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S.C. Wack
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Unfortunately it appears that no one else is as sure as you are, according to Kirk-Othmer, Gmelin's, and Ullmann's, so please excuse me for sticking
with the literature.
Why should I have to build an arc furnace to prove Hermann Hilbert, Albert Frank, Jonas Kamlet, and Nikodem Caro, PhD's all, full of shit, because you
don't believe what they say, even though no one has any reason to doubt them?
BTW the phosphates of iron and aluminum are also known to be reduced by carbon, in addition to the mercury and lead, long ago.
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len1
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No its your interpretation of what you have read that I dont take for gospel- why should I, as you havent actually done anything.
If all you do is read stuff without ever trying to do any of it, not only are you a receptacle for a lot of rubbish as well as all the good stuff, you
have no ability to be able to differentiate amongst it. Thats something I commented to Sauron about as well. You at least do not write your posts as
if youre about to actually do something practical.
By the way I should add the results are in now - several thousand posts of what he was going to do - he's gone, none of it done. It was all bullshit.
[Edited on 22-11-2009 by len1]
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DJF90
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Len1 - I think you'll find a chemists eyesight is a necessary peripheral; without such, many things cannot be done. I have not heard from Sauron from
a long time. Short of kicking the bucket, this is the only factor I can think of as to why he has not replied to emails/posted here etc, especially as
his eyesight was failing when he was last active here. Even other friends of his have not heard from him. If anyone has been in contact recently,
please U2U me.
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entropy51
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Quote: Originally posted by len1  | No its your interpretation of what you have read that I dont take for gospel- why should I, as you havent actually done anything.
If all you do is read stuff without ever trying to do any of it, not only are you a receptacle for a lot of rubbish as well as all the good stuff, you
have no ability to be able to differentiate amongst it. Thats something I commented to Sauron about as well. You at least do not write your posts as
if youre about to actually do something practical.
By the way I should add the results are in now - several thousand posts of what he was going to do - he's gone, none of it done. It was all bullshit.
[Edited on 22-11-2009 by len1] |
It must be such a burden to have to deal with those of us who believe that
most of the chemical literature is not bullshit. Sounds like the voice of someone who's not published much himself, else he would know that peer
review, though imperfect, does tend to filter out the rubbish. | Quote: Originally posted by len1 | | As for the patent Im afraid the patent world is full of bullshit - but thats nothing new if one regularly visits the world of practical chemistry.
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The literature is bullshit. Patents are bullshit. What are we to do? Whom are we to believe? Luckily we
have len1 to show us the truth!
[Edited on 22-11-2009 by entropy51]
[Edited on 22-11-2009 by entropy51]
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len1
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Anyonw who says the above has just not tried to do much in the real world. Lost in the clouds.
DJF90 - well in that case he could have written Im sorry I can not do this or that, can someone check it out for me. That would have earned much more
respect. When you start lying, youre finished as a scientist.
PS I thought Ill add to this, because the relevance of the second sentence of the above post at first escaped me. What the poster is saying is that
maybe in my experimental work here I was free to flag some literature work as bullshit, but if I tried to publish it I would be put straight. Yes
that is correct, part of the human condition is promulgating undeserved respect to others at the expense of honesty. I have several published papers
to the effect that this or that publication is 'bullshit'. Each time I had to fight to get them accepted - sometimes in a different journal, one in
particular took 3 years. What the poster is saying is that we soon learn not to write such things, in essence helping each other lie. But I dont want
to give the impression that sources such as 'kirk-othmer' deliberately lie. It contains errors because its a compilation, its writers mostly have no
direct knowledge of what they are reporting. Errors creap in because of misunderstandings with what the original work was trying to say, and because
the science in some of the many original works it references is faulty. In the given instance Im not saying the phosphrus entry lies, the poster
does.
[Edited on 22-11-2009 by len1]
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blogfast25
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| Quote: Originally posted by len1 | Anyonw who says the above has just not tried to do much in the real world. Lost in the clouds.
DJF90 - well in that case he could have written Im sorry I can not do this or that, can someone check it out for me. That would have earned much more
respect. When you start lying, youre finished as a scientist.
PS I thought Ill add to this, because the relevance of the second sentence of the above post at first escaped me. What the poster is saying is that
maybe in my experimental work here I was free to flag some literature work as bullshit, but if I tried to publish it I would be put straight. Yes
that is correct, part of the human condition is promulgating undeserved respect to others at the expense of honesty. I have several published papers
to the effect that this or that publication is 'bullshit'.
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Those are serious allegations, len1.
You've been able to flag some literature as bullshit and I can easily believe that. But it appears to be on those grounds that you believe also to be
right in this case?
That clearly seems to be the train of thought:
"I showed some literature to be BS and I was right.
I believe this literature to be BS too, and since I was right about these other cases, ergo I must be right on this one too."
Not very empirical either.
I take it then that you have compared, back to back (silica/no silica), in controlled conditions, the alleged effect of silica?
Where you write "Yes that is correct, part of the human condition is promulgating undeserved respect to others at the expense of honesty.", I
completely agree. But your statement doesn't mean you're right on this particular case.
From a thermochemical point of view, I don't think it matters much what form the phosphorus is in, as long as the species derives from P2O5. High
temperature reaction of the phosphate with carbon pushes the equilibrium:
phosphate + C ---> n P4 (g) + m CO (g)
to the right due to the volatility and distilling off of the P4 and the CO - Law of Mass Action.
A Gibbs Free Energy change calculation ΔG = ΔH - TΔS could probably show a negative number (or close to 0) due to a strong entropic
term.
It's possible the reaction is somehow facilitated by the presence of silica but the evidence doesn't seem to point strongly to that.
This reaction is similar to the reduction of chlorates (+V to -I), perchlorates (+VII to -I), nitrates (+V to o) or sulphates (+VI to -II) in thermite
reactions.
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len1
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Hey? No this was just my reply to that one who believes the literature is all good.
The lack of participation of silica in the reaction, was claimed by that wack in the tirade. Still the formula including silica is in the sources he
mentioned, so it seemed little point discussing it. Instead I pointed out the interpretations of someone who only reads literature and imagines he can
understand everything from that are likely to be misguided. I found the same to be the case with Sauron, he posted interesting literature, but his
interpretation was of someone who had little first hand experience.
In the high temperature phosphate reaction the first stage is generally written as
Ca3(PO4)2 + 3SiO2 -> 3CaSiO3 + P2O5
with subsequent reduction by carbon. To see how silica drives the equilibrium, one only has to calculate the free energy change in the formation of
CaSiO3 from the two oxides.
At very high temperatures you can get the reduction to proceed without silica as you say but the whole point of the metaphosphate process is that it
goes at much easier attained temperatures
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blogfast25
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If you suppose a significant difference in DH for these reactions:
Ca3(PO4)2 ---> 3 CaO + P2O5
3 CaO + 3 SiO2 ---> 3 CaSiO3
Then
Ca3(PO4)2 + 3 SiO2 --> 3 CaSiO3 + P2O5
could be significantly exothermic. Do you have some data?
And roughly what temperature for the metaphosphate process?
Here's a source that does confirm use of silica:
http://mysite.du.edu/~jcalvert/phys/phosphor.htm#Mine
"Elemental phosphorus is produced in electric [arc?] furnaces by heating phosphate rock, sand and coke. The silica combines with the phosphate rock to
give calcium silicate, a slag, and phosphorus pentoxide. The pentoxide is then reduced by the coke to give phosphorus vapor and carbon monoxide."
Personally, I like garage Chemist's idea of thermiting a phosphate with Al powder (previous page of this thread), I'm just not sure why he wanted
silica in there. Same reason as here?
I don't think it needs the silica: sulphates for instance are very successfully (and very hotly) reduced by Al. Al is of course much, much 'keener' on
oxygen than carbon...
[Edited on 22-11-2009 by blogfast25]
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S.C. Wack
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No, you want to obscure with your assclown trolling the fact that you've got nothing to back you up, while I can find supporting references for my
position only.
So I have to build an arc furnace to be right about carbon reducing phosphate without silica? Nonsense. Why can't someone else use theirs? Where in
the references given, and in any of my posts, have I got something wrong? Feel free to look through all 5 1/2 years, to point out these misguided
interpretations which you accuse me of. Why is it your word that must be taken as gospel when everyone disagrees with you, and how is your value
higher than that of those who specialized in this field for years?
I merely present relevant work of certain published scientists at face value for informational purposes, because of the dearth, especially early on
here, of same; sometimes for comparison with internet ramblings of bumbling anonymous amateurs, and invite debate. Sadly len wants none of this when
it does not support him, not unlike Muslims in backwards countries banning schools. If you don't believe real scientists (especially when they patent
their discovery) who tend to bother with details and analyses, then what can anyone here say about anything?
The fuck I'm a brainless receptacle incapable of critical thinking, I reject your rubbish because I do know it when I see it. Naturally anything
published before 1930, especially in IEC, is bullshit because chemists were inept, unaware liars then. Other spouters of nonsense even in 1986 cite
them anyways, such as in http://dx.doi.org/10.1007/BF02657149
Attachment: tirade.zip (1.8MB)
This file has been downloaded 724 times
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entropy51
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| Quote: Originally posted by len1 | When you start lying, youre finished as a scientist.
I have several published papers to the effect that this or that publication is 'bullshit'. Each time I had to fight to get them accepted - sometimes
in a different journal, one in particular took 3 years. |
How very odd. I have published four journal
articles reporting that I was unable to replicate another scientist's results. I had no problem whatsoever getting those papers into print. No
fight. No delay. In fact they were all published in better journals than the original work which I could not reproduce.
Did your manuscripts perhaps contain the words "liar", "dishonest" or "bullshit"? This might explain your problems.
[Edited on 23-11-2009 by entropy51]
[Edited on 23-11-2009 by entropy51]
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blogfast25
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Well, the paper attached by S.C.Wack (tirade.zip or Reduction of Tricalcium Phosphate by Carbon, Effect of Silica and Alumina on the Reaction, by K.
D. Jacob, D. S. Reynolds, and W. L. Hill in IEC, Nov. 1929) actually strongly supports the role of silica (but also alumina and for similar reasons)
as a rate-determining factor in the high temperature reduction of Ca triphosphate with carbon. And a very through investigation it was indeed.
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blogfast25
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I wanted to test the hypothesis that it's possible to react tricalciumphosphate (TCP) with Al powder in an aluminothermic reaction:
Ca3(PO4)2 + 10/3 Al ---> 4/3 CaO + 5/3 CaAl2O4 + 1/2 P4
But I've no TCP or bone ash lying around. I did however have quite a surplus of ammonium dihydrogenphosphate (NH4H2PO4 or ADHP) from a crystal growing
set (it grows lovely crystals) and decided to convert some to TCP by neutralising the ADHP to tertiary phosphate with NaOH and adding CaCl2 to that
solution.
I set out to prepare 50 g of TCP (about 1/6 mol) from 37.2 g ADHP, 25.8 g NaOH and 53.7 g CaCl2 according:
NH4H2PO4 + 2 NaOH + 3/2 CaCl2 ---> 1/2 Ca3(PO4)2 + NH4Cl + 2 NaCl + 2 H2O
The solutions were quite concentrated: without reactions the solution strength would have been:
about 2/3 M ADHP
about 4/3 M NaOH
about 1 M CaCl2
about 500 ml.
After the first neutralising step (ADHP + NaOH, a whiff of ammonia can then be observed) I added the concentrated solution of CaCl2 to the tertiary
phosphate solution. To my surprise, at first nothing seemed to happen. But the solution turned quite viscous, as a perfectly transparent gel of CTP
started to form. Stirring caused the gel to start turning opaque/white, as did adding small amounts of water. I didn't expect such behaviour from such
a thoroughly insoluble substance... The changes came about over several minutes.
I then added about another 500 ml of water to the 500 ml of 'slurry', stirred it and brought the thick, gelatinous mass slowly to the boil. The slurry
gradually thinned out but remained viscous enough for the precipitate to remain fully suspended. I'm now filtering, washing and drying it.
I may be talking through my backside here but this type of precipitating may be useful in bone development, with newly excreted TCP gelling onto
existing bone and gradually grafting itself onto it and maturing over time.
The dry and clean technical TCP should ready for the weekend...
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Oxydro
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I'm contemplating a phosphorus retort, although with me there are a great deal of projects planned that never happen. Money is the limiting factor,
with time running a close second - I'm sure many of you are familiar with this!
The idea is to build a small electric furnace, fired with MoSi2 elements. Inside the furnace, I will have a "flask" made of either clay or iron. The
problem with iron is that I don't know how long it will last at these temperatures. The problem with clay is that I don't know how to make airtight
connections between sections (that have to be removable)
From the flask, a pipe runs into a water trap, in the same style as BromicAcid's experiments. However, I intent to use an inert gas flood over my
watertrap to prevent problems with the P floating to the surface (As someone experienced, I think Bromic again). Is there a gain to be had from
running inert gas through the reaction space as well? I suspect it might help the P distill over, but it will also carry valuable heat away from the
reaction.
Nitrogen, CO2 or argon are all possibilities for an inert gas over the collection vessel. However, if I was to be running it through the hot section,
I don't think CO2 would work ( carbon will likely reduce it to monoxide ). I have access to cylinders of gas, I work at a garage that is also a Linde
distributor.
Problems to be solved include deciding what refractory from which to build the furnace, locating suitable moly disilicide elements, figuring out a
power supply, and picking the best material for the reaction vessel.
"Our interest's on the dangerous side of things" -- Browning
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Sedit
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| Quote: | The problem with clay is that I don't know how to make airtight connections between sections (that have to be removable)
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I have a kiln and am pretty well versed in working with ceramics making me contemplate making a phosphorus retort on a number of occasions. Next time
I fire up the kiln I no doubt will have a couple of retorts and ceramic tubes for other high temperature works. Any way my point is I thought about
the same problem about sealing up the two sections until my common sence kicked in and I realized all I had to do is buy some very well named retort
cement. Its sodium silicate and as it heats up it turns to SiO2 so it basicly just melts then solidifys as glass yet will still break along the seams
if you want to. We use it quite often when working with boilers.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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entropy51
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| Quote: | | Any way my point is I thought about the same problem about sealing up the two sections until my common sence kicked in and I realized all I had to do
is buy some very well named retort cement |
For what it's worth, some of the 200 year old books on www.archive.org give recipes for "luting" or something like that. They used all kinds of strange ingredients, as you will see if you investigate.
Is wonder if sodium silicate by itself will stand up to making phosphorus. What about some of the stuff made for repairing fireplace brick?
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12AX7
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"Furnace Cement" is bonded with sodium silicate, as far as I know. Sticky stuff, and very thick (like clay) fresh from the bucket. It tends to skin
over, so you'd probably end up with steam bubbles (or worse, cracked glass) if you tried using it directly on glass joints.
Tim
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blogfast25
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Well, my TCP is ready to go but it's raining cats and dogs here.
From the standard heats of formation of TCP (-4,132 kJ/mol, Wiki), CaO (- 635 kJ/mol, Wiki) and Al2O3 (-1,676 kJ/mol, NIST) can be deduced that the
standard heat of reaction of:
Ca3(PO4)2 + 10/3 Al ---> 3 CaO + 5/3 Al2O3 + 2 P
must be about -566 kJ/mol (of TCP). That's pretty exothermic, almost as high as the HoF of CaO!
Hopefully the rain clears up later today or tomorrow...
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blogfast25
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Well, well, well, somewhat unexpectedly I couldn't get the mixture of Ca3(PO4)2 powder = 1 mol, Al powder = 10/3 mol to light using a bit of KClO3/Al
mix and a piece of Mg ribbon.
It was a small test: total batch weight 4.75 g.
I will now add some CaSO4/Al booster mix, the formulation will then be:
Ca3(PO4)2.............1 mol
CaSO4....................0.4 mol
Al...............................4.4 mol
The CaSO4 booster reacts like this:
CaSO4 +8/3 Al ---> CaS + 4/3 Al2O3
and will hopefully provide the missing heat.
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garage chemist
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You need either SiO2, or calcium metaphosphate, Ca(PO3)2. CaO will not form in this reaction.
All you will get from Al and orthophosphate is phosphide.
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blogfast25
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| Quote: Originally posted by garage chemist | You need either SiO2, or calcium metaphosphate, Ca(PO3)2. CaO will not form in this reaction.
All you will get from Al and orthophosphate is phosphide.
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What makes you so sure of that?
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garage chemist
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There are cartridges for rodent eradication that consist of a simple phosphate-aluminum mixture. When ignited, they burn like thermite, but slower,
producing a slag containing phosphide which then reacts with aerial and soil moisture generating phosphine.
They do not release any phosphorus during burning.
A patent for such a device is buried in this or another thread.
Additionally, a german article has been posted here which also concerned Al reduction of phosphates and clearly demonstrated the essential role of
silica- unless reactive silica (diatomite, kieselguhr) was added to the mixture, the phosphorus yield was small.
Sodium metaphosphate (NaPO3 in any of its modifications) heated with Al or better Mg will produce some phosphorus of its own, but only a fraction of
that which is released when silica is present.
See my last experiment in this thread, and try to repeat what is known to work. My recommendation.
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len1
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Stephan my hat of to you for having the patience to explain when asked in such a tone. I have long since stopped bothering
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kclo4
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| Quote: Originally posted by Sedit | I have a kiln and am pretty well versed in working with ceramics making me contemplate making a phosphorus retort on a number of occasions. Next time
I fire up the kiln I no doubt will have a couple of retorts and ceramic tubes for other high temperature works. Any way my point is I thought about
the same problem about sealing up the two sections until my common sence kicked in and I realized all I had to do is buy some very well named retort
cement. Its sodium silicate and as it heats up it turns to SiO2 so it basicly just melts then solidifys as glass yet will still break along the seams
if you want to. We use it quite often when working with boilers.
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Have you ever thought about selling ceramic retorts that you make?
If you made them well, I bet a lot of people would be interested in this sort of thing, and might aid a few people in producing phosphorous, and who
knows what other cool things.
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Sedit
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Haven't made one yet although it should be a breeze and I never really thought about selling them. I normaly sell the sculptures and potts not the
morter/pestles and weird things like that I make. I suppose if I get good at it then Ebay couldn't hurt. Its been quite a while since I fired that
kiln up because everytime I make something my kids destroy it before it makes it to the kiln. Lord knows I could use a little extra cash. Perhaps
trade people for some real glassware
[Edited on 2-12-2009 by Sedit]
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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unome
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Often wondered.... As silicon is fairly easily arrived at via a mild variation of the standard thermite process (such as here), could we utilize the reducing power of Si itself in this reaction? I mean, I don't pretend to be a scientist - not even a little bit (and try hard not to tell porkies,
even of the ever-present social variety, makes for some tough social encounters let me tell you), but isn't Si above P in the table (kind of a shock
really, given that it doesn't burst into flame on contact with air)?
Just asking a question, but flame, flame away if it so pleases you... Just seemed to me that a solid crystal mass (like that Si block) should be a
sight easier to crush/break up into small enough pieces than Al...
[Edited on 3-12-2009 by unome]
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