The extent of thallation of cellulose by reaction with thallous ethylate in benzene is advanced as a method for measuring the accessibility of cellulose. The method is demon strated by its application to a series of samples of fibers that have been swollen to varying degrees by immersion in different solvents and transferred by solvent exchange to ben zene. The extent of reaction is related to the swelling power of the immersion liquid and to the assumed microfibrillar structure of the fiber wall. About 14% of the hydroxyl groups are found to be accessible in water swollen cotton fibers while 0.9% are accessible in the same fibers dried from water. The measurement of accessibility of cellulose to a reagent of moderate molecular size and under conditions which do not affect the sample accessibility offers advantages over alternative methods.
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References
1.
Andrews, C.M. and Oberg, A.G., Textile Res. J.33, 330-343 (1963).
2.
Assaf, A.G., Haas, R.H., and Purves, C.B., J. Am. Chem. Soc.66, 59, 66 (1944).
Brickman, W.J. , Dunford, H.B., Tory , E.M., Morrison, J.L., and Brown, R.K., Can. J. Chem . 31, 550 (1953).
5.
Conrad, C.M., in "Chemistry and Chemical Technology of Cotton," ed. K. Ward, Jr., New York, Interscience Publishers, 1955, p. 31.
6.
Cowling, E.B. and Stamm, A.J., J. Polymer Sci. 2C, 243 (1963).
7.
Escard, J., Saulquin, A., and Girardy, E., Assoc. Tech. Ind. Papertiere Bull.5, 366 (1951).
8.
Fear, C.M. and Menzie, R.C., J. Chem. Soc.937 (1926 ).
9.
Forziati, F.H. , Brownell, R.M., and Hunt, C.M., J. Res. Natl. Bur. Stds. 50, 139 (1953).
10.
Frey-Wyssling, A., in "Fundamentals of Papermaking Fibres," Symposium held at Cambridge, ed. F. Bolam , Brit. Paper & Board Makers Assoc., Kenley, England, 1958.
11.
Frey-Wyssling, A. and Speich, H., Helv. Chim. Acta25, 1474 (1942 ); J. Soc. Dyers Colourists59, 203 (1943).
12.
Harris, C.A. and Purves, C.B., Paper Trade J.110. 29 (1940).
13.
Hermans, P.H. , "Physics and Chemistry of Cellulose Fibers ," New York, Elsevier Publishing Co., 1949, p. 210.
14.
Hessler, L.E. and Power, R.E., Textile Res. J. 24, 822-827 (1954).
15.
Hillebrand, W.F. , Lundell, G.E.F., Bright, H.A., and Hoffman, J.I., "Applied Inorganic Analysis," 2nd edition, New York, John Wiley and Sons, 1953, p. 478.
16.
Luce, J.E., Ph.D. Thesis, McGill University ( 1960 ).
17.
Luce, J.E. and Robertson, A.A., J. Polymer Sci. 51, 317 (1961).
18.
Maggs, F.A.P. , in "The Structure and Properties of Porous Materials," ed. D. H. Everet and F. S. Stone, London, Butterworths Scientific Publications, 1958, pp. 341-42.
19.
Magne, F.C. and Skau. E.L., Textile Res. J. 22, 748-756 (1952).
20.
Manley, R. St.John, Nature204, 1155 (1964).
21.
Merchant, M.V. , Tappi40, 771 (1957).
22.
Meredith, R. , in "Moisture in Textiles," ed. J. W. S. Hearle and R. H. Peters, jointly published by the Textile Inst. and Butterworths Scientific Publications, London, 1960, p. 144.
23.
Minhas, P.S. , Ph.D.Thesis, McGill University (1965).
24.
Moore, A.T. , Scott, L.W., deGruy , I.V., and Rollins, M.L., Textile Res. J. 20, 620-630 (1950).
25.
Muhlethaler, K., Das Papier 17 (10A), 546 (1963 ).
26.
Muhlethaler, K., Z. Schweiz. Forstv. 30, 55 (1960).
27.
Ohad, I., Danon, D., and Hestrin, S., J. Cell Biology12, 31 (1962).
28.
Ott, E., Spurlin, H.M., and Grafflin, M.W., "Cellulose and Cellulose Derivatives," New York , Interscience Publishers, 1954 , p. 273.
29.
Preston, R.D. , "The Interpretation of Ultrastructures," ed. R. J. C. Harris, New York , Academic Press, 1962.
30.
Preston, R.D. , Polymer3(3), 511 (1962).
31.
Purves, C.B. and Hudson, C.S., J. Am .Chem. Soc.59, 49 (1937).
32.
Quynn, R.G. , Textile Res. J.33, 21-34 (1963).
33.
Richter, G.A. , Herdle, L.E., and Wahtera, W.E., Ind. Eng. Chem.49, 907 (1957).
34.
Robertson, A. A., unpublished data.
35.
Robertson, A.A., Pulp Paper Mag. Can. 65, T171 (1964 ).
