JOURNAL OF RAMAN SPECTROSCOPY, VOL.

28, 891899 (1997)

Raman Spectral Study of Solutions of N O and 2 4 N O in Nitric Acid 2 5

Jackson E. Harrar,* Lester P. Rigdon and Steven F. Rice
Lawrence Livermore National Laboratory, Livermore, California 94550, USA

Solutions of N O and N O in anhydrous and aqueous nitric acid were examined by Raman spectroscopy to gain 2 4 2 5 a more detailed knowledge of the species present in these solutions and to assess the applicability of Raman spectroscopy as an analytical measurement technique. Solutions of N O in HNO show evidence of the presence 2 4 3 of the associated species, 3NO NO (N O2), which had been identied previously in a solid compound. The 3 4 6 eects of water on the spectra of these solutions were also examined. The nitronium cation, NO , is the dominant 2 species in solutions of N O in anhydrous HNO , and the spectra of concentrated solutions of N O exhibit a 2 5 3 2 5 band that has not been reported previously. This weak band, which may be the same as a band found in the spectra of solids containing the nitronium cation, has been attributed to a second vibrational mode of the molecule. This indicates a nonlinear conformation of the NO ion, and suggests that it is strongly associated with other species 2 in solution. The Raman data indicate that N O in HNO is completely ionized at concentrations to at least 3.0 2 5 3 mol l1 (21 wt% ). ( 1997 John Wiley & Sons, Ltd.
J. Raman Spectrosc. 28, 891899 (1997) No. of Figures : 7. No. of Tables : 2. No. of References : 64.

INTRODUCTION An electrolytic process1,2 has recently been developed for preparing solutions of N O in nitric acid, which are 2 5 used in the nitration of organic compounds. The basic process involves the oxidation of N O , in nearly anhy2 drous HNO , in a specially designed 4ow electrolyzer. 3 The electrolyzer is of the divided-cell type, in which anolyte solution containing the product N O HNO 3 is separated from the catholyte by means2 of5 an ionexchange membrane or porous diaphragm. The electrosynthesis is carried out as a batch process, and initially the catholyte is HNO , which is reduced during the 3 course of the reaction to form a mixture of N O , H O 2 4 2 and HNO . The basic chemistry and the electrochem3 compounds in the strong nitric acid media istry of these and the various reactions that occur in this process are described in Refs 1 and 2 and in several comprehensive reviews.3h6 During the development of the electrolytic process, it was of interest to examine the N O N O HNO 2 4 5 3 solutions by Raman spectroscopy because it2was known from previous work that these spectra are rich in information. This Raman spectral study was undertaken with two objectives. The rst goal was to learn more about the speciation of N O and N O in the HNO 2 4 2 5 3 solutions, especially because this information might shed further light on the mechanisms of some of the electrolytic cell reactions. Beyond the basic dissociation
* Correspondence to : J. E. Harrar. Environmental Protection Department, L-626, Lawrence Livermore National Laboratory, Livermore, CA 94550, USA Present address : Sandia National Laboratories, Livermore, CA 94550, USA. This article is US Government work and, as such, is in the public domain in the USA.
CCC 03770486/97/11089109 $17.50 ( 1997 John Wiley & Sons, Ltd.

equilibria that are known to exist in these solutions, there is an incomplete knowledge of the association of the species and how these compounds may interact with the solvent. There have been a number of Raman and infrared studies of N O , N O and their compounds 2 4 2 Ref. 7 for a recent comin the gas and solid phases (see 5 pilation of vibrational band data), but relatively few investigations have dealt with these compounds in solution. This paper presents a detailed analysis of the Raman spectra of the ions and neutral molecules in solutions of N O and N O in anhydrous and aqueous nitric acid. 2 4 N2O5 ionizes completely into the nitronium cation, 2 5 and nitrate ion, NO ~, and the spectrum of NO `, NO2 ` is found to exhibit a 3 weak band that is attrib2 uted to a bending mode of the ion. The spectra of N O 2 4 solutions show the presence of the nitrosonium cation, NO`, NO ~ and a complex, N O2` (3NO` NO ~), 3 3 that has been identied in solids. 4 6 A second objective was to examine the feasibility of using Raman spectroscopy to measure the concentrations of N O and/or N O in the large-scale N O 2 4 2 5 2 5 process2 solutions. Among the numerous possible analytical techniques, Raman spectroscopy is the only one that directly measures N O as NO `. The techniques 5 2 previously developed for2 on-line, chemical analysis of the process solutions are complicated,2 and the potential use of Raman spectroscopy using instrumentation that is currently available, such as that based on ber optics, appears to be an attractive alternative. EXPERIMENTAL Chemicals Anhydrous nitric acid was prepared by distillation from a mixture of ACS reagent-grade 90% HNO and 3
Received 13 March 1997 Accepted 30 June 1997

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fuming (30% free SO ) H SO in a glass apparatus at 3 2 4 4050 C and 2.6 kPa (20 Torr). The 90% HNO was 3 pretreated by the addition of urea (0.4 wt%), and by sparging with air while being mixed with the H SO . 4 The N O was obtained as C.P. grade 99.5%2 pure 2 4 nitrogen dioxide from Air Products & Chemicals and Matheson Gas Products. To purify the N O further, it 2 4 was distilled at low heat, while sparging with oxygen. Solutions of N O in HNO were prepared by electro2 5 3 lysis using the techniques described previously,1 except that the starting anolyte was semiconductor-grade red fuming nitric acid, obtained from Allied Chemical. This acid contains approximately 20 wt% N O and 1.6 2 4 wt% H O, and yields approximately 20 wt% solutions 2 of N O when completely electrolyzed. Anhydrous 5 HNO2 and solutions of N O and N O , if not used 3 2 4 2 5 immediately, were refrigerated at ]5 or [80 C. The solutions of N O in HNO , and with H O or N O , 2 4 3 2 2 5 in HNO , were prepared by weighing and adding the 3 O from a water-cooled buret to chilled liquid N 4 HNO or2the N O HNO solutions obtained from the 3 5 3 electrolysis. The2procedures used for the analysis of the electrolysis solutions are described in Ref. 2 and the references cited therein. Instrumentation and measurement procedures The Raman spectrometer was a Spex Industries Model 1488 Analytical Raman System. It was equipped with a 488 nm argon ion laser, a 0.22 m double-dispersion monochromator and a computer control/data acquisition system. A ow-through capillary was fabricated for this work so that all of the spectra in a series could be obtained without repositioning the cell. This cell was made from 3 mm o.d., 1.5 mm i.d. glass tubing and connected to a solution pump via uorocarbon polymer tubing and ttings. Using this arrangement, some of the spectra of the electrolysis anolyte solutions were measured on-line, in a closed system, by connecting the pumping apparatus to the laboratory electrolysis cell.8 The spectrometer response was optimized and calibrated using carbon tetrachloride, and the spectra were measured while the solutions were owing so that bubble formation in the solutions (especially in the less stable N O solutions) would have less eect. All 2 5 spectra except those of the N O HNO solutions, and 2 5 3 some of the most concentrated N O H OHNO 2 4 2 measured 3 mixtures, which were chilled to 510 C, were at ambient temperature. Unless noted otherwise, the spectra were recorded with a resolution of 7 cm~1 and a step width of 2 cm~1. The accuracy of the positions of the bands is estimated to be ^4 cm~1. RESULTS AND DISCUSSION Anhydrous nitric acid Figure 1 shows the Raman spectrum of so-called anhydrous or 100% nitric acid. In addition to the six major bands of the HNO molecule, the spectrum of the analytically anhydrous3acid shows the weak Raman lines at 1050 and 1400 cm~1 arising from small concentrations of the nitrate anion, NO ~, and of the nitronium 3 cation, NO `, respectively.9h11 Pure, 100% nitric acid 2
( 1997 John Wiley & Sons, Ltd.

Figure 1. Raman spectrum of anhydrous nitric acid. Molecular HNO bands are at 612, 678, 928, 1294, 1542 and 1672 cm1. 3

is actually an equilibrium mixture depicted by the reaction4 2HNO 3 H O ] NO ` ] NO ~ 2 2 3 0.4 1.1 1.5 wt% (1)

Also indicated are the approximate weight percentages of the species present in the liquid at room temperature. Thus the nominally anhydrous acid is not actually anhydrous, but contains 0.4 wt% water, and also signicant concentrations of nitronium and nitrate ions. As described in more detail below, these two ions are also derived from the dissociation of N O , thus their pres2 5 ence in the acid is the same as an equivalent concentration of N O , which is the anhydride of nitric acid. 2 is As water 5 added to the 100% acid, the band due to NO ` disappears, because NO ` reacts with the water 2 2 to form HNO . The other bands in the spectrum also 3 change in intensity because, as the nitric acid is diluted with water, the HNO further ionizes to form more 3 NO ~ and oxonium ions, H O`. Detailed Raman and 3 3 infrared studies by Irish and Brooker12 and HerzogCance and co-workers,13h15 the latter over a wide region of 503600 cm~1, have revealed that many complex species exist in both the anhydrous nitric acid and its aqueous solutions. The work of these investigators and a Raman study of HNO H O mixtures have 3 2 been summarized previously.16 In brief, there is evidence that, in addition to the fundamental species, the following species also exist in these solutions : oligomer (HNO ) chains, solvated ions such as 3x (NO 3HNO )~, hydrogen-bonded ion pairs, 3 3 H OH` ONO ~, and molecular association com2 2 plexes, H O HONO . These and analogous com2 2 plexes probably also exist in the nitric acid solutions of N O and N O to be discussed below, and they 2 4 2 5 undoubtedly inuence the shapes and positions of the bands in the spectra of these solutes. N O HNO solutions 2 5 3 In solvents of high dielectric constant, such as anhydrous HNO , N O behaves as a strong electrolyte, 3 2 5 and ionizes as follows :5,6,11 N O ] NO ` ] NO ~ 2 5 2 3 (2)

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There have been several previous investigations of the Raman spectra of solutions of N O in 2 5 HNO .9h11,17h19 In the nitration of organic com3 pounds, the nitronium cation, NO `, is known to be 2 the primary reactant, and the intensity of its Raman band at 1400 cm~1 is a good indicator of its concentration. The NO ` ion is also present at high concentra2 tions in HNO mixtures with H SO and in highly 3 2 4 acidic, nitronium salt (e.g. NO BF ) solutions, hence 2 4 there have also been a number of related studies of these solutions using Raman spectroscopy.20h22 The Raman spectrum of a concentrated, high-purity solution of N O in HNO , which was prepared by 2 5 3 electrolysis,1 is shown in Fig. 2. This spectrum also exhibits the six major bands of molecular HNO , in addition to the strong bands of both NO ~ (at 3 1050 3 cm~1) and NO ` (at 1400 cm~1), the ions which are 2 present at high concentrations in this solution. The very sharp 1400 cm~1 line, which, as noted, is also seen in the anhydrous nitric acid spectrum (Fig. 1), is due to l , the ONO symmetric stretch mode of the NO 1 ` 2 ion.11 The more dilute solutions of N O in HNO , like 2 bands of molecu3 anhydrous nitric acid, exhibit only the 5 lar HNO , NO ~ ion and the 1400 cm~1 line of 3 3 NO `. As the solutions become more concentrated in 2 , a new band appears, as shown in Fig. 2, at 555 N O 2 5 cm~1. This band cannot be attributed to a weaker band of the NO ~ ion, because it is not seen in similarly concentrated, 323 mol l~1 solutions of NaNO in anhy3 drous HNO .16 It is due to either a vibration of 3 or the bending mode of the NO ` ion. molecular N O 2 5 2 Most investigators have found, by Raman and other measurements, that at the lower concentrations of N O , ionization is complete and no molecular N O 5 2 5 is 2present.5,11 However, there is some disagreement as to the highest concentration at which N O remains 2 completely dissociated. Ingold and Millen11 5found no evidence of molecular N O up to approximately 2 5 1 mol l~1 (6 wt%). The data of Odokienko et al.17 indicate complete dissociation up to at least 2 mol l~1 (15 wt%). These investigators found a deviation in the line intensities of the NO ` ion above this concentration, 2 but this was attributed to decomposition of the N O . 2 5

Edwards and Fawcett20,21 examined an analogous, ionic solutesolvent system, NO BF , in H SO , and 2 4 2 4 found a linear relationship between the integrated intensity of the 1400 cm~1 Raman line and concentrations of the nitronium compound up to 3 mol l~1. In the spectrum shown in Fig. 2, there is an additional weak band at approximately 2240 cm~1. This band is probably the major band that is present in the spectra of solutions of N O in nitric acid, and which is 2 4 attributed to a cation arising from the ionization of N O (namely N O2` ; see discussion below). As dis2 4 4 6 cussed by Odokienko et al.,17 N O may be present in 2 4 the N O solutions at low concentrations because of 2 5 the decomposition of the N O . Based on the spectra 2 5 obtained for more concentrated solutions of N O (see below), the concentration of N O in the N O 2 4 solution 2 4 2 5 used to obtain the spectrum in Fig. 2 is estimated to have been less than 0.1 ml l~1. In the present study, concentrations up to approximately 3 mol l~1 (21 wt%) were examined, with the results shown in Fig. 3. This plot shows that the integrated intensity of the 1400 cm~1 NO ` line is some2 what non-linear, increasing slightly with concentration of N O . Because incomplete dissociation would cause 2 5 a decrease in intensity with concentration, these data indicate that N O is still completely dissociated, even 2 5 at these high concentrations. It should be noted that the higher concentration solutions of N O are unstable. 2 5 Decomposition continuously generates gaseous oxygen, which causes experimental difficulties in the measurements. Accurate spectra must therefore be obtained, as was done here, very promptly after synthesis, with cold solutions.
Covalent N O . Although it appears from the data on 2 the intensity 5 the primary NO ` band vs. concentraof 2 tion that molecular N O is not present in these solu2 5 to consider whether N O tions, it is still worthwhile 5 could give rise to the band at 555 cm~1 that 2 we observe, or possibly other bands. A number of studies have dealt with the infrared and Raman spectra of covalent N O , in non-polar solvents, in the solid state 5 and in the 2gaseous state. In the solid state, depending

Figure 2. Raman spectrum of 3.0 mol l1 N O (21 wt%) in 2 5 anhydrous nitric acid. ( 1997 John Wiley & Sons, Ltd.

Figure 3. Intensity of Raman band at 1400 cm1 vs . concentration of N O in anhydrous nitric acid. 2 5 J. Raman Spectrosc., Vol. 28, 891899 (1997)

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J. E. HARRAR, L. P. RIGDON AND S. F. RICE

on how it is prepared, N O can be either covalent or 2 5 ionic.23 In the gas phase, N O is unambiguously cova2 5 lent. Table 1 summarizes data from the investigation of Hisatsune et al.24 and several of the most recent studies of the vibrational spectra of covalent N O . Some of 2 5 this information is also included in the reviews of Melen and Herman7 and Jacox.25 Stirling et al.30 have recently published a theoretical study of the vibrational frequencies of the nitrogen oxides, including N O . 2 5 Theoretically, each of the vibrational modes listed in Table 1 should be Raman active,7 and the l NO wag 9 2 wavenumber corresponds approximately to that of the 555 cm~1 band that we observe for N O HNO solu2 5 3 tions. However, in the only Raman spectral studies of N O , Chedin31 and Hisatsune et al.24 observed 2 5 Raman lines only at 707, 860, 1033, 1240 and 1335 cm~1, with the strongest lines being those at 860 and 1240 cm~1. If molecular N O were present in the nitric 2 5 acid solution, some of these bands, particularly that at 860 cm~1, should be observed in the Raman spectra. The bands at 1240 and 1335 cm~1 would probably be obscured by the strong HNO band at approximately 1300 cm~1. Because a Raman 3 band near 555 cm~1 has not been observed previously for molecular N O , and 2 because no other unidentied bands are present 5in the N O HNO solution spectra, it is concluded that the 2 5 dissolved N 3 is completely ionized and that the 555 O 2 5 cm~1 band must be attributed to NO `. 2
Nitronium ion. Theoretically, if the NO ` ion is linear, no vibrations other than l at 1400 2 cm~1 would be 1 Raman active. However, there are several indications that the 555 cm~1 band is due to a second vibrational mode, l , of the nitronium ion. Previous work on the 2 vibrational spectra of solid N O , when it is prepared in the ionic state,23,32 as NO 2 5 ~, and other com`NO 2 3 pounds of the nitronium cation33h35 provide an indication of the nature of this vibrational band. First, the 555 cm~1 band occurs near the 538 cm~1 band that has been assigned to l , the ONO deformation mode, in earlier infrared 2studies of NO ` in 2 solid, ionic N O .24,36 Wilson and Christe32 obtained 2 5 Raman spectrum of solid N O and a very precise laser 2 band found the l vibration at 534 cm~1. This Raman 5 2

has also been observed in the following ionic compounds at the wavenumbers given : NO ClO 571,33 2 4 NO SO F 58734 and NO BF 530 cm~1.35 In the last 2 3 2 4 compound, the NO ` cation is known, from an x-ray 2 diraction study,37 to be slightly bent (nONO \ 175.2 ^ 1.4), thus the non-linear cation may give rise to additional bands in the infrared and Raman vibrational spectra. Evidently, such distortion of the NO ` ion also 2 occurs in the other compounds. In the gas phase,38 the NO ` ion is linear, and the l 2 2 ONO bending mode appears at 639 cm~1. In the present work, the bending mode (which is not Raman active in linear, D symmetry) is observed in the =h Raman spectrum at a much lower energy in solution, and at wavenumbers similar to those observed for the various solids described above. This is strong evidence of a slightly bent NO ` ion in HNO solutions, and an 2 3 indication that the ion is associated with other species in the solution. This association causes the bent geometry and gives rise to the band in the Raman spectrum. As is the case with nitrate ion (see above), the nitronium ion probably is solvated by HNO , for example, 3 to form species such as NO (HNO ) `. There is good 2 3 x of this type in evidence for a strong association complex the calorimetric and NMR studies of Lagodzinskaya et al.39 They also examined solutions of N O in HNO 2 5 3 and found that the heats of solution exhibited sharp peaks at N O : HNO ratios of 1 : 12 and 1 : 32, which 2 5 3 they attributed to intermolecular association species. Prakash et al.,40 on the basis of the 17O NMR spectrum and theoretical calculations of the structure of the nitronium cation in superacid media, have recently proposed the presence of a bent, protonated form, the ONOH2` cation. From kinetic considerations, an analogous species, H NO ` [NO ` H O] has been 2 3 2 suggested20,21 to be the2 nitrating species in HNO H SO H O mixtures. 3 2 4 2 N O HNO solutions 2 4 3 As mentioned above, N O also ionizes when dissolved 2 4 in HNO , although denitely not as completely as 3

Table 1. Observed infrared vibrational bands and assignments for covalent N O 2 5

Wavenumber (l) 8 Hisatsune et al .24 (solid) l/cm1 Seibert et al .26 (gas)a l/cm1 8 Lovejoy et al .27 (gas) l/cm1 8 Cantrell et al .28 (gas)b l/cm1 8 Koch et al .23 (solid)b l/cm1 8 Bencivenni et al .29 (solid in Ar) l/cm1 8 Band assignments from Refs 7, 24 and 29

1742 1702 1335 1245 853 732 712 600 580 380 337

1720

1700 1340 1250 860 750

1246 743

1764 1705 1340 1258 864 760 714

570 350

557

1742.4 1702.7 1339.8 1243.0 863.1 737 715 639.7 569.4 343.9

l NO a-stretch, in-phase 1 2 l NO a-stretch, out-of-phase 11 2 l NO s-stretch, in-phase 2 2 l NO s-stretch, out-of-phase 12 2 l N-O a-stretch, (NON) 13 l NO bend, in-phase 3 2 l NO bend, out-of-phase 14 2 l NO rock (in-plane) 4 2 l NO wag (out-of-plane) 9 2 l NON s-stretch and 5 l NO rock (in-plane)7 15 2

a Studied in the 250650 cm1 region only. b Studied in the region above 700 cm1 only. ( 1997 John Wiley & Sons, Ltd. J. Raman Spectrosc., Vol. 28, 891899 (1997)

RAMAN STUDY OF N O AND N O IN NITRIC ACID 2 4 2 5

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N O . The primary equilibrium is 2 5 N O NO` ] NO ~ (3) 2 4 3 and the nitrosonium cation, NO`, is an important species. Based on an NMR technique developed earlier,41 which measures the proton chemical shift in HNO due to NO ~, Happe42 estimated the appar3 3 ent equilibrium constant of this reaction and found it to be approximately 4.5 mol l~1.16 Ishchenko and coworkers43h45 also examined the N O HNO system 2 4 3 by Raman spectroscopy and found a degree of dissociation of similar magnitude. However, the true equilibrium constant of reaction (3) cannot be calculated from the measured concentrations of its species, because, as will be discussed below, there is at least one additional equilibrium coupled to reaction (3). Nevertheless, it is useful to know that, in the range of concentrations of interest in the present study (0.57 mol l~1), N O is approximately 5090% dissociated. 2 4 homolytic dissociation The N O 2NO (4) 2 4 2 also exists in these solutions, but the concentration of NO , although giving these solutions their intense 2 orange color, is believed to be very small (\0.1 wt%).4,44,46 Millen and Watson46 found that no NO 2 bands were observed in the infrared spectra of N O HNO solutions, and all of the Raman bands 2 3 that 4they observed could be accounted for by the species in reaction (3). The basic species in the N O HNO solutions are thus molecular N O , 2 4 2 4 NO`, HNO3 , NO ~ and, to a much lesser extent, 3 3 NO . 2 The rst in a series of Raman spectra obtained for the N O HNO solutions is shown in Fig. 4, for the spec2 region 3 tral 4 from approximately 200 to 1800 cm~1, marked with the bands due to molecular N O , HNO 2 4 3 and NO ~. These bands have been identied on the 3 basis of previous studies of the Raman spectra of solid N O , liquid N O and solutions of N O in HNO . 2 4 2 4 2 4 3 Some of this information is also summarized in reviews cited above7,25 and in Ref. 47. First considering the N O bands, Table 2 summarizes the data from the 2 more4 detailed studies and compares it with the measurements of the present work. Note that the descriptions denoted in Table 2 by NO are those for this 2 moiety in the N O molecule. 2 4

Figure 4. Raman spectrum of a solution of 4.7 mol l1 N O (27 2 4 wt%) in anhydrous nitric acid.

Goulden and Millen50 examined both liquid N O 2 4 and its solutions in HNO (up to approximately 3 1.6 mol l~1) and saw no evidence of Raman bands for molecular NO itself. More recently, Miaskiewicz and 2 Kecki54 also obtained Raman spectra of N O as the 2 HNO , liquid and in a variety of solvents other than 4 3 and did not report bands for NO . The concentration 2 of NO , as noted above, is apparently too low to be 2 observed by this technique. Moharum51 measured the Raman spectra of highly concentrated solutions of N O in HNO , and 2 4 3 observed ve of the expected six bands ; the only one not being reported was the l NO wag band at 677 2 cm~1, which has been seen 8 only in solid, crystalline N O .48,49 This mode is virtually impossible to see in 2 4 HNO solutions, because the d ONO scissors band of HNO3 occurs at exactly the same wavenumber.11,16 3 This band was attributed by Audinos53 to molecular NO ; however, it cannot be due to NO , because other 2 2 work48,55 on solid NO has shown that it does not 2 have a band near that wavenumber. Like N O , solid 2 5 N O can exist in both covalent or ionic [NO`NO ~] 2 4 and also amorphous or crystalline forms, each of 3 forms, which have distinctive vibrational spectra.56h58 In the present work, as shown in Table 2 and Fig. 4, the principal bands observed for molecular N O in 2 4 HNO are at 265, approximately 468, 810 and 1380 3The weaker l and l bands become much more cm~1. 6 5

Table 2. Mode descriptions and wavenumbers of the Raman bands of N O 2 4

Wavenumber (l) 8 Solid N O : 2 4 Bolduan et al .48 l/cm1 8 Solid N O : 2 4 Andrews and Anderson49 l/cm1 8 Liquid N O : 2 4 Goulden and Millen50 l/cm1 8 44 wt% N O 2 4 in HNO : 3 Moharum51 l/cm1 8 N O 2 4 and H O 2 in HNO : 3 Audinos52,53 l/cm1 8

N O modea 2 4

This work l/cm1 8

l NN stretch 283 279, 283 265 3 l NO rock 498 496 500 6 2 l NO wag 677 677 Not obs. 8 2 l NO sym. bend 811 811 811 2 2 l NO sym. stretch 1382 1377, 1384 1382 1 2 l NO asym. stretch 1724 1727 1724 5 2 a Taken from Ref. 48. b Attributed to molecular NO , but probably is HNO ; see text. 2 c Observed only in N O H OHNO solutions ; see 3 text. 2 4 2 3 ( 1997 John Wiley & Sons, Ltd.

266 484 Not obs. 809 1381 1717

280 481 680b 810 1380 1715

265 468482 Not obs. 810 1380 1714c

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distinct when water is present in the solutions, and in these media (see below) are found at 482 and 1714 cm~1, respectively. The wavenumbers of the ve bands are thus in good agreement with the measurements of Moharum.51 Figure 5 shows a series of Raman spectra of solutions of N O in anhydrous HNO from 400 to the higher 2 4 3 2800 cm~1 wavenumber range. Of particular interest is the manner in which the bands in the 22002500 cm~1 region change as the solution becomes more concentrated. Two peaks, one broad and one sharp, are clearly resolved in the spectra of the 0.4 and 1.0 mol l~1 solutions. In more concentrated solutions, the sharp feature is obscured by the very intense primary band. Previous investigators50h53 of the spectra of these solutions have reported only one band in this vicinity and most have attributed it to the fundamental, l , stretch mode of the 1

NO` cation. Goulden and Millen50 originally proposed that the single band that they observed at 2240 cm~1 (there was some shift with concentration of N O ) was 2 4 due to the species NO NO`, but this idea was later 2 retracted by Millen and Watson.46 Audinos53 and Moharum51 found this primary band at 2230 and 2235 cm~1, respectively. When N O is examined as a solid, and when associ2 4 ated with other compounds, a shift and a splitting of the NO` Raman band near 2250 cm~1 has also been observed, and is attributed to the dierent environments of the NO` ion.57h60 In the N O HNO solution, as 2 4 3 marked in Fig. 5, we believe that the sharp band at 2302 cm~1 is actually due to the NO` ion, and that the major band at 2246 cm~1 corresponds to the band observed in the previous studies, and should be assigned to the species 3NO` NO ~ [N O2`]. The evidence 3 4 6 for this is as follows. Although it had not been identied in solution, x-ray crystallographic and Raman studies of iron nitrateN O adducts by investigators at the University 2 4 of Nottingham61,62 identied the N O2` moiety in one 4 6 of the adducts, and led them to speculate61 that this ion might exist in solution. In the 1 : 1.5 iron compound adduct, Addison et al.61 found that the Raman l vibra1 tional mode of NO` in the N O2` group occurred at 4 free NO` in the 1 : 1 6 2250 cm~1, whereas that of the adduct occurred at 2302 cm~1. As shown in the middle spectrum of Fig. 5, the wavenumbers of these bands are almost exactly the same as those of the bands that we observe. Three other weak bands observed in the spectra of the N O HNO solutions are of interestthose 2 4 3 marked in Fig. 5(c) at 1454, 2342 and 2546 cm~1. The 1454 cm~1 band (also designated as NO ~ at ca. 1450 3 cm~1 in Fig. 4) is attributed to the l vibration of the 314001500 cm~1 NO ~ ion, which is observed in the 3 region in the spectra of aqueous solutions containing high concentrations of nitrate.12,13,16 The bands at 2342 and 2546 cm~1 in Fig. 5(c) correspond to the bands found by Moharum51 at 2374 and 2545 cm~1 in the spectra of similarly concentrated N O HNO solutions. Because the intensities of both 4 3 of2these bands are proportional to the intensity of the nearby 2246 cm~1 band attributed to N O2`, it appears that these bands are also associated 4 6 this with molecule. It can further be speculated that these bands arise from the three NO` vibrations in the complex ion. The combination of three NO stretching modes transforms as A@ and E@ symmetry in D . Both modes are 1 Raman active. Thus, one intense,3htotally symmetric Raman band and one degenerate feature should be observable in high symmetry. The presence of two weaker bands at dierent wavenumbers suggests a lowering of the D symmetry in the HNO solutions, 3h 3 such that the E@ mode appears split. However, no predictions can be made regarding the intensity pattern of these two features. N O HNO H O solutions 2 4 3 2

Figure 5. Raman spectra of solutions of N O in anhydrous nitric 2 acid : (a) 0.4 mol l1 (2.5 wt%) ; (b) 1.0 mol4 l1 (5.9 wt%) ; (c) 7.1 mol l1 (40 wt%). ( 1997 John Wiley & Sons, Ltd.

Mixtures of N O and HNO with water are also of 2 4 3 interest because these three components are present in the catholytes of the N O electrosynthesis process.1,2 2 5
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RAMAN STUDY OF N O AND N O IN NITRIC ACID 2 4 2 5

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NO ~ ion. Increasing ionization of nitric acid increases 3 the concentration of free NO ~. Assuming the existence 3 of the N O2` ion, the following dual equilibrium can 4 6 be written : 3N O 3NO` ] 3NO ~ 3NO` NO ~] 2NO ~ 2 4 3 3 3 [N O2`] 4 6 (5) The HNO ionization equilibrium is coupled to these 3 equilibria and, as the concentration of NO ~ increases, 3 the combined equilibrium depicted in reaction (5) would be driven both to the left, forming more N O , and to 2 4 the right, creating more N O2` ion. In the bottom 4 6 spectra of Fig. 6, the two N O bands, the l asym2 4 5 metric stretch at 1714 cm~1 and the l NO rocking 6 2 mode at 482 cm~1, are identied. As nitric acid solutions of N O are further diluted 4 with water, the compound N O2 is formed, via the dis2 3 a dehydration equiproportionation reaction and librium : N O ] H O ] HNO ] HNO (6) 2 4 2 2 3 2HNO N O ] H O (7) 2 2 3 2 These solutions are distinguished by the bright, cobalt blue color of N O . In examining the Raman spectra of 2 3 solutions containing high concentrations of water,16 we nd a strong band at 258 cm~1, which probably corresponds to the band at 253 cm~1 assigned by Hisatsune and Devlin63 as the l NN stretch mode. They investigated solutions of N6O in CH Cl at [ 30 C. This 2 2 band is not present 2 in3 N O HNO H O mixtures 2 4(D20 wt%) 2 O. 3 containing less than 16 mol l~1 H 2

N O N O HNO solutions 2 5 2 4 3 In the electrosynthesis process,1,2 the anolyte product is a mixture of N O and N O , and electrolysis is 2 concentration of N O is as low as 2 4 carried out until the 5 2 4 possible. Thus an analytical method based on Raman spectroscopy should be capable of measuring both of these substances in the same solution. There is a complication in this task, however, because one of the principal lines of N O , its l line at 1380 cm~1 is very 2 4 1 close to the l line of NO ` at 1400 cm~1. This is illus1higher resolution spectrum shown in Fig. 2 trated in the 7. Both of these lines also appear on the shoulder of the intense HNO band, and are shifted somewhat in wavenumber from3the values found when N O and N O 2 as 2 5 are present alone. Another complication, 4 discussed above, is the eect of the common ion NO ~ on the 3 intensities of both the N O and N O bands. The 2O4 and N O 5 present in 2 are result is that, when both N 2 5 4 signicant concentrations, accurate 2 analyses would require some type of multivariate calibration technique.63 Measurement of the intensities of several lines of the N O , and perhaps also the HNO , together 2 line of NO `, should be a straightforward 3 with the l 4 1Such a chemometric technique would also 2 approach. have to be used to measure the concentrations of N O 2 4
J. Raman Spectrosc., Vol. 28, 891899 (1997)

Figure 6. Raman spectra of solutions of N O and H O in anhy2 drous nitric acid : (a) 1.9 mol l1 (11.4 wt%)4N O , 2 4.2 mol l1 2 4 (4.9 wt%) H O ; (b) 4.0 mol l1 (24 wt%) N O , 8.2 mol l1 (9.6 2 5.3 mol l1 (33 wt%) N O , 2 4mol l1 (14 wt%) wt%) H O ; (c) 12 2 4 H O. 2 2

Figure 6 shows the Raman spectra of three HNO solu3 tions containing both water and N O . Comparing 2can be seen rst 4 these spectra with those in Fig. 5, it that, with increasing concentrations of water, the bands due to molecular HNO become less dominant. As shown by reaction (1), 3 anhydrous nitric acid is not highly ionized ; however, as water is added to the acid, dissociation is enhanced, so that, for example, in common aqueous nitric acid (approximately 16 mol l~1) the HNO is completely dissociated. Second, as water is 3 added, the sharp NO` band at 2302 cm~1 disappears into the intense N O2` band. Third, two of the bands 6 of molecular N O 4become more distinct. 2 4for the changes in these spectra can An explanation be oered on the basis of the common ion eect of the
( 1997 John Wiley & Sons, Ltd.

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J. E. HARRAR, L. P. RIGDON AND S. F. RICE

Figure 7. Raman spectrum of a solution of 4.5 mol l1 (26 wt%) N O and 2.3 mol l1 (15 wt%) N O in anhydrous nitric acid. 2 4 2 5

in the electrolytic catholytes, if desired, because of the complex interactions involving the water in these solutions. In the analysis of the anolytes in the electrolytic process during the period when the product solution is approaching its nal composition, the concentration of N O is relatively low compared with that of the N2O4 . In that case, the eect of the N O on the mea2 5 2 4 surement of the N O (as NO `) becomes negligible. 2 5 should2 then be sufficient to The NO ` line alone 2 monitor these solutions accurately.

tions. There appear to be a number of complex interactions between the primary species and those of the HNO solvent. Solutions of N O in HNO show evi3 2 4 3 dence of the presence of an associated species, 3NO` NO ~ (or N O2`), in addition to the well 3 4 6 known nitrosonium cation, NO`. The equilibria in these solutions are strongly inuenced by the concentration of water, because it inuences the degree of dissociation of HNO and hence the concentration of NO ~ 3 3 ion. In the Raman spectra of solutions of N O in 2 5 HNO , the change in intensity of the strong line at 3 1400 cm~1, vs. the concentration of N O , indicates 2 5 that N O is completely ionized into the nitronium 2 5 cation, NO`, and the NO ~ anion at concentrations up 2 3 to at least 3.0 mol l~1 (21 wt%). The spectra of concentrated solutions of N O also exhibit a previously unre2 5 ported band at 555 cm~1, which is attributed to the bending mode of the NO ` ion. This weak band, which 2 appears to be the same as a band observed in the spectra of solids containing the nitronium cation, indicates non-linearity in the conformation of the NO ` 2 ion, and further suggests that it is strongly associated with other species in solution. The use of Raman spectroscopy as an analytical technique to monitor the concentrations of the primary species in these solutions is feasible, but because of the complex interactions among the species in most of the concentration ranges, analysis will require careful calibration using a multiple-band, multivariate approach.

SUMMARY AND CONCLUSIONS Examination of the Raman spectra of mixtures of N O 4 and N O in aqueous and anhydrous nitric acid 2has 2 several interesting characteristics of these solu5 revealed

Acknowledgements
The support of Raymond R. McGuire in this work is gratefully acknowledged. This work was performed under the auspices of the US Department of Energy under contract No. W-7405-ENG-48. Funding was provided by the Plant Modernization Program of the US Army Materiel Command.

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J. Raman Spectrosc., Vol. 28, 891899 (1997)