy, so I never bring it up. It's not like I'm good at remembering to take communion under even in the most accommodating circumstances, anyway. I contented myself with writing my name and home town in the big visitors' book.

That's me and flying these days. I have in the past scoffed at those with unreasoning fear of airplanes; it's easy to quote probabilities to show their fears are overblown. But it's about more than probability when it comes down to it. The chance of dying in a motor accident may be greater but you have some illusory control over your fate. You tell yourself that, so long as you're careful and alert, you'll be on the winning side of chance. I've only been in one serious accident, and that was "serious" only in that it rendered my vehicle temporarily undrivable; there was no threat to life at any time. All the same, even as it was happening, I remember thinking that I probably could have avoided it, if only I'd been a little faster and a little smarter. If you're a passenger on a plane, though, speed and smarts are meaningless. It may not happen often, but when it does happen, all you can do is sit there and take it, knowing that you're probably going to die along with everyone else on board. I am ashamed to say after tonight that I'm not equipped to handle it. I've been on turbulent plane rides before but this one really unnerved me for some reason, and all I could do was grab Misha's hand and look to the good book for comfort, the book being Sir Edward Thorpe's Dictionary of Applied Chemistry. I suspect that Dr. Gregory House was right when he said that there is no death with dignity, but I suppose there are worse things to die with than simultaneous thoughts of one's true love and also the preparation and utility of K₂Mg(SO₄)₂·6H₂O. The Catholic is shakier than the chemist, unfortunately.

Eh, what can I say. It wasn't a pleasant flight from Charlotte, NC, back to Seattle, but I've had worse, aside from the attacks of timor mortis. The Eee was a lifesaver; its battery lasted almost the entire flight. I know now that, when it comes to keeping myself entertained on an airplane, nothing is more effective than a bunch of chemistry books. I may not be improving my mind with great works of fiction, like I've tried to do in the past on long flights, but at least I'm not checking my watch every ten minutes.

Another Anthrocon is over, leaving behind the usual feeling of deflation mixed with relief. As it happened, despite my earlier worries, I enjoyed myself for the most part, but I did have some bad passages. Worries about money and employment, troubling news from home, and a strong desire to resume my chemical hobbies--I spent many hours this AC struggling to read Chem Abstracts and Google Scholar using the hotel's semi-functional wireless portal--all coalesced on Sunday afternoon into an overpowering desire to get Anthrocon over as quickly as possible.

On the plus side, I got to meet sporty_fox again after a long hiatus for a little pleasant conversation. I also met for the first time one of my longest-running online furry friends, dixieland_doe, and her mate redneckfur. Our dinner together was a lot of fun and I'm sorry we couldn't spend more time together. Dixie, you're a real sweetie, I just want to say that, and a great friend. I also saw (albeit for a few moments) a couple furs I haven't seen in years.

On the other hand I managed once again not to run into a bunch of online acquaintances, including a good many on my LJ list and some folks I used to know from F*rtopia. I'm not sure what I should think about this. I like to think I'm amiable enough in person in small gatherings. However, in large parties, I often become the guy who sits in the corner with the book and only gets up to grab more food. Nothing makes me feel so isolated and desolate as a room crowded with strangers. I would have got nothing, therefore, out of going to some random room party in the hotel. Hence one avenue for meeting up with other furs is closed to me.

But there's something else that gets in the way, whenever I think of seeking folks out. I perceive, rightly or wrongly, that some of the furs I'm slightly familiar with online, and whom I sometimes think I ought to visit given the chance at AC, really...well...aren't exactly in the market for new friends. Cliques, once assembled, do not often leave space for more pieces. Also I sometimes get the feeling that strutting, rather than socializing, is the goal of some furs. It's an unpleasant reminder that fursuiting is sometimes less about the suit and more about the elaborate, excessively polished shtick that goes along with it; this has done a lot of damage to my modest interest in suiting. I'm not sure I ever will tackle a suit again. I have other hobbies, at least as time-consuming and more intellectually appealing, that I don't want to rob of time in order to work on a fursuit. And no one who knows me at all will expect me to be content with commissioning one.

But that's enough sour grapes from me. Er, for a few sentences anyway. I did the right thing this Anthrocon and did research on artists first, going through the list of Dealers' Den entries. I didn't get all the way through the list--I didn't get halfway through the list--but my incomplete research was nevertheless sufficient to get at least some of the commissions I wanted right off the bat, knowing ahead of time who could draw good horsies. Next time, though, I should pay more attention to the Artists' Alley. One of the best badges I got this year was from an artist there. I'll scan everything in when I get a chance, of course. I also got my first ever sketchbook commission; I was hoping for a second but didn't make it in time.

I bought no prints and bid on no artwork. That was the downside of aggressively seeking out badge and sketch commissions this year. I felt like I was making up for past indecision, but it also ran through the money I'd withdrawn and a little more besides. I also didn't buy the convention shirt. Last year I bought the shirt the Steel City Diner was selling, but this year their shirt was this weird shade of chartreuse with basically the same design. The sub sandwich shop next door, Fernando's, was selling a better, blue T-shirt and both Misha and I bought that as our quasi-con shirt.

We spent way too much money on food and drink. By accident we discovered a restaurant called Kaya selling "Island" cuisine. Misha, net-cat, and I ate there once then took Procyon, Dixie, and RedneckFur with us the second. Everything we ate was good but between the meals and the free-flowing alcohol the total expenditure ran into the hundreds. We also spent a fair amount at Buca di Beppo in Station Square and at the hotel bar. I learned that I should probably discard any mistaken notion that I can drink alcohol "safely", and I say that even though I had fewer drinks overall than Misha, who otherwise never drinks. We enjoyed sandwiches a couple of times at Fernando's and also ate a few meals at the Steel City Diner, as we usually do, but they disappointed us this year. The food just seemed blander and the service worse. Misha tells me he was served cold food, too. We also tried a place that sold acceptable, but uninspired, corned beef sandwiches; also I got into this strange argument with another conventioneer about Edsger Djikstra and how software engineering ought to be taught. He hated Djikstra's emphasis on the mathematical side of programming, which I told him was the only aspect of computer science that was worth teaching. The man who wants to jump straight to practicalities and has no patience for all that theoretical stuff is a third-rate intellect at best. The second-rate intellect, like mine (I hope), is weak on theory but knows he is weak. I concede that not everyone can master theory or can afford to take the time necessary to master it--I'll never be a proper electrical engineer, for example, even though I've learned a few commonsense tricks of circuit design--but one should recognize and accept that ignorance of theory is nothing but a flaw and a disability, albeit a disability that can usually be lived with. You shouldn't be proud of not knowing something, ever.

I was talking about Anthrocon, eh? I attended no panels this year and, for once, didn't feel too bad about that. I already know from previous years that the writing panels are skippable, and I've had some real instruction in creative writing since then, enough to get it out of my system, you could say. I know I'm not working on a fursuit any time soon, so I didn't worry about missing those. And since I don't play any of the games played at Anthrocon with the exception of "Rock Band", I lost nothing by missing those events. I screwed up taking pictures of the fursuit parade but I think I got in a few halfway decent ones. I went to see Uncle Kage, of course, although there was something half-finished about his stories this year (with one exception) and, I must confess, my mind was elsewhere anyway. I once again managed to miss 2's Rant. Part of me wants to give him a chance, but the other part says that the guy is a one-dimensional poseur and essentially a bore. I'll bet he likes Dan Savage. But I've only ever endured him for about a half-hour maybe.

I missed the 4th of July fireworks but you already know that. The four of us rode up the Monongahela Incline after our last meal together, and wandered about and admired the view. I stepped into a little Catholic parish church that was up there; I forget the name. Only the foyer was open so I signed my name in the book and left. We forgot to take a group picture after all that time.

Overall I probably got more out of this year's AC than in any previous visit, but as I said, I was really wanting it to be over by the end. It would be nice to be able to visit a convention one of these days in peace, without a thousand worries intervening and spoiling my enjoyment. All the same, I'm glad I went.

Why do I do this to myself? There is no safe way for me to drink. It's not a question of amount. The point is that drinking makes me feel good for about thirty minutes, maybe, and then I feel like crap and want to drink more because it's the quickest way to feel like something other than crap for a little while anyway. I've ruined the rest of my evening. There are fireworks and other furs to meet and everything and all I want to do is lie down and be depressed.

The subject of interest is the detection of sodium, potassium, magnesium, and calcium in the presence of one another. Ammonium too, possibly, but it's not difficult both to tell it apart from everything else and to remove it from everything else.

As I've mentioned before, I'm trying to prepare a pure set of representative compounds of the elements. In doing so, I want to test for purity, at least in a rough way. There are many preparations I've attempted in the past that would possibly have succeeded if I'd troubled to apply qualitative tests--at the very least, I might have known to abandon a bad procedure instead of blundering ahead and hoping it would all work out OK in the end. This is how, for example, I spent a day or two thinking that a deposit of salt crystals was actually a small yield of sebacic acid.

Any impurities in salts of Na, K, Mg, or Ca are most likely to be salts of one or more of the remaining metals in that set. They are often found together and sometimes crystallize together (e.g. MgCl₂ and KMgCl₃ along with KCl when obtaining potassium chloride from brines.) So a reliable set of tests for these metals is I think vital to this project.

It's Na and K that give the real trouble because, whereas many reagents give insoluble precipitates or characteristic colors with Mg and Ca (e.g. ammoniacal NaNH₄HPO₄ to ppt. Mg, ammonium oxalate for Ca), very few reagents give insoluble compounds of Na and K. There is the flame test, which I'm inclined to regard as useless for Na and of doubtful utility for K. With a proper flame photometer or spectrometer it would be different but I haven't got one of those.

The choices are better with potassium. Tests have been devised exploiting slightly soluble K salts of perchlorate, fluosilicate, bitartrate, hexanitritocobaltate(III), hexachloroplatinate(IV), trithiosulfatobismuthate(III), and others. Some of the reagents for these tests are probably accessible to me--I've embarked on another "pink bismuth" processing with this in mind--so I've more than one chance of success.

With sodium it's trickier. So far I've found evidence for only three salts of Na usable for a qualitative test, not one of them common: the dihydroxytartrate NaO(C=O)C(OH)₂C(OH)₂(C=O)ONa, the dihydrogen pyroantimonate Na₂H₂Sb₂O₇, and the mixed uranyl acetates of the form Na(M)(UO₂)₃(OAc)₉ where M is Mg or Zn or sometimes Co. The mixed uranyl acetate precipitation is by far the most highly recommended in the literature but it uses uranium for heaven's sake. Dihydroxytartaric acid is a chemical curiosity prepared in the 1890s by the noted organic chemist H. F. H. Fenton (he of "Fenton's reagent") from tartaric acid. Fenton had a hard time isolating dihydroxytartaric acid because it decomposes with extreme ease in solution, although it's stable when dry. I'm not confident that I could duplicate Fenton's synthesis. That leaves the pyroantimonate test, poorly documented. I have Sb₂O₃ to start with to make the necessary reagent K₂H₂Sb₂O₇ but no recipe as yet.

And, of course, I'd have to carry out extensive testing on controls before accepting any of these qualitative tests. Lots of work to be done.

No, I don't really think that Pittsburgh is a superior city to Rome, although the roads are better at least. But my first and only day in Rome, where I stopped for a day on my way to Naples in 1999, I mostly spent in the hotel room. The long flights had worn me out and I wasn't feeling adventurous. I did rouse myself in late afternoon to walk to St. Peter's but that was it.

Misha and I arrived for Anthrocon under somewhat similar circumstances, and we did in fact spend a good deal of the rest of the day in our hotel room. procyonid and thevirtualcat had yet to arrive. Misha and I did, however, have the initiative to make use of our temporary solitude. A couple uses, in fact.

The poor and unreliable Internet service is annoying me, and if I was having trouble yesterday, with the hotel largely empty, it's going to be useless when the rest of the conventioneers arrive. I spent a couple hours yesterday trying to find the web pages (DA, FA, VCL, wherever) for all the artists listed on the Dealers' Room list to get an idea of whom to approach for sketch or badge requests. I got maybe 10% through. It's not easy to look at a bunch of artwork when it's taking three weeks to load each image. Even so I'm already better prepared than last year or any year before.

Also didn't help that I was trying to read through Chem Abstracts and Google Scholar at the same time. I just don't give up.

I had set aside the first, not very large batch of sodium chlorate extracted from the saline residue from evaporating bleach. I got a small crop of colorless crystals from it, which I collected, washed, and dried. I just tested a small crystal, dissolving it in water and adding silver nitrate. No precipitate! Not even any convincing turbidity to be seen with sidewise light in a dark room (a time-honored way to detect a very small quantity of suspended particles in a liquid that looks clear.) Somehow I'd actually prepared NaClO₃ free from chloride, which I thought would require more work. To confirm chlorate I added a little solid sodium metabisulfite. Now you get the white AgCl precipitate from reduction of ClO₃^-.

There is more work, though, because so far I've only gotten a few grams of NaClO₃ out of the fifty or sixty that should be found in the bleach evaporite. I extracted the hell out of the residue, at least eight or nine times, with boiling water, collecting the extracts and evaporating as I did yesterday. And the remaining solid still tests positive for chlorate! An obvious positive, too, with plain separation of I₂ in the potassium iodide test and not just a faint tinge. Time for Plan B, extraction with alcohol, which I've been trying to avoid. Denatured alcohol isn't all that cheap these days. Isopropyl alcohol has too strong a tendency to form immiscible layers with concentrated solutions of inorganic salts.

One last note: sodium chlorate must have a higher than usual index of refraction. The crystals sparkle like little diamonds in the light.

Some months back I discovered that the local department store was stocking a new solvent. They called it "green all-purpose solvent" or something of the sort, but the ingredient on the label says it's ethyl lactate. I'd heard of the stuff before and, while it was a bit costly ($10 for a quart) I bought a tin of the stuff.

So far I haven't really done much with it aside from trying it out for cleaning a beaker encrusted with beeswax-rosin mixture. It did a fairly good job after a long soak, although whether it worked any better than (say) xylene, I can't say. One feature of ethyl lactate that's both a plus and a minus is that it's miscible with water and therefore easy to clean up, but it gradually hydrolyzes to ethyl alcohol and lactic acid, so you can't make stable aqueous dilutions. But its ease of hydrolysis also means that another potentially useful organic compound is now open to me, lactic acid, which has a few uses to recommend it.

I have tried to find definite information on ethyl lactate's behavior as a solvent. After all, if it's being touted as a replacement for more conventional, well-characterized organic solvents, surely there must be some available research into what ethyl lactate can dissolve, what solutes are incompatible with it, and so forth. From what I can tell, there's almost nothing. I can't believe that a chemical that's been commended in every book on "green chemistry" that I've looked at is so poorly documented.

It got me to thinking I could actually contribute something here and compile some solubility data. This is not an easy job, though, to do correctly. You need an accurately controlled heating bath or oven, and also lots of time: merely throwing some KCl (say) into the liquid and weighing the residue after stirring for an hour is not good enough because it often takes many hours and even days for equilibrium to be reached. Atherton Seidell's mammoth Solubilities of Inorganic and Organic Compounds, which I consult frequency, cites sources for all the numbers and sometimes give details of the procedures used. There's one determination where the mixtures were given forty days to equilibrate.

A project for some other time. Even rough figures would be better than nothing.

I've broken five piece of glassware in the last week. None of it was that valuable; the collective cost is probably about $20. Still, it's a sign that I am being too hasty and as a result too careless and clumsy. One of these days if I don't train myself to be methodical it's not going to a $5 Erlenmeyer flask in my kitchen but a $500 ground glass 3-necked distillation flask in a full-scale lab.

Results of it all? Well, so-so.

Na₂SO₄·10H₂O - made from "safe pickle" (sodium bisulfate) and baking soda, then twice crystallized and set aside for now. In the long run I don't want to store sodium sulfate as the decahydrate, which effloresces in about fifteen seconds after opening the bottle. I need to work out a good way to turn it into the monohydrate.

NaO(C=O)CH₃·3H₂O - made from glacial acetic acid and baking soda, then once recrystallized. It's on its second recrystallization now, but refusing actually to crystallize even after hours of refrigeration and attempts to seed the solution. The stuff is temperamental and loves to turn from a solution to a solid mass in seconds.

NaCl - I made one try at purifying good old canning salt (the only variety I found that didn't list any other ingredient but salt on the box) by crystallization from hot aqueous isopropyl alcohol. NaCl's not much more soluble in boiling water than in cold, but after looking at a bunch of solubility data I thought I could get a better yield using an alcohol. The amount that separated, though, was still quite small. The books recommend purification by gassing a saturated salt solution with hydrogen chloride gas, which I am not going to try.

NaClO₃ - the plan was to boil an entire bottle of chlorine bleach to dryness, decomposing the hypochlorite to chloride and chlorate, then extracting the residue with boiling water, which preferentially dissolves the NaClO₃ or so I hoped. The evaporation went well, if slowly, and I got about 350 g of mixed salts. But multiple extractions with boiling water, with plenty of time given for each portion of water to do its work, was far from complete. I made use of two quick tests for chlorate. In one, a small sample is acidified and then treated with a drop of potassium iodide; chlorate if present oxidizes the KI to iodine, detectable with a little soluble starch (turns blue) or by shaking with a drop of toluene (the toluene turns red.) In the other, an acidified sample is treated with just enough indigo carmine to turn it blue, then a grain of sodium metabisulfite added; chlorate if present is hence reduced to hypochlorite or chlorine, which destroys the blue color. Anyway, the residue from the boiling water extractions still gave a strong positive test for chlorate, meaning the hot water didn't do its job. My only consolation was that the combined extracts, when boiled down a bit and then filtered, left a copious white solid on the filter that gave only a weak positive test, showing that it was mostly NaCl. The filtrate deposited a modest amount of NaClO₃ cubes. Maybe, then, if I carry out the boiling water extraction many many times, I'll eventually get most of the NaClO₃, but there must be a better way.

Na₂CO₃·10H₂O - once recrystallized from Arm & Hammer washing soda and awaiting a second crystallization in the fridge. It, too, is refusing to form crystals. As with the sodium sulfate, I intend to convert the sodium carbonate to the monohydrate, which is more stable during storage. A portion of this carbonate, more thoroughly purified, may go to making high-quality NaCl. Out of the box the washing soda gives a weak positive test for chloride (cloudiness on acidifying a sample and adding silver nitrate) but negative for sulfate (no reaction with barium chloride.) So the stuff isn't too bad to start with.

For a couple of years I've kept two sets of instant messenging accounts, "monoceroset" and "mono31416". I had some ill-formed idea that I should have a "furry" and "non-furry" set of contacts. That idea went by the boards pretty quickly and I ended up adding new buddies to one account or the other or both almost at random.

Anyway, I'm killing "mono31416". The accounts will still exist--it's a pain in the ass to try to cancel one--but I've deleted all buddies from it and will never log on to them again. For what it's worth.

Since I probably offended or at least nettled more than one of my LJ correspondents with my flippant post yesterday about asexuality, permit me to apologize to all of you at once. It was wrong of me to imply that all persons who identify themselves as asexual are deceiving themselves somehow. My use of "valid orientation" also was thoughtless. It would have been more accurate to say "innate" or "inborn". It is, after all, widely accepted (certainly not by all) that homosexuality, for example, is at least partly a behavior one is born with and not merely a conscious choice of lifestyle. But these are complicated matters, too complicated for me to imply that there's an absolute division betwen "innate" and "willful". At any rate, I'm very sorry.

Is "asexual" a valid sexual orientation? I just came across a comment from some random Internet denizen that he or she was "Asexual" (with that upper case). I find it hard to believe that "I am asexual" means anything but "I am trying very hard to convince myself that I'm not really just too scared to ask anyone out."

I have a lot of goofy ideas that never make it past the "thought experiment" stage. The great thing about a thought experiment is that it always looks feasible and inventive, and gets good results. Coming up with a clever "thought experiment" to solve a problem makes me feel smart. Actually carrying out the experiment makes me feel like an idiot.

The problem I set myself yesterday was, how do I purify "muriatic acid"? This is a form of hydrochloric acid still available in hardware stores, with a density of 20 °Be and concentration about 10.0 mol/L. It's very useful stuff, not quite "concentrated" HCl (which is 38% acid), but rather uncertain in quality. In particular, the muriatic acid often has a yellow tinge. I used to assume that this was contamination with ferric iron, because iron is common and in HCl solutions forms a bright yellow complex ion, FeCl₄^-. But nothing I've seen supports the hypothesis. Zinc dissolved in the acid and treated with sodium carbonate throws down a pure white precipitate; if iron were present it would be brown. Salicylic acid in solution acidified with the muriatic acid remains colorless; even very dilute Fe³⁺ solutions are colored purple by salicylic acid. So I have no clue what the yellow color might be now.

The most direct way of purifying hydrochloric acid is by distillation, but I haven't the equipment for even the simplest distillation. Even if I did I'd be afraid of trying--I don't want to risk breathing in a lungful of boiling HCl vapor. There was, I thought, an easier way: freezing the acid. The freezing point of hydrochloric acid solutions drops dramatically with increasing concentration until, at about 25%, it freezes at -85 °C. After that, however, it starts rising again, attaining a maximum of -24.4 °C for 40% acid, corresponding to a trihydrate HCl·3H₂O. So, I hypothesized, if you placed a quantity of muriatic acid in a dry ice bath at temperature -78 °C, the trihydrate would begin to freeze out until the remaining liquid became too dilute to freeze any further, at maybe 25% as estimated by the graph I've shown (from J. Wm. Mellor's Modern Inorganic Chemistry.) I could either throw out this weaker, less pure acid or (better) save it for uses not requiring high quality, and collect the crystals of HCl·3H₂O, diluting them with a little water to obtain the conventional 38% or 12M hydrochloric acid.

That was the thought experiment. Yesterday I tried it out with 200 mL of muriatic acid and a bath of dry ice in 99% isopropyl alcohol. The local market sells dry ice for $0.99 a pound, but you need to buy whole blocks, about 8 lbs. I actually figured at the start that this much dry ice would suffice for many freezing experiments. No such luck. Even after six hours of freezing, with constant replenishment of the dry ice, the most I got was a thin, almost milky suspension of minute crystals that would probably have gone right through a filter. I had been expecting large crystals, like when ice begins to form, and of course I expected more of them. After six hours I flushed the acid, dumped the alcohol and let the rest of the ice evaporate in the sink, thoroughly disgusted. I should have tried just a little bit in a test tube first.

The only other idea I have for purifying the muriatic acid involves running it through ion exchange packings, but I haven't worked that out yet. That stuff is expensive, too. :(

Many years ago Hugh Grant had a career, and one of his outings was a sweet little nothing of a movie from many years ago, The Englishman Who Went Up a Hill and Came Down a Mountain. Hugh plays a surveyor for Her Majesty's Ordnance Survey Office who comes to a small Welsh town to determine the height of the local peaks. He does so, makes his initial triangulation, and determines that the nearby "first mountain in Wales", Ffynnon Garw, is a few feet short of the official 1,000 feet needed to be a legitimate Mountain. The surveyor explains to incensed townsfolk that the first measurement is only a preliminary figure, needing later adjustment to make it definitive. A local man is unimpressed. The following exchange takes place:

"And how d'you know later?"
"Well, we've made, um, we've made measurements with those two hills, and we already know the height of Newton Beacon and Whitchurch Hill..."
"But how were they measured?"
"The same way, by comparing them with other hills."
"But who measured the first hill?"

The surveyor is at a loss, but near at hand is the pastor of the town church, who has a superbly laconic answer. "God, my boy," he whispers. "God."

You'll see why I bring up is in a few paragraphs. Same thing with the pretty picture of fire.

In my last post I described how, in order to conduct experiments in analytical chemistry with a complete set of tools, I needed to prepare representative compounds, in acceptable purity, of all the elements or ions that I would to test for or determine. It's a big job but I've made a small start. I've prepared a quantity of Glauber's salt, sodium sulfate decahydrate, Na₂SO₄·10H₂O, from Sparex, a form of sodium bisulfate sold for removing scale and oxidation from metals. The Glauber's salt still needs a bit of cleaning up and probably conversion to anhydrous Na₂SO₄, which has better shelf life. I've also been experimenting with ways to recrystallize sodium chloride that have been disappointing so far.

There are a number of ways of purifying a chemical compounds, although only the easiest ones are open to me. A browse through W. L. F. Armarego's textbook Purification of Laboratory Chemicals will turn up some intimidating schemes with multiple steps and using noxious reagents to clean up one compound. Ordinary water-soluble metal salts, though, can often be purified by the simple job of dissolving as much of it as possible in water or some other solvent, cooling or heating or evaporating as necessary to reduce the solubility of the compound, and waiting for the excess to form crystals. Collect the crystals and you have a purer version of your original salt. The method works because the desired salt has exceeded its maximum solubility but the smaller quantities of impurities haven't--ideally. Also the crystal as it forms tends to exclude substances that don't fit well into the existing lattice, but the substance you want crystallizes with ease. There are many, many departures from this ideal behavior that make purifying by recrystallizing difficult or impossible for a lot of things, but it works often enough to make it the first line of attack before I start resorting to tricks like solvent extraction and chemical separation.
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Maybe you've occasionally heard about people making real-life periodic tables with real samples of as many elements as possible, placed in neat little boxes arranged in periodic-table fashion. It's a nifty little project, to be sure, and something I wanted to do myself once. Like this:

No Effort Required


But...eh, that's kid stuff. Anyone can buy little samples of elements from an online catalogue. Collecting (say) mineral samples for each element is more impressive, but still you're basically just buying things. Unless there is some intrepid rockhound out there trying to collect all of his ore samples by hand. If I ever run into that rockhound, I'm going to buy him a drink, or more than one.

I'm going to do these guys several dozen better. I've decided that I should prepare at least two compounds of every element on the periodic table that I'm not afraid of. I have a reason for this, though, other than the novelty of amassing such a collection.

To start with: I've made a number of little attempts at kitchen-sink analytical chemistry over the years, some of which I've described here. A lot of it has been fruitless, some of it has been fun, and perhaps two or three percent of it has been, I daresay, rather impressive. Getting a max. 1% error on a gravimetric determination of magnesium using mostly stuff I got at the supermarket--I'm kind of proud of that one.

Going through Identification of Materials over the last few days, though, has reminded me of something that's been on my mind. I've been attacking this or that problem as fancy took me. Maybe one day I'd think of trying out some KMnO₄ titrations. That would necessitate a lengthy preparation of reagents and compounds that I usually didn't have on hand. That would often be so frustrating a process in itself that I'd never actually get to titrating anything useful before moving on to something else. Then I'd end up moving on to something totally unrelated, like trying to make chloranil or whatever.

This dilettantism has led me down some intriguing alleys. Unfruitful searches for better compounds for standardizing HCl solutions did lead me to prepare the novel compound potassium pentaborate tetrahydrate, KB₅O₈·4H₂O, which I hadn't even known existed before starting. Failed attempts to grow large crystals of potassium chloride for messing about with infrared optics did at least mean that I had a decent supply of fairly pure KCl for other needs, and the knowhow to make more from unbelievably dirty garden-store "muriate of potash". So my playing-around hasn't been fruitless. But my disorganized approach has contributed to a fearful clutter both of goals and of supplies and equipment that's become a serious obstacle to progress. Equipment gets jumbled because I'm using it almost out of whim, my supply of chemicals has grown into an unwieldy collection of things made offhand and then often poorly stored and forgotten, and the state of my record-keeping is a disgrace.

I must step back and form more general and unified plans. What's my overall goal? Probably nine-tenths or more of my hobby projects, both what I've done and what I've only dreamed about, pertains to chemical analysis at least indirectly. Doing experiments in analysis demands a basic toolkit, a particular set of equipment, reagents and other chemicals, and structured approach. A lot of textbooks on (say) qualitative analysis of the common ions actually provide comprehensive lists of everything that will be needed for all experiments in the book. I haven't got that on hand, just a miscellaneous jumble. Even with my spastic dabbling in electronics I've exercised better judgment: while I do have a lot of crap in my tool boxes that I got on impulse somewhere, I did take care at the very start to assemble a basic collection of all the vital components--resistors and capacitors in a wide range of values, a minimum selection of general purpose semiconductors and ICs, and so forth. Aside from being utilitarian, that basic toolkit has forced some organization on the rest of my collection of haphazardly acquired parts because they already had a place to go--usually. I might grab a fistful of PNP transistors on a whim from some surplus shop, but they'd get filed neatly with the other transistors. That never happened with my chemical supplies.

So it's time to make it happen, drop all entertaining digressions, and start building that toolkit, and one of the most vital parts is a set of standard "unknowns". Basically, you need to have on hand at least one representative compound of every species you want to test for, so you can test the tests. That means needing at least one compound of every element on the periodic table. At minimum.

Complicating the task is that not every compound is suitable. Ideally, you want something that's a "primary standard"--that is, whose exact composition and purity can be trusted and which "keeps". You also want a compound which isn't going to be incompatible with compounds of other elements in some way. Sulfates are incompatible with barium and lead, for example, and chlorides are incompatible with silver. Tartrate and citrate interfere with analytical reactions of many elements, which is a shame, because some heavy metals form tartrates or citrates that are easy to prepare and keep, like the "tartar emetic" salt of antimony.

Another attractive aspect of this mammoth project is that certain other experiments that I've been wanting to play with arise naturally from its needs. The purity of the standard "unknowns" needs to be tested, even if only roughly and qualitatively. For some things it's easy; traces of iron, say, or of chloride are detectable with very simple tests. For other things it'll be a healthy challenge. How do you detect a little sodium in the presence of a lot of potassium? The process of working these things out will be a bit digressive, perhaps, but it will provide a degree of self-correction.

I estimate that about half the periodic table is immediately open to me. Another 10-20% will probably need to bought online in some fashion. Certain elements are probably permanently closed to me, and not just the radioactive ones. I'm not sure I want to mess with thallium, for example. First up: lithium, sodium, and potassium salts. Might as well start small.

Last night I completed the long time of transcribing and condensing material from an old book that I need to return to the University of Washington within a day or two. I suppose I could have photocopied it, but at considerable cost, and in any case I wanted a searchable document. I've never tried scanning and OCR but I'll bet it would have taken me at least as long to get it working as it did for me to type it up by hand, especially because of the huge number of chemical terms and symbols that the OCR software would gag on. Even Word gagged on them: I was finishing the last page when Word flashed the alert that there were too many spelling errors for the program to underline them all with the customary red squiggle.

What book was it? When I was a teenager I found it in the main San Diego public library that would change my life--really. It was an old chemistry book, A. A. Benedetti-Pichler's Identification of Materials via Physical Properties, Chemical Tests, and Microscopy. This text covers an area of chemistry that surely must be as dead as stone now, the determination of the chemical composition of substances by "wet" chemical methods, as opposed to instrumental methods using spectroscopy and chromatography and so forth. Benedetti-Pichler's book was especially devoted to methods requiring minute, even microscopic quantities of material. The contemporary chemistry student might still be taught a few aspects of "semimicro" qualitative analysis using reactions that can be carried out in test tubes. Identification of Materials covers techniques that can be performed on microscope slides, capillary tubes, and single fibers using quantities a thousandfold smaller than needed when working in test tubes.

A lot of the book was over my head (it didn't help that some pages had been cut out for who knows what reason) but it captivated me and I checked the book out multiple times even though there was no way I could actually do any of the things it described. I doubt whether I could explain the fascination with minutiae of chemical practice that must seem strange and boring to the uninitiate, with centrifuging sealed capillary tubes and watching for color changes on spot plates and examining the growth of crystals on microscope slides. Years later I read a passage from Graham Greene's The Power and the Glory about a minor character, a dentist named Tench, who breathed the same spirit:

Mr. Tench’s father had been a dentist too--his first memory was finding a discarded cast in a wastepaper basket--the rough toothless gaping mouth of clay, like something dug up in Dorset--Neanderthal or Pithecanthropus. It had been his favorite toy: they tried to tempt him with Meccano, but fate had struck. There is always one moment in childhood when the door opens and lets the future in.

Anyway I got older and a lot of other stuff happened and I almost forgot about the book. Every now and again I'd remember some little bit of it fondly and wished I could get hold of the book again but by this time I'd forgotten its name and its author. When Google Books got rolling I had a little hope of turning it up because I had some vague notion it was really old; I had rediscovered through Google Books another book from my adolescence, the decrepit but engrossing Chemistry: General, Medical, and Pharmaceutical of John Attfield (1879!) But, although Google Books does have some other textbooks on chemical microanalysis, none of them was what I wanted.

Google Books did come through for me in the end. A couple of months ago, while killing time in the UW chemistry library, it occurred to me that the library might have the book, if only I knew how to find it. I browsed likely sections of the collection but without success. Then I tried Google Books again with the sudden insight that the book might not be that old--it might not be readable online but it could still be indexed. I did find it by remembering that there was a test for bismuth making use of a sky-blue luminescence when heated with lime. (Yes, I did remember that after more than fifteen years.) To my delight, UW carried the title, although for some reason it wasn't shelved in the chemistry library.

As I've said, the modern chemical laboratory has little need for the techniques of Identification of Materials. Instrumental methods exist now that can quantitatively identify most elements in samples less than a micrometer across. They might be fun to play with on my own, though--a challenge.

4.0 in Chem 429 (chemical separations), 4.0 in Chem 520 (current problems in analytical chemistry), 3.4 in Chem 455 (quantum chemistry, the subject that gave me so much trouble.) 3.80 GPA overall. Not bad for someone whose Caltech sophomore year GPA was about 1.5, eh?

It's a bit of balm to soothe the pain of losing my job, anyway.