Sciencemadness Discussion Board

Silver Nitrate + Ethanol = Ethyl Nitrate?

rot - 15-4-2006 at 09:27

This is what I've found on an MSDS for Ethanol:
Quote:

Ethanol forms explosive products in reaction with the following
compound : ammonia + silver nitrate (forms silver nitride and silver fulminate), iodine + phosphorus (forms ethane
iodide), magnesium perchlorate (forms ethyl perchlorate), mercuric nitrate, nitric acid + silver (forms silver
fulminate) silver nitrate (forms ethyl nitrate) silver(I) oxide + ammonia or hydrazine (forms
silver nitride and silver fulminate), sodium (evolves hydrogen gas).


Is this really true? I mean, can you really make Ethyl nitrate from Silver Nitrate and Ethanol?

The_Davster - 15-4-2006 at 10:18

OH is not really a good leaving group here, I know that ethyl chloride and silver nitrate form ethyl nitrate, but am unsure how well simple ethanol would work.

MSDS often present worst scenario situations, like magnesium pderchlorate reacting with ethanol to make ethyl perchlorate, which does not really happen if I remember correctly the stuff that Blaster said a long time ago.

rot - 15-4-2006 at 10:34

Isn't Ethyl Chloride prepared by bubbling Chlorine gas through Ethanol?
And how about other Nitrate Salts like Ammonium Nitrate?

The_Davster - 15-4-2006 at 10:47

No, that is chloral hydrate.

This reaction is driven by the insolubility of the silver chloride formed, so something like ammonium nitrate would not work.

TheBear - 22-5-2006 at 11:45

Quote:

"I know that ethyl chloride and silver nitrate form ethyl nitrate".


Has anyone tried this? Refluxing methanol with conc. HCl (aq) and leading formed gas (MeCl) through a concentrated AgNO3 solution should result in methyl nitrate, which should form a separate layer on the bottom (denisty = 1.203 g * cm ^ -3). Don't know how practical it would be though.

simply RED - 25-5-2006 at 00:03

R-Cl + AgNO3 = R-O-NO2 + AgCl
Tried and working.

gregxy - 26-5-2006 at 18:12

I think EtOH and AgNO3 makes silver fulminate AgCNO. (But maybe you need extra HNO3 for this. I used to make it when I was a teenager.)

Chris The Great - 26-5-2006 at 20:00

Yes, the AgNO3 is in a solution of nitric acid.

Bromine - 30-9-2006 at 10:27

Could it be done by Pb(NO3)2 and ethanol?

Nicodem - 30-9-2006 at 10:55

No, alcohols and nitrates don't form alkyl nitrates without the presence of a strong acid. The MSDS sheets are not made to be chemical reference. They are what their acronym stands for, material safety sheets and nothing more. If you use such information as a chemical reference you need to be really naive to take it seriously.
The only nitrate salts that can form nitrate esters from alcohols, are those that are themselves strong enough Lewis acids (and AgNO3 is too weak acid to do that, same goes for Pb(NO3)2).

If you want to prepare ethyl nitrate from ethanol than do it like it is usually done, by the esterification with nitric acid. If having no nitric acid, it can also be done with NaNO3 or KNO3 in the presence of H2SO4. But these methods are already described enough at this forum.

Edit: But then again, the last questions were perhaps about the fulminates? Damn, I hate threads that shift the topic three times on the same page without any warning. Bromine, clarify on which topic does your question relate.


[Edited on 30-9-2006 by Nicodem]

Bromine - 30-9-2006 at 22:48

It was about ethyl nitrate.

Zinc - 18-10-2006 at 03:51

Quote:
Originally posted by simply RED
R-Cl + AgNO3 = R-O-NO2 + AgCl
Tried and working.


Could Pb(NO3)2 work instead AgNO3?

solo - 18-10-2006 at 07:41

Interesting Reading on the topic of Alkyl Nitrates



Alkyl Nitrate Formation from the Reaction of a Series of Branched RO 2 Radicals with NO as a Function of Temperature and Pressure
ROGER ATKINSON,* SARA M. ASCHMANN, and ARTHUR M. WINER
Journal of Atmospheric Chemistry 5 (1987), 91 -102.


Abstract
Alkyl nitrate yields from the NO x photooxidations of neopentane, 2-methylbutane and 3-methylpentane have been determined over the temperature and pressure ranges 281-323 K and 54-740 tort, respectively. The formation of the alkyl nitrates is attributed to the reaction pathway

RO2 + NoM'~RONO2 (lb)

and rate constant ratios klb/(kla + klb) are estimated, where (la) is the reaction pathway

RO2 + NO ~ RO + NO 2 . (la)

A method for estimating this rate constant ratio for primary, secondary and tertiary alkyl peroxy radicals is presented.

Key words. Alkane, alkyl nitrate, tropospheric chemistry, nitrogen oxides, alkyl peroxy radical.

Attachment: Alkyl Nitrate Formation from the Reaction of a Series of Branched RO 2 Radicals with NO as a Function of Temperature and (528kB)
This file has been downloaded 1193 times

Sergei_Eisenstein - 18-10-2006 at 12:55

Quote:
R-Cl + AgNO3 = R-O-NO2 + AgCl
Tried and working.

Could Pb(NO3)2 work instead AgNO3?



The role of silver ion is to assist the halogen X from leaving R-X. Assuming we are discussing an SN2-type of reaction, more charge will be developed in the transition state on the X-substituted carbon when silver is used than when it's not. Alkyl halides react as soft electrophiles, but will react as hard electrophiles when silver ions (or other Lewis acids, e.g. Zn2+) are used. As such, addition of Lewis acids will promote a hard-hard type of reaction with the nitrite ion. In the latter, the nitrogen is the soft center. A hard-hard interaction will take place between the Ag-mediated TS and an oxygen from the nitrite ion. A soft-soft interaction will take place when no Lewis acids are used (e.g. NaNO2 as nitrite source). In practice, solvent effect is important as well (it has an influence on the TS in substitution reactions), just as the characteristics of the halide (Cl, Br, I, OTs, OMs) have to be taken into account as well.

You can explain the reactivity by approaching the HOMO/LUMO interactions. If it interests you, read up on frontier orbitals.


{EDIT} BANG! I noticed too late that we were discussing nitrates instead of nitrites. My apologies; once you have something in your mind, you read it on the screen as it is in your mind as well... I won't remove the post as some people may find it still interesting {/EDIT}

[Edited on 18-10-2006 by Sergei_Eisenstein]

Nitrojet - 24-10-2006 at 10:52

Ethyl Nitrate can be successfully synthesized via the following procedure:
ETHYL NITRATE 1
Concentrated nitric acid (d. 1-4, 250 c.c.) is boiled with 30 g. of
urea nitrate. After the solution has been cooled one half is poured
into a tubulated retort containing 30 g. of urea nitrate and 150 c.c.
of alcohol. A moderate-sized condenser is attached to the retort,
which is then carefully heated on a sand bath. After about one
third of the material has been distilled the remainder of the boiled
urea nitrate-nitric acid solution, mixed with 100 c.c. of alcohol, is
allowed to run slowly into the retort from a dropping funnel inserted
through the tubulure. The operation must be carried out without
interruption: the mixture of alcohol and nitric acid must not be
allowed to stand for any length of time. When all the liquid in the
funnel has been added and that in the retort has been reduced by
distillation to 50-100 c.c, the ethyl nitrate which has passed over
is freed from alcohol by being shaken in a separating funnel twice
with water, then once with dilute sodium carbonate solution, and
finally once more with water (ethyl nitrate is heavier than water !).
After being dried over calcium chloride it is distilled from a water
bath in which the distilling flask should be immersed. Boiling
point of ethyl nitrate 86°. (Goggles should be worn in this experiment.)

Ethyl nitrate

Zinc - 4-7-2008 at 05:38

I know that ethyl nitrate can be made from ethyl bromide and silver nitrate. But how is that done? Is the silver nitrate dissolved in some solvent and then EtBr is poured in and EtONO2 forms as a layer of liquid?

As far as I know the solvent for the reaction must be a solvent in which AgNO3 (or Pb(NO3)2) are soluble but AgCl (or PbCl2) are not and in which EtBr is significantly ionized.

I have heard that acetone can be used. Can it be?

And could AgNO3 be replaced by Pb(NO3)2?

Axt - 4-7-2008 at 11:14

If you "know" something without doing it you must take it from a credible source (even then the word "know" is too strong) and to be a credible source it should either give the preparation or references to it. If you state the source of your information one can try track down the original preparation. Ethanol seems like the logical solvent, though whether dilution will seperate the EtONO2 who knows, you have to take the ease of extraction into account.

While it seems like a probable reaction, it sure doesn't sound like a practical one. While it is prone to runaway oxidation during nitration, its still usable on the lab scale. I believe boomer posted its preparation on apc forum some time ago, via careful nitration with mixed acids.

[Edited on 5-7-2008 by Axt]

garage chemist - 4-7-2008 at 11:27

You are probably thinking about the reaction of silver nitrIte with ethyl bromide. This gives ethyl nitrIte and nitroethane in approximately equal proportions. Go look it up on Rhodium (they use ethyl iodide there).

Whether silver nitrAte even reacts with ethyl bromide I do not know.

But what I do know is that ethyl nitrAte is made by direct esterification of ethanol with nitric acid!
There's a procedure for this on lambdasyn.
No H2SO4 is used. The process uses distillation of 65% HNO3 with ethanol under addition of urea nitrate to prevent accumulation of nitric oxides in the mix, which would lead to runaway oxidation of the ethanol.

Zinc - 4-7-2008 at 12:31

Yes I am aware of the HNO3+ethanol method.

I have seen the nitrite synthesis on Rhodium.


I have checked if (PbNO3)2 is soluble enough in ethanol to see if ethanol could work, but the solubility is too low (1 g/2500 ml)

Axt - 4-7-2008 at 13:16

You failed to state you source of how you "know" this.

Checking scifinder yields your best bet with:

<b>Evidence against ion-pair formation in the reactions of ethyl halides with silver salts</b>. Kevill, Dennis N.; Fujimoto, Edward K. Journal of the Chemical Society, Chemical Communications (1983), (20), 1149-50.

Abstract

The product ratio from the reaction of EtI with AgNO3 in EtOH varies with salt concn., and is very similar to that for the corresponding SN2 reactions of Et3O+ PF6-. These results provide evidence that the reaction is SN2 in character and does not occur via rate-detg. formation of ion-pair or quadrupole-ion intermediates as previously reported.

Just because one reactant has low solubility doesnt mean the reaction wont run. Though I'm still lost as to why one would pursue this route.

The only mixed acid nitration I could find was utilising oleum in Memorial des Poudres (1953), 35 71-82. There are plenty descibing the ~70% HNO3 nitration garage chemist mentioned, distilling it off the heated mixture as it forms.

Zinc - 4-7-2008 at 13:49

Quote:
Originally posted by Axt
You failed to state you source of how you "know" this.


Sorry, I dint express my self correctly. I don't know that. I just thought it is like that.
Quote:
Originally posted by Axt
The only mixed acid nitration I could find was utilising oleum in Memorial des Poudres (1953), 35 71-82. T


Here is one I found at http://www.sciencemadness.org/talk/viewthread.php?tid=253&am...

Ethyl Nitrate without distillation
Author: Fly
Procedure: Prepare a nitrating mix using 260 ml 65% HNO3 and 300 ml 96% H2SO4. Slowly add the H2SO4 to the HNO3 with cooling and constant stirring. Let the nitrating mix cool down to 0°C in a refrigerator. In another container place 160 ml of pure ethyl alcohol and slowly add 16 ml 96% H2SO4 with cooling and stirring. Let this mix cool down to 0°C as well. Prepare a salted ice bath and place a 1L or larger beaker in it. Pour the cold nitrating mix into the beaker, place a thermometer in it and begin the addition of the cold ethanol mix. Keep stirring the mixture, adjust the rate of addition so that the temperature stays around 5°C, do not allow the temperature to rise above 10°C. When the addition is complete, continue stirring the mixture for another 5 mins. Transfer the mixture into a separatory funnel and let it stand for 15 mins. The crude ethyl nitrate should separate out, drain the acid portion. The separation should not be carried out for more than 15 mins., after that the product might start oxidizing. The crude ethyl nitrate is washed by 300 ml of cold water (shake the mixture thoroughly in a plastic bottle). Repeat the separation and wash the product again with 300 ml water, then add a small amount of NH3 solution to the mixture and shake it again. Repeat the NH3 addition until the solution is pH neutral. Repeat the separation and washing steps, check that the product is clear and colorless. Now the product can be finally separated, dried over CaCl2 and filtered. The product obtained in this way should not be stored.

chemoleo - 4-7-2008 at 17:20

Merged your posts with this thread, Zinc.

This is a thread right on the subject, took me 30 seconds to find it.
No need to pretend that you want an exotic route to ethylnitrate if all you are after is the final product, as you make clear in your last post. But I do suspect there was simply some confusion on ethylnitrIte and ethylnitrAte.

Search next time, and be warned.

[Edited on 5-7-2008 by chemoleo]

Zinc - 5-7-2008 at 13:05

Quote:
Originally posted by chemoleo
No need to pretend that you want an exotic route to ethylnitrate if all you are after is the final product, as you make clear in your last post.


I am not pretending. I just wanted to know if that method is usable. Yes all I am after the final product. There is no shame in admitting that.

Sorry for not searching first.

[Edited on 5-7-2008 by Zinc]

ScienceSquirrel - 5-7-2008 at 18:31

You can recrystallise silver nitrate from ethanol /water.
I would guess that refluxing silver nitrate in ethanol for long enough might produce something nasty.

Formatik - 5-7-2008 at 19:29

AFAIK, you need quite a bit of nitrogen oxides to initiate that reaction.

garage chemist - 5-7-2008 at 22:41

Zinc, just tell us: do you have a distillation setup?

Zinc - 6-7-2008 at 03:30

Unfortunately I don't have one:( But I did use improvised ones a few times.

[Edited on 6-7-2008 by Zinc]

Picric-A - 20-7-2008 at 14:07

ouch, improvised distillation apparatus whe dealing with explosives, be careful!
maybe a bit off the topic but has anyone heard that silver fulminate can be prepared by reacting silver oxide with ammonia? this would beat silver nitrate + nitric acid + EtOH anyday!
I wonder if it works with other salts, eg lead? :P

Zinc - 21-7-2008 at 08:08

Silver oxide and ammonia produce silver nitride, not silver fulminate.

Picric-A - 21-7-2008 at 12:18

oh kk, this must be wrong then :P
http://www.saltlakemetals.com/MSDS_Silver_Oxide.htm

S.C. Wack - 21-7-2008 at 12:56

Quote:
Originally posted by Picric-A
oh kk, this must be wrong then :P
http://www.saltlakemetals.com/MSDS_Silver_Oxide.htm


An amazing feat of transmutation, but unfortunately to carbon instead of gold.

nitro-genes - 21-7-2008 at 14:24

http://en.wikipedia.org/wiki/Silver_fulminate

http://en.wikipedia.org/wiki/Fulminating_silver

Picric-A - 22-7-2008 at 15:34

lol soz my mistaque.
i sent the company an email and asked them to change it, i have just checked and they have :P