of the exchange capacity, sorption approaches the exchange capacity of 200 meq. per 100 grams. Washing removed and sorbed material absorbed a t low concentrations indicating, probably, adsorption on the surface. At higher concentrations, the structure is apparently forced apart, allowing interlamellar adsorption. This observation is supported somewhat by x-ray analysis on the low concentration range amine-contracted clay, the intermediate, and the high concentration range. The low concentration range indicates the structure to be all sodium vermiculite, the high range indicates the structure to be saturated with amine, and intermediate which shows vermiculite either containing no amine (the Na-vermiculite structure) or completely saturated. I n no case was it indicated that partial saturation of the structure was obtained. X-ray study of the washed, samples showed the AC-axis spacing to be 5.4 A. when saturated. From the area per unit change, 75 sq. A., and the area of the butylamine, 44 to 40 sq. A., over 50% of the area is covered. Therefore. the possibility of stacking is indicated. Sorption data for dodecylamine are given in Table 11. Vermiculite sorbs almost all of the organic ions for concentrations below 200 meq. per 100 grams. At higher concentrations, the constant value of about 300 meq. per 100 grams is reached. This is about 50% in excess of the exchange capacity compared to about 110% for montmorillonite. This is logically based upon the larger area per unit change for montmorillonite. Washing removes amine in excess of the exchange capacity indicating again
the excess is held in place by much weaker f o r m than those for the material held by ion exchange. X-ray diffraction studies indicated vermiculite to have a A C-axis spacing of 13.5 A. when the exchange sites were saturated. This would require that ions be adsorbed at some angle to the C-axis or that there was a distortion of the organic molecule. CONCLUSIONS
Sodium montmorillonite and sodium vermiculite will sorb the butylamine molecule, butylammonium ion, or butylammonium acetate in quantities slightly less than the exchange capacity. Both clay forms will sorb in some form the dodecylamine molecule, ion, or salt in quantities in excess of their exchange capacities. LITERATURE CITED
(1) Cowan, C.T., White, D., Trans. Faraday SOC.54, 691-7 (1958). (2) Grim, R.E., “Clay Minerology,” pp. 43-77. McGraw-Hill, New York, 1953. (3) Ibid., 11. 128-34. (4) Grim, R.E., Allaway, W.H., Cuthbert, F.L., J . A m . Ceramic SOC.30, 137-42 (1947). (5) Hendricks, S.B., J. Phys. Chem. 45, 65-81 (1941). (6) Jordan, J.W., J . Phys. & Colloid, Chem. 53, 294-306 (1949). (7) Myers, H.E., Soil Sci.44, 331-59 (1937). (8) Smith, C.R., J . A m . Chem. SOC.56, 1561-3 (1934). (9) Tamamushi, B., Tamaki, K., Trans. Faraday SOC.55, 1013-16 (1959). RECEIVED for review October 10, 1960. Accepted March 23, 1961.
Molar Refraction The Extension of the Eisenlohr-Denbigh System of Correlation to Liquid Organotin Compounds RALPH SAYRE’, S t a m f o r d Laboratories, Central Research Division. American C y a n a m i d Co., Stamford, Conn.
THE
DENBIGH (3, 24) system of bond refractivities, based on the classical Lorenz-Lorentz equation
has been successfully employed in the field of organotin compounds by West and Rochow (30) and by Vogel, Cresswell, and Leicester (27). The subject is treated briefly in a recent review by Gillis ( 5 ) . Because of the demon-
’ Retired, present address, 381 Winthrop
Ave., New Haven. Conn.
strated superiority of the combined Eisenlohr and Denbigh concepts in providing a useful tool for research on liquid organophosphorus compounds (22), the present investigation was undertaken primarily to evaluate the merits, in their application to liquid organotin compounds, of each of four systems of correlation-uiz., two using refractivities (atomic and bond) based on the Lorenz-Lorentz equation, and two using refraction constants (atomic and bond) based on the empirical Eisenlohr molar refraction product, M R E = M ~( ~4 )D .
Table I. Calculated Parameters
Atomic Refractivities Sn 14.156
I
-CH
3.791
I I
-C-
I
5 60
2.981
Bond Sn-Cd
Bond Refractivities West & Vogel, Rochow (30) others (27) 4.09 (prim.) 4.16 4.24 (sec.)
Present
work 4.170
Atomic Refraction Constants Sn
I
Sn-C, Sn-C1 Sn-Br
3.54 8.81 12.02
3.78 8.91 12.00
4.548 8.664 11.971
-CH
Sn-1 Sn-0 Sn-S Sn-Sn
17.95 3.84
17.92 3.84
-C-
10.96
10.77
17.407 2.928 7.631 10.683
197.90
Sn-Cd
54.09
22.00
Sn-C, Sn-Cl Sn-Br
64.14 100.75 179.65
Sn-I Sn-0 Sn-S Sn-Sn
259.40 61.81 84.46 114.81
I
I I
Bond Refraction Constants
23.41
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i
3 3 3
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3 3 3
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Atomic, group, and bond values from Vogel’s tables (25, 26) have been used in this work for elements other than tin. Atomic and bond values for tin, as well as special
I
group values for -CH
I
I I
and -C-,
were computed by the
least squares method from literature data on 147 representative tin compounds. The newly derived parameters are given in Table I. Table I1 shows literature data and observed molar values for each compound, together with molar values calculated in accordance with each of the four systems. Refractive indices measured a t temperatures other than 20” C. have been corrected approximately by means of the coefficient -0.0004 per C. For an accurate evaluation of the four systems, the following coefficients of variation have been calculated: Property Atomic Bond
Refractivity (Lorenz-Lorentz)
Refraction Product (Eisenlohr)
0.094 0.068
0.055 0.019
These coefficients are about as clear an indication of the superiority of the Eisenlohr-Denbigh system of correlation as were those obtained in the work on phosphorus compounds (21). Most of the bond refractivities derived in the present work are in fairly close agreement with those previously calculated by West and Rochow (30) and by Vogel and others (27); there is, however, conspicuous disagreement in the relative magnitude of the values for Sn-Cd and Sn-C,, the earlier investigators assigning a higher value to the former, whereas present work indicates the reverse. While there seems to have been no general awareness of the need for differentiating between aliphatic and aromatic carbon atoms, Vogel’s table (26) gives higher bond refractivity and bond refraction constants for Car-C,, than for C-C, Warrick (28) and Vogel and others (27) reported a higher refractivity for Si-C,, than for Si-Cd, and Weidmann and Zimmerman (29) have recently assigned a slightly higher refractivity to B-C, than to B-Cd. The disagreement noted in the case of the Sn-Cd and Sn-C, refractivities has impelled a search for further evidence as to the consistency of the relative magnitude of values for the two varieties of carbon atoms. As a preliminary and partial test, rough calculations were made using literature data on 19 compounds containing the P-C,, bond; a few of these compounds had been included in the phosphorus investigation cited above (21), but no distinction had been made between P-C,I and P-C,,. Owing in part to the less rigorous method of calculation employed, but chiefly to serious discrepancies in some of the density measurements, no claim is made for the correctness of the calculated values for P-C,, R L = 5.4 and R E = 30.5; there can be no doubt, however, that the true values are substantially higher than the fairly reliable ones for P-C (3.575 and 25.57, respectively). Furthermore, least squares computations now in progress show that the refractivity of
5 64
the B-C, bond exceeds that of the B-Cd bond by a considerably wider margin than that reported by Weidmann and Zimmerman (29). I n the light of the literature cited in the preceding paragraph and of further evidence just adduced, it seems rather improbable that the refractivity of any aliphatic linkage will be found to exceed that of the corresponding aromatic linkage, and there are good reasons for believing that greater exactitude in refractive correlation may be achieved when separate values for Cd and C, linkages have been calculated for many of the other elements. LITERATURE CITED Anderson, H.H., Vasta, J.A., J . Org. Chem. 19, 1300 (1954). Arntzen, C.E., Iowa State Coll. J . Sci. 18, 6 (1943). Denbigh, K.G., Trans. Famday SOC.36,936 (1940). Eisenlohr, F., “Spektrochemie Organischen Verbindungen,” pp. 12-14, Enke, Stuttgart, 1912. Gillis, R.G., Reus. Pure and Appl. Chem. (Australia) 10, 25 (1960).
Griittner, G., Ber. 50, 1808 (1917). Gruttner, G., Krause, E., Ibid., 50, 1802 (1917). Gruttner, G.. Krause, E., Wiemik, M.. Ibid., 50, 1549 (1917). Holemann, P., 2. physik. Chem. B 32,358 (1936). Jones, W.J., Evans, D.P., Gulwell, T., Griffiths, D.C., J . Chem. SOC.1935.39. Korsching, H., is. Naturforsch. 1, 219 (1946). Krause, E., Ber. 51, 1447 (1918). Krause, E., Grosse, A., von, “Die Chemie der Metallorganischen Verbindungen,” p. 352, Gebriider Borntrager. Berlin, 1937. Manulkin, Z.M., Zhur. Obshchel Khim. 13, 42, 46 (1943); 14, 1047 (1944): 16, 235 (1946).
-
Rosenbere. S.U.. Debreczeni. E.. Weinberz. E.L.. J . A m . Chem. S o l 81,973 (1959). ’ Rosenberg, S.D., Gibbons, A.J., Jr., Ibid., 79, 2139 (1957). Rosenberg, S.D., Gibbons, A.J., Jr., Ramsden, H.E., Ibid., 79,2138 (1957).
Ross, Alexander, Metal & Thermit Corp., Rahway, N. J., private communication. Sasin, G.S., J . 0%.Chem. 18, 1142 (1953). Sasin, R., Sasin, G.S., Ibid., 20, 770 (1955). Sayre, Ralph, J . A m . Chem. SOC.80, 5438 (1958). Seyferth, D., Ibid., 79, 2134 (1957). Seyferth, D., Stone, F.G.A., Ibid., 79, 515 (1957). Vickery, B.C., Denbigh, K.G., Trans. Faraday SOC.45, 61 (1949).
Vogel, A.I., J . Chem. SOC.1948, p. 1842. Vogel, A.I., Cresswell, W.T., Jeffery, G.H., Leicester, J., Ibid., 1952, 531. Vogel, A.I., Cresswell, W.T., Leicester, J., J . Phys. Chem. 58, 174 (1954).
Warrick, E.I.. J . A m . Chem. SOC.68, 2455 (1946). Weidmann, H., Zimmerman, H.K., Jr., J . Phys. Chem. 64, 182 (1960).
West, R., Rochow, E.G., J . A m . Chem. SOC.74, 2490 (1952). West, R., Webster, M.H., Wilkinson, G., Ibid., 74, 5794 (1952).
RECEIVED for review May
21, 1960. Accepted March 10, 1961.
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