A Kinetic Study of the Mechanism of Nitrosomethane Formation and

Soc. , 1960, 82 (1), pp 1–5. DOI: 10.1021/ja01486a001. Publication Date: January 1960. ACS Legacy Archive. Note: In lieu of an abstract, this is the...
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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (Registered in U. S. Patent Office)

(0Copyright, 1960, by the American Chemical Society)

JANUARY 20, 1960

VOLUME82

NUMBER 1

PHYSICAL A N D INORGANIC CHEiMISTRY [CONTRIBUTION FROM THE

MCPHERSON CHEMICAL LABORATORY, THEOHIO

STATE UNIVERSITY ]

A Kinetic Study of the Mechanism of Nitrosomethane Formation and Decay in the Photolysis of Azomethane-Nitric Oxide Mixtures BY JACK G. CALVERT, SANDRA S. THOMAS AND PHILIPL. HANST RECEIVED JUNE 5, 1959 T h e rates of formation and decay of nitrosomethane, formed in the photolysis of azomethane-nitric oxide mixtures at 2 5 O , were determined by infrared absorption spectrometry. The nitrosomethane reached a steady-state concentration, [CHsNOj,.,, after a few minutes irradiation. The function [ C H ~ N O ] m a x / P ~ ewas r ~ nfound i / ~ to be independent of the azomethane pressure. T h e rate-determining step in the decay of nitrosomethane monomer in the dark was found to be a homogeneous gas phase reaction which was second order in nitrosomethane. The only measurable final product of the methyl radical-nitric oxide reaction at 25" was the dimer of nitrosomethane. These data are in accord with the simple mechanism: (CH&NZ f hv 2CH3 NP ( I ) ; CH3 NO CHaNO (1); 2CHaNO (CHaN0)z ( 2 ) ; (CH,NO)z (CH3NO)Z (solid at the cell wall). From studies of the rate of methanol formation in azomethane-oxygen mixture and observations of the initial rate of nitrosomethane formation in azomethane-nitric oxide mixtures, the molar absorbancy index of CHaNO a t 6.32 p , U M = 77 (l./mole-cm.), and the rate constant at 25', kt = 87 (l./mole-sec.), were derived.

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The fast reaction between nitric oxide and methyl radical has been studied repeatedly over the years. However, some uncertainty still exists in the nature of the products formed under different conditions and the detailed reaction mechanism which describes the transformations between the different possible products. Probably there would be general agreement t h a t the initial product of the interaction of methyl radical and nitric oxide is nitrosomethane CHI

+ NO +CHsXO

(1)

but a quantitative description of the fate of this species is impossible a t present. In explanation of nitric oxide inhibition of acetaldehyde photolyses, Mitchell and Hinshelwood' suggested t h a t the over-all chemical changes which occur when methyl radicals and nitric oxide react may be: CH3 NO C H 3 N 0 -+ CHF NOH + HCN H20, and/or 2CHaN0 CHI CO HzO Nf. Taylor and Bender2 followed the course of the thermal decomposition of formaldoxime and concluded that the methylnitric oxide reaction was explained adequately on the basis of the formation and subsequent decomposition of formaldoxime. Raley, Rust and

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( 1 ) J.

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W,hritchell and C. N. Hinshelwood, Proc. R o y . SOC.(Loir'

d o n ) , A l S 9 , 32 (1937). (2) H. A. Taylor and H Bender, J . ( h e m . Phrs., 9, 701 (lU41).

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Vaughan3 first proved that formaldoxime is a major product of the reaction under certain conditions ; they identified formaldoxime among the products of the thermal decomposition of di-tbutyl peroxide in nitric oxide (225"). More recently Bryce and Ingold4 have successfully followed the methyl-nitric oxide reaction and determined the rate constant for the reaction 1 through mass spectrometric studies of the thermal decomposition of dimethylmercury in nitric oxide. In short reaction times a t high temperatures (480-900") the major product of the methylnitric oxide interaction was a compound of parent mass 45, presumed to be CHINO. With long reaction times, "3, H20, HCN, CO, Nz, COz and CHZCN were also detected; neither (CH3NO)z nor (CHZ=NOH)~was found. Sleppy and Calvert6 could not find nitrosomethane or its reaction products in the flash photolysis of azomethane-nitric oxide-neopentane mixtures. However, their analysis procedure required repeated condensation and vaporization of the products and excess reactants. Dimerization and/or isomerization to non-volatile products probably resulted under these conditions, and CH3N0, (3) J. H. Raley, I?, F, Rust a n d W. E Varighan, THISJ O U R N A L , 7 0 , 88 (1948). (1) W A. Bryce and K. U. Ingold, J . C h e m P h y s . , 23, 1968 (1955). ( 5 ) W. C. Sleppy and J. G. Calvert, THISJ O U R N A L , 81, 7tiY (1959).

J. G.C-ILVERT, S.s. nioM.Is

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AND

P. L.H , W S ~

TABLE I h r l l DATAO N TIIE FORMATION AND DECAY OF CHaxo (MEASURED AT 6.32 p ) I N THE PHUTOLYSIS OXIDEMIXTURESAT ROOMTEMPERATURE

VOl. s2

OF i ~ Z O M G l H A N B - ~ I T K I C

5.0 5 0.57 0.60 0.0232 0.0255 25.9 0.112 5.10 1.14 11.0 11 1.52 1.54 ,0362 .0381 42.5 ,118 3.46 1.15 20.0 19 (2.05)' 2.52 .0487 ,0525 51.7 ,106 2.63 1.17 4 40.0 42 3.45 3.25 ,0519 ,0666 62.6 ,120 1.67 1.05 5 80.0 52 5.06 4.36 ,0594 ,0897 73.4 ,123 1.12 1.00 Gd 0.26 0.68 .. 0.00566 ,00241 ... 2.3 ,097 .. .. T!ie rates are represented as d(1og la/l),'dt with the time in sec. Tlie [CH1NO] values are the quantities log (Io/I) diicli are proportional to the actual concentration. Since the extinction coeficient of CHINO which we derive in this work is of very limited accuracy, we have chosen this method of presentation. t is the time at which the arc was turned off. This value has considerable uncertainty since a n error in the timing at the start of the run was likely. This run was made in the long-path cell using 20 m. of path. The mixture was prepared with nitrogen carrier gas which was present during the run at 744 mm. pressure. The measured quantity, log (Io/I)was divided by 200 in this case t o represent correctly the rates and concentrations based on the 10 cm. cell experiments. 1 2 3

CHt=NOH, and possibly other products, would not be detected by infrared spectrophotometric measurements on the volatilized fraction of the condensate. Coe and Doumanie have observed t h a t acetone and a stable dimer of nitrosomethane are the major products of the photodecomposition of t-butyl nitrite a t 25". It was suggested that dimer formation from nitrosomethane rnoiiomer follows the primary process (CH3)aCOXO f h~ +CHaCOCH, CHIXO

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Chilton, Gowenlock and Trotman7s8have prepared and characterized clearly two forms of the nitrosomethane dimer which appear to be cis- and trans-isomers. They have described the experimental conditions which favor the formation of each of the dimers and the rearrangement into the isomeric formaldoxime. Recently Luttkes has prepared the monomeric nitrosomethane by heating the dimer. H e observed t h a t the characteristic infrared band of the monomer (1.334 cm.-') formed in experiments a t 160' but quickly disappeared as the absorption bands due to forinaldoxime appeared. In this work we have utilized the analytical method of infrared spectroscopy, incorporating signal amplification and long path techniques, to follow directly the concentration of nitrosomethane formed in the photolysis of azomethane in nitric oxide. Some interesting new details of the methyl radical-nitric oxide reaction mechanism a t room temperature have been established. Experimental Materials.-Azomethane was prepared and purified by the method of Renaud and Leitch.'o Nitric oxide tank gas :%yoNO) from Mathesoii was purified by passing the gas in succession through four gas scrubbers, two containing concentrated sulfuric acid, one containing a saturated solution of potassium hydroxide, one containing mercury and finally through a cold trap at -78". Nitrous oxide was the only impurity which could be detected by infrared absorption. This impurity was inert and remained unchanged during the (6) C. S. Coe and 7'. F. Doumani, THISJOERNAL, 7 0 , 1516 (1948). ( 7 ) IT. ?'. J . Cliiltoii, B. (;, (>owellluck and J. Trotman, Cliririisfry ripid I l t d u s l r y , 538 (1955). (8) H. G . Oumeiilock and J . Trotman, J . Chem. SOC.,4100 (19X). (VI W. Luttke, % Ekklrociiem., 61, 302 (1957). (IO) 11. Renauil a d L. C. Leitch, Can. J . Chein., 32, 5-45 (1951).

course of a n experiment so t h a t no attempt was made to remove it. Equipment.-Most of the reactions were carried out in a 10 cm. infrared absorption cell which was placed in the sample beam of the Perkin-Elmer Model 21 infrared spectrophotometer. Fixed in position about twelve inches from the side of the cell was an AH-6 high pressure mercury arc (General Electric). The incident light intensity was essentially constant in experiments 1-5 of Table I . T h e Pyrex jacket on t h e arc and the Pyrex cell body limited the light entering the reaction cell to wave lengths greater than 3000

A.

In run 6 of Table I, the experiment was carried out using the Perkin-Elmer dual multiple reflections cells which were adjusted t o provide a 20 m. path length. T h e photolysis was effected by the 3600 A. region of radiation from a G.E. black-light fluorescent tube mounted inside the long path reaction cell. T h e original optical black finish of the cell interior supplied by the company proved t o be highly reactive and absorbent. T h e inner surface of the cells was removed and the wall covered with aluminum-grey baked enamel, similar t o t h a t used on the exterior of the PerkinElmer equipment. I t proved t o be very inert to reactive gases such as S O , NO1 and 03,and there was no noticeable effect on the infrared signals due to scattered light.

Procedures and Results Products of the Reaction.-The usual products of azomethane photolysis, ethane and methane, are not formed in azomethane-nitric oxide mixture photolyses under our conditions. In the homogeneous gas phase reaction which occurs under most conditions only one product (other than nitrogen), nitrosomethane, was observed. When azomethane was photolyzed in mixtures with nitric oxide, the characteristic band of CH3N0 a t 63-6.4~appeared.9 Figure 1 shows the spectrum of the products of an extensive photolysis (15 min.) in a preliminary run made with 4 mm. of azomethane and 8 mm. of nitric oxide in one atmosphere of nitrogen gas. The spectrum was determined in a 1-m. Perkin-Elmer metal cell with untreated walls as furnished by the manufacturer. Under these conditions the C H 3 N 0 band (6.3-6.4~) decreased as the CHFNOH bands near llp and a t the OH region increased. However, the appearance of formaldoxime in the products was peculiar to the use of the 1-m. cell. In all of the rate studies made in the 10 cni. glass-NaCl cell and the long path cells with inert walls, no trace (less than 0.5% of the total product) of the possible product, formaldoxime could be found by infrared analysis. However, a sniall number of

3

i? o---2

~ _ _ _ _ _ _ _ _ _ . .

,

4

6

E MICRONS

10

2

14

Fig. 1.-The infrared spectrum of the products of the extensive photolysis of azomethane (4 mm.) and nitric oxide (8 mm.) in nitrogen (740 mm.); the spectrum was determined in a I-m. path length metal cell with the original untreated interior surface provided by manufacturer; the charis due t o monomeric nitrosoacteristic band at 63-6.4 methane.O

small white crystals of a solid product built up on the cell walls as a run progressed. These crystals had all of the characteristics of the dimers (CHINO)*, described by Coe and DoumanP and Gowenlock, et al.798 A positive nitroso test (blue color) was observed using diphenylamine in concentrated sulfuric acid. The impure sample of the solid taken directly from the cell wall after a run had a melting range (94-97") in the vicinity of the cis-isomer of (CHIN0)2 reported by Gowenlock (97.5") The cis-isomer might be formed under these conditions since Gowenlock reports the trans to cis transformation is promoted by ultraviolet irradiation. Some small needle-like crystals, similar in appearance to those pictured by Coe and Doumani,6 were observed in samples which had been aged before investigation. These melted sharply a t about 120'; the trans-isomer of (CHSN0)2 is reported to melt a t 122".6-8 Kinetic Studies.-The absorption due to CHINO was determined a t 6 . 3 2 ~a t regular intervals (15 to 30 sec.) during the build up period of the photolysis. The rate data are summarized in Fig. 2 and Table I for runs a t different azomethanenitric oxide pressures. Throughout this paper we have chosen to represent the values of [CH3NO]as the quantity log (lo/I) which is proportional to the actual concentration, since the extinction coefficient of C H 3 N 0 which we derive in this work is of rather limited accuracy. When the absorption due to C H 3 N 0 had reached its maximum or plateau region (see Fig. 2 ) , the arc was turned off (note the breaks in the curves of Fig. 2 ) , and the decay of CH3N0 was followed in a similar fashion. The pressures of CHINO were low (1.4 to 0.06 mm. initial pressures in runs 5 and 6, respectively, of Table I ) , 1 1 but the small changes in absorption could be followed readily in runs with the 10-cm. cell through the use of the 10-fold or 5-fold scale expansion feature of the Perkin-Elmer instrument, or with no amplification when the long path cells were employed. In the runs with the long path cells, oxygenfree nitrogen gas was used to purge the cell repeatedly, and then the reactants were flushed into the system with nitrogen gas, so that the reaction cell contained essentially 1 atm. of nitrogen with very small pressures of reactants. Since the in(11) Calculated using the approximate extinction coefficient for CHaNO which is derived in this work.

T8me.

5s.

Fig. 2.-The time dependence of the concentration of monomeric CHINO in the photolysis of approxiniately equimolar mixtures of azomethane and nitric oxide; P M ~ ~ v , = 5, 11, 20, 40 and 80 mm. for runs 1-5, respectively; the break in each curve indicates the point a t which the arc wns turned off in that experiment.

cident intensity was greatly different in this experiment and no theoretical significance could be attributed to the initial rate of formation in this case, the rate of build up of nitrosomethane was not determined . Figure 3 shows the concentration-time plot for the determination of the initial rates of decay of CH3NO. The time scale is much too small to show the decrease in concentration of C H 3 N 0found in run 6. Through similar plots the initial rates of formation of CHZNO were determined. These are summarized in Table I.

00

50 .e

5PT

Fig 3.-A plot of the initial CH,?;O concentration-time dependence in the experiments a t varied initial conrentrations; the numbers refer to the runs of Table I ; initial rates of decomposition (column 4 of Table I ) were determined from the initial slopes of these curves.

The Rate of Methyl Radical Formation in Azomethane Photolysis.-The rate of photolysis of azomethane was determined in two experiments in which azomethane and oxygen were mixed in the

photolysis cell. The initial rates of formation of In view of these probable sources o f the ohsen-et1 t l i ~product niethanol were tletcrrninerl. 1:ntlcr icattrr o f the data wc coiisider tlic. ,igrr.cmeiit oE the, conditions used the only iniportant proclucts of the values o f colunin S as reasonable proof o f the the methyl radicalhxygen reaction have been second-order kinetics for the rate of decay of shown to be methanol and formic acid in approxi- nitrosomethane. mately equal amounts, and 2(d [CH30H]/dt) = T h a t the rate determining step in this reaction the rate of methyl radical formation from azo- is a purely homogeneous second-order gas phase methane photolysis.12 The incident light intensity reaction is suggested by the following facts: (a) in our present azomethane-oxygen experiments the second-order rate constant (or its equivalent was the same as that in runs 1-5 of Table I. The in column S of Table I) was the same in esperipertinent rate data of methanol formation found inents with a “clean” cell wall and with cell walls in the azomethane-oxygen photolyses are given containing a deposit of dimer; (b) the secondherewith: 0.00335 mm. CH30H/’sec.,P L ~ = ~ ~ order N ~ rate constant was independent of a seven22.5 mm., PO, = 720 mm.; 0.01616mm. CHsOH,/ fold change in surface to volume ratio (long path sec., P M ~ ~=s ,102 mm., PO, = 640 mm. From cell to 10 cm. cell); (c) there was no effect of a these data i t can be seen that the rate of methyl third body on the reaction rate as evidenced by radical formation in mm./sec.-mm. azomethane is the fact that the rate constant was essentially a constant within the experimental error inde- unchanged in experiments from 10 t o 700 mm. pendent of the pressure of azomethane (0.000298 pressure. and 0.00031i for runs a t 22.5 and 102 mm. of The Mechanism of Nitrosomethane Formation azomethane, respectively). Thus for our condi- and Decay.-The following simple mechanism tions the rate of methyl radical formation (mm. adequately describes our results of nitrosomethane CHa radicals/sec.) in experiments 1-5 of Table I formation and decay in the photolysis of azois given by ( 0 . 0 0 0 3 0 8 ) ( P ~ ein2 ~mm.), 2 or the equiv- methane in nitric oxide. alent rate in moles,’l.-sec. = (1.66 X mole (CHY)LK2 h v --j 2CHB S? (1) CH:,radicals,/l.-sec.-mm.MeaNy) (PhsIe,x,in mm.). CII, + S O --+ CHSNO (1) Discussion 2 C H 3 S 0 --+ (CH,SO)? (gay) (2) The Kinetics of the Decay of Nitrosomethane.(CIT,KO)? (gas) --f (CHyNO)2 (solid at wall) ( 3 ) Nitrosomethane was prepared through the phoUnder our conditions of equal pressures of tolysis of mixtures of azomethane and nitric oxide. Nitrosomethane monomer is not a stable final nitric oxide and azomethane, reactions of the product but decays rapidly as it is formed so that a methyl radical other than (1) are unimportant. steady-state concentration of nitrosomethane is I t has been shown in a preceding section that the established after a few minutes irradiation (see rate of formation of methyl radicals in (I), which is Fig. 2). %‘hen the steady state had been reached, equal to the rate of formation of CH3NO monthe light was turned off (at the break in the curves omer, is directly proportional to the pressure of of Fig. 2), and the decay of the monomeric nitro- azomethane used under our conditions. Incorsomethane was followed by absorption measure- porating this information with the above niechments a t 6 . 3 2 ~in the characteristic band for anism we expect the rate law 4 to describe CH,NO CH3N0.S The initial portion of the decay curves formation is shown in Fig. 3. The rates of decay determined _ d[CH3K01 _ _ _= 21,#1 - ICH,rXO]2k2= dt from these data are given in column 4 of Table I. UPM~~ N[CHBNO]*k: , (4’ These instantaneous rates correspond to times near the start of the dark period when the concentra- I, is the intensity of the absorbed light; 41 is the tions were those shown in column 5. The quanti- primary quantum efficiency of photodecomposities, (- d(1og Io)/dt)/(log 10/l)and (- d(1o.g 10,‘ tion of azomethane; and a is a proportionality I)/dt),/(log I0,‘1)?,are shown in columns 7 and 5, constant (0.000308mm. of CH3NO/sec.-mm. azorespectively, of Table I. The figures of column methane for experiments 1-5 of Table I ) . There 7 are far from a constant value which is required are two simple tests which show the compatifor a first-order process. However, the figures of bility of the data with rate law 4. column 8 of Table I are essentially a constant over (a) The initial rate of formation of nitrosothe 10-fold initial concentration range that the methane is determined by the first term of the rate reaction was studied; this is the requirement for law 4, 21& or uPM~,N,, since [CHqNO] = 0 a t second-order kinetics. The minor variations from zero time. After the steady-state concentration constancy are not surprising in view of the several of nitrosomethane has been established in a given uncertainties associated with the determination of experiment (the plateau region of Fig. 2 ) , then the small quantities of CH3NO: (a) the deposition d[CH3NO]/dt = 0, and 21,~$1 = [CH7N0I2k2. of dimeric nitrosomethane with subsequent scat- Now when the light is turned off the initial rate of tering of the infrared beam was noticeable partic- decay of CH3NO should equal 21ad1; that is, the ularly in the runs 4 and 5 a t the highest nitro- initial rate of decay should equal the initial rates of somethane concentrations ; some uncertainty as formation of nitrosomethane. Compare the initial to the correct value of the transmission at infinite rates of formation and decay of C H 3 N 0 in columns time resulted in these cases; (b) deviations from 3 and 4, respectively, of Table I. The near the assumed Beer’s law dependence of absorption identity of these two independent rate measureon concentration may occur for CH&O at 6 . 3 2 ~ . ments for the experiments 1-4 lends credence to the interpretation given In run 5 the greater ( 1 2 ) P. I,. Hanst a n d J. G. Calvert. J . Phvs. Chpm., 63,71 (1959).

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Jan. 5 , 1960

FLASH PHOTOLYSIS AND COMBINATION OF IODINE IN RRNZENE

8 )

Estimate of the Rate Constant for the Homogeneous Dimerization of Nitrosomethane.-Since no direct observation of the pressure of nitrosomethane monomer present in the reaction mixtures is possible, and the extinction coefficient of nitrosomethane is unknown, an indirect method of estimation of these quantities must be made. I t has been established through the azomethaneoxygen mixture photolyses (described in the Results section) that the rate of formation of radicals, which is also equal to the initial [CH3NOlmax= (21,61/kz)'/z = ( ~ I ' M ~ ~ N ~( 5/ )~ ~ ) 'methyl /Z rate of formation of CH3N0, is given by The near constancy of the ratio [ C H s N O ] m a x / X,,N, PM~,N~'/Z of column 10 of Table I is consistent with ( ~ ~ C H ~ N O ~ / ~ ) / P = 1.66 X 10-8 mole CH,NO/l.-sec.-mm. Me2X2 (6) the relation 5 . If the destruction of nitrosomethane were first order the function [ C H I N O ] ~ ~ ~ / ~ M ~ An ~ N average , , of the most accurate rate data (runs column 9 of Table I, would have been a constant. 1 , 2 and 3 of Table I) gives The evidence given provides abundant proof (d 11% Io/Il /dt)/Pareznl of the homogeneity of the reactions of formation 0.128 X IO-( (sec.-mm. MeZSz)-l ( 7 ) and removal of nitrosomethane. The dimer which Since log (1011) = ahr6c (where UM is the molar accumulates on the cell wall is the likely origin of absorbancy index, b is the path length (10 cm.), the oxime product which is found under certain conditions. Only in our preliminary experiments and c is the molar concentration), then relation 8 with the 1-m. cell (with untreated, chemically follows reactive walls) was the spectrum of formaldoxime (d [logI0/11/ d t ) / P ~ e , ~=, aMb(d [CHISO]/ d t ) / P & , ~ , ( 8 ) observed as the band of nitrosomethane decayed. From (€I), (7) and (8) we estimate O,M = 77 (l./ Formaldoxime could not be detected in the prod- mole-cm.) for the molar absorbancy index of ucts from any of the photolyses in the 10-cm. monomeric CH,NO a t 6 . 3 2 ~ (resolution, 927; cell or in the long-path cell. I t seems well es- slit width, 5 6 ~ ) . Using this estimate of U M and tablished from our findings and the results of the the average value of the rate function given in many previous studies that dimeric nitrosomethane column 8 of Table I, we derive that k2 = 87 (l./ is the major final product of the reaction between mole-sec.) a t 25". Suitable equipment for the methyl radicals and nitric oxide a t room tempera- determination of kz a t temperatures other than 25" ture under normal experimental conditions. Isom- are not now available to us, so that a measureerization of the dimer to the oxime is rapid and ment of E2 must be delayed. the oxime and the products of its decomposition Acknowledgment.-The authors gratefully are the dominant products of the reaction when metallic or other reactive surfaces are in contact acknowledge the support of this work by the with the product, when the temperature is above United States Public Health Service, National the melting point of the dimers or when water or Institutes of Health, Bethesda, Maryland. certain non-aqueous solvents contact the dimer.8 COLUMBUS. OHIO

uncertainty in the [CH,NO] values as a result of the more extensive dcposition of dimer in this run a t the higher concentration, may account for the significant difference between the two rates for this experiment. (b) According to the mechanism I, 1, 2 and 3, the concentration of nitrosomethane a t the maximum or plateau region should be related to the absorbed light intensity or azomethane pressure according to (5).

[CONTRIBUTION FROM

THE

DEPARTMENT O F CHEMISTRY, RENSSELAER POLYTECHNIC

IKSTITUTE]

Complex Formation in the Flash Photolysis and Combination of Iodine in Benzene1 BY S. J. RANDAND R. L. STRONG RECEIVEDMAY8, 1959 T h e flash photolysis of iodine in liquid benzene at room temperature produces a transient intermediate that absorbs light in the visible region, although no over-all photochemical reaction occurs. It is proposed t h a t this is a complex formed between a n iodine atom and a benzene molecule, and the absorption is a charge-transfer spectrum. The disappearance of the

k

complex is second order, consistent with the combination mechanism: 2CsHa.I +C6H6.12(+ c ~ H a ) . Values of k / e , where e, is the molar extinction coefficient of the complex, are independent of initial iodine Concentration (0.65 to 5.5 X M ) . An IBM-650 digital computer has been used t o calculate values of k and eo for various assumed values of the primary quantum yield of dissociation of iodine in benzene.

Introduction The combination of iodine atoms in several "inert" solvents has been studied by the flash photolysis techniqueze4and by the allyl iodide and (1) Presented a t the 135th meeting of the American Chemical Society, Boston, Massachusetts, April, 1959. (2) R. Marshall and N. Davidson, J . Chcm. Phys., 21, 2086 (1953). (3) R. L. Strong and J. E. Willard, THISJOURNAL, 79, 2098 (1957). (4) S. Aditya and J. E. Willard, ibid.,79,2680 (1957).

oxygen scavenger technique combined with rotating sector measurements.6s6 The primary quantum yield of dissociation 4, defined for these systems as the quantum yield for producing a pair of atoms that escape from each other and ultimately combine with atoms from other dissociations,6 ( 5 ) F. W. Lampe and R. M. Noyes, ibid.,76,2140 (1954). (6) H. Rosman and R. M. Noyes, ibid.,80,2410 (1958).