Sciencemadness Discussion Board

Google Books is becoming useful (tutorial now included)

Polverone - 23-6-2007 at 15:34

I remember that I took a look at Google Books when it was first launched, and I was very underwhelmed. Now it seems to be a useful resource for chemistry. The materials that allow only snippet views are usually near-worthless, but the limited preview and full view materials are quite nice.

As an example, here are some topics that have been extensively discussed on Sciencemadness that happen to be well-addressed through material on Google Books:

-Reduction of nitrates to nitrites with carbon or metals
-Production of piperic acid from pepper as its potassium salt and subsequent oxidation to piperonal
-Production of cyanides via numerous methods, including high-temperature cyanate reduction and many other now-unused processes
-Production and medical use of chlorobutanone (chloretone)
-Production of 2,4 dinitrophenol
-Reduction of phosphoric acid and phosphates using metals

Since most of the full-view materials are those old enough to have entered the public domain from the expiration of their copyrights, some knowledge of archaic terminology/synonyms may be useful when employing Google Books. But of course this is also true when looking at older books in an ordinary library.

In some cases there's no new information available in Google Books compared to what has already been posted to threads here, but the information is a lot easier to find via Google than it was with old-fashioned research in the stacks. In other cases the information is broadly the same as what was known before, but is presented in more detail than what could be gleaned from previously known sources. In some cases the information found has not been presented at all in previous threads about these topics.

I've also found that Google sometimes mis-categorizes/mis-recognizes the works it is storing and serving, so you will occasionally stumble across an opportunity to download full copies of works that are still in copyright and probably not intended for downloading (for example, I found a full volume of JACS from the 1960s that was available for download). Coverage is currently spotty, but it looks like a lot of older journals will be available in full, and for free, in addition to the books proper. There are dozens of other online collections containing older chemistry material, but none is so easily searched as Google Books, which makes a tremendous difference during research.

[Edited on 6-24-2007 by Polverone]

Organikum - 24-6-2007 at 03:08

My Google books searching skills suck. I just spent half an hour searching for the reduction of phosphoric acid and phosphates using metals and came up with nothing useful.

Might it be possible that those who have superior searching skills post their findings in a dedicated thread?
Or a tutorial "How to search at Google Books for idiots" maybe?
If those skilled in the art would disclose in such a thread what search terms they used then this might serve a double purpose. The information and the means to dig things up by oneself.

regards

[Edited on 24-6-2007 by Organikum]

Polverone - 24-6-2007 at 12:33

The books can be harder to search than the Web, since terms aren't hyperlinked together across publications. You have to be better at guessing words that are likely to appear together in materials of interest. It can also be worthwhile to dig several pages deep into the results, since the ordering by relevance given is not quite so good for books as for the Web.

In the case of phosphorus, I start out with

aluminum phosphorus reduced

since aluminum has shown promise as a reducing agent according to our existing (and very long) thread, and since aluminum has been widely investigated as a high temperature reducing agent. I also set the view to "limited preview" so I don't waste any time with snippets. Finally, under "advanced book search," I constrain the time period from 1880 to 1930. It seems unlikely that earlier materials will address my interests, due to the very limited availability of aluminum, and later materials seem unlikely to be useful due to the well-established dominance of arc furnace production of phosphorus using carbon as reducing agent.

The second hit comes from The Mineral Industry, published 1899, and begins "L. Franck has found that sodium metaphosphate mixed with an excess of aluminum powder and heated to dull redness is reduced energetically, the phosphorus being eliminated in part as vapor... When (bone ash treated with hydrochloric acid) was heated to redness with aluminum powder and diatomaceous earth, the phosphorus, to within a very small fraction, distilled off quietly."

In the same book, shortly following the passage about reduction of phosphates with aluminum, is found this interesting bit which may later form the basis of a new series of searches:
"L. Dill, of Frankfort-am-Main, proposes to produce alloys of phosphorus with metals by subjecting phosphoric acid or a concentrated solution of an acid phosphate salt to electrolysis with with a carbon electrode and an electrode of the metal to be alloyed. By passage of the current the phosphorus separates and combines with the metal of the electrode, which melts down."

Now it is possible to make a narrower search:

aluminum phosphorus franck

This immediately shows a hit on the 1898 Journal of the American Chemical Society, which essentially recaps the information given above but re-emphasizes that calcium metaphosphate is the preferred material, and states that the quality of phosphorus thus produced is excellent. The same article mentions a couple of other unusual processes which may be noteworthy if not practical: "Collardeau makes calcium phosphide in the electric furnace, generates hydrogen phosphide with it, and decomposes the gas by passing it through a strongly heated coke-lined tube, and collects the phosphorus liberated; and Boubleque decomposes electrolytically the iron phosphide obtained by fusing together iron compounds and calcium phosphate and removes the liberated phosphorus by a current of indifferent gas."

It appears that Franck's name is a good keyword, but a bit too narrow; we only get a page of results back. Since the materials found emphasize metaphosphate salts, let's try

aluminum phosphorus metaphosphate

This produces as a result the 1894 Proceedings of the American Pharmaceutical Association, which attributes the aluminum/metaphosphate process to Frank and Rossel, and additionally gives a primary reference: "A. Rossel and L. Frank, Ber. d. Chem. Ges. (Rep.), 1894, 38."

It describes Rossel's variation also: "It is prepared by a process patented by Rossel, of Bern, by which glacial phosphoric acid or alkaline metaphosphates are heated with metallic zinc or aluminum; the metals dissolve in fused acid or its salts, and phosphorus distills over; this reaction takes place at a low red heat, whereas in the older process of reducing the metaphosphate with carbon a very intense heat was necessary."

Note that here it is L. Frank rather than L. Franck, so it is worth keeping the alternate spellings in mind when doing any further searches using the name as a keyword. Likewise, it may be useful to repeat searches substituting "aluminium" for "aluminum," in order to get non-American literature as well as some older American publications.

Another result produced from the previous search string is the Experiment 226 from the 1904 book The School Chemistry: A New Text-book for High Schools and Academies:
"Mix intimately 25 grams of aluminum powder with 60 grams of sodium metaphosphate and 20 grams of powdered silica. Place the mixture in a good-sized combustion-tube (about a meter in length), the mouth of which is bent to dip beneath water. Slowly heat the mixture to a moderate red heat, at the same time passing a slow current of hydrogen through the tube. Phosphorus will collect in the front part of the tube and may be expelled by heat into the water."

The details offered here immediately suggest that this may be a practical method for amateur production of phosphorus. Other modifications or improvements -- such as the substitution of tank nitrogen or argon for the more flammable and difficult-to-buy hydrogen, or the substitution of calcium metaphosphate for sodium, as suggested in previous readings -- also immediately come to mind.

All the methods seem united in the use of aluminum and silica to reduce various salts to phosphorus. Search for

aluminum reduce phosphorus silica

and one of the hits on the first page is 1905's The Production of Aluminum and its Industrial Use. It contains the following passage:
"Accidentally, during his investigations as to the possibility of soldering aluminum, Professor Rossel in Bern observed that phosphates are reduced by aluminum. When Rossel heated a mixture of aluminum-foil and phosphoric substances (phosphates) in a porcelain crucible, he observed that little flames spurted out at the side of the melt. He repeated the experiment in a closed tube... to reduce all the phosphoric acid to phosphorus, to the mixture of aluminum and phosphates (or, better, metaphosphates) silica had to be added."

Oddly, this passage does not appear when searching for Rossel and phosphorus, probably due to OCR error. Performing slightly altered, nearly redundant searches can be useful since not all text is recognized perfectly and different keywords may be needed to hit all relevant material. The passage is useful in that it indicates the aluminum used need not be an extremely fine powder and that in fact foil itself may be employed.

From Google Books we have found:
--That aluminum and zinc are suitable reducing agents for the production of elemental phosphorus
--The optimal conditions for the use of aluminum as the reducing agent, including the need for fine silica (diatomaceous earth) to complete the liberation of phosphorus
--Concrete instructions for the laboratory-scale production of phosphorus using aluminum
--That it may be possible to substitute aluminum foil for powder, should powder not be available

I am not sure that anything useful and not already known or suspected by contributors to the phosphorus thread has been revealed by this time spent with Google Books. But it was possible to learn a lot of useful information through a single interface and in a relatively short period of time. That is the great advantage compared to traditional library research or to digitally searching for material in older chemistry journals/books scattered across several sites (Making of America, Internet Archive, Digital Library of India, Gallica.bnf.fr, etc.). We also have promising initial leads for phosphide and phosphine processes should the urge strike to investigate those (likely harder and more hazardous) routes to elemental phosphorus and useful phosphorus compounds.

Google Books is still annoying in a few ways. There is no way to copy text directly from the interactive book view, and downloaded PDFs do not contain OCR text. OCR text is imperfect. The search engine's ranking by relevance also seems not as good for books as for the web, as previously mentioned. I think it's already a great resource for this sort of arcane/historical digging, though, and likely to get better as search, OCR, and catalog size improve.

[Edited on 6-24-2007 by Polverone]

tito-o-mac - 1-7-2007 at 00:33

I suggest wikibooks are user-friendlier. But I still think websites are better. If you're the crazy pryomaniac guy, I found this website very useful. Not just that, it includes step by step instructions on how to make chemical weapons too! http://www.roguesci.org/megalomania/explosives.html

S.C. Wack - 11-8-2007 at 20:56

I still have no problem viewing and downloading books there, but today discovered that I have a problem with full view journals. For me at least they are no longer downloadable or even viewable, though they linked to as full view. French, German, everything - every chemistry journal from Arch. Pharm. to Z. anorg. is now unavailable to me...It was working not long ago, I downloaded JACS 1879-1903, 1918, +partial 08, 12, 19, and '20 just 14 days ago. Is this just me or the USA or WTF???

kclo4 - 11-8-2007 at 22:03

http://www.jimmyr.com/mp3.php
this is a wonderful site!
finds music, and everything
but it has a PDF search, it searches for only PDF documents and most of them are pretty good :)
i use it and like it a lot

Polverone - 12-8-2007 at 10:20

Quote:
Originally posted by S.C. Wack
I still have no problem viewing and downloading books there, but today discovered that I have a problem with full view journals. For me at least they are no longer downloadable or even viewable, though they linked to as full view. French, German, everything - every chemistry journal from Arch. Pharm. to Z. anorg. is now unavailable to me...It was working not long ago, I downloaded JACS 1879-1903, 1918, +partial 08, 12, 19, and '20 just 14 days ago. Is this just me or the USA or WTF???

It's not just you. Now when I try searching for "journal of" and confine my search to full text results, I get only snippet views and no downloads, despite the results being marked as full text on the search page. I wonder if Google has disabled full-text for journals for now because of their occasional misclassification problems where they thought certain journal publications were older than they actually are, and wrongly made them available in full text form.

Polverone - 7-9-2007 at 21:47

It looks like the journals are working again. There's also now an option to view OCR text only, instead of scanned page images.

Hathi Trust -- a valuable supplement to Google Books

Polverone - 21-6-2009 at 16:20

I don't know how I missed Hathi Trust for so long. It brings together (among other things) the Google Books scans that Google has given to the different libraries Google gathers content from. Not every participating library is part of Hathi Trust but a fair number are, and the collection also includes content from a number of smaller e-text projects that predate the Google effort. The Hathi Trust just added experimental full text search at the end of April. Their online book viewer is cruder than that available from Google Books or the Internet Archive. So why use the Hathi Trust collection?

The Hathi Trust has much of the content Google Books offers, but with less stringent (more correct) copyright restrictions. Unless publishers specifically opt-in or never held copy right (like with some government publications), Google Books will not show full text for post-1922 volumes. Hathi Trust appears to be actually checking copyright status rather than assuming post-1922 publications were always renewed. This means that there are volumes you can download full-text from Hathi Trust that are not available from the Internet Archive or Google Books.

For example, Advanced Organic Chemistry by Reynold C. Fuson, copyright 1950, is completely absent from the Internet Archive. It is present in Google Books, but not viewable. The full text, scanned by Google, is available from the Hathi Trust.

Edit: Another example: Volume VI of Reid's Organic Chemistry of Bivalent Sulfur is also available in full-text.

Hathi Trust also does not offer one-click download for a complete book, so if any especially interesting items are found I will have to script the download process.

[Edited on 6-27-2009 by Polverone]