NOTES
808
infrared absorption bands, an indication of the hornoge~ieit~y of the material. Physical constants are given in Table I. TABLE I Vap. P . mm. 3 3 a t Oo 77 at 16' 16 at 18O 1 1 at - 1 2 O 80 at 22.5O
Mol. wt.
..
Ethylene ozonide Thia work Harries' 84.84' Propylene oaonide This work 85.5' I~obutyleneozonide This work 9O.e Criegee'
no 1.386 at 20.0' 1.4099 at 17.5' 1.386 a t 20.1
25 at 18.4' 143 at43-43.5'
..
1 .a88 a t 18.0' 1.38728t20'
a F. p. depremion in glacial acetic acid. volume at room temperature.
b
From vapor
The refractive index for isobutylene ozonide agrees with Criegee's determination. No comparisons are available for propylene ozonide. Our values for ethylene ozonide show a lower refractive index and a higher vapor pressure than obtained by Harries. His values, including a high molecular weight, 84.84, deviate from ours in the direction expected for material containing an appreciable amount of high boiling ozonization residue still present in his sample. Vapor phase infrared spectra were taken at or below the vapor pressure of the ozonides with no added inert gas ( I 0 cm. path) with a Perkin-Elmer Model 21 recording spectrophotometer. The spectra are shown in the figure. It will be noticed that
IJ
0
1
1
1
V 1
u ~
isobutylene ozonide 1
J
~
Vol. 60
tion t o the ozonide structure. Witkope and Bellamy' have questioned this assignment. Goodwin, Johnson and Witkop8 validly maintain that the 5.60 p absorption of the crystalline ozonide of diphenyl fumarate is the ester carbonyl stretching frequency. However, it might be argued on the basis of Briner's work, that the ozonide structure also absorbs a t this wave length. The three ozonide spectra presented here, which have no prominent carbonyl region absorption: offer unambiguous support for Witkop's conclusion. It is clear that the identification of ozonides should be based upon the characteristic bands in other spectral regions, such as 9-9.5, 10.5 and 12 p . (6) B. Witkop, J. Patrick and H. Kissman. Bey., 8 6 , 961 (1952). (7) L. Beusmy, "The Infrared Spectra of Complex Moleoules," Methuon, London, 1954, p. 107. (8) g. Goodwir, N. Johnson and B. Witkop, J . Am. Chem. SOC., I S , 4273 (1953). (9) NOTBIADDED I N PBOOF.-R. Criegee, A. Kerckow and H. Zinke, Ber., 88, 1878 (15155), report the absence of such absorptions by other oionides.
MONTMORILLONITE COMPLEXES WITH SATURATED R I N G COMPOUNDS BY R. GREENE-KELLY Rothameted Ezperimental Station, Harpenden, Herts, England Received November 29#1866
The sorption of aromatic compounds by montmorillonite has been shown' t o produce complexes of two main types: the first giving a 001 spacing of 12.5 kx. which is generally independent of the type of ring system and the nature and position of substituents and the second which gives a 001 spacing which in contrast is markedly dependent on the shape, size and charge distribution of the molecule and which has a minimum value of about 15 kx. It was concluded that the first type of complex was one where the aromatic molecules were intercalated with their rings parallel to the planes of the silicate sheets and the second type where the molecules have reoriented so that their rings are now approximately perpendicular t o the sheets. An analogous phenomenon has now been found with saturated ring compounds. Experimental I ~ ~of preparation ~ . The methods and examination by X-ray diffraction were identical to those described in an earlier paper.
Results and Discussion Tables I gives the 001 spacings of a selection of complexes of simple saturated ring compounds and sodium montmorillonite. They fall into two groups those of spacing 13.3-13.6 kx. (type A) and those of 14.6-14.8 kX.(type B). Steric considerations suggest that a type A complex is one where the saturated and no longer planar molecule is oriented with its mean plane parallel to the silicate sheets. Figure 1 (a) shows the result of a one dimensional Fourier synthesis along the normal t o the silicate sheets using the structure factors given in Table 11. The method of carrying this out has been discussed elsewhere.' The electron density sketch appears t o favor the above configura(1) R . Greene-Kelly, Trans. Faraday Soc., 61, 412 (1955).
NOTES
June, 1956 TABLE I (CALCULATED FROM THE SPACINGS OF 1IIUIfER ORDERS) O F A SELECTION OF COMPLEXES OF MONTMORILLONITE
AfEAN 1'1IE
809
001
180. I
SPACINGS
Complexing substance
Obsd. doat (f0.1 kX.)
Type A Tetrahydropyrrole Piperidine hydrochloride a-Methylpiperidine hydrochloride a-Methylcyclohexanone
13.3 13.3 13.5 13.6
Type €3 Tetrahydrofuran Piperidine Cyclohexanol Cyclohexanone
14.6 14.7 14.6 14.8
tion with an approximately coplanar arrangement of the ring atoms.2 TABLE I1 OBSERVEDSTRUCTURE FACTORS OF THE 001 REFLECTIONS OF THE TETRAHYDROPYRROLE A N D PIPERIDINE COMPLEXES 'THE SIGNS BEING ALLOCATED FROM CALCULATIONS ON TRTAL STRUCTURES Tetrahydropyrrole
00 1 002 003 004 005 006
24 6
Bi
37 12 14
Piperidine
27 -_0 20 15 24 0
007 008 009
00,lO 00,ll 00, 12
Tetrahydropyrrole
Piperidine
..
13 10 0 8 10 6
22 8 11 17 9
...
Type B complexes have similar 001 spacings to the corresponding aromatic complexes and this is consistent with a reoriented molecule with its plane perpendicular to that of the sheet. Figure 1 (b) shows an electron density sketch of the piperidine complex and whilst the details are not resolved it seems to confirm that the intercalated molecule is oriented with its plane perpendicular to the silicate sheets. The spacings of type B complexes are nearly constant and this clearly indicates that the oxygen atoms in the cyclohexanol and cyclohexanone complexes do not determine the separation of the silicate sheets. As with similar aromatic complexes it therefore seems unlikely that hydrogen bonding of the organic hydroxyl group takes place to the silicate oxygens. Attempts to produce type B complexes of more complex molecules (e.g., a-methylpiperidine) were not successful as with aromatic molecules (e.g., a-picoline) and in all cases type A complexes resu1ted.I It is interesting to note that the calculated4 001 spacings of type A complexes of 14.4 kx.and type B of 16.0 kx. are over 1 A. greater than the observed values. This effect has also been observed with aromatic complexes and is suggestive that the projected van der Waals contact distances6 as(2) The limited number of observed 001 reflections clearly do not permit any conclusions concerning ring puckering as suggested b y Pitzer.8 (3) K. S. Pitzer, Science, 101, 672 (1945). (4) Assuming a random arrangement of moleculea between the ailicate sheets in otientationa analogous to those of aromatic complexes.1 (6) L. Pauling, "Nature of the Chemical Bond," Cornell Univ. Press, Ithaca, N. Y., 1944.
Fig. I.-The result of a one-dimensional Fourier synthepis of: (a) tetrahydropyrrole complex d ~ =, 13.3 kX.; (t)) piperidine complex dWl = 14.7 kX. Note the spurior1.s peaks a t X dge to the short sequences used in the synthesis. The deduced orientation of the intercalated molecule i H shown.
sumed between the silicate sheet oxygens and the organic molecules are too large.
A NOTE ON VISCOSITY OF MIXTURES. 11. LIQUID-LIQUID TERNARY MIXTURES BY R. P. SHUKLA A N D R. P. BHATNAGAR Department of Chemislry, Holkar College, Indore, India Received December 6 , 1966
The viscosity equation (TJm)'/a
=
d(r,R,
+ szRz +.
* * ' * *
*+ZnRn)
MIl
recently suggested' has been tested for ternary liquid-liquid mixtures. Experimental.-All the liquids taken were of Analar quality of the British Drug House; however, they were distilled again and the fractions distilling a t the correct boiling point were collected in glass-stoppered Pyrex flasks, Ethers and alcohols were kept over dry pure NaOH to keep them moisture free; the hydrocarbons were dried by keeping them over sodium wire. The viscosity was determined by an Ostwald viscometer and was multiplied by the viscosity of water to get absolute viscosity. Table I gives the viscosity as calculated and determined. (veal is the calculated viscosity and TJob. is the viscosity observed, while z,d and M , have usual meaning.)
Conclusion.-It will be seen from the table that the maximum error possible is of only 4% and hence it may be concluded that the viscosity of ternary mixtures can also be calculated from the equation suggested by us. Hence as there are no limitations for the number of components we can conclude that viscosity of any liquid mixtures can be cal(1) R. P. Shukla and R. P. Bhatnagar, (1966).
THISJOURNAL,69, 888
