Some Quantitative Tests of Intermolecular Bonding Between Aromatic Sulphonates and Simple Carbohydrates in Water,and its Relation to Cellulose Dyeing 1

Abstract

The method of continuous variations, using refractometry, shows that complexes form between sucrose in aqueous solution and non-azo aromatic sulfonates, but not between either sucrose or methyl-β-D-glucopyranoside (used as models of cellulose) and sulfonated azo dyes. Yoshida's method has been applied to determine thermodynamic parameters Entropy values of comllex formation are high, especially for the complex between sucrose and a sulfonated anthra quinone dye—probably indicating that the complexes form by face-to-face association of the molecules. It is suggested that a new type of π-bond is formed in which the π-electrons are attrated simultaneously by protons on the closely adjacent carhohydrate hydroxy-groups. This bond is not prevented by the water of solvation as are normal hydrogen bonds. The azo group appears to reduce the π-electron density in the aromatic nuclei and so prevents the bond forming The result supports the hypothesis that neither hydrogen bonds nor any form of π-bonds directly bind dyes to cellulose and is consistent with other recent work in pointing to a purely aggregation effect as the operative factor in cellulose dyeing.

Keywords

Aromatic sulphonates sucrose methy-β-D- glucopyranoside water. Intermolecular bonding. Detection comptexes. Cellulose dyeing mechanism.

Get full access to this article

View all access options for this article.

References

Agnihotri, V.G. and Giles, C.H. , The Cellulose—Dye Adsorption Process. A Study by the Monolayer Method, J. Chem. Soc. Perkin 2, 2241 2246 (1972 ).

Arshid, F.M. , Giles, C.H. , and Jain, S.K. , Studies in Hydrogen-Bond Formation. Part IV: The Hydrogen-Bonding Properties of Water in Nonaqueous Solution and of Alcohols, Aldehydes, Carbohydrates, Ketones, Phenols, and Quinones in Aqueous and Nonaqueous Solutions, J. Chem. Soc . 559 569 (1956).

Bach, H. , Pfeil, E. , Phillipar, W. , and Keich, M. , Molekülbau und Haftung substantiver Farbstoffe auf Cellulose, Angew. Chemie 75, 407 416 (1963).

Hamford , ('. H., General Discussion, Kobinson, C., Atomic Models. Part 3. Some Stereochemical Problems in Dyeing, Discuss. Faraday Soc . 16, 229-230 (1954).

Campbell, D.S.E. , Cathcart, D. , and Giles, C.H. , Studies in Hydrogen-Bond Formation. VI—The Role of Hydrogen Bonds in Dyeing Processes, J. Soc. Dyers Colourists 73, 546-553 (1957). Note: The solutions used were 0.001 M and not as given.

Giles, C.H. , An Outline of the Chemistry of Dyeing Processes—Part II: Dye-Fiber Interactions , Chem. Ind., 137-150 (1966).

Giles, C.H. , Soc. Dyers Colourists, Forthcoming publication.

Giles, C.H. , Gallagher, J. , McIntosh, A. , and Nakhwa, S.N. , Some Quantitative Tests of Hydrogen-Bonding in Solution, J. Soc. Dyers Colourists 88, 360-363 (1972).

Giles, C.H. and Hassan, A.S.A. , Adsorption at Organic Surfaces. V--A Study of the Adsorption of Dyes and other Organic Solutes by Cellulose and Chitin, J. Soc. Dyers Colourists 74, 846-857 (1958).

10.

Giles, C.H. and McKay, R.B. , Studies in Hydrogen-Bond Formation. XI. Reactions between a Variety of Carbohydrates and Proteins in Aqueous Solutions , J. Biol. Chem. 237, 3388-3392 (1962).

11.

Giles, C.H. and Soutar, A.H. , Surface Tension of Ionized Dye Solutions , J. Soc. Dyers Colourists 87, 301-304 (1971).

12.

Lead, W.L. , Dyeing Theory Again, J. Soc. Dyers Colourists 73, 464 (1957).

13.

Morton, T.H. , The Dichroic Behaviour of Substantive Dyes: Molecular Theory of Dyeing Cellulose, J. Soc. Dyers Colourists 62, 272 280 (1946).

14.

Preston, J.M. , The Cellulose-Dyestuff Complex, I—The Structure of Cellulose Fibers, J. Soc. Dyers Colourists 47, 312 319 (1931).

15.

Vickerstaff, T. , "The Physical Chemistry of Dyeing,' Edinburgh, Oliver and Boyd, 2nd Edn., 1954.

16.

Yoshida, Z. , Ōsawa, E. , and Oda, R. , Intermolecular Hydrogen-Bond Involving a π-Base as the Proton Acceptor. I. Detection by the Refractive Index Method, J. Phys. Chem. 68, 2895 2898 (1964 ).