Author Topic: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?  (Read 132 times)

NeilPatrickHarris

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best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« on: July 30, 2010, 03:27:11 AM »
swim stumbled across a friedrich condenser recently but always used allihn condensers in al/hg dreams of past. so this leaves swim with a few questions, in regards to refluxing a nitro al/hg focused on whether having the right condenser (right type and right size) is the best bet or substituting water for a different solvent to feed through the condenser to reach subzero temps, but without tearing up a plastic water pump seems impossible

1. is a friedrich condenser worth it over an allihn, is it really that much more efficient in hopes of returning MeAm-laden MeOH back to the vessel?
2. any ideas on a setup using dry ice / acetone as a coolant for a reflux condenser to actually get it so cold that it can condense the MeAm gas and reflux the liquified MeAm so you don't lose any MeAm at all? i can't think of any water recirculating pumps that could withstand not being destroyed by trying to pump through supercold acetone through them so i'm not sure how to pull that off plus i'm unsure of how introducing such a subzero temp MeAm would affect the al/hg. would the excessive heat of the al/hg heat up the subzero MeAm so quickly that it wouldn't matter or would the subzero MeAm cool off the al/hg enough to cause problems such as favoring side reactions, etc, like alcohol formation.
3. or is simply using ice cold water feeding through a really efficient and long condenser like a friedrich going to cool off the MeOH so much that it increases the MeAm(g) solubility in the condensing MeOH to the point where the MeAm(g) will readily dissolve back in the cold MeOH and reflux right back down, with no worry of MeAm(g) escaping while the MeOH condenses cuz the MeOH may not be cold enough to dissolve the MeAm(g) as readily as one would hope?

the biggest flaw of the nitro al/hg is that it runs so hot and drives off MeAm, so am trying to figure out the best way to keep that MeAm from escaping the reflux condenser.

Vesp

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #1 on: July 30, 2010, 03:43:21 AM »
Would a Dewar condenser with dry ice and acetone work for what you need?

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Sedit

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #2 on: July 30, 2010, 04:43:19 AM »
Methylamine is abreviated as MeNH3 or MMA for mono methylamine although the latter could get confusing in organic chemistry to the prior is the best and clean cut variation.


Its boiling point is -6 °C which seems low but translates to 21 °F which can be reached with Ice/Salt. Ice and salt can drop the temperature in best conditions down to -21 °C so you can see that there is plenty of room for condensation. I would have to say theres atlest one bee out there somewhere that would do it this way if he where to do it at all.

Control the temperature by keeping that on an ice and salt bath at the same time with limited(controlled)addition rate as well. The reaction from what I hear is pretty tame until the nitro/ketone mix starts to contact the amalgum then its ballz to the wall with each drop.
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NeilPatrickHarris

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #3 on: July 30, 2010, 05:52:42 AM »
Idea #1:
i found this hive post at "hiveboard/newbee/000494095.html" which brought up a good point:
A solution of dry ice/IPA (much safer than dry ice/acetone) would give a solution of ~ -78C. The reflux temp of an Al/Hg would be 65-70C using MeOH as the solvent. Pyrex has a thermal shock rating of ~160C and the temp difference mentioned above is ~150C so you're really getting pretty close to the danger zone of running a risk of thermal shock. Perhaps using the reaction flask on the bottom, then stack my typical allihn condenser fed with cold water attached to that reaction flask, then put a dewar condenser attached to the top of the allihn condenser. This way the allihn condenser in the middle would act as a buffer to at least slightly cool the vapors some before they reach the dewar.

my only worry about this is that the subzero MeAm dripping back into the nitro Al/Hg might be so cold that it could cause the reaction to come to a halt. Do you think this is a worry or that the nitro al/hg runs so hot that it would simply heat that subzero MeOH/MeAm condensate in no time? Rhodium once stated that if using freezer-cold ketone it would slow imine formation and give a competing reaction - the formation of the alcohol - more of an advantage to occur. I've seen no references or other claims for this aside from Rhodium's one comment. But there is also the worry that such cold condensate being refluxed down is so cold that it might be equivalent of putting the flask in an ice bath (or am i really overestimating the impact of such cold condensate refluxing back down?), which from what i've read is a big no-no and can cause the reaction to come to a halt. Does anyone think this would be a real concern or is the nitro al/hg hot enough to handle the subzero condensate?

Option #2:
If the subzero condensate is indeed too cold and might kill the al/hg or slow imine formation considerably then perhaps instead of using a dewar at all with a dry ice-chilled coolant, abandon that idea for using a longer condenser (allihn or friedrich?) and feed that reflux condenser with subzero salt water that is being recirculated from a bucket of saturated NaCl water solution that has an equal amount of crushed ice in hopes of reaching -10C to -20C range in temps. That should be good enough to condense some MeAm (bp = -6C) or at least increase its solubility in the MeOH condensate considerably due to the lower temp. I read that CaCl2 + H2O can reach even colder than NaCl + H2O and would be a happy medium, however i think CaCl2 might very well kill the water recirculating pump, so if CaCl2 + H2O were employed then it should probably be best kept in a dewar like Option #1.

Here's where I got the info on the NaCl + H2O and the CaCl2 + H2O temps:
h**p://www2.uni-siegen.de/~pci/versuche/english/v105-2.html

i know it doesn't take much to condense the MeOH, but condensed semi-hot MeOH doesn't hold MeAm very well so the MeAm still escapes, it's the MeAm i'm concerned with. so far it seems like the best way to go would be a nice, long friedrich condenser fed with ice cold salt water or ice cold CaCl2 water, if the CaCl2 doesn't clog up / destroy the water recirculating pump. is a friedrich condenser really going to be more efficient for this purpose than an allihn? i only have experience with allihn and liebig condensers

=================================================
the bottom line:
sorry for this long post but i'm brainstorming out loud. here is an excellent SM post (h**p://www.sciencemadness.org/talk/viewthread.php?tid=10444) about freezing different mixtures, the CaCl2 + H2O mixture gets some recognition here for possibily being able to condense NH3 and MeAm, exactly what i'm looking for. just not sure if a plastic water recirculating pump can handle a super cold CaCl2/H2O solution to pump through a reflux condenser or if that type of solution is more of a job for a dewar
« Last Edit: July 30, 2010, 12:19:58 PM by NeilPatrickHarris »

NeilPatrickHarris

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #4 on: July 30, 2010, 06:03:34 AM »
my last post took so long to type that it timed out and i had to re-post it.

thanks for the reply sedit, yeah i'm thinking salt water would be better than just ice water but like you said, once the nitro al/hg gets up on its feet it's really balls to the wall even without using an overly aggressive drip-rate.  so i'm curious about some more proactive cooling for the condensate, cooling strong enough to actually condense MeAm(g).  The CaCl2 + H2O sounds like a nice happy medium but the use of a dewar + ipa/dry ice sounds like the ultimate plan.  my only concern with that is, as stated above, maybe cooling the MeAm/MeOH too cold to where it would hinder the reaction by either slowing down the al/hg or slowing down imine formation.  Unless the nitro al/hg is hot enough to heat that supercold condensed MeAm/MeOH right back up and not vice versa (the condensate cooling off the reaction too much)

jon

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #5 on: July 30, 2010, 09:48:29 AM »
why not run the variation where you reduce the nitro methane first?
to avoid all the exotherm from two reactions taking place at the same time?
also one could also try antifreeze i read it's gentle on pumps.
just add dry ice to the antifreeze to keep it's temperature in range.

lugh

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #6 on: July 30, 2010, 11:34:18 AM »
Quote
why not run the variation where you reduce the nitro methane first?
to avoid all the exotherm from two reactions taking place at the same time?

Jon is right; overall yields are always better by producing the methylamine first, then using it in the al-hg reduction  8)
« Last Edit: July 30, 2010, 12:07:06 PM by lugh »
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NeilPatrickHarris

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #7 on: July 31, 2010, 04:24:36 PM »
thanks for the input jon, you're referring to abacus' method?  i've thought of giving that a try but then thought if i go that far, might as well just make one's own MeAm.HCl and do it Osmium style.  i guess there would be a benefit to Abacus' method though because i would think reducing nitro would make a much cleaner product than making MeAm through other routes.  the only problem is that i've heard some bees say a 5-6% solution of MeAm is the best you're going to get in MeOH... or is that number based on the concentration after distillation of the meoh to remove it form the al sludge?

jon

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #8 on: July 31, 2010, 08:11:37 PM »
umm i know a few things about al/hg runs a lot of variables come into play.
check your pm.

lugh

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Re: best method for condensing MeAm(g) during nitro al/hg? condenser vs coolant?
« Reply #9 on: August 01, 2010, 01:11:04 AM »
Abacus's method is your best option if you have nitromethane since you won't have to purify it  8)
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