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All 12 posts Subject: P2P tube furnace write up attempt Please login to post Down

Mastermind
(Hive Bee)
07-23-00 01:44
No 31892
      P2P tube furnace write up attempt

OK, Osmium. This is what I came up with for a write up (P2P from PAA and acetic acid; tube furnace method). Since the apparatus isn't too common it might be confusing to some people.

Description of the apparatus

The apparatus utilizes a 98% silica glass (pyrex also works according to Organic Synthesis) combustion tube (refered to as catalyst tube here) about 1.1 meters long and about 2.5 cm in diameter with a ground glass 29/42 female to 24/40 male straight adapter glued onto the outlet end of the catalyst tube using epoxy glue. The thermocouple used to monitor the temperature includes a number of cylindrical ceramic beads (arranged in a line), each having two holes, with each hole adapted to receive a thermocouple wire. The cylindrical beads hold the two thermocouple wires parallel to each other while providing electrical insulation. The thermocouple wires are twisted at one end and bent upward slightly so that they contact the catalyst tube when held against it. The thermocouple is placed about 0.3 meters from the inlet end and on the outside of the catalyst tube (pointing away from the inlet end of the catalyst tube) and the catalyst tube and thermocouple are wrapped with a heating tape rated at about 800 degrees C maximum along about 0.5 meters length at the center of the catalyst tube leaving about 0.3 meters uncovered at both ends of the catalyst tube. Glass ribbons or strings provided at each end of the heaing tape are tied around the tube to hold the heating tape and thermocouple in place. The portion of the catalyst tube covered with the heating tape is then wrapped with glass wool for insulation. A glass wool plug is placed through the outlet end of the glass tube and pushed using a wooden or glass rod to the point where the heating tape ends to support the catalyst.

The part of the catalyst tube covered with the heating tape is filled with pea sized pumice supporting the catalyst (described later) and supported using standard ring stands and clamps at an angle of about 10-15 degrees from the horizontal. An angled (110 degree) adapter adapted to receive a #4 stopper at one end and narrows to about 3/8 inches in diameter at the other end is connected to the inlet of the catalyst tube using a one hole stopper. A two hole #4 stopper supporting a seperatory or dropping funnel and a short piece of glass tubing having a 90 degree bend is connected to the inlet of the angled adapter. A standard angled (110 degree) adapter having 24/40 ground glass joints at both ends is connected to the straight adapter at the outlet or lower end of the catalyst tube and a round bottom flask is connected to the outlet end of the vacuum adapter to receive the products from the catalyst tube. A length of rubber tubing is connected to the side arm of the vacuum adapter. A stiff piece of tubing, such as, metal or glass can be connected to the other end of the rubber tubing and can bee lead outside through a window, to a window fan or, preferably, to a container of water to allow observation of the rate of gases passing through the catalyst tube by observing bubbles produced in the container of water.

The seperatory funnel at the inlet end is used to control the addition of a mixture of PAA and acetic acid in the catalyst tube and the 90 degree piece of glass tubing at the inlet end (supported by the two hole #4 stopper) is used to introduce air to process or regenerate the catalyst, or to introduce an inert gas, such as CO2 or N2, into the catalyst tube when making the ketone.

Here's a picture of the tube furnace:

Mastermind
(Hive Bee)
07-23-00 01:47
No 31893
      Re: P2P tube furnace write up attempt

This is the catalyst I described in the newbie section.

The catalyst.

The magnesia catalyst was made using pea sized pumice (some patents were seen supporting similar catalytic materials using perlite for cracking petroleum hydrocarbons; other art). Enough pea sized pumice to fill FOAF's combustion (now catalyst) tube was covered with enough Milk of Magnesia so that the pumice 'had looked like it had been white washed' (good description) and at the same time the pores were not clogged (for maximum catalytic surface area). A 98% silica combustion tube was used which was wrapped with a heating tape (max temp 800 degrees C) and was covered with glass wool as insulation. 2-3 teaspoons of calamine lotion (ZnO and Fe oxide; see US patent 5750795, for example, especially tables 1 and 2) was added to the catalyst and it was heated, alternately, on a gas stove and in a microwave oven to dry it and convert it to MgO. It was found that when the catalyst was placed in the tube and heated to about 500+ degrees C (with air pumped through it) that the Mg(OH)2 could more easily be dehydrated (H2O given off and condensed) and converted to MgO.

*Note: add calamine lotion before putting in combustion tube

Mastermind
(Hive Bee)
07-23-00 01:49
No 31894
      Re: P2P tube furnace write up attempt

P2P tube furnace process.

The tube furnace is heated to 430-450 degrees C, and simultaneously the tube is swept out
thoroughly with an inert gas, such as N2 or CO2, introduced through the 90 degree glass
tubing bend (at the inlet end). The inert gas can be passed first through a wash bottle
to estimate the rate of flow or the flow can be observed by placing the rubber tubing from
the vacuum adapter in a container of water (for observing the rate in bubbles per second).
A solution of 136 g. (1 mole) of phenyl acetic acid (PAA) in 120 cc. of glacial acetic acid
(120 g., 2 moles) is placed in the seperatory funnel and introduced into the tube furnace
at a rate of twelve to fifteen drops per minute. Meanwhile, a very slow stream of the
inert gas (one bubble per second) is passed through the tube to keep the gases in motion.
After all of the solution has been added, the seperatory funnel is rinsed with 10 cc. of
glacial acetic acid, and this is passed through the catalyst tube to facilitate removal
of the product. The distillate consists of a red or brown red oily layer and an aqueous
layer. Both layers are treated with about 300 cc of water and NaHCO3 is added until the
effervescence stops and the mixture is alkaline to litmus or pH paper (NaHCO3 turns pH
paper green). The P2P layer is seperated (the emulsion can be easily seperated with a
centrifuge if available) and the aqueous layer is extracted with an organic solvent (ie.
3X 30 ml of toluene). The solvent is dried and evaporated to get more the P2P. The P2P
can be distilled under a vacuum or at atmospheric pressure (fraction collected at 210-230
degrees C). The yield is typically about 70 %.

References:
Vogels
Organic Synthesis Col. Vol. II pg. 389-391 (methyl benzyl ketone)
US patents:
2108156
2612524
2697729
2811559
3075016
3660491
4172097
4754074
5750795

Mastermind
(Hive Bee)
07-23-00 02:08
No 31901
      Re: P2P tube furnace write up attempt

Maybe the description of the apparatus is too detailed. A generalized description might be better if you wanted to put it on Rhodiums page. Various ways to set it up are possible. The tube itself can be glass, ceramic or metal. One problem with metal is that it conducts electricity and might be a problem if a heating tape becomes frayed (starts to lose insulation). Also, you don't want to short out the thermocouple either. Glass has the advantage that you can see through it and both glass and ceramic have been used in combustion tubes. Ceramic also might be a good choice since its tougher than glass and doesn't conduct electricity.

WizardX
(Wizard Master)
07-23-00 02:53
No 31910
User Picture       Re: P2P tube furnace write up attempt

Mastermind: Have the combustion tube vertical, as gravity will help move the GAA/PAA solution through the combustion tube with the N2 gas flow. Al2O3 works as well as a catalyst.

Mastermind
(Hive Bee)
07-23-00 04:14
No 31936
      Re: P2P tube furnace write up attempt

WizardX, The apparatus was modeled as closely as possible to the apparatus from the Organic Synthesis article which shows a picture of the tube furnace tilted slightly from the horizontal. I've seen other similar things where the reaction tube is horizontal or vertical. For example, US patent 2,811,559 shows a vertical tube furnace which is used for the same type of reaction (ie. cross decarboxylation of carboxylic acids). The catalyst is MgO and the products in examples I-IV are methyl undecyl ketone and stearaldehyde. The problem with having the tube furnace vertical is that maybe the reactants would come through too fast and wouldn't have time to react, depending on the porousity of the catalyst. It was felt that if pea sized pumice was used as in the Organic Synthesis article that the catalyst tube should be set at the same angle as shown in the article.

PVnRT_NC8
(Newbee)
07-23-00 05:58
No 31964
      Re: P2P tube furnace write up attempt

wow very nice looking appratus, as far as heating goes this thing it is wrapped with nicrome wire heating ellement right??

A010

Mastermind
(Hive Bee)
07-23-00 06:12
No 31971
      Re: P2P tube furnace write up attempt

For your entertainment and mine and since I like posting pictures, here's a picture of the thorium nitrate bottle used to make the thoria catalyst in the early 80's (farther back than the statute of limitations (7years)) according to the Organic Synthesis article. The thorium nitrate was used a number of times to make the thoria catalyst. It was found that when the thoria catalyst was fresh the yield of P2P wasn't too bad, but the catalyst tended to lose activity after a couple of runs. Masking tape was put on the bottle to conceal the source. Also, as many of you know, thorium is radioactive and not the best thing to play around with.

Mastermind
(Hive Bee)
07-23-00 06:27
No 31978
      Re: P2P tube furnace write up attempt

PVnRT_NC8, I'm familiar with the PV=nRT from the repetative word problems from all the chemistry courses, especially PChem a long time ago, but what is the NC8 for?

To answer your question, PV, the combustion (catalyst) tube is wrapped with a heating tape which is coated with a woven fiber glass covering. The heating tape was supposed to be rated at 800 degrees C. Over time the fiber glass covering tended to fray (come apart) and expose the wire heating element. After it was used for some ketene experiments at 800 degrees C that was when the fiber glass covering started to come apart. It might be best if you copied and pasted all of my posts to notepad and store it on a floppy disc or your hard drive, etc., or even print it all out if you're interested in this. It might take time to study it all. You can download these threads directly, but then they're stored as HTML and you need a browser to read it offline.

PVnRT_NC8
(Newbee)
07-23-00 21:17
No 32193
      Re: P2P tube furnace write up attempt

Mastermind,
   The NC8 was actually supposed to be ZC8, I suppose it was a typo...It was supposed to stand for N<infinity...I have come to belive that in xrystalizations the classical litature reports that, (thoght not specifically.) Yeilds were supprisingly higher than expected! See the classic on Rhod's page dealing with isomeric differences and yeilds concerning the catlike-ephedrines. The documents make me tend to belive these high yields were not expected [at this time]and this was a rather historic and revolutionary discovery; more specifically... the procedure where the one isomer is issolated put into etoh-i-proh tartaric acid mixture, left for "X" days and reseperated and components weighed, I have not repeated the experiments but I am hopefull that in fact there really is something more there between the lines than most people inturpet upon the first few perusals.

Thorium is still available in the form of black looking needle like crystals if ya know where to dig them ussing a giger counter would make rocking them up real simple, I seem to recall they are a aloy of lead and radioactive thorium, the Beartooths/ Bitteroots?? Ranges pop into recent memory, we had a few around the house apparently they are at the university and in a priviate collection now.

A010

wayupnorth
(Stranger)
07-26-00 04:26
No 33194
      Re: P2P tube furnace write up attempt

Fresh stuff at universities where they have petroleum engineering departments. So much college stuff with so little care when it disapears, if your not greedy and leave them some to work with till they get more. You should see the
Journalism photo department storage rooms. Students love not being broke and when their just getting some for a friends development use, they or no one else really cares. The rooms at most universities are unlock more often than locked. And photo classes have so many new non full time students taking classes in the evening.

Mastermind
(Hive Bee)
07-28-00 00:46
No 34007
      Re: P2P tube furnace write up attempt

The point of using the magnesia catalyst is as an alternative to the thoria catalyst in the Organic Synthesis article. Thorium is radioactive and isn't OTC anyway. It was found, surprising, that the magnesia catalyst gave high yields of P2P.

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	All 12 posts		Subject: P2P tube furnace write up attempt		Please login to post		Down


		Mastermind (Hive Bee) 07-23-00 01:44 No 31892				P2P tube furnace write up attempt
						OK, Osmium. This is what I came up with for a write up (P2P from PAA and acetic acid; tube furnace method). Since the apparatus isn't too common it might be confusing to some people. Description of the apparatus The apparatus utilizes a 98% silica glass (pyrex also works according to Organic Synthesis) combustion tube (refered to as catalyst tube here) about 1.1 meters long and about 2.5 cm in diameter with a ground glass 29/42 female to 24/40 male straight adapter glued onto the outlet end of the catalyst tube using epoxy glue. The thermocouple used to monitor the temperature includes a number of cylindrical ceramic beads (arranged in a line), each having two holes, with each hole adapted to receive a thermocouple wire. The cylindrical beads hold the two thermocouple wires parallel to each other while providing electrical insulation. The thermocouple wires are twisted at one end and bent upward slightly so that they contact the catalyst tube when held against it. The thermocouple is placed about 0.3 meters from the inlet end and on the outside of the catalyst tube (pointing away from the inlet end of the catalyst tube) and the catalyst tube and thermocouple are wrapped with a heating tape rated at about 800 degrees C maximum along about 0.5 meters length at the center of the catalyst tube leaving about 0.3 meters uncovered at both ends of the catalyst tube. Glass ribbons or strings provided at each end of the heaing tape are tied around the tube to hold the heating tape and thermocouple in place. The portion of the catalyst tube covered with the heating tape is then wrapped with glass wool for insulation. A glass wool plug is placed through the outlet end of the glass tube and pushed using a wooden or glass rod to the point where the heating tape ends to support the catalyst. The part of the catalyst tube covered with the heating tape is filled with pea sized pumice supporting the catalyst (described later) and supported using standard ring stands and clamps at an angle of about 10-15 degrees from the horizontal. An angled (110 degree) adapter adapted to receive a #4 stopper at one end and narrows to about 3/8 inches in diameter at the other end is connected to the inlet of the catalyst tube using a one hole stopper. A two hole #4 stopper supporting a seperatory or dropping funnel and a short piece of glass tubing having a 90 degree bend is connected to the inlet of the angled adapter. A standard angled (110 degree) adapter having 24/40 ground glass joints at both ends is connected to the straight adapter at the outlet or lower end of the catalyst tube and a round bottom flask is connected to the outlet end of the vacuum adapter to receive the products from the catalyst tube. A length of rubber tubing is connected to the side arm of the vacuum adapter. A stiff piece of tubing, such as, metal or glass can be connected to the other end of the rubber tubing and can bee lead outside through a window, to a window fan or, preferably, to a container of water to allow observation of the rate of gases passing through the catalyst tube by observing bubbles produced in the container of water. The seperatory funnel at the inlet end is used to control the addition of a mixture of PAA and acetic acid in the catalyst tube and the 90 degree piece of glass tubing at the inlet end (supported by the two hole #4 stopper) is used to introduce air to process or regenerate the catalyst, or to introduce an inert gas, such as CO2 or N2, into the catalyst tube when making the ketone. Here's a picture of the tube furnace:



		Mastermind (Hive Bee) 07-23-00 01:47 No 31893				Re: P2P tube furnace write up attempt
						This is the catalyst I described in the newbie section. The catalyst. The magnesia catalyst was made using pea sized pumice (some patents were seen supporting similar catalytic materials using perlite for cracking petroleum hydrocarbons; other art). Enough pea sized pumice to fill FOAF's combustion (now catalyst) tube was covered with enough Milk of Magnesia so that the pumice 'had looked like it had been white washed' (good description) and at the same time the pores were not clogged (for maximum catalytic surface area). A 98% silica combustion tube was used which was wrapped with a heating tape (max temp 800 degrees C) and was covered with glass wool as insulation. 2-3 teaspoons of calamine lotion (ZnO and Fe oxide; see US patent 5750795, for example, especially tables 1 and 2) was added to the catalyst and it was heated, alternately, on a gas stove and in a microwave oven to dry it and convert it to MgO. It was found that when the catalyst was placed in the tube and heated to about 500+ degrees C (with air pumped through it) that the Mg(OH)2 could more easily be dehydrated (H2O given off and condensed) and converted to MgO. *Note: add calamine lotion before putting in combustion tube



		Mastermind (Hive Bee) 07-23-00 01:49 No 31894				Re: P2P tube furnace write up attempt
						P2P tube furnace process. The tube furnace is heated to 430-450 degrees C, and simultaneously the tube is swept out thoroughly with an inert gas, such as N2 or CO2, introduced through the 90 degree glass tubing bend (at the inlet end). The inert gas can be passed first through a wash bottle to estimate the rate of flow or the flow can be observed by placing the rubber tubing from the vacuum adapter in a container of water (for observing the rate in bubbles per second). A solution of 136 g. (1 mole) of phenyl acetic acid (PAA) in 120 cc. of glacial acetic acid (120 g., 2 moles) is placed in the seperatory funnel and introduced into the tube furnace at a rate of twelve to fifteen drops per minute. Meanwhile, a very slow stream of the inert gas (one bubble per second) is passed through the tube to keep the gases in motion. After all of the solution has been added, the seperatory funnel is rinsed with 10 cc. of glacial acetic acid, and this is passed through the catalyst tube to facilitate removal of the product. The distillate consists of a red or brown red oily layer and an aqueous layer. Both layers are treated with about 300 cc of water and NaHCO3 is added until the effervescence stops and the mixture is alkaline to litmus or pH paper (NaHCO3 turns pH paper green). The P2P layer is seperated (the emulsion can be easily seperated with a centrifuge if available) and the aqueous layer is extracted with an organic solvent (ie. 3X 30 ml of toluene). The solvent is dried and evaporated to get more the P2P. The P2P can be distilled under a vacuum or at atmospheric pressure (fraction collected at 210-230 degrees C). The yield is typically about 70 %. References: Vogels Organic Synthesis Col. Vol. II pg. 389-391 (methyl benzyl ketone) US patents: 2108156 2612524 2697729 2811559 3075016 3660491 4172097 4754074 5750795



		Mastermind (Hive Bee) 07-23-00 02:08 No 31901				Re: P2P tube furnace write up attempt
						Maybe the description of the apparatus is too detailed. A generalized description might be better if you wanted to put it on Rhodiums page. Various ways to set it up are possible. The tube itself can be glass, ceramic or metal. One problem with metal is that it conducts electricity and might be a problem if a heating tape becomes frayed (starts to lose insulation). Also, you don't want to short out the thermocouple either. Glass has the advantage that you can see through it and both glass and ceramic have been used in combustion tubes. Ceramic also might be a good choice since its tougher than glass and doesn't conduct electricity.



		WizardX (Wizard Master) 07-23-00 02:53 No 31910				Re: P2P tube furnace write up attempt
						Mastermind: Have the combustion tube vertical, as gravity will help move the GAA/PAA solution through the combustion tube with the N2 gas flow. Al2O3 works as well as a catalyst.



		Mastermind (Hive Bee) 07-23-00 04:14 No 31936				Re: P2P tube furnace write up attempt
						WizardX, The apparatus was modeled as closely as possible to the apparatus from the Organic Synthesis article which shows a picture of the tube furnace tilted slightly from the horizontal. I've seen other similar things where the reaction tube is horizontal or vertical. For example, US patent 2,811,559 shows a vertical tube furnace which is used for the same type of reaction (ie. cross decarboxylation of carboxylic acids). The catalyst is MgO and the products in examples I-IV are methyl undecyl ketone and stearaldehyde. The problem with having the tube furnace vertical is that maybe the reactants would come through too fast and wouldn't have time to react, depending on the porousity of the catalyst. It was felt that if pea sized pumice was used as in the Organic Synthesis article that the catalyst tube should be set at the same angle as shown in the article.



		PVnRT_NC8 (Newbee) 07-23-00 05:58 No 31964				Re: P2P tube furnace write up attempt
						wow very nice looking appratus, as far as heating goes this thing it is wrapped with nicrome wire heating ellement right?? A010



		Mastermind (Hive Bee) 07-23-00 06:12 No 31971				Re: P2P tube furnace write up attempt
						For your entertainment and mine and since I like posting pictures, here's a picture of the thorium nitrate bottle used to make the thoria catalyst in the early 80's (farther back than the statute of limitations (7years)) according to the Organic Synthesis article. The thorium nitrate was used a number of times to make the thoria catalyst. It was found that when the thoria catalyst was fresh the yield of P2P wasn't too bad, but the catalyst tended to lose activity after a couple of runs. Masking tape was put on the bottle to conceal the source. Also, as many of you know, thorium is radioactive and not the best thing to play around with.



		Mastermind (Hive Bee) 07-23-00 06:27 No 31978				Re: P2P tube furnace write up attempt
						PVnRT_NC8, I'm familiar with the PV=nRT from the repetative word problems from all the chemistry courses, especially PChem a long time ago, but what is the NC8 for? To answer your question, PV, the combustion (catalyst) tube is wrapped with a heating tape which is coated with a woven fiber glass covering. The heating tape was supposed to be rated at 800 degrees C. Over time the fiber glass covering tended to fray (come apart) and expose the wire heating element. After it was used for some ketene experiments at 800 degrees C that was when the fiber glass covering started to come apart. It might be best if you copied and pasted all of my posts to notepad and store it on a floppy disc or your hard drive, etc., or even print it all out if you're interested in this. It might take time to study it all. You can download these threads directly, but then they're stored as HTML and you need a browser to read it offline.



		PVnRT_NC8 (Newbee) 07-23-00 21:17 No 32193				Re: P2P tube furnace write up attempt
						Mastermind, The NC8 was actually supposed to be ZC8, I suppose it was a typo...It was supposed to stand for N<infinity...I have come to belive that in xrystalizations the classical litature reports that, (thoght not specifically.) Yeilds were supprisingly higher than expected! See the classic on Rhod's page dealing with isomeric differences and yeilds concerning the catlike-ephedrines. The documents make me tend to belive these high yields were not expected [at this time]and this was a rather historic and revolutionary discovery; more specifically... the procedure where the one isomer is issolated put into etoh-i-proh tartaric acid mixture, left for "X" days and reseperated and components weighed, I have not repeated the experiments but I am hopefull that in fact there really is something more there between the lines than most people inturpet upon the first few perusals. Thorium is still available in the form of black looking needle like crystals if ya know where to dig them ussing a giger counter would make rocking them up real simple, I seem to recall they are a aloy of lead and radioactive thorium, the Beartooths/ Bitteroots?? Ranges pop into recent memory, we had a few around the house apparently they are at the university and in a priviate collection now. A010



		wayupnorth (Stranger) 07-26-00 04:26 No 33194				Re: P2P tube furnace write up attempt
						Fresh stuff at universities where they have petroleum engineering departments. So much college stuff with so little care when it disapears, if your not greedy and leave them some to work with till they get more. You should see the Journalism photo department storage rooms. Students love not being broke and when their just getting some for a friends development use, they or no one else really cares. The rooms at most universities are unlock more often than locked. And photo classes have so many new non full time students taking classes in the evening.



		Mastermind (Hive Bee) 07-28-00 00:46 No 34007				Re: P2P tube furnace write up attempt
						The point of using the magnesia catalyst is as an alternative to the thoria catalyst in the Organic Synthesis article. Thorium is radioactive and isn't OTC anyway. It was found, surprising, that the magnesia catalyst gave high yields of P2P.

All 12 posts	End of thread	Top