symboom
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Hexammine Nickel Chlorate
Synthesis of Hexammine Nickel Chlorate
Procedure 1:
barium chlorate added to nickel sulfate
Precipitate of barium sulfate filtered nickel chlorate solution then added ammonium hydroxide
Procedure 2:
Preparation of ammonium chlorate 2 ways
1 Magnesium sulfate is added to ammonium hydroxide
Ammonium sulfate and insoluble magnesium hydroxide forms
Barium chlorate is reacted with ammonium sulfate to form a solution of ammonium chlorate and insoluble barium sulfate
2 Barium chlorate reacts with magnesium sulfate to form magnesium chlorate
--this is added to ammonium hydroxide to form ammonium chlorate and magnesium hydroxide
A blue complex formed from ammonia being added to nickel chlorate no precipitate yet method 1 is a bust it seems like there needs to be an excess of
chlorate ions to form complex
Expect a purple insoluble complex
Destruction of ammonium chlorate
A soluble potassium salt is added forming potassium chlorate
To regenerate ammonium chlorate
potassium chlorate is added to ammonium tartrate
[Edited on 11-4-2017 by symboom]
[Edited on 11-4-2017 by symboom]
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PHILOU Zrealone
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Nice experiment, but would be nicer with pictures and values ;-) like weights.
Ni(NO3)2 complex with ammonia (NH3) is just like the one of Cu(NO3)2 ...deep blue and soluble.
Why would you expect the chlorate complex to behave differently (to be unsoluble and purple)?
Why do you make NH4ClO3 to destroy it and finally regenerate it?
...it is also not into use to make your Ni(NH3)6(ClO3)2.
To precipirate your complex, you will need ethanol or isopropanol...and eventually diethylether.
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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symboom
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Quote: Originally posted by PHILOU Zrealone  | Nice experiment, but would be nicer with pictures and values ;-) like weights.
Ni(NO3)2 complex with ammonia (NH3) is just like the one of Cu(NO3)2 ...deep blue and soluble.
Why would you expect the chlorate complex to behave differently (to be unsoluble and purple)?
Why do you make NH4ClO3 to destroy it and finally regenerate it?
...it is also not into use to make your Ni(NH3)6(ClO3)2.
To precipirate your complex, you will need ethanol or isopropanol...and eventually diethylether. |
I would think that but hexammine nickel perchlorate is insoluble in water
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PHILOU Zrealone
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| Quote: Originally posted by symboom | | Quote: Originally posted by PHILOU Zrealone | Nice experiment, but would be nicer with pictures and values ;-) like weights.
Ni(NO3)2 complex with ammonia (NH3) is just like the one of Cu(NO3)2 ...deep blue and soluble.
Why would you expect the chlorate complex to behave differently (to be unsoluble and purple)?
Why do you make NH4ClO3 to destroy it and finally regenerate it?
...it is also not into use to make your Ni(NH3)6(ClO3)2.
To precipirate your complex, you will need ethanol or isopropanol...and eventually diethylether. |
I would think that but hexammine nickel perchlorate is insoluble in water |
Solubility of chlorates tends to be into the range of the solubility of the nitrates...usually the solubility of perchlorates is else (or less soluble
or more soluble...depending onto the cation...).
Perchlorate is not chlorate; and both display different properties and also usually different behaviour.
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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| Quote: Originally posted by symboom | | Quote: Originally posted by PHILOU Zrealone | Nice experiment, but would be nicer with pictures and values ;-) like weights.
Ni(NO3)2 complex with ammonia (NH3) is just like the one of Cu(NO3)2 ...deep blue and soluble.
Why would you expect the chlorate complex to behave differently (to be unsoluble and purple)?
Why do you make NH4ClO3 to destroy it and finally regenerate it?
...it is also not into use to make your Ni(NH3)6(ClO3)2.
To precipirate your complex, you will need ethanol or isopropanol...and eventually diethylether. |
I would think that but hexammine nickel perchlorate is insoluble in water |
Solubility of chlorates tends to be into the range of the solubility of the nitrates...usually the solubility of perchlorates is else (or less soluble
or more soluble...depending onto the cation...).
Perchlorate is not chlorate; both display different properties and also usually different behaviour.
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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woelen
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I just made some nickel hexammine perchlorate. This material indeed is insoluble in water.
Making this is fairly easy. Dissolve nickel oxide in dilute perchloric acid (I used appr. 20% by weight). Use a little excess oxide. Heat until no
more oxide dissolves. Dissolving the oxide in the acid is not that easy, you need to heat for quite some time and even then, some oxide does not
dissolve, while the solution still is quite acidic.
Next, I let the solid matter settle at the bottom and decanted the clear dark green solution. I diluted this solution with another equal volume of
water. To this, I added a large excess amount of 30% ammonia. To my surprise, I did not get a nice deep blue/purple solution, but a pale purple
precipitate (initally a green precipitate is formed, but on shaking the precipitate becomes purple).
The liquid becomes thick of slimy precipitate, not very nice. I allowed this precipitate to settle somewhat and decanted the supernatant liquid. Next,
I put the thick slurry on a petri dish and allowed this to dry for one day. I had a purple solid, which was covered by a thin green/blue layer. In
contact with air, the solid slowly loses ammonia.
The resulting material is quite energetic. If you heat the solid, it quickly burns, like very well mixed black powder.
The material loses ammonia on drying, and some basic insoluble green material is formed. Most likely the following happens:
[Ni(NH3)6](ClO4)2 + 2 H2O --> Ni(OH)2 + 2 NH4ClO4 + 4 NH3
The insoluble green material is not energetic anymore.
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Another easier synth, requiring no perchloric acid is the following:
- Dissolve nickel sulfate in water. Make a saturated solution.
- Add excess 5% ammonia, so that the precipitate, which initially is formed on adding ammonia, redissolves again and you get a nice clear deep blue
solution of nickel hexammine sulfate in excess ammonia.
- In a separate vessel, dissolve ammonium perchlorate in water. Even better is the use of sodium perchlorate, which allows more concentrated
solutions, but in the EU that is not available anymore to the general public, due to concerns about terrorism.
- Add the solution of ammonium perchlorate to the solution of nickel hexammine sulfate.
- On mixing, a precipitate is formed, but not immediately. Within seconds, small crystals are formed and over a period of a few minutes, a lot of
small crystals are formed and these nicely settle at the bottom, giving a compact precipitate.
- Decant nearly all colorless liquid above the solid and add a small amount of cold distilled water and let the crystals settle again.
- Again decant the water.
- The crystal mass is allowed to dry in a petri dish.
The resulting solid material again is pale purple/blue. It is as energetic as the material from the previous experiment.
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This also is a nice test on perchlorate ion. It is even more sensitive than adding potassium ions to a perchlorate solution. I was surprised to see
how little nickel hexammine perchlorate dissolves in water.
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woelen
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A related complex, nickel bis-(dien) perchlorate. Here (dien) stands for diethylenetriamine, H2N-CH2CH2-NH-CH2CH2-NH2. This is a tridentate ligand,
which replaces three ammonia molecules.
I had fantastic results with making Ni(dien)2(ClO4)2. I prepared nickel perchlorate as described in the previous post and added (dien) until the
liquid becomes really purple (when too little (dien) is added, then the liquid is blue and the precipitate also is blue). I then added a little extra
(dien), just to be sure that there is enough of the ligand. The material is only very sparingly soluble in cold water, so I got a lot of very fine
precipitate. I heated the solution until it started boiling, and then added little amounts of water, while heating and stirring, until I obtained a
completely clear very dark purple solution. I then set aside the hot solution and let it cool down. First in a cold room, then for the final stage in
a fridge. I obtained a lot of purple crystallize solid, which easily can be separated from the liquid, which now only is pale purple. I pressed it dry
in filter paper, between two thick layers of paper tissue. I rinsed once with cold distilled water and again pressed dry in filter paper (actually:
coffee filter) between paper tissue. I left it drying and occasionaly stirred the solid in a petri dish, put on our central heating system, which
becomes nice warm on the outside, but not very hot.
I now have a few tens of grams of perfectly dry crystalline Ni(dien)2(ClO4)2. Most of it I ampouled in a 20 ml ampoule as beautiful display sample
(which is nearly full), I left out a few grams for experiments.The material is quite energetic, it is easier to ignite than Ni(en)3(ClO4)2, it is more
sensitive for heat, despite the worse oxygen balance of this new compound.
If you look at the two compounds Ni(dien)2(ClO4)2 and Ni(en)3(ClO4)2, then you hardly see any difference. If you gave me a sample of both compounds,
then I would not be able to tell which one is the (en) complex and which one is the (dien) complex. Both complexes, however, look quite different from
the ammonia complex, described in the previous post. The color of the (en) and (dien) complexes is much more vivid/saturated.
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Rosco Bodine
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Glycine and Betaine should form Nickel complexes also that may be interesting, and likewise but use great caution would be complex with Semicarbazide.
These may form shared complex with ammonium complex partly displaced by heavier Molecular weight complex, or may form mixed salt complex with ammonium
complex.
Likewise similarly may occur complexation reactions for copper and cobalt as for nickel.
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