Ammonium Amalgam

[h***@mbox.bol.bg]

All of this talk about mercury has caused me to remember the curious
case of Ammonium Amalgam. This is a spongy substance that floats on
water made by reacting concentrated aqueous ammonium chloride with
sodium amalgam. It readily decomposes to mercury, ammonia and hydrogen
at ordinary tempratures.... probably meaning that it is stable at low
temp. In some ways it behaves like a mixture of it's constituents, in
others like an amalgum of the pseudo-metal, ammonium.

A google search shows that it has some applications in organic
synthesis.

But my thoughts were... if ammonium amalgam, why not
tetramethyl-ammonium amalgam, or triethanolammonium amalgam, or
hydroxylammoniun amalgum or hydrazinnium amalgam, with apologies for
the spelling?

The so-called amalgam is made with aqueous solutions, and water would
reasonably be expected to react with it, so what about a non-aqueous
synthesis? Say, in liquid ammonia, or an organic amine.

[Scrim]

Can also be made by electrolysing an ammonium salt solution with a mercury
cathode.
Worked well when I tried it years ago - had the consistency of butter.
I think it continued to decompose, by bubbling, even when dry after removal
from the solution.
Strange stuff.

Scrim

Post by h***@mbox.bol.bg
All of this talk about mercury has caused me to remember the curious
case of Ammonium Amalgam. This is a spongy substance that floats on
water made by reacting concentrated aqueous ammonium chloride with
sodium amalgam. It readily decomposes to mercury, ammonia and hydrogen
at ordinary tempratures.... probably meaning that it is stable at low
temp. In some ways it behaves like a mixture of it's constituents, in
others like an amalgum of the pseudo-metal, ammonium.
A google search shows that it has some applications in organic
synthesis.
But my thoughts were... if ammonium amalgam, why not
tetramethyl-ammonium amalgam, or triethanolammonium amalgam, or
hydroxylammoniun amalgum or hydrazinnium amalgam, with apologies for
the spelling?
The so-called amalgam is made with aqueous solutions, and water would
reasonably be expected to react with it, so what about a non-aqueous
synthesis? Say, in liquid ammonia, or an organic amine.

[h***@mbox.bol.bg]

Post by Scrim
Can also be made by electrolysing an ammonium salt solution with a mercury
cathode.
Worked well when I tried it years ago - had the consistency of

butter.

Post by Scrim
I think it continued to decompose, by bubbling, even when dry after removal
from the solution.
Strange stuff.

oooo.... let's try it with a quatenary salt... If I still had a job
at the bench my long-suffering boss would be wondering what on earth I
was doing again wasting his money on some crazy experiment.

[Oscar Lanzi III]

If you do try it with a quaternary salt, I suppose there could be side
reactions involving the alkyl groups at the cathode. Yes? No? Maybe?

--OL

[h***@mbox.bol.bg]

Post by Oscar Lanzi III
If you do try it with a quaternary salt, I suppose there
could be side reactions involving the alkyl groups at the
cathode. Yes? No? Maybe?

You mean, the same reactions that you'd get with a
platinum electrode? Most probably. I have no idea
what those would be, however.... I haven't studied
electrochemical reactions, though I've read of many
interesting examples.

No, what I was wondering is if substituted analogues
of ammonium amalgam, such as tetramethyl ammonium
amalgam were possible, and what their reactions would
be. I'd imagine that that one would decompose to
ethane and trimethylamine, and would it be any use
as a methyl donor or an amine donor? But who knows.

[h***@mbox.bol.bg]

oops, would there be any possability of mercury alkyls?

[Libor Striz]

Post by h***@mbox.bol.bg
oops, would there be any possability of mercury alkyls?

Maybe you remember poisoning of japanese fishers by dimethylmercury,
caused by leaking mercury from industry into sea water....

[muha]

It was "methylmercury" poisoning, Me-Hg-Hg-Me in fact. What was leaking
there was actualy inorganic mercury (I think some mercury-based
catalyst used to make acetaldehyde from acetylene) from a company
up-river from the bay. The microbes metabolized it into organomercury
which accumulated in the fish eaten by villagers in the bay.

Dimethyl mercury Me-Hg-Me is different. (Dimethyl mercury accute
poisoning claimed lives of 2 chemists, one at Dartmouth College
recently and one in Prague back in 70s.)

Post by Libor Striz

Post by h***@mbox.bol.bg
oops, would there be any possability of mercury alkyls?

Maybe you remember poisoning of japanese fishers by dimethylmercury,
caused by leaking mercury from industry into sea water....
--
Any supposed offense is because of bad english or idea formulation
and was not intended in any way.
ForPrivateResponseRemoveDelAndThisFromAboveAddress.

[Angelo]

Post by muha
It was "methylmercury" poisoning, Me-Hg-Hg-Me in fact. What was leaking
there was actualy inorganic mercury (I think some mercury-based
catalyst used to make acetaldehyde from acetylene) from a company
up-river from the bay. The microbes metabolized it into organomercury
which accumulated in the fish eaten by villagers in the bay.

I think the main poisoning species is CH3-Hg+.
For what I can remember the Me-Hg-Hg-Me is
likely too unstable vs. self decomposition leading
to Me2Hg and Hg, in such dilute conditions.

Post by muha
Dimethyl mercury Me-Hg-Me is different. (Dimethyl mercury accute
poisoning claimed lives of 2 chemists, one at Dartmouth College
recently and one in Prague back in 70s.)

Didn't know about these accidents, thanks for the info.
Best regards,
Angelo

[Chris Cooksey]

The first case of dimethyl mercury poisoning arose amongst research
workers at St Bartholomew's Hospital in 1865 as they tried to
manufacture organic mercurial compounds. Three technicians had
significant methyl mercury exposure and two subsequently died as a
result.

Death is not immediate but occurs up to six months after exposure. But
it appears to be inevitable.

[G. N. Edwards, 2 cases of poisoning by mercuric methide. St
Bartholomew's Hospital Reports, Vol 1. Longmans, Green and Co: London,
1865, pp 141-150]

Chris C.

Post by muha
It was "methylmercury" poisoning, Me-Hg-Hg-Me in fact. What was leaking
there was actualy inorganic mercury (I think some mercury-based
catalyst used to make acetaldehyde from acetylene) from a company
up-river from the bay. The microbes metabolized it into organomercury
which accumulated in the fish eaten by villagers in the bay.
Dimethyl mercury Me-Hg-Me is different. (Dimethyl mercury accute
poisoning claimed lives of 2 chemists, one at Dartmouth College
recently and one in Prague back in 70s.)

Post by Libor Striz

Post by h***@mbox.bol.bg
oops, would there be any possability of mercury alkyls?

Maybe you remember poisoning of japanese fishers by dimethylmercury,
caused by leaking mercury from industry into sea water....
--
Any supposed offense is because of bad english or idea formulation
and was not intended in any way.
ForPrivateResponseRemoveDelAndThisFromAboveAddress.

[Libor Striz]

Interesting article about death poisoning of profecional chemist
by dimethylmercury is here:

http://www.altcorp.com/DentalInformation/dimethylmercury.htm

[donald j haarmann]

Post by Scrim
Can also be made by electrolysing an ammonium salt solution with a mercury
cathode.
Worked well when I tried it years ago - had the consistency of butter.
I think it continued to decompose, by bubbling, even when dry after removal
from the solution.
Strange stuff.
Scrim

----------
A historical note borrowed from Mellor's 16 volume tome:—


IN 1808 immediately after H. Davy's announcement of the discovery of potassium and
sodium, T. J. Seebeck placed mercury in a cavity cut into a piece of ammonium carbonate
resting on a metal plate ; the latter was placed in connection with the positive pole, and mercury
with the negative pole of a battery. The mercury swelled up into a frothy mass, with the
consistency of butter. The product is considered to be ammonium amalgam. Almost simultaneously,
J. J. Berzelius and M. M. Pontin passed a current through a conc. aq. son. of ammonium
chloride, in such a way that the cathode dips into mercury, and obtained a similar frothy
product. In place of T. J. Seebeck's ammonium carbonate, H. Davy, and J. B. Tommsdorff used
ammonium chloride and J. L. Gay Lussac and L. J. Thénard, the sulphate of or phosphate, and
showed that the salt itself could be connected directly with the positive pole of the battery.

H. Moissan electrolyzed a soln. of ammonium mercury iodide (NH4)2HgI4 in liquid ammonia, or
an aq. soln. of ammonium iodide, mercuric iodide and water at -40o.

S. von Laszcynsky electrolyzed a soln. of ammonium thiocyanate with a mercury cathode.

Davy. Mercury containing about 1% sodium potassium or barium in moistened ammonium salt,
in aq. soln. in conc. aq. ammonia.

Wetherill. Sodium amalgam on a soln. of methylamine oxalate free from ammonia.

Pfeil & Leffman. Likewise with a sat. soln. of trimelthylamine ammonium chloride

Moissan. Dry ammonium iodide or chloride in liquid ammonia, shaking at about -35o with sodium
amalgam.

---------
It never ceases to amaze me ... how these early chemist jumped on this stuff!! Someone boils something
new... published it .... and they all jump on it! Amazing what they developed using the "by guess and by gosh"
method.



donald j haarmann
-----------------------------------------
Science never solves a problem
without creating ten more.
GB Shaw

[jacques jedwab]

Perhaps not entirely unrelated: there are 3 natural minerals containing Hg
AND N (gianellaite, kleinite and mosesite). The two last ones contain also
Cl and SO4. Chances are that ammonium amalgam ends up as one of these when
left in the open.

J.J.

Post by h***@mbox.bol.bg
All of this talk about mercury has caused me to remember the curious
case of Ammonium Amalgam. This is a spongy substance that floats on
water made by reacting concentrated aqueous ammonium chloride with
sodium amalgam. It readily decomposes to mercury, ammonia and hydrogen
at ordinary tempratures.... probably meaning that it is stable at low
temp. In some ways it behaves like a mixture of it's constituents, in
others like an amalgum of the pseudo-metal, ammonium.
A google search shows that it has some applications in organic
synthesis.
But my thoughts were... if ammonium amalgam, why not
tetramethyl-ammonium amalgam, or triethanolammonium amalgam, or
hydroxylammoniun amalgum or hydrazinnium amalgam, with apologies for
the spelling?
The so-called amalgam is made with aqueous solutions, and water would
reasonably be expected to react with it, so what about a non-aqueous
synthesis? Say, in liquid ammonia, or an organic amine.

[Angelo]

Hi all,

Post by h***@mbox.bol.bg
All of this talk about mercury has caused me to remember the curious
case of Ammonium Amalgam. This is a spongy substance that floats on
water made by reacting concentrated aqueous ammonium chloride with
sodium amalgam. It readily decomposes to mercury, ammonia and

hydrogen

Post by h***@mbox.bol.bg
at ordinary tempratures.... probably meaning that it is stable at low
temp. In some ways it behaves like a mixture of it's constituents, in
others like an amalgum of the pseudo-metal, ammonium.

Yes, IOW the odd-electron species NH4 (not to be mistaken
for NH4(+), of course). I think you are right in calling it a
pseudo-metal, at least in the amalgam state. I read from the
NIST site that its ionization energy is 4.73 eV, a value in
between those of Na and K. This rules out a conceivably
Rydberg state for the outermost electron in NH4. So how to
place this electron 'inside' that species paying attention to
Pauli exclusion principle?
Also, if NH4 could be generated in a sufficiently low temp
and sufficiently high pressure, would it be a better candidate
than hydrogen to become metallic, or in every case NH4
needs another metal host lattice to do so?

Post by h***@mbox.bol.bg
A google search shows that it has some applications in organic
synthesis.

This seems quite reasonable in view of the easy removal
of that last electron.

Post by h***@mbox.bol.bg
But my thoughts were... if ammonium amalgam, why not
tetramethyl-ammonium amalgam, or triethanolammonium amalgam, or
hydroxylammoniun amalgum or hydrazinnium amalgam, with apologies for
the spelling?

I think that tetramethyl-NH4, or related substituted species,
are simply too big (ionic radii) to possibly enter a Hg or other
metal host lattice: let's think of H2 which easily enters the Pd
one (and the resulting phase is still metallic at least at low
H2 / Pd mole ratio), at variance with CH4 (H-CH3) which
does not even enter.

Post by h***@mbox.bol.bg
The so-called amalgam is made with aqueous solutions, and water would
reasonably be expected to react with it, so what about a non-aqueous
synthesis? Say, in liquid ammonia, or an organic amine.

That seems to me a very good idea, but I'm not aware if it has
been tried.

Best regards,
Angelo