WEBVTT 00:02.610 --> 00:05.790 Prof: So we know something about all these 00:05.790 --> 00:09.500 powerful tools that had been developed: quantum mechanics 00:09.501 --> 00:12.961 around 1925, '26 actually; and then all these much more 00:12.961 --> 00:14.961 modern things, including scanning probe 00:14.958 --> 00:17.268 microscopy, which is really quite recent. 00:17.270 --> 00:21.760 But the most powerful tool in organic chemistry, 00:21.760 --> 00:25.180 for everyday practice, and certainly for anybody who's 00:25.180 --> 00:29.180 not a professional chemist and into quantum mechanics and stuff 00:29.181 --> 00:32.461 like that, is bonds; this amazing invention of 00:32.463 --> 00:36.693 bonds, and how people knew what things were like before any of 00:36.694 --> 00:38.574 these tools were dreamt of. 00:38.566 --> 00:39.256 Right? 00:39.260 --> 00:42.580 And, for that, we go back in time and look at 00:42.575 --> 00:46.715 these guys in the nineteenth century who invented it. 00:46.720 --> 00:51.580 And we begin with what's called -- whoops -- we begin with -- 00:51.580 --> 00:56.280 sorry, here we go again -- okay, we begin with the Chemical 00:56.278 --> 00:57.168 Revolution. 00:57.169 --> 00:58.059 Right? 00:58.060 --> 01:01.980 That's a name that historians of science have given this 01:01.976 --> 01:04.466 period, beginning with Lavoisier. 01:04.468 --> 01:06.808 So really that's where we'll start. 01:06.810 --> 01:10.540 But he didn't just spring from nowhere. 01:10.540 --> 01:13.220 There was a long tradition of some kinds of chemistry before 01:13.224 --> 01:15.824 that, and we're going to just review that very briefly. 01:15.819 --> 01:21.049 There's a background in ancient art and lore. 01:21.049 --> 01:21.819 Okay? 01:21.819 --> 01:24.469 So, for example, here's a mosaic from Montreale, 01:24.470 --> 01:30.330 in Sicily, of Noah, as making wine and then falling 01:30.331 --> 01:36.781 victim to it and having his shame hidden by his sons. 01:36.780 --> 01:37.570 Okay? 01:37.569 --> 01:39.459 And here's his flask, right? 01:39.459 --> 01:41.109 Student: Oh no. 01:41.110 --> 01:44.900 Prof: This is like 3000 years ago. 01:44.900 --> 01:49.180 The mosaic is about 1000 years; it's twelfth century, 01:49.175 --> 01:51.495 it's 800 or 900 hundred years old. 01:51.500 --> 01:52.190 Okay? 01:52.190 --> 01:58.220 Here is a Roman glass perfume vial, that's 2000 years old. 01:58.220 --> 02:01.960 So they made perfume, obviously, and extracted the 02:01.956 --> 02:05.996 stuff from flowers and whatever that would do that. 02:06.000 --> 02:07.310 Okay? 02:07.310 --> 02:11.590 There's the Chemical Research Building when it was five days 02:11.593 --> 02:12.033 old. 02:12.030 --> 02:12.760 Okay? 02:12.758 --> 02:15.058 And we already saw Francis Bacon who said: 02:15.061 --> 02:18.431 "All the philosophy of nature which is now received, 02:18.430 --> 02:20.380 is either the philosophy of the Grecians, 02:20.379 --> 02:22.169 or that of the alchemists." 02:22.169 --> 02:24.839 So the alchemists are in a sense our ancestors. 02:24.840 --> 02:27.990 He didn't have a very high opinion of them. 02:27.990 --> 02:30.820 He said: "The one is gathered out of a few vulgar 02:30.824 --> 02:33.444 observations" (that's the Greek philosophers) 02:33.443 --> 02:36.763 "and the other out of a few experiments of a furnace. 02:36.758 --> 02:39.598 The one never faileth to multiply words, 02:39.597 --> 02:43.377 and the other ever faileth to multiply gold." 02:43.378 --> 02:46.728 So even at this time, when science was beginning to 02:46.732 --> 02:48.612 get underway, modern science, 02:48.609 --> 02:51.089 alchemy was already in disrepute. 02:51.090 --> 02:53.690 But it did contribute some things. 02:53.690 --> 02:57.730 It didn't contribute much to theory, because the theory 02:57.728 --> 03:01.238 depended on Greek, well on the Greek antecedents 03:01.242 --> 03:04.462 and authority, rather than observation. 03:04.460 --> 03:06.650 But they did fiddle around. 03:06.650 --> 03:11.120 Here's a painting of an alchemist from 1663. 03:11.120 --> 03:15.090 And remember, Newton did more work in alchemy 03:15.085 --> 03:17.155 than he did in physics. 03:17.157 --> 03:17.967 Right? 03:17.970 --> 03:21.100 And he wrote an enormous amount but never published anything 03:21.104 --> 03:21.694 about it. 03:21.688 --> 03:25.348 There's a great website now, from the University of Indiana, 03:25.352 --> 03:29.142 of all Newton's alchemical works, and you can look at them. 03:29.139 --> 03:32.119 But this was to be kept a secret. 03:32.120 --> 03:37.520 That was the idea of alchemy, that it was occult, 03:37.520 --> 03:39.320 it was hidden. 03:39.319 --> 03:39.999 Okay? 03:40.000 --> 03:43.460 And in fact there's a show that's coming up on alchemy at 03:43.458 --> 03:47.758 the Beinecke Library, in January, of their holdings 03:47.764 --> 03:50.804 in alchemy, and the title of the show is 03:50.804 --> 03:52.834 "The Book of Secrets." 03:52.831 --> 03:53.341 Right? 03:53.340 --> 03:55.750 And that's Harry Potter as well, right? 03:55.750 --> 03:56.660 > 03:56.660 --> 03:58.850 So here's one of the things that's going to be shown. 03:58.848 --> 04:02.728 It's part of a really long scroll, which is the Visio 04:02.729 --> 04:05.409 Mystica of Arnold of Villanova, 04:05.408 --> 04:10.058 who was a thirteenth century alchemist who was into medicine 04:10.057 --> 04:15.097 and was considered the greatest medical authority of its time. 04:15.098 --> 04:18.208 This particular scroll was written in England in 1570. 04:18.209 --> 04:20.259 So a lot of it's in English. 04:20.259 --> 04:24.979 It says, "the red sea, the red lune , 04:24.983 --> 04:27.173 the red sol ." 04:27.173 --> 04:28.213 Right? 04:28.209 --> 04:30.469 All sorts of mystical things. 04:30.470 --> 04:35.190 And then, and you see here is the corpus, the body, 04:35.192 --> 04:39.032 which is earth; and here's the soul, 04:39.029 --> 04:42.669 which is oil; and here's the spirit or the 04:42.668 --> 04:45.118 air, the breath, which is water. 04:45.120 --> 04:48.200 So there was -- everything was a symbol for something else. 04:48.199 --> 04:52.499 Or if you look at the four corners of this, 04:52.495 --> 04:55.665 on the bottom right we have air. 04:55.666 --> 04:56.686 Right? 04:56.690 --> 04:58.630 "Eeyre", it says, "is hott and 04:58.632 --> 04:59.252 moyst." 04:59.250 --> 04:59.870 Right? 04:59.870 --> 05:04.240 Or on the top left is earth, which is cold and dry; 05:04.240 --> 05:05.960 the opposite of air. 05:05.959 --> 05:11.409 And down here is fire, which is hot and dry. 05:11.410 --> 05:17.660 And up there is water, which is cold and moist. 05:17.661 --> 05:18.751 Right? 05:18.750 --> 05:22.830 So this was supposed to be something profound and 05:22.826 --> 05:23.926 mysterious. 05:23.930 --> 05:25.990 Another thing they're going to show is this book, 05:25.990 --> 05:28.310 On the Philosopher's Stone, which was written in 05:28.310 --> 05:29.470 the thirteenth century. 05:29.470 --> 05:32.460 The particular copy they have is from 1571. 05:32.459 --> 05:35.249 But it looks like somebody's organic chemistry text, 05:35.254 --> 05:38.494 after they've highlighted it in preparation for the exam. 05:38.490 --> 05:40.140 Every word is underlined. 05:40.139 --> 05:41.049 > 05:41.050 --> 05:41.480 Right? 05:41.480 --> 05:45.290 And all in the margin are these fingers pointing to important 05:45.285 --> 05:45.725 things. 05:45.728 --> 05:46.298 Right? 05:46.300 --> 05:49.880 And if you look there, you'll see great words like 05:49.879 --> 05:53.239 alchemy there, you see elixir. 05:53.240 --> 05:56.770 I forget, there are a lot of key words. 05:56.769 --> 06:00.529 But fundamentally it's all nonsense, all the theory. 06:00.528 --> 06:03.268 The reason people kept it secret, really, 06:03.267 --> 06:06.137 was, I think, not to keep other people from 06:06.144 --> 06:09.094 finding it out, but to hide the fact that it 06:09.088 --> 06:10.388 was nonsense. 06:10.389 --> 06:13.619 That's just my own theory, so maybe that's wrong. 06:13.620 --> 06:17.230 Okay, but Paracelsus, in the early 1500s, 06:17.230 --> 06:20.490 was an alchemist, a traveling physician, 06:20.490 --> 06:25.030 and he developed what had been long before that, 06:25.028 --> 06:27.498 which was the Doctrine of Sympathies, 06:27.500 --> 06:30.490 and one aspect of that was in nature, 06:30.490 --> 06:35.810 antidotes for poisons are to be found near the source of the 06:35.807 --> 06:36.527 illness. 06:36.528 --> 06:37.338 Right? 06:37.339 --> 06:40.019 So, for example, you know what that is? 06:40.019 --> 06:43.619 Student: Poison ivy. 06:43.620 --> 06:45.660 Prof: Poison ivy. Right? 06:45.660 --> 06:50.070 But near poison ivy you're likely to find jewelweed, 06:50.069 --> 06:53.099 which is an antidote for poison ivy. 06:53.095 --> 06:53.955 Right? 06:53.959 --> 06:57.949 Or -- poison ivy is a New World thing, so that didn't interest 06:57.952 --> 07:01.032 the alchemists -- but this one certainly did. 07:01.028 --> 07:05.068 Willow -- Salix is the Latin name for willow -- which is 07:05.067 --> 07:07.047 found in malarial swamps. 07:07.050 --> 07:09.530 So you go into a swamp, you get malaria, 07:09.528 --> 07:11.878 but you also find the willow there. 07:11.879 --> 07:15.249 And the willow bark, extracting from the willow bark 07:15.249 --> 07:17.359 you can get Salicin, a glycoside, 07:17.363 --> 07:20.343 which is a sugar plus an aromatic thing there. 07:20.336 --> 07:21.126 Right? 07:21.129 --> 07:25.939 And if you hydrolyze that to get the sugar off, 07:25.935 --> 07:30.315 and oxidize that to make a carboxylic acid, 07:30.322 --> 07:32.102 you get this. 07:32.100 --> 07:33.440 What's that? 07:33.440 --> 07:34.250 Students: Salicylic acid. 07:34.250 --> 07:34.940 Prof: Right. 07:34.940 --> 07:37.350 Salicylic acid, from alix. 07:37.348 --> 07:38.118 Right? 07:38.120 --> 07:41.210 So it's good for fevers and so on, for your malaria. 07:41.209 --> 07:44.079 Okay, so that's a theory. 07:44.079 --> 07:45.609 This is another thing they're going to show, 07:45.610 --> 07:47.440 a Vade Mecum -- come along with me -- 07:47.440 --> 07:51.530 which is a lab manual that was kept by Caspar Harttung vom 07:51.526 --> 07:54.196 Hoff, in 1557, in Austria. 07:54.199 --> 07:56.799 So you can see he draws various -- what he's, 07:56.800 --> 08:00.230 he's reading various things, and writing extracts and notes 08:00.230 --> 08:01.650 to himself about it. 08:01.649 --> 08:04.009 It's like your pre-lab preparation. 08:04.012 --> 08:04.572 Right? 08:04.569 --> 08:10.679 Okay, and you notice who he's quoting up here? 08:10.680 --> 08:13.660 Arnold, that guy from the thirteenth century who did the 08:13.658 --> 08:15.008 thing we've showed first. 08:15.012 --> 08:15.502 Right? 08:15.500 --> 08:17.740 Arnold of Villanova. 08:17.740 --> 08:20.740 Okay, but he shows distillation apparatus. 08:20.740 --> 08:23.070 These things are called pelicans. 08:23.069 --> 08:24.429 Isn't that interesting? 08:24.430 --> 08:27.380 And here's a lamp. 08:27.379 --> 08:30.109 And here's somebody, he's filtering something 08:30.105 --> 08:32.825 through some kind of screen or grid there. 08:32.830 --> 08:33.490 Okay? 08:33.490 --> 08:39.450 So they developed tools that were of great use to chemistry, 08:39.451 --> 08:42.181 once chemistry got going. 08:42.178 --> 08:45.298 So there was a lot of -- even though the theory was nonsense 08:45.303 --> 08:48.593 -- there was a lot of practical background in preparing various 08:48.585 --> 08:49.745 elixirs and so on. 08:49.750 --> 08:51.440 So this was crucial. 08:51.440 --> 08:55.610 Now here is a lab that could easily be mistaken for an 08:55.610 --> 08:59.310 alchemical laboratory, but in fact it's an early 08:59.309 --> 09:01.199 chemical laboratory. 09:01.200 --> 09:02.990 And I'll show it to you here. 09:02.990 --> 09:08.440 It's this book, it's this picture here from 09:08.440 --> 09:14.410 1777, from a book about Air and Fire. 09:14.408 --> 09:18.128 And it reports the discovery of a new element, 09:18.129 --> 09:19.369 in this book. 09:19.370 --> 09:27.600 And it's by Carl Wilhelm Scheele, who was in Uppsala; 09:27.600 --> 09:30.160 "Upsala", in Sweden. 09:30.158 --> 09:34.808 What do you think he discovered with light and fire -- or pardon 09:34.807 --> 09:38.247 me, with air and fire; Luft und dem Feuer? 09:38.250 --> 09:39.190 Student: Oxygen. 09:39.190 --> 09:45.530 Prof: Ah ha, we'll see. 09:45.529 --> 09:48.019 So that's his laboratory, Scheele's laboratory, 09:48.017 --> 09:50.447 or at least some artist's impression of it. 09:50.450 --> 09:52.160 And here he is. 09:52.158 --> 09:55.158 He's before the Chemical Revolution, but he's an 09:55.163 --> 09:57.343 important precedent, as you'll see, 09:57.337 --> 09:59.317 to the Chemical Revolution. 09:59.320 --> 10:03.080 He was by practice a pharmacist but he spent most of his time 10:03.080 --> 10:05.650 doing what is really chemical research. 10:05.649 --> 10:09.869 Here's a picture of a stamp, a Swedish stamp, 10:09.865 --> 10:11.585 showing Scheele. 10:11.590 --> 10:12.920 Except it's not Scheele. 10:12.918 --> 10:16.758 It turns out the costume he's wearing wouldn't have been 10:16.759 --> 10:20.179 developed until forty years after Scheele died. 10:20.178 --> 10:25.808 Okay, but he purified organic compounds, that weren't easy to 10:25.806 --> 10:29.366 purify; in particular, carboxylic acids. 10:29.370 --> 10:33.530 So he got an acid from -- that he called lactic acid; 10:33.529 --> 10:35.109 which we now know has that structure. 10:35.110 --> 10:36.000 Where did he get it? 10:36.000 --> 10:37.380 <> 10:37.379 --> 10:39.159 Prof: From sour milk. 10:39.159 --> 10:39.869 Okay? 10:39.870 --> 10:45.050 So here's his paper about that, "On Milk and its 10:45.048 --> 10:47.338 Acid" from 1780. 10:47.340 --> 10:51.400 So he purified these acids as salts that he could crystallize. 10:51.399 --> 10:53.139 That was the method of purifying. 10:53.139 --> 10:56.429 So here's several reports in that paper. 10:56.429 --> 10:59.619 Item 7: "Bismuth, cobalt, antimony, tin, 10:59.618 --> 11:03.168 mercury, silver and gold were attacked by lactic acid, 11:03.168 --> 11:06.058 either by digestion" (that's just sitting there 11:06.057 --> 11:07.867 under it) "or by boiling. 11:07.870 --> 11:11.200 After standing over tin, the acid caused a black 11:11.195 --> 11:14.655 precipitate to form in a solution of gold and aqua 11:14.662 --> 11:16.292 regia." Right? 11:16.288 --> 11:19.398 So this is not mysterious writing. 11:19.403 --> 11:20.163 Right? 11:20.158 --> 11:22.828 It's talking in language that we can understand, 11:22.831 --> 11:25.221 even though it's translated from German. 11:25.220 --> 11:29.150 Iron and zinc were dissolved with a formation of flammable 11:29.154 --> 11:29.574 air. 11:29.570 --> 11:33.030 What do you suppose -- he reacted acid with zinc and he 11:33.028 --> 11:34.308 got flammable air. 11:34.309 --> 11:36.089 What do you suppose that was? 11:36.090 --> 11:36.460 Student: Hydrogen gas. 11:36.460 --> 11:38.120 Prof: Hydrogen, right? 11:38.120 --> 11:41.440 "The iron solution was brown and gave no 11:41.441 --> 11:44.231 crystallization, but the zinc solution 11:44.232 --> 11:45.972 crystallized." 11:45.970 --> 11:47.550 Why was that important? 11:47.548 --> 11:50.908 Student: He could purify it. 11:50.908 --> 11:53.648 Prof: Because he could purify it if it crystallized, 11:53.648 --> 11:54.738 and get just that salt. 11:54.735 --> 11:55.155 Right? 11:55.158 --> 11:57.858 So that's how he got pure samples of acids. 11:57.855 --> 11:58.365 Right? 11:58.370 --> 12:00.750 "With copper, our solution first took on a 12:00.749 --> 12:02.869 blue color, then green, finally dark blue, 12:02.870 --> 12:06.110 but did not crystallize"; unfortunately. 12:06.110 --> 12:09.130 And 10: "Lead dissolved after several days of digestion. 12:09.129 --> 12:11.759 The solution acquired a sweet, tart taste," 12:11.755 --> 12:13.205 > 12:13.210 --> 12:15.030 "but did not crystallize." 12:15.033 --> 12:15.453 Right? 12:15.450 --> 12:19.670 So what do you do when you don't have IR and NMR, 12:19.667 --> 12:20.367 right? 12:20.370 --> 12:21.160 Student: Eat. 12:21.159 --> 12:21.939 Student: Taste. 12:21.940 --> 12:22.380 Prof: Sure. 12:22.379 --> 12:24.909 So he tasted all these things. 12:24.909 --> 12:27.649 Cyanide too. 12:27.649 --> 12:29.549 Okay, so he got citric acid. 12:29.549 --> 12:31.279 Where did he get that? 12:31.279 --> 12:32.049 Student: Lemons. 12:32.049 --> 12:34.759 Prof: From lemons, okay? 12:34.759 --> 12:39.789 And he got uric acid; obvious. 12:39.789 --> 12:42.119 He got tartaric acid. 12:42.120 --> 12:44.510 Tartaric acid, his discovery, 12:44.514 --> 12:48.534 turns out to one of the -- probably the single most 12:48.529 --> 12:50.129 important, maybe the second, 12:50.129 --> 12:52.729 no probably the most important compound in the nineteenth 12:52.731 --> 12:55.161 century, as you'll see. 12:55.159 --> 12:55.549 Okay? 12:55.548 --> 12:58.968 That comes from tartar, which is the deposit on the 12:58.971 --> 13:02.531 inside of wine casks, after you've fermented wine. 13:02.529 --> 13:03.049 Okay? 13:03.048 --> 13:09.048 Benzoic acid came from gum benzoin, a product of the Far 13:09.046 --> 13:09.806 East. 13:09.809 --> 13:10.709 Okay? 13:10.710 --> 13:12.350 And oxalic acid. 13:12.350 --> 13:18.390 Where do you think that came from? 13:18.389 --> 13:21.589 It came from rhubarb. 13:21.590 --> 13:25.330 Now why oxalic; why oxy? 13:25.330 --> 13:28.010 Oxy means sharp. 13:28.009 --> 13:36.799 So what does sharp have to do with it, with rhubarb? 13:36.798 --> 13:38.028 Student: It has a sharp taste? 13:38.029 --> 13:41.239 Prof: Yes, so you know oxy as a 13:41.235 --> 13:42.835 root, meaning sharp. 13:42.840 --> 13:46.420 Oxymoron doesn't mean a stupid ox. 13:46.418 --> 13:50.698 What it means is sharp, and moron means dull. 13:50.700 --> 13:53.660 So it's a sharp dullness, is an oxymoron. 13:53.658 --> 13:56.828 It's a self-contradictory word. 13:56.825 --> 13:57.535 Right? 13:57.539 --> 14:01.839 So what's sharp about rhubarb? 14:01.840 --> 14:02.600 Student: Its taste. 14:02.600 --> 14:04.380 Prof: Its taste; it tastes acidic. 14:04.379 --> 14:07.539 In fact, the word acidic comes from the Latin 14:07.538 --> 14:09.958 acidus; which comes from acre, 14:09.957 --> 14:11.377 to be sour; which comes from, 14:11.384 --> 14:13.454 the root is ac, which means sharp. 14:13.450 --> 14:17.110 So it's the same thing, acid and oxy. 14:17.110 --> 14:17.250 Okay? 14:17.250 --> 14:19.060 So look at all these things. 14:19.059 --> 14:22.089 They have what? 14:22.090 --> 14:24.750 The carboxylate group, which makes them acidic. 14:24.746 --> 14:25.206 Right? 14:25.210 --> 14:26.670 And we know why it makes it acidic; 14:26.668 --> 14:29.508 this is a review from last time, this functional group. 14:29.509 --> 14:33.989 It's not a carbonyl alcohol, it's a carboxylic acid. 14:33.990 --> 14:37.210 The high HOMO is stabilized in the acid. 14:37.210 --> 14:40.170 But it's even more stabilized when it's an anion, 14:40.172 --> 14:42.212 because you have a higher HOMO. 14:42.210 --> 14:47.100 So it changes the acidity, the ease of dissociation of 14:47.102 --> 14:49.692 H^+, by a factor of 10^11th. 14:49.687 --> 14:50.517 Right? 14:50.519 --> 14:54.829 Which depends on the energy difference between those two. 14:54.830 --> 14:58.860 So if you more stabilize the anion product than you stabilize 14:58.860 --> 15:02.150 the starting material, then you shift the reaction 15:02.150 --> 15:04.230 toward product, here by 10^11th; 15:04.232 --> 15:05.512 a big change. 15:05.509 --> 15:06.939 Okay? 15:06.940 --> 15:09.830 But actually there's more to it than just that resonance, 15:09.832 --> 15:11.592 just that HOMO/LUMO interaction. 15:11.590 --> 15:14.490 There's a thing called "inductive effects" 15:14.491 --> 15:16.371 that we'll talk about later on. 15:16.370 --> 15:19.300 But a large part of it is due to that. 15:19.298 --> 15:21.938 Okay, but you notice there's one exception here. 15:21.940 --> 15:33.650 Uric acid doesn't have a carboxylate group in it. 15:33.649 --> 15:35.529 So there's what it has. 15:35.529 --> 15:40.059 And notice that it has an unshared-pair on nitrogen. 15:40.058 --> 15:43.068 Like an amide, it's stabilized by a carbonyl; 15:43.070 --> 15:48.080 in fact, it's stabilized by two carbonyls, two adjacent LUMOs to 15:48.077 --> 15:49.267 stabilize it. 15:49.269 --> 15:53.629 Now if that were just stable, it wouldn't be a reason to get 15:53.625 --> 15:55.835 rid of it, to lose a proton. 15:55.840 --> 15:59.170 But the anion that you get if you lose the proton from 15:59.174 --> 16:01.004 nitrogen has a higher HOMO. 16:01.000 --> 16:03.140 So it's even more stabilized. 16:03.139 --> 16:06.649 The same trick as in carboxylic acid, but even more so, 16:06.653 --> 16:08.023 as you'll see here. 16:08.019 --> 16:11.579 The pK_a of this compound is 5.8. 16:11.580 --> 16:13.390 It's pretty acidic. Right? 16:13.389 --> 16:18.209 But a normal amine, like ammonia losing a proton, 16:18.208 --> 16:19.918 has a pK_a of 38. 16:19.916 --> 16:20.816 Right? 16:20.820 --> 16:24.430 So this is thirty-two powers of ten helped out, 16:24.426 --> 16:28.106 because it has such a high HOMO on the nitrogen, 16:28.110 --> 16:31.090 and two carbonyls to stabilize it. 16:31.090 --> 16:36.490 Okay, so uric acid is indeed an acid, like carboxylic acids. 16:36.490 --> 16:40.010 Okay, now Scheele not only did these organic acids, 16:40.009 --> 16:42.539 he also discovered, or co-discovered, 16:42.542 --> 16:43.882 seven elements. 16:43.879 --> 16:46.499 They're listed here according to what row of the periodic 16:46.500 --> 16:47.390 table they're in. 16:47.389 --> 16:51.449 Notice down at the bottom here you have tungsten. 16:51.452 --> 16:52.132 Right? 16:52.129 --> 16:53.909 Tungsten comes from Swedish. 16:53.909 --> 16:54.759 He was Swedish. 16:54.759 --> 16:56.209 It's "tung" "sten", 16:56.206 --> 16:56.736 heavy stone. 16:56.740 --> 16:59.870 Being way down, it's got lots of protons and 16:59.870 --> 17:02.200 neutrons and is very, very dense. 17:02.201 --> 17:02.931 Right? 17:02.928 --> 17:05.808 So it's heavy -- the stones that it comes from are very 17:05.808 --> 17:06.128 heavy. 17:06.130 --> 17:06.610 Right? 17:06.608 --> 17:10.828 But by contrast, these up here are gases. 17:10.828 --> 17:15.968 And in fact that's what got the 19th Century chemistry going. 17:15.970 --> 17:18.700 That's what launched the Chemical Revolution, 17:18.695 --> 17:20.985 was the ability to work with gases. 17:20.990 --> 17:24.780 Because to be a gas, something has to be a small 17:24.775 --> 17:29.845 molecule and therefore simple, or at least relatively simple. 17:29.848 --> 17:33.488 So you had to start with simple things before you could get the 17:33.490 --> 17:35.430 complex ones, like salicylic acid, 17:35.428 --> 17:37.188 in terms of understanding. 17:37.190 --> 17:40.500 Now Scheele, in 1771, had heated silver 17:40.499 --> 17:45.289 carbonate, and he found that he got CO_2 out of them; 17:45.288 --> 17:48.798 he didn't know it was CO_2, but the gas came out. 17:48.799 --> 17:50.509 Okay? 17:50.509 --> 17:55.249 And if you heated that still more, greater than 340 Celsius, 17:55.249 --> 17:58.859 then you get silver, and oxygen comes out from 17:58.864 --> 18:02.364 silver oxide; this gas, this 18:02.355 --> 18:06.605 feuerluft, fire air. 18:06.609 --> 18:08.599 That's what the book is about. 18:08.599 --> 18:09.439 Okay? 18:09.440 --> 18:12.750 So he wrote the book. 18:12.750 --> 18:17.870 But the book starts, as I'll show you here -- 18:17.868 --> 18:21.108 sorry, there we go -- the book starts with an introduction, 18:21.108 --> 18:26.688 a "vorbericht", 18:26.690 --> 18:29.440 which is translated, it says, from Swedish. 18:29.440 --> 18:31.860 And let's see where it says here. 18:31.858 --> 18:36.348 And it's by Torbern Bergman, written in 1777. 18:36.348 --> 18:40.778 He had this book written for two years, waiting for this 18:40.779 --> 18:42.229 preface to come. 18:42.230 --> 18:45.030 Bergman was a busy guy. Right? 18:45.029 --> 18:47.979 And during the time that this book was sitting, 18:47.980 --> 18:51.380 ready, the manuscript was sitting ready to be printed, 18:51.382 --> 18:54.272 Priestley, in England, discovered oxygen. 18:54.269 --> 18:56.569 So this book came out after Priestley. 18:56.568 --> 19:01.948 But there's no doubt that Scheele had discovered it 19:01.952 --> 19:03.032 earlier. 19:03.029 --> 19:05.269 His lab books from 1771 show it. 19:05.269 --> 19:10.759 And here, in 1774, is his draft of a letter that 19:10.757 --> 19:13.207 he wrote to France. 19:13.210 --> 19:16.420 And it begins -- or it actually begins with a couple of words on 19:16.424 --> 19:18.174 the previous sheet -- but it says: 19:18.174 --> 19:20.674 "…since I have no large burning glass, 19:20.670 --> 19:22.570 I beg you to try with yours..." 19:22.568 --> 19:25.508 Because he had to do this by heating things in an oven, 19:25.511 --> 19:28.401 at a really high temperature, which was hard to do. 19:28.400 --> 19:31.630 But if you could do it with a focused light of the sun to heat 19:31.631 --> 19:33.911 it, then it would be much more practical. 19:33.910 --> 19:38.070 And, in France, they had such a big magnifying 19:38.071 --> 19:41.311 glass, that would allow to do it. 19:41.308 --> 19:43.968 But that letter, although it was sent, 19:43.970 --> 19:45.480 was never answered. 19:45.480 --> 19:50.080 And you know who it was sent to, presumably. 19:50.078 --> 19:53.758 Lavoisier, the founder of the Chemical Revolution, 19:53.755 --> 19:56.375 and another discoverer of oxygen. 19:56.380 --> 19:57.820 Okay? 19:57.818 --> 20:01.518 Okay, so now we're going to talk about Lavoisier, 20:01.516 --> 20:05.976 who was -- wasn't a perfect person, but he was really very, 20:05.980 --> 20:07.060 very good. 20:07.058 --> 20:09.658 Okay, now the Chemical Revolution. 20:09.660 --> 20:14.210 You can say it started in 1789, the Chemical Revolution. 20:14.210 --> 20:17.350 And that's not the only revolution that started in 20:17.351 --> 20:18.311 France in 1789. 20:18.313 --> 20:18.893 Right? 20:18.890 --> 20:20.580 Do you know what this is? 20:20.579 --> 20:21.949 What? 20:21.950 --> 20:22.710 Student: Tennis Court Oath. 20:22.710 --> 20:23.750 Prof: It's the Tennis Court Oath, 20:23.750 --> 20:28.230 when the legislators, so to say, gathered to say that 20:28.228 --> 20:33.048 they wouldn't disband until the king granted them certain 20:33.051 --> 20:35.681 things; and you know what that led to, 20:35.675 --> 20:36.175 in 1789. 20:36.180 --> 20:40.530 The only guy that didn't agree was this guy here. 20:40.529 --> 20:43.429 He's the only one that didn't sign it. 20:43.430 --> 20:48.030 But at any rate, it was radical. 20:48.029 --> 20:51.539 Now there's an Indo-European word, that's the root of many 20:51.536 --> 20:55.226 words, called Werad; and it gives words in all sorts 20:55.234 --> 20:56.104 of languages. 20:56.099 --> 20:59.339 Like it means root. 20:59.339 --> 21:01.119 Okay? 21:01.118 --> 21:03.718 And Wurzel, in German, means root; 21:03.720 --> 21:05.240 and wort, like St. 21:05.242 --> 21:06.832 John's wort, is a root. 21:06.829 --> 21:09.879 Licorice; glukos rhiza, 21:09.876 --> 21:12.906 Greek, the rhiza is root; 21:12.910 --> 21:14.070 sweet root it means. 21:14.069 --> 21:14.599 Okay? 21:14.599 --> 21:18.939 Race; razza in Italian is the 21:18.935 --> 21:20.785 root of your being. 21:20.788 --> 21:21.568 Right? 21:21.569 --> 21:23.909 Rutabaga. 21:23.910 --> 21:29.020 Radix in Latin; and you know lots of words come 21:29.022 --> 21:31.632 from radix, like radish is a root. 21:31.630 --> 21:36.360 Or eradicate, what does that mean? 21:36.358 --> 21:38.668 Prof: It means to pull it out by the roots. 21:38.670 --> 21:39.590 Okay? 21:39.589 --> 21:42.649 Or radical; something that's radical is 21:42.654 --> 21:45.964 something that goes right to the root, back to the very origin of 21:45.958 --> 21:46.628 something. 21:46.630 --> 21:48.770 And that word, used in that way, 21:48.766 --> 21:51.796 if you look in the Oxford English Dictionary, 21:51.797 --> 21:55.447 it was coined in mathematics in the 16th Century. 21:55.450 --> 21:57.830 The root of a number is its origin. 21:57.828 --> 21:58.388 Right? 21:58.390 --> 22:01.580 If you take the square root of a number, and multiply it by 22:01.576 --> 22:03.166 itself, you get the number. 22:03.170 --> 22:06.870 So it's the root of the number; the radical. Right? 22:06.868 --> 22:09.258 Or in politics, it was used in 18th Century in 22:09.263 --> 22:10.843 England, and in chemistry, 22:10.836 --> 22:14.006 in 18th Century in France, the idea of radical as the root 22:14.009 --> 22:15.909 of things, began to be used; 22:15.910 --> 22:16.920 which we'll see. 22:16.920 --> 22:19.620 Okay, so 1787, radical was introduced as a 22:19.622 --> 22:22.652 political term, according to the Oxford English 22:22.653 --> 22:25.623 Dictionary, by J. Jebb, whoever he was; 22:25.619 --> 22:28.339 presumably a politician. 22:28.338 --> 22:31.088 Or in 1787, there was this radical document, 22:31.085 --> 22:32.735 "We the People." 22:32.744 --> 22:33.324 Right? 22:33.318 --> 22:37.828 But that same year, 1787, radical was introduced as 22:37.828 --> 22:41.618 a chemical term, by Louis Bernard Guyton de 22:41.616 --> 22:42.696 Morveau. 22:42.700 --> 22:48.500 And it was in the context of developing nomenclature for 22:48.502 --> 22:49.772 chemistry. 22:49.769 --> 22:52.689 So he, together with Berthollet and Fourcroy, 22:52.693 --> 22:56.353 developed a new method for nomenclature in chemistry. 22:56.349 --> 22:58.059 And here's a book. 22:58.058 --> 23:01.358 This is not the original French, but it's the first 23:01.358 --> 23:04.528 English translation, which you see comes from the 23:04.526 --> 23:07.096 Yale University Library, back when. 23:07.099 --> 23:10.949 It's from 1788. 23:10.950 --> 23:11.410 Okay? 23:11.410 --> 23:14.790 So A Method of Chemical Nomenclature, 23:14.786 --> 23:18.396 by Guyton de Morveau, Lavoisier, Berthollet and 23:18.398 --> 23:19.418 Fourcroy. 23:19.420 --> 23:25.190 So the fourth author of this new method of chemical 23:25.194 --> 23:28.434 nomenclature is Lavoisier. 23:28.430 --> 23:29.950 So there's Lavoisier with his wife. 23:29.950 --> 23:33.610 This is part of an enormous picture that's in the 23:33.606 --> 23:34.746 Metropolitan. 23:34.750 --> 23:38.030 It was commissioned by Lavoisier and his wife, 23:38.030 --> 23:41.240 who hired Jacques-Louis David to paint it. 23:41.240 --> 23:44.990 And they paid 7000 pounds, to the artist to paint it; 23:44.990 --> 23:48.380 which is the equivalent of $300,000 today. 23:48.380 --> 23:50.240 They were quite well-to-do. 23:50.240 --> 23:52.590 They had an income of the order of a million dollars a year, 23:52.592 --> 23:55.312 or the equivalent; it depends on how you translate 23:55.309 --> 23:56.549 numbers, of course. 23:56.549 --> 23:57.619 It's hard. 23:57.618 --> 24:02.288 So here he is at the age of 45, in 1789, 24:02.288 --> 24:05.118 and he's working on drafting -- so these guys, 24:05.118 --> 24:06.688 when they had their portraits painted, 24:06.690 --> 24:09.310 always put something important in it. 24:09.309 --> 24:11.019 So what did he choose to have? 24:11.019 --> 24:15.659 He chose to be working on a manuscript, and the manuscript 24:15.656 --> 24:19.396 he's working on is the manuscript of this book, 24:19.400 --> 24:20.540 from 1789. 24:23.144 --> 24:26.414 Chimie; the Elementary Treatise on 24:26.405 --> 24:27.775 Chemistry. 24:27.778 --> 24:34.598 And the other stuff he put in the picture is the equipment he 24:34.603 --> 24:35.403 used. 24:35.400 --> 24:39.530 So here you see various equipment from one of the plates 24:39.525 --> 24:41.395 at the end of the book. 24:41.400 --> 24:43.680 And you can see these items in the picture. 24:43.680 --> 24:45.930 There's that bell jar. 24:45.930 --> 24:50.170 There's that device. 24:50.170 --> 24:56.400 There's that big sixteen-pint flask, with a brass fitting on 24:56.401 --> 24:56.931 it. 24:56.930 --> 25:01.850 There's that valve that you attach to the bottom of the 25:01.849 --> 25:02.579 flask. 25:02.578 --> 25:06.138 And over here is a portfolio, and the portfolio says, 25:06.135 --> 25:09.145 down in the corner, "Paulze Lavoisier 25:09.145 --> 25:10.715 sculpsit." 25:10.720 --> 25:13.450 That means this was drawn by Paulze Lavoisier, 25:13.448 --> 25:14.598 who was his wife. 25:14.598 --> 25:18.158 She was his assistant in the laboratory, kept all the 25:18.157 --> 25:19.917 notebooks; read English for him, 25:19.923 --> 25:21.453 because he couldn't read English. 25:21.450 --> 25:23.520 So if he had to do anything with Priestley, 25:23.519 --> 25:24.849 she would read it to him. 25:24.849 --> 25:25.949 But she drew all these things. 25:25.950 --> 25:29.160 She studied with David, drawing, in order to be able to 25:29.155 --> 25:29.745 do this. 25:29.750 --> 25:36.860 Okay, she painted this portrait of their family friend. 25:36.859 --> 25:37.839 Who's that? 25:37.838 --> 25:38.818 Student: Benjamin Franklin. 25:38.818 --> 25:40.078 Prof: Yes, Benjamin Franklin. 25:40.078 --> 25:42.848 I showed you that picture earlier, said we'd refer to it 25:42.846 --> 25:43.246 again. 25:43.250 --> 25:46.830 So this is that particular plate in the book, 25:46.830 --> 25:49.680 and it relates to weighing a gas. 25:49.680 --> 25:54.790 It'll turn out that the most important thing for Lavoisier, 25:54.788 --> 25:58.798 and for the whole 19th Century -- all this development that led 25:58.804 --> 26:01.074 to bonds and their arrangement -- 26:01.069 --> 26:03.789 weighing was the key thing. 26:03.789 --> 26:05.709 But how do you weigh a gas? 26:05.710 --> 26:09.510 So you need gases so they're simple enough to deal with, 26:09.506 --> 26:10.816 and easy to purify. 26:10.817 --> 26:11.437 Right? 26:11.440 --> 26:13.970 But you need to weigh them. 26:13.970 --> 26:16.360 So how can you weigh a gas? 26:16.358 --> 26:19.148 Well you can collect a gas, as shown in this picture, 26:19.150 --> 26:23.590 by generating it in this retort G, and it comes and it bubbles 26:23.592 --> 26:26.912 up, displacing water or mercury, 26:26.910 --> 26:30.200 most often mercury, from a bell jar. 26:30.200 --> 26:31.840 You've done this kind of thing? 26:31.839 --> 26:31.969 Student: Yes. 26:31.970 --> 26:33.030 Prof: Some of you. 26:33.029 --> 26:34.149 But you can see how it would work; 26:34.150 --> 26:35.810 as it bubbles up the mercury comes down. 26:35.809 --> 26:36.409 Okay. 26:36.410 --> 26:38.130 So now you have the gas. 26:38.130 --> 26:41.440 Now we'll shift attention down to the bottom right here, 26:41.442 --> 26:42.952 and see how this works. 26:42.950 --> 26:45.420 So we have this bell jar on the bottom, 26:45.420 --> 26:47.510 which is fitted with valves on the top, 26:47.509 --> 26:50.529 is filled with mercury, and it's in a pool of mercury, 26:50.529 --> 26:55.369 and then this big sixteen-pint flask is evacuated. 26:55.369 --> 26:56.839 You use one of these pumps. 26:56.838 --> 27:01.848 Remember, 100 years before this, Hooke -- or 130 years 27:01.847 --> 27:07.327 before this -- Hooke made a great vacuum pump for Boyle. 27:07.328 --> 27:11.628 Boyle is the only person on the front of the building older than 27:11.632 --> 27:12.322 Lavoisier. 27:12.315 --> 27:12.925 Right? 27:12.930 --> 27:15.750 And that was dealing with gases and Boyle's Law, 27:15.750 --> 27:18.630 how pressure and volume relate to one another. 27:18.630 --> 27:22.030 Okay, so anyhow, he could evacuate that with a 27:22.027 --> 27:25.497 pump, then seal it off, turn the valves off. 27:25.500 --> 27:26.760 And he's got mercury in that thing. 27:26.759 --> 27:29.989 And now he puts a tip underneath it and generates gas. 27:29.990 --> 27:36.360 And it bubbles up and fills this container with a gas. 27:36.358 --> 27:39.088 And it's sitting in a mercury pool so that it's not 27:39.086 --> 27:41.916 communicating with the atmosphere, other than through 27:41.923 --> 27:44.273 the pressure, through the mercury pool. 27:44.269 --> 27:48.009 Okay, so now he opens the valves. 27:48.009 --> 27:52.039 So the vacuum starts sucking up the mercury; 27:52.038 --> 27:55.128 that is, pulling the air in, up to a certain point. 27:55.134 --> 27:55.634 Right? 27:55.630 --> 27:57.100 Then the mercury stops rising. 27:57.099 --> 27:58.519 Okay? 27:58.519 --> 28:02.789 And now, at this point you know that the pressure of that gas is 28:02.788 --> 28:06.308 atmospheric pressure, less whatever the height of the 28:06.314 --> 28:07.534 mercury column is. 28:07.534 --> 28:08.284 Right? 28:08.279 --> 28:11.149 That's how a barometer works. 28:11.150 --> 28:16.740 So he knows how much gas, what volume of gas he has in A. 28:16.740 --> 28:20.960 He filled it with water first and weighed it to see what its 28:20.960 --> 28:21.890 volume was. 28:21.890 --> 28:24.230 Now he knows the volume, he knows the pressure. 28:24.230 --> 28:27.340 So he knows how much gas there would be, at atmospheric 28:27.335 --> 28:27.845 pressure. 28:27.852 --> 28:28.372 Right? 28:28.368 --> 28:31.408 And now, of course, he just turns off these things, 28:31.410 --> 28:34.630 unscrews one, the thing on top, 28:34.633 --> 28:38.633 and weighs it, and sees how much heavier it is 28:38.625 --> 28:41.065 than it was when it was evacuated. 28:41.068 --> 28:42.598 And that's how much the air weighs. 28:42.598 --> 28:45.308 And he knows how much volume, how much pressure. 28:45.308 --> 28:48.488 So he knows how much whatever gas he collected weighed. 28:48.490 --> 28:50.390 So he could weigh a gas. 28:50.390 --> 28:53.030 Pretty clever, huh? 28:53.029 --> 28:57.359 Okay, here he is working with one of these bell jars. 28:57.358 --> 29:02.158 Now these bell jars were filled with mercury. 29:02.160 --> 29:07.340 I don't know if you've -- here, would you help me out Wilson? 29:07.338 --> 29:09.428 Lift this up and show it to the class. 29:09.430 --> 29:13.120 But don't lift it high, hold it above the thing. 29:13.119 --> 29:14.279 Did it surprise you? 29:14.279 --> 29:14.839 Student: Yes. 29:14.838 --> 29:17.528 Prof: He said it surprised him. 29:17.528 --> 29:20.208 And you can come up afterwards, if you want to, 29:20.205 --> 29:22.995 and be surprised yourself, by lifting this up. 29:23.000 --> 29:25.470 But keep it over this, because people are so panicked 29:25.471 --> 29:26.661 about mercury nowadays. 29:26.660 --> 29:28.490 I heard on the way over to class, while I was bringing 29:28.492 --> 29:30.712 this, I heard there's a new law in 29:30.710 --> 29:34.870 the European Union that it's going to be illegal to transport 29:34.866 --> 29:37.496 mercury over international borders. 29:37.500 --> 29:38.760 Go figure. 29:38.759 --> 29:42.889 Anyhow, there's Lavoisier doing an experiment with this big 29:42.894 --> 29:44.114 thing of mercury. 29:44.107 --> 29:44.747 Right? 29:44.750 --> 29:47.390 He must've been a stout person. 29:47.390 --> 29:48.350 Okay? 29:48.348 --> 29:52.298 This is him in his library, with Madame Lavoisier taking 29:52.298 --> 29:55.458 his dictation, as he does his experiments. 29:58.130 --> 30:02.390 and I'll show you the -- this actually is a facsimile, 30:02.390 --> 30:04.570 not the real thing. 30:04.568 --> 30:11.168 But here's the title page of the first volume. 30:11.170 --> 30:12.910 Okay. 30:12.910 --> 30:14.460 So you can look at that if you want to. 30:14.460 --> 30:16.850 And at the end, I'll just note here, 30:16.848 --> 30:22.258 at the end of the second volume, are all these pages, 30:22.259 --> 30:27.479 which are devices -- like here's this is the one we just 30:27.480 --> 30:28.620 looked at. 30:28.619 --> 30:30.829 Okay? 30:30.828 --> 30:33.168 So if you want to look at them, feel free. 30:33.170 --> 30:35.290 Don't handle the other one though; 30:35.289 --> 30:36.919 it's real. 30:36.920 --> 30:40.980 Okay, so Elementary Treatise of Chemistry, 30:40.980 --> 30:44.540 Presented in a New Order -- this is the Revolution -- 30:44.538 --> 30:46.038 According to Modern Discoveries, 30:46.039 --> 30:49.789 With Figures; as I just showed you. 30:49.788 --> 30:55.618 And 1789 is the date, the same as the French 30:55.617 --> 30:57.377 Revolution. 30:57.380 --> 31:00.060 Okay, you notice he's a member of all different academies, 31:00.063 --> 31:01.243 including Philadelphia. 31:01.240 --> 31:03.500 Why in the world would he have been a member of the Scientific 31:03.503 --> 31:04.473 Academy of Philadelphia? 31:04.470 --> 31:06.020 He never went there. 31:06.019 --> 31:06.679 Student: Ben Franklin was -- 31:06.680 --> 31:08.630 Prof: Right, his pal. 31:08.630 --> 31:10.080 Okay, 1789. 31:10.078 --> 31:12.848 So it has the most wonderful Introduction, 31:16.230 --> 31:18.720 And he says: "My only object, 31:18.720 --> 31:22.250 when I began this work" -- or, "I had no other object 31:22.249 --> 31:25.819 when I began the following work, than to extend and explain more 31:25.819 --> 31:27.949 fully the memoir, which I read at the public 31:27.945 --> 31:30.455 meeting of the Academy of Science in the month of April, 31:30.460 --> 31:33.840 1787" (remember when radical was introduced and so 31:33.838 --> 31:37.408 on) "on the necessity of reforming and completing the 31:37.405 --> 31:39.655 nomenclature of Chemistry." 31:39.660 --> 31:43.800 So that's all he was trying to do was get a proper nomenclature 31:43.804 --> 31:46.744 that would be useful, in contrast to all this 31:46.744 --> 31:48.354 alchemical nonsense. 31:48.349 --> 31:48.879 Okay? 31:48.880 --> 31:50.640 "While engaged in this employment, 31:50.640 --> 31:53.090 I perceived, better than I had ever done 31:53.090 --> 31:55.280 before, the justice of the following 31:58.357 --> 32:00.367 Logic and some other works." 32:00.369 --> 32:02.229 So this is what Condillac said. 32:02.230 --> 32:04.710 "We think, only through the medium of 32:04.705 --> 32:05.185 words. 32:05.190 --> 32:08.380 Languages are true analytical methods. 32:08.380 --> 32:12.090 Algebra, which is adapted to its purpose in every species of 32:12.088 --> 32:13.898 expression, in the most simple, 32:13.903 --> 32:15.823 most exact, and best manner possible, 32:15.818 --> 32:20.378 is at the same time a language and an analytical method. 32:20.380 --> 32:25.280 The art of reasoning is nothing more than language, 32:25.275 --> 32:27.425 well arranged." 32:27.430 --> 32:31.380 So Lavoisier goes on to say: "Thus, while I thought 32:31.382 --> 32:34.582 myself employed only in forming a Nomenclature, 32:34.578 --> 32:37.568 and while I proposed to myself nothing more than to improve the 32:37.567 --> 32:41.297 chemical language, my work transformed itself by 32:41.300 --> 32:43.410 degrees, without my being able to 32:43.413 --> 32:45.723 prevent it, into a treatise upon the 32:45.715 --> 32:47.725 Elements of Chemistry." 32:47.730 --> 32:51.020 So in the process of reforming the language, 32:51.021 --> 32:55.081 he reformed the whole understanding of the science. 32:55.078 --> 32:58.478 "The impossibility of separating nomenclature of a 32:58.477 --> 33:02.007 science from the science itself, is owing to this, 33:02.008 --> 33:06.538 that every branch of physical science must consist of three 33:06.538 --> 33:09.198 things; the series of facts 33:09.195 --> 33:11.935 which are the object of the science, 33:11.940 --> 33:15.570 the ideas which represent these facts, 33:15.568 --> 33:20.028 and the words by which the ideas are expressed. 33:20.028 --> 33:24.558 Like three impressions of the same seal, the word ought to 33:24.557 --> 33:28.367 produce the idea, and the idea to be a picture of 33:28.369 --> 33:29.879 the fact." 33:29.880 --> 33:32.690 So all these things have to be harmonious. 33:32.691 --> 33:33.241 Right? 33:33.240 --> 33:36.770 Three impressions of the same seal. 33:36.769 --> 33:40.219 "And, as ideas are preserved and communicated by 33:40.215 --> 33:43.285 means of words, it necessarily follows that we 33:43.291 --> 33:47.121 cannot improve the language of any science without at the same 33:47.117 --> 33:49.437 time improving the science itself; 33:49.440 --> 33:51.540 neither can we, on the other hand, 33:51.541 --> 33:54.601 improve a science, without improving the language 33:54.601 --> 33:57.151 or nomenclature which belongs to it. 33:57.150 --> 34:00.340 However certain the facts of any science may be, 34:00.338 --> 34:04.458 however just the ideas we may have formed of these facts, 34:04.460 --> 34:08.330 we can only communicate false impressions to others, 34:08.329 --> 34:11.309 while we want words by which these may be properly 34:11.309 --> 34:12.279 expressed." 34:12.282 --> 34:12.832 Right? 34:12.829 --> 34:17.649 So clarity, as opposed to obscurity, was his goal; 34:17.650 --> 34:20.120 as opposed to Newton or the alchemists. 34:20.119 --> 34:20.639 Right? 34:20.639 --> 34:26.089 Facts, ideas and words, and they all have to tie into 34:26.088 --> 34:30.908 one another as impressions of the same seal. 34:30.909 --> 34:31.659 Okay? 34:31.659 --> 34:34.309 So he presented things, as he had advertised, 34:34.313 --> 34:36.753 in a new order; very different from any book on 34:36.753 --> 34:38.583 chemistry that had been written before. 34:38.579 --> 34:42.309 First was doctrine, -- that is, the theory -- the 34:42.309 --> 34:46.429 first part of the book, which is a two-volume book. 34:46.429 --> 34:50.019 So almost all of the first -- no, about two-thirds, 34:50.019 --> 34:53.179 I think, of the first volume are doctrine. 34:53.179 --> 34:56.519 And then nomenclature; that's what he had set out to 34:56.518 --> 34:56.758 do. 34:56.760 --> 35:00.370 And finally operations, how you can actually repeat 35:00.371 --> 35:03.911 this stuff for yourself, what devices you need. 35:03.909 --> 35:07.429 Of course, he was very wealthy and could employ people to 35:07.429 --> 35:10.069 manufacture all the equipment he needed; 35:10.070 --> 35:12.580 not everybody could do that. 35:12.579 --> 35:16.159 But he showed exactly how it was done and gave great -- it's 35:16.155 --> 35:18.635 easy to understand exactly what he did. 35:18.639 --> 35:22.469 Now, one of the first things he turned his attention to was 35:22.472 --> 35:23.202 elements. 35:23.199 --> 35:26.179 He says: "…if by the name 35:26.175 --> 35:28.915 elements we mean to designate the simple, 35:28.920 --> 35:32.620 indivisible molecules" (molecule just means little 35:32.617 --> 35:35.627 thing, right?) "that make up substances, 35:35.630 --> 35:39.330 it is probable we do not know what they are." 35:39.329 --> 35:41.619 (They're just too small. Right?) 35:41.619 --> 35:43.449 "But if, on the contrary, 35:43.445 --> 35:46.085 we associate with the name of elements, 35:46.090 --> 35:50.000 or the principles of substances, the idea of the 35:50.001 --> 35:53.831 furthest stage to which analysis can reach, 35:53.829 --> 35:58.069 all substances that we have so far found no means to decompose 35:58.067 --> 36:02.027 are elements for us… they behave with respect to us 36:02.027 --> 36:04.317 like simple substances." 36:04.320 --> 36:07.970 So it's an operational, not a philosophical, 36:07.971 --> 36:10.011 definition of element. 36:10.010 --> 36:13.340 If you can't break it apart, consider it an element until 36:13.342 --> 36:14.832 you can break it apart. 36:14.829 --> 36:17.349 We have elements here, the chemical elements. 36:17.349 --> 36:22.049 Are they elements, according to Lavoisier's 36:22.045 --> 36:23.495 definition? 36:23.500 --> 36:26.310 Like here we see cerium, praseodymium, 36:26.307 --> 36:29.417 neodymium, promethium, samarium, europium, 36:29.420 --> 36:30.560 gadolinium. 36:30.559 --> 36:33.329 Are they elements, according to Lavoisier? 36:33.329 --> 36:33.989 Students: No. 36:33.989 --> 36:34.749 Prof: Why not? 36:34.750 --> 36:35.520 Students: You can break them. 36:35.518 --> 36:38.328 Prof: You can break them apart, into nuclei and 36:38.333 --> 36:38.973 electrons. 36:38.969 --> 36:41.939 The nuclei you can break apart into protons and neutrons, 36:41.936 --> 36:45.166 and you can break these things apart into quarks and so on. 36:45.170 --> 36:47.180 But, for Lavoisier, or for chemists, 36:47.181 --> 36:49.891 those are elements, because you don't break them 36:49.885 --> 36:50.455 apart. 36:50.460 --> 36:52.320 Okay? 36:52.320 --> 36:54.990 So here's a table of simple substances, 36:54.989 --> 36:56.889 in the first English translation of the 36:59.090 --> 36:59.840 Chimie. 36:59.840 --> 37:01.830 So here's a table of the elements: "Simple 37:01.827 --> 37:04.157 substances belonging to all the kingdoms of nature, 37:04.159 --> 37:07.019 which may be considered as the elements of bodies." 37:07.018 --> 37:10.398 So what are the first two elements, things that you can't 37:10.396 --> 37:11.236 break apart? 37:11.239 --> 37:13.519 Student: Light. 37:13.518 --> 37:17.158 Prof: Light and heat are the first two elements -- which 37:17.163 --> 37:19.693 we don't see in Mendeleev's table, right? 37:19.690 --> 37:22.460 Because they're fundamentally different from the other 37:22.460 --> 37:24.920 elements, because they don't have any weight. 37:24.920 --> 37:28.850 You can weigh a gas but you can't weigh light, 37:28.851 --> 37:31.211 and you can't weigh heat. 37:31.210 --> 37:31.950 Okay? 37:31.949 --> 37:36.429 So he gives new names to these things -- light and caloric -- 37:36.429 --> 37:38.519 and what the old name was. 37:38.518 --> 37:41.548 Light used to be called light too, but in his new system he's 37:41.552 --> 37:44.082 going to keep the old name; or "caloric", 37:44.079 --> 37:46.429 he's going to use for what used to be called heat; 37:46.429 --> 37:48.549 or "the principle or element of heat"; 37:48.550 --> 37:50.980 or "fire"; or "igneous fluid"; 37:50.980 --> 37:52.750 or "the matter of fire or heat". 37:52.750 --> 37:55.380 Those were terms people had used before, but he's going to 37:55.382 --> 37:56.862 call them "caloric". 37:56.860 --> 37:57.660 Okay? 37:57.659 --> 38:01.869 Now, if you have caloric, you must be able to measure it. 38:01.869 --> 38:04.239 If you can't weigh it, what you can do; 38:04.239 --> 38:06.519 you can use a "calorimeter" 38:06.523 --> 38:07.543 to measure it. 38:07.539 --> 38:10.939 And this is the calorimeter manufactured and used by 38:10.940 --> 38:12.740 Lavoisier; and also Laplace, 38:12.737 --> 38:15.907 a younger man who was his colleague, who became a great 38:15.909 --> 38:18.199 mathematician, as you probably know. 38:18.199 --> 38:19.349 So here's the thing. 38:19.349 --> 38:20.739 It's big. 38:20.739 --> 38:23.579 That's a three-foot rule. 38:23.579 --> 38:25.579 So this thing stood this high off the table, 38:25.577 --> 38:25.947 right? 38:25.949 --> 38:27.389 Okay? 38:27.389 --> 38:28.209 Now here's what it is. 38:28.210 --> 38:30.360 There's a lamp that's going to make fire. 38:30.360 --> 38:33.270 There's oil in the well of the lamp. 38:33.268 --> 38:36.778 You're going to measure how much heat you get out of burning 38:36.775 --> 38:37.425 that oil. 38:37.429 --> 38:41.519 So you put it inside this bucket, and you put the bucket 38:41.518 --> 38:44.418 in this mesh cage and put the lid on. 38:44.420 --> 38:47.490 Then you put that cage, and its lid, 38:47.485 --> 38:49.145 up into this can. 38:49.150 --> 38:50.040 Okay? 38:50.039 --> 38:54.579 And now you light the flame, in there. 38:54.579 --> 38:55.959 You want to measure how much heat it gives. 38:55.960 --> 38:58.500 How do you measure the heat? 38:58.500 --> 39:03.320 What you do is surround it by melting ice. 39:03.320 --> 39:05.920 So the heat will melt the ice. 39:05.920 --> 39:07.810 Now there's going to be a problem. 39:07.809 --> 39:10.559 Obviously the more heat, the more ice you melt. 39:10.559 --> 39:13.319 But that's not the only place heat's coming from. 39:13.320 --> 39:15.920 Where else will it come from, to melt the ice? 39:15.920 --> 39:16.410 Students: Outside. 39:16.409 --> 39:17.959 Prof: From outside. 39:17.960 --> 39:20.420 So this is where the thing is clever. 39:20.420 --> 39:23.350 So there's another can, outside that can, 39:23.347 --> 39:26.787 and you fill it with ice, which is an insulator, 39:26.789 --> 39:28.179 for the inside. 39:28.179 --> 39:31.159 So no heat comes from the -- any heat that comes from the 39:31.164 --> 39:33.994 outside, melts the outside ice, not the inside ice. 39:33.989 --> 39:36.579 Only the flame will melt the inside ice. 39:36.579 --> 39:39.739 Okay, and notice that the lids also are covered with ice too. 39:39.739 --> 39:43.249 So it's completely surrounded by ice, and then by another 39:43.248 --> 39:44.188 layer of ice. 39:44.190 --> 39:47.300 So your flame burns, burns, burns, 39:47.295 --> 39:48.045 burns. 39:48.050 --> 39:51.410 And you fill -- water comes up as they melt in both of them. 39:51.409 --> 39:55.409 And then you put that thing underneath and turn the tap, 39:55.405 --> 39:58.015 and see how much water was melted; 39:58.019 --> 40:00.949 only by the flame, right? 40:00.949 --> 40:03.279 And that measures how much heat. 40:03.280 --> 40:07.000 Pretty clever, huh? 40:07.000 --> 40:11.240 Okay, so that's a fact, is measuring how much heat 40:11.237 --> 40:12.187 there is. 40:12.190 --> 40:14.210 But analysis in general is it. 40:14.210 --> 40:18.520 This is from the Oxford English Dictionary, which Yale has a 40:18.523 --> 40:19.843 subscription to. 40:19.840 --> 40:22.150 So you can look up words to your heart's content. 40:22.150 --> 40:23.510 It's a lot of fun. 40:23.510 --> 40:26.390 This year is the 80th anniversary of the Oxford 40:26.393 --> 40:27.713 English Dictionary. 40:27.710 --> 40:29.730 There was a symposium, down the hill, 40:29.726 --> 40:32.696 sponsored by the library, including the guy that wrote 40:32.697 --> 40:35.217 that The Professor and the Madman. 40:35.219 --> 40:37.959 Has anyone read that book about the Oxford English Dictionary? 40:37.960 --> 40:41.630 It's a wonderful short book, and the madman was a Yale 40:41.628 --> 40:42.388 graduate. 40:42.389 --> 40:43.789 Really, it's an interesting story. 40:43.789 --> 40:47.429 And the other guy was one who read the Oxford English 40:47.425 --> 40:51.475 Dictionary, cover to cover, 20 volumes, within one year. 40:51.480 --> 40:53.740 He wrote a book about that, during the last year. 40:53.739 --> 40:54.509 It was a fun thing. 40:54.510 --> 40:57.240 But anyhow, this is -- it's fun to look up things in the Oxford 40:57.235 --> 40:58.155 English Dictionary. 40:58.159 --> 41:00.909 And here's analysis. 41:00.909 --> 41:05.959 So you see it comes from ana, and I think it's 41:05.963 --> 41:10.023 lisein; but I can get some help on that. 41:10.019 --> 41:11.309 Student: luein. 41:11.309 --> 41:12.919 Prof: luein, okay. 41:12.920 --> 41:15.290 Anyhow, but it means "to loose," according to the 41:15.293 --> 41:16.443 Oxford English Dictionary. 41:16.440 --> 41:19.980 So it's to loose back; to take things apart is the 41:19.983 --> 41:20.823 sense of it. 41:20.820 --> 41:24.350 And generally it's the resolution or breaking up of 41:24.349 --> 41:28.019 anything complex into its various simple elements. 41:28.018 --> 41:32.768 So you can analyze a passage in literature. 41:32.769 --> 41:34.359 Okay? 41:34.360 --> 41:38.550 It's the opposite of synthesis. 41:38.550 --> 41:40.150 Okay? 41:40.150 --> 41:45.200 "The exact determination of the elements or components of 41:45.204 --> 41:48.474 anything complex; specifically in chemistry, 41:48.474 --> 41:52.134 the resolution of a chemical compound into its proximate, 41:52.128 --> 41:54.148 or ultimate, elements." 41:54.150 --> 41:56.820 Now, proximate and ultimate, what does that mean? 41:56.820 --> 41:59.160 You can see down in the historical uses of it what 41:59.155 --> 42:00.915 proximate and ultimate mean. 42:00.920 --> 42:04.550 1791, this same time -- 1789, remember, 42:05.786 --> 42:07.576 -- said, "the quantity of 42:07.581 --> 42:10.441 charcoal, which something yields by 42:10.443 --> 42:11.863 analysis." 42:11.860 --> 42:13.770 So you find out how much charcoal is in it. 42:13.768 --> 42:16.948 That's the word -- we now say carbon. 42:16.949 --> 42:18.729 So that's elemental analysis. 42:18.730 --> 42:21.690 That's ultimate analysis; take things all apart to the 42:21.693 --> 42:24.273 chemical elements, see how much of each one. 42:24.268 --> 42:26.718 But there's also this thing called proximate 42:26.719 --> 42:28.849 analysis, which you can see from this 42:28.851 --> 42:29.811 quote in 1831. 42:29.809 --> 42:32.169 "Sugar, starch and gum are proximate 42:32.166 --> 42:34.816 principles, and these we obtained by proximate 42:34.820 --> 42:35.940 analysis." 42:35.940 --> 42:38.630 So you can take some foodstuff and see what percentage of 42:38.628 --> 42:41.268 protein, what percentage of sugar, or what percentage of 42:41.268 --> 42:42.948 this, that and the other thing. 42:42.949 --> 42:46.069 So what you read on a candy bar, or something like that, 42:46.072 --> 42:48.342 that's proximate analysis, not elemental, 42:48.342 --> 42:49.822 not ultimate analysis. 42:49.820 --> 42:53.970 So both kinds are important in Lavoisier's work, 42:53.974 --> 42:55.304 as we'll see. 42:55.300 --> 42:59.650 Okay, so we looked at light and caloric. 42:59.650 --> 43:01.780 Now let's look at a few of these elements, 43:01.782 --> 43:03.292 the ultimate elements here. 43:03.289 --> 43:09.139 He had the fact, the theory and the word for 43:09.139 --> 43:11.179 these things. 43:11.179 --> 43:14.039 So how about Azote? 43:14.039 --> 43:17.179 Why is that word -- that's the French name for -- 43:17.179 --> 43:21.169 the French still call nitrogen azote, 43:21.170 --> 43:25.490 and in this English translation it was called that in 1790 or 43:25.487 --> 43:25.917 '91. 43:25.920 --> 43:30.070 Okay, where does that word come from? 43:30.070 --> 43:34.270 What does the prefix a mean? 43:34.269 --> 43:37.039 Student: Without. 43:37.039 --> 43:38.049 Prof: Without. 43:38.050 --> 43:39.720 And how about zo? 43:39.719 --> 43:42.419 It's great we have somebody taking Greek. 43:42.420 --> 43:43.190 Student: Life. 43:43.190 --> 43:45.100 Prof: Without life. 43:45.099 --> 43:48.909 In what sense is that an appropriate name, 43:48.911 --> 43:51.981 a meaningful name for nitrogen? 43:51.980 --> 43:53.510 Alex? 43:53.510 --> 43:54.940 Student: I think they performed the tests on nitrogen 43:54.943 --> 43:56.393 first and it was -- Prof: What kind of tests? 43:56.389 --> 43:57.789 Student: They would suffocate like a bird in 43:57.788 --> 43:58.088 nitrogen. 43:58.090 --> 44:01.490 Prof: Yes, if you put a mouse in an 44:01.485 --> 44:04.875 atmosphere of nitrogen, it's azote. 44:04.880 --> 44:05.710 Right? 44:05.710 --> 44:07.610 So that's what the name meant. 44:07.610 --> 44:11.130 It used to be called phlogisticated air, 44:11.132 --> 44:15.112 or gas, or mephitis, or the base of mephitis. 44:15.106 --> 44:16.006 Right? 44:16.010 --> 44:20.000 Azote is the name that Lavoisier decided to use for it. 44:20.000 --> 44:24.090 Or hydro-gen. 44:24.090 --> 44:26.560 How about it, help us out? 44:26.559 --> 44:30.349 Student: Hdor would've been water. 44:30.349 --> 44:31.529 Prof: Pardon me? 44:31.530 --> 44:32.410 Student: Water. 44:32.409 --> 44:34.209 Prof: What about water? 44:34.210 --> 44:34.740 Hydro is water. 44:34.739 --> 44:37.439 What's gen? 44:37.440 --> 44:39.550 Student: To leave water. 44:39.550 --> 44:41.450 Prof: It makes water. 44:41.454 --> 44:41.934 Right? 44:41.929 --> 44:46.439 So if you burn hydro-gen, you generate water. 44:46.440 --> 44:47.260 Right? 44:47.260 --> 44:48.740 So hydrogen. 44:48.739 --> 44:49.759 Okay. 44:49.760 --> 44:53.820 How about oxy-gen? 44:53.820 --> 44:55.730 What does it generate? 44:55.730 --> 44:57.290 Students: Acid. 44:57.289 --> 44:59.429 Prof: Acid, sourness. 44:59.429 --> 45:02.589 So oxygen is the element that generates sourness, 45:02.590 --> 45:04.040 that generates acid. 45:04.039 --> 45:08.149 And that is the key element in Lavoisier's theory, 45:08.148 --> 45:10.998 the oxygen theory of combustion. 45:11.000 --> 45:14.100 Okay, so oxygen, plus a base, 45:14.096 --> 45:16.526 or radical -- right? 45:16.530 --> 45:19.940 So these two terms meant the same thing to Lavoisier, 45:19.938 --> 45:23.278 the fundamental radical, the root of some substance, 45:23.284 --> 45:23.944 right? 45:23.940 --> 45:27.630 And you react it with oxygen and it makes the stuff into an 45:27.634 --> 45:28.084 acid. 45:28.079 --> 45:32.949 Can you think of an example of an element that you react with 45:32.951 --> 45:35.551 oxygen and it becomes an acid? 45:35.550 --> 45:37.880 Well let's just look in his table. 45:37.880 --> 45:41.550 Sulfur; you burn it and it becomes 45:41.550 --> 45:44.340 sulfuric acid, or sulfurous acid. 45:44.344 --> 45:45.134 Right? 45:45.130 --> 45:47.450 Phosphorous generates phosphoric acid. 45:47.449 --> 45:49.529 Carbon generates carbonic acid. 45:49.530 --> 45:53.520 Muriatic radical -- which we don't know; 45:53.518 --> 45:56.848 they haven't discovered the muriatic radical yet, 45:56.849 --> 46:01.149 the base of that acid -- but if you burn it and combine it with 46:01.150 --> 46:03.510 oxygen, you get muriatic acid. 46:03.510 --> 46:06.080 Does anybody know what muriatic acid is? 46:06.079 --> 46:06.539 Student: Hydrochloric acid. 46:06.539 --> 46:07.389 Prof: Hydrochloric acid. 46:07.389 --> 46:09.099 How much oxygen is in it? 46:09.099 --> 46:09.779 Student: None. 46:09.780 --> 46:11.210 Prof: None, right? 46:11.210 --> 46:13.120 But that was the theory, that you take a base, 46:13.115 --> 46:14.975 you react it with oxygen, you get an acid. 46:14.980 --> 46:19.360 So there must have been a muriatic radical. 46:19.360 --> 46:20.040 Okay? 46:20.039 --> 46:21.949 Unfortunately that part of it was wrong. 46:21.949 --> 46:25.519 The same for fluoric radical. 46:25.519 --> 46:25.979 Okay? 46:25.980 --> 46:29.300 But then there were also compound radicals, 46:29.302 --> 46:33.262 radicals that were only proximate, not ultimate; 46:33.260 --> 46:37.560 radicals that had several other elements in them. 46:37.561 --> 46:38.281 Right? 46:38.280 --> 46:41.980 And here were some of those, a list of those radicals, 46:41.980 --> 46:45.890 with the names that Lavoisier decided to use for them. 46:45.889 --> 46:48.539 And many of them, all the ones indicated by an 46:48.539 --> 46:51.719 arrow, are ones that Scheele had already discovered; 46:51.719 --> 46:54.089 like tartaric, citric, oxalic, 46:54.094 --> 46:55.574 benzoic, lactic. 46:55.570 --> 46:58.380 Lithic acid was another one that I didn't mention before, 46:58.376 --> 47:02.416 which comes from stones; see, it's from urinary calculus. 47:02.420 --> 47:05.580 Okay, so those were compound radicals. 47:05.579 --> 47:09.469 And that's the end of today's lecture. 47:09.469 --> 47:14.999