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Author: Subject: Phosphorus Chlorides
Formatik
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[*] posted on 22-2-2009 at 14:25


Quote:
Originally posted by Sauron @Formatik, are the 7th edition vols on Google Books downloadable? That is, were they published prior to 1923?


Yes. Here are the links:

Vol.1.
Vol.2.
Vol.3.

My favorite volume is the first.
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JohnWW
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[*] posted on 22-2-2009 at 15:03


I understand that Google Books only posts old books, or parts only of books published after 1923, as GIF images, one on each web-page, which have to be individually downloaded or screen-captured, not as single PDF or DJVU files. This consumes a fair amount of time. However, I would appreciate it if someone with enough time can download it all, and upload it to rapidshare.com or elsewhere as a single PDF/DJVU/ZIP/RAR file, please.
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[*] posted on 22-2-2009 at 15:36


John, Polverone posted about this in the Ongoing Scanning Projects thread.

Google Books does offer pdf downloads for pre-1923 books, but for post 1923, most are not even viewable in preview. The few that are previewed are page by page as PNG not GIF, It is possible, but arduous and kludgy to copy them out of temporary internet files folder page by page, convert to PDF and assemble.

Note that Google does this regardless of copyright status, in other words, is a book is public domain in fact, but post 1923, Google will not offer it for download, this is their cavein deal with the publishers lobby.

Formatik, thanks but I can't view those books on those links much less d/l themm.

Google Books sucks.




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[*] posted on 22-2-2009 at 18:49


I was able to download 3 pdfs composed of scanned images. Where should I put them so people who can't get to them via Google can download them?
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[*] posted on 22-2-2009 at 19:39


Quote:
Originally posted by Sauron Formatik, thanks but I can't view those books on those links much less d/l themm.

Google Books sucks.


The fault lies in what country one wants to access it from. Google books doesn't like Thailand for some reason. You can try using a server from another country to access it.
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[*] posted on 22-2-2009 at 22:10


Thanks, formatik. I have had bad experiences with proxies in past.

I like densest's suggestion, because surely this problem is not unique to me.

I am not entirely sure that Google's alleged attitude toward Thailand is the problem.

I was able to download the entire issue of Philosophical Magazine with the Gladstone paper in it, once Polverone showed me where the icon and link were located.

But that is not the case with the three links you posted. So I am perplexed. Those old editions of Gmelin are way before 1923.

[Edited on 23-2-2009 by Sauron]




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[*] posted on 24-5-2009 at 15:08


FUCK PROXIES - go take out an acct on webs.com - setup a basic website in your username (using whatever email addy you like)... Upload your pdf files to that site in a folder marked pdf then into sub-folders

For example: "The Thermal Decomposition of Copper(II) Nicotinate and Isonicotinate" Thermochemica Acta, 138 (1989), 233-9
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[*] posted on 16-11-2010 at 09:18


I found this on Synthetikal.

Phosphorous Trichloride via TSP(tri-sodium phosphate)
Sat Feb 18, 2006 7:42 am
--------------------------------------------------------------------------------
Phosphorus trichloride
can be prepared in a three-step process starting with the formation of calcium phosphate. This crude technical grade of calcium phosphate is prepared by mixing aqueous solutions of trisodium phosphate and calcium chloride.

The mixing causes the water insoluble calcium phosphate to precipitate. The precipitate is readily filtered-off, washed, and then dried in the usual manner. Thereafter, the crude calcium phosphate is then roasted at high temperature in the presence of carbon, whereby it gets reduced to calcium phosphide. Note: some elemental phosphorus may be liberated in the reaction, so use proper ventilation.

The calcium phosphide crude mixture is then chlorinated to form a mixture of compounds, one of which being the desired phosphorus trichloride. After the chlorination process, the reaction mixture is filtered, and then distilled using a conventional distillation apparatus to remove the methylene chloride solvent. Finally, the remaining crude liquid left over after removal the methylene chloride, is then fractionally distilled to recover the liquid product of phosphorus trichloride. The distilled phosphorus trichloride can be re-distilled if desired.

Hazards: Use good ventilation when working with chlorine gas, and avoid inhalation of the fumes. Use caution when heating the calcium phosphate as small amounts of white phosphorus may be evolved.
Procedure:

Step 1: Preparation of calcium phosphate

Into a suitable beaker or similar container, place 250 grams (8.8 grams) of technical grade (store bought) trisodium phosphate, and then add in 750 milliliters (25.2 fluid oz.) of warm water, and then stir the mixture to dissolve all of the trisodium phosphate (technical grade). Note: technical grade and store bought trisodium phosphate (TSP) contains sodium carbonate and maybe some sodium hydroxide to prevent the product from caking. This sodium carbonate and any other alkaline product needs to be neutralized before the initial reaction. To do this, first, place 250 grams (8.8 grams) of the dry TSP product from the packaging container into a suitable crucible or similar container, and then roast it at 150 to 250 Celsius for 1 hour to remove several moles of water of hydration. Thereafter, break-up the re-solidified TSP product from the crucible or similar container, and then dissolve it into 750 milliliters (25.2 fluid oz.) of water contained in a suitable beaker or container. Thereafter, drip hydrochloric acid, battery acid, or sulfuric acid into the trisodium phosphate solution until the evolution of carbon dioxide gas ceases. Once this point is achieved, the sodium carbonate has been neutralized. Now, to this trisodium phosphate solution, add in a calcium chloride solution prepared by adding and dissolving 250 grams (8.8 oz.) of anhydrous calcium chloride into 750 milliliters (25.2 fluid oz.) of cold water—heat will be evolved upon dissolving. Note: anhydrous calcium chloride is obtained by placing a sample of at least 300+ grams of technical grade calcium chloride, available in hardware stores and grocery stores sold as “ice melter”, into a crucible or similar container, and then roast the technical grade calcium chloride at 200+ Celsius to remove the water of hydration. Thereafter, the anhydrous calcium chloride can be dissolved into the 750 milliliters (25.2 fluid oz.) of water, once the anhydrous salt has cooled. Upon mixing the two solutions of trisodium phosphate and calcium chloride, a precipitate of crude calcium phosphate tribasic, mixed with a small amount of other calcium phosphates, will form a chunky and messy precipitate. Thereafter, filter-off this chunky precipitate using gravity filtration, or preferably vacuum filtration, and then wash this precipitate with three 500 milliliter (three 16.9 fluid oz. portions) portions of warm water. Thereafter, vacuum dry or air-dry the washed filtered-off precipitate. Finally, place the dried calcium phosphate into a crucible or similar container, and then roast it at 100 to 150 Celsius for an hour or so to remove any moisture or water of hydration. Thereafter, pulverize the heated calcium phosphate into a fine powder, once it has cooled.

Step 2: Preparation of calcium phosphide

Now, into a zip lock bag, or similar plastic container, place the pulverized calcium phosphate (prepared in step 1), followed by 100 grams (3.5 oz.) of finely powdered wood charcoal (average charcoal used for cooking, with no quick-light garbage or other chemical addictives), and then shake the bag thoroughly for about 10 to 15 minutes to thoroughly mix both solids. Thereafter, place this mixed powdered mixture into any high heat resistant crucible, such as stainless steel crucible, nickel, or quartz crucible, or equivalent, and then blast this mixture at 1000 Celsius using a high temperature Meeker Bunsen burner or equivalent for about 1 hour or so. If a high temperature Bunsen burner is unavailable, you can use a fire or some other means of heat. After the roasting process, remove the heat source, and allow the hot mixture to cool to room temperature. Now, at this point, the blackish-gray mixture will be composed of calcium phosphide, calcium oxide, a little calcium carbide, unreacted calcium phosphate, and un-reacted charcoal. Keep this mixture as is for use in step 3.

Step 3: Preparation of phosphorus trichloride

Into a suitable apparatus, as illustrated below, place the crude product obtained in step 2, and then add in 250 milliliters (6.9 fluid oz.) of methylene chloride. Then begin the motorized stirrer on moderate speed, and then bubble into the mixture, 200 grams (7 oz.) of extra dry chlorine gas over a period of 2 to 6 hours while stirring the reaction mixture on moderate speed. Note: dry chlorine can be obtained by passing the chlorine through multiple anhydrous calcium chloride drying tubes. During the addition of the chlorine gas, phosphorus trichloride will form, and will be taken-up into the methylene chloride. The by-products, will form insoluble precipitates along with the carbon. After the addition of the chlorine gas, the mixture needs to be filtered, to remove the insoluble materials, and then the resulting filtered mixture needs to be passed several times, through a silica gel column, filled with 100 grams (3.5 oz.) or so of aluminum oxide (see illustration). Thereafter, the mixture should be placed in a distillation apparatus, and first, distilled at 40 Celsius to remove the methylene chloride. Thereafter, place the remaining mixture into a fractional distillation apparatus, and fractionally distill the product mixture at 76 Celsius to collect the phosphorus trichloride. Note: during all distillations, keep a drying tube attached to the apparatus to keep moisture out.

:o

Preparation of calcium phosphide:

Attachment: Calcium phosphide (p66-68, Introduction to Chemical Preparations - Hugo Erdmann 1st ed. 1900) .pdf (272kB)
This file has been downloaded 715 times
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[*] posted on 16-11-2010 at 11:54


Quote: Originally posted by Mush  
I found this on Synthetikal...


The anonymous author's description of step 2, reduction of calcium phosphate to phosphide, is a flight of fancy. It has the combination of tantalizing theory plus vague and implausible experimental details that mark many fringe literature sources of unreliable chemistry. I would give better than even odds that step 3 is the same. Either someone wants praise without experimental effort, or they want experimental validation without experimental effort, so they write up imagined ideas as if they had already been proved by experiment and hope that others will follow in their fabricated footsteps. Sometimes it's fabrication combined with plagiarism: different old patents and procedures strung together with leaps of imagination and without acknowledgment or experimental validation.




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[*] posted on 16-11-2010 at 16:05


Step 1 is also has useless instructions. First he says that commercial ice melt CaCl2 is technical grade (commercial and technical grade are not the same, I can tell you that ice melt has all kinds of crap in it...). Then he gives bogus instructions for achieving anhydrous CaCl2 (roasting at 200C will get you likely a mixture of mono- and di- hydrate). But since we are then dissolving the CaCl2 in solution, why did we bother removing any water of hydration? Why not estimate the degree of hydration and then use CaCl2 in excess corresponding to the uncertainty in our estimate? Further, if you want 250g of anhydrous CaCl2, you would need to start with rather more than 300g of the commercial hydrate, as he would know if he had either done the prep or done any calculation.
Oh, and same thing regarding roasting the Na3PO4 in step 1: why dehydrate and then dissolve in water? If the instructions were to dehydrate first and *then* weigh, at least it would make sense as a way of getting a known (ahydrous) composition. But that's not what he does!

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[*] posted on 16-11-2010 at 16:10


We have established that the above is shot full of holes. To be expected from a drug site as there members don't wish to experiment all to often and only wish to make a buck from a confirmed TEK. However what of Phosphide production do we have any threads here on various productions of phosphides? They are useful. No I have not looked yet so excuss my ignorence.




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[*] posted on 12-6-2011 at 02:35


And yet the premise holds true (apparently - according to the illustrated practical guide shown in the attached paper - quote from page 4/5)):

Quote:
FIGURE 18.1 A color version of this figure follows page 112. Calcium phosphide heated to 240°C reacts with a dull red glow with chlorine gas, yielding PCl3, which is further oxidized to PCl5. After about three quarters of the stoichiometric amount of chlorine has been introduced, PCl5 sublimes out of the reaction zone and is deposited as light yellow cakes on the walls of the receiver flask.


Now we need a practical route to Calcium Phosphide (Ca3P2). The papers we know of show that tricalcium phosphate does, in fact, lead to phosphorus when heated with carbon. Aluminium leads (apparently) to Aluminium Phosphide (although I'm wondering why we couldn't use that instead? Aluminothermic reductions are easier to run after all.

Attachment: Lerner.Small.Scale.Synthesis.of.Laboratory.Reagents.with.Reaction.Modeling.Ch.18.Phosphorus.Pentachloride.pdf (106kB)
This file has been downloaded 4946 times

Attachment: Jacob.Reynolds.Hill.Reduction.of.Tricalcium.Phosphate.by.Carbon.Effect.of.Silica.and.Alumina.on.the.Reaction.pdf (948kB)
This file has been downloaded 1068 times

Attachment: Jacob.Reynolds.Reduction.of.Tricalcium.Phosphate.by.Carbon.pdf (1008kB)
This file has been downloaded 521 times

Can anyone get hold of the french papers cited in this last paper? They detail (apparently) the reduction of Calcium Phosphate to give the phosphide (Moissan, Comptes Rendus, 128, p.787 (1898) & Renault, Comptes Rendus, 128, pp.883-884 (1898).)

Attachment: Monroe.The.Commercial.Manufacture.of.Amorphous.Calcium.Phosphide.pdf (543kB)
This file has been downloaded 516 times

Although I've seen references to the reaction of phosphine in an atmosphere of chlorine (giving HCl + PCl5) so I'd imagine damp chlorine run into aluminium phosphide (might want to use a hood for that) should be interesting, solid + a gas = a solid plus a gas with an obvious reaction.

[Edited on 12-6-2011 by aliced25]




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