Discussion:
Interesting Azide Patents ( circa 1919 )
(too old to reply)
Anonymous Sender
2003-12-13 22:11:29 UTC
Permalink
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .

It is my guess that a buffer or special technique , would be needed
to facilitate such reactions , Is that correct ? Does anyone know
this patent reaction , and if a buffer is used , which particular one ?
Perhaps sodium bisulfite may work for this purpose ?

Abstracts :

GB128014

Salts of hydrazine are diazotized by means of a suitable nitrite, without
the use of ethyl benzoate or the like, the reaction mass being kept on
the border line between acidity and alkalinity. For example, hydrazine
sulphate is treated with sodium nitrite; the sodium azide produced,
without being separated, may be caused to react with silver nitrate for
the production of silver azide. When lead azide is to be prepared,
hydrazine nitrate may be used in place of the sulphate.

GB129152

An insoluble azide is produced by diazotizing a hydrazine salt in
practically neutral solution and in presence of a salt, such as silver
nitrate, adapted to produce the insoluble azide. The azide is then
treated with a solution of a salt such as sodium chloride to obtain the
desired azide and an insoluble silver salt. From the sodium azide, other
azides such as lead azide may be obtained by double decomposition in the
known manner.
LOUIS
2003-12-14 13:56:12 UTC
Permalink
AgN3 may be prepared by action of NH2-NH2.H2O on AgONO (silver
nitrite-almost unsoluble in water).
HN3 can be prepared by action of HONO on NH2-NH2; the usual procedure uses
nitrite esters of moderate volatility (isopropyl, n-butyl, isoamyl, ...)
wich free upon contact with water and NH2-NH2 continuously HONO.

NH2-NH2.HONO --> NH2-NH-N=O + H2O ----> HN3 + 2H2O

Other hydrazine related compounds react the same way...
NH2-NH-CO-NH2 + HONO --> NH2-NH-CO-NH2.2HONO -->
N3-CO-NH-NO --> N3-COOH + N2 --> HN3 + CO2 + N2

C6H5-NH-NH2 + HONO --> C6H5-N3 + 2H2O

For the buffer NaHCO3/H2CO3 is good too.
Post by Anonymous Sender
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .
It is my guess that a buffer or special technique , would be needed
to facilitate such reactions , Is that correct ? Does anyone know
this patent reaction , and if a buffer is used , which particular one ?
Perhaps sodium bisulfite may work for this purpose ?
GB128014
Salts of hydrazine are diazotized by means of a suitable nitrite, without
the use of ethyl benzoate or the like, the reaction mass being kept on
the border line between acidity and alkalinity. For example, hydrazine
sulphate is treated with sodium nitrite; the sodium azide produced,
without being separated, may be caused to react with silver nitrate for
the production of silver azide. When lead azide is to be prepared,
hydrazine nitrate may be used in place of the sulphate.
GB129152
An insoluble azide is produced by diazotizing a hydrazine salt in
practically neutral solution and in presence of a salt, such as silver
nitrate, adapted to produce the insoluble azide. The azide is then
treated with a solution of a salt such as sodium chloride to obtain the
desired azide and an insoluble silver salt. From the sodium azide, other
azides such as lead azide may be obtained by double decomposition in the
known manner.
LOUIS
2003-12-15 09:10:27 UTC
Permalink
Post by LOUIS
AgN3 may be prepared by action of NH2-NH2.H2O on AgONO (silver
nitrite-almost unsoluble in water).
HN3 can be prepared by action of HONO on NH2-NH2; the usual procedure uses
nitrite esters of moderate volatility (isopropyl, n-butyl, isoamyl, ...)
wich free upon contact with water and NH2-NH2 continuously HONO.
NH2-NH2.HONO --> NH2-NH-N=O + H2O ----> HN3 + 2H2O
Other hydrazine related compounds react the same way...
NH2-NH-CO-NH2 + HONO --> NH2-NH-CO-NH2.2HONO -->
N3-CO-NH-NO --> N3-COOH + N2 --> HN3 + CO2 + N2
C6H5-NH-NH2 + HONO --> C6H5-N3 + 2H2O
For the buffer NaHCO3/H2CO3 is good too.
Post by Anonymous Sender
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .
It is my guess that a buffer or special technique , would be needed
to facilitate such reactions , Is that correct ? Does anyone know
this patent reaction , and if a buffer is used , which particular one ?
Perhaps sodium bisulfite may work for this purpose ?
GB128014
Salts of hydrazine are diazotized by means of a suitable nitrite, without
the use of ethyl benzoate or the like, the reaction mass being kept on
the border line between acidity and alkalinity. For example, hydrazine
sulphate is treated with sodium nitrite; the sodium azide produced,
without being separated, may be caused to react with silver nitrate for
the production of silver azide. When lead azide is to be prepared,
hydrazine nitrate may be used in place of the sulphate.
GB129152
An insoluble azide is produced by diazotizing a hydrazine salt in
practically neutral solution and in presence of a salt, such as silver
nitrate, adapted to produce the insoluble azide. The azide is then
treated with a solution of a salt such as sodium chloride to obtain the
desired azide and an insoluble silver salt. From the sodium azide, other
azides such as lead azide may be obtained by double decomposition in the
known manner.
Louis ,
Reactions which involve free hydrazine and nitrite esters are related ,
but involve different reactants and more difficult conditions than these
abstracts which describe using more common materials in aqueous solutions .
-NH2-NH2 aqueous and HONO aqueous at low temperature produces good amounts of HN3.
Those are no difficult conditions or very different reactants.
There is a similar , yet different mechanism for the reactions described
by the abstracts above , which use hydrazine sulfate as a reactant with
sodium nitrate in aqueous solution . I have tried several variations
of such a reaction to produce copper azide , using sodium acetate as
a buffer , and none of the experiments were successful . I also tried
-Here comes the mistake, note that I have seen it in books too (so you are not to
blame)...NITRITE not NITRATE!
NaONO isn't NaONO2 absolutely different chemophysical properties.

NH2-NH2.H2SO4 is an acidic salt (pH of solution of the salt must be > 6)
You thus have:
NH2-NH2.H2SO4 <=--> NH2-NH3(+) + HSO4(-) (moderate solubility of hydrazine sulfate)
NH2-NH3(+) = NH2-NH2 + H(+)
NaONO --H2O-> Na(+) + ONO(-)
Na(+) + HSO4(-) <--> NaHSO4
NaHSO4 + NaNO2 ----> Na2SO4 + HONO
(HSO4(-) is about 20 times acider than HONO; HONO is thus displaced from its salts
by hydrogenosulfate salts-and naturally from H2SO4 wich is 100.000 times acider than
HSO4(-) itself).

So in short simplified chemical equation:
NH2-NH2.H2SO4 + 2NaONO -----> NH2-NH2.HONO + HONO + Na2SO4 ---->
And then following what I have explained HN3 from hydrazine nitrite.
HN3 + 2H2O + HONO + Na2SO4

In theory there is no reason to trim the reaction since NH2-NH2 salts of strong
acids are by definition buffers and so does sodium salts of polyacids in acidic
media.

For operational purpose it would be better to use hydrazine acetate, nitrate or
perchlorate (in dilluted form) with a soluble nitrite (sodium is the best and
cheaper) since then later admixion of metal salts to precipitate azides of heavy
metal will only precipitate the azide...all acetates, nitrates and perchlorates of
metals are indeed soluble.
sodium bicarbonate as a buffer without any improvement . If you
-No mather the buffer is you have used nitrates salts instead of nitrites you will
only end up with a mix of salts NH2-NH2.H2SO4 + NaNO3 mainly as initial reactants,
and NH2-NH2.HNO3 + NaHSO4 as minor ingredients; the addition of heavy metal salts
will only result in side reactions precipitations since no HONO is present and this
only allow the transformation of NH2-NH2 into HN3.
had success using sodium bicarbonate in solution in "soda water"
then maybe the "soda water" does the trick . Please share any details
of your experiments . I chose the copper compound because of the
solubility of the sulfate .
-Copper carbonate is unsoluble but as you see there are acids evolving in the cursus
of the reaction and so finally Cu(N3)2 will result with evolution of CO2 bubbles;
but you have to add the copper (or other salts to precipitate azides at the end of
the reaction since hydrazine doesn't like transition complexation metals wich
catalyses its decomposition).
Have you ever tried to precipitate copper azide from a reaction mixture
of hydrazine sulfate and sodium nitrate ? Did the reaction product
in the beaker fulfill the predicted reaction worked out on paper ?
-Copper azide is unsoluble I have precipitated it from NaN3 solution and CuSO4....I
don't want to waste my precious NH2-NH2.H2SO4 and NH2-NH2.H2O ;-).
Again NITRITE not nitrate.
Not in my own experiments does this work straightforwardly .
I fully expect that such reactions do require specific conditions
of temperature and pH and concentration of reactants , or a particular
buffer , and required many experiments for the inventors to work out
a useful method .
-Not really specific conditions, simply not too high pH (too concentrated at base)
not too low pH (too concentrated at acid) since heat of neutralisation and
precipitation might give troubles aside with loss of heat dissipation in the
precipitate by increase of the viscosity. Buffer will only increase the yield to
optimise the amount, the precipitation efficiency.
In COPAE there is mention of silver azide having been made by mixing
saturated solutions of silver nitrite and hydrazine sulfate and allowing
the mixture to stand in the cold for a short time . No specific ratios
or yield are given . The reaction is referenced to Angeli ( Italian ? )
the citation is Rend. acc. Lincei , [5] 2 , I , 599 ( 1893 )
So silver azide has been around for a hundred and ten years !
-This is related to the reaction I have mentionned about using NH2-NH2.H2O with
AgONO.
It works with the sulfate of hydrazine just the same way as with NaONO.But here,
Ag2SO4 is unsoluble but being less unsoluble than AgN3....AgN3 precipitate in
priority and thus upon little time AgN3 is the major precipitate.
Davis goes on further to mention that free hydrazoic acid can be produced
in aqueous solution of hydrazine sulfate with potassium nitrite , but again
no reaction details are described . The reaction is referenced by Davis
to Dennstedt and Gohlich ( German or Swiss ? ) Chem.-Ztg. , 21 , 876 ( 1897 )
-Same as the short simplified chemical equation I have written above.
Probably the patent reactions are an evolution of data from those two
and perhaps other early sources . Do you have any specific information
about such reactions which involve hydrazine sulfate and alkaline nitrites
in an aqueous reaction medium ?
I would like to know more about the reaction condition details
involved in these interesting patents .
Rosco
-All infos needed are above.

Ph Z
Rosco P. Coaltrain
2003-12-15 21:19:12 UTC
Permalink
Post by LOUIS
For operational purpose it would be better to use hydrazine acetate, nitrate or
perchlorate (in dilluted form) with a soluble nitrite (sodium is the best and
cheaper) since then later admixion of metal salts to precipitate azides of heavy
metal will only precipitate the azide...all acetates, nitrates and perchlorates of
metals are indeed soluble.
Yes , I understand the choice of which acid salt of hydrazine used
must not precipitate the corresponding low solubility salt
of the metal which is desired to form a metal azide instead .
I have also tried hydrazine nitrate in the reaction with sodium nitrite
with and without buffers for different metal azides and those
experiments failed also . I have not yet tried the silver compound .
But copper and lead both failed to work in several different experiments
to produce their azides .
Post by LOUIS
sodium bicarbonate as a buffer without any improvement . If you
-No mather the buffer is you have used nitrates salts instead of nitrites you will
only end up with a mix of salts NH2-NH2.H2SO4 + NaNO3 mainly as initial reactants,
and NH2-NH2.HNO3 + NaHSO4 as minor ingredients; the addition of heavy metal salts
will only result in side reactions precipitations since no HONO is present and this
only allow the transformation of NH2-NH2 into HN3.
had success using sodium bicarbonate in solution in "soda water"
then maybe the "soda water" does the trick . Please share any details
of your experiments . I chose the copper compound because of the
solubility of the sulfate .
-Copper carbonate is unsoluble but as you see there are acids evolving in the cursus
of the reaction and so finally Cu(N3)2 will result with evolution of CO2 bubbles;
but you have to add the copper (or other salts to precipitate azides at the end of
the reaction since hydrazine doesn't like transition complexation metals wich
catalyses its decomposition).
Have you ever tried to precipitate copper azide from a reaction mixture
of hydrazine sulfate and sodium nitrate ? Did the reaction product
in the beaker fulfill the predicted reaction worked out on paper ?
-Copper azide is unsoluble I have precipitated it from NaN3 solution and CuSO4....I
don't want to waste my precious NH2-NH2.H2SO4 and NH2-NH2.H2O ;-).
Again NITRITE not nitrate.
Yes , I did use the nitrous acid salt of sodium , and I know the difference ,
In hasty typing I simply misspelled the term .

I have also made copper azide from sodium azide and soluble copper salts ,
copper acetate is the copper salt I used . Those reactions are simple .
But sodium azide is several synthetic steps from hydrazine sulfate as
a precursor for synthesis of heavy metal azides , so sodium azide is
a more "precious" and uncommon material than hydrazine sulfate .
Please do waste some of your hydrazine sulfate in actual experiments
and you will see that the reaction which seems so simple on paper
and in theory , does not work so easily in practice .
Post by LOUIS
Not in my own experiments does this work straightforwardly .
I fully expect that such reactions do require specific conditions
of temperature and pH and concentration of reactants , or a particular
buffer , and required many experiments for the inventors to work out
a useful method .
-Not really specific conditions, simply not too high pH (too concentrated at base)
not too low pH (too concentrated at acid) since heat of neutralisation and
precipitation might give troubles aside with loss of heat dissipation in the
precipitate by increase of the viscosity. Buffer will only increase the yield to
optimise the amount, the precipitation efficiency.
In COPAE there is mention of silver azide having been made by mixing
saturated solutions of silver nitrite and hydrazine sulfate and allowing
the mixture to stand in the cold for a short time . No specific ratios
or yield are given . The reaction is referenced to Angeli ( Italian ? )
the citation is Rend. acc. Lincei , [5] 2 , I , 599 ( 1893 )
So silver azide has been around for a hundred and ten years !
-This is related to the reaction I have mentionned about using NH2-NH2.H2O with
AgONO.
It works with the sulfate of hydrazine just the same way as with NaONO.But here,
Ag2SO4 is unsoluble but being less unsoluble than AgN3....AgN3 precipitate in
priority and thus upon little time AgN3 is the major precipitate.
Davis goes on further to mention that free hydrazoic acid can be produced
in aqueous solution of hydrazine sulfate with potassium nitrite , but again
no reaction details are described . The reaction is referenced by Davis
to Dennstedt and Gohlich ( German or Swiss ? ) Chem.-Ztg. , 21 , 876 ( 1897 )
-Same as the short simplified chemical equation I have written above.
Probably the patent reactions are an evolution of data from those two
and perhaps other early sources . Do you have any specific information
about such reactions which involve hydrazine sulfate and alkaline nitrites
in an aqueous reaction medium ?
I would like to know more about the reaction condition details
involved in these interesting patents .
Rosco
-All infos needed are above.
Ph Z
The theory and the stoichiometry are no mystery .
Why it does not work so smoothly in practice is the question .
Synthesis details described for actual experiments which work
successfully are what is missing here . You have described the
theory quite well . Can you provide a synthesis description
as an example of what has been directly observed to provide
confirmation of theory by actual experiment ?

All theoretical reactions work splendidly well on paper .
But many of these reactions are not so simple in practice
and this is one on them . Try an experiment with these
type syntheses of metal azides from salts of hydrazine
and sodium nitrite . *Then* see how interested you may be
in what the inventors discovered was needed in the way
of reaction conditions for such a synthetic scheme to proceed .

Rosco
donald j haarmann
2003-12-15 22:13:42 UTC
Permalink
Post by Rosco P. Coaltrain
But copper and lead both failed to work in several different experiments
to produce their azides .
--------
Ahhhhhhhhh whey would anyone want to produce "copper azide"?!!?

Good old Marshall Vol. II 1917 provides the following drop test results from
Wöhler (no citation):-

500gm

Hg fulminate 75-100
Ag fulminate 140
Silver azide 310
Pb azide (fine) 260
Basic Cupric 315
Cuprous 260
Cupric 0 [sic]
Mercuric xtyls 3mm 0 [sic]


Urbanski (who you would do well to read) cites Marin for the following values:

Impact (work in kgm/cm3)

Ag 13.97
Pb 4.76
Mercurous 4.76
Cd 18.54
Zn 17.83
Cuprous 2.66
Ni 5.46
Co 5.88
Mn 6.30
Ba 7.70
Sr 9.10
Ca 10.14
Li no explosion
Th 16.18

Things to do .... work on organic azides.



--
donald j haarmann - independently dubious
Rosco P. Coaltrain
2003-12-16 08:13:48 UTC
Permalink
Post by donald j haarmann
Post by Rosco P. Coaltrain
But copper and lead both failed to work in several different experiments
to produce their azides .
--------
Ahhhhhhhhh whey would anyone want to produce "copper azide"?!!?
Two reasons . The hydrazoic acid salt of copper being precipitated
from the mixture would be a simple indicator proving whether the reaction
worked out on paper worked in practice as in theory .

Secondly , if you read more patents and knew Dr. Friedrichs
work , you wouldn't be asking as if the copper azide had no
practical usefulness otherwise . To explain :

One historically noteworthy researcher in this area was named
Dr. Walter Friedrich . He may best answer your question in
one of his many patents . See GB417763 ( 1934 ) for an answer .
Copper Azide was cited as being a useful component of
detonating mixtures , where its advantage over lead azide
was greater chemical stability . Friedrich is an authoritative
source .

Admittedly copper azide alone is among the more sensitive primaries ,
but only about half as sensitive as silver fulminate , which has
practical usefulness in small amounts in pyrotechnics , where the
sensitivity is desired .
Post by donald j haarmann
Good old Marshall Vol. II 1917 provides the following drop test results from
Wöhler (no citation):-
500gm
Hg fulminate 75-100
Ag fulminate 140
Silver azide 310
Pb azide (fine) 260
Basic Cupric 315
Cuprous 260
Cupric 0 [sic]
Mercuric xtyls 3mm 0 [sic]
Urbanski (who you would do well to read)
Looks like we could both do some reading :-)
Urbanski is some reading I would like to do . But the books are expensive
to obtain and not presently available online in English , so far as I know .
I understand they may become available in the near future . Do you know
if Urbanski elaborates and gives synthesis examples relevant to the two
patents which were the title subject of this thread ?
Post by donald j haarmann
Impact (work in kgm/cm3)
Ag 13.97
Pb 4.76
Mercurous 4.76
Cd 18.54
Zn 17.83
Cuprous 2.66
Ni 5.46
Co 5.88
Mn 6.30
Ba 7.70
Sr 9.10
Ca 10.14
Li no explosion
Th 16.18
Things to do .... work on organic azides.
organic ?

The topic of this thread and discussion regards inorganic azides ,
and involves a very specific reaction route to alkali and metal
azides via hydrazine sulfate or hydrazine nitrate in reaction
with sodium nitrite in aqueous solution . Unless you know that
organic azides are somehow involved , can our discussion here
be kept on topic , as an exchange of useful information pertinent
to the specified reaction scheme of those patent abstracts ?

Rosco
donald j haarmann
2003-12-17 14:44:53 UTC
Permalink
"Rosco P. Coaltrain" <***@yahoo.com>

[snip]
Post by Rosco P. Coaltrain
Secondly , if you read more patents and knew Dr. Friedrichs
work , you wouldn't be asking as if the copper azide had no
One historically noteworthy researcher in this area was named
Dr. Walter Friedrich . He may best answer your question in
one of his many patents . See GB417763 ( 1934 ) for an answer .
Copper Azide was cited as being a useful component of
detonating mixtures , where its advantage over lead azide
was greater chemical stability . Friedrich is an authoritative
source .
-----------
Forsooth!

A patent is nothing more than a fantasy. The hope - the invention will have commerical use.
Which this idea didn't. Detonators use aluminium cups specificaly to prevent the formation of
copper azide!!

--
donald j haarmann
------------------------------
For a successful technology,
reality must take precedence
over public relations,
for Nature cannot be fooled.
[The late] Richard Feynman
Commenting on the 1st Space
Shuttle mess.
Rosco P. Coaltrain
2003-12-17 23:22:33 UTC
Permalink
Post by donald j haarmann
[snip]
Post by Rosco P. Coaltrain
Secondly , if you read more patents and knew Dr. Friedrichs
work , you wouldn't be asking as if the copper azide had no
One historically noteworthy researcher in this area was named
Dr. Walter Friedrich . He may best answer your question in
one of his many patents . See GB417763 ( 1934 ) for an answer .
Copper Azide was cited as being a useful component of
detonating mixtures , where its advantage over lead azide
was greater chemical stability . Friedrich is an authoritative
source .
-----------
Forsooth!
A patent is nothing more than a fantasy. The hope - the invention will have commerical use.
Which this idea didn't. Detonators use aluminium cups specificaly to prevent the formation of
copper azide!!
It is not the *generalized condemnation* of copper azide itself which
is
declared by the choice of non-copper casings to prevent unintended *in
situ*
formation of copper azide in firing train elements where that is
undesirable . Copper azide is an offending presence in lead azide
detonators having a copper casing because it spoils the physical
integrity of the other charge elements in that firing train with the
presence of copper azide crystals which slowly grow into sensitive
deposits from "corrosion" between lead azide and the copper casing .
However , if a different firing train composition is used which
contains no lead azide , and copper azide of controlled small
crystalline form is *deliberately* made a component of detonating
mixture , then the danger of copper azide is not present in the same
way as is to be avoided by choosing other than copper casings for
detonators which contain lead azide . You see it is the *context* in
how the copper azide is formed , and in combination with what other
materials , which makes it useful or hazardous . Did you read the
Friedrich patent and not understand this distinction from what you
read ?

Do you by any chance have a Derwent patent databse account ?
If so , then please check and see if the two British patents
at the top of this thread are available from that private collection
and post them here for everyones judgement of their technical merit.

*If* the content of the patents does not withstand scrutiny ,
then we all may ridicule the "fanatsy" of the inventors as
they deserve , and we can all see the vindication of your claims
made here freely , as superior knowledge to those "fantastic claims"
made officially by dreamers whom the patent office charged for their
indulgence in delusion . It is only fair to reveal the technology
being ridiculed or criticized , and specify where the claims are wrong
.

Rosco
donald j haarmann
2003-12-18 02:10:26 UTC
Permalink
"Rosco P. Coaltrain" <***@yahoo.com> >
----------
Yea But - Was it ever used commericaly?
--
donald j haarmann - independently dubious
-----------------------------------------------------------------------
Post by Rosco P. Coaltrain
It is not the *generalized condemnation* of copper azide itself which
is
declared by the choice of non-copper casings to prevent unintended *in
situ*
formation of copper azide in firing train elements where that is
undesirable . Copper azide is an offending presence in lead azide
detonators having a copper casing because it spoils the physical
integrity of the other charge elements in that firing train with the
presence of copper azide crystals which slowly grow into sensitive
deposits from "corrosion" between lead azide and the copper casing .
However , if a different firing train composition is used which
contains no lead azide , and copper azide of controlled small
crystalline form is *deliberately* made a component of detonating
mixture , then the danger of copper azide is not present in the same
way as is to be avoided by choosing other than copper casings for
detonators which contain lead azide . You see it is the *context* in
how the copper azide is formed , and in combination with what other
materials , which makes it useful or hazardous . Did you read the
Friedrich patent and not understand this distinction from what you
read ?
Do you by any chance have a Derwent patent databse account ?
No.
Rosco P. Coaltrain
2003-12-18 07:41:19 UTC
Permalink
Post by donald j haarmann
----------
Yea But - Was it ever used commericaly?
I have no idea what use was made of Friedrichs discovery .
That unique copper azide research was one of several
interesting patents which were published by him . Many research
findings have been published by patent , and the commercial use
of a technology is not always a proper index of the technical
accuracy or merit of the work . There are many obscure works
which at their time of publication reflected the "state of the art"
for that moment , but were superseded almost immediately by new
discoveries by others or even improvements by the same researcher .
Anyway , Dr. Walter Friedrich was a serious German chemist with a Phd.
Friedrichs work speaks for itself , and gives the impression he
knew his science well enough to be considered reliable .

It shouldn't be too difficult to test the validity of Friedrichs claims .
Post by donald j haarmann
donald j haarmann - independently dubious
-----------------------------------------------------------------------
Post by Rosco P. Coaltrain
It is not the *generalized condemnation* of copper azide itself which
is
declared by the choice of non-copper casings to prevent unintended *in
situ*
formation of copper azide in firing train elements where that is
undesirable . Copper azide is an offending presence in lead azide
detonators having a copper casing because it spoils the physical
integrity of the other charge elements in that firing train with the
presence of copper azide crystals which slowly grow into sensitive
deposits from "corrosion" between lead azide and the copper casing .
However , if a different firing train composition is used which
contains no lead azide , and copper azide of controlled small
crystalline form is *deliberately* made a component of detonating
mixture , then the danger of copper azide is not present in the same
way as is to be avoided by choosing other than copper casings for
detonators which contain lead azide . You see it is the *context* in
how the copper azide is formed , and in combination with what other
materials , which makes it useful or hazardous . Did you read the
Friedrich patent and not understand this distinction from what you
read ?
Do you by any chance have a Derwent patent databse account ?
No.
Anybody on this list have a Derwent "patent store" account ( Delphion ) ?
Or maybe access to an archive that has old British patents on microfiche ?

Rosco
donald j haarmann
2003-12-19 00:31:41 UTC
Permalink
Post by Rosco P. Coaltrain
I have no idea what use was made of Friedrichs discovery .
That unique copper azide research was one of several
interesting patents which were published by him .
[snip]


-----------
Let us put this to rest by applying my good friends William of Ocham depilatory device.
We can both agree that unsafe explosives are usless! Both lead and cupric azide were
discoverd by T Curtis and J Rissom ca. 1898. [Journ. prat. Chem., (2) 58, 277, 1898.]
Cupric azide was found to be so sensitive that it "explodes by friction, even
loosening the solid from the filter-paper suffices for detonation..." [Mellor (8) 318] It is
also extremely shock sensitive.

The first lead azide detonator patent is that of M. Hyronimus BP 1 819, 1908. He also described
the manufacture of Pb azide founded on the process used by Wislicenus (Ber. 1892, 25, 2084).
This being the sodamide method of producing Na azide. [Martin and Barbour. Industrial Nitrogen
Compounds and Explosives. D. Appleton & Co. New York 1915.]

"Lead azide was first proposed for British Service in 1915." It was put into use ca. 1925. Production
in the USA dates to 1930. [TM 9-1910]

Although an "incident" occured "very likely to have involved Cu azide" (Austria 1914) in items that
had been stored for two years, it was not until after WW II that the British discoverd that - in the presence
of moisture and CO2 - Pb azide and copper will form Cu azide. [Proceedings of the Symposium on Lead and
Copper Azides held on 25th-26th October 1966. Waltham Abey, England]

Comes now the question .... why would anyone add Cu azide to a detonator?!!?


donald j haarmann
----------------------------------
Utinam tam facile vera invenire
possem quam falsa convincere.
Cicero
Don T
2003-12-19 01:09:42 UTC
Permalink
I MUST take exception to your post here Don. It were William of Occam (or
Ockham, take your choice) who is credited with summarizing the simplest of
all razors but when said razor do be applied it do cut the mightiest swath.
HeH. HeH.
--
"The bravest are surely those who have the clearest vision of what is before
them, glory and danger alike, and notwithstanding go out to meet it."-
Thucydides
Post by donald j haarmann
Post by Rosco P. Coaltrain
I have no idea what use was made of Friedrichs discovery .
That unique copper azide research was one of several
interesting patents which were published by him .
[snip]
-----------
Let us put this to rest by applying my good friends William of Ocham depilatory device.
We can both agree that unsafe explosives are usless! Both lead and cupric azide were
discoverd by T Curtis and J Rissom ca. 1898. [Journ. prat. Chem., (2) 58, 277, 1898.]
Cupric azide was found to be so sensitive that it "explodes by friction, even
loosening the solid from the filter-paper suffices for detonation..." [Mellor (8) 318] It is
also extremely shock sensitive.
The first lead azide detonator patent is that of M. Hyronimus BP 1 819,
1908. He also described
Post by donald j haarmann
the manufacture of Pb azide founded on the process used by Wislicenus (Ber. 1892, 25, 2084).
This being the sodamide method of producing Na azide. [Martin and Barbour.
Industrial Nitrogen
Post by donald j haarmann
Compounds and Explosives. D. Appleton & Co. New York 1915.]
"Lead azide was first proposed for British Service in 1915." It was put
into use ca. 1925. Production
Post by donald j haarmann
in the USA dates to 1930. [TM 9-1910]
Although an "incident" occured "very likely to have involved Cu azide"
(Austria 1914) in items that
Post by donald j haarmann
had been stored for two years, it was not until after WW II that the
British discoverd that - in the presence
Post by donald j haarmann
of moisture and CO2 - Pb azide and copper will form Cu azide. [Proceedings
of the Symposium on Lead and
Post by donald j haarmann
Copper Azides held on 25th-26th October 1966. Waltham Abey, England]
Comes now the question .... why would anyone add Cu azide to a
detonator?!!?
Post by donald j haarmann
donald j haarmann
----------------------------------
Utinam tam facile vera invenire
possem quam falsa convincere.
Cicero
donald j haarmann
2003-12-20 05:15:30 UTC
Permalink
Post by Don T
I MUST take exception to your post here Don. It were William of Occam (or
Ockham, take your choice) who is credited with summarizing the simplest of
all razors but when said razor do be applied it do cut the mightiest swath.
HeH. HeH.
[Ockham's Razor:]
Frustra fit per plura, quod fieri potest per pauciora.
It is vain to do with more what can be done with less.
or
Essentia non sunt multiplicanda praeter necessitatem.
Entities should not be multiplied unnecessarily.



------
KISS (Keep It Simple Stupid]
When you hear hoof beats; think horses not zebra.

My view.
If you have a problem and discover several solutions; the simplest one is best.



--
donald j haarmann — independently dubious
Rosco P. Coaltrain
2003-12-19 10:00:29 UTC
Permalink
Post by donald j haarmann
Post by Rosco P. Coaltrain
I have no idea what use was made of Friedrichs discovery .
That unique copper azide research was one of several
interesting patents which were published by him .
[snip]
-----------
Let us put this to rest by applying my good friends William of Ocham depilatory device.
Occams razor ? hmmmmmmm okay .
Post by donald j haarmann
We can both agree that unsafe explosives are usless!
Indeed we agree upon that . But there's more !
Post by donald j haarmann
Both lead and cupric azide were
discoverd by T Curtis and J Rissom ca. 1898. [Journ. prat. Chem., (2) 58, 277, 1898.]
Cupric azide was found to be so sensitive that it "explodes by friction, even
loosening the solid from the filter-paper suffices for detonation..." [Mellor (8) 318]
Haven't you ever heard of "dry" humor ? Sensitivity tends
to relate directly to crystalline size . Even lead azide
is liable to detonate spontaneously and under water , even
before it is filtered , if the crystals are allowed to grow
to sufficent size . The potential for extreme sensitvity
is therefore not a property unique to the copper compound .
I am not advocating the use of copper azide as an unadulterated
crystalline primary pressed into a pellet as is done with
lead azide . It is evidently unfit for such use . The
composition which Dr. Friedrich patented used a colloidal form
of the azide dispersed and coprecipitated with other materials
to produce a mixture which he claimed had merit for use as
a detonating composition . This could be true , and still
at the same time does not dispute the earlier researchers
observations that the pure ordinary crystalline material
is unduly sensitive for practical use .
Post by donald j haarmann
It is also extremely shock sensitive.
No doubt . That property could make it an excellent
component of priming mixtures if the sensitivity
was controlled within reliable and safe limits .
Molecular compounds which embody the desired properties
in a single material are more desirable and predictable
in their behavior than mixtures , and this is probably
why Friedrichs copper azide compositions were never
utilized , because they were made obsolete by other
mixed salts being discovered , which were superior
in performance as well as safety .
Post by donald j haarmann
The first lead azide detonator patent is that of M. Hyronimus BP 1
819, 1908. He also described
Post by donald j haarmann
the manufacture of Pb azide founded on the process used by Wislicenus (Ber. 1892, 25, 2084).
This being the sodamide method of producing Na azide. [Martin and Barbour. Industrial Nitrogen
Compounds and Explosives. D. Appleton & Co. New York 1915.]
"Lead azide was first proposed for British Service in 1915." It was put into use ca. 1925. Production
in the USA dates to 1930. [TM 9-1910]
Although an "incident" occured "very likely to have involved Cu azide" (Austria 1914) in items that
had been stored for two years, it was not until after WW II that the British discoverd that - in the presence
of moisture and CO2 - Pb azide and copper will form Cu azide. [Proceedings of the Symposium on Lead and
Copper Azides held on 25th-26th October 1966. Waltham Abey, England]
Comes now the question .... why would anyone add Cu azide to a detonator?!!?
donald j haarmann
----------------------------------
Utinam tam facile vera invenire
possem quam falsa convincere.
Cicero
Comes now the answer . At the time of Friedrichs patent ,
it made sense as a workaround for using copper capsules.
Aluminum was an extremely expensive metal in those days .
And copper azide might have usefulness in "lead free"
primer compositions even today . But there is no argument
that there are better things by far than copper azide
compositions in detonators . All that I am trying to
establish is the point that in the history of the art ,
before that technology was superseded by better things ,
that a useful application was found for copper azide .
That being true calls attention to the fact that in
certain limited ways of usefulness , that copper azide
was observed to have value , and not to be an entirely
worthless material to be absolutely ruled out for
any applications . I did not use the copper azide
as an explosive in my own experiments . It was simply
an indicator which would form an identifiable precipitate
for a specific reaction . Other than a few droplets
of the wet precipitate which were dried to test for
response to a glowing splint , the remaining sample
was kept wet and later was deliberately decomposed
and neutralized prior to disposal. Copper azide is
really nothing of relevance to the two patents at the
top of this thread , but the discussion of it has not
before received much attention in this group , so it
was probably overdue . However the two patents are
far more interesting as obscure technology from the
past , because those syntheses *do* lead to more
useful and accepted materials by a simplified method
using cheaper and less toxic precursors than other
well known methods . ( If those patents are accurate )
they are indeed an interesting find . I too would like
to have the texts for them and see what conditions
are specified for the reactions .

Rosco
LOUIS
2003-12-19 17:19:40 UTC
Permalink
OK I'll give a try to that reaction for copper, lead and silver...answer next week.

Ph Z
Post by Rosco P. Coaltrain
Post by LOUIS
For operational purpose it would be better to use hydrazine acetate, nitrate or
perchlorate (in dilluted form) with a soluble nitrite (sodium is the best and
cheaper) since then later admixion of metal salts to precipitate azides of heavy
metal will only precipitate the azide...all acetates, nitrates and perchlorates of
metals are indeed soluble.
Yes , I understand the choice of which acid salt of hydrazine used
must not precipitate the corresponding low solubility salt
of the metal which is desired to form a metal azide instead .
I have also tried hydrazine nitrate in the reaction with sodium nitrite
with and without buffers for different metal azides and those
experiments failed also . I have not yet tried the silver compound .
But copper and lead both failed to work in several different experiments
to produce their azides .
Post by LOUIS
sodium bicarbonate as a buffer without any improvement . If you
-No mather the buffer is you have used nitrates salts instead of nitrites you will
only end up with a mix of salts NH2-NH2.H2SO4 + NaNO3 mainly as initial reactants,
and NH2-NH2.HNO3 + NaHSO4 as minor ingredients; the addition of heavy metal salts
will only result in side reactions precipitations since no HONO is present and this
only allow the transformation of NH2-NH2 into HN3.
had success using sodium bicarbonate in solution in "soda water"
then maybe the "soda water" does the trick . Please share any details
of your experiments . I chose the copper compound because of the
solubility of the sulfate .
-Copper carbonate is unsoluble but as you see there are acids evolving in the cursus
of the reaction and so finally Cu(N3)2 will result with evolution of CO2 bubbles;
but you have to add the copper (or other salts to precipitate azides at the end of
the reaction since hydrazine doesn't like transition complexation metals wich
catalyses its decomposition).
Have you ever tried to precipitate copper azide from a reaction mixture
of hydrazine sulfate and sodium nitrate ? Did the reaction product
in the beaker fulfill the predicted reaction worked out on paper ?
-Copper azide is unsoluble I have precipitated it from NaN3 solution and CuSO4....I
don't want to waste my precious NH2-NH2.H2SO4 and NH2-NH2.H2O ;-).
Again NITRITE not nitrate.
Yes , I did use the nitrous acid salt of sodium , and I know the difference ,
In hasty typing I simply misspelled the term .
I have also made copper azide from sodium azide and soluble copper salts ,
copper acetate is the copper salt I used . Those reactions are simple .
But sodium azide is several synthetic steps from hydrazine sulfate as
a precursor for synthesis of heavy metal azides , so sodium azide is
a more "precious" and uncommon material than hydrazine sulfate .
Please do waste some of your hydrazine sulfate in actual experiments
and you will see that the reaction which seems so simple on paper
and in theory , does not work so easily in practice .
Post by LOUIS
Not in my own experiments does this work straightforwardly .
I fully expect that such reactions do require specific conditions
of temperature and pH and concentration of reactants , or a particular
buffer , and required many experiments for the inventors to work out
a useful method .
-Not really specific conditions, simply not too high pH (too concentrated at base)
not too low pH (too concentrated at acid) since heat of neutralisation and
precipitation might give troubles aside with loss of heat dissipation in the
precipitate by increase of the viscosity. Buffer will only increase the yield to
optimise the amount, the precipitation efficiency.
In COPAE there is mention of silver azide having been made by mixing
saturated solutions of silver nitrite and hydrazine sulfate and allowing
the mixture to stand in the cold for a short time . No specific ratios
or yield are given . The reaction is referenced to Angeli ( Italian ? )
the citation is Rend. acc. Lincei , [5] 2 , I , 599 ( 1893 )
So silver azide has been around for a hundred and ten years !
-This is related to the reaction I have mentionned about using NH2-NH2.H2O with
AgONO.
It works with the sulfate of hydrazine just the same way as with NaONO.But here,
Ag2SO4 is unsoluble but being less unsoluble than AgN3....AgN3 precipitate in
priority and thus upon little time AgN3 is the major precipitate.
Davis goes on further to mention that free hydrazoic acid can be produced
in aqueous solution of hydrazine sulfate with potassium nitrite , but again
no reaction details are described . The reaction is referenced by Davis
to Dennstedt and Gohlich ( German or Swiss ? ) Chem.-Ztg. , 21 , 876 ( 1897 )
-Same as the short simplified chemical equation I have written above.
Probably the patent reactions are an evolution of data from those two
and perhaps other early sources . Do you have any specific information
about such reactions which involve hydrazine sulfate and alkaline nitrites
in an aqueous reaction medium ?
I would like to know more about the reaction condition details
involved in these interesting patents .
Rosco
-All infos needed are above.
Ph Z
The theory and the stoichiometry are no mystery .
Why it does not work so smoothly in practice is the question .
Synthesis details described for actual experiments which work
successfully are what is missing here . You have described the
theory quite well . Can you provide a synthesis description
as an example of what has been directly observed to provide
confirmation of theory by actual experiment ?
All theoretical reactions work splendidly well on paper .
But many of these reactions are not so simple in practice
and this is one on them . Try an experiment with these
type syntheses of metal azides from salts of hydrazine
and sodium nitrite . *Then* see how interested you may be
in what the inventors discovered was needed in the way
of reaction conditions for such a synthetic scheme to proceed .
Rosco
Rosco P. Coaltrain
2003-12-20 05:27:36 UTC
Permalink
Post by LOUIS
OK I'll give a try to that reaction for copper, lead and silver...answer next week.
Ph Z
[snip]

Louis ,

It's the holidays so don't be troubled trying to solve a chemical
version of Rubick's cube and spoil the chance for some down time .
Curiosity is why experiments are proposed and done however , and
should you pursue this , let me review what I was thinking when
I finished the first few experiments I did with this attempt at
an unconventional route to azides .

From the experiments which failed with lead and copper , my next
effort and what seems to be the most promising candidate is the
silver salt . What I have proposed to do as a next experiment
will be to first form a solution of hydrazine nitrate by adding
portionwise solid hydrazine sulfate to a well stirred strong
solution of calcium nitrate until no more precipitate is formed .
Then add a little excess of calcium nitrate to assure the equivalent
was not overshot , and filter the calcium sulfate . To that
filtered hydrazine nitrate solution , would then be added solid
silver nitrate . The well stirred solution of hydrazine nitrate
and silver nitrate would then be treated dropwise with a strong
solution of sodium nitrite , as fingers are kept crossed while
expecting silver azide to precipitate . I think it should happen
but it may be a reaction that requires cold or hot , slow or fast ,
and pH control to make work as planned . My skepticism
derives from the earlier failed experiments to get lead azide
under similar conditions , however it may have just been sloppy
work on my part . Those experiments were hastily done one day
when I had some time to burn and just decided to give it a try
and see if such reactions were straightforward . I suspected
that they were not so simple and sufficiently proved that to
myself , discovering that more reading and thought was needed
to avoid a lot of wastage of reagents and time . However ,
without trying the silver salt , I have remained curious
and not completely convinced that the reaction won't work .
I still believe there is some synthesis detail ,
some reaction condition that I am not aware , is likely
what caused the earlier experiments to fail and perhaps
silver would be more productive . On the other hand I know
of no reason why the reaction wouldn't be general for any
metallic azides . This could be a similar scheme as for fulminates
where only some few metals form fulminates directly but the
method is not general for all of them . This line of experiments
should be one for the books , if it is not already there .
Somewhere in the great beyond , in that big laboratory in the sky ,
there may be some chemist clinking beakers and playing a harp ,
looking back across the astral realm and chuckling , saying
"Been there , done that , and that's exactly what got me here!" :-)

Rosco
LOUIS
2003-12-21 17:20:53 UTC
Permalink
Maybe only an order of reactants problem.
First know this;
Hydrazine is decomposed by Cu(2+)...the complex of NH2-NH2 and Cu(NO3)2 evolves N2
bubbles and reduces Cu(2+) to metallic copper dust.Sometimes a precipitates forms which
takes fire spontaneously.

The same happens with hydrazine and AgNO3; N2 and silver dust.

AgNO2 is quite unsoluble.

So following me:
NH2-NH2.H2SO4 + 2NaNO2 --> Na2SO4 + NH2-NH2.HNO2 + HNO2 --> Na2SO4 + HN3 + HNO2 + 2H2O

Trying with Pb(2+) will result in PbSO4 precipitation, Pb(N3)2 precipitation and
Pb(NO2)2 (stable?)
With Cu(2+) hydrazine decomposition, Cu(N3)2 precipitation and Cu(NO2)2 decomposition.
With Ag(+) hydrazine decomposition, AgN3 precipitation and AgNO2 precipitation.
The question is which reaction takes the advanatge on the others.

So
NH2-NH2.H2SO4 must be added to Ca(NO2)2 solution under agitation then CaSO4.xH2O
precipitates
NH2-NH2.H2SO4 + Ca(NO2)2 --> NH2-NH2.HNO2 + CaSO4 (s) + HNO2
Then filtrate the unsoluble sulfate; The clear liquid is mainly HNO2 + HN3 + 2H2O
Note that Ca(N3)2 is unsoluble and sensitive and so no excess of Ca(NO2)2 must be added.

Urea can be used to decompose the HNO2 into H2O, N2 and CO2.
Then mix CuCO3, PbCO3 or Ag2CO3 in the solution....
HN3 is more acidic than H2CO3, HCO3(-) and so CO2 bubbles will evolve and the desired
azide remain in the media.

pH is a key word in this reaction.

Ph Z
Post by donald j haarmann
Post by LOUIS
OK I'll give a try to that reaction for copper, lead and silver...answer next week.
Ph Z
[snip]
Louis ,
It's the holidays so don't be troubled trying to solve a chemical
version of Rubick's cube and spoil the chance for some down time .
Curiosity is why experiments are proposed and done however , and
should you pursue this , let me review what I was thinking when
I finished the first few experiments I did with this attempt at
an unconventional route to azides .
From the experiments which failed with lead and copper , my next
effort and what seems to be the most promising candidate is the
silver salt . What I have proposed to do as a next experiment
will be to first form a solution of hydrazine nitrate by adding
portionwise solid hydrazine sulfate to a well stirred strong
solution of calcium nitrate until no more precipitate is formed .
Then add a little excess of calcium nitrate to assure the equivalent
was not overshot , and filter the calcium sulfate . To that
filtered hydrazine nitrate solution , would then be added solid
silver nitrate . The well stirred solution of hydrazine nitrate
and silver nitrate would then be treated dropwise with a strong
solution of sodium nitrite , as fingers are kept crossed while
expecting silver azide to precipitate . I think it should happen
but it may be a reaction that requires cold or hot , slow or fast ,
and pH control to make work as planned . My skepticism
derives from the earlier failed experiments to get lead azide
under similar conditions , however it may have just been sloppy
work on my part . Those experiments were hastily done one day
when I had some time to burn and just decided to give it a try
and see if such reactions were straightforward . I suspected
that they were not so simple and sufficiently proved that to
myself , discovering that more reading and thought was needed
to avoid a lot of wastage of reagents and time . However ,
without trying the silver salt , I have remained curious
and not completely convinced that the reaction won't work .
I still believe there is some synthesis detail ,
some reaction condition that I am not aware , is likely
what caused the earlier experiments to fail and perhaps
silver would be more productive . On the other hand I know
of no reason why the reaction wouldn't be general for any
metallic azides . This could be a similar scheme as for fulminates
where only some few metals form fulminates directly but the
method is not general for all of them . This line of experiments
should be one for the books , if it is not already there .
Somewhere in the great beyond , in that big laboratory in the sky ,
there may be some chemist clinking beakers and playing a harp ,
looking back across the astral realm and chuckling , saying
"Been there , done that , and that's exactly what got me here!" :-)
Rosco
Rosco P. Coaltrain
2003-12-22 04:31:43 UTC
Permalink
Post by LOUIS
Maybe only an order of reactants problem.
Yes , the order of addition and the rate of addition ,
temperature , pH , concentration of recatants , time of reaction ,
and alignment of the planets must all be correct , and as
if fishing for a slippery catch , it is also important to
hold your mouth right :)
Post by LOUIS
First know this;
Hydrazine is decomposed by Cu(2+)...the complex of NH2-NH2 and Cu(NO3)2 evolves N2
bubbles and reduces Cu(2+) to metallic copper dust.Sometimes a precipitates forms which
takes fire spontaneously.
The same happens with hydrazine and AgNO3; N2 and silver dust.
Yes , freebase hydrazine is a powerful reducing agent and
even reacts with the oxygen of the air . But it is *not*
freebase hydrazine with which we are working in this reaction ,
but an acid bound , salt form of hydrazine .Sure the solution
of a hydrazine salt may still exhibit some reducing power
at high temperatures , and moreso for the solid hydrazine
salts which find usefulness as soldering fluxes for this
reason . But in this aqueous solution , I would bet the
chance of getting a metallic precipitate is remote .
Maybe a metal oxide or hydroxide would be more likely
for a product , where a metal was precipitated as atoms
in water , because such a metal would be highly reactive
and would react with the water in which it precipitated .
Post by LOUIS
AgNO2 is quite unsoluble.
Yes , that is why the scheme I proposed for adding
the sodium nitrite dropwise , the silver nitrite
would form in very highly dilute form and have time
to participate in the reaction instead of falling to
the bottom of the beaker as an unchanged precipitate
of the undesired product . Silver nitrite is not wanted
except as a transitional intermediate species formed
in the mixture and then converted to silver azide .
Post by LOUIS
NH2-NH2.H2SO4 + 2NaNO2 --> Na2SO4 + NH2-NH2.HNO2 + HNO2 --> Na2SO4 + HN3 + HNO2 + 2H2O
The above reaction route seems impossible , since
hydrazoic acid and nitrous acid cannot coexist ,
but react to their mutual destruction . This fact
is utilized for cleanup of spills of azides by weak
solutions of nitrous acid , and azides are a whole
lot more stable than the parent acid . So *no* ,
I believe another reaction scheme is required ,
which produces no equivalent of nitrous acid on
the right side of the equation , alongside hydrazoic acid .
It may look okay as stoichiometry , but in terms of
physical chemistry ,the equation above is an oxymoron .
The same is true for the transition species which
you show in the middle of the reaction , for the same reason .
Hydrazine is a powerful reducing agent , and nitrous acid
is a powerful oxidizer , and the two don't bond to
form an intermediate , but react on contact to form
hydrazoic acid under favorable conditions ,
( which is the crux of the reaction we intend ,
discovering what exactly is "favorable" conditions ? )
If the conditions for the formation of hydrazoic acid
are not present then hydrazine and nitrous acid are
mutually destroyed in their reaction . There are different
equations which can be written which show no nitrous acid
as a free product and such reactions are more plausible .
In COPAE , Davis made reference to the original discovery ,
but went on to say something contradictory to the reaction
he wrote , qualifying the reaction as proceeding best under
*alkaline* conditions , while clearly everything on both sides
of the equation as written below is acidic . Go figure .
Anyway , the following reaction is what Davis attributed
to be the method of Dennstedt and Gohlich .
Chem.-Ztg., 21, 876 (1897) This would be a place to start .

NH2-NH2-H2SO4 + KNO2 ----> KHSO4 + 2H2O + HN3

Apparently the hydrazoic acid was distilled from the solution .
My expectation is that this was probably done by dropwise addition
of the KNO2 and distilling the HN3 as rapidly as it was formed .
But I haven't read the original work and I don't know for certain .
The mixture may have been allowed to stand in the cold for a week
and then distilled under vacuum for all I know .
Post by LOUIS
Trying with Pb(2+) will result in PbSO4 precipitation,
Pb(N3)2 precipitation and
Pb(NO2)2 (stable?)
With Cu(2+) hydrazine decomposition, Cu(N3)2 precipitation
and Cu(NO2)2 decomposition.
With Ag(+) hydrazine decomposition, AgN3 precipitation
and AgNO2 precipitation.
Not necessarily so for solutions of a hydrazine salt .
Post by LOUIS
The question is which reaction takes the advanatge on the others.
On that much we can agree .
Post by LOUIS
So
NH2-NH2.H2SO4 must be added to Ca(NO2)2 solution under agitation then CaSO4.xH2O
precipitates
NH2-NH2.H2SO4 + Ca(NO2)2 --> NH2-NH2.HNO2 + CaSO4 (s) + HNO2
This is unlikely for the same reason as I explained above ,
Post by LOUIS
Then filtrate the unsoluble sulfate; The clear liquid
is mainly HNO2 + HN3 + 2H2O
You won't have anything except an effervescing of nitrogen
from the inert residue . Try it and see .
Post by LOUIS
Note that Ca(N3)2 is unsoluble and sensitive and so no excess of Ca(NO2)2 must be added.
Actually Ca(N3)2 is highly soluble and insensitive as is typical of
Post by LOUIS
Urea can be used to decompose the HNO2 into H2O, N2 and CO2.
Davis mentioned ammonium sulfate as useful for
the decomposition of any nitrous acid being added
to the above reaction mixture before distillation .
Post by LOUIS
Then mix CuCO3, PbCO3 or Ag2CO3 in the solution....
HN3 is more acidic than H2CO3, HCO3(-) and so CO2 bubbles
will evolve and the desired
azide remain in the media.
pH is a key word in this reaction.
Just one of the many keys in this reaction , I promise :)
Post by LOUIS
Ph Z
[snip]

Another thing which I have thought about is doing
the reaction using dihydrazine sulfate instead of
hydrazine sulfate , since the dihydrazine salt is
far more soluble . This could be useful if the
concentration of the reactants is an important factor .
It is simple to convert hydrazine sulfate to
dihydrazine sulfate by halfway neutralizing it with NaOH .
When this is reacted with the Ca(NO3)2 then the mononitrate
of hydrazine is what remains in the filtered solution .
Actually , I tried this route too , and it doesn't work either .
Nothing like perplexity for making complicated what
should be such a simple reaction . Good luck "cracking"
this reaction Louis , hehehe , a lot of luck is what you
are going to need .

Rosco
LOUIS
2003-12-25 17:39:16 UTC
Permalink
Post by Rosco P. Coaltrain
Post by LOUIS
Maybe only an order of reactants problem.
Yes , the order of addition and the rate of addition ,
temperature , pH , concentration of recatants , time of reaction ,
and alignment of the planets must all be correct , and as
if fishing for a slippery catch , it is also important to
hold your mouth right :)
-I really mean what I wrote, the order of addition of the reactants is important.
Post by Rosco P. Coaltrain
Post by LOUIS
First know this;
Hydrazine is decomposed by Cu(2+)...the complex of NH2-NH2 and Cu(NO3)2 evolves N2
bubbles and reduces Cu(2+) to metallic copper dust.Sometimes a precipitates forms which
takes fire spontaneously.
The same happens with hydrazine and AgNO3; N2 and silver dust.
Yes , freebase hydrazine is a powerful reducing agent and
even reacts with the oxygen of the air . But it is *not*
freebase hydrazine with which we are working in this reaction ,
but an acid bound , salt form of hydrazine .Sure the solution
of a hydrazine salt may still exhibit some reducing power
at high temperatures , and moreso for the solid hydrazine
salts which find usefulness as soldering fluxes for this
reason . But in this aqueous solution , I would bet the
chance of getting a metallic precipitate is remote .
Maybe a metal oxide or hydroxide would be more likely
for a product , where a metal was precipitated as atoms
in water , because such a metal would be highly reactive
and would react with the water in which it precipitated .
-If you mix NH2-NH2.H2O and Cu(NO3)2 in water all what results are N2, H2O, NOx and Cu dust +
Cu2O...
NH2-NH2 + H2O <--> NH2-NH3(+) + OH(-)
Cu(NO3)2 -aq-> Cu(2+) + 2 NO3(-)
By definition of ionic species the mix of NH2-NH3OH and Cu(NO3)2 in water is equivalent to
the mix of Cu(OH)2 and NH2-NH3NO3.
This means that no mather the way you look at the problem NH2-NH2 + Cu(2+) or NH2-NH3(+) +
Cu(2+) can't coexist for long without decomposition.

The same occurs with NH4OH and Cu(NO3)2 or NH4NO3 + Cu, CuO or Cu(OH)2 the tetraamino copper
nitrate results as a major product.
Post by Rosco P. Coaltrain
Post by LOUIS
AgNO2 is quite unsoluble.
Yes , that is why the scheme I proposed for adding
the sodium nitrite dropwise , the silver nitrite
would form in very highly dilute form and have time
to participate in the reaction instead of falling to
the bottom of the beaker as an unchanged precipitate
of the undesired product . Silver nitrite is not wanted
except as a transitional intermediate species formed
in the mixture and then converted to silver azide .
-Yes but if Ag(+) is present at the same time as NH2-NH2 /NH2-NH3(+)....---> N2+ Ag +....
Post by Rosco P. Coaltrain
Post by LOUIS
NH2-NH2.H2SO4 + 2NaNO2 --> Na2SO4 + NH2-NH2.HNO2 + HNO2 --> Na2SO4 + HN3 + HNO2 + 2H2O
The above reaction route seems impossible , since
hydrazoic acid and nitrous acid cannot coexist ,
but react to their mutual destruction . This fact
is utilized for cleanup of spills of azides by weak
solutions of nitrous acid , and azides are a whole
lot more stable than the parent acid . So *no* ,
I believe another reaction scheme is required ,
which produces no equivalent of nitrous acid on
the right side of the equation , alongside hydrazoic acid .
It may look okay as stoichiometry , but in terms of
physical chemistry ,the equation above is an oxymoron .
The same is true for the transition species which
you show in the middle of the reaction , for the same reason .
Hydrazine is a powerful reducing agent , and nitrous acid
is a powerful oxidizer , and the two don't bond to
form an intermediate , but react on contact to form
hydrazoic acid under favorable conditions ,
( which is the crux of the reaction we intend ,
discovering what exactly is "favorable" conditions ? )
If the conditions for the formation of hydrazoic acid
are not present then hydrazine and nitrous acid are
mutually destroyed in their reaction . There are different
equations which can be written which show no nitrous acid
as a free product and such reactions are more plausible .
In COPAE , Davis made reference to the original discovery ,
but went on to say something contradictory to the reaction
he wrote , qualifying the reaction as proceeding best under
*alkaline* conditions , while clearly everything on both sides
of the equation as written below is acidic . Go figure .
Anyway , the following reaction is what Davis attributed
to be the method of Dennstedt and Gohlich .
Chem.-Ztg., 21, 876 (1897) This would be a place to start .
NH2-NH2-H2SO4 + KNO2 ----> KHSO4 + 2H2O + HN3
-Indeed NH2-NH3ONO is a "view" of the mind but in the same view NH4ONO shouldn't exist but
stil it does and is isolable despite it is unstable and explosive.
NH4ONO --> N2 + 2H2O
The process you expose will end quite fast or restrain strongly the yield since while you add
dropwise KNO2 in the system it frees locally HNO2 but the amount of HN3 which is originally
low is increasing and so decomposition increases too.
In the practice lab preparation of NaN3:
NH2-NH2OH + R-ONO + NaOH is used under mild heating ; the NaOH hydrolyses the nitrous ester
and free continuous but smoothly NO2(-) in basic media then the only products of the reaction
are:
R-OH (an alcool), NaN3 and NaOH.More than certainly the reason you invoqued of impossible
coexistance of HNO2 and HN3 calls for basic hydrolysis of the ester instead of the acidic
one.

Anyway, to me the best way is to neutralise a little more than half an equivalent of H2SO4
(in the hydrazine sulfate salt) with NaOH, Na2CO3 or NaHCO3 to get NH2-NH2.HSO4(-) and then
allow the NaNO2 to enter dropwise into the system.Then no big amount of HNO2 can be present
and The major products will be Na2SO4 and NaN3.
The very best way is to get NH2-NH3OH from NH2-NH2.H2SO4 and to allow this to react with
NaNO2 as it happens in the "normal" lab procedure for NaN3 from nitrous ester.This is equal
to a complete equivalent neutralisation of the H2SO4.
Post by Rosco P. Coaltrain
Apparently the hydrazoic acid was distilled from the solution .
My expectation is that this was probably done by dropwise addition
of the KNO2 and distilling the HN3 as rapidly as it was formed .
But I haven't read the original work and I don't know for certain .
The mixture may have been allowed to stand in the cold for a week
and then distilled under vacuum for all I know .
-CO2 flow and condensation.
Post by Rosco P. Coaltrain
Post by LOUIS
Trying with Pb(2+) will result in PbSO4 precipitation,
Pb(N3)2 precipitation and
Pb(NO2)2 (stable?)
With Cu(2+) hydrazine decomposition, Cu(N3)2 precipitation
and Cu(NO2)2 decomposition.
With Ag(+) hydrazine decomposition, AgN3 precipitation
and AgNO2 precipitation.
Not necessarily so for solutions of a hydrazine salt .
-Necessarily from the definition of ionic reactions (in water media).
Post by Rosco P. Coaltrain
Post by LOUIS
The question is which reaction takes the advanatge on the others.
On that much we can agree .
-Yes.
Post by Rosco P. Coaltrain
Post by LOUIS
So
NH2-NH2.H2SO4 must be added to Ca(NO2)2 solution under agitation then CaSO4.xH2O
precipitates
NH2-NH2.H2SO4 + Ca(NO2)2 --> NH2-NH2.HNO2 + CaSO4 (s) + HNO2
This is unlikely for the same reason as I explained above ,
-OK but if half or complete neutralisation of NH2-NH2.H2SO4...
Post by Rosco P. Coaltrain
Post by LOUIS
Then filtrate the unsoluble sulfate; The clear liquid
is mainly HNO2 + HN3 + 2H2O
You won't have anything except an effervescing of nitrogen
from the inert residue . Try it and see .
-I believe you from what I know about basic media formation from the nitrous ester.
Post by Rosco P. Coaltrain
Post by LOUIS
Note that Ca(N3)2 is unsoluble and sensitive and so no excess of Ca(NO2)2 must be added.
Actually Ca(N3)2 is highly soluble and insensitive as is typical of
-Ca azide is more sensitive than Ag azide and much more sensitive than alkali azides.
Li <<Na<K<<Pb and Ag
Explosion has been mentionned in a lab where a spill of HN3 on marmor (CaCO3.xH2O) was made
accidentally.
The salt detonated under mild friction from the spill.
Post by Rosco P. Coaltrain
Post by LOUIS
Urea can be used to decompose the HNO2 into H2O, N2 and CO2.
Davis mentioned ammonium sulfate as useful for
the decomposition of any nitrous acid being added
to the above reaction mixture before distillation .
-NH4ONO and NH2-CO-NH3ONO exist in the cold but are hell unstable because of dehydratations,
rearrangements, inner oxydoredox.
Post by Rosco P. Coaltrain
Post by LOUIS
Then mix CuCO3, PbCO3 or Ag2CO3 in the solution....
HN3 is more acidic than H2CO3, HCO3(-) and so CO2 bubbles
will evolve and the desired
azide remain in the media.
pH is a key word in this reaction.
Just one of the many keys in this reaction , I promise :)
Another thing which I have thought about is doing
the reaction using dihydrazine sulfate instead of
hydrazine sulfate , since the dihydrazine salt is
far more soluble . This could be useful if the
concentration of the reactants is an important factor .
It is simple to convert hydrazine sulfate to
dihydrazine sulfate by halfway neutralizing it with NaOH .
When this is reacted with the Ca(NO3)2 then the mononitrate
of hydrazine is what remains in the filtered solution .
Actually , I tried this route too , and it doesn't work either .
-Dihydrazine sulfate? (NH2-NH3)2SO4 or 2 NH2-NH2.H2SO4?
If you half neutralise hydrazinium sulfate with NaOH you should get sodium/hydrazinium
sulfate Na(NH2-NH3)SO4 or NH2-NH2.NaHSO4 what looks pretty much to what I thought to do to
avoid HNO2 being present in HN3 media.
Never eard of this compound but wel about hydrazine diperchlorate where the two NH2 are
protonated.
Post by Rosco P. Coaltrain
Nothing like perplexity for making complicated what
should be such a simple reaction . Good luck "cracking"
this reaction Louis , hehehe , a lot of luck is what you
are going to need .
-Yes, chance Rosco ;-).

Ph Z
Rosco P. Coaltrain
2003-12-26 07:26:25 UTC
Permalink
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
Maybe only an order of reactants problem.
Yes , the order of addition and the rate of addition ,
temperature , pH , concentration of recatants , time of reaction ,
and alignment of the planets must all be correct , and as
if fishing for a slippery catch , it is also important to
hold your mouth right :)
-I really mean what I wrote, the order of addition of the reactants is important.
Affirmative , I know you meant the order of addition is important ,
and I agree . But there is something more that is probably needed
also , some variable which we are probably unaware . For example ,
suppose there is something necessary to be added to the aqueous system ,
which may form an organic nitrite in situ as an intermediate or catalyst
for the reaction , perhaps for example ethylene glycol or something similar .
And perhaps without such an organic material present as a catalyst ,
no attempts will be successful to have the reaction proceed
regardless of how well it appears to work on paper .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
First know this;
Hydrazine is decomposed by Cu(2+)...the complex of NH2-NH2 and Cu(NO3)2 evolves N2
bubbles and reduces Cu(2+) to metallic copper dust.Sometimes a precipitates forms which
takes fire spontaneously.
The same happens with hydrazine and AgNO3; N2 and silver dust.
Yes , freebase hydrazine is a powerful reducing agent and
even reacts with the oxygen of the air . But it is *not*
freebase hydrazine with which we are working in this reaction ,
but an acid bound , salt form of hydrazine .Sure the solution
of a hydrazine salt may still exhibit some reducing power
at high temperatures , and moreso for the solid hydrazine
salts which find usefulness as soldering fluxes for this
reason . But in this aqueous solution , I would bet the
chance of getting a metallic precipitate is remote .
Maybe a metal oxide or hydroxide would be more likely
for a product , where a metal was precipitated as atoms
in water , because such a metal would be highly reactive
and would react with the water in which it precipitated .
-If you mix NH2-NH2.H2O and Cu(NO3)2 in water all what results are N2, H2O, NOx and Cu dust +
Cu2O...
NH2-NH2 + H2O <--> NH2-NH3(+) + OH(-)
Cu(NO3)2 -aq-> Cu(2+) + 2 NO3(-)
By definition of ionic species the mix of NH2-NH3OH and Cu(NO3)2 in water is equivalent to
the mix of Cu(OH)2 and NH2-NH3NO3.
This means that no mather the way you look at the problem NH2-NH2 + Cu(2+) or NH2-NH3(+) +
Cu(2+) can't coexist for long without decomposition.
The same occurs with NH4OH and Cu(NO3)2 or NH4NO3 + Cu, CuO or Cu(OH)2 the tetraamino copper
nitrate results as a major product.
Post by Rosco P. Coaltrain
Post by LOUIS
AgNO2 is quite unsoluble.
Yes , that is why the scheme I proposed for adding
the sodium nitrite dropwise , the silver nitrite
would form in very highly dilute form and have time
to participate in the reaction instead of falling to
the bottom of the beaker as an unchanged precipitate
of the undesired product . Silver nitrite is not wanted
except as a transitional intermediate species formed
in the mixture and then converted to silver azide .
-Yes but if Ag(+) is present at the same time as NH2-NH2 /NH2-NH3(+)....---> N2+ Ag +....
Perhaps AgNO3+(NH2NH2)HNO3 ---> AgNO3+(NH2NH2)HNO3 (no reaction?)

I am not certain , but I think that the silver will be
more basic than the hydrazine and remain in solution .
It would be easy enough to test to see if there is
any reaction between solutions of silver nitrate and
hydrazine nitrate mixed together . Have you done this before ?
Whether or not silver precipitates as a consequence of reaction
with hydrazine is certainly pH dependent . Freebase Hydrazine is
only weakly basic , much less than ammonia . It is more like
urea than ammonia in terms of basicity . So the above reaction
would be similar to mixing solutions of urea nitrate and silver
nitrate . It could react , but I see no obvious reason to
believe it would react *unless* there was some complexation
reaction which could produce a highly insoluble precipitate even
in acidic conditions . You could possibly get a silver analogue
of "PHILOU's Salt" ( nickel trihydrazine nitrate :) It may even
be likely , since silver does form a diammine , it is certainly
possible it could form a complex salt with hydrazine nitrate
which may have interesting properties itself , and possibly
even superior properties to silver azide . The possibilities
of this experiment get more interesting because of this .
A "failed" experiment to produce an intended result sometimes
results in discovery of something more valuable than what was
being first intended to be produced .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
NH2-NH2.H2SO4 + 2NaNO2 --> Na2SO4 + NH2-NH2.HNO2 + HNO2 --> Na2SO4 + HN3 + HNO2 + 2H2O
The above reaction route seems impossible , since
hydrazoic acid and nitrous acid cannot coexist ,
but react to their mutual destruction . This fact
is utilized for cleanup of spills of azides by weak
solutions of nitrous acid , and azides are a whole
lot more stable than the parent acid . So *no* ,
I believe another reaction scheme is required ,
which produces no equivalent of nitrous acid on
the right side of the equation , alongside hydrazoic acid .
It may look okay as stoichiometry , but in terms of
physical chemistry ,the equation above is an oxymoron .
The same is true for the transition species which
you show in the middle of the reaction , for the same reason .
Hydrazine is a powerful reducing agent , and nitrous acid
is a powerful oxidizer , and the two don't bond to
form an intermediate , but react on contact to form
hydrazoic acid under favorable conditions ,
( which is the crux of the reaction we intend ,
discovering what exactly is "favorable" conditions ? )
If the conditions for the formation of hydrazoic acid
are not present then hydrazine and nitrous acid are
mutually destroyed in their reaction . There are different
equations which can be written which show no nitrous acid
as a free product and such reactions are more plausible .
In COPAE , Davis made reference to the original discovery ,
but went on to say something contradictory to the reaction
he wrote , qualifying the reaction as proceeding best under
*alkaline* conditions , while clearly everything on both sides
of the equation as written below is acidic . Go figure .
Anyway , the following reaction is what Davis attributed
to be the method of Dennstedt and Gohlich .
Chem.-Ztg., 21, 876 (1897) This would be a place to start .
NH2-NH2-H2SO4 + KNO2 ----> KHSO4 + 2H2O + HN3
-Indeed NH2-NH3ONO is a "view" of the mind but in the same view NH4ONO shouldn't exist but
stil it does and is isolable despite it is unstable and explosive.
NH4ONO --> N2 + 2H2O
The process you expose will end quite fast or restrain strongly the yield since while you add
dropwise KNO2 in the system it frees locally HNO2 but the amount of HN3 which is originally
low is increasing and so decomposition increases too.
The low solubility of the metal azide would remove the HN3 by
precipitation as quickly as the HN3 was formed .
Post by LOUIS
NH2-NH2OH + R-ONO + NaOH is used under mild heating ; the NaOH hydrolyses the nitrous ester
*Negative* , the hydrazine hydrate and the organic nitrite react directly
and then the hydrazoic acid which is produced is neutralized by the NaOH .
That reaction is preferential so long as the concentration of the NaOH
is not too great . Any hydrolysis of the organic nitrite by the NaOH
results in an undesired by product of NaNO2 , which does not react
with the hydrazine hydrate . Low temperatures favor this desired
reaction of the hydrazine with the organic nitrite , warmer temperatures
favor the hydrolysis of the nitrite which is undesired .
Post by LOUIS
and free continuous but smoothly NO2(-) in basic media then the only products of the reaction
R-OH (an alcool), NaN3 and NaOH.More than certainly the reason you invoqued of impossible
coexistance of HNO2 and HN3 calls for basic hydrolysis of the ester instead of the acidic
one.
The two acids HNO2 and HN3 are incompatable in the same manner
as mixing hydrogen peroxide and hydrazine , a hypergolic decomposition .
In that scenario think of it as a detonation at the molecular level ,
the two species simply tear each other apart like matter and anti-matter
brought in contact .
Post by LOUIS
Anyway, to me the best way is to neutralise a little more than half an equivalent of H2SO4
(in the hydrazine sulfate salt) with NaOH, Na2CO3 or NaHCO3 to get NH2-NH2.HSO4(-) and then
allow the NaNO2 to enter dropwise into the system.Then no big amount of HNO2 can be present
and The major products will be Na2SO4 and NaN3.
The very best way is to get NH2-NH3OH from NH2-NH2.H2SO4 and to allow this to react with
NaNO2 as it happens in the "normal" lab procedure for NaN3 from nitrous ester.
That would be fine if the reaction proceeded as you suppose , but the
purpose of using an organic nitrite is not as a source for nascent sodium
nitrite to participate in the reaction . The nitrosation of the hydrazine
is performed directly by the nitrite ester , not by sodium nitrite .
Post by LOUIS
This is equal
to a complete equivalent neutralisation of the H2SO4.
Post by Rosco P. Coaltrain
Apparently the hydrazoic acid was distilled from the solution .
My expectation is that this was probably done by dropwise addition
of the KNO2 and distilling the HN3 as rapidly as it was formed .
But I haven't read the original work and I don't know for certain .
The mixture may have been allowed to stand in the cold for a week
and then distilled under vacuum for all I know .
-CO2 flow and condensation.
?????? gas entrainment distillation ???
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
Trying with Pb(2+) will result in PbSO4 precipitation,
Pb(N3)2 precipitation and
Pb(NO2)2 (stable?)
With Cu(2+) hydrazine decomposition, Cu(N3)2 precipitation
and Cu(NO2)2 decomposition.
With Ag(+) hydrazine decomposition, AgN3 precipitation
and AgNO2 precipitation.
Not necessarily so for solutions of a hydrazine salt .
-Necessarily from the definition of ionic reactions (in water media).
Post by Rosco P. Coaltrain
Post by LOUIS
The question is which reaction takes the advanatge on the others.
On that much we can agree .
-Yes.
We both understand that there are competing reactions which are
influenced by reaction conditions to proceed in a way which favors
the desired reactions and disfavors the undesired reactions ,
as an implementation of "process chemistry" .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
So
NH2-NH2.H2SO4 must be added to Ca(NO2)2 solution under agitation then CaSO4.xH2O
precipitates
NH2-NH2.H2SO4 + Ca(NO2)2 --> NH2-NH2.HNO2 + CaSO4 (s) + HNO2
This is unlikely for the same reason as I explained above ,
-OK but if half or complete neutralisation of NH2-NH2.H2SO4...
Post by Rosco P. Coaltrain
Post by LOUIS
Then filtrate the unsoluble sulfate; The clear liquid
is mainly HNO2 + HN3 + 2H2O
You won't have anything except an effervescing of nitrogen
from the inert residue . Try it and see .
-I believe you from what I know about basic media formation from the nitrous ester.
Post by Rosco P. Coaltrain
Post by LOUIS
Note that Ca(N3)2 is unsoluble and sensitive and so no excess of Ca(NO2)2 must be added.
Actually Ca(N3)2 is highly soluble and insensitive as is typical of
-Ca azide is more sensitive than Ag azide and much more sensitive than alkali azides.
Li <<Na<K<<Pb and Ag
Explosion has been mentionned in a lab where a spill of HN3 on marmor (CaCO3.xH2O) was made
accidentally.
The salt detonated under mild friction from the spill.
It is a miracle that HN3 did not detonate in midstream halfway
to a floor made of any material , calcium or not :)
In solution , the Ca(N3)2 material should be safe .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
Urea can be used to decompose the HNO2 into H2O, N2 and CO2.
Davis mentioned ammonium sulfate as useful for
the decomposition of any nitrous acid being added
to the above reaction mixture before distillation .
-NH4ONO and NH2-CO-NH3ONO exist in the cold but are hell unstable because of dehydratations,
rearrangements, inner oxydoredox.
Perhaps formed in situ as blowing agents because they immediately decompose
and produce a lot of nitrogen to expand foams .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
Then mix CuCO3, PbCO3 or Ag2CO3 in the solution....
HN3 is more acidic than H2CO3, HCO3(-) and so CO2 bubbles
will evolve and the desired
azide remain in the media.
pH is a key word in this reaction.
Just one of the many keys in this reaction , I promise :)
Another thing which I have thought about is doing
the reaction using dihydrazine sulfate instead of
hydrazine sulfate , since the dihydrazine salt is
far more soluble . This could be useful if the
concentration of the reactants is an important factor .
It is simple to convert hydrazine sulfate to
dihydrazine sulfate by halfway neutralizing it with NaOH .
When this is reacted with the Ca(NO3)2 then the mononitrate
of hydrazine is what remains in the filtered solution .
Actually , I tried this route too , and it doesn't work either .
-Dihydrazine sulfate? (NH2-NH3)2SO4 or 2 NH2-NH2.H2SO4?
Dihydrazine Sulfate (NH2NH2)2 - H2SO4 is highly soluble
should form a nearly neutral pH solution .
Post by LOUIS
If you half neutralise hydrazinium sulfate with NaOH you should get sodium/hydrazinium
sulfate Na(NH2-NH3)SO4 or NH2-NH2.NaHSO4 what looks pretty much to what I thought to do to
avoid HNO2 being present in HN3 media.
I dont think you will ever see such a double salt as the hydrazine
will form whatever mixture of monobasic or dibasic hydrazine salts
corresponds with the pH of the system .
Post by LOUIS
Never eard of this compound but wel about hydrazine diperchlorate where the two NH2 are
protonated.
Post by Rosco P. Coaltrain
Nothing like perplexity for making complicated what
should be such a simple reaction . Good luck "cracking"
this reaction Louis , hehehe , a lot of luck is what you
are going to need .
-Yes, chance Rosco ;-).
Ph Z
How far can a frustrated chemist throw a beaker ?
If nothing else , perhaps this experiment can provide
useful datas on trajectories :)

Rosco
LOUIS
2003-12-30 13:03:14 UTC
Permalink
Post by Rosco P. Coaltrain
Affirmative , I know you meant the order of addition is important ,
and I agree . But there is something more that is probably needed
also , some variable which we are probably unaware . For example ,
suppose there is something necessary to be added to the aqueous system ,
which may form an organic nitrite in situ as an intermediate or catalyst
for the reaction , perhaps for example ethylene glycol or something similar .
And perhaps without such an organic material present as a catalyst ,
no attempts will be successful to have the reaction proceed
regardless of how well it appears to work on paper .
-Yes often old text are rather unclear or unprecise.
Post by Rosco P. Coaltrain
Perhaps AgNO3+(NH2NH2)HNO3 ---> AgNO3+(NH2NH2)HNO3 (no reaction?)
-Not done yet!Last serie of experiments to come.
Post by Rosco P. Coaltrain
I am not certain , but I think that the silver will be
more basic than the hydrazine and remain in solution .
-Silver is silver and is not basic as such while hydrazine is strongly basic otherwise pure
hydrazine wouldn't corrode glass as does solid NaOH...a proof of its basicity is the ease with
wich it forms salts when exposed to acid fumes (smog) or the strong violet color it displays when
exposed to phenolphtalein indicator.
True that it should be a little less basic than pure NH3 but NH3 is limited to 30% solutions while
NH2-NH2 can go as high as 100%. pKa of NH2-NH2 should conceptually be between NH3 and NH2-OH but I
owing to a special effect (mesomer giver) I remember it is stronger base than NH3 is...after all
NH3 even liquid doesn't corrode glass!
Post by Rosco P. Coaltrain
It would be easy enough to test to see if there is
any reaction between solutions of silver nitrate and
hydrazine nitrate mixed together . Have you done this before ?
Whether or not silver precipitates as a consequence of reaction
with hydrazine is certainly pH dependent . Freebase Hydrazine is
only weakly basic , much less than ammonia . It is more like
urea than ammonia in terms of basicity . So the above reaction
would be similar to mixing solutions of urea nitrate and silver
nitrate . It could react , but I see no obvious reason to
believe it would react *unless* there was some complexation
reaction which could produce a highly insoluble precipitate even
in acidic conditions . You could possibly get a silver analogue
of "PHILOU's Salt" ( nickel trihydrazine nitrate :) It may even
be likely , since silver does form a diammine , it is certainly
possible it could form a complex salt with hydrazine nitrate
which may have interesting properties itself , and possibly
even superior properties to silver azide . The possibilities
of this experiment get more interesting because of this .
A "failed" experiment to produce an intended result sometimes
results in discovery of something more valuable than what was
being first intended to be produced .
-No silver complexe is formed to my feelings; but stil I'll try that AgNO3/N2H5NO3 experiment
aside with Cu(NO3)2, Co(NO3)2, Ni(NO3)2 and Pb(NO3)2.Last set of experiments.
Post by Rosco P. Coaltrain
Post by LOUIS
Post by Rosco P. Coaltrain
NH2-NH2-H2SO4 + KNO2 ----> KHSO4 + 2H2O + HN3
-Indeed NH2-NH3ONO is a "view" of the mind but in the same view NH4ONO shouldn't exist but
stil it does and is isolable despite it is unstable and explosive.
NH4ONO --> N2 + 2H2O
The process you expose will end quite fast or restrain strongly the yield since while you add
dropwise KNO2 in the system it frees locally HNO2 but the amount of HN3 which is originally
low is increasing and so decomposition increases too.
The low solubility of the metal azide would remove the HN3 by
precipitation as quickly as the HN3 was formed .
Solubility of azides is sometimes high enough to be supperior to N2H5HSO4 solubilities! So no
precipitate is observed but the azide might be in!
Also despite what you think unsoluble doesn't mean unsoluble but means poorly soluble.
There is always an equilibrium reaction that allow the solubilisation, for any single salt!
Post by Rosco P. Coaltrain
Post by LOUIS
NH2-NH2OH + R-ONO + NaOH is used under mild heating ; the NaOH hydrolyses the nitrous ester
*Negative* , the hydrazine hydrate and the organic nitrite react directly
and then the hydrazoic acid which is produced is neutralized by the NaOH .
That reaction is preferential so long as the concentration of the NaOH
is not too great . Any hydrolysis of the organic nitrite by the NaOH
results in an undesired by product of NaNO2 , which does not react
with the hydrazine hydrate . Low temperatures favor this desired
reaction of the hydrazine with the organic nitrite , warmer temperatures
favor the hydrolysis of the nitrite which is undesired .
-The ultimate test would be to mix N2H5OH with Pb(NO2)2 saturated solution.
2N2H5OH + Pb(NO2)2 ---> (2N2H5ONO + Pb(OH)2(s)) --> 2HN3 + 4H2O + Pb(OH)2(s)
2HN3 + 4H2O + Pb(OH)2(s) ---> Pb(N3)2 + 6H2O (upon time)
Post by Rosco P. Coaltrain
Post by LOUIS
and free continuous but smoothly NO2(-) in basic media then the only products of the reaction
R-OH (an alcool), NaN3 and NaOH.More than certainly the reason you invoqued of impossible
coexistance of HNO2 and HN3 calls for basic hydrolysis of the ester instead of the acidic
one.
The two acids HNO2 and HN3 are incompatable in the same manner
as mixing hydrogen peroxide and hydrazine , a hypergolic decomposition .
In that scenario think of it as a detonation at the molecular level ,
the two species simply tear each other apart like matter and anti-matter
brought in contact .
-True I have made the test. But in basic media...something interesting occurs!
Post by Rosco P. Coaltrain
Post by LOUIS
Anyway, to me the best way is to neutralise a little more than half an equivalent of H2SO4
(in the hydrazine sulfate salt) with NaOH, Na2CO3 or NaHCO3 to get NH2-NH2.HSO4(-) and then
allow the NaNO2 to enter dropwise into the system.Then no big amount of HNO2 can be present
and The major products will be Na2SO4 and NaN3.
The very best way is to get NH2-NH3OH from NH2-NH2.H2SO4 and to allow this to react with
NaNO2 as it happens in the "normal" lab procedure for NaN3 from nitrous ester.
That would be fine if the reaction proceeded as you suppose , but the
purpose of using an organic nitrite is not as a source for nascent sodium
nitrite to participate in the reaction . The nitrosation of the hydrazine
is performed directly by the nitrite ester , not by sodium nitrite .
-Why the hell do they use NaOH then? Since NH2-NH3OH is a strong enough base to hydrolyse the
nitrite ester...
Hydrazonolyse performs easier than ammonolyse since NH2-NH2 can be very concentrated and liquid.
NaOH is there to catch the HN3 immediatelly and form NaN3 stable towards the heat of the reaction
(arround 40°C) and not as volatile as N2H5N3/ HN3.(toxic)
Post by Rosco P. Coaltrain
Post by LOUIS
-CO2 flow and condensation.
?????? gas entrainment distillation ???
-Yes CO2 will displace the volatile gas HN3 from its solution.A flow of air will work aswel.
Post by Rosco P. Coaltrain
We both understand that there are competing reactions which are
influenced by reaction conditions to proceed in a way which favors
the desired reactions and disfavors the undesired reactions ,
as an implementation of "process chemistry" .
-Seems it is the case.
Post by Rosco P. Coaltrain
It is a miracle that HN3 did not detonate in midstream halfway
to a floor made of any material , calcium or not :)
In solution , the Ca(N3)2 material should be safe .
-I don't know and don't trust something I haven't experienced if it seems unstable.
Post by Rosco P. Coaltrain
Dihydrazine Sulfate (NH2NH2)2 - H2SO4 is highly soluble
should form a nearly neutral pH solution .
-Excess NH2-NH2 should make it from NH2NH2.H2SO4
Post by Rosco P. Coaltrain
I dont think you will ever see such a double salt as the hydrazine
will form whatever mixture of monobasic or dibasic hydrazine salts
corresponds with the pH of the system .
-Yes maybe.
Post by Rosco P. Coaltrain
How far can a frustrated chemist throw a beaker ?
If nothing else , perhaps this experiment can provide
useful datas on trajectories :)
-I'll post my research on the subject at least what I have done and observed in a day or two.

Ph Z
Rosco P. Coaltrain
2003-12-31 05:24:20 UTC
Permalink
Post by LOUIS
Post by Rosco P. Coaltrain
Affirmative , I know you meant the order of addition is important ,
and I agree . But there is something more that is probably needed
also , some variable which we are probably unaware . For example ,
suppose there is something necessary to be added to the aqueous system ,
which may form an organic nitrite in situ as an intermediate or catalyst
for the reaction , perhaps for example ethylene glycol or something similar .
And perhaps without such an organic material present as a catalyst ,
no attempts will be successful to have the reaction proceed
regardless of how well it appears to work on paper .
-Yes often old text are rather unclear or unprecise.
Very true . And sometimes the essential detail is deliberately
kept secret for added protection to a patent process . Like the
formula for coca-cola kept proprietary and confidential ,
and sometimes art is lost forever , like the ancient process
for Damascus steel .
Post by LOUIS
Post by Rosco P. Coaltrain
Perhaps AgNO3+(NH2NH2)HNO3 ---> AgNO3+(NH2NH2)HNO3 (no reaction?)
-Not done yet!Last serie of experiments to come.
Post by Rosco P. Coaltrain
I am not certain , but I think that the silver will be
more basic than the hydrazine and remain in solution .
-Silver is silver and is not basic as such while hydrazine is strongly basic otherwise pure
hydrazine wouldn't corrode glass as does solid NaOH...a proof of its basicity is the ease with
wich it forms salts when exposed to acid fumes (smog) or the strong violet color it displays when
exposed to phenolphtalein indicator.
True that it should be a little less basic than pure NH3 but NH3 is limited to 30% solutions while
NH2-NH2 can go as high as 100%. pKa of NH2-NH2 should conceptually be between NH3 and NH2-OH but I
owing to a special effect (mesomer giver) I remember it is stronger base than NH3 is...after all
NH3 even liquid doesn't corrode glass!
Sodium silicate attacks glass too , but you can
wash your hands with it . Try that with strong ammonia
water and severe burns will result , so it's not really
definitive about a base whatever it does to glass .
A better index would be the pH of solutions of its salts
with various acids . Anyway , I was actually looking
at the electrical potential there and did not check
any tables to be sure , expecting that the silver
would stay with the nitrate radical instead of being
reduced , and if it did react it would likely be
to form a double salt or complex . Just guessing here ,
I'm not sure what , if anything , will develop there .
I have the reagents and can also do the reactions ,
when I am able . Presently I have been ailing
with some shoulder problems that have limited my
mobility and work .
Post by LOUIS
Post by Rosco P. Coaltrain
It would be easy enough to test to see if there is
any reaction between solutions of silver nitrate and
hydrazine nitrate mixed together . Have you done this before ?
Whether or not silver precipitates as a consequence of reaction
with hydrazine is certainly pH dependent . Freebase Hydrazine is
only weakly basic , much less than ammonia . It is more like
urea than ammonia in terms of basicity . So the above reaction
would be similar to mixing solutions of urea nitrate and silver
nitrate . It could react , but I see no obvious reason to
believe it would react *unless* there was some complexation
reaction which could produce a highly insoluble precipitate even
in acidic conditions . You could possibly get a silver analogue
of "PHILOU's Salt" ( nickel trihydrazine nitrate :) It may even
be likely , since silver does form a diammine , it is certainly
possible it could form a complex salt with hydrazine nitrate
which may have interesting properties itself , and possibly
even superior properties to silver azide . The possibilities
of this experiment get more interesting because of this .
A "failed" experiment to produce an intended result sometimes
results in discovery of something more valuable than what was
being first intended to be produced .
-No silver complexe is formed to my feelings; but stil I'll try that AgNO3/N2H5NO3 experiment
Another thought , and something I'll probably try
at that point if nothing results , is to add a bit
of ammonium perchlorate and see if anything interesting
in the way of a possible , theoretical complex drops out,
maybe Silver Dihydrazine Perchlorate ?
Post by LOUIS
aside with Cu(NO3)2, Co(NO3)2, Ni(NO3)2 and Pb(NO3)2.Last set of experiments.
Post by Rosco P. Coaltrain
Post by LOUIS
Post by Rosco P. Coaltrain
NH2-NH2-H2SO4 + KNO2 ----> KHSO4 + 2H2O + HN3
-Indeed NH2-NH3ONO is a "view" of the mind but in the same view NH4ONO shouldn't exist but
stil it does and is isolable despite it is unstable and explosive.
NH4ONO --> N2 + 2H2O
The process you expose will end quite fast or restrain strongly the yield since while you add
dropwise KNO2 in the system it frees locally HNO2 but the amount of HN3 which is originally
low is increasing and so decomposition increases too.
The low solubility of the metal azide would remove the HN3 by
precipitation as quickly as the HN3 was formed .
Solubility of azides is sometimes high enough to be supperior to N2H5HSO4 solubilities! So no
precipitate is observed but the azide might be in!
Also despite what you think unsoluble doesn't mean unsoluble but means poorly soluble.
I know everything is soluble to some extent , even gold ,
diamond , and glass . Look out ! They will soon be selling
"diamond water" , but it will only be supplied as
a very dilute solution ;)
Post by LOUIS
There is always an equilibrium reaction that allow the solubilisation, for any single salt!
Post by Rosco P. Coaltrain
Post by LOUIS
NH2-NH2OH + R-ONO + NaOH is used under mild heating ; the NaOH hydrolyses the nitrous ester
*Negative* , the hydrazine hydrate and the organic nitrite react directly
and then the hydrazoic acid which is produced is neutralized by the NaOH .
That reaction is preferential so long as the concentration of the NaOH
is not too great . Any hydrolysis of the organic nitrite by the NaOH
results in an undesired by product of NaNO2 , which does not react
with the hydrazine hydrate . Low temperatures favor this desired
reaction of the hydrazine with the organic nitrite , warmer temperatures
favor the hydrolysis of the nitrite which is undesired .
-The ultimate test would be to mix N2H5OH with Pb(NO2)2 saturated solution.
2N2H5OH + Pb(NO2)2 ---> (2N2H5ONO + Pb(OH)2(s)) --> 2HN3 + 4H2O + Pb(OH)2(s)
2HN3 + 4H2O + Pb(OH)2(s) ---> Pb(N3)2 + 6H2O (upon time)
I would bet money that is not the mechanism by which
the reaction proceeds . There are some ideas I have
about this , but I shall await your findings ,
because I am uncertain my ideas are correct ,
they are still developing as we are having this dialogue .
But I suspect that you are about to discover
some puzzling results in what seem like simple experiments ,
and if that proves true please do not be frustrated ,
knowing that we are on the same page and joined in
the same search for answers . Some time back you
posted in another thread about organic nitrites that
you hoped to find your "alter ego" in online discussion .
And these experiments are related to the organic nitrite esters ,
in the answers to this puzzle , just *possibly* :)
That's my guess anyway , from experiments I have done
already trying to grasp the subtleties of these reactions .
I have plenty of sodium azide made from the straightforward
reaction of hydrazine hydrate and isopropyl nitrite in
methanolic sodium hydroxide , so there is no quest by me
for a source for sodium azide . What is my interest
is pure scientific curiosity peaked by some failed experiments
for which I see no conspicuous reason . Failed experiments
which seem like they should work are indication
that there is more to be learned , and present
a puzzle to be solved , where other things may be
learned along the way as serendipity .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
and free continuous but smoothly NO2(-) in basic media then the only products of the reaction
R-OH (an alcool), NaN3 and NaOH.More than certainly the reason you invoqued of impossible
coexistance of HNO2 and HN3 calls for basic hydrolysis of the ester instead of the acidic
one.
The two acids HNO2 and HN3 are incompatable in the same manner
as mixing hydrogen peroxide and hydrazine , a hypergolic decomposition .
In that scenario think of it as a detonation at the molecular level ,
the two species simply tear each other apart like matter and anti-matter
brought in contact .
-True I have made the test. But in basic media...something interesting occurs!
How would you have two un-ionized *acids* present to react in a *basic* medium??
That is like saying you are going to determine how well hydrochloric and acetic
acid react together in a bucket of limewater . All you would determine is
if there is a reaction between calcium chloride and calcium acetate in
calcium hydroxide solution . With acidity and basicity , buffered pH 7
is the only place where you can (sort of) "have your cake and eat it too" .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
Anyway, to me the best way is to neutralise a little more than half an equivalent of H2SO4
(in the hydrazine sulfate salt) with NaOH, Na2CO3 or NaHCO3 to get NH2-NH2.HSO4(-) and then
allow the NaNO2 to enter dropwise into the system.Then no big amount of HNO2 can be present
and The major products will be Na2SO4 and NaN3.
The very best way is to get NH2-NH3OH from NH2-NH2.H2SO4 and to allow this to react with
NaNO2 as it happens in the "normal" lab procedure for NaN3 from nitrous ester.
That would be fine if the reaction proceeded as you suppose , but the
purpose of using an organic nitrite is not as a source for nascent sodium
nitrite to participate in the reaction . The nitrosation of the hydrazine
is performed directly by the nitrite ester , not by sodium nitrite .
-Why the hell do they use NaOH then? Since NH2-NH3OH is a strong enough base to hydrolyse the
nitrite ester...
That is *exactly* what the hydrazine hydrate does , simultaneously hydrolyzing
the organic nitrite ester , and being "nitrosated" or "diazotized" by it ,
more accurately would perhaps be to say the hydrazine is "hydrazoitized" ?
Hypnotized or mesmerized , anyway it is converted to hydrazoic acid and
the NaOH then neutralizes the HN3 to form NaN3 .
Post by LOUIS
Hydrazonolyse performs easier than ammonolyse since NH2-NH2 can be very concentrated and liquid.
NaOH is there to catch the HN3 immediatelly and form NaN3 stable towards the heat of the reaction
(arround 40°C) and not as volatile as N2H5N3/ HN3.(toxic)
In my flask , hydrazine and isopropyl nitrite react immediately and
exothermically even at 0 degrees in dilute methanol solution or even
in the vapor phase , to form hydrazoic acid directly . And what the
NaOH does is tie up the HN3 as a non volatile and stable NaN3 salt ,
and probably also as you point out , it also prevents the unreacted
hydrazine from combining with the hydrazoic acid , to form
any "hydrazine hydrazoate" or "hydrazine azide" (which is a material
I don't even like the sound of being in my vicinity ) Sounds like
a rocket fuel with attitude , energy , and unpredictability .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
-CO2 flow and condensation.
?????? gas entrainment distillation ???
-Yes CO2 will displace the volatile gas HN3 from its solution.A flow of air will work aswel.
Sounds like somebody wants to avoid any use of even
"gentle heating" in that particular distillation .
Distillation is conducted in a shielded apparatus ,
under an atmosphere of pure anticipation ?
Post by LOUIS
Post by Rosco P. Coaltrain
We both understand that there are competing reactions which are
influenced by reaction conditions to proceed in a way which favors
the desired reactions and disfavors the undesired reactions ,
as an implementation of "process chemistry" .
-Seems it is the case.
Post by Rosco P. Coaltrain
It is a miracle that HN3 did not detonate in midstream halfway
to a floor made of any material , calcium or not :)
In solution , the Ca(N3)2 material should be safe .
-I don't know and don't trust something I haven't experienced if it seems unstable.
Post by Rosco P. Coaltrain
Dihydrazine Sulfate (NH2NH2)2 - H2SO4 is highly soluble
should form a nearly neutral pH solution .
-Excess NH2-NH2 should make it from NH2NH2.H2SO4
Cheaper and easier to just half neutralize , using NaOH .
Post by LOUIS
Post by Rosco P. Coaltrain
I dont think you will ever see such a double salt as the hydrazine
will form whatever mixture of monobasic or dibasic hydrazine salts
corresponds with the pH of the system .
-Yes maybe.
I'm pretty certain I have some references on this .
Maybe old Bayer patents ?
Post by LOUIS
Post by Rosco P. Coaltrain
How far can a frustrated chemist throw a beaker ?
If nothing else , perhaps this experiment can provide
useful datas on trajectories :)
-I'll post my research on the subject at least what I have done and observed in a day or two.
Ph Z
I look forward to hearing your findings , observations , and ideas .
It's a pleasure comparing notes with you Louis , and I am going to
do some future experiments along these lines too .

Rosco
LOUIS
2004-01-03 09:33:11 UTC
Permalink
Post by Rosco P. Coaltrain
Post by LOUIS
-Yes often old text are rather unclear or unprecise.
Very true . And sometimes the essential detail is deliberately
kept secret for added protection to a patent process . Like the
formula for coca-cola kept proprietary and confidential ,
and sometimes art is lost forever , like the ancient process
for Damascus steel .
-:-)
Post by Rosco P. Coaltrain
Post by LOUIS
-Silver is silver and is not basic as such while hydrazine is strongly basic otherwise pure
hydrazine wouldn't corrode glass as does solid NaOH...a proof of its basicity is the ease with
wich it forms salts when exposed to acid fumes (smog) or the strong violet color it displays when
exposed to phenolphtalein indicator.
True that it should be a little less basic than pure NH3 but NH3 is limited to 30% solutions while
NH2-NH2 can go as high as 100%. pKa of NH2-NH2 should conceptually be between NH3 and NH2-OH but I
owing to a special effect (mesomer giver) I remember it is stronger base than NH3 is...after all
NH3 even liquid doesn't corrode glass!
Sodium silicate attacks glass too , but you can
wash your hands with it . Try that with strong ammonia
water and severe burns will result , so it's not really
definitive about a base whatever it does to glass .
A better index would be the pH of solutions of its salts
with various acids . Anyway , I was actually looking
at the electrical potential there and did not check
any tables to be sure , expecting that the silver
would stay with the nitrate radical instead of being
reduced , and if it did react it would likely be
to form a double salt or complex . Just guessing here ,
I'm not sure what , if anything , will develop there .
I have the reagents and can also do the reactions ,
when I am able . Presently I have been ailing
with some shoulder problems that have limited my
mobility and work .
-N2H4 + H2O --> N2H5(+) + OH(-) Kb25° = 8,5*10E-7 so pKa = 7,93
N2H5(+) + H2O --> N2H6(2+) + OH(-) Kb25° = 8,9*10E-16 so pKa = -1,05
NH2OH + H2O --> NH3OH(+) + OH(-) Kb25° = 6,6*10E-9 so pKa = 5,82
NH3 + H2O --> NH4(+) + OH(-) Kb25° = 1,81*10E-5 so pKa = 9,25
H2SiO3 --> H(+) + HSiO3(-) pKa25° = 9,7
HSiO3 --> H(+) + SiO3(2-) pKa25° = between 13 and 15

Are you sure about washing your hands with sodium silicate?
NH2-NH2 is only 13 times less basic than ammonia but concentration can be 3-4 times higher this makes
it about 3 times less basic.
Post by Rosco P. Coaltrain
Post by LOUIS
-No silver complexe is formed to my feelings; but stil I'll try that AgNO3/N2H5NO3 experiment
Another thought , and something I'll probably try
at that point if nothing results , is to add a bit
of ammonium perchlorate and see if anything interesting
in the way of a possible , theoretical complex drops out,
maybe Silver Dihydrazine Perchlorate ?
-I give you a good advice...tiny amounts and behind a screen with thick glooves....GOOGLES.
When Ni(NO3)2 is mixed with NH2-NH3OH, you get a quite stable complex while Cu complex is unstable and
prompt to self-decomposition, Co complex is stable and looks like Ni complex except its color isn't
violet pink but red-orange.But if you use Ni(ClO4)2 detonation of the all water solution has occured
from a glass rod swirling the solution.
Co perchlorate might give more stability but Cu should be a hell.
Hydrazine perchlorate is quite resistant to heating but if hit can detonate with a very loud report
(0,3g of the substance completely twisted a tea spoon I was holding and did a serious notch in its side
before the spoon flew in the air (2 meters) spinning at about 150 rpm. HP is considerably more
hygroscopic than HN and more sensitive to shock too.
Concentrated HClO4 explodes upon contact with various metals
SO
expect any mixing of NH4ClO4, N2H5ClO4 with AgNO3, Ag, Ag2O, AgOH, Ag2CO3, ... or AgClO4 with N2H4 or
N2H5(+) to be extremely dangerous
Post by Rosco P. Coaltrain
Post by LOUIS
Solubility of azides is sometimes high enough to be supperior to N2H5HSO4 solubilities! So no
precipitate is observed but the azide might be in!
Also despite what you think unsoluble doesn't mean unsoluble but means poorly soluble.
I know everything is soluble to some extent , even gold ,
diamond , and glass . Look out ! They will soon be selling
"diamond water" , but it will only be supplied as
a very dilute solution ;)
-I meant that the azide might be in but not unsoluble because N2H5HSO4 needs a lot of water to
dissolve.
Also
If HN3 is the weaker acid between N2H5HSO4, HNO2 and HN3; it is also reversiblely the stronger base as
N3(-) vs NO2(-) and SO4(2-) and so HN3 will always be in solution as the last lasting acid despite the
"unsolubility" of the azide.
NaN3 + HSO4(-) --> HN3 + NaSO4(-)
NaN3 + HNO2 --> HN3 (immediate decomposition) + NaNO2
Post by Rosco P. Coaltrain
Post by LOUIS
-The ultimate test would be to mix N2H5OH with Pb(NO2)2 saturated solution.
2N2H5OH + Pb(NO2)2 ---> (2N2H5ONO + Pb(OH)2(s)) --> 2HN3 + 4H2O + Pb(OH)2(s)
2HN3 + 4H2O + Pb(OH)2(s) ---> Pb(N3)2 + 6H2O (upon time)
I would bet money that is not the mechanism by which
the reaction proceeds . There are some ideas I have
about this , but I shall await your findings ,
because I am uncertain my ideas are correct ,
they are still developing as we are having this dialogue .
But I suspect that you are about to discover
some puzzling results in what seem like simple experiments ,
and if that proves true please do not be frustrated ,
knowing that we are on the same page and joined in
the same search for answers . Some time back you
posted in another thread about organic nitrites that
you hoped to find your "alter ego" in online discussion .
And these experiments are related to the organic nitrite esters ,
in the answers to this puzzle , just *possibly* :)
That's my guess anyway , from experiments I have done
already trying to grasp the subtleties of these reactions .
I have plenty of sodium azide made from the straightforward
reaction of hydrazine hydrate and isopropyl nitrite in
methanolic sodium hydroxide , so there is no quest by me
for a source for sodium azide . What is my interest
is pure scientific curiosity peaked by some failed experiments
for which I see no conspicuous reason . Failed experiments
which seem like they should work are indication
that there is more to be learned , and present
a puzzle to be solved , where other things may be
learned along the way as serendipity .
- I won't be puzzled ;-).
Post by Rosco P. Coaltrain
Post by LOUIS
-True I have made the test. But in basic media...something interesting occurs!
How would you have two un-ionized *acids* present to react in a *basic* medium??
That is like saying you are going to determine how well hydrochloric and acetic
acid react together in a bucket of limewater . All you would determine is
if there is a reaction between calcium chloride and calcium acetate in
calcium hydroxide solution . With acidity and basicity , buffered pH 7
is the only place where you can (sort of) "have your cake and eat it too" .
Read this and conclude by yourself:
N2H5OH diluted in water + phenolphtalein --> deep violet coloration
NaNO2 saturated solution + phenolphtalein --> uncoloured
When an exces of NaNO2 solution is added to the hydrazine solution no single bubble is observed but
discoloration occurs...if the hydrazine remains unaffected no discolouration should have occured.
N2H5OH + NaNO2 --aq--> N2H5(+) + OH(-) + Na(+) + NO2(-)
By definition of ionic species the mix of hydrazine hydrate and sodium nitrite is equivalent to a mix
of sodium hydroxyde and hydrazine nitrite (which can only be HN3 as you said).There is no reason the pH
would drop except if HN3 is formed.
So
N2H5OH + NaNO2 -aq-> N2H5NO2 + NaOH --> HN3 + 2H2O + NaOH --> NaN3 + 3H2O
Post by Rosco P. Coaltrain
In my flask , hydrazine and isopropyl nitrite react immediately and
exothermically even at 0 degrees in dilute methanol solution or even
in the vapor phase , to form hydrazoic acid directly . And what the
NaOH does is tie up the HN3 as a non volatile and stable NaN3 salt ,
and probably also as you point out , it also prevents the unreacted
hydrazine from combining with the hydrazoic acid , to form
any "hydrazine hydrazoate" or "hydrazine azide" (which is a material
I don't even like the sound of being in my vicinity ) Sounds like
a rocket fuel with attitude , energy , and unpredictability .
Post by LOUIS
-Yes CO2 will displace the volatile gas HN3 from its solution.A flow of air will work aswel.
Sounds like somebody wants to avoid any use of even
"gentle heating" in that particular distillation .
Distillation is conducted in a shielded apparatus ,
under an atmosphere of pure anticipation ?
-You got the idea.
Post by Rosco P. Coaltrain
Post by LOUIS
-I'll post my research on the subject at least what I have done and observed in a day or two.
Ph Z
I look forward to hearing your findings , observations , and ideas .
It's a pleasure comparing notes with you Louis , and I am going to
do some future experiments along these lines too .
-I'll post those tonight.
Post by Rosco P. Coaltrain
Rosco
PhZ
LOUIS
2004-01-04 16:17:48 UTC
Permalink
Here follows the results of my investigation:
I played with saturated solutions in distillated water at 20°C

I) Mixes of nitrates and sodium nitrite.
Ni(NO3)2 (emerald green)+ NaNO2 (water clear) --> transparent emerald
green solution
Cu(NO3)2 (deep blue) + NaNO2 --> dark yellow-green solution
Pb(NO3)2 (water clear) + NaNO2 --> orange-yellow transparent solution
Co(NO3)2 (deep red) + NaNO2 --> ???? (forgot this one)
AgNO3 (water clear) + NaNO2 --> white precipitate of AgNO2

II) Mixes of nitrates with hydrazinium sulfate and then addition of
sodium nitrite.
Ni(NO3)2 + N2H6SO4 (water clear) --> transparent green
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and
stil green.

Cu(NO3)2 + N2H6SO4 --> blue trouble and tiny bubbles
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and
dark green.

Pb(NO3)2 + N2H6SO4 --> amorphous white precipitate of lead sulfate
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and
orange yellow supernatant.

Co(NO3)2 + N2H6SO4 --> ????(frogot this one too)
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and .

AgNO3 + N2H6SO4 --> cristalline white precipitate of Ag2SO4
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and
more white precipitate of AgNO2.

III) Mixes of hydrazinium hydroxyde with NaNO2 and then addition of
nitrates:
NaNO2 + PP (Phenolphtalein) --> transparent
N2H5OH + PP --> deep violet
N2H5OH + PP + NaNO2 --> passes from deep violet to colourless when
excess NaNO2 is added.
Sole explanation, formation of N2H5NO2 and smooth transformation into
HN3 residual NaOH neutralise it immediately to form NaN3.

The last solution with excess NaNO2 will be named X in the future; it is
only 2 minutes old.

X + Ni(NO3)2 --> pink precipitate of Ni(NH2-NH2)3(NO3)2
X + Cu(NO3)2 --> decomposition into bubbles and black brown dark
deposit.
X + Pb(NO3)2 --> yellow or white precipitate with yellow supernatant
X + Co(NO3)2 --> orange-red precipitate of Co(NH2-NH2)3(NO3)2
X + AgNO3 --> white precipitate and immediate darkening to form a silver
mirror.(AgOH, Ag2O account for this behavior while AgNO2 is the white
precipitate).

Tests remaining to perform:
-I) and II) for Co(NO3)2
-Color of the various azides from NaN3 solution with nitrates of the
metal and estimation of their solubilities.
-III) left and observed for a longer time than 2 minutes (a day or so)
-Cristallisation and isolation of nitrites of the metals prior to
reaction with N2H5OH
-Hydrazine nitrate with NaNO2 and other metal nitrites
-Hydrazine nitrate with metal nitrates

Conclusions:
-Interesting results from the NaNO2/N2H5OH mix.
-Need for various azide infos as color and solubility to see if it might
be present or not from the test II and III.
Indeed the various reaction that takes place in the various tests like
bubbles, competitive precipitation or strong coloration might mask the
presence of azide or the fact the use of N2H6SO4 calls for a strong
dillution owing to the poor solubility of the salt.This should be
circumvented by the use of the hydrazine nitrate wich will reduce
acidity of the media whom pH will be closer to 7 than with N2H6SO4.

Ph Z
donald j haarmann
2004-01-04 19:42:14 UTC
Permalink
LOUIS" ***@SKYNET.be

Here follows the results of my investigation:
I played with saturated solutions in distillated water at 20°C


[snip]

I do not think the chemistry is this simple! Sorry. Here is a procedure for Na azide.
The industrial method is alot easier! <
"As an example, 8.1 g of sodium methylate (0.14 mol) is disolved in 50 ml methanol and cooled
to 10oC. Six grams hydrazine hydrate (85% - 0.1 mol) is added followed by a solution of 15.5 g
butyl nitrite (0.15 mol) in 100 ml ether. With occasional stiring the mixture is kept for 1 hour below
room temperature. Sodium azide precipitates and, after standing at room temperature overnight, is
seperated and washed with acetone. With respect to hydrazine the yield of the crude product is 88.8% (5.7 g)."

The classical hydrazine method for the production of Na azide has also used:

ethyl nitrite
propyl nitrite
buytl nitrite
ethylate
hydroxide in alcoholic/alcoholoic-ethereal/aqueous solution.
--
donald j haarmann - colophon
Rosco P. Coaltrain
2004-01-05 02:13:49 UTC
Permalink
Post by LOUIS
I played with saturated solutions in distillated water at 20°C
[snip]
I do not think the chemistry is this simple! Sorry.
Bullseye , You got that right ,
Halleluiah ...haarmann has arrived !
That is exactly what I have been trying to declare .
This is one of those reactions where the chemistry "looks"
so simple ...but it is *NOT* simple at all . It is a reaction
that is somewhere between very difficult and damn near impossible
to make work the way it appears it would work in theory .
And that is exactly why those two patents seem so very ,
very interesting , because they claim to have found a method
which works straightforwardly for a reaction which experiments
will reveal isn't so simple as it "looks like" it should be .
Post by LOUIS
Here is a procedure for Na azide.
The industrial method is alot easier! <
Right again , the industrial and laboratory method of
reacting hydrazine hydrate with any of several
organic nitrite esters works like a champ .
You see , that newer method is well described in patents and easily
proven to have technical merit . No one disputes the practical
value of the newer methods which are easy enough to verify , by
experiments which confirm those well described syntheses .
No mystery is there about those modern syntheses which perform
exactly as promised . Louis is familiar with those proven methods
and has probably done those syntheses just as I have done them ,
and found few surprises there .

But those two patents at the top of the thread describe
an older method which uses simpler precursors under milder conditions .
But experiments done to try to confirm that "simpler method" leave
one scratching ones head and wondering "what's the secret?" to
getting those "simpler" reactions to work . There are several
possible reaction schemes which can be expressed as proper equations
where everything appears to work and the chemist will be confident
about the result . The reagents can be carefully weighed and
the solutions prepared , and the reactions attempted by different
methods ....without joy in producing the predicted and expected result .

The question which then follows directly is of course ....Why?

Rosco
Post by LOUIS
"As an example, 8.1 g of sodium methylate (0.14 mol) is disolved in 50 ml methanol and cooled
to 10oC. Six grams hydrazine hydrate (85% - 0.1 mol) is added followed by a solution of 15.5 g
butyl nitrite (0.15 mol) in 100 ml ether. With occasional stiring the mixture is kept for 1 hour below
room temperature. Sodium azide precipitates and, after standing at room temperature overnight, is
seperated and washed with acetone. With respect to hydrazine the yield of the crude product is 88.8% (5.7 g)."
ethyl nitrite
propyl nitrite
buytl nitrite
ethylate
hydroxide in alcoholic/alcoholoic-ethereal/aqueous solution.
Don T
2004-01-05 18:56:11 UTC
Permalink
Post by Rosco P. Coaltrain
Post by LOUIS
I played with saturated solutions in distillated water at 20°C
[snip]
I do not think the chemistry is this simple! Sorry.
Bullseye , You got that right ,
Halleluiah ...haarmann has arrived !
That is exactly what I have been trying to declare .
This is one of those reactions where the chemistry "looks"
so simple ...but it is *NOT* simple at all . It is a reaction
that is somewhere between very difficult and damn near impossible
to make work the way it appears it would work in theory .
And that is exactly why those two patents seem so very ,
very interesting , because they claim to have found a method
which works straightforwardly for a reaction which experiments
will reveal isn't so simple as it "looks like" it should be .
Post by LOUIS
Here is a procedure for Na azide.
The industrial method is alot easier! <
Right again , the industrial and laboratory method of
reacting hydrazine hydrate with any of several
organic nitrite esters works like a champ .
You see , that newer method is well described in patents and easily
proven to have technical merit . No one disputes the practical
value of the newer methods which are easy enough to verify , by
experiments which confirm those well described syntheses .
No mystery is there about those modern syntheses which perform
exactly as promised . Louis is familiar with those proven methods
and has probably done those syntheses just as I have done them ,
and found few surprises there .
But those two patents at the top of the thread describe
an older method which uses simpler precursors under milder conditions .
But experiments done to try to confirm that "simpler method" leave
one scratching ones head and wondering "what's the secret?" to
getting those "simpler" reactions to work . There are several
possible reaction schemes which can be expressed as proper equations
where everything appears to work and the chemist will be confident
about the result . The reagents can be carefully weighed and
the solutions prepared , and the reactions attempted by different
methods ....without joy in producing the predicted and expected result .
The question which then follows directly is of course ....Why?
Simple. Those experiments were carried out following laboratory proceedures
current *at that time* not those current today. You would need a complete
curricula from ca 1880 to 1901 or thereabouts to find out what lab practices
were taken for granted that EVERYONE KNEW and thus were not detailed in the
write-ups of the time. But you KNEW that. Right? You being so much smarter
than everyone else posting here.

I would posit that Donald Haarmann knows a hell of a lot more than he is
willing to share with a complete asshole such as yourself. Several others
the same. Your name is NOT G-d and you cannot COMMAND people to give you
answers. Nor can you COMMAND respect when you come here denigrating your
betters. Much better that you ASK than that you DEMAND.
--
Don Thompson

"The bravest are surely those who have the clearest vision of what is before
them, glory and danger alike, and notwithstanding go out to meet it."-
Thucydides

"Men are never really willing to die except for the sake of Freedom:
Therefore they do not believe in dying completely."-
Albert Camus
Post by Rosco P. Coaltrain
Rosco
Post by LOUIS
"As an example, 8.1 g of sodium methylate (0.14 mol) is disolved in 50
ml methanol and cooled
Post by Rosco P. Coaltrain
Post by LOUIS
to 10oC. Six grams hydrazine hydrate (85% - 0.1 mol) is added followed
by a solution of 15.5 g
Post by Rosco P. Coaltrain
Post by LOUIS
butyl nitrite (0.15 mol) in 100 ml ether. With occasional stiring the
mixture is kept for 1 hour below
Post by Rosco P. Coaltrain
Post by LOUIS
room temperature. Sodium azide precipitates and, after standing at room
temperature overnight, is
Post by Rosco P. Coaltrain
Post by LOUIS
seperated and washed with acetone. With respect to hydrazine the yield
of the crude product is 88.8% (5.7 g)."
Post by Rosco P. Coaltrain
Post by LOUIS
ethyl nitrite
propyl nitrite
buytl nitrite
ethylate
hydroxide in alcoholic/alcoholoic-ethereal/aqueous solution.
Rosco P. Coaltrain
2004-01-05 23:10:58 UTC
Permalink
Post by Don T
Post by Rosco P. Coaltrain
Post by LOUIS
I played with saturated solutions in distillated water at 20°C
[snip]
I do not think the chemistry is this simple! Sorry.
Bullseye , You got that right ,
Halleluiah ...haarmann has arrived !
That is exactly what I have been trying to declare .
This is one of those reactions where the chemistry "looks"
so simple ...but it is *NOT* simple at all . It is a reaction
that is somewhere between very difficult and damn near impossible
to make work the way it appears it would work in theory .
And that is exactly why those two patents seem so very ,
very interesting , because they claim to have found a method
which works straightforwardly for a reaction which experiments
will reveal isn't so simple as it "looks like" it should be .
Post by LOUIS
Here is a procedure for Na azide.
The industrial method is alot easier! <
Right again , the industrial and laboratory method of
reacting hydrazine hydrate with any of several
organic nitrite esters works like a champ .
You see , that newer method is well described in patents and easily
proven to have technical merit . No one disputes the practical
value of the newer methods which are easy enough to verify , by
experiments which confirm those well described syntheses .
No mystery is there about those modern syntheses which perform
exactly as promised . Louis is familiar with those proven methods
and has probably done those syntheses just as I have done them ,
and found few surprises there .
But those two patents at the top of the thread describe
an older method which uses simpler precursors under milder conditions .
But experiments done to try to confirm that "simpler method" leave
one scratching ones head and wondering "what's the secret?" to
getting those "simpler" reactions to work . There are several
possible reaction schemes which can be expressed as proper equations
where everything appears to work and the chemist will be confident
about the result . The reagents can be carefully weighed and
the solutions prepared , and the reactions attempted by different
methods ....without joy in producing the predicted and expected result .
The question which then follows directly is of course ....Why?
Simple. Those experiments were carried out following laboratory proceedures
current *at that time* not those current today. You would need a complete
curricula from ca 1880 to 1901 or thereabouts to find out what lab practices
were taken for granted that EVERYONE KNEW and thus were not detailed in the
write-ups of the time. But you KNEW that. Right?
Wrong .

That is huge assumption which you are making and it is incorrect .
Fundamental methods in syntheses were well established by that period
and for the most part are identical to the procedures used today .
Post by Don T
You being so much smarter
than everyone else posting here.
First you reveal your ignorance about synthesis and scientific method ,
and then you personally attack me . You just go from dumb to dumber .
Post by Don T
I would posit that Donald Haarmann knows a hell of a lot more than he is
willing to share with a complete asshole such as yourself. Several others
the same. Your name is NOT G-d and you cannot COMMAND people to give you
answers. Nor can you COMMAND respect when you come here denigrating your
betters. Much better that you ASK than that you DEMAND.
What I have done here is to participate in a legitimate exchange of
information and a legitimate discussion sharing and seeking knowledge .
If you have something to contribute in that regard , then wonderful ,
I politely ask that you share in kind . Tell me everything you know ,
I have five minutes .

Alternately , I have not *demanded* nor have I *commanded* anything ,
nor have I claimed to be god . Where do you get this stuff ?

Rosco
Post by Don T
--
Don Thompson
"The bravest are surely those who have the clearest vision of what is before
them, glory and danger alike, and notwithstanding go out to meet it."-
Thucydides
Therefore they do not believe in dying completely."-
Albert Camus
Post by Rosco P. Coaltrain
Rosco
Post by LOUIS
"As an example, 8.1 g of sodium methylate (0.14 mol) is disolved in 50
ml methanol and cooled
Post by Rosco P. Coaltrain
Post by LOUIS
to 10oC. Six grams hydrazine hydrate (85% - 0.1 mol) is added followed
by a solution of 15.5 g
Post by Rosco P. Coaltrain
Post by LOUIS
butyl nitrite (0.15 mol) in 100 ml ether. With occasional stiring the
mixture is kept for 1 hour below
Post by Rosco P. Coaltrain
Post by LOUIS
room temperature. Sodium azide precipitates and, after standing at room
temperature overnight, is
Post by Rosco P. Coaltrain
Post by LOUIS
seperated and washed with acetone. With respect to hydrazine the yield
of the crude product is 88.8% (5.7 g)."
Post by Rosco P. Coaltrain
Post by LOUIS
The classical hydrazine method for the production of Na azide has also
ethyl nitrite
propyl nitrite
buytl nitrite
ethylate
hydroxide in alcoholic/alcoholoic-ethereal/aqueous solution.
Don T
2004-01-06 03:30:59 UTC
Permalink
Post by Rosco P. Coaltrain
I politely ask that you share in kind . Tell me everything you know ,
I have five minutes .
I got your "five minutes" right HERE motherfucker. Now. THAT was as polite
as your "invitation". If you are so blind that you can't even see your own
bullshit how in the hell are you going to ever learn anything new?
--
Don Thompson

"The bravest are surely those who have the clearest vision of what is before
them, glory and danger alike, and notwithstanding go out to meet it."-
Thucydides

"Men are never really willing to die except for the sake of Freedom:
Therefore they do not believe in dying completely."-
Albert Camus
Rosco P. Coaltrain
2004-01-06 07:54:02 UTC
Permalink
Post by Don T
Post by Rosco P. Coaltrain
I politely ask that you share in kind . Tell me everything you know ,
I have five minutes .
I got your "five minutes" right HERE motherfucker. Now. THAT was as polite
as your "invitation". If you are so blind that you can't even see your own
bullshit how in the hell are you going to ever learn anything new?
--
Don Thompson
Wow Don , that's impressive . You know a lot about chemistry .

Okay you've had your five minutes . Now go away .

Rosco
Don T
2004-01-06 16:51:59 UTC
Permalink
Post by Rosco P. Coaltrain
Post by Don T
Post by Rosco P. Coaltrain
I politely ask that you share in kind . Tell me everything you know ,
I have five minutes .
I got your "five minutes" right HERE motherfucker. Now. THAT was as polite
as your "invitation". If you are so blind that you can't even see your own
bullshit how in the hell are you going to ever learn anything new?
--
Don Thompson
Wow Don , that's impressive . You know a lot about chemistry .
Okay you've had your five minutes . Now go away .
Make me "Rosco". I was here before you rode in and I will be here after you
crawl away. So fuck you and the horse you rode in on. What I know about
Chemistry you will never learn. But you "might" check the professional
registry before you pass judgement. If you are smart enough that is.
--
Don Thompson

"The bravest are surely those who have the clearest vision of what is before
them, glory and danger alike, and notwithstanding go out to meet it."-
Thucydides

"Men are never really willing to die except for the sake of Freedom:
Therefore they do not believe in dying completely."-
Albert Camus
Post by Rosco P. Coaltrain
Rosco
Rosco P. Coaltrain
2004-01-07 01:36:38 UTC
Permalink
Post by Rosco P. Coaltrain
Post by Rosco P. Coaltrain
Post by Don T
Post by Rosco P. Coaltrain
I politely ask that you share in kind . Tell me everything you know ,
I have five minutes .
I got your "five minutes" right HERE motherfucker. Now. THAT was as
polite
Post by Rosco P. Coaltrain
Post by Don T
as your "invitation". If you are so blind that you can't even see your
own
Post by Rosco P. Coaltrain
Post by Don T
bullshit how in the hell are you going to ever learn anything new?
--
Don Thompson
Wow Don , that's impressive . You know a lot about chemistry .
Okay you've had your five minutes . Now go away .
Make me "Rosco". I was here before you rode in and I will be here after you
crawl away. So fuck you and the horse you rode in on. What I know about
Chemistry you will never learn. But you "might" check the professional
registry before you pass judgement. If you are smart enough that is.
--
Don Thompson
If you are a professional then why don't you act like it , instead
of trashing a legitimate thread in an engineering news group with
toilet mouth and bad attitude ?


Rosco
Rosco P. Coaltrain
2004-01-06 07:03:42 UTC
Permalink
Post by LOUIS
I played with saturated solutions in distillated water at 20°C
I) Mixes of nitrates and sodium nitrite.
Ni(NO3)2 (emerald green)+ NaNO2 (water clear) --> transparent emerald
green solution
Cu(NO3)2 (deep blue) + NaNO2 --> dark yellow-green solution
Pb(NO3)2 (water clear) + NaNO2 --> orange-yellow transparent solution
Co(NO3)2 (deep red) + NaNO2 --> ???? (forgot this one)
AgNO3 (water clear) + NaNO2 --> white precipitate of AgNO2
II) Mixes of nitrates with hydrazinium sulfate and then addition of
sodium nitrite.
Ni(NO3)2 + N2H6SO4 (water clear) --> transparent green
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and
stil green.
Cu(NO3)2 + N2H6SO4 --> blue trouble and tiny bubbles
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and
dark green.
Pb(NO3)2 + N2H6SO4 --> amorphous white precipitate of lead sulfate
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and
orange yellow supernatant.
Co(NO3)2 + N2H6SO4 --> ????(frogot this one too)
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and .
AgNO3 + N2H6SO4 --> cristalline white precipitate of Ag2SO4
when NaNO2 is added --> strong evolution of bubbles (nitrous+???) and
more white precipitate of AgNO2.
III) Mixes of hydrazinium hydroxyde with NaNO2 and then addition of
NaNO2 + PP (Phenolphtalein) --> transparent
N2H5OH + PP --> deep violet
N2H5OH + PP + NaNO2 --> passes from deep violet to colourless when
excess NaNO2 is added.
Sole explanation, formation of N2H5NO2 and smooth transformation into
HN3 residual NaOH neutralise it immediately to form NaN3.
Hope springs eternal :)
Post by LOUIS
The last solution with excess NaNO2 will be named X in the future; it is
only 2 minutes old.
X + Ni(NO3)2 --> pink precipitate of Ni(NH2-NH2)3(NO3)2
Here's the bust , if there had been free hydrazoic acid present in
"solution X" , then the precipitate would be nickel azide ,
*not* the hydrazine complex - nickel trihydrazine nitrate .
Post by LOUIS
X + Cu(NO3)2 --> decomposition into bubbles and black brown dark
deposit.
X + Pb(NO3)2 --> yellow or white precipitate with yellow supernatant
X + Co(NO3)2 --> orange-red precipitate of Co(NH2-NH2)3(NO3)2
The cobalt complex with hydrazine is further proof same as for the
nickel complex above , that there is still plenty of hydrazine in
"solution X" which has not converted to hydrazoic acid .
Cadmium nitrate would also produce such a complex .
Post by LOUIS
X + AgNO3 --> white precipitate and immediate darkening to form a silver
mirror.(AgOH, Ag2O account for this behavior while AgNO2 is the white
precipitate).
-I) and II) for Co(NO3)2
-Color of the various azides from NaN3 solution with nitrates of the
metal and estimation of their solubilities.
-III) left and observed for a longer time than 2 minutes (a day or so)
-Cristallisation and isolation of nitrites of the metals prior to
reaction with N2H5OH
-Hydrazine nitrate with NaNO2 and other metal nitrites
Those are the particular experiments which should be most promising .
Post by LOUIS
-Hydrazine nitrate with metal nitrates
-Interesting results from the NaNO2/N2H5OH mix.
-Need for various azide infos as color and solubility to see if it might
be present or not from the test II and III.
Indeed the various reaction that takes place in the various tests like
bubbles,
Caution regarding the bubbles , the composition of the vapor being unknown .

competitive precipitation or strong coloration might mask the
Post by LOUIS
presence of azide or the fact the use of N2H6SO4 calls for a strong
dillution owing to the poor solubility of the salt.This should be
circumvented by the use of the hydrazine nitrate wich will reduce
acidity of the media whom pH will be closer to 7 than with N2H6SO4.
Ph Z
--
Rosco
LOUIS
2004-01-06 09:45:02 UTC
Permalink
-SNIP-
Post by LOUIS
III) Mixes of hydrazinium hydroxyde with NaNO2 and then addition of
NaNO2 + PP (Phenolphtalein) --> transparent
N2H5OH + PP --> deep violet
N2H5OH + PP + NaNO2 --> passes from deep violet to colourless when
excess NaNO2 is added.
Sole explanation, formation of N2H5NO2 and smooth transformation into
HN3 residual NaOH neutralise it immediately to form NaN3.
Hope springs eternal :)
-Actually it is strange that
N2H4 + H2O <---> N2H5(+) + OH(-) strongly alkaline solution
NaNO2 <---> Na(+) + NO2(-) (almost neutral)
and
N2H5NO2 <--> N2H5(+) + NO2(-) (almost neutral)
NaOH <---> Na(+) + OH (-) strongly alkaline solution
Thus
N2H5OH + NaNO2 <---> NaOH + N2H5NO2
According to ionic species the quantity of OH(-) remains the same and so no
noticeable pH change should occure since the amount of acid remains the same Na(+)
and N2H5(+) and the amount of base too OH (-) and NO2(-) (no precipitation reaction,
no bubbles no neutralisation).

So the only possible change that occurs is the transformation of the N2H5NO2 into
HN3 wich then reacts with OH(-) to form N3(-) and H2O --> the pH passes from quite
basic to almost neutral...reason of the discouloration of the violet pink solution
of phenolphatlein.Of course it seems that this reaction isn't as fast as the
reaction of nitrite ester with N2H4
Post by LOUIS
The last solution with excess NaNO2 will be named X in the future; it is
only 2 minutes old.
X + Ni(NO3)2 --> pink precipitate of Ni(NH2-NH2)3(NO3)2
Here's the bust , if there had been free hydrazoic acid present in
"solution X" , then the precipitate would be nickel azide ,
*not* the hydrazine complex - nickel trihydrazine nitrate .
-Not so obvious since the trihydrazine dinitrate nickel (II) complex as its Co(II)
brother are hell unsoluble and their solubility might be lower than the respective
azide.As a rule the most unsoluble compound will precipitate first.
Also since those complex are strongly coloured even in the case of a coprecipitation
if the azides are of mild coloration they wouldn't be seen.Reason why I should study
the azides of those salts prior to any affirmation and final conclusions.
Post by LOUIS
X + Cu(NO3)2 --> decomposition into bubbles and black brown dark
deposit.
X + Pb(NO3)2 --> yellow or white precipitate with yellow supernatant
X + Co(NO3)2 --> orange-red precipitate of Co(NH2-NH2)3(NO3)2
The cobalt complex with hydrazine is further proof same as for the
nickel complex above , that there is still plenty of hydrazine in
"solution X" which has not converted to hydrazoic acid .
Cadmium nitrate would also produce such a complex .
-Not certain until proof of the contrary.
Post by LOUIS
X + AgNO3 --> white precipitate and immediate darkening to form a silver
mirror.(AgOH, Ag2O account for this behavior while AgNO2 is the white
precipitate).
-I) and II) for Co(NO3)2
-Color of the various azides from NaN3 solution with nitrates of the
metal and estimation of their solubilities.
-III) left and observed for a longer time than 2 minutes (a day or so)
-Cristallisation and isolation of nitrites of the metals prior to
reaction with N2H5OH
-Hydrazine nitrate with NaNO2 and other metal nitrites
Those are the particular experiments which should be most promising .
-Indeed as the isolation of a solution of N2H5NO2 from N2H5Cl with Pb(NO2)2 or other
metathesis
Post by LOUIS
-Hydrazine nitrate with metal nitrates
-Interesting results from the NaNO2/N2H5OH mix.
-Need for various azide infos as color and solubility to see if it might
be present or not from the test II and III.
Indeed the various reaction that takes place in the various tests like
bubbles,
Caution regarding the bubbles , the composition of the vapor being unknown .
-Absolutely.

Ph Z
Rosco P. Coaltrain
2004-01-06 17:34:09 UTC
Permalink
Post by LOUIS
-SNIP-
Post by LOUIS
III) Mixes of hydrazinium hydroxyde with NaNO2 and then addition of
NaNO2 + PP (Phenolphtalein) --> transparent
N2H5OH + PP --> deep violet
N2H5OH + PP + NaNO2 --> passes from deep violet to colourless when
excess NaNO2 is added.
Sole explanation, formation of N2H5NO2 and smooth transformation into
HN3 residual NaOH neutralise it immediately to form NaN3.
Hope springs eternal :)
-Actually it is strange that
N2H4 + H2O <---> N2H5(+) + OH(-) strongly alkaline solution
NaNO2 <---> Na(+) + NO2(-) (almost neutral)
and
N2H5NO2 <--> N2H5(+) + NO2(-) (almost neutral)
NaOH <---> Na(+) + OH (-) strongly alkaline solution
Thus
N2H5OH + NaNO2 <---> NaOH + N2H5NO2
According to ionic species the quantity of OH(-) remains the same and so no
noticeable pH change should occure since the amount of acid remains the same Na(+)
and N2H5(+) and the amount of base too OH (-) and NO2(-) (no precipitation reaction,
no bubbles no neutralisation).
So the only possible change that occurs is the transformation of the N2H5NO2 into
HN3 wich then reacts with OH(-) to form N3(-) and H2O --> the pH passes from quite
basic to almost neutral...reason of the discouloration of the violet pink solution
of phenolphatlein.Of course it seems that this reaction isn't as fast as the
reaction of nitrite ester with N2H4
Post by LOUIS
The last solution with excess NaNO2 will be named X in the future; it is
only 2 minutes old.
X + Ni(NO3)2 --> pink precipitate of Ni(NH2-NH2)3(NO3)2
Here's the bust , if there had been free hydrazoic acid present in
"solution X" , then the precipitate would be nickel azide ,
*not* the hydrazine complex - nickel trihydrazine nitrate .
-Not so obvious since the trihydrazine dinitrate nickel (II) complex as its Co(II)
brother are hell unsoluble and their solubility might be lower than the respective
azide.As a rule the most unsoluble compound will precipitate first.
Very good rule for solutions which contain stable "free radical"
ionic species . However , I am very doubtful that a reversible
reaction type of equilibrium exists in this particular case ,
where the hydrazoic species can revert back to the hydrazinic
species in order to satisfy precipitation expectation for
the least soluble of the two possible products . I tend to
believe that once the hydrazine has been "azotized" to
form hydrazoic acid , that the system is not reversible ,
and then is committed to only produce the azide as a precipitate
for that portion of the hydrazine which has already been converted
to hydrazoic acid . The possiblity of a mixed precipitate ,
or even a double salt seems very real and *Extremely* interesting ,
since such a mixed salt would likely resolve the ignition difficulties
reported for the pure complexes , which would otherwise be
good initiators themselves if more easily ignited .
Post by LOUIS
Also since those complex are strongly coloured even in the case of a coprecipitation
if the azides are of mild coloration they wouldn't be seen.Reason why I should study
the azides of those salts prior to any affirmation and final conclusions.
Yes , excellent observation . This is a very interesting possibility .
Perhaps the "serendipity" I have mentioned , a very promising material
if what you speculate is true has indeed occurred . Recommend comparison
of this material with the material otherwise obtained by the usual method
which would surely contain no azide . This could be an unreported compound
of value , one for the books if this is true .
Post by LOUIS
Post by LOUIS
X + Cu(NO3)2 --> decomposition into bubbles and black brown dark
deposit.
X + Pb(NO3)2 --> yellow or white precipitate with yellow supernatant
X + Co(NO3)2 --> orange-red precipitate of Co(NH2-NH2)3(NO3)2
The cobalt complex with hydrazine is further proof same as for the
nickel complex above , that there is still plenty of hydrazine in
"solution X" which has not converted to hydrazoic acid .
Cadmium nitrate would also produce such a complex .
-Not certain until proof of the contrary.
Post by LOUIS
X + AgNO3 --> white precipitate and immediate darkening to form a silver
mirror.(AgOH, Ag2O account for this behavior while AgNO2 is the white
precipitate).
-I) and II) for Co(NO3)2
-Color of the various azides from NaN3 solution with nitrates of the
metal and estimation of their solubilities.
-III) left and observed for a longer time than 2 minutes (a day or so)
-Cristallisation and isolation of nitrites of the metals prior to
reaction with N2H5OH
-Hydrazine nitrate with NaNO2 and other metal nitrites
Those are the particular experiments which should be most promising .
-Indeed as the isolation of a solution of N2H5NO2 from N2H5Cl with Pb(NO2)2 or other
metathesis
Post by LOUIS
-Hydrazine nitrate with metal nitrates
-Interesting results from the NaNO2/N2H5OH mix.
-Need for various azide infos as color and solubility to see if it might
be present or not from the test II and III.
Indeed the various reaction that takes place in the various tests like
bubbles,
Caution regarding the bubbles , the composition of the vapor being unknown .
-Absolutely.
Ph Z
Just curious if you have some ammonium perchlorate on hand :) ?

Rosco
LOUIS
2004-01-09 15:32:52 UTC
Permalink
Post by Rosco P. Coaltrain
Post by LOUIS
SNIP
-Not so obvious since the trihydrazine dinitrate nickel (II) complex as its Co(II)
brother are hell unsoluble and their solubility might be lower than the respective
azide.As a rule the most unsoluble compound will precipitate first.
Very good rule for solutions which contain stable "free radical"
ionic species . However , I am very doubtful that a reversible
reaction type of equilibrium exists in this particular case ,
where the hydrazoic species can revert back to the hydrazinic
species in order to satisfy precipitation expectation for
the least soluble of the two possible products . I tend to
believe that once the hydrazine has been "azotized" to
form hydrazoic acid , that the system is not reversible ,
and then is committed to only produce the azide as a precipitate
for that portion of the hydrazine which has already been converted
to hydrazoic acid . The possiblity of a mixed precipitate ,
or even a double salt seems very real and *Extremely* interesting ,
since such a mixed salt would likely resolve the ignition difficulties
reported for the pure complexes , which would otherwise be
good initiators themselves if more easily ignited .
-I don't know if HN3 turns back into N2H4, and never said so; what I told was more that
the time of reaction was not long enough for all the N2H4 to turn into HN3...so as an
instant picture after a few minutes in the media, we have:
N2H5OH, NaNO2, N2H5NO2, NaOH and little HN3; when I added Co(NO3)2, Ni(NO3)2 it diplays
some possibilities:
Precipitation of green Ni(OH)2 or red Co(OH)2, precipitation of the hydrazinonitrato
complexes (which occured), precipitation of azides...Thus a few minute of reaction
doesn't seems long enough for noticeable disparition of N2H4 to make it minor ingredient
vs HN3.This explains why I will study this back but for 1h and 1 day or a week.
Post by Rosco P. Coaltrain
Post by LOUIS
Also since those complex are strongly coloured even in the case of a coprecipitation
if the azides are of mild coloration they wouldn't be seen.Reason why I should study
the azides of those salts prior to any affirmation and final conclusions.
Yes , excellent observation . This is a very interesting possibility .
Perhaps the "serendipity" I have mentioned , a very promising material
if what you speculate is true has indeed occurred . Recommend comparison
of this material with the material otherwise obtained by the usual method
which would surely contain no azide . This could be an unreported compound
of value , one for the books if this is true .
-Yes if the reaction takes place right in the middle if precipitation occurs, one should
get a mixed complex that would ally sensitivity of azides and power of the
hydrazinonitrato complexes. Also who knows maybe there is an azidohydrazino complex that
may be unsoluble or in the contrary help solubilise the azide complexes are
fellowbollonies!
Post by Rosco P. Coaltrain
Just curious if you have some ammonium perchlorate on hand :) ?
-Yes why that question?And also some pure 70% HClO4 and Hexamethylene tetramine
diperchlorate.
Post by Rosco P. Coaltrain
Rosco
Rosco P. Coaltrain
2004-01-09 23:04:39 UTC
Permalink
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
SNIP
-Not so obvious since the trihydrazine dinitrate nickel (II) complex as its Co(II)
brother are hell unsoluble and their solubility might be lower than the respective
azide.As a rule the most unsoluble compound will precipitate first.
Very good rule for solutions which contain stable "free radical"
ionic species . However , I am very doubtful that a reversible
reaction type of equilibrium exists in this particular case ,
where the hydrazoic species can revert back to the hydrazinic
species in order to satisfy precipitation expectation for
the least soluble of the two possible products . I tend to
believe that once the hydrazine has been "azotized" to
form hydrazoic acid , that the system is not reversible ,
and then is committed to only produce the azide as a precipitate
for that portion of the hydrazine which has already been converted
to hydrazoic acid . The possiblity of a mixed precipitate ,
or even a double salt seems very real and *Extremely* interesting ,
since such a mixed salt would likely resolve the ignition difficulties
reported for the pure complexes , which would otherwise be
good initiators themselves if more easily ignited .
-I don't know if HN3 turns back into N2H4, and never said so;
Not eplicitly , but in message 34 above you were describing the
"solution X" and said :
( quote )
Post by LOUIS
-Actually it is strange that
N2H4 + H2O <---> N2H5(+) + OH(-) strongly alkaline solution
NaNO2 <---> Na(+) + NO2(-) (almost neutral)
and
N2H5NO2 <--> N2H5(+) + NO2(-) (almost neutral)
NaOH <---> Na(+) + OH (-) strongly alkaline solution
Thus
N2H5OH + NaNO2 <---> NaOH + N2H5NO2
By drawing the arrow pointing both ways in the last reaction
just above , you in effect said that the reaction is reversible .
I disagree . I suspect there is an "equilibrium mixture" that
is determined by the pH of the system .
In your reaction above the N2H5NO2 is equivalent to HN3 + 2 H20 .
Therefore , the above reaction could be rewritten as

N2H5OH + NaNO2 ------> NaN3 + 3 H2O

Not wishing to seem disagreeable ,
but I still do not expect the reaction
which we are seeking occurs this way ,
and it would seem even less likely with
a double arrow indicting reversability .
Post by LOUIS
According to ionic species the quantity of OH(-) remains the same and so no
noticeable pH change should occure since the amount of acid remains the same > Na(+)
and N2H5(+) and the amount of base too OH (-) and NO2(-)
(no precipitation reaction, no bubbles no neutralisation).
So the only possible change that occurs is the transformation of the N2H5NO2 > into
HN3 wich then reacts with OH(-) to form N3(-) and H2O --> the pH passes from > quite
basic to almost neutral...reason of the discouloration of the violet
pink solution of phenolphatlein.Of course it seems that this reaction
isn't as fast as the reaction of nitrite ester with N2H4
( end quote )
Post by LOUIS
what I told was more that
the time of reaction was not long enough for all the N2H4 to turn into HN3...so as an
N2H5OH, NaNO2, N2H5NO2, NaOH and little HN3; when I added Co(NO3)2, Ni(NO3)2 it diplays
Precipitation of green Ni(OH)2 or red Co(OH)2, precipitation of the hydrazinonitrato
complexes (which occured), precipitation of azides...Thus a few minute of reaction
doesn't seems long enough for noticeable disparition of N2H4 to make it minor ingredient
vs HN3.This explains why I will study this back but for 1h and 1 day or a week.
" Study " of a reaction of this sort can get complicated . This
is one of those reaction studies which will be a test of patience .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
Also since those complex are strongly coloured even in the case of a coprecipitation
if the azides are of mild coloration they wouldn't be seen.Reason why I should study
the azides of those salts prior to any affirmation and final conclusions.
Yes , excellent observation . This is a very interesting possibility .
Perhaps the "serendipity" I have mentioned , a very promising material
if what you speculate is true has indeed occurred . Recommend comparison
of this material with the material otherwise obtained by the usual method
which would surely contain no azide . This could be an unreported compound
of value , one for the books if this is true .
-Yes if the reaction takes place right in the middle if precipitation occurs, one should
get a mixed complex that would ally sensitivity of azides and power of the
hydrazinonitrato complexes. Also who knows maybe there is an azidohydrazino complex that
may be unsoluble or in the contrary help solubilise the azide complexes are
fellowbollonies!
fellowbollonies ????
Is that Belgian for it probably isn't either one ,
much less both ! :-)
Post by LOUIS
Post by Rosco P. Coaltrain
Just curious if you have some ammonium perchlorate on hand :) ?
-Yes why that question?And also some pure 70% HClO4 and Hexamethylene tetramine
diperchlorate.
It was just a thought that when you get to mixing hydrazine nitrate
solution with various metal nitrates , that a metal hydrazine perchlorate
complex , or a double salt of that with the metal hydrazine nitrate ,
could also be interesting possibilities to examine while doing other
experiments that are in the neighborhood .

Another thought which keeps recurring to me is the possible usefulness
of "R-Salz" as a nitrosation agent , instead of Sodium Nitrite , but it
could happen that a polymer might result from interaction of R-Salt and
hydrazine , I just don't know . It's another one of those experiments
that is on my "experiments to do" list . A water soluble organic "nitrite"
might possibly react better with the hydrazine than does sodium nitrite .

Rosco
donald j haarmann
2004-01-10 01:19:03 UTC
Permalink
Post by Rosco P. Coaltrain
It was just a thought that when you get to mixing hydrazine nitrate
solution with various metal nitrates , that a metal hydrazine perchlorate
complex , or a double salt of that with the metal hydrazine nitrate ,
could also be interesting possibilities to examine while doing other
experiments that are in the neighborhood .
---------
Been done! Hydrazine nitrate and and aq. solution of sodium nitrITE. From
a secondary source, not seen by me.

Primary -

BP Orelkin & et al.
Journ. Russ. Phys. Chem, Soc

&

J Thiele [Reference out of order in da book therefore, I am not sure they are correct!]

Liebig's Ann., 270. 1, 1892
Ber., 41. 2681, 1908

Warning - Be careful you do not produce sodium hydrazine (NH2.NHNa) in your
experiments!!! "It was found to be most violently explosive. A mere breath of air, or a
trace of moisture or alcohol, sufficed to produce disastrous reslults."

Amazing what you can find in books! And this book a standard/obvious starting source.
--
donald j haarmann - colophon
LOUIS
2004-01-12 12:16:37 UTC
Permalink
Post by Rosco P. Coaltrain
Post by LOUIS
-I don't know if HN3 turns back into N2H4, and never said so;
Not eplicitly , but in message 34 above you were describing the
( quote )
Post by LOUIS
-Actually it is strange that
N2H4 + H2O <---> N2H5(+) + OH(-) strongly alkaline solution
NaNO2 <---> Na(+) + NO2(-) (almost neutral)
and
N2H5NO2 <--> N2H5(+) + NO2(-) (almost neutral)
NaOH <---> Na(+) + OH (-) strongly alkaline solution
Thus
N2H5OH + NaNO2 <---> NaOH + N2H5NO2
By drawing the arrow pointing both ways in the last reaction
just above , you in effect said that the reaction is reversible .
I disagree . I suspect there is an "equilibrium mixture" that
is determined by the pH of the system .
In your reaction above the N2H5NO2 is equivalent to HN3 + 2 H20 .
Therefore , the above reaction could be rewritten as
N2H5OH + NaNO2 ------> NaN3 + 3 H2O
-Yes I wrote double arrows but the last reaction you wrote and wich I implied is the motor of
the reaction since there you have an irreversible reaction, it is the determinant step of all
the equilibriums that shift those to the right side.
And nowhere I wrote N2H5OH + NaNO2 <---> NaN3 + 3H2O which would mean one could get an
alkaline solution from a neutral solution of NaN3....
Stil I wonder how you account for the fact of colour disappearance of phenolphtaleinated
hydrazinium hydroxyde when admixed with saturated NaNO2...?
Post by Rosco P. Coaltrain
Not wishing to seem disagreeable ,
but I still do not expect the reaction
which we are seeking occurs this way ,
and it would seem even less likely with
a double arrow indicting reversability .
-All the reactions I wrote are reversible since those are solubilisation reactions or mixing
of soluble salts without acid-base reaction, without precipitation or without evolution of a
gaseous product wich would favors the shift of equilibrium to one side...the only possible
acid-base reaction which is a simple arrow is the last one that we wrote.
Post by Rosco P. Coaltrain
Post by LOUIS
According to ionic species the quantity of OH(-) remains the same and so no
noticeable pH change should occure since the amount of acid remains the same > Na(+)
and N2H5(+) and the amount of base too OH (-) and NO2(-)
(no precipitation reaction, no bubbles no neutralisation).
So the only possible change that occurs is the transformation of the N2H5NO2 > into
HN3 wich then reacts with OH(-) to form N3(-) and H2O --> the pH passes from > quite
basic to almost neutral...reason of the discouloration of the violet
pink solution of phenolphatlein.Of course it seems that this reaction
isn't as fast as the reaction of nitrite ester with N2H4
( end quote )
Post by LOUIS
what I told was more that
the time of reaction was not long enough for all the N2H4 to turn into HN3...so as an
N2H5OH, NaNO2, N2H5NO2, NaOH and little HN3; when I added Co(NO3)2, Ni(NO3)2 it diplays
Precipitation of green Ni(OH)2 or red Co(OH)2, precipitation of the hydrazinonitrato
complexes (which occured), precipitation of azides...Thus a few minute of reaction
doesn't seems long enough for noticeable disparition of N2H4 to make it minor ingredient
vs HN3.This explains why I will study this back but for 1h and 1 day or a week.
" Study " of a reaction of this sort can get complicated . This
is one of those reaction studies which will be a test of patience .
-Yes patience and experimentation :-) ;-).
Post by Rosco P. Coaltrain
Post by LOUIS
-Yes if the reaction takes place right in the middle if precipitation occurs, one should
get a mixed complex that would ally sensitivity of azides and power of the
hydrazinonitrato complexes. Also who knows maybe there is an azidohydrazino complex that
may be unsoluble or in the contrary help solubilise the azide complexes are
fellowbollonies!
fellowbollonies ????
Is that Belgian for it probably isn't either one ,
much less both ! :-)
-;-) simple complexes are weird objects; sometimes they help solubilise unsoluble compounds
and sometimes they make it precipitate...that's simply what I meant, if an hydrazinoazido
complex occurs; it might be unsoluble or hell good solubilisator of unsoluble azides; problem
might thus be a little harder in tha later case.
Post by Rosco P. Coaltrain
Post by LOUIS
Post by Rosco P. Coaltrain
Just curious if you have some ammonium perchlorate on hand :) ?
-Yes why that question?And also some pure 70% HClO4 and Hexamethylene tetramine
diperchlorate.
It was just a thought that when you get to mixing hydrazine nitrate
solution with various metal nitrates , that a metal hydrazine perchlorate
complex , or a double salt of that with the metal hydrazine nitrate ,
could also be interesting possibilities to examine while doing other
experiments that are in the neighborhood .
-Yes but tiny tiny amounts, perchlorate is way more dangerous than nitrate and too much
undone or not well studied experiments side by side in the explosive field is a wish for
troubles :-(.
Post by Rosco P. Coaltrain
Another thought which keeps recurring to me is the possible usefulness
of "R-Salz" as a nitrosation agent , instead of Sodium Nitrite , but it
could happen that a polymer might result from interaction of R-Salt and
hydrazine , I just don't know . It's another one of those experiments
that is on my "experiments to do" list . A water soluble organic "nitrite"
might possibly react better with the hydrazine than does sodium nitrite .
-Yes, R-salt must be a good alternative...and indeed theorically:

(-CH2-N(-N=O)-)3 + 3NH2-NH2 --> (-CH2-N(-N=N-NH2)-)3 + 3 H2O and possible intermolecular or
intramolecular cyclisations....resulting in a polymer of high nitrogen content....(CH2N3)x
the solution should become coloured and darkens with increasing molecular weight .

Ph Z
Rosco P. Coaltrain
2004-01-12 23:47:21 UTC
Permalink
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
-I don't know if HN3 turns back into N2H4, and never said so;
Not eplicitly , but in message 34 above you were describing the
( quote )
Post by LOUIS
-Actually it is strange that
N2H4 + H2O <---> N2H5(+) + OH(-) strongly alkaline solution
NaNO2 <---> Na(+) + NO2(-) (almost neutral)
and
N2H5NO2 <--> N2H5(+) + NO2(-) (almost neutral)
NaOH <---> Na(+) + OH (-) strongly alkaline solution
Thus
N2H5OH + NaNO2 <---> NaOH + N2H5NO2
By drawing the arrow pointing both ways in the last reaction
just above , you in effect said that the reaction is reversible .
I disagree . I suspect there is an "equilibrium mixture" that
is determined by the pH of the system .
In your reaction above the N2H5NO2 is equivalent to HN3 + 2 H20 .
Therefore , the above reaction could be rewritten as
N2H5OH + NaNO2 ------> NaN3 + 3 H2O
-Yes I wrote double arrows but the last reaction you wrote and wich I implied is the motor of
the reaction since there you have an irreversible reaction, it is the determinant step of all
the equilibriums that shift those to the right side.
And nowhere I wrote N2H5OH + NaNO2 <---> NaN3 + 3H2O which would mean one could get an
alkaline solution from a neutral solution of NaN3....
Stil I wonder how you account for the fact of colour disappearance of phenolphtaleinated
hydrazinium hydroxyde when admixed with saturated NaNO2...?
What I was thinking as I read your report concerning
the color change was to question if the integrity of
the phenolphthalein indicator remained intact in a reaction
system containing hydrazine and nitrous and azide which
are all highly reactive , and may actually chemically bind
and react with the indicator itself , making any color change
of dubious value as an indicator of what may actually be
occurring in terms of pH change . I would have removed an aliquot
of the reaction mixture and basified it with NaOH to see if the
indicating ability of the indicator was intact , in order
to set aside this question to some extent .
Post by LOUIS
Post by Rosco P. Coaltrain
Not wishing to seem disagreeable ,
but I still do not expect the reaction
which we are seeking occurs this way ,
and it would seem even less likely with
a double arrow indicting reversability .
-All the reactions I wrote are reversible since those are solubilisation reactions or mixing
of soluble salts without acid-base reaction, without precipitation or without evolution of a
gaseous product wich would favors the shift of equilibrium to one side...the only possible
acid-base reaction which is a simple arrow is the last one that we wrote.
Post by Rosco P. Coaltrain
Post by LOUIS
According to ionic species the quantity of OH(-) remains the same and so no
noticeable pH change should occure since the amount of acid remains the same > Na(+)
and N2H5(+) and the amount of base too OH (-) and NO2(-)
(no precipitation reaction, no bubbles no neutralisation).
So the only possible change that occurs is the transformation of the N2H5NO2 > into
HN3 wich then reacts with OH(-) to form N3(-) and H2O --> the pH passes from > quite
basic to almost neutral...reason of the discouloration of the violet
pink solution of phenolphatlein.Of course it seems that this reaction
isn't as fast as the reaction of nitrite ester with N2H4
( end quote )
Post by LOUIS
what I told was more that
the time of reaction was not long enough for all the N2H4 to turn into HN3...so as an
N2H5OH, NaNO2, N2H5NO2, NaOH and little HN3; when I added Co(NO3)2, Ni(NO3)2 it diplays
Precipitation of green Ni(OH)2 or red Co(OH)2, precipitation of the hydrazinonitrato
complexes (which occured), precipitation of azides...Thus a few minute of reaction
doesn't seems long enough for noticeable disparition of N2H4 to make it minor ingredient
vs HN3.This explains why I will study this back but for 1h and 1 day or a week.
" Study " of a reaction of this sort can get complicated . This
is one of those reaction studies which will be a test of patience .
-Yes patience and experimentation :-) ;-).
Actually these experiments are very interesting because
of the not so commonly known chemistry , and the potential
for many useful compounds which may be found as products
from these reaction mixtures . Ionic theory is a useful method
for theoretical expression , but I have always had my belief
that it is not a hundred per cent applicable to describing
*all* reactions , for it is indeed possible for reactions
to occur between materials which are in no way ionized ,
but react directly anyway , as whole molecules of one material
actively reacting with whole molecules of another . Sugar
dissolves very well in water , but it isn't ionized .
And there are quite irreversible reactions possible which
run very happily to completion while defying any prediction
based upon solubilities . Chemistry has general rules which
shape our expectation and define our predictions , and yet
the substances mixed in the beaker will react or not react ,
not always according to what we guess they should do ,
but more just as they please , in spite
of our theories or best laid plans .
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
-Yes if the reaction takes place right in the middle if precipitation occurs, one should
get a mixed complex that would ally sensitivity of azides and power of the
hydrazinonitrato complexes. Also who knows maybe there is an azidohydrazino complex that
may be unsoluble or in the contrary help solubilise the azide complexes are
fellowbollonies!
fellowbollonies ????
Is that Belgian for it probably isn't either one ,
much less both ! :-)
-;-) simple complexes are weird objects; sometimes they help solubilise unsoluble compounds
and sometimes they make it precipitate...that's simply what I meant, if an hydrazinoazido
complex occurs; it might be unsoluble or hell good solubilisator of unsoluble azides; problem
might thus be a little harder in tha later case.
Did you test a dried portion of that precipitate
to flame sensitivity ? If so , how did it compare
to the usual complex which contains no azide ?

Unstable fellowbollonies should be avoided . Ingestion of even
microscopic amounts is well known to result in acute and incurable
simultaneous stuttering , hemorrhoids and hives ;) It is an affliction
very similar to enduring trolls at an engineering news group !
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
Post by Rosco P. Coaltrain
Just curious if you have some ammonium perchlorate on hand :) ?
-Yes why that question?And also some pure 70% HClO4 and Hexamethylene tetramine
diperchlorate.
It was just a thought that when you get to mixing hydrazine nitrate
solution with various metal nitrates , that a metal hydrazine perchlorate
complex , or a double salt of that with the metal hydrazine nitrate ,
could also be interesting possibilities to examine while doing other
experiments that are in the neighborhood .
-Yes but tiny tiny amounts, perchlorate is way more dangerous than nitrate and too much
undone or not well studied experiments side by side in the explosive field is a wish for
troubles :-(.
A spot test from a few milliliters in a polypropylene culture tube was
all I had in mind there .
Post by LOUIS
Post by Rosco P. Coaltrain
Another thought which keeps recurring to me is the possible usefulness
of "R-Salz" as a nitrosation agent , instead of Sodium Nitrite , but it
could happen that a polymer might result from interaction of R-Salt and
hydrazine , I just don't know . It's another one of those experiments
that is on my "experiments to do" list . A water soluble organic "nitrite"
might possibly react better with the hydrazine than does sodium nitrite .
(-CH2-N(-N=O)-)3 + 3NH2-NH2 --> (-CH2-N(-N=N-NH2)-)3 + 3 H2O and possible intermolecular or
intramolecular cyclisations....resulting in a polymer of high nitrogen content....(CH2N3)x
Sounds like it would be an interesting experiment , but definitely
microscale until toxicity of the product could be evaluated .
Some of these hydrazine compounds have high potential physiological
activity aside from any other properties . Could be even more
dangerous than fellowbollonies ;-)
Post by LOUIS
the solution should become coloured and darkens with increasing molecular weight .
Ph Z
LOUIS
2004-01-13 10:14:58 UTC
Permalink
Post by Rosco P. Coaltrain
Post by LOUIS
-Yes I wrote double arrows but the last reaction you wrote and wich I implied is the motor of
the reaction since there you have an irreversible reaction, it is the determinant step of all
the equilibriums that shift those to the right side.
And nowhere I wrote N2H5OH + NaNO2 <---> NaN3 + 3H2O which would mean one could get an
alkaline solution from a neutral solution of NaN3....
Stil I wonder how you account for the fact of colour disappearance of phenolphtaleinated
hydrazinium hydroxyde when admixed with saturated NaNO2...?
What I was thinking as I read your report concerning
the color change was to question if the integrity of
the phenolphthalein indicator remained intact in a reaction
system containing hydrazine and nitrous and azide which
are all highly reactive , and may actually chemically bind
and react with the indicator itself , making any color change
of dubious value as an indicator of what may actually be
occurring in terms of pH change . I would have removed an aliquot
of the reaction mixture and basified it with NaOH to see if the
indicating ability of the indicator was intact , in order
to set aside this question to some extent .
-Nice idea, I also have other colour indicators :-).
Hydrazine on its own doesn't alterate the colour...it last long.
NaNO2 is neutral and so no coulour change occurs but a few drops of NaOH will prove if the
indicator is unchanged or not.
NaN3 will say if the indicator is stable in that media and NaOH reveals its perenity.
Then a mix of NaNO2 and NaN3, N2H5OH and NaN3 and finally N2H5OH, NaNO2 prior to NaOH.
Post by Rosco P. Coaltrain
Post by LOUIS
Post by Rosco P. Coaltrain
" Study " of a reaction of this sort can get complicated . This
is one of those reaction studies which will be a test of patience .
-Yes patience and experimentation :-) ;-).
Actually these experiments are very interesting because
of the not so commonly known chemistry , and the potential
for many useful compounds which may be found as products
from these reaction mixtures . Ionic theory is a useful method
for theoretical expression , but I have always had my belief
that it is not a hundred per cent applicable to describing
*all* reactions , for it is indeed possible for reactions
to occur between materials which are in no way ionized ,
but react directly anyway , as whole molecules of one material
actively reacting with whole molecules of another . Sugar
dissolves very well in water , but it isn't ionized .
And there are quite irreversible reactions possible which
run very happily to completion while defying any prediction
based upon solubilities . Chemistry has general rules which
shape our expectation and define our predictions , and yet
the substances mixed in the beaker will react or not react ,
not always according to what we guess they should do ,
but more just as they please , in spite
of our theories or best laid plans .
Post by LOUIS
-;-) simple complexes are weird objects; sometimes they help solubilise unsoluble compounds
and sometimes they make it precipitate...that's simply what I meant, if an hydrazinoazido
complex occurs; it might be unsoluble or hell good solubilisator of unsoluble azides; problem
might thus be a little harder in this later case.
Did you test a dried portion of that precipitate
to flame sensitivity ? If so , how did it compare
to the usual complex which contains no azide ?
-No I didn't; but indeed it must be a way to see if azides coprecipitated or not; the
trihydrazinodinitrato Ni(II) complex as the one of Co(II) burn fiercely in the open...(if not
selfconfined) and only detonate when confined.The presence of azide will make it detonate or
deflagrate immediatelly... and maybe much more senitive to friction and shock.
Post by Rosco P. Coaltrain
Unstable fellowbollonies should be avoided . Ingestion of even
microscopic amounts is well known to result in acute and incurable
simultaneous stuttering , hemorrhoids and hives ;) It is an affliction
very similar to enduring trolls at an engineering news group !
-:-)
Post by Rosco P. Coaltrain
Post by LOUIS
-Yes but tiny tiny amounts, perchlorate is way more dangerous than nitrate and too much
undone or not well studied experiments side by side in the explosive field is a wish for
troubles :-(.
A spot test from a few milliliters in a polypropylene culture tube was
all I had in mind there .
-Just what I thought one must do remember that Ni(NH2-NH2)3(ClO4)2 detonates from its water
solution when swirling...not even dry stuff or cristal wet stuff :-(.
Post by Rosco P. Coaltrain
Post by LOUIS
Post by Rosco P. Coaltrain
Another thought which keeps recurring to me is the possible usefulness
of "R-Salz" as a nitrosation agent , instead of Sodium Nitrite , but it
could happen that a polymer might result from interaction of R-Salt and
hydrazine , I just don't know . It's another one of those experiments
that is on my "experiments to do" list . A water soluble organic "nitrite"
might possibly react better with the hydrazine than does sodium nitrite .
(-CH2-N(-N=O)-)3 + 3NH2-NH2 --> (-CH2-N(-N=N-NH2)-)3 + 3 H2O and possible intermolecular or
intramolecular cyclisations....resulting in a polymer of high nitrogen content....(CH2N3)x
Sounds like it would be an interesting experiment , but definitely
microscale until toxicity of the product could be evaluated .
Some of these hydrazine compounds have high potential physiological
activity aside from any other properties . Could be even more
dangerous than fellowbollonies ;-)
-CH2N2 is a gas hell reactive and explosive compound used in organic chemistry under a diluted
form to perform methylation or methylenation...here (CH2N3)x if it forms will be a coloured
hardening 3D polymer with a unknown sensitivity (friction and impact) what may stand between penta
or tetrazolic rings (very sensitive) and cyanuric triazide...but its density will be higher than
tetrazolic/pentazolic rings.
It is most suitable to work with diluted R-salt and hydrazine since condensation reactions and
polymerisation will make the media heat a lot...wich could result in batch explosion.
Post by Rosco P. Coaltrain
Post by LOUIS
the solution should become coloured and darkens with increasing molecular weight .
-So does viscosity by the way.
Post by Rosco P. Coaltrain
Post by LOUIS
Ph Z
Rosco P. Coaltrain
2004-01-14 15:24:49 UTC
Permalink
LOUIS <***@SKYNET.be> wrote in message news:<***@SKYNET.be>...

[snip]
Post by LOUIS
Post by Rosco P. Coaltrain
Post by LOUIS
Post by Rosco P. Coaltrain
Another thought which keeps recurring to me is the possible usefulness
of "R-Salz" as a nitrosation agent , instead of Sodium Nitrite , but it
could happen that a polymer might result from interaction of R-Salt and
hydrazine , I just don't know . It's another one of those experiments
that is on my "experiments to do" list . A water soluble organic "nitrite"
might possibly react better with the hydrazine than does sodium nitrite .
(-CH2-N(-N=O)-)3 + 3NH2-NH2 --> (-CH2-N(-N=N-NH2)-)3 + 3 H2O and possible intermolecular or
intramolecular cyclisations....resulting in a polymer of high nitrogen content....(CH2N3)x
Sounds like it would be an interesting experiment , but definitely
microscale until toxicity of the product could be evaluated .
Some of these hydrazine compounds have high potential physiological
activity aside from any other properties . Could be even more
dangerous than fellowbollonies ;-)
-CH2N2 is a gas hell reactive and explosive compound used in organic chemistry under a diluted
form to perform methylation or methylenation...here (CH2N3)x if it forms will be a coloured
hardening 3D polymer with a unknown sensitivity (friction and impact) what may stand between penta
or tetrazolic rings (very sensitive) and cyanuric triazide...but its density will be higher than
tetrazolic/pentazolic rings.
It is most suitable to work with diluted R-salt and hydrazine since condensation reactions and
polymerisation will make the media heat a lot...wich could result in batch explosion.
Post by Rosco P. Coaltrain
Post by LOUIS
the solution should become coloured and darkens with increasing molecular weight .
-So does viscosity by the way.
A similar reaction as using R-Salt may possibly occur by
mixing solutions of hexamine dinitrate , sodium nitrite ,
and hydrazine nitrate in correct proportions and with a
favorable pH adjusted with nitric acid or NaOH as needed .
In such a system the R-Salt could potentially form in situ
and then further react with the hydrazine , or the theoretical
polymer may possibly form directly from such a mixture .

I have never seen described such a "polymer" as we are
theorizing may exist . Since anything is possible for
a theoretical material , I would speculate that it could
even be a soluble crystalline material , and have acidic properties
and a series of associated salts , all of this being purely
theoretical of course . I promise that I am not being
cryptic , for if I had actually made such a material I would
freely declare it . My experiments are a work in progress
with conclusions not yet available . This idea is shared as
being a personal curiosity which may be of interest for parallel
experiments by others .

Rosco
LOUIS
2004-01-17 14:04:55 UTC
Permalink
Hexamine dinitrate and hydrazine nitrate will buffer the solution somehow as a mild acidic media :-).
pH will be between 5 and 7 :-).
First we need to see what happens with HN alone when admixed with NaNO2; then HDN with NaNO2.

Ph Z
Post by Rosco P. Coaltrain
A similar reaction as using R-Salt may possibly occur by
mixing solutions of hexamine dinitrate , sodium nitrite ,
and hydrazine nitrate in correct proportions and with a
favorable pH adjusted with nitric acid or NaOH as needed .
In such a system the R-Salt could potentially form in situ
and then further react with the hydrazine , or the theoretical
polymer may possibly form directly from such a mixture .
I have never seen described such a "polymer" as we are
theorizing may exist . Since anything is possible for
a theoretical material , I would speculate that it could
even be a soluble crystalline material , and have acidic properties
and a series of associated salts , all of this being purely
theoretical of course . I promise that I am not being
cryptic , for if I had actually made such a material I would
freely declare it . My experiments are a work in progress
with conclusions not yet available . This idea is shared as
being a personal curiosity which may be of interest for parallel
experiments by others .
Rosco
Rosco P. Coaltrain
2004-01-17 23:53:27 UTC
Permalink
Post by LOUIS
Hexamine dinitrate and hydrazine nitrate will buffer the solution somehow as a mild acidic media :-).
pH will be between 5 and 7 :-).
First we need to see what happens with HN alone when admixed with NaNO2; then HDN with NaNO2.
Ph Z
Yes it would seem that conditions favorable for azotization
would be present in such a system . What I had in mind for
an experiment here would be to add 13 grams of Ca(OH)2
gradually to a well stirred mixture of 25ml 68 percent nitric
acid and 50 ml distilled H2O to form a solution of Ca(NO3)2 .
Then gradually add 22.5 grams of finely powdered NH2NH2(H2SO4)
to the stirred solution of Ca(NO3)2 and filter the precipitated
CaSO4 to provide a mostly clear solution of NH2NH2-(HNO3)2
containing slight residual amount of unreacted Ca(NO3)2 and HNO3 .

A second solution of 11.5 grams of NaNO2 in distilled H2O would be made .

A third solution of 13.5 grams of hexamine dinitrate in distilled H2O
would also be prepared .

My best guess as to how to proceed would be to adjust the pH
of the hydrazine nitrate solution with additional nitric acid
if required to pH 1 where the formation of R-Salt is favorable .
*(If the pH is too high then trinitrosopentamethylenetetramine formation
may occur , resulting in a different product for the reaction ,
which may be of interest for other experiments where that is desired. )
Adjust the volumes of the NaNO2 solution and the Hexamine Dinitrate
so they are equal and place each solution in a separate addition
funnel . Then do a simultaneous addition at equal drip rates
for the two cold solutions into the cold hydrazine nitrate solution
and see what happens .

If nothing drops out as a precipitate , I would store the mixture
in the cold for several days . I would test an aliquot to see if
any precipitate is produced from addition of lead nitrate .
And finally I would evaporate the water observing for crystals
and testing to see what isn't sodium nitrate . Perhaps also
extract the dry residue with alcohol or acetone , as well as
do flame and impact tests on the residue .

Aside from the polymer which we have speculated , it seems also
possible that the cyclic structure of the "cyclotrimethylene" group
could remain intact and result in something for which I would
have to check rules of nomenclature to accurately name , but
perhaps could be called , cyclotrimethyleneaminoazide ?
The formula would be as you mentioned above (-CH2-N(-N=N-NH2-)3
The possible existence of such a material is indeed very interesting .
This is the material I speculated could be crystalline , soluble ,
and acidic . So there are two chances there for a compound of
value , the cyclic compound , as well as a potential polymer .
You can bet this experiment has just risen to the top of my
"experiments to do" list :-) .

BTW , In reading some patents recently I came across a reference to
a compound which you mentioned in an earlier reply , hydrazine azide .
The brief reference described it as a soluble white crystalline material
stable at ordinary temperatures , but decomposing explosively at
even moderately elevated temperatures for example 100 degrees Centigrade .
Post by LOUIS
Post by Rosco P. Coaltrain
A similar reaction as using R-Salt may possibly occur by
mixing solutions of hexamine dinitrate , sodium nitrite ,
and hydrazine nitrate in correct proportions and with a
favorable pH adjusted with nitric acid or NaOH as needed .
In such a system the R-Salt could potentially form in situ
and then further react with the hydrazine , or the theoretical
polymer may possibly form directly from such a mixture .
I have never seen described such a "polymer" as we are
theorizing may exist . Since anything is possible for
a theoretical material , I would speculate that it could
even be a soluble crystalline material , and have acidic properties
and a series of associated salts , all of this being purely
theoretical of course . I promise that I am not being
cryptic , for if I had actually made such a material I would
freely declare it . My experiments are a work in progress
with conclusions not yet available . This idea is shared as
being a personal curiosity which may be of interest for parallel
experiments by others .
Rosco
Rosco P. Coaltrain
2004-01-19 20:46:53 UTC
Permalink
Post by LOUIS
Hexamine dinitrate and hydrazine nitrate will buffer the solution somehow as a mild acidic media :-).
pH will be between 5 and 7 :-).
First we need to see what happens with HN alone when admixed with NaNO2; then HDN with NaNO2.
Ph Z
Post by Rosco P. Coaltrain
A similar reaction as using R-Salt may possibly occur by
mixing solutions of hexamine dinitrate , sodium nitrite ,
and hydrazine nitrate in correct proportions and with a
favorable pH adjusted with nitric acid or NaOH as needed .
In such a system the R-Salt could potentially form in situ
and then further react with the hydrazine , or the theoretical
polymer may possibly form directly from such a mixture .
I have never seen described such a "polymer" as we are
theorizing may exist . Since anything is possible for
a theoretical material , I would speculate that it could
even be a soluble crystalline material , and have acidic properties
and a series of associated salts , all of this being purely
theoretical of course . I promise that I am not being
cryptic , for if I had actually made such a material I would
freely declare it . My experiments are a work in progress
with conclusions not yet available . This idea is shared as
being a personal curiosity which may be of interest for parallel
experiments by others .
Rosco
Thinking further about this , hexamine alone may serve
well as both a buffer for the pH and as an organic intermediate
or catalyst in the reaction where it is attempted to react
hydrazine nitrate with sodium nitrite to produce hydrazoic
acid and/or sodium azide . This could be of value aside
from any efforts at producing reactions involving a nitrosamine
in other ways .

While reading some other old patents , I have found that it is not
a new idea to use a nitrosamine for the azotization of hydrazine ,
and that at least one nitrosamine has been used successfully for
the production of sodium azide . Diphenyl nitrosamine has been
reacted with freebase hydrazine in methanolic sodium hydroxide
to produce sodium azide in 70 per cent yield . This was reported
by the 1913 German patent , DE273667 . Also there was a brief
reference to this German patent by a British patent GB170359 ,
which relates to cyanuric triazide , which may be produced
by reaction of cyanuric trihydrazide similarly with a nitrosamine ,
although no details are described . Since R-Salt has three nitroso
groups and is a non-volatile reagent , it could be a very good
nitrosation agent if it reacts as efficiently as is reported for
diphenylnitrosamine . A possible advantage of a nitrosamine is
certainly lower volatility and perhaps greater stability in
aqueous solution than organic nitrites .

It appears certain that a narrow pH range is going to apply to any
reaction where hydrazine is being azotized to hydrazoic acid ,
probably because the azide group is an unstable resonance ring ,
whose formation is a "delicate balance" easily prevented ,
and also easily disrupted once formed . The very instability
which makes azide compounds energetic materials , also establishes
a narrow range of conditions where their formation is possible .
It would seem also that because the azide group is a resonance
ring structure , that the chemistry and theory regarding its behavior
is more complex than the usual "ionic theory" as would generally apply
to inorganic compounds . The behavior of these hydrazine and azide
reactions is sensitive to conditions like the complex reactions
of organic ring compounds , more than it resembles the typical and
easily understood reactions for inorganic compounds .

Just when you believe you know inorganic chemistry very well ,
here comes hydrazine and inorganic "nitrogen ring" chemistry !

Rosco
Rosco P. Coaltrain
2004-02-04 18:25:04 UTC
Permalink
[SNIP]

The reply link for the message at the top of the thread is
returning a server error , so I am posting the text for the
patent which was the start of this discussion here .

GB128014 , Complete Specification ,
Improvements in and relating to the Production of Azides
application date: June 17 , 1918 No. 9952 / 18
complete accepted : June 17 , 1919

I , William Richard Hodgkinson , C.B.E. , of Ordnance College ,
Woolwich , London , S.E. 18 , Professor of Chemistry and Metallurgy ,
do hereby declare the nature of this invention and in what manner
the same is to be performed , to be particularly described and
ascertained in and by the following statement :

This invention relates to the production of azides .

The object of the invention is to provide a process of producing
azides from salts of hydrazine without the employment of
ethyl benzoate or the like , and the formation of benzoyl hydrazine .
According to the invention , salts of hydrazine are diazotised
by means of a suitable nitrite under such conditions that the
reaction mass is at no time so distinctly acid as to redden
litmus paper , but appears on the border line of acidity and
alkalinity . The conditions of acidity under which the reaction
is carried out according to the invention , are preferably
comparable with the conditions of acidity as indicated by
litmus paper , of , for instance a solution of boric acid .
Thus in accordance with the invention , the nitrite solution
is brought together with a salt of hydrazine in approximately
the proportions required on the basis of theory to diazotise
the hydrazine , under such conditions that the acidity never
exceeds the degree of acidity indicated above , and an
acidified salt of the metal of which the azide is required ,
is introduced into the mixture , or alternatively the mixture
is added to the solution of the salt of the metal .

For example , silver azide is formed by adding a neutral solution
of hydrazine sulphate and sodium nitrite in molecular proportions
to a solution of silver nitrate of a degree of acidity with
nitric acid enabling the conditions in regard to acidity
set forth above to be realised , while avoiding the precipitation
of silver sulphate . Thus,for example 130 grams of hydrazine sulphate
is converted to the neutral hydrazine ammonium sulphate , which is
more soluble in water than is the simple hydrazine sulphate ,
by the addition of ammonia solution , the mixture being made up
to about 500 ccs . To this solution contained in a vessel in which
it can be violently agitated , the calculated amount of sodium nitrite
dissolved in 500 ccs. of water is added slowly so that the temperature
does not rise much above 30 degrees Centigrade .

The reaction resulting in the formation of sodium azide may be
represented by the following equation :

N2H4-H-NH3-H-SO4 + NaNO2 -----> NH4HSO4 + NaN3 + 2 H2O

From this equation it will be seen that the solution would
become acid as the result of the reaction were it not for
the fact that sodium nitrite is never pure but is alkaline ,
the alkali in the nitrite ordinarily being sufficient to maintain
the solution on the border line of acidity and alkalinity ,
and addition of a small quantity of alkali being made
should such not be the case . The solution thus made contains
sodium azide , some unchanged reagents , and the by-products
of the reaction .

The sodium sulphate and sodium azide contained in the solution
may be separated by crystallisation but preferably the solution
is added gradually to an acidified solution of silver nitrate
produced by adding 1.0 cc. of 70% of nitric acid to 1000 ccs.
of a normal solution of silver nitrate which is violently agitated
during such adding , the temperature of the reaction mass being
prevented from rising much higher than 30 - 40 degrees Centigrade .
With adequate cooling and agitation the yield of silver azide may
be obtained equivalent to 85 % of the calculated possible amount .
Instead of adding the diazotised solution to the acidifed
silver nitrate solution , the latter may be added to the former .

When starting from hydrazine nitrate which is also an acid salt ,
a solution of ammonia should be added in order to form the
neutral hydrazine ammonium salt or , if desired ,
the neutral hydrazine sodium salt may be produced ,
the remaining steps of the process being then carried out
as above described .

In producing lead azide , a solution of a hydrazine salt
of an acid which will not result in the precipitation
of an insoluble lead salt of the acid in question ,
for instance hydrazine nitrate , is employed , and
the reaction mass in this case should be only just acid ,
as lead azide is particularly easily acted on by acids ,
while in producing silver azide the acidity of the
reaction mass may be greater in order to avoid the precipitation
of silver sulphate and agitation indicated in the foregoing example .

The azides produced in accordance with the invention are
usually amorphous , and in this state they are safer to handle
than when crystalline .

Having now particularly described and ascertained the nature
of my said invention and in what manner the same is to be performed ,
I declare that what I claim is :

1. The process of producing azides from salts of hydrazine
in which salts of hydrazine are diazotised by means of a
suitable nitrite under such conditions that the reaction mass
is at no time so distinctly acid as to redden litmus paper ,
but appears on the border line of acidity and alkalinity .

2. The process as claimed in Claim 1 in which the conditions
of acidity under which the reaction is carried out according
to the invention are preferably comparable with conditions
of acidity as indicated by litmus paper , of , for instance ,
a solution of boric acid .

3. The process of producing azides from salts of hydrazine ,
substantially as hereinbefore described .

Dated this 10th day of December , 1918
Rosco P. Coaltrain
2004-02-12 05:35:42 UTC
Permalink
The use of a buffer to control the pH within the narrow range
specified by Hodgkinsons patent process for azides has been
suggested . There may be benefit in using a simple acetate
or citrate buffer in experiments which may be done with the
Hodgkinson process . Provided below are a couple of links
for a handy online calculator , where you may find the
required composition for a buffer solution supplying the
desired pH and concentration of the buffer . The calculated
buffer solutions may alternately be formulated using an
adjusted amount of citric or acetic acid and substituting the
sodium hydroxide equivalent to achieve the same value buffer
solutions . This will simplify preparation if the sodium salts
of the acids are not on hand .


http://www.columbia.edu/~scb2001/tools/acetate/acetate.html


http://www.columbia.edu/~scb2001/tools/citric/cit.htm

Rosco P. Coaltrain
2003-12-15 10:52:04 UTC
Permalink
Post by LOUIS
AgN3 may be prepared by action of NH2-NH2.H2O on AgONO (silver
nitrite-almost unsoluble in water).
HN3 can be prepared by action of HONO on NH2-NH2; the usual procedure uses
nitrite esters of moderate volatility (isopropyl, n-butyl, isoamyl, ...)
wich free upon contact with water and NH2-NH2 continuously HONO.
NH2-NH2.HONO --> NH2-NH-N=O + H2O ----> HN3 + 2H2O
Other hydrazine related compounds react the same way...
NH2-NH-CO-NH2 + HONO --> NH2-NH-CO-NH2.2HONO -->
N3-CO-NH-NO --> N3-COOH + N2 --> HN3 + CO2 + N2
C6H5-NH-NH2 + HONO --> C6H5-N3 + 2H2O
For the buffer NaHCO3/H2CO3 is good too.
Post by Anonymous Sender
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .
It is my guess that a buffer or special technique , would be needed
to facilitate such reactions , Is that correct ? Does anyone know
this patent reaction , and if a buffer is used , which particular one ?
Perhaps sodium bisulfite may work for this purpose ?
GB128014
Salts of hydrazine are diazotized by means of a suitable nitrite, without
the use of ethyl benzoate or the like, the reaction mass being kept on
the border line between acidity and alkalinity. For example, hydrazine
sulphate is treated with sodium nitrite; the sodium azide produced,
without being separated, may be caused to react with silver nitrate for
the production of silver azide. When lead azide is to be prepared,
hydrazine nitrate may be used in place of the sulphate.
GB129152
An insoluble azide is produced by diazotizing a hydrazine salt in
practically neutral solution and in presence of a salt, such as silver
nitrate, adapted to produce the insoluble azide. The azide is then
treated with a solution of a salt such as sodium chloride to obtain the
desired azide and an insoluble silver salt. From the sodium azide, other
azides such as lead azide may be obtained by double decomposition in the
known manner.
Louis ,
Reactions which involve free hydrazine and nitrite esters are related ,
but involve different reactants and more difficult conditions than these
abstracts which describe using more common materials in aqueous solutions .
There is a similar , yet different mechanism for the reactions described
by the abstracts above , which use hydrazine sulfate as a reactant with
sodium ( nitrite ) in aqueous solution . I have tried several variations
of such a reaction to produce copper azide , using sodium acetate as
a buffer , and none of the experiments were successful . I also tried
sodium bicarbonate as a buffer without any improvement . If you
had success using sodium bicarbonate in solution in "soda water"
then maybe the "soda water" does the trick . Please share any details
of your experiments . I chose the copper compound because of the
solubility of the sulfate .
Have you ever tried to precipitate copper azide from a reaction mixture
of hydrazine sulfate and sodium( nitrite ) ? Did the reaction product
in the beaker fulfill the predicted reaction worked out on paper ?
Not in my own experiments does this work straightforwardly .
I fully expect that such reactions do require specific conditions
of temperature and pH and concentration of reactants , or a particular
buffer , and required many experiments for the inventors to work out
a useful method .
In COPAE there is mention of silver azide having been made by mixing
saturated solutions of silver nitrite and hydrazine sulfate and allowing
the mixture to stand in the cold for a short time . No specific ratios
or yield are given . The reaction is referenced to Angeli ( Italian ? )
the citation is Rend. acc. Lincei , [5] 2 , I , 599 ( 1893 )
So silver azide has been around for a hundred and ten years !
Davis goes on further to mention that free hydrazoic acid can be produced
in aqueous solution of hydrazine sulfate with potassium nitrite , but again
no reaction details are described . The reaction is referenced by Davis
to Dennstedt and Gohlich ( German or Swiss ? ) Chem.-Ztg. , 21 , 876 ( 1897 )
Probably the patent reactions are an evolution of data from those two
and perhaps other early sources . Do you have any specific information
about such reactions which involve hydrazine sulfate and alkaline nitrites
in an aqueous reaction medium ?
I would like to know more about the reaction condition details
involved in these interesting patents .
Rosco
Louis ,

Note above the two references in my reply were misspelled ,
sodium nitrate should correctly read "sodium nitrite" .
I did use sodium nitrite , not sodium nitrate , in
the experiments .

Rosco
Rosco P. Coaltrain
2003-12-15 06:01:11 UTC
Permalink
Post by LOUIS
AgN3 may be prepared by action of NH2-NH2.H2O on AgONO (silver
nitrite-almost unsoluble in water).
HN3 can be prepared by action of HONO on NH2-NH2; the usual procedure uses
nitrite esters of moderate volatility (isopropyl, n-butyl, isoamyl, ...)
wich free upon contact with water and NH2-NH2 continuously HONO.
NH2-NH2.HONO --> NH2-NH-N=O + H2O ----> HN3 + 2H2O
Other hydrazine related compounds react the same way...
NH2-NH-CO-NH2 + HONO --> NH2-NH-CO-NH2.2HONO -->
N3-CO-NH-NO --> N3-COOH + N2 --> HN3 + CO2 + N2
C6H5-NH-NH2 + HONO --> C6H5-N3 + 2H2O
For the buffer NaHCO3/H2CO3 is good too.
Post by Anonymous Sender
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .
It is my guess that a buffer or special technique , would be needed
to facilitate such reactions , Is that correct ? Does anyone know
this patent reaction , and if a buffer is used , which particular one ?
Perhaps sodium bisulfite may work for this purpose ?
GB128014
Salts of hydrazine are diazotized by means of a suitable nitrite, without
the use of ethyl benzoate or the like, the reaction mass being kept on
the border line between acidity and alkalinity. For example, hydrazine
sulphate is treated with sodium nitrite; the sodium azide produced,
without being separated, may be caused to react with silver nitrate for
the production of silver azide. When lead azide is to be prepared,
hydrazine nitrate may be used in place of the sulphate.
GB129152
An insoluble azide is produced by diazotizing a hydrazine salt in
practically neutral solution and in presence of a salt, such as silver
nitrate, adapted to produce the insoluble azide. The azide is then
treated with a solution of a salt such as sodium chloride to obtain the
desired azide and an insoluble silver salt. From the sodium azide, other
azides such as lead azide may be obtained by double decomposition in the
known manner.
Louis ,

Reactions which involve free hydrazine and nitrite esters are related ,
but involve different reactants and more difficult conditions than these
abstracts which describe using more common materials in aqueous solutions .

There is a similar , yet different mechanism for the reactions described
by the abstracts above , which use hydrazine sulfate as a reactant with
sodium nitrate in aqueous solution . I have tried several variations
of such a reaction to produce copper azide , using sodium acetate as
a buffer , and none of the experiments were successful . I also tried
sodium bicarbonate as a buffer without any improvement . If you
had success using sodium bicarbonate in solution in "soda water"
then maybe the "soda water" does the trick . Please share any details
of your experiments . I chose the copper compound because of the
solubility of the sulfate .

Have you ever tried to precipitate copper azide from a reaction mixture
of hydrazine sulfate and sodium nitrate ? Did the reaction product
in the beaker fulfill the predicted reaction worked out on paper ?
Not in my own experiments does this work straightforwardly .
I fully expect that such reactions do require specific conditions
of temperature and pH and concentration of reactants , or a particular
buffer , and required many experiments for the inventors to work out
a useful method .

In COPAE there is mention of silver azide having been made by mixing
saturated solutions of silver nitrite and hydrazine sulfate and allowing
the mixture to stand in the cold for a short time . No specific ratios
or yield are given . The reaction is referenced to Angeli ( Italian ? )
the citation is Rend. acc. Lincei , [5] 2 , I , 599 ( 1893 )
So silver azide has been around for a hundred and ten years !

Davis goes on further to mention that free hydrazoic acid can be produced
in aqueous solution of hydrazine sulfate with potassium nitrite , but again
no reaction details are described . The reaction is referenced by Davis
to Dennstedt and Gohlich ( German or Swiss ? ) Chem.-Ztg. , 21 , 876 ( 1897 )

Probably the patent reactions are an evolution of data from those two
and perhaps other early sources . Do you have any specific information
about such reactions which involve hydrazine sulfate and alkaline nitrites
in an aqueous reaction medium ?

I would like to know more about the reaction condition details
involved in these interesting patents .

Rosco
donald j haarmann
2003-12-15 17:34:19 UTC
Permalink
Post by Anonymous Sender
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .
[snip]

I would not in passing ..........

Escales & Strettbacher
Die Explosivistoffe: Initialexplosivstoffe
Verlag von Veit & Comp
Leipzig 1917


--
donald j haarmann — colophon
Rosco P. Coaltrain
2003-12-15 23:45:30 UTC
Permalink
Post by donald j haarmann
Post by Anonymous Sender
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .
[snip]
I would not in passing ..........
Why not ? This information is purely scientific .
Sodium azide is readily accessible by several
alternative routes and well published syntheses.
Are the patents sensitive by reason of copyright ,
and the nature of the thing patented irrelevant?
Post by donald j haarmann
Escales & Strettbacher
Die Explosivistoffe: Initialexplosivstoffe
Verlag von Veit & Comp
Leipzig 1917
Any relevant syntheses you may translate and share ?

An English translation of the book being available is unlikely .
But English patents are already written in English .

Rosco
stkolev
2003-12-16 15:45:24 UTC
Permalink
What is the speed of the H2N-NH2.HONO "decomposition" into azide.
Rosco P. Coaltrain
2003-12-17 22:01:03 UTC
Permalink
Post by stkolev
What is the speed of the H2N-NH2.HONO "decomposition" into azide.
Theoretical species may exist for any length of time which theory is
pleased to assign , however in the real world , compounds which exist
for no longer than zero seconds under ordinary conditions ,
have an equally brief half-life .

Rosco
Peter Prucker
2003-12-28 22:41:39 UTC
Permalink
Post by donald j haarmann
Post by Anonymous Sender
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .
[snip]
I would not in passing ..........
Escales & Strettbacher
Die Explosivistoffe: Initialexplosivstoffe
Verlag von Veit & Comp
Leipzig 1917
Most volumes of the Escales-books are reprinted now in Germany. This on
too.

Selled also by Amazon.

Greetings
P.Prucker
my_2¢
2003-12-30 18:06:02 UTC
Permalink
I read German but most fellows here do not. English version of the
book available?




On Sun, 28 Dec 2003 23:41:39 +0100, Peter Prucker
Post by Peter Prucker
Post by donald j haarmann
Post by Anonymous Sender
The freely accesible full texts for patents only
go back to 1920 , so I can provide only the abstracts
for these two very old patents . If anyone should
have access to full texts for these patents , please
share them .
[snip]
I would not in passing ..........
Escales & Strettbacher
Die Explosivistoffe: Initialexplosivstoffe
Verlag von Veit & Comp
Leipzig 1917
Most volumes of the Escales-books are reprinted now in Germany. This on
too.
Selled also by Amazon.
Greetings
P.Prucker
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donald j haarmann
2003-12-30 20:52:43 UTC
Permalink
Not that I know of.


--
donald j haarmann - independently dubious
Post by my_2¢
I read German but most fellows here do not. English version of the
book available?
Post by Peter Prucker
Post by donald j haarmann
Escales & Strettbacher
Die Explosivistoffe: Initialexplosivstoffe
Verlag von Veit & Comp
Leipzig 1917
Most volumes of the Escales-books are reprinted now in Germany. This on
too.
Selled also by Amazon.
Greetings
P.Prucker
donald j haarmann
2003-12-19 22:48:13 UTC
Permalink
"Anonymous Sender" <***@remailer.metacolo.com>

NB

Safety—
What can go wrong?!!
What happens IF something goes wrong!!!

Cupric acid wet is a sensitive as when dry!!

There are 6 (?) "copper azides" including "brass azide"!

Lead azide exists as one of 3 polymorphs.

Even in the best run plants (Waltham Abbey) a batch goes KAFUCKINGBOOM for unknown reasons.
I am 4 hr from my library an cannot supply details at this instant.

(My reactor is being upgraded and I cannot use my quantum transporter. Last time I tried
to power it from the commercial grid ........ August 14.....!!!)

Hydrazine &c. are used to make Na azide.

--------------
Library?

Azides and Nitrenes: Reactivity and Utility
by Eric F.V. Scriven (Editor)


Supplement D2: The Chemistry of Halides, Pseudo-Halides and Azides, Pt. 1 & 2
by Saul Patai, Zvi Rappoport



List Price: $1,395.00
Price: $1,395.00



I got a really good price one of these volumes, I don't remember which one! When the FBI get done
reading it (they read all my mail) I'll let you know if it is of use.


-----------
Chloride of azote (Chlorine azide)

Nitrogen chloride is considered to be one of the most dangerous bodies to
handle, owing to the facility with which it explodes, by shock, friction, or contact
with various bodies.

M. Berthelot 1892


Nitrogen trichloride was discovered by my good friend, physician and professor
of physics at the École Polytechnique Pierre Louis Dulong. I first meet him at
Berthollet's home at Arcueil just south of Paris, where Berthollet had settled
following his return from Napoleon's abortive Egyptian campaign. All the greats
meet their; Berthollet's neighbour Laplace, Arago, Bérand, Biot, Amédée
Berthollet (Claude's son), Chaptal, Collet-Desostils, de Candolle, Gay-Lussac,
Humboldt, Malus, Poisson and Thernard. Napoleon showed his approval of our
meetings by allowing the use of the title "Société d'Arcueil" for our gatherings.

Pierre D. first published notice of his discovery in Schweigger's J. Chem. Pharm.
8, 32 (1812). Shortly there after he lost and eye and three fingers when a sample
exploded in his laboratory!! Indeed, our mutual friend Humphrey Davy was also
severely injured although happily not maimed by an unexpected explosion of a
small quantity of Pierre's "une nouvelle substance detonnante". [Later Gay-
Lussac and Thernard suffered from inhaling hydrogen fluoride fumes.]

"The preparation and handling of this compound requires the greatest care.
Every vessel employed must be washed by alkali-lye in order to free it from
grease; even grease from the fingers may cause an explosion. The substance
[yellow oily liquid] is very liable to spontaneous explosion, and thick gloves, and a
face shield are indispensable." It is also possible to cause it to explode by
exposure to strong sun light or the light of a magnesium flame!

------------
Explosion of detonator composition ; Circumstances attending an——-which
occurred at the factory of Messrs. Kynoch, Ltd., at Holford Mills, near
Birmingham, Staffs, on July 29, 1913. Major T. H. Crozier, H.M. Inspector of
Explosives. (Cd. 7090.1


Tim first explosion appears to have occurred at the priming machine, and was
probably caused by some action of the workwoman in connection with this
apparatus. It was possible, that a small quantity of fulminate composition might
have adhered to the underside of the plate, or the guides for the block, and that it
might have been fired by the action of sliding the block into position. The camel's
hair brush used for spreading the composition over the tray was a flat one with a
light wooden handle. The metal socket holding the hair was bound round
carefully with indiarubber tape, and the brush had been in use nearly a fortnight.
It was perhaps possible that a blow from the wooden handle might be sufficient
to explode a thin film of fulminate composition. The second explosion was
caused by the first, which shook down the cement lining, bringing with it a
cupboard containing a bowl of fulminate composition, and this bowl exploded on,
or near, the floor below the position of the cupboard. The inspector considers
that the explosion was entirely accidental and that no blame could be attached to
any person in connection with it. Work was proceeding in a regular manner and
the only suggestion made is that the brush employed for spreading the
composition on the tray of the priming machine should have sonic form of handle
other than wood. A handle either of buff leather or indiarubber would be
preferable-C. W. McD.


----------
The Dance of Death

Two girl employees of an explosive factory in Westquater were engaged in
carrying a box containing detonating caps and priming composition for
same form the magazine into the workroom. They set the box on the ground
and began to dance together. One of the girls stumbled and turned over the
box of explosives, which caused the explosion of the whole load, and both
girls were blown to pieces.

J. Phillips, The Handling of Dangerous Goods, 249; 1896
In:— H Brunswig "Explosives" John Wiley & Sons
New York 1912

-------
Explosion of Fulminate Composition ; Circumstances attending an—--, at the
Factory of the Blenheim Engineering Co., Ltd., at Tunnel Lane, Greenwich
Marshes, on Dec. 18, 1903. By Major A. Cooper-Key, H.M. Inspector of
Explosives.

The explosion, which seriously injured a workwoman, took place during the filling
of tubes with a composition of potassium chlorate. antimony sulphide, and
amorphous phosphorus, and was undoubtedly due to the friction caused by the
wooden rammer which fitted too tightly. The explosion was communicated to
some 3 to 4 oz. of composition lying on the table, and this caused the chief
damage.—G. W. McD.



--------
" On one occasion a small quantify of an ethereal solution of nitroglycerin as
allowed to evaporate in a glass dish. The residue of nitroglycerin was certainly
not more than 2 or 3 centigrams. On heating the dish over a spirit lamp a most
violent explosion resulted, and the dish was broken to atoms. On another
occasion a drop contained in a test tube was being heated when it detonated
with great violence, and pieces of glass cut my face and hands severely and also
injured others standing some distance away in the room."

Ascanio Sobrero "Some New Fulminating Products Obtained by the Action of
Nitric Acid on some Vegetable Organic Substances." Torino. Mem. Acad. (1847),
195-203. In:— GW McDonald "Historical Papers on Modern Explosives." Whittaker
& Co. 1912


----------
CHAPTER I

HOWARD'S DISCOVERY OF FULMINATE OF MERCURY (1800)

[snip]


With this view he mixed such substances with alcohol and nitric acid, as he thought
might, by predisposing affinity, favour, as well as attract an acid combination of the
hydrogen of the one to the oxygen of the other. The pure red oxide of mercury
appeared suitable for this purpose. It was, therefore, intermixed with alcohol, and upon
both nitric acid was affused. The acid did not act upon the alcohol so immediately as
when these fluids are alone mixed together, but first gradually dissolved the oxide. After
some minutes had elapsed a smell of ether was perceptible and a white dense smoke
was emitted with ebullition. A dark-coloured precipitate was thrown down which, by
degrees, became nearly white. The precipitate was separated by filtration aid consisted
of small acicular crystals having a saline taste. Finding that a part of the mercury was
volatilized in the white fumes, Howard states that he was not altogether without hope
that muriatic acid had been formed, and united to the oxide of mercury. He, therefore,
for obvious reasons, poured sulphuric acid upon the dry crystalline mass. A violent
effervescence ensued, and, to his great astonishment, an explosion took place. The
singularity of this explosion induced him to repeat the process several times, and,
finding that he always obtained the same kind of powder, he prepared a considerable
quantity of it. He gives the following method as the most satisfactory for the preparation
of fulminate of mercury:— [xxxxxxxx] He once poured six drams of concentrated sulphuric
acid on fifty grains of
fulminate. An explosion took place, almost at the instant of contact. He states that lie
was wounded severely and most of his apparatus was destroyed, and then adds, "I
must confess I feel more disposed to prosecute other chemical subjects."


[snip]

A gunpowder proof barrel holding eleven grains of fine gunpowder was filled with
fulminate, and fired with a flint and steel. The report was sharp but not loud. The person
who held the proof barrel in his hand felt no recoil, but the explosion laid open the upper
part of the barrel nearly from touch-hole to muzzle, and struck off the hand of the re-
gister. A gun holding 68 grains of gunpowder was charged with 34 grains of fulminate
and fired from the shoulder. The breech was torn open, the touch-hole driven out and
the barrel split. Two blocks of wood of the same size were bored to the same depth.
One was charged with half an ounce of best Dartford gunpowder; the other with half an
ounce of fulminate. Both blocks of wood were buried in sand and the explosives were
fired by a train. The block containing the gunpowder simply burst into three pieces, and
had its parts fairly separated. That charged with fulminate burst in every direction and
the parts immediately contiguous to the fulminate were absolutely powdered. Yet the
whole hung together; in short, fulminate acted with the greatest energy, but only within
certain limits.

[snip]



HISTORICAL PAPERS ON MODERN EXPLOSIVES
By
George W. MacDonald, M.Sc. (Melb.)
(Head Of Research, Messrs Curtis's & Harvey, Ltd.
Former 1851 Exhibition Scholar, The University Of Melbourne.)
With An Introduction By
Sir Andrew Noble, Bart., K.C.B., F.R.S.
Whittaker & Co.,
2 White Hart Street, Paternoster Square. London, E.C.
And 64-66 Fifth Avenue, New York.
1912


&c., &c.


donald j haarmann
----------------------
Coalbunny
2003-12-20 01:26:04 UTC
Permalink
On Fri, 19 Dec 2003 22:48:13 GMT, "donald j haarmann"
Post by donald j haarmann
--------------
Library?
Azides and Nitrenes: Reactivity and Utility by Eric F.V. Scriven (Editor)
Supplement D2: The Chemistry of Halides, Pseudo-Halides and Azides, Pt. 1 & 2 by Saul Patai, Zvi Rappoport
List Price: $1,395.00
Price: $1,395.00
I got a really good price one of these volumes, I don't remember which one! When the FBI get done
reading it (they read all my mail) I'll let you know if it is of use.
Never can keep you out of trouble, can we? :)
Carl

--
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my_2¢
2003-12-22 17:10:32 UTC
Permalink
If you get a chance please see my post on "DESIGNER EXPLOSIVES"...the
patents therein delved into azo-clathrates which have a yield of 100%
and better. They just may be one of the most efficient azide
explosives/propellents developed in the 20th century. The patents now
belong to private firms but they were originated with a joint NATO
effort (I was told).
Ag azide has been used often in the past in very expensive detonation
devices and I had been informed that it's stability (outside of UV
sensitivity) is great. Apparently it has more sensitivity than Pb, not
requiring a styphnate to initiate (not that LA NEEDS a styphnate but
it seems that detonators in the past have incorporated that into their
train for effeciency).


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Rosco P. Coaltrain
2003-12-22 23:16:32 UTC
Permalink
Post by my_2¢
If you get a chance please see my post on "DESIGNER EXPLOSIVES"...the
patents therein delved into azo-clathrates which have a yield of 100%
and better. They just may be one of the most efficient azide
explosives/propellents developed in the 20th century. The patents now
belong to private firms but they were originated with a joint NATO
effort (I was told).
Ag azide has been used often in the past in very expensive detonation
devices and I had been informed that it's stability (outside of UV
sensitivity) is great. Apparently it has more sensitivity than Pb, not
requiring a styphnate to initiate (not that LA NEEDS a styphnate but
it seems that detonators in the past have incorporated that into their
train for effeciency).
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Yes , I saw your earlier post but I think many people
are probably unfamiliar with that advanced class
of exceptional primary explosives . To call those
azide containing clathrate compounds "designer explosives"
is very appropriate , because they are exactly that ,
"designed" according to certain specific molecular formulas
which are unique compositions of matter and have a very specific
and consistent crystalline form , very stable and predictable
in their performance . Those "azo-clathrates" are indeed
a beauty of simplicity and efficiency and performance ,
one of the more elegant examples of the many things developed
in the art of explosives technology , I fully agree .
I read about those compounds at the page linked below
and the results of my own experiments with that class
of compounds is consistent with the observations made
by the anonymous author of that *interesting* and
informative thread .

http://www.sciencemadness.org/talk/viewthread.php?tid=501

Actually , I have been accused of occasional attempts at poetry :)
but chemistry is more my forte .

Rosco
my_2¢
2003-12-28 12:59:08 UTC
Permalink
Neat link....I guess I am "old-hat" and the whole deal has been out in
the public domain for awhile now.
I read the whole topic at the link you posted and the folks who were
interested in it sounded like they didn't understand "Mr. Anonymous"
fully. He was speaking of yield potential and from that perspective
the AZO-CLATHRATES are quite unique. I have no idea if they are used
today in the commercial field or military. But compared with history
and the original fulminating compounds I suppose a corporation gets
"more bang for it's buck" with the clathrates. (sorry....that was bad)
Post by Rosco P. Coaltrain
Yes , I saw your earlier post but I think many people
are probably unfamiliar with that advanced class
of exceptional primary explosives . To call those
azide containing clathrate compounds "designer explosives"
is very appropriate , because they are exactly that ,
"designed" according to certain specific molecular formulas
which are unique compositions of matter and have a very specific
and consistent crystalline form , very stable and predictable
in their performance . Those "azo-clathrates" are indeed
a beauty of simplicity and efficiency and performance ,
one of the more elegant examples of the many things developed
in the art of explosives technology , I fully agree .
I read about those compounds at the page linked below
and the results of my own experiments with that class
of compounds is consistent with the observations made
by the anonymous author of that *interesting* and
informative thread .
http://www.sciencemadness.org/talk/viewthread.php?tid=501
Actually , I have been accused of occasional attempts at poetry :)
but chemistry is more my forte .
Rosco
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Rosco P. Coaltrain
2003-12-28 20:20:41 UTC
Permalink
Post by my_2¢
Neat link....I guess I am "old-hat" and the whole deal has been out in
the public domain for awhile now.
I am "old school" and "old hat" myself when it comes to chemistry .
Chemistry is one area where it is often possible to
"teach an old dog new tricks" :)
Post by my_2¢
I read the whole topic at the link you posted and the folks who were
interested in it sounded like they didn't understand "Mr. Anonymous"
fully. He was speaking of yield potential and from that perspective
the AZO-CLATHRATES are quite unique. I have no idea if they are used
today in the commercial field or military. But compared with history
and the original fulminating compounds I suppose a corporation gets
"more bang for it's buck" with the clathrates. (sorry....that was bad)
Someone performed an independent verification regarding that
4/12 azo-clathrate compound and posted a picture of the product .
Here's the link .

Loading Image...

You may have to open a second browser and copy and paste
the URL , because geocities often blocks hyperlinks .

Anyway , the proof is in the pudding ,
or in this case , in the weighing beaker .

That particular synthesis is not in the books ,
and the material itself surpasses many things which
are in the books and more well known .

To go beyond the azo-clathrates to anything comparable
or better , would involve modified triazole or tetrazole compounds ,
possibly with some variants involved in analogous
clathrate or multiple salt complexes .

( P.S. I tried to post this reply earlier and got a server error ,
with no message confirmation , so please forgive me
if an unintended double post occurs . I would have to wait
six hours to see for certain if the earlier post went through )

Rosco

[snipped]
my_2¢
2003-12-30 17:55:01 UTC
Permalink
On 28 Dec 2003 12:20:41 -0800, ***@yahoo.com (Rosco P.
Coaltrain) wrote:

I saw the picture...exactly what I figured...orange finely divided
"powder"..... as the Pb used would be red oxide.

I wonder if you know anything about this...

If metal azides are manufactured at certain temps a "powder" of fine
crystals develops but there can be a formation of needle crystals (not
disirable)....why and what are the temp differers? I have read patents
that insist on low temps (5c, etc) for formation: would an elevation
in temp affect the "needle" shape?


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Rosco P. Coaltrain
2003-12-31 01:13:41 UTC
Permalink
Post by my_2¢
I saw the picture...exactly what I figured...orange finely divided
"powder"..... as the Pb used would be red oxide.
It looks like a powder but actually it is fine crystals ,
very evident in sunlight , moreso when wet , or under
a microscope. The orange coloration is from the
basic lead picrate matrix component .

The material is more like a very fine and dense "hourglass sand"
than being a powder . It is distinctly microcrystalline and I am
not certain the name for the crystal form , but it is a parallelogram
shaped solid . The best way I can describe it is if you had a
cube shaped frame of rods whose ends were fitted with movable
ball joints forming the corners of the cube , so that you could
tilt the framework out of square . And you moved front plane
of the cube to one side , and then pushed the top horizontal
part the framework away from you , so the cube was moved
out of square two different ways , resulting in all six
face planes being a parallelogram . This shape is plainly evident
at fifty or more diameters magnification .

The crystal size is definitely influenced by temperature ,
concentration of the solutions brought into reaction ,
efficiency of agitation , time duration of reaction and
rate of additions , and the tempering or finishing time
when the mixture is stirred while it slowly cools .
Crystalsmithing is an art governed by known factors
that apply to these materials just like is general
for other crystalizations . The conditions can be varied
to get uniform crystals across a range of sizes and
bulk densities . The control of crystal development
is actually implemented inherently to a certain extent
for the azo-clathrates by virtue of the manner in
which they are made . Dilutions , times and temperatures
could be increased to obtain a more coarse material
if it was desired for some reason like for impact primers .
But the material useful for detonator primaries is obtained
directly from that method as described by Mr. Anonymous .
Post by my_2¢
I wonder if you know anything about this...
If metal azides are manufactured at certain temps a "powder" of fine
crystals develops but there can be a formation of needle crystals (not
disirable)....why and what are the temp differers? I have read patents
that insist on low temps (5c, etc) for formation: would an elevation
in temp affect the "needle" shape?
There are reaction strategies possible where the
composition of the reaction mixture remains constant
for the first crystal to precipitate , to the
last one formed , so that the product is very uniform
in granulation . I have succesfully done that for lead
azide , but it is an unpublished method so far as I know.
There are patents relating to control of crystal size
by another similar method for lead azide .
Two good pertinent patents for you to see are GB160953
and US1914530 .

Rosco
my_2¢
2004-01-05 21:31:02 UTC
Permalink
Thanks for the tip on the patents...nice stuff there... and I like the
term "crystalsmithing" - I'm going to make that one mine. Sounds like
exactly what takes place.

have a Happy New Year (Jan 22) - fat choi !


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donald j haarmann
2003-12-26 19:41:56 UTC
Permalink
Well....... looking in my recently arrived copy of:—

HD Fair and RF Walker Ed's.
Energetic Materials - 1
Physics and Chemistry of the Inorganic Azides
Plenum Press New York 1977

I find that using the Thiele Process (hydrazine &c.) [J Thiele, Ber. Dtch. Chem. Ges., 2681 (1908)]
the following azides have been produced:

Li - Na - K - Ba - Ag (1893!)

------------
".....the following combinations have been used to successfully used for azide syntheses
a + b, a + e, b + b, b +c, b + g, and b + i.

a/ NH3

b/ NH2
|
NH2

c/ NH3
|
OH

d/ N2

e/ N2O

f/ NO

g/ N2O3

(NHO2)

h/ NO2

i/ N2O5

(NHO3)

--------------
Speaking of Mg azide.

"When obtained as long crystal needles, the same azide explodes at the slighest provocation.
A large particle, slowly sinking in a water-filled beaker, was seen to explode when touching the bottom."

----------
You might want to try you hand at radium azide or which little is known. All the alpha particles should do
something!

--------
To impress your friends you can grow Pb azide xtls 5 X 5 X 10mm!



--
donald j haarmann — colophon
Rosco P. Coaltrain
2003-12-28 16:37:23 UTC
Permalink
Well....... looking in my recently arrived copy of:?
HD Fair and RF Walker Ed's.
Energetic Materials - 1
Physics and Chemistry of the Inorganic Azides
Plenum Press New York 1977
I find that using the Thiele Process (hydrazine &c.) [J Thiele, Ber. Dtch. Chem. Ges., 2681 (1908)]
( hydrazine &c. ) What is the unabbreviated expression for
that name reaction which you are referencing ?
Li - Na - K - Ba - Ag (1893!)
------------
".....the following combinations have been used to successfully used for azide syntheses
a + b, a + e, b + b, b +c, b + g, and b + i.
a/ NH3
b/ NH2
|
NH2
c/ NH3
|
OH
d/ N2
e/ N2O
f/ NO
g/ N2O3
(NHO2)
h/ NO2
i/ N2O5
(NHO3)
--------------
Speaking of Mg azide.
"When obtained as long crystal needles, the same azide explodes at the slighest provocation.
A large particle, slowly sinking in a water-filled beaker, was seen to explode when touching the bottom."
----------
You might want to try you hand at radium azide or which little is known. All the alpha particles should do
something!
--------
To impress your friends you can grow Pb azide xtls 5 X 5 X 10mm!
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .

Rosco
donald j haarmann
2003-12-29 01:32:04 UTC
Permalink
Post by Rosco P. Coaltrain
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .
Rosco
---------
You want someone with "hands on" experience with a process that hasn't been
used in over a hundred years!!? You a funny person. Snick-snicker, tee-hee, chortle,
guffaw!
--
donald j haarmann - colophon
Rosco P. Coaltrain
2003-12-29 07:53:43 UTC
Permalink
Post by donald j haarmann
Post by Rosco P. Coaltrain
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .
Rosco
---------
You want someone with "hands on" experience with a process that hasn't been
used in over a hundred years!!? You a funny person. Snick-snicker, tee-hee, chortle,
guffaw!
That's not what I said , but ridicule has been
your style in this thread so why change the trend .

Go imagine you know anything about the synthesis which
has been attempted to be discussed here , and be content with
your illusion you do . But don't try to play cryptic
librarian with general non-specific references to various
books that you submit have answers , without even a
summary of the pertinent reference , chapter and verse
you are citing which refer to the two patents unequivocally .

One of the requiremnents for patents is that the thing
being patented must be novel and not something already
well known in the art , and since some references you
have mentioned predate the British patents by several
years , it would seem extremely doubtful that such a
reference would cover the same matter and be pertinent .
It only makes sense that something of value and significance
was probably discovered which led to the filing and issuance of
those patents . And I see no way you can get around that probable
fact , and attempt to discount those patents significance by
reciting all sorts of references which do not specifically
mention the technology involved in those two patents .
Is that too complicated for you to understand ?

Any more good jokes about crystal gardens and such ?

Rosco
Pyro Doug
2003-12-29 11:21:35 UTC
Permalink
I think you missed Don haarmann's point, And as him having his own
illusion most likely would be true, and I for one wouldn't follow the
worm down the same hole, remember 100 years ago there were stupid men
that didn't live past there own experiments! Any information gained from
a 100 year old patent would be filled with several dangerous
possiblities that we now know today as lutacrist, I think he was just
playing you like a fiddle. No need to take everything so personal.

PD
Post by Rosco P. Coaltrain
Post by donald j haarmann
Post by Rosco P. Coaltrain
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .
Rosco
---------
You want someone with "hands on" experience with a process that hasn't been
used in over a hundred years!!? You a funny person. Snick-snicker, tee-hee, chortle,
guffaw!
That's not what I said , but ridicule has been
your style in this thread so why change the trend .
Go imagine you know anything about the synthesis which
has been attempted to be discussed here , and be content with
your illusion you do . But don't try to play cryptic
librarian with general non-specific references to various
books that you submit have answers , without even a
summary of the pertinent reference , chapter and verse
you are citing which refer to the two patents unequivocally .
One of the requiremnents for patents is that the thing
being patented must be novel and not something already
well known in the art , and since some references you
have mentioned predate the British patents by several
years , it would seem extremely doubtful that such a
reference would cover the same matter and be pertinent .
It only makes sense that something of value and significance
was probably discovered which led to the filing and issuance of
those patents . And I see no way you can get around that probable
fact , and attempt to discount those patents significance by
reciting all sorts of references which do not specifically
mention the technology involved in those two patents .
Is that too complicated for you to understand ?
Any more good jokes about crystal gardens and such ?
Rosco
Rosco P. Coaltrain
2003-12-29 14:50:50 UTC
Permalink
Post by Pyro Doug
I think you missed Don haarmann's point,
Oh , I got haarmanns meaning very clearly early in this thread .
Read the tone of haarmanns replies throughout this thread
and it doesn't require much depth of discerning to peg
a "pretended expert" having fun with someone he underestimates
as being an easy mark for such foolishness .
Post by Pyro Doug
And as him having his own illusion most likely would be true,
You got that right .
Post by Pyro Doug
and I for one wouldn't follow the worm down the same hole,
Yeah , a rabbit hole is no place to dive for pearls , when
rabbit pills is as close as you will find at the bottom of things .
Post by Pyro Doug
remember 100 years ago there were stupid men
that didn't live past there own experiments!
But also some very smart men too . And even the most brilliant men
are fallable and mortal . Whether that is one of the Wright brothers ,
a hundred years ago , or the seven who went down with Columbia last February .
Post by Pyro Doug
Any information gained from
a 100 year old patent would be filled with several dangerous
possiblities that we now know today as lutacrist, I think he was just
playing you like a fiddle. No need to take everything so personal.
If an engineer gets into a brawl with a philosopher , put your
money on the engineer :) .

I must say that I have never seen so legitimate a technical topic
posted in this group get such shabby treatment from a bunch of
stuffy academics and theoreticians who frankly don't know what they
are talking about .

Gerald Hurst , where are you !

A technician has been marooned upon an island teeming with philosophers !
Or are they only fiddler crabs :)

Rosco
Rosco P. Coaltrain
2003-12-29 14:53:22 UTC
Permalink
Post by Pyro Doug
I think you missed Don haarmann's point,
Oh , I got haarmanns meaning very clearly early in this thread .
Read the tone of haarmanns replies throughout this thread
and it doesn't require much depth of discerning to peg
a "pretended expert" having fun with someone he underestimates
as being an easy mark for such foolishness .
Post by Pyro Doug
And as him having his own illusion most likely would be true,
You got that right .
Post by Pyro Doug
and I for one wouldn't follow the worm down the same hole,
Yeah , a rabbit hole is no place to dive for pearls , when
rabbit pills is as close as you will find at the bottom of things .
Post by Pyro Doug
remember 100 years ago there were stupid men
that didn't live past there own experiments!
But also some very smart men too . And even the most brilliant men
are fallable and mortal . Whether that is one of the Wright brothers ,
a hundred years ago , or the seven who went down with Columbia last February .
Post by Pyro Doug
Any information gained from
a 100 year old patent would be filled with several dangerous
possiblities that we now know today as lutacrist, I think he was just
playing you like a fiddle. No need to take everything so personal.
If an engineer gets into a brawl with a philosopher , put your
money on the engineer :) .

I must say that I have never seen so legitimate a technical topic
posted in this group get such shabby treatment from a bunch of
stuffy academics and theoreticians who frankly don't know what they
are talking about .

Gerald Hurst , where are you !

A technician has been marooned upon an island teeming with philosophers !
Or are they only fiddler crabs :)

Rosco
Don T
2003-12-29 04:11:41 UTC
Permalink
Actually it would be much LESS impressive that some foolish person decided
that just because *some* things found in *some* "authoritative texts" are
found to be "untrue" ( more likely those things were TRUE given the state of
the art at the time the experiment were conducted ) that it therefore
follows that ALL things found in ALL "authoritative texts" and re-does all
those experiments, true or not. Advancements can only come by assimilating
facts and then using those facts to pursue other facts. If you know a thing
to be true you are wasting your, and everybody else's, time to do the
experiment which proves the thing to be true. That is exactly what makes
"authoritative texts" so useful. They keep you from following the same worm
down the same hole to the same dead end. "Facts don't cease to exist because
they are ignored": Aldous Huxley
--
Don Thompson

"The bravest are surely those who have the clearest vision of what is before
them, glory and danger alike, and notwithstanding go out to meet it."-
Thucydides

"Men are never really willing to die except for the sake of Freedom:
Therefore they do not believe in dying completely."-
Albert Camus
Post by Rosco P. Coaltrain
Well....... looking in my recently arrived copy of:?
HD Fair and RF Walker Ed's.
Energetic Materials - 1
Physics and Chemistry of the Inorganic Azides
Plenum Press New York 1977
I find that using the Thiele Process (hydrazine &c.) [J Thiele, Ber.
Dtch. Chem. Ges., 2681 (1908)]
Post by Rosco P. Coaltrain
( hydrazine &c. ) What is the unabbreviated expression for
that name reaction which you are referencing ?
Li - Na - K - Ba - Ag (1893!)
------------
".....the following combinations have been used to successfully used for azide syntheses
a + b, a + e, b + b, b +c, b + g, and b + i.
a/ NH3
b/ NH2
|
NH2
c/ NH3
|
OH
d/ N2
e/ N2O
f/ NO
g/ N2O3
(NHO2)
h/ NO2
i/ N2O5
(NHO3)
--------------
Speaking of Mg azide.
"When obtained as long crystal needles, the same azide explodes at the
slighest provocation.
Post by Rosco P. Coaltrain
A large particle, slowly sinking in a water-filled beaker, was seen to
explode when touching the bottom."
Post by Rosco P. Coaltrain
----------
You might want to try you hand at radium azide or which little is known.
All the alpha particles should do
Post by Rosco P. Coaltrain
something!
--------
To impress your friends you can grow Pb azide xtls 5 X 5 X 10mm!
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .
Rosco
Rosco P. Coaltrain
2003-12-29 15:44:03 UTC
Permalink
Post by Don T
Actually it would be much LESS impressive that some foolish person decided
that just because *some* things found in *some* "authoritative texts" are
found to be "untrue" ( more likely those things were TRUE given the state of
the art at the time the experiment were conducted ) that it therefore
follows that ALL things found in ALL "authoritative texts" and re-does all
those experiments, true or not. Advancements can only come by assimilating
facts and then using those facts to pursue other facts. If you know a thing
to be true you are wasting your, and everybody else's, time to do the
experiment which proves the thing to be true. That is exactly what makes
"authoritative texts" so useful. They keep you from following the same worm
down the same hole to the same dead end. "Facts don't cease to exist because
they are ignored": Aldous Huxley
--
Don Thompson
There is no parallel there with what I said , except as a farcical
rewritten rendition . I never said that the wheel must be reinvented .
Nor have I said that all things known must be continually rediscovered
and reproven . You are attributing generalizations which I have not
made . I think the biggest problem for many egos which inhabit this
group resides in those most difficult to utter of all words .....

I DO NOT KNOW .

But I for one can say that without any feeling of inadequacy , and
without needing to pretend having knowledge that is not yet mine
to impress anyone with how smart I must be .

This *is* an engineering news group , correct?

A thread like this has started with a very specific technical topic
that should get somewhere with technical disclosure , not deteriorate
into a philosophical debate by those struggling with the reality
they haven't an understanding of the technology .

The driving force behind my own curiosity concerning those patents
at the top of this thread , is a sneaking suspicion that they are
*not* valid , and that is precisely what intrigues me about them .
They are either "vanity patents" or they disclose an obscure and
interesting reaction which is confounding to me . So my curiosity
about what is the story concerning those patents is quite legitimate .

It is not a waste of time to put such things to the test and
confirm or disprove the matter to give it closure . That is
the whole nature of experimentation .



[snip]
Post by Don T
Post by Rosco P. Coaltrain
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .
Rosco
Rosco P. Coaltrain
2003-12-29 15:45:50 UTC
Permalink
Post by Don T
Actually it would be much LESS impressive that some foolish person decided
that just because *some* things found in *some* "authoritative texts" are
found to be "untrue" ( more likely those things were TRUE given the state of
the art at the time the experiment were conducted ) that it therefore
follows that ALL things found in ALL "authoritative texts" and re-does all
those experiments, true or not. Advancements can only come by assimilating
facts and then using those facts to pursue other facts. If you know a thing
to be true you are wasting your, and everybody else's, time to do the
experiment which proves the thing to be true. That is exactly what makes
"authoritative texts" so useful. They keep you from following the same worm
down the same hole to the same dead end. "Facts don't cease to exist because
they are ignored": Aldous Huxley
--
Don Thompson
There is no parallel there with what I said , except as a farcical
rewritten rendition . I never said that the wheel must be reinvented .
Nor have I said that all things known must be continually rediscovered
and reproven . You are attributing generalizations which I have not
made . I think the biggest problem for many egos which inhabit this
group resides in those most difficult to utter of all words .....

I DO NOT KNOW .

But I for one can say that without any feeling of inadequacy , and
without needing to pretend having knowledge that is not yet mine
to impress anyone with how smart I must be .

This *is* an engineering news group , correct?

A thread like this has started with a very specific technical topic
that should get somewhere with technical disclosure , not deteriorate
into a philosophical debate by those struggling with the reality
they haven't an understanding of the technology .

The driving force behind my own curiosity concerning those patents
at the top of this thread , is a sneaking suspicion that they are
*not* valid , and that is precisely what intrigues me about them .
They are either "vanity patents" or they disclose an obscure and
interesting reaction which is confounding to me . So my curiosity
about what is the story concerning those patents is quite legitimate .

It is not a waste of time to put such things to the test and
confirm or disprove the matter to give it closure . That is
the whole nature of experimentation .



[snip]
Post by Don T
Post by Rosco P. Coaltrain
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .
Rosco
my_2¢
2003-12-30 18:03:50 UTC
Permalink
Post by Rosco P. Coaltrain
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .
Rosco
Bang-bang! You hit it on the head. There is a book entitled "The
Preparatory Manual of Explosives" and I have spoken with the
author...a nice fellow, but the book has many errors. Nothing serous,
and the work is not "teeny-bomber garbage" but some of the resulting
"products" would be junk. here were two factors at work, one: he
didn't proof all his copy, two: the editors knew NOTHING about
chemistry. He does have a couple of neat formulas, but he had a multi
million dollar lab to work with and could cheat on some methodologies
(ie temp settings).


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Rosco P. Coaltrain
2003-12-30 23:29:34 UTC
Permalink
Post by my_2¢
Post by Rosco P. Coaltrain
What would be more impressive still would be some knowledgeable
replies from "hands on" *chemists* who are cognizant about the subtleties
involved in the syntheses described by the two patents at the top
of this thread , instead of a never ending series of taunts from
a chemist wannabe who trusts for knowledge whatever can be read
in a book , without having directly observed any experimental
verifications for those reactions which is speculated have some
validity . I am one of those old fashioned sorts who believes
more what I find in the beaker , than what is indexed in the
ostensibly authoritative text , because more than a few times
it has happened that the texts are simply wrong .
Rosco
Bang-bang! You hit it on the head. There is a book entitled "The
Preparatory Manual of Explosives" and I have spoken with the
author...a nice fellow, but the book has many errors. Nothing serous,
and the work is not "teeny-bomber garbage" but some of the resulting
"products" would be junk. here were two factors at work, one: he
didn't proof all his copy, two: the editors knew NOTHING about
chemistry. He does have a couple of neat formulas, but he had a multi
million dollar lab to work with and could cheat on some methodologies
(ie temp settings).
There are many good scientists whose handwritten lab notes
are legible only to themselves and god . And there remain
many secrets gathering dust forever , due to unconventional
shorthand and misplaced eyeglasses , and transriptionists
who divide their work between deciphering lab notebooks ,
when they are not translating tax records from the reign
of Ramses in ancient Egypt :) . Also many scientists are
poor technical writers or simply don't bother to publish
things that are never recognized as being useful in some way .
Proofreaders may know nothing of chemistry and not catch the
errors or omissions , and there is evidence of this later
in the thing published , even as a college textbook , patent ,
or journal article . I know because I have detected and
reported such errors when I find them , not typographical
errors or misspelled words , but actual content that is
just wrong . Human beings make mistakes and it often shows .

For a person who doesn't really grasp the full nature of
the thing they are reading , or has never actually tried
to reproduce results by a method which has been misreported ,
the error in the text is unseen for what it is , and mistaken
for fact , accepted as true only because it was something
they read . People should not fully believe what they read
any more than what they hear , but keep a bit of reservation
especially about those things where skepticism seems indicated .
Trust but verify , is a good policy for followers of technical
publications . Also there are "exceptions to the general rule"
in chemistry especially ,where within a narrow range of
special circumstances , entirely different things may occur
than what is generally true . So it is a science that is full
of surprises . A good example is the first LSD trip ever
experienced by its discoverer , who after inadvertantly
absorbing a tiny amount of the material from his experiment ,
encountered "a whole new world" which made difficult the
operation of his bicycle when he departed the laboratory
and left off further experimenting for the day :)
Yes , a peculiar hydrazide derivative had claimed its first
smiling face :) It was probably some interesting transcription
work for whomever was attending Hoffman's notes from that day
making them ready for publication . It is undoubtedly for that
interest in accuracy and confirmation , that Hoffmans experiment
was exhaustively investigated by so many chemists world wide ,
only wishing to not seem stingy about extending the courtesy of
peer review and leave Hoffman wanting for independent verification :)

Rosco
my_2¢
2004-01-05 21:40:57 UTC
Permalink
On 30 Dec 2003 15:29:34 -0800, ***@yahoo.com (Rosco P.

It's funny you should mention Hoffman, as I was a young man when he
was "published" by a textbook at my University and I can attest to
what you say in regards to misinterpretation of lab notes....I thought
he was originally dealing with ergotine (sp?) poisoning!
Have you read that book Preparatory Manual of Explosives? Overall, the
guy does a good job; & I wouldn't want anyone to think I was putting
it down...but it's really a work in progress. I think he should just
have another go at it and catagorize the primaries, secondaries, and
propellents...it's sort of...jumbled.


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Rosco P. Coaltrain
2004-01-06 05:21:29 UTC
Permalink
Post by my_2¢
It's funny you should mention Hoffman, as I was a young man when he
was "published" by a textbook at my University and I can attest to
what you say in regards to misinterpretation of lab notes....I thought
he was originally dealing with ergotine (sp?) poisoning!
It was an ergotamine derivative , yes the same ergotamine
that poisons grain from a fungus of a specific variety .
What made me think about Hoffman was the intermediates he
was working with was a photosensitive hydrazide and other
photosensitive materials . I have been trying to think of
*any* variables which might influence reactions like those
two patents at the top of the thread , and make them difficult
to duplicate , and photosensitivity is one of the factors
that came to mind as a possibile variable . Another variable
is the possible required presence of an organic material ,
like the gelatin that is needed to be present in some hydrazine
syntheses , but I'm thinking that good candidate organics
would include glycerin , ethylene glycol , or possibly isopropanol .
There's obviously a piece of the puzzle missing , that is
an essential detail in getting such reactions to work .
I don't take it personally when an experiment doesn't work ,
but it does get me curious about why . I think some "experts"
at this group get angry when questions are posted for which
they have no good answers . It is incompatable with their egos
to admit they don't know , so they pretend they have the answer
but can't reveal it because it's top secret or something ...
which is ridiculous . So I salute people like Louis who keep
to the science , and the spirit of sharing data from
intelligent experiments formulated by an intelligent mind .
Post by my_2¢
Have you read that book Preparatory Manual of Explosives? Overall, the
guy does a good job; & I wouldn't want anyone to think I was putting
it down...but it's really a work in progress. I think he should just
have another go at it and catagorize the primaries, secondaries, and
propellents...it's sort of...jumbled.
I haven't read the book , but from the excerpts that I have seen ,
I wouldn't buy it . Somebody will likely scan and OCR it and
upload it to a server somewhere , and then I'll download the
free e-version release . If it isn't a waste of paper ,
then I'll print myself a copy :) . In my experience , most significant
technology finds its way into the patents database , so the value
of patents generally as a valid technical reference is undeniable .

Rosco
Post by my_2¢
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donald j haarmann
2004-01-02 01:42:02 UTC
Permalink
Post by donald j haarmann
Well....... looking in my recently arrived copy of:—
HD Fair and RF Walker Ed's.
Energetic Materials - 1
Physics and Chemistry of the Inorganic Azides
Plenum Press New York 1977
Ag azide?

Silver nitrite (AgNO2) and hydrazine will do it. [A. Angeli. Ber. Ges. Chem. Ges. 26, 885, (1893)]
Silver azide was at one time used in place of silver bromide in photography. Therefore, work
in the dark or under red light, protect the product from light.
--
donald j haarmann
-----------------------------
As if ordained by Fate, Nitre, that admirable salt,
hath made as much noise in Philosophy as in
War, all the world being filled with its thunder.

John Mayow
Ttractalus Quinque Medico-Physici, 1674
donald j haarmann
2004-01-07 15:37:20 UTC
Permalink
Here from a secondary reference in the chemicaly trivial syntheses of beryllium
azide.

Pure dimethyberillium is sublimed into a reaction vessel cooled with liquid N2; then an
absolutely dry ether solution of excess HN3 in condensed on top of the dimethylberillium
layer. As the reaction mixture thaws, a vigorous reaction with evolution of methane starts
even before all of the ether in melted (m.p. -116oC, and Be(N3)2 seperates out as a
white precipitate. The ether and excess of NH3 are then distilled off under high vacuum.

Primary ref (not seen by me):—

Wiberg and H. Michaud, Z. Naturforsch. 9b, 202 (1954).

Al azide is even more fun!!
--
donald j haarmann — colophon
LOUIS
2004-01-09 15:12:02 UTC
Permalink
Post by donald j haarmann
SNIP
Al azide is even more fun!!
-Why?
Post by donald j haarmann
--
donald j haarmann — colophon
donald j haarmann
2004-01-10 01:27:51 UTC
Permalink
I would not in passing the only reason I am willing to describe the preperation
of Na azide is that is it NOT an explosive. However, this does not make it safe!!

---------
Blasts and fires at air bag factories injure workers and slow production

By Tom Incantalupo STAFF WRITER
New York Newsday 16iii92

IN THIRTEEN YEARS of police work, Sgt. Gwen White-Erickson has seen plenty of
rubble. But the Michigan state police fire investigator wasn't ready for what greeted her
when she pulled up to TRW's plant in Romeo, Mich., last Dec. 17.

An hour and a half earlier, an explosion of automobile air bag propellant had leveled a
concrete block building that was about 40 feet long and wide.

"The walls sort of blew out; the roof just sort of collapsed in," she recalled. "It was just a
bunch of rubble. . .I’ve never seen concrete blocks laid out that way."

It was an awesome display of the power of the chemicals used to inflate air bags — and
an unpleasant side of the air bag success story.

Anyone who watches TV has seen videotape of air bags inflating in slow motion just in
time to cushion a test dummy before it slams into a steering column. By all accounts the
widespread installation of air bags in cars is saving lives and preventing injuries, and
the devices themselves have been remarkably reliable.

Federal safety regulators forecast that 2,400 lives will have been saved in the five years
ending at the close of 1995 and 29,000 serious injuries avoided, thanks to air bags -
nylon sacks that inflate with nitrogen gas in a fraction of a second to cushion
passengers in a crash.

But manufacturing those systems has proved on occasion to be a risky business, one
that involves working with highly unstable and explosive chemicals.

Since 1988, there have been at least 18 explosions or fires in factories that make air
bag components, mix the propellant that inflates air bags or handle waste products from
either. No one has been killed, but 23 workers have been injured, four seriously. Eleven
workers at the Romeo plant, about 30 miles north of Detroit, were slightly injured and
were treated for smoke inhalation and trauma.

But the accidents have not only affected workers; they are one reason why car makers
have been unable to install air bags in more models more quickly.

In one instance, a factory was shut down for almost a year and it created shortages of
air bag propellant that forced Ford Motor Co. to build 75,000 1991 Lincoln's without
passenger side air bags. They were later retrofitted.

Despite the manufacturing mishaps, experts say drivers don't have to worry about the'
propellant in their own air bag-equipped cars. Only a small amount of the chemical is in
the car, hermetically sealed.

State regulators say air bag manufacturing plants use some of the most stringent safety
practices of any industry. Much of the work is done by robots or by remote control. Still,
some of the mishaps have resulted from seemingly innocuous actions by workers.

The Michigan explosion, for instance, was the result of a spark created by a worker with
an allen wrench who was turning a screw to adjust a machine. The spark ignited some
propellant dust and a vacuum system carried the fire to another room where a barrel of
dust exploded, said White-Erickson.

An explosion in Mesa, Ariz., was set off when some water was dropped on burned air
bag propellant. Two months later, an enormous explosion at the same desert site
occurred because an aluminum scoop - similar to one a grocery shopper would use to
fill a bag I with bulk produce - was left in a mixing trough and the contact threw off
sparks. A worker in a Canadian factory set off an explosion when he tapped a hammer
on a pipe clogged with propellant.

At least one workplace safety activist says the 18 incidents are cause for concern.

"Clearly, there should be an investigation to see what can be done to reduce these
kinds, of explosions," says Joseph A. Kinney, executive director of a nonprofit research
group in Chicago. The National Safe Workplace Institute.

"Clearly, this industry, which is new, has not done its homework."

Similar concerns by a Michigan congressman led to a study in 1990 by the General
Accounting Office into the accidents up to that point. The GAO report was not critical,
but Rep. John Dingell (D-Mich.), who requested the study, expressed concerns in a
letter to the secretaries of labor and transportation and the administrator of the U.S.
Environmental Protection Agency about whether the states involved were adequately
monitoring the industry.

Still, there is no statistical evidence that the air bag industry's safety record is any worse
than any other handling highly-explosive substances - or any other industry, period.

In fact, state officials in Utah, Arizona, Michigan and Tennessee, where the industry is
concentrated, praise the companies operating within their borders for their safety
procedures and cooperation in investigating mishaps.

Further, the number of accidents has to be viewed in the context of the industry's
production volume. The Insurance Institute for Highway Safety, a trade group, says
almost 6 million air bag-equipped cars have been sold in this country since the 1980s
and it says most air bag systems were produced in North America — including those in
many imported cars.

Noel Baker, senior vice president for marketing at a new company getting into the
manufacture of propellant and the cannisters that hold it, says the accidents were an
unfortunate but not surprising byproduct of the industry efforts to handle greater
amounts of material to satisfy burgeoning demand"

"What you've seen, I think, are some of the strains produced by this
tremendous ramp-up," Baker said. His company, Breed Automotive,
which is based in New Jersey but has set up its plant in Florida, will mix
propellant with a new process that involves producing small batches simultaneously
rather than one large batch and by shaking, not stirring, ingredients.

Concerns about the safety of air bags goes beyond the mixing of propellant and its
placement in inflator modules. The United Auto Workers Union is worried about
inadvertent deployments -of air bags - perhaps from electrical short circuits or static
electricity - as its. people install the systems in cars on assembly lines. Though that
hasn't happened yet, one concern is that a deployment — a loud and violent
occurrence — could push a worker into running machinery.

"It has the potential to be a real big problem," said Dick Monczka, who represents the
union at a workers health and safety center it runs jointly with General Motors near
Pontiac Mich. The center has written a 70-page safety manual and produced A
videotape to train workers handling the equipment.

There is concern as well about safe disposal of unused propellant when, cars are
scrapped. Some auto recyclers are worried about explosions or poisoning of workers
with the chemical involved.

Eventually, all cars and light trucks will have air bags on both the driver, and passenger
side — by the 1998 model year for cars, the 1999 model year for light trucks.

The industry that produces air bags, in North America is dominated by TRW Safety
Systems Inc., based in Washington, Mich., with plants in Mesa, Romeo, Cookeville,
Tenn., and McMasterville,, Quebec; Morton International, with,, plants in Ogden,
Brigham City and Promontory, Utah and, in a joint venture with Allied Signal's Bendix
unit, in Maryville, Tenn.

So far, most of the accidents reported have involved operations that mix chemicals that
make propellant — the material that is ignited to form the nitrogen gas that inflates the
bag. One occurred in a factory installing propellant in inflators, two occurred in facilities
manufacturing the basic ingredient of propellant, sodium azide, and one explosion
occurred at a facility handling waste propellant.

Sodium azide is flammable but not explosive. However, it can form explosives when it
comes into contact with water, acidic solutions or with heavy metals such as copper or
lead. The finished propellant, as installed in cars also is highly flammable, but not
explosive.

The fact that no one has been killed in 18 incidents is attributable to intensive safety
measures, industry officials say.

Buildings are constructed with three specially reinforced walls and one that is
designed to give way easily if there is an explosion, to channel the force of blasts away
from the people working inside.

Much of. the work in high-danger areas, such as where propellant is
mixed or pressed into pellets or wafers done by robot or remote control, with operators
monitoring work via TV cameras. Cement block walls separate workers performing
different manufacturing steps. Buildings have state-of-the-art fire suppression systems.

“In all of the things you do, in the factories you build and the procedures you use, you
function as though there could be an incident with pyrotechnics says George Virchoff,
vice president for automotive programs at Morton. "You always function so that, you:
had an incident, you would have injury to personnel."

Cleanliness, he said, is practiced religiously. Propellant, once mixed, is moved in small
quantities to the plan where it will be loaded into inflators.

The machines that do the loading Kirchoff said, operate automatically and are vented
through a stack that juts up through the building’s roof,
that any fire or explosion would b channeled up and out of the structure. He said the
two explosions at Morton' facilities did minimal damage and, while their precise causes
was proprietary information, the company ha learned from the experience.

"We have mixed more than 1.5 million pounds of gas generants [propellants] since
those accidents without incident," Kirchoff said.

The mishaps have occurred as pressure has built on the industry to increase
production; Americans have largely been sold on the lifesaving benefits of air bags but
the supply of them is limited. While it is difficult to draw a connection between limited air
bag supplies and the accidents, the industry has not been found entirely blameless
when officials have investigated the accidents.

Chemical Waste Management, an Illinois hazardous waste disposal company to whom
TRW had been trucking waste propellant from Arizona, agreed last month to pay the
Illinois Environmental Protection Agency a $1.9 million fine - without admitting wrong-
doing - for violations of state environmental law after explosions in January, and
February, 1991, at Chemical Waste's hazardous waste incinerating plant in Sauget, Ill.

Only the January explosion involved air bag propellant. But the incidents caused
problems for TRW: It had no place else to send waste propellant. Called in by TRW in
February of last year, Arizona state officials found thousands of pounds of it at one of
TRW's Mesa plants. Some of the propellant had exceeded a 90-day state storage limit.
Under a settlement signed last September, TRW paid a $35,000 penalty.

TRW has paid other fines in Arizona in connection with its air bag operations. Before
the first accident, Arizona’s Division of Occupational Safety and Health fined TRW $400
for failing to properly train and inform workers about hazardous chemicals. Another
state fine, for $640, was for an explosion July 28, 1989, at its plant on the north side of
Mesa.

"We're not perfect — no one is," said Tom Cresante, director of operations at the TRW
plant. "We're dealing with pyrotechnics, and we're trying to do something that maybe
other industries haven't done —bringing it to a high volume

The Boom in Air Bags

The probable causes of reported fires and explosions at air bag manufacturing sites or
the sites their wastes are handled.

Dec. 17, 1991: TRW, Romeo, Mich. Eleven workers injured, building destroyed, when
air bag propellant explodes. A spark from wrench set off explosion.

Jan. 25,1991: Chemical Waste Management, Sauget, Ill. Cannister of waste propellant
falls into dumpster of hot ash, explodes. No injuries.

January, 1991: TRW, Mesa, Ariz. No injuries, no damage from what fire official describe
as minor fire.

April 1991: TRW, Mesa. Small fire; no injuries.

March 14,19-": Sabag lnc., Quebec, Canada. Three workers seriously hurt in explosion
atop conveyor pipe full of propellant, Caused by spark from mallet blow to unclog pipe.

Dec. 8,1989: Sabag Inc. Propellant ignited when employees drill above equipment used
to grind sodium azide. Drill cuttings ignite propellant mix. No injuries.

Nov. 1, 1989 ICI Explosives, Canada Inc., Quebec. Fire begins from chemical reaction
between wet sodium azide stored in drums and raw sodium that had been in same
drums. Drums had not been cleaned as required. No injuries.

Oct. 8, 1989. ICI Explosives, Quebec. Pressure-reducing valve regulating steam heat
going to sodium azide dryer was too close to dryer, causing sodium azide to overheat
and ignite. No injuries.

Aug. 14,1989 Morton International, Utah. Propellant mixture ignited by unknown source.
No injuries.

July 28, 1989 TRW, Mesa. Five workers Injured, building heavily damaged when friction
from aluminum scoop left in mixing bay produces sparks, ignites propellant.

July 24, 1989: Morton international. Propellant ignites when broken piece of press falls
into press die. No injuries.

July 13,1989: Sabag Inc. Moisture from dry ice contacts sodium azide, forms explosive
chemical, fire occurs. No injuries.

June 16,17,18, 1989: Talley Defense Systems, Mesa. Series of three explosions set off
by friction igniting propellant dust in ball bearing assembly of a mixer. No injuries.

May 1989. Talley Defense Systems. Two workers hurt in explosion In open bum pit
when water poured into pit reacts with sodium residue of burn propellant.

March 11, 1989: Sabag Inc. Spark from static electricity ignites propellant. No injures.

Feb 17, 1968: Sabag Inc. One worker injured seriously, three others hurt, when spark
from screwdriver ignites propellant
--
donald j haarmann — independently dubious
LOUIS
2004-01-10 10:01:22 UTC
Permalink
NaN3:
Decomposes somewhat explosively above its melting point, particularly if heated rapidly; liable
to explode with bromine, carbon disulfide, chromyl chloride, ...; when water is added to the
strongly heated azide there is a violent reaction that takes place.
Irritating to skin and eyes in solution or in dust, causes blistering.Assumed to be very irritant
and poisonous if taken by mouth.

From "Hazard in the chemical laboratory"- pp 383,384 - G.D. Muir 2nd Edition

Following me,
Sodium azide being a soluble azide must be considered as dangerous as plain azothydric acid
because it may form sensitive azides by anionic exchange with other bare metals or their salts.

Ph Z
Post by donald j haarmann
I would not in passing the only reason I am willing to describe the preperation
of Na azide is that is it NOT an explosive. However, this does not make it safe!!
LOUIS
2004-01-10 10:17:14 UTC
Permalink
TLV = 0,1 ppm

Ph Z
Post by LOUIS
Decomposes somewhat explosively above its melting point, particularly if heated rapidly; liable
to explode with bromine, carbon disulfide, chromyl chloride, ...; when water is added to the
strongly heated azide there is a violent reaction that takes place.
Irritating to skin and eyes in solution or in dust, causes blistering.Assumed to be very irritant
and poisonous if taken by mouth.
From "Hazard in the chemical laboratory"- pp 383,384 - G.D. Muir 2nd Edition
Following me,
Sodium azide being a soluble azide must be considered as dangerous as plain azothydric acid
because it may form sensitive azides by anionic exchange with other bare metals or their salts.
Ph Z
Post by donald j haarmann
I would not in passing the only reason I am willing to describe the preperation
of Na azide is that is it NOT an explosive. However, this does not make it safe!!
Rosco P. Coaltrain
2004-01-10 16:18:42 UTC
Permalink
Post by donald j haarmann
I would not in passing the only reason I am willing to describe the preperation
of Na azide is that is it NOT an explosive. However, this does not make it safe!!
[snip]

Actually the high solubility and extreme toxicity of NaN3 and its
reactivity potential are quite similar to NaCN and this is a far more
worrisome hazard than the energetic hazards . Azide solutions must
be treated with the same cautions as cyanide solutions .

The business of this engineering news group is *explosives* .
If you have reservations about being involved in open discussions
involving specific technical aspects of the chemistry and other
processes concerning explosive materials , then for what reason
do you post messages in this group ?

Many chemical processes , if not in fact *most* of them , are
dangerous to varying degree , and involve materials which are
also dangerous . Chemistry is not a science which suffers fools
or the careless . Chemistry tends to very early maim or kill
the reckless , as well as having claimed more than a few skilled
and knowledgeable scientists who become victims sooner or later
of an experiment gone wrong for equipment failure or for any of
many other possible reasons .

Cave diving and mountaineering are also dangerous pursuits , as are
many other activities which are paths to discovery . Should all
hazardous activities be ceased immediately due to the possibility
of an accident ? Then no one should ever again make use of an
automobile . And no horseback riding either , because you might fall .
Be very careful of the books especially when turning the pages ,
as you may suffer a "paper cut" ;-) .

You could copy and paste horror stories about ammonium nitrate ,
ammonium perchlorate , black gunpowder .....even propane has
its disaster potential . A can of gasoline is a dangerous thing
when mishandled . Let's assume that people who are understanding
of hydrazine chemistry have enough on the ball to put the oily rags
in a firesafe container and abide the other usual safety protocols ,
dispense with the "topic avoidance" and get to it ....*if* you
have any good information to share about azide synthesis in
aqueous media according to the reaction schemes of the two patents
at the top of this thread .

Patents are not "top secret" nor is the technology they describe ,
especially patents from eighty-five years ago . So again I ask ,
if you have pertinent information about those syntheses to share .....

Why not ?

Rosco
donald j haarmann
2004-01-10 20:09:03 UTC
Permalink
Post by Rosco P. Coaltrain
Patents are not "top secret" nor is the technology they describe ,
especially patents from eighty-five years ago . So again I ask ,
if you have pertinent information about those syntheses to share .....
Why not ?
Rosco
--------------
Why? Because this is America 2004 and at my age 20 years is a life
sentence!!


Safety -
Personal - yours.
Political - MINE!!



--
donald j haarmann
------------------------
Professor Edgeworth of All Soul's avoided
conversational English, persistently using words
and phrases one expects to meet only in books.
One evening, Lawrence [the famous Lawrence of
Arabia] returned from a visit to London, and
Edgeworth met him at the gate. "Was it very
caliginous in the metropolis?"

"Some what caliginous, but not altogether
inspissated," Lawrence replied gravely.
Rosco P. Coaltrain
2004-01-11 07:48:36 UTC
Permalink
Post by donald j haarmann
Post by Rosco P. Coaltrain
Patents are not "top secret" nor is the technology they describe ,
especially patents from eighty-five years ago . So again I ask ,
if you have pertinent information about those syntheses to share .....
Why not ?
Rosco
--------------
Why? Because this is America 2004 and at my age 20 years is a life
sentence!!
Safety -
Personal - yours.
Political - MINE!!
--
donald j haarmann
Politically correct chemistry ?
Now I've heard it all .

Rosco
donald j haarmann
2004-01-12 15:23:35 UTC
Permalink
"Rosco P. Coaltrain" >
Post by Rosco P. Coaltrain
Politically correct chemistry ?
Now I've heard it all .
Rosco
Nope .... survival chemistry.



--
donald j haarmann - independently dubious
Coalbunny
2004-01-11 01:56:25 UTC
Permalink
On 10 Jan 2004 08:18:42 -0800, ***@yahoo.com (Rosco P. Coaltrain)
carved in granite...
Post by donald j haarmann
Post by donald j haarmann
I would not in passing the only reason I am willing to describe the preperation
of Na azide is that is it NOT an explosive. However, this does not make it safe!!
[snip]
Actually the high solubility and extreme toxicity of NaN3 and its
reactivity potential are quite similar to NaCN and this is a far more
worrisome hazard than the energetic hazards . Azide solutions must
be treated with the same cautions as cyanide solutions .
The business of this engineering news group is *explosives* .
If you have reservations about being involved in open discussions
involving specific technical aspects of the chemistry and other
processes concerning explosive materials , then for what reason
do you post messages in this group ?
Many chemical processes , if not in fact *most* of them , are
dangerous to varying degree , and involve materials which are
also dangerous . Chemistry is not a science which suffers fools
or the careless . Chemistry tends to very early maim or kill
the reckless , as well as having claimed more than a few skilled
and knowledgeable scientists who become victims sooner or later
of an experiment gone wrong for equipment failure or for any of
many other possible reasons .
Cave diving and mountaineering are also dangerous pursuits , as are
many other activities which are paths to discovery . Should all
hazardous activities be ceased immediately due to the possibility
of an accident ? Then no one should ever again make use of an
automobile . And no horseback riding either , because you might fall .
Be very careful of the books especially when turning the pages ,
as you may suffer a "paper cut" ;-) .
You could copy and paste horror stories about ammonium nitrate ,
ammonium perchlorate , black gunpowder .....even propane has
its disaster potential . A can of gasoline is a dangerous thing
when mishandled . Let's assume that people who are understanding
of hydrazine chemistry have enough on the ball to put the oily rags
in a firesafe container and abide the other usual safety protocols ,
dispense with the "topic avoidance" and get to it ....*if* you
have any good information to share about azide synthesis in
aqueous media according to the reaction schemes of the two patents
at the top of this thread .
Patents are not "top secret" nor is the technology they describe ,
especially patents from eighty-five years ago . So again I ask ,
if you have pertinent information about those syntheses to share .....
Why not ?
Rosco
Rosco and Don, I gotta interrupt you gentlemen for a sec. I am not a
professional in the explosives industry, but I enjoy learning more about it and
yes, even hearing the horror stories and the pics would be a benefit. While I
enjoy hearing the technica data, I also realize that there are people out there
that have just a tad bit less comon sense than a broomstick and probrobly have
less intellegence than a cockroach.

Wait until you piss of some snot-nosed 16 year old mental case and find an
improvised pipe bomb under your truck. I'm damn thankful that kid didn't know
shit from steak when it comes to that stuff.
Carl

--
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donald j haarmann
2004-01-11 20:11:40 UTC
Permalink
Post by Coalbunny
Rosco and Don, I gotta interrupt you gentlemen for a sec. I am not a
professional in the explosives industry, but I enjoy learning more about it and
yes, even hearing the horror stories and the pics would be a benefit. While I
enjoy hearing the technica data, I also realize that there are people out there
that have just a tad bit less comon sense than a broomstick and probrobly have
less intellegence than a cockroach.
Wait until you piss of some snot-nosed 16 year old mental case and find an
improvised pipe bomb under your truck. I'm damn thankful that kid didn't know
shit from steak when it comes to that stuff.
Carl
--
---------
Amen!

HURT WHILE MAKING HUGE FIRECRACKER
New York Daily News 4 July 1989

A Bronx teenager’s hands were blown off and his brother and a friend were
severely mangled when a huge firecracker they were trying to make exploded
yesterday.

The three had stuffed the powder from a number of small but powerful
firecrackers into a pipe.

They were hammering a sealing cap onto it when it blew up, sending white-hot
pieces of metal flying.

Police found several severed fingers at the scene in a basement apartment on
Bronx Park East in the Pelham Parkway section near the Bronx Zoo.

“My stupid sons! One of them lost both his hands, the other one lost a hand and
hurt his leg,” Joseph Perlmutter, superintendent of the building, told a neighbor
after the blast.

Police sealed off the building after the explosion, shortly before 7 p.m. Bomb
squad officers removed another pipe bomb.

One of the victims, Harry Perlmutter, 18, who had been holding the pipe lost both
hands in the blast, cops said.

His brother, Joesph Jr. 28, lost four fingers on his left hand and suffered leg
injuries.

A friend, Dante Bang [sic] 18, of Wallace Ave. lost an index finger on his right
hand and suffered shrapnel injuries to his groin and ankles.

Police said the three working in a 6-foot-by-14-foot bedroom in the basement
apartment, had taken about “30 to 40” powerful M-80 firecrackers apart and were
stuffing the powder into the pipe.

The three had planned to ignite the pipe today in the park across the street from
the six-story apartment building, police said.

------------------
The three most important safety rules for making fireworks are:
NO METAL
NO METAL
NO METAL

/djh/


--------------
01-02-89
[rewritten from a UPI News Wire story djh]

BETHESDA, Md. - Four teenagers described by friends as intelligent and as
having a fascination with chemistry and rocketry were tinkering with a
homemade bomb this weekend when the experiment went awry. Relatives of the
foursome described them as studious, curious and fascinated with science.
Diego S-R, who graduated from Walt Whitman High in 1988 and was close
friends with Gustasvo M. and Bruno P. described the youths as "the best
chemistry students in the school." A family friend of the Dov F. described him as
"always a brilliant child, extraordinarily brilliant." The friend speculated the young
men were planning New Year's fireworks. "(They were likely) trying to find out
how much power they could get out of mixing chemicals," Diego S-R told the
Washington Post. "They were probably going to go to some field and see how
big a hole they could make. They were peaceful people. They would never try to
hurt anybody."

The young men had made a potent pipe bomb as "a prank," but it exploded as
two of the youths were leaning over it. The youths, Samir G. 17, and Dov F. 18,
were killed instantly, 15-year-old Gustavo M. and Bruno P. 18, died hours after
the blast. Gustavo M. was a sophomore at Walt Whitman High School while the
others had graduated from the school last year.


Why do you laugh? Change the name,
and the story is told of you.
Horace


Cardboard/paper; Fireworks
Metal; Bombs


--------From: Sandi Rakovec \
To: <donald-***@worldnet.att.net>
Subject: Re: shit happens 17
Date: Tuesday, June 20, 2000 11:13 AM

Hello

It seems that you realy annoy some of the juvenils at rec.pyrotechnics here
is another one that you can use in your succesfull posts.
If you think that it would be better that I post it than reply.

This is a translation of an article in Slovenian newspaper. The original
source is below.

Start of an article

It seems that all calls for a big caution while producing home made
explosive devices weren't enough. How dangerous that kind of act could be
have tasted yesterday 13 years old S.Z. and 16 years old R.P. both from the
same town. After a strong explosion of a home made explosive have both of
them ended with massive injuries in a local hospital.

Explosion went off immediately after 12 A.M. Rescuers were notified that
residents of an apartment block heard an explosion, a large amount of smoke
from a basement and calls for help. Rescuers sent a vehicle immediately on a
place of explosion while police have secured the area.

General prosecutor and state pyro team have looked the place of explosion
afterwards. Rescuers have found there two boys with a substantial damages on
a face and hands.

The police stated that they have produced an unknown mixture which they want
to use for pyrotechnical purposes. While doing that the massive explosion
occurred which ruined the basement wall (that you can see on a picture) and
also with a severe damage on other neighboring apartments.

Neighbors told us that both juveniles were mixing an unknown mixture with
acetone and fill with it a plastic containers. They have made a successful
attempt few days ago because they were seen enjoying a place where an
explosion damaged a road asphalt.

Jani Alic

End of article

Afterwards they have confirmed that it was acetone peroxide what they have
been producing. A source of how to information was internet.

Translated by Sandi Rakovec
You can find original source of an article and a picture of a ruined wall
at http://www.dnevnik.si/doc/dn/1999/12/30/rdjhv.hts

Sorry link no longer works.


--
donald j haarmann
-----------------------------
A little knowledge is a dangerous thing;
Drink deep, or taste not the Pierian spring:
There shallow draughts intoxicate the brain,
And drinking largely sobers us again.

Alexander Pope [1688-1744]
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