J O U R N A L OF COLLOID SCI ENCE

19, 291-293 (1964)

COAGULATION SYMPOSIUM INTRODUCTION

Last year, the American Chemical Society's Divisions of Colloid and Surface Chemistry and of Water and Waste Chemistry decided independently to hold symposia on the increasingly important recent developments in the problems of coagulation and coagulant aids. The projects matured into a joint session of these Divisions for the annual meeting in Los Angeles of April, 1963. Dr. T. E. Larson of the Illinois State Water Survey organized the papers dealing with water purification. Professor Egon Matijevie of Clarkson College of Technology, Potsdam, New York, solicited a wide assortment of papers dealing with the colloidal aspects of coagulation. Readers interested in the theoretical and scientific aspects of this broad subject will be appreciative and grateful to Professor Matijevie for his untiring efforts of organization, selection, and helpful revision of the papers which appear in this issue. As might be expected for a series of papers dealing with water purification, zeta potential, coagulation, coagulant aids, floeculation, filtration, light scattering, etc., of colloidal suspensions, a lively controversial and spirited discussion, which was one of the high points of the Los Angeles meeting, resulted. All participants profited by listening to the presentation of opposing views. In the light of the discussion, this Editor now feels that the title "Coagulant Aids" has become a misnomer. The "aids to coagulation" are, almost without exception, natural or recently developed synthetic high polymers which produce their effect by an entirely different mechanism, which we prefer to call floeeulation to differentiate it from coagulation. The term coagulation comes from the Latin "coagulare" meaning to drive together. This is an appropriate term for the effect of neutral salts on a colloidal dispersion, where the mechanism generally accepted today results from a reduction of the repulsive potential of the electric doublelayer surrounding the particles. The zeta potential may or may not be the significant measure of this reduction of double layer potential and consequent increase in extent of coagulation; that remains to be seen. In 1951, R. H. Smellie, Jr., and V. K. La Mer found that potato starch, which contains 0.13 % phosphoryl ester, in contrast to corn starch, which contains no phosphorous, rapidly flocculated eo!loidal dispersions of fine clays and similar pure materials in the presence of calcium or other phosphate binding ions by erosslinking the particles on which the starch molecule 291

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had adsorbed. No flocculating effect for potato starch was noted in the presence of non-phosphate binding ions like Na, K, etc. The flocs produced filtered rapidly in striking contrast to the compact nonporous coagula which resulted from coagulating the clays with electrolytes alone such as limewater! Soon thereafter, it was shown by others and by ourselves that the synthetic polyelectrolytes flocculated by the bridging action of their polymer threads between the colloidal particles producing flocs which filtered rapidly. In contrast to coagulation, where the primary force appears to be interionic attraction, flocculation acts by a chemical bridging mechanism; where the specific chemical forces residing in the chemical radical of the polymer operate most effectively at very close distances. Electrostatic interaction can be entirely absent in flocculation or play at most a subsidiary role to the specific chemical forces of polymer interaction. Flocculation comes from the Latin "flocculare," meaning to form a floe, i.e., a tuft of wool or a highly fibrous porous structure. This was the original usage of the term in colloid chemistry. We should revive this clear-cut distinction. At the present time, most of our modern monographs and text books either use only one of these terms to the complete neglect of the other, or they use both terms indiscriminately and interchangeably, repeatedly, in the same sentences! This is not due to carelessness; rather, it is due to a failure to understand the underlying concepts involved. Paraphrasing Percy Bridgman and Irving Langmuir's writings of thirty years ago, I reiterate that to communicate properly, we must use words that have clear-cut meanings, representing distinguishable basic concepts, which, in turn, must be based upon recognized operations and results. A concept for which a distinguishing operation does not exist, either physically or in thought, is meaningless. In a series of papers in the Journal of Colloid Science 1956-1958, and more recently in the Journal of Physical Chemistry (67, 2417, 1963) on "The Role of Filtration in Investigating Flocculation . . . " we point out that flocculation produces a network of flocs the porous structure of which permits a rapid rate of filtration which follows an eighth (8th) power law in respect to concentration of floceulant. Only when floceulation is induced by adding the flocculant slowly under the optimum conditions of rate of addition and duration and intensity of agitation do we get the highly reproducible and significant results confirming the eighth power law. This surprising new law of colloidal behavior follows logically from the postulate (since confirmed by direct measurement) that a fraction 0 of the surface of the particle is covered by the adsorbed flocculant in accordance with a Langmuir type of expression. Theta (0) appears in the theory as a factor [0(1 -- 0) 2] in the equation for rate of flocculation as a correction to the Smoluchowski collision law and as a factor [0~(1 - 0/] in the equation for the ensuing rate of filtration through flocs.

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If colloid chemistry is to maintain its position as a science, we can no longer treat coagulation and floeculation indiscriminately as synonymous or interchangeable terms. Instead, they should be distinguished in terms of the active agent and its molecular characteristics, microscopic examination, final sediment volume, and particularly dependence of rate of filtration upon concentration of additive. The use of mathematics in treating poorly defined concepts only compounds confusion with more confusion to the detriment of eolIoid chemistry as a science. VICTOR K. LANIER