Sciencemadness Discussion Board

Azide of Millon’s Base

vano - 2-1-2021 at 05:26

Hi. I have new idea. I want to make Millon’s Base azide.

1) The bromide can be obtained by reacting mercury (II) bromide with ammonia. I think this bromide is soluble.

2HgBr2 + 4 NH3 = [Hg2N]Br + 3 NH4Br

Azide may be insoluble.
2) [Hg2N]Br + NaN3 = [Hg2N]N3 + NaBr

Do you have any idea before I do this reaction. Has anyone tried it before?

de wikipedia



[Edited on 2-1-2021 by vano.kavt]

[Edited on 2-1-2021 by vano.kavt]

Bedlasky - 2-1-2021 at 07:57

I wouldn't be surprised if [Hg2N]Br is insoluble.

Be careful, heavy metal azides are quite sensitive explosives.

vano - 2-1-2021 at 08:27

I remember reading somewhere that iodide was soluble. Was it Polish or German, I can not find now. I may be wrong. I have to try to understand exactly. I have experience with azides. I have already switched to exotic azides. I just do not post on energetic compounds.

Bedlasky - 2-1-2021 at 09:45

Remy says about amido and nitrido salts of mercury(II) this:

If you add ammonia in to the solution of HgCl2 containing large amount of NH4Cl, "meltable white precipitate" is formed. When you heat this compound, it melts and decomposes. It is slowly hydrolysed by water back to ammonia and HgCl2. It is soluble in dilute sulfuric, nitric and acetic acids (to form HgCl2 and ammonium salt). It can be also prepared by action of liquid ammonia on HgCl2. Some amines like N2H4 or pyridine forms similar compounds. Analogous bromide also exist.

HgCl2 + 2NH3 --> [Hg(NH3)2]Cl2

If you add ammonia in to the solution of HgCl2 without NH4Cl or with low concentration of NH4Cl, "unmeltable white precipitate" is formed. When you heat this compound, it doesn't melt and decomposes in to Hg2Cl2, N2 and NH3.

HgCl2 + 2NH3 --> Hg(NH2)Cl + NH4Cl

6Hg(NH2)Cl --> 3Hg2Cl2 + N2 + 4NH3

If you add ammonia in to suspension of HgO, you get pale yellow precipitate - Millon's base.

HgO + NH3 --> [(HgOH)2(NH2)]OH ([Hg2N](OH).2H2O is simplified formula for [(HgOH)2(NH2)]OH)

When you let solid stand in ammoniacal atmosphere over KOH, it dehydrates:

[(HgOH)2(NH2)]OH --> [Hg2O(NH2)] + H2O ([Hg2N](OH).2H2O is simplified formula for [Hg2O(NH2)])

Heating in ammonia atmosphere at 125°C leads to complete dehydration and formation of dark brown highly explosive powder:

[Hg2O(NH2)] --> [Hg2N]OH + H2O

[Hg2O(NH2)] and [(HgOH)2(NH2)]OH are explosive as well.

Salts of Millon's base can be make by dissolving Millon's base in coresponding acid (here is mention, that precipitate doesn't dissolve):

[Hg2N](OH).2H2O + HX --> [Hg2N]X + 3H2O

Salts of Millon's base can be also make by action of aqueous ammonia on strongly dissociated Hg(II) salts (Hg(NO3)2, Hg(ClO4)2 not HgCl2 or HgBr2 which are just weakly dissociated).

Weakly dissociated Hg(II) salts form "white precipitates" as mentioned above. If you boil them in water or hydroxide solution, they are converted in to Millon's base salts. The same happens when you boil basic mercury(II) salts or mercury(II) halide complexes in water or hydroxide solution.

2[Hg(NH3)2] + H2O --> [HgN]Cl.H2O + 3 NH4Cl

2Hg(NH2)Cl + H2O --> [HgN]Cl.H2O + NH4Cl

HgCl2.HgO + 2NH3 --> [HgN]Cl.H2O + NH4Cl

2[HgI4]2- + NH3 + 3OH- --> [HgN]I.H2O + 7I- + 2H2O

I read on wiki, that when Nessler's reagent reacts with ammonia, basic iodide of Millon's base (HgO·Hg(NH2)I) is formed:

https://en.wikipedia.org/wiki/Potassium_tetraiodomercurate(I...

So maybe also some basic salt exists. Remy's inorganic chemistry is book from 1961, so don't take it as absolute truth, lots of progress in chemistry was developed during 50 years.

vano - 2-1-2021 at 10:23

Thanks Bedlasky. I will probably make it in a few days. I often come in contact with tetrahalomercurates. I posted it yesterday too.

Diachrynic - 3-1-2021 at 08:43

Here is some information in German, it's from Gmelins Handbook of inorganic chemistry, mercury part B-1, page 164.

image00213.png - 2.5MB
Quote:
Azide of Millons Base, Hg2NN3
Preparation:
From a hot aq. solution of Hg(N3)2 it is precipitated by the addition of concentrated aq. ammonia solution as a yellow explosive crystal powder, if the filtrate is evaporated on the water bath further crops of the compound can be obtained. If solid Hg(N3)2 is treated with a concentrated aq. ammonia solution the azide turns yellow, and the solution is shaken for half an hours, then from the filtrate Hg2NN3 is obtained in well defined crystals on evaporation; if the ammonia solution additionally contained ammonium azide the mercury azide will dissolve to a considerable extend and from the solution Hg2NN3 crystallizes as well.
A general method for Hg2NX compounds can be applied as well, it is obtained from Hg2NNO3 with NaN3 in ammonia. The Hg2NNO3 solution was obtained by dissolving 103 g of mercury(II)-nitrate (0,3 mol) in 500 mL water, to which 50 mL conc. nitric acid have been added, and by adding 450 mL of conc. aq. ammonia solution to the nitrate solution; the resulting solution contains 71,5 g Hg2NNO3 per liter and is 0,15 molar. To prepare Hg2NN3, 66 mL of this solution are added to 650 mL of a 1% sodium azide solution (0,1 mol), the precipitate is filtered off, is washed with the sodium azide solution, then with water and dried between paper.

Properties and reactions:
Hg2NN3 is a yellow crystalline powder and contains 1 mol of water, that is given off between 40 and 80 °C in the desiccator over conc. sulfuric acid, the compound changes color to a yellow-red. The description of it as a trihydrate is therefore unlikely. - The azide is extremely sensitve towards impact and detonates. It explodes under a 2 kg hammer at 35 cm. On rapid heating it detonates, but under normal conditions it is stable. On slow heating, it is stable at 200 °C for about 2 hours, if the temperature is slowly raised to 340 °C (the explosion temperature) it decomposes without explosion.
Hg2NN3 is insoluble in water and alcohol, as well as in most common organic solvents, it is soluble in formic and acetic acid on heating. If H2S is passed into its suspension in water, all mercury is precipitated, addition of excess Na2S on heating results in Hg precipitation and ammonia evolution, acids evolve HN3



[Edited on 3-1-2021 by Diachrynic]

vano - 3-1-2021 at 09:55

Thanks Diachrynic. It is quite simple. I buy nitric acid these days now what I have I do not think will be enough. When I do I will post it here. Can you give me a link where I can download this book?

Diachrynic - 3-1-2021 at 11:20

It's not digitalized anywhere yet, the scan is from my own physical copy, and I am still working on cleaning the scans (not fully happy with how badly readable some pages are yet).

vano - 3-1-2021 at 11:50

Quote: Originally posted by Diachrynic  
It's not digitalized anywhere yet, the scan is from my own physical copy, and I am still working on cleaning the scans (not fully happy with how badly readable some pages are yet).


It is bad that there is no digital version. I hope that when you finish working then you will share it with me. It looks like a pretty good book. I love old German sources. I can imagine how many similar German books would not have a digital version.

Diachrynic - 3-1-2021 at 12:04

Sure, I will tell you once I'm done. The fact that there are no digital versions sadly holds true for many of the books in this series. They are a real hidden gem. Most university libraries here have them in their collection however.

vano - 3-1-2021 at 12:17

Quote: Originally posted by Diachrynic  
Sure, I will tell you once I'm done. The fact that there are no digital versions sadly holds true for many of the books in this series. They are a real hidden gem. Most university libraries here have them in their collection however.


Thank you! You are lucky there are many good books available in your language.