Chemical Forums
Chemistry Forums for Students => Undergraduate General Chemistry Forum => Problem of the Week Archive => Topic started by: Borek on March 05, 2012, 08:39:39 AM
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1.4511 g sample of a yellow, anhydrous ionic compound A, was roasted in the air stream, leaving a black residue. All gaseous products of the roasting were absorbed in the KOH pellets, increasing their mass by 1.4960 g. The black residue was dissolved in an acid yielding a green solution that was electrolysed on a platinum electrode, increasing its mass by almost exactly half a gram. Product of the electrolysis was removed from the electrode by a stream of the carbon monoxide, yielding exactly 1.4511 g of a volatile, highly toxic liquid B.
1. Using information from the question give formulas of both compounds A and B. If you are not sure about the exact formula, give the most probable one.
2. Give names of both compounds (don't worry if you don't know them outright – you can use any sources you want).
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I haven't done any math with the numbers yet, but from the descriptive chemistry provided I believe compound A is NiCl2 (nickel chloride anhydrous) and compound B is Ni(CO)4 (nickel tetracarbonyl).
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Check if they survive the math then.
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I can't seem to get my numbers to work out right from the get go.
NiCl2= 129.6g/mol and would produce 2 moles of HCl during roasting.
1.4511 g of NiCl2 x 129.6 g/mol x 2 mol HCl/1 mol x 36 g/ mol HCl = .817g of HCl.
However the problem suggests we need to be able to generate 1.4960g of gas so NiCl2 would fall short.
NiBr2 is also yellow but would only provide 1.07g of HBr.
I'll have to think more...
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Well I'm stuck so I'll throw out some of my thoughts and see if others can point out my errors, or if they can use my thoughts to solve it. I can't seem to figure out what A is but I still think B is Ni(CO)4
Since the moles of whatever metal is in this ionic compound doesn't change, and the weight of A used eventually provides the same weight of B, then shouldn't A and B have the same molecular weight? By my assumptions, A should have a molecular weight of 170 since Ni(CO)4= 170 g/mol. Furthermore, the anion portion of A must have a molecular weight of 112 since 170 - 58 (since I assume the metal is nickel) = 112. I can't think of any combination of anions or polyatomic anions which would equal 112 though.
The fact that the weight of the KOH pellets increases by more than the amount of A used implies that the anion of A is being oxidized by O2 during roasting. Otherwise, how could we add more weight to the KOH than we started with? So perhaps the anion has a sulfur in it, which would be oxidized to sulfate or sulfite?
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Plenty of good and correct ideas in what you posted. Don't be surprised by the fact identity of A is not obvious - I was surprised to learn about the compound.
As Sherlock Holmes once said - "When you have eliminated the impossible, whatever remains, however improbable, must be the truth" :P
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Nickel thiosulfate has a molecular weight of 170 and some sulfurs which could get oxidized in the roasting process. What exactly thiosulfate gets oxidized to I'm not sure.
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Well I imagine thiosulfate would be oxidized to sulfate/sulfuric acid, but the math doesn't hold up with that either.
I think the problem of the week has bested me this time :)
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Hint: both A and B have exactly the same mass.
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Borek, after your Sherlock quote I was quite tempted to say that A = B = NiCO4 but I don't really consider nickel tetracarbonyl to be an ionic compound as described in the problem. Perhaps it's just semantics.
Well, after your last comment, I'll go ahead and throw it out there.... A=B= NiCO4.
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Aha!
Roasting NiCO4 would result in 4 moles of CO2.
1.4511 / 170.7 x 4 x 44 = 1.496. So the math would work out as well.
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You are just a step away from an interesting discovery.
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Well, after your last comment, I'll go ahead and throw it out there.... A=B= NiCO4.
A is a yellow solid, B is liquid. I agree that the molecular formulas must be the same though...
Ni(CO)4 and Nickel but-2-ynedioate?
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Nickel but-2-ynedioate?
That's not the compound I had on mind, but the answer you gave shows the question has a potential of being even more interesting. Apparently it was not precise enough.
But with some more effort you can probably square this question up ;)
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There are potentially a very large number of candidates for A any number of which could be yellow. There is an old compound that could fit neetly if it is yellow, particulally with yellow being the colour of honey, but I can see from the last hint that probably isn't the one you were thinking of.
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There are potentially a very large number of candidates for A any number of which could be yellow.
Care to list some of them?
Before starting the thread I was aware of two - A and B. Now I know there is a chance there exists also a third one (although I wonder if it really does - but we will get there once someone names A). If the list goes further - I would love to see other compounds.
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But with some more effort you can probably square this question up ;)
37354-82-8?
If so, sir, I must say I admire your clever use of English! I wasn't able to find the synthesis, however. Would you happen to have a reference?
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Yes, A was intended to be an anhydrous nickel squarate.
See http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/19730063214_1973063214.pdf - they started with dihydrate and were able to produce anhydrous salt.
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I struggle through this all week, then, once I'm a few steps from the end, folks jump in and help ;) Ah well better late than never. It would have taken me too long to get to the squarate anyway. Plus it was fun to think about during the workday
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Dan I was aware that NiCO4 didn't fit the description given of A...but I couldn't find any obvious alternative left at that point.
Nice problem Borek :)
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Now the cat is out of the bag I'll lay my cards on the table. Is that metaphor mixed enough? The candidate I was most happy with was nickel mellitate, which is normally hydrated and I don't know how easy it is to make in anhydrous form. The aluminium salt is a rare mineral called honeystone and the structures may ring bells in fans of obscure oxides of carbon. I thought about Dan's compound and the dimer. On a more theoretical basis I also considered nickel cubane octacarboxylate and C60(CO2)60Ni30 and a few others but once you get it down to salts of C-CO2 it's pretty much Lego.
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I am an idiot. I visited mellitic acid when looking for ideas, but I got so fascinated by deltate, squarate, croconate and rhozidonate I forgot about it completely. One of the versions of the question contained determination of the molar mass through the freezing point depression, but I removed it as it could be confusing and I had no time to check details properly (does the squarate hydrolyze? does the Ni2+ hydrolyze? what is value of the Van 't Hoof factor?).
Initially I wanted to prepare a question about croconate, but decided putting nickel squarate and nickel tetracarbonyl side by side makes the question much more interesting.
Oh well, time to start to think about next week's problem. I am afraid it may be not that surprising - good ideas don't grow on trees ::)