ninhydric1
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Calcium hydroxide and ammonium nitrate product?
I was looking into making some calcium nitrate as I don't have access to it nearby, and Wikipedia happens to say that:
It can also be prepared from an aqueous solution of ammonium nitrate, and calcium hydroxide:
2 NH4NO3 + Ca(OH)2 → Ca(NO3)2 + 2 NH4OH
I was planning to do this last weekend as I have both chemicals on hand. But then I recalled that calcium ammonium nitrate was the double salt. So if
I were to indeed perform the above reaction, would some calcium ammonium nitrate be produced? If it is produced, how would I convert it back to
calcium and ammonium nitrate?
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unionised
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An excess of calcium hydroxide will ensure that all of the ammonium ions are converted to ammonia and can be removed by evaporation/ distillation.
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ninhydric1
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Alright. Thanks for the input.
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Bert
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If you are new enough to chemistry to ask the question- Some safety aspects should be mentioned. Just in case you don't have a nice fume hood, and
possibly work indoors?
Ammonia. Gas.
Once your solution is saturated, that ammonia is coming off the reaction (and it will be looking for your water containing tissues to dissolve itself
into- starting with your sinuses, eyes and LUNGS). Ouch. Since you don't want to waste a lot of time and energy to recover your nitrate, you will be
working with about as concentrated a solution as possible, one would expect.
Also, the warmer the reaction solution, the less of the ammonia that will be able to stay dissolved, and the more you will need to deal with as an
escaping gas. Your reaction releases HEAT. Lots of heat, potentially enough to boil the water.
Think carefully before hand about how large a synthesis you might want to run, and how you're going to handle that ammount of ammonia gas.
Best do this outside?
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ninhydric1
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I plan to either do this outside or do it in an Erlenmeyer flask with a tube leading into an acetic acid trap to neutralize the ammonia gas, depending
on the weather conditions of my area. Worst case scenario my lab area has adequate ventilation so if any of the ammonia gas does escape from the acid
trap it would be removed from the area.
EDIT: To add on, I do have experience with the ammonium salt + NaOH reaction, but because it doesn't form a double salt, I was questioning if calcium
hydroxide would form the double salt, so I was wondering about any other required reaction conditions. Wikipedia sadly doesn't give enough information
about these reactions.
[Edited on 10-29-2017 by ninhydric1]
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Bert
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Heck, lead the ammonia through a dryer cartridge, then perhaps collect it as a liquid via a collection flask immersed in a mixture of dry ice &
alcohol.
Your very own anhydrous ammonia source. Followed by building yourself an Ostwald process plant, and all the nitric acid you need?
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ninhydric1
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Oh, I wish. $1500 for 0.01 cubic meters of Pt-Rh mesh? As tempting as practically infinite nitric acid sounds, my wallet thinks otherwise. 
Who knows? If I suddenly win the lottery, I'll send you a liter for free  .
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macckone
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you can get five ft of wire for as little as $340, make your own mesh, I am guessing five ft will make a nice ball in a glass tube.
https://www.surepure.com/Platinum-Rhodium/a/1433
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Bert
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You don't need expensive mesh or wire. You don't even need platinoid family metal, good results are available from Cobalt, see example #4 of the
below.
Attachment: 00x31vl3d220.pdf (3MB)
This file has been downloaded 681 times
If you can get access to a kiln and the chemicals, you can make a ceramic foam catalyst without super expensive materials. Note my statement of "now,
about a cheap source of ammonia gas"...
http://www.sciencemadness.org/talk/viewthread.php?tid=2329
Quote: Originally posted by Bert  | Rather than start a new thread, here is a patent of interest to those contemplating (or electroplating!) Ostwald process catalysts...
Catalyst for production of nitric acid by oxidation of ammonia
US 5336656 A
http://www.google.com/patents/US5336656
Example #4 caught my eye... No noble metals. A catalyst and substrate that a sophisticated amateur might make at reasonable cost. LOW PRESSURE
OPERATION WITH HIGH EFFICIENCY.
Now about finding a cheap source of ammonia gas?
| Quote: |
EXAMPLE 4 A foam structure 8 inches in diameter and 0.8 inches thick and containing 30 pores per inch was produced by immersing a polyurethane
expanded foam into a ceramic slurry of cordierite (magnesia alumina silicate) powder, After firing to temperatures in excess of 1300° C. the ceramic
foam was dipped into an aqueous colloidal dispersion of alumina containing about 20% by weight of Al2 O3. The sample was dried and calcined to 500°
C. for one hour, The foam was found to have picked up 8% by weight alumina. The alumina coated foam was dipped onto a solution of 12% zinc as zinc neo
decanoate in toluene. The weight pick up measured after calcination to 500° C. was 5%. This zinc oxide and alumina coated foam was then dipped into a
12% cobalt as cobalt neo decanoate in toluene and dried and calcined at 500° C. The weight pick up was 15% as cobalt oxide. This catalyst was placed
in the ammonia oxidation reactor and ignited with the electric spark ignitor. The reactor was run for two weeks before evaluation, Analysis of the
ammonia input to the reactor showed 10% ammonia in air, The output was measured at between 9.1 and 9.4% NO giving a corrected conversion of 92 to 95%.
Pilot Plant Trial Experience (comparison with Pt gauze) The reactor chamber of the pilot unit utilizes 16, 8 inch diameter gauzes. The flow rate is
600 scfm which gives a linear velocity of 1.355 meters per second and an approximate pressure drop of 1.9 inches of water. The feed is approximately
6.7% ammonia in air. The reactor operates at 4 psig and atmospheric pressure is about 13 psig. A platinum catalyst on foam was prepared with 10.5% Pt
on an 8 inch diameter 0.80 inches thick, 30 pores per linear inch alumina foam. This catalyst loading had a platinum loading of 1.38 troy ounces in
the reactor. (The metal contained in the gauzes pack was 9.94 troy ounces.) At this metal loading the metallized ceramic catalyst is electrically
conductive with a resistance of about 0.4 ohms per inch. This metallized foam was placed on a non metallized alumina support segment and mounted in
the reactor. The gauze reactor was operated at 760°-800° C. The performance of the catalyst was checked by taking samples of the reacted gases and
titrating for nitric acid and ammonia. Twelve samples were taken over a six hour run. The results showed that the gauze converted 95% of the ammonia
to nitric acid and furthermore in the absorption system used approximately 45-46% acid was produced. The metallized foam converted up to 96% of the
ammonia to nitric acid and for unexplained reasons gave a stronger acid strength of about 50%. After these tests were completed only the acid strength
was used to monitor the performance and nitric acid was produced for an additional 60 days. At the end of the 60 days, the catalyst was performing
acceptably, with no evidence of reduced activity and the run was stopped only to recover the catalyst for analysis. Assay showed that there was no
metal loss (assay in 10.50% assay out 10.54%) and there was no loss of performance was detected. TABLE
2______________________________________Comparisons of Foams to Gauze Thickness of Foamto Match Gauze(Surface Area of 80 mesh gauze is 1.53 Square
meters of wire persquare meter gauze) Pressure Drop at 1.355 m/sec, (inPores Per Linear Inch Thickness of Foam H2
O)______________________________________10 0.229 cm 0.7220 0.114 cm 1.3830 0.076 cm 1.9050 0.046 cm 6.11______________________________________ From
about 12 to 15% Pt by weight the metallized structure has a continuous and electrically conductive film. The ceramic surface is substantially coated.
Table 3 below shows the platinum reduction achievable by using the coated form. This made possible because the ceramic makes up the core and the
platinum is on the surface where it is effective as a catalyst. TABLE 3______________________________________Comparisons of Pt loadings on Gauze and
MetallizedCeramic Foams(Coated at 12% by weight)(80 mesh wire gauze has 1.78 troy ounce per square footof gauze)Pores per linear inch TO/Sq
Ft______________________________________10 0.114520 0.057230 0.038250 0.0229______________________________________ It is estimated that the catalysts
and process according to the present invention, if substituted for the conventional platinum gauze can reduce the metal content of the catalyst charge
over 90%.
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[Edited on 30-10-2017 by Bert]
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ninhydric1
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Wow, I didn't know polyurethane could stand such high temperatures. I might actually consider this project in the future. It would be interesting to
be able to replicate a standard textbook catalysis reaction.
EDIT: That is, if I can also find a way to replicate the Haber process.
[Edited on 10-30-2017 by ninhydric1]
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Bert
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Gah.
THE POLYURETHANE BURNS AWAY. THINK "LOST WAX PROCESS".
And if the smiley didn't give it away, no, I don't think the "beginnings" forum quite supports this fabrication technique or the referenced pilot
plant size process line.
(But I won't be mad if you prove me wrong about that last).
[Edited on 30-10-2017 by Bert]
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macckone
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That patent is a good find. It looks like a combination zinc/cobalt/aluminum oxide catalyst. Any substrate appears to work with just the zinc/cobalt
oxide catalyst.
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ninhydric1
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But is decanoic acid even a commonly accessible reagent? Wikipedia says metal salts are used as paint driers and polymerization initiators,
interestingly. Time to look at MSDSs.
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Bert
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Is US $98.00 a kilo too expensive?
I actually have no idea what it would take to synthesize the Zn and Co decanoates, but I have seen the Co salt listed as the primary active
ingredient in non Lead based "Japan dryers" for oil paints, so possibly accessible OTC. The Zn compound I have not seen mentioned elsewhere, you might
have to synthesize that yourself. Hmm. Where are Zn and Co relative to eachother in the reactivity series...
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AJKOER
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Per this source: https://www.academia.edu/292096/Kinetics_and_Mechanism_of_Co... and my experience with this reaction, suggests to me that the reaction of Cu with
aqueous NH3 and H2O2 forms primarily [Cu(NH3)4(H2O)2](OH)2 and a significant amount of NH4NO2 also (have ammonia and H2O2 well in excess of copper).
This is evident from the amount of N2 released in about 10 minutes into the reaction from the unstable (and very toxic) NH4NO2. Other sources on this
forum claimed that adding NaOH or Na2CO3 is said to promote a stable nitrite product. Here is an extract (http://www.sciencemadness.org/talk/viewthread.php?tid=11781):
| Quote: Originally posted by Formatik | There is info on it, but you have not looked hard enough. The following below from Gmelin mentions the catalysts are NaOH, Na2CO3, Zn dust, Pt, or
Pd-H2.
Ammonium nitrite is also a sensitive explosive with about the power of tetryl: http://www.sciencemadness.org/talk/viewthread.php?action=pri...
Reaction between H2O2 and aq. NH3 can also give an azine when a ketone is present. This is the basis for the "Peroxide process" for production of
hydrazine.
[Edited on 5-10-2011 by Formatik] |
So, I would try adding Ca(OH)2 in place of NaOH, and see if you get any of the very soluble Ca(NO2)2 with possible conversion of the latter into the
nitrate with added steps.
Note: the solution must remain alkaline, as otherwise aqueous NH4NO2 may decompose violently (reported source of lab explosions). Here is a comment I
once extracted from Wikipedia (link: http://en.wikipedia.org/wiki/NH4NO2 ):
"Ammonium nitrite solution is stable at higher pH and lower temperature. If there is any decrease in pH lower than 7.0, It may lead to explosion. It
is desirable to maintain pH by adding Ammonia solution. The mole ratio of Ammonium Nitrite to Ammonia must be above 10% mole ratio.
NH4NO2 → N2 + 2 H2O "
Caution: the dried salt may be unstable (energetic, like in explosive) owing to a possible copper impurity, so I would not recommend
obtaining/employing a dry salt for safety reasons.
[Edited on 30-10-2017 by AJKOER]
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Melgar
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I'd imagine long-chain fatty acids could substitute for each other easily enough, (they're just going to burn away anyway) in which case you could
just get MCT oil from a health food store, and hydrolyze the triglycerides. "MCT" stands for medium-chain triglycerides, and it's basically oil that
has fatty acids with carbon chains between 6 and 12 carbons long.
edit: Why would Ca(OH)2 + NH4NO3 metathesis release heat? It'd be endothermic, no? NH4NO3 dissolution is endothermic, plus you have two endothermic
phase changes.
Also, if you want cheap anhydrous ammonia gas, the best you can do is probably thermal decomposition of urea. My dad buys that by the ton for
spreading on his fields, and I know he's not rich. It produces LOTS of ammonia gas, and leaves cyanuric acid residue. Cyanuric acid can be thermally
decomposed into isocyanic acid at significantly higher temperatures, which hydrolyzes into CO2 and NH3 when dissolved in water. Most of the CO2
bubbles out, leaving aqueous ammonia solution.
[Edited on 10/30/17 by Melgar]
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