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Chemical Education Today

Letters
Nitrogen Triiodide
The reaction of iodine with aqueous ammonia to yield explosive crystals, said to be nitrogen triiodide, was recently mentioned in this Journal (1). The dry crystals are extremely shock sensitive and they explode violently, producing a cloud of purple-brown iodine vapor, just when touched lightly with a feather! Impressive images of this detonation can be seen in both textbooks (2) and movies (3). The aim of this letter is to correct some common misconceptions about nitrogen triiodide and to suggest some useful calculations that students can perform easily. Although they are sometimes referred to as nitrogen triiodide (1, 4), the black, explosive crystals formed by reaction of iodine with concentrated aqueous ammonia are not NI3, but NI3NH3. This material does not contain discrete NI3 molecules but it has a polymeric structure with tetrahedral NI4 units sharing two corners to give zigzag chains. In addition, one NH3 molecule is attached by a weaker bond to alternate nonbridging iodine atoms along the chain (5). Many textbooks, including some published in recent years (68), state that unsolvated NI3 has not been isolated. Nevertheless, it was prepared in 1990 by reaction of boron nitride with IF in CFCl3, and characterized by Raman and 15 N NMR spectroscopies (9), as acknowledged in Cotton and Wilkinsons textbook (10). Some simple calculations help students to understand that, while NF3 is thermodynamically stable, the NX3 (X = Cl, Br, I) are explosive dangerous materials. By using the data and equations reported in ref 11, it can be seen that reaction 1 is exothermic when X = F, but highly endothermic when X = Cl, Br, I.
1 2 N2(g)

formed, thus providing the driving force for the reactions. For example, the reaction of iodine crystals with aqueous ammonia is represented by eq 3: 3I2(c) + 5NH3(aq) NI3 NH3(c) + 3NH4I(aq) (3) Although the enthalpy of formation of NI3 NH3(c) is +146 kJ/mol, the enthalpies of formation of NH3(aq) (80 kJ/mol) and NH4I(aq) (188 kJ/mol), lead to an enthalpy change for reaction 3 of 18 kJ/mol, the stability of NH4I(aq) being a critical factor for the reaction to take place. Also, the formation of gaseous NI3 according to eq 4 is a thermodynamically favored process because of the high stability of BF3. Indeed, the enthalpies of formation of BN(c) (254 kJ/mol), IF(g) (96 kJ/mol), BF3(g) (1136 kJ/mol), and NI3(g) (+287 kJ/mol) lead to a calculated enthalpy change for reaction 4 of 307 kJ/mol. BN(c) + 3IF(g) BF3(g) + NI3(g) Literature Cited
1. Waddell, T. G.; Rybolt, T. R. J. Chem. Educ. 2000, 77, 471. 2. Gillespie, R. J.; Eaton, D. R.; Humphreys, D. A.; Robinson, E. A. Atoms, Molecules and Reactions; Prentice Hall: Englewood Cliffs, NJ, 1994; p 318. 3. Jacobsen J. J.; Moore, J. W. Chemistry Comes Alive! Vol. 3; J. Chem. Educ. Software 2000, SP 23. 4. Hambly, G. H.; Peters, R. J. Chem. Educ. 1993, 70, 943. 5. Jander, J. Adv. Inorg. Chem. Radiochem. 1976, 19, 1. 6. Lee, J. D. Concise Inorganic Chemistry, 5th ed.; Chapman & Hall: London, 1996; p 495. 7. Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements, 2nd ed.; Butterworth-Heinemann: Oxford, 1997; p 441. 8. Shriver, D. F.; Atkins, P. W. Inorganic Chemistry, 3rd ed.; Oxford University Press: Oxford, 1999; p 379. 9. Tornieporth-Oetting, I. C.; Klaptke, T. M. Angew. Chem., Int. Ed. Engl. 1990, 29, 677. 10. Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed.; Wiley: New York, 1999; p 338. 11. Kildahl, N. K. J. Chem. Educ. 1995, 72, 423. 12. Davies, R. H.; Finch, A.; Gates, P. N. J. Chem. Soc., Chem. Commun. 1989, 1461.
David Tudela Departamento de Qumica Inorgnica Universidad Autnoma de Madrid 28049-Madrid, Spain david.tudela@uam.es

(4)

+ 32 X 2(g) NX 3(g)

(1)

With the data in ref 11 and the sublimation enthalpy of iodine (62 kJ/mol), the enthalpy of formation of NI3(g) can be calculated to be +272 kJ/mol, in good agreement with the published value of +287 23 kJ/mol (12). The gaseous compound is greatly stabilized by formation of the crystalline adduct with ammonia, since the enthalpy of formation of NI3 NH3(c) is +146 6 kJ/mol (12). Still, NI3 NH3 explodes according to eq 2 and the enthalpies of formation of NH3(g) (46 kJ/mol) and I2(g) (+62 kJ/mol) lead to a calculated enthalpy change for reaction 2 of 99 kJ/mol. NI3 NH3(c) NH3(g) + 12 N2(g) + 32 I2(g) (2) Students may ask why chemical reactions can lead to the formation of very unstable compounds such as NI3 and NI3 NH3. The answer is that very stable compounds are also

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Journal of Chemical Education Vol. 79 No. 5 May 2002 JChemEd.chem.wisc.edu