deltaH
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The dinitritoarginate(I) anion, [Ag(NO2)2]- and friends
I stumbled across an old article that mentions the salt Na[Ag(NO)2] prepared from the electrolysis of sodium nitrite solutions using a silver anode.
http://pubs.rsc.org/en/Content/ArticleLanding/1920/TF/tf9201...
This dinitritoargenate(I) anion intrigued me because of the range of interesting and possibly useful energetic primaries that could be formed from it,
e.g. [C(NH2)3]Ag(NO2)2 and many more.
However, there's doubts whether this anion is even real?
Here's the information that I could find on this so far:
http://wwwbrr.cr.usgs.gov/projects/GWC_chemtherm/pubs/wq4fdo...
Log K° =2.22 for reaction
Ag+ + 2NO2- => Ag(NO2)2-
Source is referenced as:
NBS Technical Notes 270 (Wagman and others, 1968, 1969; Parker and others, 1971)[/url]
http://www.degruyter.com/view/j/zkri.1978.146.issue-1-6/zkri...
x-ray diffraction crystallographic structure assignment of [Ag(NH3)2]Ag(NO2)2
https://books.google.co.za/books?id=JUj-BAAAQBAJ&pg=PA472&lpg=PA472&dq=%22Ag(NO2)2%22&source=bl&ots=VB0HaEHg-v&sig=eZOy
DQR4dXpXrpCY781oVcB_4Yw&hl=en&sa=X&ved=0CDoQ6AEwB2oVChMIj-aN4orHyAIVQ88UCh2gfAIC#v=onepage&q=%22Ag(NO2)2%22&f=false
Mentions that alkali nitrites can form double nitrites among which Cs[Ag(NO2)2] is mentioned.
https://books.google.co.za/books?id=Dv_F03cdKPUC&pg=PA273&lpg=PA273&dq=%22Ag(NO2)2%22&source=bl&ots=lbYdEYQYTY&sig=J5b2
9LGsyQjo_Z_jOyYOtseDm-A&hl=en&sa=X&ved=0CCwQ6AEwA2oVChMIj-aN4orHyAIVQ88UCh2gfAIC#v=onepage&q=%22Ag(NO2)2%22&f=false
Oxidised nitrogen. Solutions of AgNO2 with KNO2 or Ba(NO2)2 yield K[Ag(NO2)2].½H2O or Ba[Ag(NO2)2]2.H2O.
… next page not part of free book review 
https://books.google.co.za/books?id=vsE1Ptt1qsIC&pg=PA167&lpg=PA167&dq=%22Ag(NO2)2%22&source=bl&ots=1oPduJep8M&sig=rI_i
QW9P1Onw1URNswZxJ6UCRSg&hl=en&sa=X&ved=0CC8Q6AEwBGoVChMIj-aN4orHyAIVQ88UCh2gfAIC#v=onepage&q=%22Ag(NO2)2%22&f=false
mentions that the ions [Ag(NO2)2]- and even higher aggregates like [Ag2(NO2)3]- , but to a lesser extent, have been studied by mass spectroscopy in
acetonitrile solutions.
This is referenced to this paper:
A. Cingolani, et. Al. Inorg. Chem., 2002, 41, 6633.
http://chemiday.com/en/reaction/3-1-0-2483
AgNO2 + KNO2 → K[Ag(NO2)2]
Notes KNO2 concentrated
http://chemiday.com/en/reaction/3-1-0-2500
AgNO3 + 2KNO2 → K[Ag(NO2)2] + KNO3
[Edited on 16-10-2015 by deltaH]
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PHILOU Zrealone
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Interesting!  
Just beware that the title tread contains a confusing naming mistake!
Arginic acid is H2N-C(=NH)-NH-CH2-CH2-CH2-CHOH-CO2H (thus a guanidine and pentanoic acid derivative)... so "dinitritoarginate" will refer to a
dinitrite derivative of arginic acid.
Should be "nitrito-silver nitrite complex" or "dinitrito-silver-ate" or "dinitrito-argent-ate" instead.
Note that there seems to be confusion in the naming also from writers "diamminesilver dinitroargentate" .. thus combining "silver" from English and
"argent" from French in the same chemical nomenclature... not smart nor best  .
Ammonium dinitritosilverate or hydrazinium or hydroxylaminium compounds must be unstable but who knows maybe just on the edge of existance -->
primaries?
Other aminium cations may be more stable like ethylene-diaminium or guanidinium...
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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deltaH
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Yay, somebody responded to this finally
Well spotted PHILOU. I was following the complex naming rules from this site below rather blindly:
http://www.chemistry.wustl.edu/~edudev/LabTutorials/naming_c...
which said to use 'argenate', which I now realised I misspelt as 'arginate'. I agree, argentate, makes it very unambiguous on reading.
Yes, the guanidinium salt is my favourite hypothetical because of the nice OB and inertness of the cation.
I still think it will be a primary though, though hopefully a relatively behaved one.
[Edited on 20-10-2015 by deltaH]
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DraconicAcid
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Quote: Originally posted by PHILOU Zrealone  |
Note that there seems to be confusion in the naming also from writers "diamminesilver dinitroargentate" .. thus combining "silver" from English and
"argent" from French in the same chemical nomenclature... not smart nor best. |
That's not confusion on the part of the writers- that's the rules. For a cation, you use the English name of the metal (silver, iron, copper). For
an anion, you use the Latin base with the suffix "-ate" (argentate, ferrate, cuprate) for any metal that has a symbol based on the Latin equivalent.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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PHILOU Zrealone
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| Quote: Originally posted by DraconicAcid | | Quote: Originally posted by PHILOU Zrealone |
Note that there seems to be confusion in the naming also from writers "diamminesilver dinitroargentate" .. thus combining "silver" from English and
"argent" from French in the same chemical nomenclature... not smart nor best. |
That's not confusion on the part of the writers- that's the rules. For a cation, you use the English name of the metal (silver, iron, copper). For
an anion, you use the Latin base with the suffix "-ate" (argentate, ferrate, cuprate) for any metal that has a symbol based on the Latin equivalent.
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Thank you DraconicAcid,
Glad to learn something new! Every day has its tiny wonders!
I would never have thought that English chemical nomenclature would be harder than the French one... being native french speaker, in French we would
use both latin roots:
For (H3N)2Ag2(ONO)2
"complexe Diamino argent dinitroargentate"
or
"complexe Diammine argent dinitroargentate"
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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deltaH
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According to Wikipedia (1), crystals of tetraamminecopper(II) hydroxide are oxidised by oxygen to form copper ammine nitrites, Cu(NO2)2.(NH3)n,
(2)(3).
Now I wonder if mixing a silver nitrate solution into an excess of conc. ammonium hydroxide to prepare Tollens' reagent so that
(H3N)2Ag2(ONO)2.2NH4NO3 might form if the solution evaporates while airing with oxygen (by an analogous oxidation of ammonia)?
Furthermore, since such a salt is oxygen positive, it would benefit from combining with a fuel, so I have this idea that one might drip a couple of
drops of the Tollens Reagent onto a tiny amount of chopped nitrocellulose or perhaps even a double base propellant and spread it out over a piece of
plastic to dry, to make sensitised nitrocellulose that could be used as a powerful primary composition?
Yes, yes, I know there's plenty of primaries in the world already, but I like thinking up ideas for new ones, even if I can't carry them out.
References:
(1)https://en.wikipedia.org/wiki/Schweizer%27s_reagent
(2)Y. Cudennec; et al. (1995). "Etude cinétique de l'oxydation de l'ammoniac en présence d'ions cuivriques". Comptes Rendus Académie Sciences
Paris, série II,Méca; phys. chim. astron. 320 (6): 309–316.
(3)Y. Cudennec; et al. (1993). "Synthesis and study of Cu(NO2)2(NH3)4 and Cu(NO2)2(NH3)2". European journal of solid state and inorganic chemistry.
30(1-2): 77–85.
[Edited on 25-10-2015 by deltaH]
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PHILOU Zrealone
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| Quote: Originally posted by deltaH | According to Wikipedia (1), crystals of tetraamminecopper(II) hydroxide are oxidised by oxygen to form copper ammine nitrites, Cu(NO2)2.(NH3)n,
(2)(3).
Now I wonder if mixing a silver nitrate solution into an excess of conc. ammonium hydroxide to prepare Tollens' reagent so that
(H3N)2Ag2(ONO)2.2NH4NO3 might form if the solution evaporates while airing with oxygen (by an analogous oxidation of ammonia)?
Furthermore, since such a salt is oxygen positive, it would benefit from combining with a fuel, so I have this idea that one might drip a couple of
drops of the Tollens Reagent onto a tiny amount of chopped nitrocellulose or perhaps even a double base propellant and spread it out over a piece of
plastic to dry, to make sensitised nitrocellulose that could be used as a powerful primary composition?
Yes, yes, I know there's plenty of primaries in the world already, but I like thinking up ideas for new ones, even if I can't carry them out.
References:
(1)https://en.wikipedia.org/wiki/Schweizer%27s_reagent
(2)Y. Cudennec; et al. (1995). "Etude cinétique de l'oxydation de l'ammoniac en présence d'ions cuivriques". Comptes Rendus Académie Sciences
Paris, série II,Méca; phys. chim. astron. 320 (6): 309–316.
(3)Y. Cudennec; et al. (1993). "Synthesis and study of Cu(NO2)2(NH3)4 and Cu(NO2)2(NH3)2". European journal of solid state and inorganic chemistry.
30(1-2): 77–85.
[Edited on 25-10-2015 by deltaH] |
I would be a nice way to make nitrous acid and nitric acid from ammonia (or urea).
The reaction of AgNO3 with NH4OH will also make the dangerous fulminating silver mirror (Ag3N, Ag2NH and AgNH2).
AgNO2 is said to yield AgN3 upon reaction with H2N-NH2...
I don't know what is the result of NH2-OH or NH3...
[Edited on 27-10-2015 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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deltaH
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We do know that for the case of ammonia, according to the reference in the opening post, [Ag(NH3)2]Ag(NO2)2 is isolated, so ammonia doesn't react with
the nitro group.
The key question here is whether a similar compound can be isolated by evaporating thin films of Tollens reagent over non-reducing materials, like
nitrocellulose.
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PHILOU Zrealone
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Worth a test in TINY quantity.
Or safer... silver acetylide nitrato complex mixed with NC
--> with the help of a good solvent...
1°) to be evaporated --> hard detonating block of suited shape.
2°) or not --> detonating gel ... like nitromethane-NC gel with suspended dispersion of SADS.
[Edited on 27-10-2015 by PHILOU Zrealone]
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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PHILOU Zrealone
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I have to think a bit about it...
You mentionned log K°= 2.22 for equation Ag(+) + 2 NO2(-) --> Ag(NO2)2(-)
All the way down we must think to other reactions and equilibriums (equilibria):
1°) Ks of AgNO2
AgNO2(s) <=water=> Ag(+) + NO2(-)
2°) Ks of AgCl
AgCl(s) <=water=> Ag(+) + Cl(-)
3°) Ks of Ag2SO4
Ag2SO4(s) <=water=> 2 Ag(+) + SO4(2-)
4°) Ke of formation of complex Ag(NH3)2(+)
Ag(+) + 2 NH3(g) <=aqueous or not?=> Ag(NH3)2(+)
If we assume the use of Ba[Ag(NO2)2]2 with [Ag(NH3)2]2SO4 to allow precipitation of BaSO4, we must think that precipitation of Ag2SO4 may be
competitive enough to ruin the dinitrito complex...I have to do the math and play with all Ke, Ks, Kc.
Also If we start from [Ag(NH3)2]Cl and K[Ag(NO2)2] to make [Ag(NH3)2Ag(NO2)2] and maybe KCl, we have to imagine that AgCl may precipitate
competitively.
Thus playing with those complexes might prove to be a real challenge.
Maybe they would require cationic and anionic exchange resins...
I wonder how they did make [Ag(NH3)2Ag(NO2)2]?
I doubt that it is by:
-simply allowing AgNO2 to be diluted in NH3(l) and excès NH3 evaporated.
-by passing dry NH3 over moist AgNO2 (or moist NH3 over dry AgNO2).
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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deltaH
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Requested for you in References, I'm curious myself now
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deltaH
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Synthesis of diamminesilver(I) dinitritoargentate(I)
The synthesis is trivial and just look at the size of those crystals!
From the paper by H. M. MAURER & ALARICH WEISS, 1977:
With a density of 2.9g/cc
[Edited on 31-10-2015 by deltaH]
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PHILOU Zrealone
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Indeed big cristals  1,1*1,1*1.6 ccm is more than 1 ccm and roughly 5.6 g
(based on density 2.9 from the paper you requested in document request -->
Thank you for that)
Nice! I definitevely have to try that, so simple and all chems at hand!
AgNO2 can be made by mixing AgNO3 solution with NaNO2 solution; it is relatively unsoluble and will precipitate as white cristals.
I just have to convince my girlfriend, it is safe  ... she is very chemophobic
... not a dream for a chemist like me...
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
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deltaH
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I personally think these authors took a gamble preparing such large crystals of a potential primary. I would never prepare more than 100mg if it were
me.
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