1330
Vol. 64
SOTES
TABLE I11 CALCULATED VALUES
FOR .4SSOCIATED
SITRIC ACID
IS
DILVTEAQITEOIXSITRIC ACID SOLITTIOM Total acid hydrogen.
Total organic acidity.
-1.I
31
3.5 3 .0 2.8 2.0 1. 5 1.CI 0.5
2.28 2 04 1 .77 1.42 1 .o; 0 .i 5 0.48
TBP, 31
which this complex has in metal extraction processes in which metals are extracted from acidic solutioiis with tri-n-butyl phosphate.
Summary
Associated nitric acid, M . aq.
Data are presented which show the values for t,he equilibrium distribution constant and the equilib1.50 rium reaction constant for the partition of as1.74 sociated nitric acid into T B P and the reaction of '1.10 .I7 this acid in TBP to form a complex as 0.19 and '1.46 .I1 19.9 f 0.5, respectively. These constants were . 0; 2 80 used to arrive at values for the concentration of as3 . O!l .04 sociated nitric acid in dilute aqueous nitric acid solutions. These data are offered as indicating The fact that the partition coefficient wab a (wn- that oiily one complex forms between TBP and stant is believed to be supporting evidence for nitric acid in a two-phase TBP-H20-H?j03 sysconsidering the nitric acid which enters the TBP tem. phase in exceqs of a 1 : 1 ratio as dissolved acid Acknowledgment.-The authors wish t o acwhich does not enter into a complexation reaction knowledge the helpful assistance of Dr. C. E. with the 1 : 1 THP HKOa complex to yield higher Crompton of the Division Staff and Dr. D. S. Arnold and W. C. 39anser of the Chemical Departcomplexes. Further data are being collected to show the role ment. 1.24
0.47 .35 .26
NOTES THE SOLTJBIT,TTI' OF NITROGEK, ARGOS, METH-iNE, E T H Y L E S E ASD E T H A N 3 IK XORIIAT, PRIMARY ALCOHOLS' B Y F R ~ ~ K IL. IBAO I E R4~h D LUII\ J BIRCHLR Furman
('hemistry
Laboratories 17anderbiIt T naiersily, Tennessee
Cashiille
was controlled a t 25" to f0.01" and at 35" to .tO.O5O. Materials.-All of the alcohols were purified by the rt'moval (if necessary) of the aldehydes and ketones, then dried and distilled. Known procedures for the purification of the alcohols were u ~ e d . ~ * 6We chose middle cuts with
Receiied February 28 1969
A study of the solubility of nitrogen, argon, methane, ethylene and ethane in a series of normal primary alcohols at the temperature5 of 25 mid 35' was made using a modified E H.Sargent Conipany manometric T'aii Slyke-Sei11 blood ga. apparatu5. The apparatus was equipped with a chamber similar to a volumetric T7an Slyke blood gas apparalu. A manometer w a y mounted at the waste w l x ent exit port, n hich w a y opened to the solution chamber during the wlution process so that the total prebsures of gai and vapor 111 the solution chamber (mild be adjuited to atmo+ pheric preqsure The procedures given by Van Slyke and Peters3 for extraction of gavh from the qolvent, and the measurement of the gas and solvent volume WZLZ folloaed To avoid the corrections attendant with meaquring the ext racted gaa precsure ox cr the solvent the solvent na. transferred to the bulb below the 1011er .topcock of the extr:zction xewel and sealed off The gai aiid solvent vapor then \{a\ brought to volume o ~ e r mercury. This also enabled u5 to make repeated extractions of the solvent to assure complete removal of gas from the solvent. The temperature ( 1 ) 4dayted f r o m Ph D t h e m of F L Bnver Vanderbilt Vnlrersitv 1959 ( 2 ) h I d u Font de \ e m 0 irs and Co , Inc Circle\llle Ohio ('3) J P Peteis a n d D D \ a n $13 ke Quantitatixr Clinical Chern iitrx T 01 TI illiamc a n d TTilhin. Co Baltimoir \ I d 1012
10 11 12 13 1-1 15 Folritdit~yparamet er (rnl.t'ci:. '*. Fig. 1. ---Solvent capacity of alrohols for gmcs arid :tlcohd soliihilitj. parameters (5'mid TBO mni.).
Hept., 1'360
1331
XOTES
TABLE I 1 ATM. PRESSURE
OSTWALD COEFFICIENT O F sOLUBILITY AT 2? AND x3 Ar CH4
Gas -. Alcohol
Lit.
ObS.
Lit.
Obs.
Lit.
Obs.
C2H4 Lit.
Obs.
C3Hs ht.
Obs.
2.34 2.31h 2.63 .. , . 0.532 . .. 0.167 0.164" 0.267$ 0.267 2.87 2.7Zb 2.56 , . . . ,539 , , . , C?HsOH ,149 .1489" .2& ,258 2.98 2 2.41 .. .. ,510 .,,., CsH70H ,133 .132* ,254 .25Ib 2.93 2.8jh 2.26 ... . CgHsOH ,122 ,1225" ,240' ,509 . ,.. , ,246 9.95 2.76b 2.23 . ... ,483 , . , . , ,229 9046 ,116 ,1225" CjHiiOH ,464 ..,.. 2.08 .. . . 2.84 . . . 114 .. ,224 . C~HI~OH C7HisOH. 105 ..... ,218 .. .. ,448 . ... . 2.05 2.76 . . ,436 , . , , 1.91 , , . . 2.66 .. ,102 , . , , . .213 ... . CXHI7OH C. B. Kretschnier, J. Xowakowskx and R. Wiebe, Ind. Eny. Chenl., 38,506 (1946). b J. C. Gjaldbaek and E L Niemarin, dcta Chenr. Sccrnd., 5 , 1'2, 1015 (1958). c G. Just, 2. physik. Chem., 37, 342 (1901). d A. Lannung, J . Am. Chen~.Soc., 5 2 , 68 (1930).
CH&H
, ,
,
. I d
,
TABLE I1 31Ol.E 1~ktACl'IOK SOLUBILITY phosphonate > phosphate. These observations allow two conclusions to be drawn. First, the affinity for water depends greatly on the degree of steric hindrance around the dipole group. Longer alkyl chains seem to prevent the accumulation of water molecules around thc dipole group. Second, the affinity for water folloir 5 the same trend as the ability to extract actinide elements and nitric acid from aqueoui nitrate solutions. The order of extractant strength is alw phosphinate > phosphonate > phosphate. Perhaps the most interesting question that arises from the data in Table I concerns the structure of organic phases that contain so much water. It is obvious that as many as 30 moleciiles of water cannot be directly fixed to the organic dipole. Instead the effect of the organic dipole must be propagated through a chain or network of water molecules. However, the normal ability of these water molecules to solvate metal ions is little, if any, impaired. Preliminary experiments s h o w d that for tracer concentrations, the extraction coefficients for cesium, strontium and promethium are all about 0.3 with 0.05 111nitric acid in the aqueous phase and with dimethyl octylphosphonate. Since cesium, in particular, is not very well extracted by esters that contain phosphorus, the extraction must be due to solvation by water. TABLE I WATER SOLUBILITY IN VARIOUSAMIDES
ASD
PHOSPHORUS C O V P O U N D S Weight Temp., Compound % HEO cC.
N,N-Dimethyloctanamide N,N-Diethyldecanamide N,N-Dibutylbutyrsmide Tributyl phosphate Dibutyl butylphosphonate Dimethyl octylphosphonate
26 3.0 3.0 6.4 10.4 71 51 35
30 30 30 30 30 0 30
Diethyl octylphosphonate
43
Octyl diethylphosphinate
22 15.4 59
0 30 60 30
60
OROANOhfole ratio HlO/organic
3.3 0.34 0.34 1.0 1.7
30 13 6.6 11
3.9 2.5 18
Preliminary experiments showed that when nitric acid is extracted, the methyl and ethyl phosphonates lose the ability to extract water. Each molecule of extracted nitric acid removes one phosphonate molecule as a water acceptor. Further experiments with these compounds are
NOTES
Sept., 19GO in progress. Solutions of water in such compounds as dimethyl octylphosphonate should be interesting solvent media and should provoke a number of questions as to the structure and properties of the solutions themselves. Measurements of the solubility of the organic compounds in the aqueous phase also are required. Qualitative indications, so far, are that such solubility is low. COXDUCTAKCE OF TETRABUTYLAMMONIUM TETRAPHENYLBORIDE I N NITRILES' BY ALANMACKENZIE BROWNA N D RAYMOND M. Fuoss Contribution No. 1616 f r o m the Sterling Chernis!ry Laboratory, Yale University,New Haven, Connecticut Received M a y 8 , 1960
Tetrabutylammonium tetraphenylboride (Bu4N. BPh,) is a useful reference electrolyte for exploring a given solvent system, because both ions have the same volume and therefore half the limiting conductance gives the single ion conductances2 of Bu4N+ and BPh4-, whereby the single conductances of other anions and cations can be obtained. Since the ions are large, ion pairs are not very stable until solvents of fairly low dielectric constants are used: at D = 25, K A is about 20, and at a concentration of 3 X for example, the decrease in conductance due t o pair formation is only about 4%. In the range D 1 25, the graphical y - x method of determining the association constants from conductance data for this salt fails because it becomes too sensitive tlo even small experimental error. The purpose of t'his note is to present a new method of determining small association constants, using as example the conductance of Bu4N. BPh4 in acetonitrile-isobutyroiiitrile as solvent. Experimental Tetrabutylammonium tetraphenylboride was prepared from recrystdlized tetrabiitylammonium bromide (20 g. to 100 ml. benzenc: a n d 20 ml. of n-hexane, m.p. 119.6") and sodium tetraplieriylboiide, and recrystallized from 2: 1 acetone-water; m.p. 2:56". Thr density of t.he salt is 1.023 g./ml. Acetonitrile was distilled from PzOj twice itnd then from anhydrous Ti2C03, using a Todd still; b.p. 81.6"; density 0.7766 g./nil.; conductance, 0.2-0.4 X viscosity at. 2 j 0 , 0.003441 poise; clielrrtric constant a t ?j0,36.2:3. Isobutyronitrile w;is shaken with concentrat>ed hydrochloric acid to remove isorri trilrs, t,hen n-it,h water and with sodium bicndmnatc. solution. It tvas dried over PZOS :tiid t\viw frartionntcd ttiroiigh thr Todd still: h.p. 103.6"; tlensity, 0.7650 g./ml.; con(liirt:ince, 0.05 X 10-6; viscosity a t 25", 0.004946 poise; diclectric: const~anta t 25', 24.90. Solutiolis wrre niilclc 111) hy weight and c&ulatcd t o voliime concentrrttions from the k n o m densities. Coilthictances wore measured a t 25.00", using cells wit,h constants 0.9021, 0.3478 and 0.08356. The experimental results arc summarized in Table I; the mixture was 79.6 wt. c70 isobutyroriitrile, with D = 27.58 and 9 = 0.004414. The data xrere a,nalyzed by a graphical method, using as the stnrting point t h e equation3 . I = A " - s':c-,]./l 4log c y J c -~ FAc KACyf'A (1) Association t o ion pairs WRE vera- slight; hcnce the graphical
+
.-
(1) Office of K a i d Rr.warcll Technical Report no. 64. This paper m a y he reprodiiceri :n whole or in part for any purpose o f the United State8 Government. (2) R . 122. E'uoss and E. Hirsch, J. Am. Chcm. Sue., 8 2 , 1013 (1960). (3) R. 11. Fioaa. ibid., 81, 26Sg (1939).
1341
1~ - x method of evaluating the constants Ao, a and KA could not be used, because the difference AA which determines y becomes far too sensitive to experimental error.' Attempts to process the data by the Kay program6 for equation 1 on the IBM-650 computer failed, also because association was slight and the computer gave negative KAvalues with an uncertainty of &loo%. When processed by the program for unassociated electrolytes ( y = 1 and K A = 0 in equation l ) , the preliminary values shown in Table I1 resulted. The small values of a (about 5 1.) show that some association is taking place, because the Jand KA-terms in (1) oppose each other and calculating a
TABLE I CONDUCTANCE OF Bu&.NBPhd 10' c
104 c
A
A
Mixture 38.610 75.88 30.889 77.28 23.532 78.86 20.670 79.53 14.682 81.33
MeCN 56.732 99.33 37.179 102.58 29.077 104.24 20.575 106.41 14.839 108.18
AT
25'
10' c
A
Me,CHCN 31.277 66.38 25.436 67.55 19.906 68.87 13.965 70.64
TABLE I1 DERIVED CONSTANTS Mixture
MeCN
MerCHCN
A. (prelim.) 119.90 f 0 . 0 6 92.77 f 0.06 81.66 f0.03 d (prelim.) 5 . 1 8 f .06 5.19 f .05 5 . 0 5 f .03 110.85 f .05 92.70 f .05 8 1 . 6 1 f .05 AO (final)
H
1780 8.2
K A
2720 14.4
3100 18.4
from the observed coefficient of the net linear term then necessarily will give too low a value t o a. Hence another method of analyzing the data was devised which promises t o be useful for other cases of slight association. To a close approximation, the quantity A'v, defined as A'?
E
A
=
A0
+ SC'/~- EC log c + FAc + HC
(2)
gives a linear plot against concentration when the association constant is small ( y = 1). Using6 F = 2.0 and the preliminary values of Ao, A'? was computed and extrapolated to give the h a 1 values of A0 (Table 11). The observed slopes H are also given in t h e table; from ( l ) ,we see that H = J - KAAD (3) Enipirir:i,Ily, J i s ~ r c a r l ylinear in a uvrr sin:tll r;trigcss of uvalues J = LI Lpa (4) wlirrc kl and l i z are determined easi1.v from a graph of J against, a (ref. 4, equation lA.34). Theoret.ically,7 if ionsolvent in teract.ion is tcmporarily neglected
+
Zin
=
~vlicrwe,for 25"
H
(.lx1Yn3)/3000)eh= n3kk?eh
+ kza -
(5)
10243~4'"" ( 6 ) In other words, thc ~ l o p cof thr A',,-c plots is a frinclion of n :tnd the dielectric constant (the latter impliritly throiigh h and k~ and explicitly in the exponential). Rearranging (6) gives a = ( H - k l ) / k 2 = a - (a3kaAo/kz) X 10243.4'aD (7) = a - pk3a3107'a (st For each system studied, we have an equation of the form kt
~ ' k a A 0X
(4) R. >I. Puoss and F. Accascina, "Electrolytic Conductance." Interscience, New York, 1959, Ch. 17. All symbols used are defined here. ( 5 ) Robert L. Kay, J . A m . Chem. Soc.. 8 4 , 2099 (1960). ( 6 ) R. M. Fuoss. J. B. Berkowitz, E. Kirsch and S. Petrucci. I'me-. iVd2. Acad. Sci., 44, 27 (1958). ( 3 ) R. h l . Fuoss, J . Am. Chem. Soc., 80, 5059 (19.58).
1342
NOTES I .0
h
I
I
I
Vol. 64
wc find E,&T = -0.185. Since both ioiis arc large, and the central charge is well shielded in the cation and distributed in the anion, the small value of E, seems reasonable. The values of K A in Table I1 are computed using the constants from Fig. 2: K.4, = 2.11 X 10-3 (8.68)310-d*.6*. Finally, plotting the apparent Stokes radius against reciprocal dielectric constant9 evaluates the hydrodynamic radius R , = 3.77, which is in excellent agreement vi.ith Hirsch’s valueZof 3.63 found for this salt in the solvent system nitrobenzene-carbon tetrachloride.
ii-_:I -!s24 09
(9) R. I f ,Fuoss, I’roc. Satl. Acad. Sci., 45, 807 (1Y>Q)
THE ULTRATIOLET ABSORPTIOS SPECTRh OF d SERIES OF *ILKYL-, CYCLOALKYL- AND CHLOKOSUBSTITUTED KETOSES1 B Y \v. It. l,lOUNTCASTLE, JR.,1). F. ShlITH A S D E!. I.,. (.+ROVE
c) -\ .
XI
L 9
O 77
Fig. 1.-Detrmninatioii
8
0
of paired (ka, (I) values for B u p X , BPh, in JIeCS.
School of Chemistry, Cniuersitu o f Alabama and t h e Department of Chemis!ry, Birmingham-Southern College, Birmingham, d labama Receired M a y 6 , I960
The vapor phase absorption spectra of a series of alkyl-, cycloalkyl- arid chloro-substitut~edketones have been determined in the 220-320 mp region. The compouiids st,udied included : eight a-niethylsubstituted ketones (including 2,2,4,4tet,ramethyl3-pentanone) ; eight a-chloro-substit8uted ketones (including 1,1,1,3,3,3-hexachloro-2-propanone) ; the two a-substituted cyclopropyl ketones; and two cyclo-ketones. The spectra of a number of these compouiids were determined in “isooctme” solution. However, no striking diff ereiices were evideiit for the spectra in t’he vapor state and in the non-polar solvent. The compouiids studied provided example3 of a simple system in which the positire iiiductive effect of the methyl group can be compared with the negative inductive effect of a chlorine atom. However, this simple effect is overcome by other effects, Le., steric requirements of t,he subst’itueiit groups, hypercoujugation, etc. Experiment a1 The vapor phase ultraviolet spectra wrrc detrrmirwd by standard methods in a 1-meter fused quartz ~ 1 using 1 an hpplied Research Laboratories, 1.5 meter, 24,400-lines per inrh grating spectrograph. Eastman Kodak S o . 103-0 t-V %mm. film was used. Absorbancy readings werp made 011 a. National Spect.rographic Laboratories, S o . 310-2, Spec-Trol, densitometer, iising as a rcftwnw an iron arc. standard, previously plnccd on thv film :ts :i, liwt of the tktermination. -111 compoiinds used were coinmrrciallg :ivailxblc or ~ w r c ~ prepareti hy methotip described in the litrratiirr. All wrrr 1)iirified hy distillation. T h r physical propcrtiw xnd A,,, of t.he compounds are sumniariaed i n Tabli. I. Tht. spc,ctr:d data for t h e thirteen cmnpounds nhirh 1ra.vc not hrrn rqmrted prrriorisly have h r n acwpted for pi~hlicittioii1)y t lit, llaniifac-tiiring Chemists hssori:ition Rrsrarc*li Projwt , (’heniir:tl and I’et,rolruni Rcsrarch L a h o m t o r ~ . Iiwti t 11te of Tr~c~liiiology , Pittsburgh 1 3 , l’c~nnsylv
8.68 i 0 05. Tlir valt1r of k? i* somen-hat sni:tller th:m thc tlicwrcltic*,il v:rliic, ( 4 T V X 10-24’3000) = 2.524 X lo-?, l i i i t if a term I S u i s r r ~ r din ( 5 ) to a h a - for solvrn-ion tntrmc*tion,fiso that h 7 4 = 2.524 x 10-3 63 exp(6 EJh.7’) (10)
+
Discussion of Results It is c’vidciit, that the near iiltru\.icilet cm-boii?,l iLbsorptioii maximum of a ketone undergoes a “red shift” as the a-hydrogens are replaced by mcthyl ic~ (I 1 T h i s invt.stization n a s ai!pporteii i n p a r t l i \ r h , . . l t < ~ t ~ i1:rlergy ( ‘ o ~ n ~ r i i s s i o n .F’rolti a dissrrtation s i i h i t i t t t r d hy \V.I8. I’rrsentrd i n p r t . l i n i I n a r j - IIIIIII a t the Southeastern Regional Xeetinp. ACS3 Cainee, illr. 1 lorirla, I l e c e m l ~ e r 12. l!I.x.
Sept., 1960
COMMUNICATIONS TO THE
COMPOUNDS USED IN THIS been cited to explain the higher Am,x of cyclopen-
RESEARCH Amax,
Compounds ?-Propanone ?-Butanone 3-PPntanone 3-~Lethvl-2-hutsnone L ,i-Diniethyl-3-pentanone 3.:~-Diniethyl-2-butano11e ?-Hexanone 2 , %-Dinietii?l-:~-licntanone ~,~,4-Trinietlivl-:(-lientanonc 2.2,4, ~-Tetrainetli?l-:J-pentanone I-Chloro-Z-groiianone 1,1-Dichloro-?-propanone 1,3-Dichloro-5-l1ropanone
mp 277 278
579 283 287 285
“79 288 290 297 289
Refractive index 1.3588 ~ Z O D 1.3788 ~ Z O D 1.3921 I L ~ 1.3881 ~ D )iZ3D 1.3b59 1 ~ 2 1.4016 0 ~ n20D 1.4003 n23n 1,4050 n% 1.4000 n2@n1,4193 n2b 1.4312 n25~ 1,4142 n201~
B.P., ‘C. 56 79 102 94 123 106 128
(mm.) (755) (748) (760) (i6l) (76%)
(755) (755)
129 (760) 136 (780) 153 (760) G I (110)
121 (760) 173 (760) m.p. 43-44’ I , l,l-Tsichloro-”-liropanunl: 281 ~ ? O D 1.4lj50 133 1,1,3,3-Tetrachlr~ro-2-rJ~o~,anone301 n18D 1.,5000 17-48 ( 5 . 5 ) 1,1.1,3-Tetrachloro-L’-l,ro]~anone 299 n16D 1,4900 47-18 (6 .0) 1 . 1 , 1 , 3 , 3 - P e n t a r l i l o ~ ~ - ~ - ~ ~ r o ~298 i a n o n c2 k 1.4955 189 (750)
1.1,1,3.3.R-€Ierachloro-2propanone Xlethrl cyc1oi)ropyl ketone Dicyclopropyl ketone E t h y l acetoacerate Cyclopentanone Cyclohexanonr
1343
The effect of strain a t the carbonyl carbon has
TABLE I AKTS OF THE
EDITOR
295
300
298 276 27(j 278 300 289
,,, , ,
. ..
n231,
i.5090 201 (750)
71%
1.4222 111 (758) 16X (760) 1.4192 50 ( 7 . 0 ) 1.4335 130 (755) 1.4497 155 (755)
n z 5 ~1.4657 1720D
n% ~ * O D
groups.’ This shift has been ascribed variously to the positive inductive effect of t8hemethyl group, or to hyperconjugation; and it, also has been described simply as the “methyl effect.” In this investigat,ion it has been observed that t’he “red shift” is more dependent on the symmetry of substitution than on the number of entering methyl groups. possible explanation for this effect is the steric requirements of t,he entering group aiid the strain produced by t’he opposiiig groups at the carbonyl carbon angle-a.
c
/ \ It, R*
tanone 1’s. ~yclohexanone.~The observation that “hexamet,hylacetone” and “hexachloroacetoneJJ have A,., values which are almost identical supports the contention that, in this case, the effect is steric. The following series can be observed for a “red shift” produced by changing the complexity of R inethl-1 < ethyl 5 n-butyl < i-propyl < t-butyl The same order is preserved for R1 cs. R2 and t’he effect is accentuated by the degree of complexity of R,and R2.4 The apparently greater effect of an i-propyl group when compared with other groups possibly could be the modifying effect of “B” strain in such a group. Where steric strain is t,he primary consideration, the case of the chloro-subdtuted ketones appears to be the same as tha,t observed in the alkyl ketones. Hovever, for tmhecompounds in which the substitution is symmetrical and a-hydrogens are present, simple st,eric effects do not appear to offer a complete explanation. The resonance estreme shown
la, 8
H ~biS H e
&c--c=a I
-
-
H
H
is possible and may be a partial a,nswer: howe\-er, this is pure conjectme. The case for the cyclo-alkyl ket’ones is perplesiiig and no simple explanation is offered for the observed spectra. Hart,5 et al., have reported these same compounds, pre7-iously, without any explanat,ion for the spectral data. ( 2 ) .4. E. (;illam and E. 8. S t e m , “An Introduction t o Electronic Absorption Spectroscopy in Organic Chemistry,” 1:dward .4rnuld Ltd., London, 1984, pp. 47-51. (3) XI. S. Newman, “Steric Effects in Organic Chemistry,” . J O ~ I I I Wiley and Sons, Inc., New York, N . Y.. 1936, pp. .i06-507. (4) R . P.XIariella and R. R . Rauhe, J. dm. Chrm. Soc.. 7 4 , 518 (1952).
H. Hart arid 0 . E. Curtis, i b i d . , 78, 112 11933).
COMMUNICATIONS TO THE EDITOR C O ~ 1 3 1 1 C ~ rOWS THE AIECH,ISISlI 0 1 ’ THE I{KACTI()s OF Awnix XITKU(:ES \VITII ETH1 I,ESIi, AS11 SITKIC‘ OXI11E h 1 I’:
11 1 s t h c plll~po.(~oi thl. ~ ’ o I ~ l l l l l l l l l ~ ’ : l t 1 to0t l SllO\\ that the ri+uIi- oi \7crhel\c a i d \\’iiihlcrl raii 1 ) ~ iiiterpretrcl t y awiiniiig that thc. oiily c.oiiititueiit of active iiitrogeu
11 hich reacts nith nitriv oxide IS atomic iiitrogeii in contradistinction to their cmic~lusion~ This reartioii is quantitative. The reh u l t s obtained for the reaction between acti1-e iiit,rogen and ethylene theii ran be explained by a iiierhanim :rn:tlogous to I;rey’< iiiechaiiiLn1 for thc 11 I‘JtiOl
< t
I
\ Ihchr dnd I
1. \ \ i n i l e r . J. Phijs C h e m . . 64, 319
