Saturday, January 19, 2013

Binary pnictogen halides

Here’s a tricky (trick?) question from the final exam of MITx course Introduction to Solid State Chemistry:

Which compound has the higher boiling point, phosphorus trifluoride (PF3) or phosphorus pentafluoride (PF5)?
Naturally, you are supposed to figure this out from the first principles, or rather, from some principles taught in this course, not from Wikipedia (or “by googling”, as some put it).

(a)(b)

The problem is, the “right” answer, PF3, is actually, factually wrong. Even though this question cost only two points (of 150), a rather animated debate followed the exam.

Those who defended the “right” but factually wrong answer (a) were proposing that what the problem was testing our thinking rather than actual knowledge, and our thinking should have been along the lines of VSEPR model. VSEPR rules correctly predict PF3 to be trigonal pyramidal and PF5 to be trigonal bipyramidal. The dipole moment of a polar molecule PF3 should make it less volatile than apolar PF5. Those who chose the “wrong” but factually correct answer (b) were arguing that polarisability of larger PF5 is higher than that of PF3 and therefore the London dispersion forces in PF5 would beat dipole-dipole interactions in PF3. The (a) party were saying that making the answer you’d get by applying principles different to the one you’d get by “googling” is a good protection against cheating. The (b) party were retorting that this is a silly way of protection, that the question asked was what has the higher boiling point, not what could be expected to have the higher boiling point, and that expecting students to come up with the factually wrong answer is not exactly pedagogical.

Truth to be told, the methods of estimating boiling or melting points of materials were simply not a part of this course. The only thing one could do was to determine whether the molecule has a non-zero dipole moment. But there is no way to figure out which effect will be stronger, the increase in dispersion forces or dipole-dipole interactions.

One would think that the physical properties of such simple compounds as binary halides of Group 15 elements (pnictogens) are studied well and long ago. Not really. I tried to compile a table of dipole moments and melting/boiling points for pnictogen tri- and pentahalides, MX3 and MX5, using various resources [1—5]. As you can see, there are still many gaps.

Trihalide μ (D) mp (°C) bp (°C) Pentahalide mp (°C) bp (°C)
NF3 0.234 –207–129
PF3 1.03 –151.5 –101.8 PF5 –93.7–84.5
AsF3 2.59 –6.062.8 AsF5 –79.8–52.8
SbF3 ? 290345 SbF5 8.3141
BiF3 ? 649900 BiF5 154.4230
NCl3 0.6 –4071
PCl3 0.97 –93.676.1 PCl5 167160s
AsCl3 2.15 –16.0130.8 AsCl5 –50?
SbCl3 2.75 73.4223 SbCl5 4140
BiCl3 4.6 233.5441 BiCl5 ??
NBr3 ? ? ?
PBr3 ? –41.5173.2 PBr5 <100d106d
AsBr3 1.66 31 221 AsBr5 ? ?
SbBr3 2.47 96288 SbBr5 ??
BiBr3 3.6 219462 BiBr5 ??
NI3 ? –20s ?
PI3 ~0 61.1227 PI5 41?
AsI3 ? 141 400 AsI5 ??
SbI3 1.58 170.5 401 SbI5 79401
BiI3 ? 408.6~542 BiI5 ??
d, decomposition
s, sublimation

What, if any, trends can we see?

  • The dipole moment of MX3 grows larger down the group of the central atom M, e.g. μ(NF3) < μ(PF3) < μ(AsF3), and grows smaller down the group of ligand atom X, e.g. μ(SbCl3) > μ(SbBr3) > μ(SbI3).
  • As the sizes of both central atom and ligands go up, so do the melting and boiling points.
  • As dipole moments go up, so do the melting and boiling points.
Something curious happens, though, when one crosses the phosphorus—arsenic borderline. AsF3 has a dipole moment of 2.59 debye. As expected, both mp and bp of AsF3 are, respectively, higher than those of AsF5. PF3, however, has much lower moment of 1.03 D. Both mp and bp of PF3 are, respectively, lower than those of PF5. Similarly, mp of AsCl3 is higher than mp of AsCl5, whereas mp of PCl3 is lower than mp of PCl5. Similarly... but no, there are too many gaps in the table “down there”.

Which shows, by the way, that “googling” does not help if the data is not available. For the future, the course authors may consider asking a very similar question about a pair of compounds from “down there”. Thus the whole conflict between the (as yet unknown) “truth” and “expected answer” could be easily avoided.

Since the electronegativities decrease down the group for both M and L, the most polar M—L bond must be Bi—F bond and BiF3 should have the largest dipole moment. Well I couldn’t find its value. But it is known that bismuth trifluoride has ionic structure, and has the highest melting (649 °C) and boiling (900 °C) points of all binary pnictogen halides. On the other side of the spectrum, we have extremely sensitive nitrogen triiodide. A feather tickle, a loud noise and, I suppose, any attempt to measure its dipole moment will set off an explosive decomposition (see the video below):

2 NI3 → N2 + 3 I2

References

  1. Earnshaw, A. and Greenwood, N. (1997) Chemistry of the Elements, 2nd Edition. Butterworth-Heinemann, Oxford.
  2. Nelson, R.D., Jr., Lide, D.R., Jr. and Maryott, A.A. (1967) Selected values of electric dipole moments for molecules in the gas phase. National Standard Reference Data Series — National Bureau of Standards 10, Washington, DC.
  3. Cotton, S. (2001) Nitrogen triiodide. Molecule of the Month collection, University of Bristol.
  4. WebElements
  5. atomistry.com