Sciencemadness Discussion Board - Copper Oxybromide

Copper Oxybromide

Rsambo - 9-6-2016 at 11:54

I have been following this forum for sometime but this is my first post here, I apologise in advance for any poor etiquette.

I have been working with Potassium Bromate / Copper (i) bromide / Nitrocellulose / Nitroguanadine pyrotechnic blues. I have some interesting results but I am finding that Copper (i) bromide oxidises in air readily to the Copper (ii) form ( which is deliquescent ) and so within a short 24 hour period the effect is lost.

I'm trying to think of ways around the problem and wondered if the analogue of Copper Oxychloride might be suitable, namely : Copper Oxybromide. I can find little information regarding the latter. Copper Oxychloride can be made by the aeration of copper metal in hydrochloric acid. Is it plausible that the oxybromide might be produced by the aeration of copper in hydrobromic acid?

[Edited on 9-6-2016 by Rsambo]

myristicinaldehyde - 9-6-2016 at 12:24

A pre cursory search of my books didn't turn up any hits for oxybromide, but I can't imagine why not. Here's a synth. of oxychloride. It might work for the bromide version.

myristicinaldehyde - 9-6-2016 at 12:50

From JSTOR- an actual preparation seems like.

Rsambo - 12-6-2016 at 13:20

Thanks very much, I'm quite tempted to give the calcium carbonate metathesis a go. I need to re-distill my hydrobromic acid and then I might have some results to show for it !

myristicinaldehyde - 13-6-2016 at 03:49

Good luck! I might just try it myself.

Rsambo - 13-6-2016 at 08:42

If you're at all into colours you should DEFINITELY try potassium bromate / copper (i) bromide with NC. It truly is an incredible blue, even if it doesn't keep. It's like a powder blue.

myristicinaldehyde - 13-6-2016 at 12:35

Quote: Originally posted by Rsambo

If you're at all into colours you should DEFINITELY try potassium bromate / copper (i) bromide with NC. It truly is an incredible blue, even if it doesn't keep. It's like a powder blue.

I DO like colors, but NC is nitrocelluose, right? Chemical acronyms bother me. Am I right in guessing it burns green? Sounds like fun stuff! (^-^)

Rsambo - 13-6-2016 at 13:22

Sorry yes, Nitrocellulose. It burns with a very nice powder blue. % by weight :

KBrO3 58%
CuBr 18%
Hexamine 10%
Nitrocellulose 14%

Rsambo - 14-6-2016 at 04:53

Well I'm not having much luck here so far. I have tried reacting CuO with my hydrobromic acid and all I get is a dark brown liquid which when I dilute to re-crystallize just seems to form what looks like Copper Sulphate crystals. Either something is majorly wrong with my hydrobromic acid synthesis or something else ? ! ?

PHILOU Zrealone - 14-6-2016 at 05:13

Quote: Originally posted by Rsambo

Well I'm not having much luck here so far. I have tried reacting CuO with my hydrobromic acid and all I get is a dark brown liquid which when I dilute to re-crystallize just seems to form what looks like Copper Sulphate crystals. Either something is majorly wrong with my hydrobromic acid synthesis or something else ? ! ?

If you get sulfate anion (SO4(2-)) from bromhydric acid (HBr); then indeed you are in big troubles...
Then run for life ... thermonuclear fusion and fission are occuring into your reactor!

[Edited on 14-6-2016 by PHILOU Zrealone]

PHILOU Zrealone - 14-6-2016 at 05:15

Quote: Originally posted by Rsambo

Sorry yes, Nitrocellulose. It burns with a very nice powder blue. % by weight :

KBrO3 58%
CuBr 18%
Hexamine 10%
Nitrocellulose 14%

What is the benefit over cheaper CuCl, KClO3, Hexamine, NC?
What also makes a wonderful blue colour...

woelen - 14-6-2016 at 06:01

Quote: Originally posted by Rsambo

"Het probleem is niet het spulleke, maar het knulleke"

There is no issue with your HBr. When you dissolve CuO in aqueous CuBr, then you get the dark brown red complex CuBr4(2-) in excess HBr. On evaporation, however, you lose water and HBr and what is left behind is hydrated CuBr2.2H2O. A better description is CuBr2(H2O)2. This is a blue compound with a greenish hue. Anhydrous CuBr2 is black, very much looking like iodine.

If the HBr is impure and also contains H2SO4, then you'll lose even more HBr on evaporation and CuSO4.5H2O remains behind, with a small amount of CuBr2(H2O)2 in it as well.

Making oxybromide of copper in this way is not possible. For that you need a more basic solution.

Rsambo - 14-6-2016 at 11:08

The benefit is the blue is substantially more saturated and "cleaner". Not only that but this is an indirect and intriguing route to an alternative blue strobe. Aside from that, it's just fun and I'm learning here.

Thanks Woelen. Google translate didn't quite get there for me on that one unfortunately. I see, so it forms a dihydrate analogous to Copper (ii) chloride dihydrate formed using Copper (ii) Carbonate and HCl. I'm rather embarrassed to say I have pondered on your last point for the last half hour but I can't quite get there.

I had wondered about the water of crystallization and in my first run I took some of the crystals and heated them and they were definitely copper sulphate as they behave exactly as such when anhydrous; and are white when dehydrated. In my second run I re-distilled my hydrobromic acid and it came over consistently at 126 degrees C, so I'll go and dry again and see if I can dehydrate these crystals to check they are black and not white when anhydrous.

I'd really love to figure 90% of this out for myself and not be spoon fed, especially with my first post but I'm feeling like I need a bump in the right direction.

PHILOU Zrealone - 14-6-2016 at 12:34

Then maybe go for CuI, KIO3, hexamine and NC ... to get another shade of blue?

Rsambo - 14-6-2016 at 13:25

Veering off topic, but since you ask :

"Recently, some of us reported copper(I) iodide as a potential “green” blue light emitter for perchlorate-free compositions. These compositions are based on a pyrotechnic formulation that involves copper iodate, guanidinium nitrate, and magnesium. The main drawback is a low burning rate of the compositions. In turn, they produce ash when burned and a blue flame of low intensity"

Dominykas Juknelevicius et al., Chemistry - A European Journal 21(43):15354 · September 2015

[Edited on 14-6-2016 by Rsambo]

PHILOU Zrealone - 14-6-2016 at 14:15

Not off topic ...
CuCl, CuBr and CuI are Cu(+) halides and as such responsible of the blue-green flame colour...in principle the blue green colour also works with Cu(2+) if halide is present into the pyrotechnic mix (via PVC glue, powder or intrinsically from the oxydiser (chlorate/perchlorate)...but Cu(2+) and chlorate anion generates storage troubles.

Nothing is thus against the use of CuCl2, CuBr2 or CuI2 into pyro comp except eventual reactivity with an ingredient of the pyro compo --> storage stability.

Rsambo - 14-6-2016 at 21:57

Hi Philou,

I didn't mean to offend. This thread is really supposed to be about how to synthesize Copper Oxybromide

CuCl2 with nitrocellulose makes an extremely beautiful blue

woelen - 14-6-2016 at 23:14

My words are hard to translate. I think PHILOU may be able to understand them and smile

What I meant with my last sentence is that making oxybromide (and also oxychloride) from CuO and the corresponding acid is not possible in those acidic solutions.

If you use excess acid, then all CuO dissolves to form the halide and the strongly colored tetrahalogen complex of copper (which is deep yellow/brown for chloride and nice purple/red/brown for bromide). If you use excess CuO, then you get a solution of the copper halide and some CuO remains undissolved.

Making oxyhalide can be done by preparing a solution of the copper halide and then carefully adding (under constant strong stirring) hydroxide. This will give you a compound of ill-defined composition, with halide ions and hydroxide ions mixed in the compound. Heating this stuff drives off water and leaves behind a mixed halide/oxide.
Another option is to prepare wet CuCl or CuBr. These are white solids and can be prepared from HCl/HBr, copper oxide and a sulfite or metabisulfite. The wet solid must be rinsed with water and then the humid compound must be put aside in contact with air. It will oxidize quickly and lose its white color. When it is dry, you need to grind very well and allow to stand in contact with air for another few days. Finally you end up with a dry, non-hygroscopic powder. The mixed oxide/chloride is green (not blue at all), I expect the mixed oxide/bromide to be green as well, probably a somewhat darker shade, green like olives. But this is my educated guess, I have no personal experience with that. If you use a sulfite/metabisulfite, use the potassium salt, such as K2S2O5. If you use the sodium salt, then the resulting copper oxide/halide also has some sodium ions in it, which spoils the blue color of the flame.

Rsambo - 15-6-2016 at 05:33

Ah ha. Thank you very much for an incredibly clear explanation. Just to make absolutely sure Philou I very much appreciate your comments, it's one of the problems with forums to worry that you aren't offending anyone ! Hey, I might just try your iodate anyway !

Woelen, I can certainly expand on your suggestion as I have synthesised the Copper (i) halide using both potassium metabisulfite and sodium sulfite so I'm going to run with that and see what I can do. Thanks enormously !

PHILOU Zrealone - 15-6-2016 at 08:09

@Woelen,
I don't know that idiom (maybe more from The Netherlands than from The Flanders?) but I think I get the feeling of it/ the idea.
"Het probleem is niet het spulleke, maar het knulleke"
-->
The problem doesn't resides into the material, but more into the operator/the process.
Correct understanding? (A la Dutch way: Is dit wel de meening ervan of ben ik compleet ernaast?)

@Rsambo,
Not offended at all, just saying it looks off the line, but stil into the debate because strongly (cor)related.

Rsambo - 15-6-2016 at 10:07

Cool.

I think the English phrase is something like "A lousy workman blames his tools" ! ?

DraconicAcid - 15-6-2016 at 10:11

I hear it phrased as "It's a wet-ware problem, not a software problem."

Bert - 15-6-2016 at 20:53

I am more oriented towards storage stability and easily repeatable affects sufficiently good for display work... An absolutely beautiful blue effects that that does not last a week in storage is a sad failure to me.

I recall watching G.H. of P. Pyrotechnics exhibit a lovely purple strobe star from air mine/horse tail shells some years back. But the stars would not keep looking good (or safely!) long enough to be an article of commerce. So, a tease and a great disappointment, however fine they looked that day.

By all means, do experiment on with the atypical halogen chemistry, but always keep in mind the requirements for a PRACTICAL mixture: Safe of formulate and handle. Stable under real world storage conditions. Easily repeatable in effect. Sufficiently cheap and widely available components...

woelen - 15-6-2016 at 23:29

All of you got the meaning of that phrase quite well

It is not meant really seriously, it has a humoristic undertone.

-------------------------------------------------------

Bert also has an important point. Some compositions may be unstable and even dangerous. I would be reluctant to use a bromate in a pyrotechnic composition, unless it is used as a lab curiousity at small scale for a fun demo (I once did, I made CsBrO3 and used that as oxidizer to get really good blue colors, but this was only meant as a nice chemistry demo at microscale, not for practical use).

In the old times (2004 or so) I once read somewhere on Google Groups sci.chem the following:

"Playing with chlorates in pyrotechnics is like playing with a deadly poisonous snake, playing with bromates in pyrotechnics is like playing with a deadly poisonous snake, which is slightly pissed off."

Bromates are more sensitive to friction and easier to ignite. In general, the bromate ion is more reactive than the chlorate ion. I know this from experience with microscale experiments.

[Edited on 16-6-16 by woelen]

PHILOU Zrealone - 16-6-2016 at 06:06

Quote: Originally posted by woelen

All of you got the meaning of that phrase quite well

It is not meant really seriously, it has a humoristic undertone.

-------------------------------------------------------

In the old times (2004 or so) I once read somewhere on Google Groups sci.chem the following:

"Playing with chlorates in pyrotechnics is like playing with a deadly poisonous snake, playing with bromates in pyrotechnics is like playing with a deadly poisonous snake, which is slightly pissed off."

Bromates are more sensitive to friction and easier to ignite. In general, the bromate ion is more reactive than the chlorate ion. I know this from experience with microscale experiments.

[Edited on 16-6-16 by woelen]

1°) Great.

2°) Yes bromates have a more oxydant power than chlorates as such their activation energy is lower and they are more prone to react with a reducer and more fiercely.

careysub - 16-6-2016 at 22:12

"Het probleem is niet het spulleke, maar het knulleke"

Dutch and English are close enough* that I, who have never studied any Germanic language but English, could read it <i>except</i> for the two nouns "spulleke" and "knulleke".

So I plugged the phrase into Google Translate (gosh, I love automatic translation software) and Google Translate did not know what they were either!
What do they mean exactly, and any theories what Translate does not recognize them?

*It is possible to write at least short paragraphs in West Frisian that are actually comprehensible as correct English.

DraconicAcid - 17-6-2016 at 07:43

I've studied (tried to learn) Dutch, Norwegian, and German (in addition to English), and I could read exactly the same amount.....

[Edited on 17-6-2016 by DraconicAcid]

PHILOU Zrealone - 17-6-2016 at 08:31

Quote: Originally posted by careysub

"Het probleem is niet het spulleke, maar het knulleke"

Dutch and English are close enough* that I, who have never studied any Germanic language but English, could read it <i>except</i> for the two nouns "spulleke" and "knulleke".

So I plugged the phrase into Google Translate (gosh, I love automatic translation software) and Google Translate did not know what they were either!
What do they mean exactly, and any theories what Translate does not recognize them?

*It is possible to write at least short paragraphs in West Frisian that are actually comprehensible as correct English.

1°) The main problem with translators is that they take the word as from a word-book (dictionary) (so idioms are often traduced litterally) but translators doesn't take into account the common language and its specificity (Dutch has very wide pronounciation change over a few kilometers distance and there are a lot of dialects that change the writing to stick to the prononciation...here in Belgium that is a very little country in the world you often see flamish/dutch speaking people from different big cities that don't understand each other while the cities are only 50 km away).

I think that this tendency is reduced by the publication of books, the printing of newspapers and closer in the time by the normalisation and common use of the television...so flemish/dutch language becomes an average called "beschaavde Nederlands" (educated/civilised Dutch).

Flemish/Dutch is only written accademically recently (one, two or maybe 3 centuries ago) (thus quite young) vs older languages with wider writing past (millenium(s)) like English, French, Italian, Spanish, German, Greek...thus most latin, greek and german languages from Europa but Dutch...

Also during the last centuries, the languages in vogue for the culture (science, food, ...) where German, English and French...and that was not helping Dutch to get widespread use since the litterate people where using mostly French, English and German.

2°) Also there is the same kind of habit from Flemish/Dutch people to add "reducer" syllabs (diminutive) at the end of the words...maybe from the Spanish influence during invasion/colonisation...
Example: In Spanish they often use -ito, -ita, -illo, -illa, -uelo, -uela, -cito, -cita, -ecito, -ecita
(or pejorative: -ucho, -ucha); (or regionally: -iño, -iña , -eto)
Carlos -> Carlito (little/tiny Charles)
Juana -> Juanita (little/tiny Jeane)
casa (house ) -> casita (little house)
pequeño (small) -> pequeñito (very small)
despacio (slowly) -> despacito (very slowly)
andando (walking) -> andandito (walking with very little steps)
callado(quiet) -> calladito (very quiet)
Un perro (a dog) -> un perrillo,(a little dog or a puppy)
Una plaza (a place, a square) -> una plazuela (a little square)
Una casa -> una casucha (a slum)
Abuela (grand-mother) -> abuelita (granny)
Mamá (mother) -> mamaíta (my little mother)
Un gato (a cat) -> un gatito (a kitty)
el papel (the paper) -> papelito (the little paper)
nube (cloud) -> nubecita(little cloud)
balón (baloon) -> baloncito (little baloon)
flor (flower) -> florecita (little flower)
puerta (door) -> puertecita (little door)

Same happens in Flemish/Dutch (inherited from Spanish?)
usually common Dutch use -je and less often -tje, -mpje, -pje of -etje.
huis (house) -> huisje (little house)
Bart (Bob) -> Bartje (Bobby)

But also more Flamish/Brusselaar using a more ancient form -ke, -eke (and less frequently -kje, -ske, -ie)
roll boll (roll balling) --> rolleke bolleke
bal (ball) --> balleke (tiny ball)

just like in our case...

het spul = the mather, the material, the object
het spulleke = the tiny mather (insignifiant/not to take into account)

het knul = the guy, the fellow, the boy
het knulleke = the little/tiny guy

[Edited on 17-6-2016 by PHILOU Zrealone]

PHILOU Zrealone - 17-6-2016 at 08:46

Quote: Originally posted by DraconicAcid

I've studied (tried to learn) Dutch, Norwegian, and German (in addition to English), and I could read exactly the same amount.....

[Edited on 17-6-2016 by DraconicAcid]

We are getting seriously out of topic here

I know Dutch/Flemisch/French/Latin/English and a little Italian, Spanish and German.

There are similitudes between the latin-greek languages (Spanish, French, Italian, ...) and between the german languages (German, English, Dutch, ...) from ancient source but there are also interconnection from multicultural brew and exchanges (invasions, commerce, science) and also specific lives of the languages on their own...to get a clear view ones has to look at the problem through a multiple prism of various languages taking into account phonetic changes, truncatures, history, other way of writing...
Just like family names that have changed a lot during the last centuries, imagine what can happen in mileniums...

For example
LOUIS name of the french Kings comes from LOVIS (in latin U is writen V) and it is related to CLOVIS (the name of the emperor ancestor of the monarchy) but it has lost a C.

Rsambo - 17-6-2016 at 10:44

de puta madre. Que explicacíon !

Tsjerk - 17-6-2016 at 12:16

Off-topic or not... Is a ''knul'' genderless in Flemish? I would say ''de knul'', not ''het knul''. Of course making the diminutive out of it will make it genderless, but a ''knul'' usually refers to a boy and is therefore ''de''.

Tsjerk - 17-6-2016 at 13:07

Off-topic or not... Is a ''knul'' genderless in Flemish? I would say ''de knul'', not ''het knul''. Of course making the diminutive out of it will make it genderless, but a ''knul'' usually refers to a boy and is therefore ''de''.

PHILOU Zrealone - 18-6-2016 at 07:34

Quote: Originally posted by Tsjerk

Off-topic or not... Is a ''knul'' genderless in Flemish? I would say ''de knul'', not ''het knul''. Of course making the diminutive out of it will make it genderless, but a ''knul'' usually refers to a boy and is therefore ''de''.

Right!
Male gender even if the subject of the idiom may be a girl... sexissism again

--> de knul, de knul, de knul

(now written in my brain for a long time)

My mistake, a long time with no practice of Dutch and while typing in English and thinking in French with a side switch to Spanish...and all those "the" from English looking a bit like "het"...it should have happened...sorry for the brain-shortcut.

PHILOU Zrealone - 18-6-2016 at 07:41

Quote: Originally posted by Rsambo

de puta madre. Que explicacíon !

Que coño!

Mi madre no tiene nada que ver con toda esta historia.

Just kidding!

[Edited on 18-6-2016 by PHILOU Zrealone]

Rsambo - 18-6-2016 at 10:21

chemrox - 6-9-2016 at 16:48

Quote: Originally posted by woelen

My words are hard to translate. I think PHILOU may be able to understand them and smile

What I meant with my last sentence is that making oxybromide (and also oxychloride) from CuO and the corresponding acid is not possible in those acidic solutions.

If you use excess acid, then all CuO dissolves to form the halide and the strongly colored tetrahalogen complex of copper (which is deep yellow/brown for chloride and nice purple/red/brown for bromide). If you use excess CuO, then you get a solution of the copper halide and some CuO remains undissolved.
Could you separate the oxide from the mix by using string mineral acid? HCl? May seem like a stupid question but when you get to it..?
Making oxyhalide can be done by preparing a solution of the copper halide and then carefully adding (under constant strong stirring) hydroxide. This will give you a compound of ill-defined composition, with halide ions and hydroxide ions mixed in the compound. Heating this stuff drives off water and leaves behind a mixed halide/oxide.
Another option is to prepare wet CuCl or CuBr. These are white solids and can be prepared from HCl/HBr, copper oxide and a sulfite or metabisulfite. The wet solid must be rinsed with water and then the humid compound must be put aside in contact with air. It will oxidize quickly and lose its white color. When it is dry, you need to grind very well and allow to stand in contact with air for another few days. Finally you end up with a dry, non-hygroscopic powder. The mixed oxide/chloride is green (not blue at all), I expect the mixed oxide/bromide to be green as well, probably a somewhat darker shade, green like olives. But this is my educated guess, I have no personal experience with that. If you use a sulfite/metabisulfite, use the potassium salt, such as K2S2O5. If you use the sodium salt, then the resulting copper oxide/halide also has some sodium ions in it, which spoils the blue color of the flame.

I added a post. No idea where my words went.. into the ether? I wanted to ask woelen if the oxide could be removed (or converted) by adding HCl?

[Edited on 7-9-2016 by chemrox]