Hg Amalgamation rates

[Vibrating_Lights]

Coul al be stored over period of a few days  in a dissolved meercuric solution if the Al was to be added to to a reduction over a few days.  Ie could the Al be left in the Alcoholic hg solution withut and degredation to the alumnin besides the oxids being removed. no further deterioriation.
VL_

[Flip]

Post 264143

(sYnThOmAtIc: "Re: Acidic Hg/Al amalgam", Methods Discourse) seems to suggest this is possible but says that it will substantially lower yeilds. Then again it says nothing about how long the Al/Hg could be kept so i'm still lookin for ya man.

[Flip]

Actually I think I misread... in this rxn you have to balance the al breakup with the drip rate.... this suggests that the breakup is not controlled by the drip rate as if the nitro was breaking up al.  Through my basic newbee logic I conclude that the HgCl2 breaks up the aluminum as well as removing Al203 and so once the amalgamation has started it can't be stopped and the nitro/ketone should be added before it's done. Wham bam thank you mam. That's what I think anyway

[Vibrating_Lights]

swim was thinking of havin a 10 gallon buchet with 1 gallon of ketone and arounf 3000 ml on nitro with 5 gallons of Meoh and having another buchet with Al/Hg and transfering the al as it was consumed  y the nitro(Lt already mentioned that) rather than adding the ketone as it was consumed.  reaction could be kept at toom temp..  Once the al is amalgamated does it degrase any further without reacting with the meoh that the Al was amalgamated on? How long can amalgamated al be stores.  there is H2O inthe tincture that the HgI is made from. bY the WAy HgI Kicks ass
VL_

[Osmium]

Don't do that. For this reaction you want a surplus of MeNH2 reacting with your ketone, not a huge amount of ketone reacting with nitromethane with methylamine as your catalyst.

Don't reinvent the wheel. Don't make things more complicated than they are. Just follow the procedure. There are reasons why it is done the way it is done.
I'm not fat just horizontally disproportionate.

[Osmium]

Thick Al/Hg can be stored for a while for several hours when water is absent. I wouldn't try that with Al foil though.
I'm not fat just horizontally disproportionate.

[Flip]

Wait, once again my obscure newbee logic has confused me...
I thought that the HgCl2 broke up the aluminum and that all nitro did was sit there and look pretty like reduced nitro or methlyamine and make stuff all hot and bubbly. Does the nitro also break up the Al?

Also I think i found an answer to satisfy vl_'s ?.  The storage time (amalgamation rate) will be dependant on the medium in which the amalgamation is kept.  Alcohols that are strong proton donors will make the amalgamation run faster, and weaker proton donors, slower. 

Those of you who have read the second part of this post are probably thinking, "Wow! That Flip is a pretty smart guy!" Do not be fooled... refer to

Post 264499

(terbium: "Re: ETOH and AL/hg", Methods Discourse). Never underestimate the power of TFSE.

[Chromic]

Amalgamation rate refers to how fast the aluminum displaces the mercuric ion from the solution to form a mercury coating on the foil. It has nothing to do with how long the amalgamated aluminum will keep.

Amalgamated foil would likely be stored a anhydrous non-polar aprotic solvent like ether in an air-tight container... if stored any other way, I don't think it'll stand a chance of keeping. (just as you must store any reactive metal away from oxygen and/or water and under a non-polar solvent)

To acheive highest yields, one would add the nitro first, then add the ketone (or at the same time...) because a high methylamine to ketone ratio is desired. The nitromethane provides oxygen to "burn" the aluminum foil, the nitromethane is what is responsible for the reaction being so exothermic. If you were running MeAm and ketone, you'd likely be able to get away without a condenser.

I don't understand why people want to scale the nitromethane approach or the oxone approach. They're ideal for small scale reductions, but are not well suited for large scale reductions... switch methods...

[Osmium]

> Would it affect the rxn Al/hg if an excess of
> nitromethane was added.. say if the synth calls for 20g
> and you give her 30.. would that cause a negative effect
> on the rxn???

Yes. Since the amount of Al present would be insufficient.
I'm not fat just horizontally disproportionate.

[Vibrating_Lights]

how about if 500m lnitro  wasa pplaced in the bucket with 1L Meoh and the activated al was added intil all the 500ML MeNo2 Had reacted Then the 1000 gm ketone added and the other 300 ml nitro along with some more MeOh. Then Activated al is added at a rate to maintainrefuly adding more MeOh as nescsary for proper stirring .that way there will be Me Am present when the ketone hits to for the imine.  then more amine will be produced as the imine that has already being produced is being reduced. 
VL_

[terbium]

Yes. Since the amount of Al present would be insufficient.
And to elaborate on Osmium's reply: This is because there are two reduction reactions being performed by the aluminum

1) reduction of nitromethane to methylamine

2) reduction of the methylimine (formed from ketone and methylamine) to MDMA.

[Vibrating_Lights]

theoreticly if one were to have ketone in meoh with activated al,  and was to gas MeAm into the solution the al would only reduce the imine produced and not the ketone alone back to the alkene before it had a chance to condense.
VL_

The original question though how does using thicker al affect the ammount need to reduce the O atoms,  or does it just provide a slower rdn rate.  Swim has herd that the weight of al/mole to be reduced is didderent than when using foil.  WIll 27gms of .005 foil reduce 20gms of ketone and 20 nitro the same as 27gms of foil would.
VL_

[isohuman]

If one were intent on doing it that way, wouldn't it work to add the ketone, nitro and the hg salt in the same bucket, and just toss in regular old unactivated aluminum over the course of the reaction.  Iso can see no reason why the new aluminum would not continue to amalgamate.

[Vibrating_Lights]

The Hg forms complexes with compounds. 

[Flip]

We all know the textbook definition of amalgamate (to bond a metal w/mercury), but chromic seems to be suggesting that its the nitro and NOT the HgCl2 that is responsible for the Al breakup. And so I am still confused.  I was under the impression that the HgCl2 broke up the foil as well as removing oxidized aluminum. And ether being a (strong?) proton donor would cause this to happen quickly.

I guess the easiest ? to ask to obtain the info I want would be will an hg/al amalgamation in an alcohol break up into grey sludge if nothing else is added (no nitro/ketone) or will the Al2O3 be the only breakup?

[noj]

Quite simply, the Hg removes the Al2O3, the oxidized Al. Once that is done, reaction will stop UNLESS the Al oxidizes again, in which the Hg will remove that again, continually until no more Al is there, or the Hg is depleted (reacted).

If the Al is unable to reoxidize from the oxygen in the air, water, etc, it will stay in the elemental Al state. This is an unlikely situation for the majority of the bees here, without the proper equipment.

The nitro will not react with Al2O3. So the only way to get it to react with the elemental Al is to remove the Al2O3 oxidation with Hg.

Since the nitro DOES react with elemental Al, it will destroy (react with) it. But only if there is no Al2O3 preventing its contact with it.

In conclusion, to keep elemental Al from reoxidizing you will need to keep oxygen from the equation. Keep it in a nonpolar solvent will help, but it won't be permanent. The thicker the Al, the longer it will keep some Al available.

Chaque un à son gout

[Bwiti]

In my dreams, cut up soda/beer cans work great, and using ethylamine/methylamine instead of nitromethane/nitroethane produces less heat. If you plan on scaling a synth up, be sure to have a good overhead stirrer.
  Btw, adding more Al/Hg than the synth calls for won't hurt anything, will it? Peace!
  Love my country. Fear my government.

[Flip]

Thanks for the explanation noj,you've enlightened me.

[Osmium]

No no no!

An amalgam is an alloy containing Hg having the interesting property of overvoltage. This means the Al wants to react and dissolve badly with alcohols and water producing H2 in the process, but this reaction is greatly hindered (NOT completely stopped, just slowed down a lot!) since H2 doesn't like to be produced on Hg surfaces.

When there is anything reducable around, like a nitro compound or an imine the Al can dissolve without having to produce H2 gas, and it readily will do so.
This reaction involves electron transfers between the reaction partners, which is just another way of saying the Al is dissolving and gives up its electrons to the Hg which in turn transfers them to the organic reactand to be reduced. It's not the Hg salt that breaks up the Al. If there is nothing around to be reduced then the Al can't get rid of those electrons, and it will not dissolve. Al/Hg in an inert solvent like hexane or toluene should be quite stable for a while. Al/hg will react with oxygen because Al is a very reactive metal which is only protected by its oxide coating (passivation), once that coating is removed it will oxidise in air, but that is usually not an option when covered by a solvent since O2 solubility is very low.

The solvolysis reaction with an alcohol will be very slow with thick Al because it has a much higher Hg loading on its surface and a much lower exposed surface area than foil.

Al/Hg in a pure alcohol: only very slow dissolving via solvolysis. Greatly enhanced by water presence (since Al2O3 formation is very exothermic and the driving force) and change to basic pH

Al/Hg in water: exothermic, will heat up considerably and might eventually react violently

Al/hg with nitro in alcohol: very exothermic reaction due to water formation, and since nitro is hot stuff  

Al/Hg with nitro in alcohol containing considerable amounts of water and a base: let's not go there, runaway reaction with foil, very exothermic with sheet

Al/Hg with an imine in alcohol with a littlewater: rather slow and gentle reaction

Foil reacts much faster than sheet!

Don't try to tweak the reaction too much and reinvent the wheel! Al/hg works, in up to 90% according to the literature and some bees experience. And when done without haste and with thick Al it can even be very volume efficient.
I'm not fat just horizontally disproportionate.

[Flip]

Wow! That's a damn good answer, very specific. Too many people on this board, including myself, know too much about the processes themselves and not enough about the science behind it. Those kind of specifics are what really strike my interest in this feild. Thanks.

[Vibrating_Lights]

Will the Al reduce the ketone to the alkene if no methylamine is present at the al surface.
VL_

[Bwiti]

Thanks Hydro! When using this method to produce meth or MDMA, side reactions create pinacol and other useless shit, which of course reduces yields. The only way I know of to minimize these side reactions is try to keep water out, and use excess methylamine. The only other thing I can think of is to make sure the Schiff's base has completely formed before the addition of Al/Hg. Should one let the methylamine/MDP-2-P sit for an hour before starting the reduction? Peace!
  Love my country. Fear my government.

[Vibrating_Lights]

Chromic..  pepole want to scale the methods because they are completely OTC and Cheap.  VL_ anticipates a increce in the quailty of street MdMa because there is about to be a great surplus.   The procedures are easy to learn and the materials to needed scaale to retirement quantaties are unbelievelbly cheap.
VL_

[Osmium]

> Should one let the methylamine/MDP-2-P sit for an hour
> before starting the reduction?

Not necessary if you follow some rules:
1. thick Al (only little surface area, so the Al doesn't have to reduce ketone to dissolve, but can concentrate on the imine instead)
2. slowly adding the ketone to the reduction already containing the methylamine (this means pushing the equilibrium to the right by having shitloads of MeNH2 around for every ketone molecule to react with, this keeps the ketone concentration low throughout the reaction)
3. employing good strirring so that the imine has a chance to get to the Al/Hg surface

Try it, it works.
I'm not fat just horizontally disproportionate.

[Bwiti]

"thick Al (only little surface area, so the Al doesn't have to reduce ketone to dissolve, but can concentrate on the imine instead)"

  Thanks! I have access to strips of aluminum that are used in mid-welding, so I'd like to use the appropriate cutting machine to saw it into chunks, then amalgamate it. The reaction would take about 2 days to react, but at least one wouldn't have to worry about it boiling over.

"employing good strirring so that the imine has a chance to get to the Al/Hg surface"

  You know that motor with a spinning dish on top of it in a microwave? Well, I'll be replacing the motor with a faster one, so the next time I need to stir a reaction, I'll put the flask on the spinning dish, then suspend a glass rod into the mixture. There's no need for the rod to spin; the dish will do all the work. Maybe marbles could be added near the end of the reaction to speed things up. Peace!
  Love my country. Fear my government.

[Osmium]

??
I'm not fat just horizontally disproportionate.

[Flip]

just a little advice..... if your really serious about that strange stirring method....... and if you ever do an AL/HG in it, DO NOT TURN IT ON!  I don't know why you would use a microwave in the first place, it seems kinda impractical to me.
Flip

[Bwiti]

"and if you ever do an AL/HG in it, DO NOT TURN IT ON!"

  I left out some important info: The door was taken off the microwave, and it's impossible to turn on, because everything above the spinning dish was cut off with oxy/acetylene with a cutting torch. A cutting torch can easily cut straight through several inches of steel; very fun! One of my hobbies is gutting various appliances for their motors, fans, step-down transformers, switches, etc.. I love fixing and inventing stuff. An over-head stirrer is kind of hard for me to make, because when I use glue/resin to fix a glass rod to the motor, it has to be on straight or it'll wobble when you turn it on. That's why a spinning flask is more practical for me. Peace!
  Love my country. Fear my government.

[terbium]

An over-head stirrer is kind of hard for me to make, because when I use glue/resin to fix a glass rod to the motor, it has to be on straight or it'll wobble when you turn it on.
That is why you use a flexible coupling - piece of thick wall rubber tubing etc. - to join the motor shaft to the stirring rod.

[Bwiti]

"That is why you use a flexible coupling - piece of thick wall rubber tubing etc. - to join the motor shaft to the stirring rod."

  Good idea! Sometime, I should take one of my motors to the hardware store, and see what tubing will best fit the shaft.
  Love my country. Fear my government.

http://www.gothicradio.com

[Cluster_Fucked]

Isn't that what is suggested here ~~>

https://www.thevespiary.org/rhodium/Rhodium/chemistry/equipment/overhead.html

Striving for normality!

[terbium]

Yes, that is what I am talking about.

[noche]

I read a post once at Rhodiums, where 1.6 mg HgCl2 where used along with 50g of thick alu foil to reduce 38ml of MD-P2P. I cant find the post anymore, but one of my frinds migh still have a print of it somewhere at home.
It was claimed that up to 50ml of MD-P2P could be used in this reaction.
1.6mg HgCl2 to 38ml MD-P2P!! That would make one gram of Hg in it´s salt form enough to reduce at least 200 kg MD-P2P, just to take it to the extremes.
The final yelds was repported to be the usual 60%.
After what I have ben reading here it should work in the theorie, but how about you? have any of you had any  experience with such small of amounts of Hg salt?

[Flip]

If what you are saying is true that would be amazing.  The ratio a la MM calls for roughly .6 grams for 38mL MDP2P.  Then again the ratio would not really be proportional to the amount of ketone but to the amount/surface area of aluminum.  I would assume that 1.6 mg of salt would not be nearly enough to amalgamate the quantity of aluminum.  What were the observations from the amalgamation?

[noche]

typing error: I meant 20kg MD-P2P not 200 kg.

[noche]

How many cm3 would one gram of Hg in salt form cover?
As for the 1.6mg Hg salt to 38ml MD-P2P ratio, I was thinking that if the surface was the limitation, then a 50g solid block of of Al could just be used instead of the Al foil in order to equalice the amount of the Hg salt to the Al surface.

Amalgamation time could proberbly easily take up to a couples of weeks maybe months, but then then again a reductivly amination of 38ml MD-P2P could be done with only 1.6 mg of Hg salt.

[baalchemist]

1.6g's of HgCl2 to reduce 38g's is absolutely way too much Hg salt. 100mgs>HgCl2 will easily reduce 150g's or more. Of course you would already know this because its only been discussed here in about 500 prior posts. 
GODISNOWHERE 710-57734

[noj]

1.6 mg not grams. This seems pretty low, but if it works for yall...

Chaque un à son gout

[Flip]

Then again it's not really possible to "over-amalgamate" an amalgamation.  Excess Hg salts will be reduced to the element.
_flip_@hushmail.com

[noche]

So 20 mg HgCl2 with 20g of thick Al foil will reduce 40g of ketone in the same yeld as with 100 mg HgCl2 except for the reaction time wich is longer. Ratios are from Bright Stars MDMA Synthesis.

[deludium]

Excess Hg salts will be reduced to the element

By what, the NaOH addition?

[Rhodium]

No, by the Aluminum.

2 Al + 3 Hg²⁺ -> 2 Al³⁺ + 3 Hg

[Flip]

Does anyone have any information as to the amalgamation rate using HgI2?  I don't remember from where but I heard that using HgI2 'substantially' increases the time required for amalgamation.

EDIT:  In addition what would be the effect of the halogens in the reaction?  Could the iodine cause any problems(side reactions)?

_flip_@hushmail.com

[Rhodium]

Yes, the information is available using TFSE.

[Flip]

Sorry boss    ... come to think of it it was one of your posts that told me that.  I just couldn't find any trials that gave a specific estimate as far as time.  I'll search harder.
_flip_@hushmail.com

[Rhodium]

The counterion (halogens etc) will not have any effect on the reaction, the only difference is the solubility of the Hg salt.

[Flip]

Thanks chief, with all of the help I have been given and with most of my materials aquired I am finally ready to begin micro-scale experimenting.  Expect some write-ups in the future from little ol' Flip.
_flip_@hushmail.com

[PoohBear4Ever]

Does anyone have any information as to the amalgamation rate using HgI2?  I don't remember from where but I heard that using HgI2 'substantially' increases the time required for amalgamation.

"Swim recorded an actual amalgamtion time, it took 17 minutes(.5g mercury blob, 30g Al). The basic procedure is to put a plastic dish on the old balance, zero it, and poke at a mercury blob until about .3-.5 grams is weighed out, then dump it into some 2% I2 tincture, the kind you buy at walmart.  I can't verify that HgI2 is formed, but I have successfully amalgamated using this procedure:
300ml methanol and 300ml of water are placed in an erlenmeyer flask with 20-40g of aluminum.  The tincture is dumped on top of it, and the amalgamation proceeds for about 30 minutes (I use 1" inch squares, thrown in the coffee grinder)..."


PB

[chem_123]

it's bee-n a while since SWIM's touched the mercury, but...

.5g mercury blob

, how are the bees measuring this? a scale is a good start, but, how should it bee handled? it's toxic...no?

My schwartz is bigger than yours!  

[Porn_Starrr]

I played with it before.. Im still alive!!!    

Id get some gloves. Tare out a dish or sumthin and roll in onto it.

[Vibrating_Lights]

Just use excess Hg it will help to convert the tincture faster.
VL_