INTENSITIES OF EMISSION LINES IN FLAMES OF METAL HALIDES WITH ACTIVE NITROGEN

L. F . PHILLIPS
Chemistry Department, University of Canterbury, Ch~istchurch, New Zealand Received April 3, 1963

ABSTRACT
The intensities of spectral lines emitted by flames of a number of metal halides with active nitrogen have been found to vary as the square of the nitrogen atom concentration. \\Then the total energy required for simultaneous dissociation of the halide and excitation of the metal atom is less than about 200 kcal/mole the energy transfer process is too efficient to be attributed to the termolecular reaction of a halide molecule with a pair of nitrogen atoms. The observations are consistent with the hypothesis t h a t in this case energy is transferred to the halide molecule during collision with a nitrogen molecule in the 2,+ state. Possible excitation mechanisms are discussed for less intense lines which would require up to 276 kcal/mole for simultaneous dissociation and excitation.

INTRODUCTION

In a previous con~munication(1) it was shown t h a t in flames of thallous halides with active nitrogen the intensity of the 5350 A thallium line is proportional to the first power of the halide concentration and t o the square of the nitrogen atom concentration. T h e rate of the overall reaction, calculated from the absolute intensity of the 5330 line and also from the rate of consumption of halide, was approximately 2X cm6molecule-2sec-~, whereas the largest value to be expected for a termolecular reaction is about cm6mole~ile-~sec-l 2 ) . ( Thallium lines were observed photographically down to 3230 '4, for which the energy required in-the case of T l F is 221 kcal/mole. The results were discussed in terms of the transfer of energy to the halide during a collision with an electronically excited nitrogen molecule (equation [I]), the excited molecule being produced during nitrogen atom recombination. In the steady state the concentration of Ng* is proportional to the square of the nitrogen atom concentration. I t was suggested that the excited molecule involved was in the %,+ state, since the amount of energy required appeared to be too great to be provided by other metastable species. In the present paper the intensity measurements are extended to all of the thallium lines and to flames of active nitrogen with some halides of other metals. For all of the emission lines the intensity varies as the square of the nitrogen atom concentration, proportionality to the halide concentration also being observed over the range of partial pressures used. T h e lines may be divided into three classes, depending on whether the total energy required to dissociate the halide and excite the metal atom is less than about 200 kcal/mole, between 200 and 225 kcal/mole, or greater than 225 kcal/mole. For lines in the first class the efficiency is in general too high for the termolecular mechanism [2]
X
=

halogen atom, lLI = metal atom of valency n

and the arguments of the previous paper (I) may be applied, leading to the conclusion t h a t energy is probably transferred from a nitrogen n~olecule the 52g+ in state. For lines
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PHILLIPS: EMISSION LINE INTENSITIES

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in the second class either of these mechanisms may operate. For lines in the third class both mechanisms may be ruled out on energetic grounds, while a termolecular mechanism involving one ground state and one excited nitrogen atom may be eliminated on grounds of efficiency because of the small proportion of excited atoms in discharged nitrogen (3). There are two other alternatives for this case, one involving a higher metastable state of S 2and the other using consecutive excitation processes similar to [I] or [2] to overcorne the high energy requiremetlt. Of these alternatives the latter is favored since it leads more readily to a dependence of intensity on the square of the atom concentration. This work is essentially a continuation of the series of observations of Strutt (4) on flames supported by active nitrogen, with the advantage t h a t in the intervening 50 years a reasonably complete theory of active nitrogen has developed (5). In the current theory most of the activity of discharged nitrogen is attributed to the presence of ground-state nitrogen atoms; however, the role of metastable nitrogen molecules has been stressed by a number of investigators (6-9, 1). Mulliken (10) has listed most of the known or predicted states of N2, together with their theoretical dissociation products and important spectroscopic constants, including the known or predicted energy of the ground vibrational level. Table I , selected from Mulliken's data, contains those states which are expected to be metastable or long lived. As pointed out by Kenty (11), a state may be slightly above another to which transition is allowed yet have a long lifetime because of smallness of the factor v 3 in the expression for the transition probability. Where a state is expected t o be long lived for this reason the nearby state t o which a transition is allowed is given in the right-hand column of Table I. As in Mulliken's table, square brackets indicate'\redicted states or values, parentheses indicate doubtful values.
TABLE I Long-lived electronic states of Nz Energy (v = 01, kcal/mole

State

Do, kcal/mole

Dissociation products

Allowed transition

--142 83 4+3 34 -+ B3ng t 170 kcal a 11721 11071 4S+2D 196 . 138 2D +2D (202) (132) 2D t 2 D allIn a t 196 kcal (222j 4Sf4S (3) [(280)1 [(Hz)] ~ S + ( S ~ ~ ~ . ~ S [I&]~ P t [(279)] + ) a kcal (Possibly other states, of high multiplicity, above this) EXPERIMENTAL T h e reaction vessel and flow system were as previously described ( 1 ) except t h a t a n improved heating jacket enabled the reaction vessel to be heated t o 550 C. This higher temperature was necessary for flames \yith sodium iodide, a temperature of 400+10 C being used with the other halides. T h e reaction vessel consisted of a length of 34 mm 0.d. quartz tubing having one end window a t right angles to the length of the tube and two parallel side windows. In the present work photometric observations were made through the side windows. Active nitrogen from a microwave discharge was pumped through the reaction tube with a linear velocity of 1.2 m/sec a t 3.0 mm Hg, the majority of the experiments being carried out a t this pressure. Metal halides were carried from a small, independently heated oven by a stream of argon, and entered the reaction vessel through a 0.2 mm jet a t the end of a 3 mm 0.d. quartz tube. This jet could be moved over a range of 6 cm along the axis of the reaction vessel. Xitrogen atom flows were determined by visual titration with nitric oxide (12). Typical partial pressures of atomic nitrogen and metal halide were 0.05 mm and 0.0005 mm respectively. Thallous halides were as used previously. The other halides were A.R. grade or else the best reagent grade available. The process of vacuum sublimation involved in producing a flame appeared to be sufficient to eliminate the effects of most impurities, especially since the greatest source of this kind of error \vould be

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the presence in the reaction vessel of traces of halides from previous experiments. Prolonged cleaning of the vessel with 20% hhydrofluoric acid was not sufficient t o entirely free the walls of metals or metal halides. Measurements were carried out in a n order which would minimize the effect of this contamination; for example T1F was studied before TlI, the intensity of emission a t all wavelengths being greater for the latter. I n every case the background intensity was measured with the argon flow cut off and a suitable correction applied: Photometric measurements were carried out using a Hilger medium quartz spectrograph fitted with a n E720 scanning unit and a 1P28 photomultiplier. The output of the photomultiplier was taken to a O250 pa meter through a cathode follower. The variation of photometer sensitivity with wavelength was determined from the response to a tungsten strip filament lamp of known temperature and emissivity (13). RESULTS

The four thallous halides, lead (11) chloride, bromide, and iodide, cuprous iodide, and sodium iodide were studied. The spectral features observed were thallium lines a t 5350, 3776, 3530, 3519, and 3230 A, lead lines a t 4058, 3683, and 3639 A and visible bands of PbX, copper lines a t 3247 and 3274 with visible bands of CuI, and sodium lines a t 5890, 5896, and 3302 A with the respective halides. Flames of this sort have often been used as sources of M X bands for spectroscopy (14). Flames of sodium and thallous halides were short and tended to be spherical a t low halide flows. Those of the other halides were much more elongated and sometimes extended well beyond the heated portion of the flow system. This suggests that the reactions leading to consumption of the latter halides are comparatively slow, and perhaps proceed in stages. Dark-colored deposits, similar to those noticed previously with thallous halides, were formed in cool parts of the reaction system with all of the halides except sodium iodide, where a white deposit was formed. Hydrofluoric acid removed the metallic appearance of the deposits, leaving solids which were similar to the original halides and which could be removed with hot water. T h e effect of variation of nitrogen atom concentration on the intensity of the emission lines is shown in Fig. 1. All of the observed lines vary in intensity as the square of the nitrogen atom concentration. T h e M X bands that appeared with halides of lead and copper were superimposed on some moderately intense afterglow emission; however it was noticed that the total intensity varied more skowIy than [N]2. Since the intensity of the afterglow alone is proportional to [NI2 (8) this suggests that the MX-band intensity depends on a lower power of the nitrogen atom concentration. For the measurements of Fig. 1 the power supplied to the discharge was varied, the atom concentration a t each power level being determined by NO titration in absence of halide. The end point of the titration is difficult to locate a t high temperatures, apparently because of reduced efficiency of the light-emitting reactions, so the calibrations of power level in terms of atom concentration were carried out near room temperature. The amount of nitric oxide required to extinguish the halide flame a t the high temperature was invariably the same as that required to titrate the nitrogen atoms a t the low temperature. In order t o determine the relative efficiencies of the various excitation processes the intensities of emission lines were measured for each flame under as nearly the same conditions as possible. Observations were made a t 2 cm from the halide inlet jet and the intensities were corrected to the same partial pressures of halide and atomic nitrogen. The same argon flow (12.1 pmoles/sec), nitrogen flow (265 pmoles/sec), total pressure (3.0 mm Hg), and temperature (400&1O0 C) were used in every case except that of sodium iodide where the temperature was 550' C. The results of the intensity measurements, normalized to a value of 200 for the rate of production of Tl(7 .2S+) atoms from TII, are given in Table 11. On this scale the nominal upper limit for the rate of a termolecular reaction is unity and emission lines which have

PHILLIPS: EMISSION LINE INTENSITIES

Atomic Nitrogen

~moleslsec

FIG. I. Variation of intensity of metallic emission lines with atomic nitrogen flow. Molecular nitrogen flow rate 265 moles/sec. Total pressure 3.0 mm Hg. Description of graphs, reading from top to bottom: T 5350 A, from TIC1; Na 5893 1 NaCI; Pb 3683 A, PbIz; T1 3230 A, TIF; Cu 3247 A, Cur; Pb 4058 A, PbC1,. Intensities in arbitrary units.

4,

relative intensities which exceed this by an order of magnitude are almost certainly excited by a different kind of process. Also listed in Table I1 are the excitation energies E of the emission lines (15) and the dissociation energies D of the halides (16, 17). For lead halides the energies for dissociation into atoms a t 400' C were calculated from a thermodynamic cycle using data from Lewis, Randall, Pitzer, and Brewer (18). These dissociation energies will be slightly high because heats of fusion of the halides were neglected and heats of vaporization were calculated directly from vapor pressure data (19) without allowance for the possible presence of polymeric species in the vapor. The results are entered in Table I1 in order of increasing D +E.
DISCUSSION

The results in Table I1 show a steady trend with increasing value of the sum (D+E), the only marked exception being found with cuprous iodide. I t is well known that in this case the vapor contains a large proportion of dimer Cu212 and extrapolation of the vapor pressures of the two species (19) indicates that a t 400' C the ratio of dimer to monomer is of the order of 100, which is sufficient to explain the low intensity. The criterion that the intensity in Table I1 should be more than about 10 for a process to be too efficient t o be accounted for by the termolecular mechanism [ 2 ] leads to an

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CANADIAN JOURNAL OF CHEMISTRY. VOL. 41. 1963

TABLE I1 Relative intensities of metal lines a t same partial pressure of halide Atomic line

E, kcal/mole

Halide XaI TI1 CuI TIC1 T1I TI1 T1F TlCl TIC1 TIF T1F PbI2 PbIz PbBrz PbC1, PbC12

D, lical/mole

D+E

Intensity

70 68 69 89 6s 68 110 89 89 110 110 125 125 152 175 175

KOTE:E = excitation energy of atomic line. D = dissociation energy of halide (at 0" K for all except lead halides, where they are calculated for 400" C ; see text).

approximate lower limit for this mechanism a t D+E = 200 kcal/mole. 'There is no theoretical reason to expect a lower limit for process [ 2 ] ;however, it is still not possible to r-ule out mechanism [2] for D f E greater than 200 kcal. This is not necessarily an upper limit for the bimolecular process [I],and there is nothing to imply t h a t the same mechanism does not operate over the whole range of D+E below 222 kcal/mole. Apart from the 5 2 , + state the only metastable states of K which might be present in appreciable concenz trations and which could supply 200 kcal/mole are the a and a' states (Table I). With both of these states the available energy is on the low side, and a further point against them is t h a t the state is probably required to be their precursor if they are to be formed from ground-state atoms. Unfortunately little is known about the relevant crossing probabilities, but the strength of the Lewis-Rayleigh afterglow suggests that most 58,+ molecules prefer to cross into the B state. The observed quenching of the afterglow in the as presence of metal halides also favors the choice of 52,+ the state of the excited N z in equation [I]. With lead halides the energy required for simultaneous dissociation and excitation of the emission lines is equal to or greater than 225 kcal/mole, which is the maximum which can be supplied by recombination of ground-state nitrogen atoms. Another kind of mechanism is therefore required. As mentioned in the introduction, a termolecular reaction of the halide with one ground state and one excited nitrogen atom would not be efficient enough to account for the observed intensities because of the small proportion of excited atoms in active nitrogen (3). I t is also difficult to see how this mechanism could lead to a dependence of intensity on the square of the (ground-state) nitrogen atom concentration. In this respect the results of Fig. 1 were surprising because it had been anticipated t h a t with lead halides the intensity would vary as some higher power of the atom concentration. T h e bimolecular mechanism [I] might explain the observations if the excited nitrogen molecule were in the predicted l2,+ state, b u t here again it is difficult to see how a dependence on [NI2could arise. The only remaining possibility is that of excitation by consecutive energy transfer steps. This mechanism can lead to a dependence of intensity

PHILLIPS: EMISSION LINE IKTENSITIES

2065

on [NI2,as is shown below, taking lead chloride as an example. In this mechanism the

+ N2* PbCl* + N2* PbCl* + Nz

PbClz PbCI* PbCl

-+

-+
4

-+ -+ -+

+ N2*
Pb*

+ C1 + N2 Pb* + C1 + Nz PbCl + N2 PbCl + hv Pb* + C1 + N 2 P b + hv'

PbCl*

[3]
14 I

11 5
161

[71 181

part of N2* could equally well be taken by a pair of uncombined nitrogen atoms. Recombination of PbCl and C1 has been neglected because of the low halide partial pressure, while quenching of excited lead atoms should be negligible because of their short lifetime (ca. sec). Halogen atoms are expected t o be removed a t the walls of the reaction vessel (20). At the steady state [PbCl*] [PbCl] [Pb*]
=

k ~ [ P b C l ~ ] [ N ~ * l / ( k ~ [ N ~ * l +KG) f ks(Nz1 (k,[N,] f k,) [PbCl*]/k.i[Nz*] k3[PbClz][Nz*]/ks.

[91
[lo]

=
=

[Ill

The intensity of PbCl emission bands is given by k~[PbCl*]. The observation that the is intensity of these bands varies more slowly than [XI2suggests that k4[Nz*] comparable in magnitude with the other terms in the denominator of equation [9]. The total intensity of P b lines is given by ks[Pb*] and is equal to the rate of the primary process [3] when recombination and quenching of Pb* are not taken into account. I t is probable that in the present experiments a completely stationary state was not reached in the short time spent by the reactants in the reaction vessel, since it was found that the Pb-line intensity increased steadily with increasing distance from the halide inlet jet. A similar consecutive excitation mechanism for thallium halides is ruled out by the observation of finite spherical flames a t low halide flows. Thallium nitride-is unknown and thallium metal has been found as a reaction product (I), so from the fact that no T1 emission occurs in the region immediately following the flame, where both thallium and active nitrogen are certainly present, it follows that the efficiency of excitation of metallic thallium by active nitrogen under the conditions of the present experiments is very low. This conclusion was tested by mixing thallium vapor with active nitrogen in a simple reaction vessel which had a fixed inlet jet and a single end window and which was able to be taken to temperatures approaching 1000" C. At a cherry red heat (ca. 800" C) the vapor pressure of the metal is similar to that of thallous iodide a t 400' C. The emission a t 5350 A with the metal a t this temperature was less than 1% of that which was observed in a subsequent experiment with the iodide a t 400" C. The behavior of lead should be similar to that of thallium in this respect, and in the mechanism just given no allowance is made for the possibility of excitation of lead atoms by Nz*.
ACKNOL47LEDGhIENTS

The author is grateful to the New Zealand University Research Grants Committee for financial support and to Mr. C. G. Freeman for assistance with many of the measurements. In addition it is a pleasure to acknowledge the contribution of discussions and correspondence with Dr. A. N. Wright of McGill University to both this and the previous paper.

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Ynrk l Q G l
A -A A

(191.5\. ,----,.

n - 169. r

19. LLANDOLT-BORNSTEIN. Tabellen. Zweiter Band, Teil 2, Bandteil a. Springer-Verlag, Berlin. 1960. p. 49. 20. E. A. OGRYZLO.Can. J. Chem. 39, 2556 (1961).

-. - - - .