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Nickel II Nitrate

JScott - 23-8-2018 at 10:28

Hi to all of my new Chemistry friends, a quick introduction:

My favorite Christmas Present? 1969, my first Chemistry set. Gabriel, there were a half dozen after that. I am a hobby nut, but Chemistry has held my interest longer than any other.

I am an electronics tech by trade. USAF trained electronics countermeasures. An old crow if there are any others out there.

Four years ago I started building a more serious lab space after mucking up a kitchen counter. I've built a fume hood and acquired a nice collection of glass ware and regents. For the last two years I've hit the books. I wanted to understand what was happening and be able to predict what might happen.

I keep good notes, take some photos and for the most part learn from YouTube and those text books. Still, things come up and it would be a lot of fun to talk with others.

Enough intro stuff, among my favorite student experiments was the synthesis of Silver Nitrate. A water soluble white crystal from a metal?!?! WOW, I was thrilled. From there I started nitrating everything. Lead, mercury, cellulose, rice hulls. I love the color of Copper Nitrate!

Anyhow, no surprises until I tired nitrating nickel. I loved growing copper sulfate crystals and mention how fond I was of the copper nitrate... but after dissolving a Canadian Nickel (US nickels aren't, wadda ya know) and producing a nice dark green fluid I was unable to dry this solution to crystals as I had with copper.

Once dried I re hydrated the now light green mass and it dissolved nicely. I tried recrystallizing from water and still, all I get is a dried mass. I assume I have created Nickel II Nitrate hexahydrate or one of the other hydrated forms.

I don't necessarily want an answer, but I would like to know what I should read. I have done a lot of Googling and have found very little regarding the wonderful green crystals the wiki has to offer.

fusso - 23-8-2018 at 10:48

AFAIK most transition metal nitrates are difficult to crystallize due to the deliquescent nature.

Deathunter88 - 23-8-2018 at 10:56

Could you elaborate a little more on your drying procedure?

JScott - 23-8-2018 at 11:22

@ Deathhunter88

I'd love to.

I started with a Nickel and it took 30 ml of 60% nitric acid (concentration determined by density) to dissolve the nickel over the course of 45 minutes at 65C. In fact .74 grams of it was left and retrieved. An odd beaver souvenir. It seemed it would never dissolve and I had been adding acid for a while.

I increased the heat to 80C and in three hours and a few minutes it had reduced to ten milliliters and had a light green crust beginning to form. Some light green precipitate could be seen. I figured that was about the right time and removed it from the heat. It hardened fairly quickly, so I gave the now fairly thick surface crust a stir and the darker fluid below it hardened as soon as it hit the air.

Now light green I dissolved it in ten milliliters of distilled water (23C). This I tried evaporating slowly in a bag with Calcium Chloride, in a vacuum desiccator with silica gel, and in both cases the fluid out lived my patience. A month on the Chloride... oh alright it was three weeks.

I then tried light heat and got the light green mass at the bottom of the dish. This dissolves easily but I have had no luck in creating the larger emerald green crystals I had hoped for.

@fusso,

Thank you, I have a word to look up, and perhaps a clue! What is AFAIK? Hope that wasn't a too foolish a question ;-)

[Edited on 8-23-2018 by JScott]

fusso - 23-8-2018 at 11:30

Oops, used the abbreviation, my bad

Thats "as far as I know"

[Edited on 23/08/18 by fusso]

[Edited on 23/08/18 by fusso]

JScott - 23-8-2018 at 16:17

@ fusso,

Deliquescent, it may be (normally), but not in the form I have now. Though it is highly soluble, it doesn't form puddles like sodium hydroxide or calcium chloride.

Thanks for the new word though! Is it a synonym for hydrophilic (how I have, I hope correctly, described the two aforementioned compounds in the past)?

[Edited on 8-24-2018 by JScott]

fusso - 23-8-2018 at 23:53

Quote: Originally posted by JScott

@ fusso,

Deliquescent, it may be (normally), but not in the form I have now. Though it is highly soluble, it doesn't form puddles like sodium hydroxide or calcium chloride.

Thanks for the new word though! Is it a synonym for hydrophilic (how I have, I hope correctly, described the two aforementioned compounds in the past)?

[Edited on 8-24-2018 by JScott]

Then maybe I should use hygroscopic? I'm not sure.

Dan Vizine - 27-8-2018 at 11:25

What year was the nickel? Only pre-1982 Canadian nickels were nickel

According to someone...
"Canadian nickels were made of 99.9% nickel for many years. From 1982 to 1999 the coin was made of 75% copper and 25% nickel, the same composition as US nickels. Starting in 2000 the Royal Canadian Mint began phasing in production of the coin using nickel-plated steel."

All of my Canadian nickels are post-2000 and act strongly ferromagnetic.

[Edited on 8/27/2018 by Dan Vizine]

MrHomeScientist - 27-8-2018 at 12:14

You may need a stronger drying agent. Nickel nitrate might have a greater affinity for water than calcium chloride or silica. I'd try sodium or potassium hydroxide next, and if that doesn't work concentrated sulfuric acid is about as good as you can get.

I wonder if you could also crash out crystals by adding acetone to your solution? I did that to prepare hexaaminenickel(II) chloride.

DraconicAcid - 27-8-2018 at 13:10

Nickel(II) nitrate is going to be much more soluble in water than hexaminenickel(II) chloride. Adding acetone to a concentrated solution of it may very well give you two layers.

Dan Vizine - 27-8-2018 at 13:15

When you think of drying as a mass transfer issue, you realize that almost nothing is faster than azeotropic distillation. Put your material into a round-bottom flask with some toluene. Azeotropically remove the water using a Dean-Stark trap. I can't promise that you'll get nice crystals, but they'll be dry.

The ultimate drying agent is molecular sieves. It'll get things drier than any other drying agent. In a glovebox, molecular sieves can establish an atmosphere of less than 1 ppm H2O.

[Edited on 8/27/2018 by Dan Vizine]

Very Happy!

JScott - 29-8-2018 at 06:31

I was worried at first, seemed like my discussion wasn't interesting anyone. I am so glad to see all of the replies! Thank you.

@Dan Visine

This nickel was a 1980, you might notice I mentioned how US nickels weren't. How disappointing ;-) I am fairly sure it was in fact a true nickel. I will try to add pictures of it and the solution. Though I have had a few minor camera problems and don't have a photo (yet) of the finished substance.

Fantastic I was waiting for my first good excuse to purchase a Dean Stark trap. EXCELLENT!!! I will keep you posted on whether or not my problem was drying. Thank you for the suggestion.

@MrHomeScientist

That also makes good sense. I have used potassium hydroxide to dry my Copper II with great success. I was very surprised how much more hydrophilic it was! I will do this directly, thank you!

@DraconicAcid

First, if there isn't a draconic acid, there should be!

Next, this is also very easy for me to try during my next lab session. Thank you for the suggestion. I will get back you after I try this... thank you very much!

Nickel Nitrate Hexahydrate Drying

FloridaAlchemist - 29-8-2018 at 10:10

Using a baking dish . Spread the wet crystals out over the large surface area and dry the crystals in a oven at ~110'C. Cool to room temperature then quickly crush up the dried chunks and transfer to a air tight container for storage.

JScott - 29-8-2018 at 11:47

@FloridaChemist,

Just to get you caught up, I can 'dry' what I've produced just fine. The problem I am having is that I would like to grow larger, translucent crystals of Nickel Nitrate as I have other salts.

At this point all of my efforts end in a light green mass at the bottom of the crystallization dish. Water soluble, but I can't get crystals to crash from this solution. I've got a couple things to try after reading the last few posts here.

I have a few pictures from when I did this last. Sadly I am having a small camera issue and it will be a few days before I can get photos of the finished product.

Heck of time getting this to post to the right part of the forum. Then I got locked out for "flooding". Maybe it's me... anyone else having issues?

[Edited on 8-29-2018 by JScott]

Loptr - 29-8-2018 at 16:09

Quote: Originally posted by JScott

@DraconicAcid

First, if there isn't a draconic acid, there should be!

It is more formally known as 4-methoxybenzoic acid.

Purification of Laboratory Chemicals

S.C. Wack - 29-8-2018 at 16:34

Nickel nitrate (6H2O) [13478-00-7] M 290.8, m 57. Crystd from water (0.3mL/g) by partial evaporation in a desiccator.

JScott - 30-8-2018 at 04:47

@DraconicAcid,

very descriptive. I will read up, too cool a name to not be curious

@S.C. Wack,

I have searched what you left me and come up with everything but what I had hoped it would lead to. My apologizes, I am new to this and imagined you had offered a key to a patent search.

Could you explain a bit more?

Sulaiman - 30-8-2018 at 05:36

Guessing:
Ethanol or IPA may be a better solvent than water for producing hydrated crystals ?

JScott - 30-8-2018 at 09:14

@Sulaiman,

Another great suggestion! This is a richer exploration given all of these new areas to check out.

I had put this on hold, having done the experiment a few times and having not changed my results one smidgen, I was moving on to other things.

All of these new suggestions have encouraged me to reapply myself to this effort.

No later than the start of the new week I will start fresh. I will try all of your ideas, and get back to all of you regarding how it went.

[Edited on 8-30-2018 by JScott]

DraconicAcid - 30-8-2018 at 13:21

Quote: Originally posted by Sulaiman

Guessing:
Ethanol or IPA may be a better solvent than water for producing hydrated crystals ?

Ethanol or methanol, maybe, but isopropanol would probably not work- it salts out too easily.

PS- Draconic acid is also known as p-anisic acid, or just anisic acid.

S.C. Wack - 30-8-2018 at 15:45

Quote: Originally posted by JScott

I have searched what you left me and come up with everything but what I had hoped it would lead to. My apologizes, I am new to this and imagined you had offered a key to a patent search.

Could you explain a bit more?

Google the subject line of that post. It's not the highest authority but is better than the internet, sounds like solid technique, and suggests you've been using too much water.

Quite often metal salt hydrates are efflorescent and don't crystallize well in air...or has a tendency to form a basic salt in solution or on heating...certainly when one warms the solution to evaporate it. Oftentimes in these situations there is excess acid to prevent hydrolysis. How much relevance that has here or even if the basic salt is soluble IDK.

BTW few of the publisher-scanned volumes of Gmelin are useful, they're usually volumes that have never been opened in a library...but (I noted when collecting the 184 available volumes) nickel is a rare exception as both the metal and compounds volumes are available...it's probably still not helpful and a waste of time like mentioning it...it wouldn't surprise me at all if this the most comprehensive paper reference is useless. In any case it's in German and at gen.lib.rus.ec aka libgen.

[Edited on 30-8-2018 by S.C. Wack]

Nickel passivation in nitric acid

Sulaiman - 31-8-2018 at 02:50

To 'have a go' at crystallising nickel nitrate I first needed some nickel nitrate,
as I have been avoiding nickel chemistry due to toxicity/waste concerns,
I used supposedly pure nickel strips of c 0.3g each so decided to use those,
aware of the possibility of passivation I used 1M nitric acid ... nothing happened
so I heated the acid to boiling ... nothing
added 1.4ml 10% hydrogen peroxide ... nothing
left overnight ... norhing.

added my last c5ml rfna ... nothing
boiled ... nothing

heated a fresh strip of nickel to red/orange heat to try to form an oxide layer
dropped in nitric acid
... vigorous reaction that consumed the entire strip, with plenty of green froth and NO₂ produced

removed the original nickel strip, heated to red/orange,
put in acid ... nothing

tried another fresh strip of nickel, heated, ... vigorous reaction

removed the original nickel strip and heated to an orange glow
put in acid ... nothing

tried another fresh nickel strip, heated, ... vigorous reaction

added dH₂O to double volume of acid, boiled ... nothing.

as write this the passivated nickel strip is sitting in boiling nitric acid ...
and changing into a brown mud

I suspect that my 'pure' nickel strips https://www.ebay.co.uk/itm/Pure-Nickel-99-96-Low-Resistance-...
may be iron, plated with nickel. :mad:

A quick test for iron/iron nitrate/iron oxide in the presence of nickel and nitric acid - anyone ?

[Edited on 31-8-2018 by Sulaiman]

JScott - 31-8-2018 at 04:30

@S.C. Wack,

Duh, I did a search on everything but the subject. Thank you, and for the digest of what I will find (when I get to the right place to begin with ;-) )

@Sulaiman,

Yes, I noted you had begun a nickel experiment on another post. Very good, and a different approach. I always deal with any passivization after the fact, but didn't think with 60% (sorry haven't done the molar math) I would have a problem. I would have expected it with more concentrated acid.

Ok, a crack at the molar math... would 60% be about 13 mole? Forgive me, a new student fumbling around.

I almost feel as though I cheated. You worked so much harder at then I did... then in the end had been ripped off with crappy nickel! All I had to do was search through thousands of US nickels and find the Canadian ones I knew would be hiding there. Then, hope they were of the correct linage to be mostly nickel. I found only four BTW, and two were of the correct date.

[Edited on 8-31-2018 by JScott]

[Edited on 8-31-2018 by JScott]

JScott - 31-8-2018 at 04:42

@S.C. Wack,

Using Duck Duck Go (yes, I'm one of those nuts), I found this pdf. Given the book sells on Amazon for nearly 130$ I thought I would rush over here and give the URL to all. A great volume for any home chemist I would think.

Don't know if that's what you were leading me to, but THANK YOU! What a super resource, I have a gob of reading to do. With winter coming, the lab will be too cold to be much fun. A volume of this depth will make the winter months far more enjoyable. Thank you again.

The Purification of Labratory Chemicals, 2009

JScott - 1-9-2018 at 06:45

I had a few minutes this morning to run a small scale experiment to check out some of the suggestions I've gotten. Not anything all that comprehensive, so don't get too excited ;-)

My first experiments left me with 16.4 grams of "product". This is a bit odd to me as the nickel only weighed approx 3.5 grams. Further, .74 grams weren't dissolved.

The photo of the small pile is the stuff I made, the result of my efforts to create the wonderful green crystals I've seen made from this nitrate. I think the darker green dots are areas of more hydrolyzed substance. But I may be using that term incorrectly (it's wetter there).

The test tubes contain, from left to right, toluene, acetone, and ethanol (95%). I dissolved 2 grams (of that aforementioned substance), one gram at a time into 2ml of distilled water. The first gram dissolved easily in less than 15 seconds. The second gram took nearly a minute to be stirred into solution. I assumed I was close to the saturation point with this solution.

I added this solution, drop wise, to the three test tubes.

Toluene: it fell to the bottom quickly leaving noting behind in the solvent. It appeared as 'oil in water' on the bottom of the test tube. I shook it vigorously and it seemed to leave a colorless 'sand like' substance along the side of the test tube, but other than that not much more happened.

Acetone: As it fell through the acetone I noticed a very fine (extremely fine) precipitate and over the course of the first minute it seemed as though my test solution was fully miscible with the acetone. Here again, explaining what I'm doing to folks who know chemistry, I wonder if I use the jargon correctly. I mean to say that it seemed to blend fully with the solvent.

Ethanol: This seemed a little more promising. The swirl of solution seemed to 'freeze' momentarily while it fell through the solvent. I had hoped for a second that it might fall directly to the bottom of the tube as a solid, but alas, this too seemed to be fully miscible in this solvent.

Perhaps my expectations for this precipitation experiment are faulty. Under a best case scenario I was hoping to see my solution turn to a solid when the drops were added. But, that would be a extreme indication. Perhaps I should be looking for smaller precipitate.

I have left the three tubes to settle some. I will filter the contents and if anything can be learned from that, I'll post my assumptions here... were they too can be filtered <giggle>

I will, on Monday spend the day on your kindly offered suggestions and advise, and try to get back to each of you in turn to let you know how I am progressing.

S.C. Wack - 3-9-2018 at 05:49

Under what conditions if any can nickels and hydrogen reduce nitrate? Or something else...not all of it, but some. Or another form of Ni...not that it's particularly known for dissolving metal reductions...but I'm open to the possibility.

[Edited on 3-9-2018 by S.C. Wack]

Sulaiman - 3-9-2018 at 06:42

* Please bear in mind that I have no nickel chemistry experience

My first experiments left me with 16.4 grams of "product". This is a bit odd to me as the nickel only weighed approx 3.5 grams. Further, .74 grams weren't dissolved.

* (Nickel nitrate hexahydrate) / (Nickel) = 290.79 / 58.69 = 4.954
(3.5 - .74) x 4.954 = 13.675 g nickel nitrate hexahydrate expected.
The rest is probably 'wetness'

The test tubes contain, from left to right, toluene, acetone, and ethanol (95%). I dissolved 2 grams (of that aforementioned substance), one gram at a time into 2ml of distilled water. The first gram dissolved easily in less than 15 seconds. The second gram took nearly a minute to be stirred into solution. I assumed I was close to the saturation point with this solution.

I added this solution, drop wise, to the three test tubes.

* This could be a problem. You need dry crystals
(not necessarily, but possibly nearer to, anhydrous. No adhering moisture)
Add the dry crystals to anhydrous solvent for crystallisation by evaporation.

JScott - 3-9-2018 at 09:22

Today I dissolved the nickel product I had made in the three aforementioned solvents. I was in the lab before I got to the forum so I hadn't seen the more recent comments.

As many had no doubt guessed it wouldn't dissolve in toluene. It dissolved in the Ethanol but was in solution in acetone more quickly.

5 ml of acetone at room temp just barely dissolved one gram. At boiling I could get another 2 grams to dissolve, so I thought perhaps as it cooled, given a dry enough environment I might see something promising.

Nothing at this point, but a night of drying... who knows?

@Sulaiman,

As I was taking my notes today and I wrote in 95% Ethanol I realized that with everything I had read since coming to the forum, that was not dry enough. And I could tell looking at the dark areas in the product I had made, it wasn't dry enough either.

The talk of a Dean Stark trap reminded me my Toluene and acetone weren't all that dry either.

I would also like to correct something I had said earlier in the post about it not attracting water and leaving a wet area like Calcium Chloride does. That was wrong, it most certainly does act that way. I think I had bottled it up from dry bags or desiccators quickly enough to have not noticed that before. Today in the lab, as I slowly added more of the product to the acetone, it absorbed water as I watched.

Reading more about how those crystals are formed I see that very toxic nickel species are normally employed. So, I am trying to live with the fact that I may have to end my experiments without realizing my ultimate goal (translucent green crystals).

However, I have created enough 'nickle product' to do a few more experiments and will continue at least until I have used my current stock.

@S.C. Wack,

Sorry, I'm not entirely clear what you are asking me. I am a new student, just learned how to balance equations a week ago. Lewis structures today.

The last two labs have left me a few things still drying. I'll back to everyone on that in the morning.

Interesting, and a partial success!

JScott - 4-9-2018 at 05:18

3 grams of the Nickel compound I have been assuming was Nickel II Nitrate, dissolved it in 5ml of acetone just at the boiling point. Cooled and dried overnight in a bag with Calcium Chloride. I understand now that as a desiccant, it may be less absorptive than my product, but I had to stop for the day and need the driest place possible to leave the still fluid acetone mixture.

Cooling alone did not produce these. My thinking is that the Chloride was able to pull some water from the acetone overnight. These crystals of the substance I've been working with don't have the same geometry of the Nickle II crystals on the wiki. But, at this point, to see any crystals of the correct color is a thrill!

I also note some white/clear crystals, different shape. Given the color is different this is not an example of polymorphic crystallization, correct? It would be a different compound?

Here again, forgive any of my amateur assumptions, I have only been studying a short time. OK, so the photo:

[Edited on 9-4-2018 by JScott]

[Edited on 9-4-2018 by JScott]

JScott - 5-9-2018 at 07:45

3Ni + 8HNO₃ → 3Ni(NO₃)₂ + 2NO + 4H₂O

I looked this up, I had written it more simply with just one mole of Ni acting on one mole of acid. Assuming I had the hexahydrate form given what I had read, I wondered where the rest of formula came from. The oxide was easy enough to imagine, but the water wasn't as obvious to me.

Ni + HNO₃ → Ni(NO₃)₂ I couldn't have hoped to balance that off course.

I have just finished reading about the nickle oxide and water.

While reading I learned a great deal more about metal salts and their formation. Thank you for your patience regarding my early steps here.

Any ideas regarding why my crystals look like they do? What are the clear/white crystals? Are they Nickle oxide?

My next attempt forming Nickel Nitrate will be via Nickle oxide, rather than the beaver coin. Researching various routes to nickle oxide I came across this:

A Versatile Route for the Synthesis of Nickel Oxide Nanostructures Without Organics at Low Temperature

Could a temperature compensated reflux setup that held the same temperature accomplish the same thing as the autoclave did under these circumstances? I would image if that route could have been taken that's what they would have done. Anyhow, off to make some nickel oxide.

I will continue to work on the crystals I have formed by crystallizing my nitrate out of acetone. At the same time trying out this other idea.

[Edited on 9-5-2018 by JScott]

[Edited on 9-5-2018 by JScott]

[Edited on 9-5-2018 by JScott]

Sulaiman - 5-9-2018 at 07:59

Quote: Originally posted by JScott

I also note some white/clear crystals, different shape. Given the color is different this is not an example of polymorphic crystallization, correct? It would be a different compound?

I do not know what the white crystaline stuff is,
but dehydrating copper sulphate gives white crystals,
and I notice that the green crystals do not seem to be very hygroscopic or deliquescent,
so, if the white crystals slowly turn green, they may just be a less hydrated form of nickel nitrate.
If they stay white then I suspect some contamination/impurities.

JScott - 5-9-2018 at 08:06

Quote: Originally posted by Sulaiman

Quote: Originally posted by JScott

I also note some white/clear crystals, different shape. Given the color is different this is not an example of polymorphic crystallization, correct? It would be a different compound?

I thought impurities as well. Given the coin was carefully cleaned, that leaves only one good route I can think of. I synthesized the acid from Stump remover and drain cleaner. I recrystallized the stump remover and distilled the drain cleaner (scary for a noob). So what would your best guess be for contaminants?

I haven't looked up what Nickle oxide looks like, but the formula tells me it's there. I do see I end up with 2 moles of oxide when all is said and done. Would I see that?

Sorry for the continuous edits, I had forgot to mention that after another 24 hours of desiccation there are more small white (square) crystals. In fact, very small ones cover the green needle like one still laying as you see them in the photo. I assume that photo shows needle like structures that will break apart when I scrape them from the dish.

I'll get another photo later to today.

[Edited on 9-5-2018 by JScott]

JScott - 19-9-2018 at 04:19

After ten more days on the desiccant most of the crystals have reverted to the dark green form seen here. The change in color is fairly accurate. The white crystals thought to be contaminant became green after continued desiccation, so I would imagine they are the same substance but with more (or less) water.

Also the shade of green has clearly changed in the days since the first photos were taken.

Thanks for all of your advice getting me this far.

@S.C. Wack,

I am here to learn. I want to understand your question, if you have a minute, drop me another line.

[Edited on 9-19-2018 by JScott]

S.C. Wack - 19-9-2018 at 13:44

The question wasn't directed at anyone except for someone who might know. There is a short list of cpds. one can obtain from air, water, nitric acid, and .999 nickel...until it occurred to me that reduction is not impossible, under strange circumstances or not.