science

Soviet study shows poiywater doesn't exist Work by Derjaguin,

staunchest defender

of water II, indicates

it is only water

plus impurities

The book on poiywater is closed. For several years water II had been the sub­ject of one of the liveliest controversies to hit chemistry in some time. Now, its staunchest defender has found that water II doesn't exist, that it is only water plus impurities leached from quartz tubes.

With publication this month of "Re­cent Advances in Adhesion" (Dr. Lieng-Huang Lee, editor, Gordon and Breach, London and New York, 1973), the storm surrounding poiywater comes to a formal end. It is being ended by the man who throughout stood at the center of the storm, noted Soviet surface physicist Dr. Boris V. Derjaguin of the Institute of Physical Chemistry of the U.S.S.R. Academy of Sciences.

Anomalous water is the generic name for the substance that numerous scien­tists prepared and that all were trying to characterize. The activity the sub­stance created in the chemical world was intense.

In the U.S. alone, "i t" attracted the attention of scientists from the Univer­sity of Maryland, Lehigh University, and Princeton University to Purdue University and the University of South­ern California; from Tyco Laboratories, Inc., Battelle Memorial Institute, and Bell Telephone Laboratories; and from the National Bureau of Standards, the Advanced Research Projects Agency, and the Office of Saline Water. Count­less others were involved.

"It" called forth the arsenal of modern instrumental analysis, putting to the test infrared and Raman spectroscopy, nuclear magnetic resonance spectros­copy, x-ray fluorescence and electron spectroscopy, mass spectrometry, neu­tron activation analysis, and electron probe microanalysis.

And over the course of the various studies, "i t" became anomalous water, water II,· poiywater, orthowater, and superwater.

Indeed, the substance, if water, was anomalous. One side in the great con­troversy was convinced that the anomaly was due to impurities. But there was much room for doubt until Dr. Derja­

guin's definitive studies convinced even him that impurities were the cause.

In September 1971, a symposium on recent advances in adhesion was held during the Washington, D.C., national meeting of the American Chemical So­ciety. It was jointly sponsored by the divisions of Organic Coatings and Plas­tics Chemistry, Colloid and Surface Chemistry, and Cellulose, Wood,. and Fiber Chemistry. Symposium papers were to appear during 1972 in the Jour­nal of Adhesion: about two thirds fi­nally appeared there. Then, following an update, they were to be collected into a book—"Recent Advances in Adhesion" —which essentially would be the sym­posium proceedings.

Dr. Derjaguin had been invited to de­liver the symposium address at the 1971 meeting. However, because of some "un­expected circumstances" he did not ap­pear, sending instead a manuscript titled "The State-of-the-Arts in Liquids' Modification by Condensation." In that paper, Dr. Derjaguin presented a critical review of worldwide research activities on anomalous water, or, as he termed it, water II.

From the paper, it is obvious that at that time still, Dr. Derjaguin believed that water II was a distinct molecular entity. Surveying work on the influence of contaminants on formation of anoma­lous water, he noted, "Unfortunately, many authors have obtained conflicting data for materials prepared without careful experimental considerations." The paper, Dr. Derjaguin said, would "present our data snowing rather con­vincingly that new types of liquids can be formed at certain regimes of vapor condensation, both for water and for some other liquids."

Revisions to the manuscript, sub­mitted by Dr. Derjaguin in January this year and included in the published ver­sion this month, change all that. The revisions tell of the work by Dr. Derja­guin and his associates that has, in the interim, caused Dr. Derjaguin to re­verse his position.

It's not difficult to understand how anomalous water caused scientists work­ing with it to draw up sides. Probably the most persistent problem throughout was the difficulty of preparing the sub­stance in more than the most minute amounts—amounts too small to get definitive analyses. Usually the sub­stance was available in only microgram amounts, whereas milligram amounts are needed for many analytical tech­niques to provide good data.

Anomalous water can be readily made

Derjaguin: enhanced dissolving power

in minute amounts but resisted at­tempts to prepare bulk quantities. Vari­ations of the preparation technique were devised but essentially they in­volved condensation of water in quartz capillaries with diameters of 1 to 10 micrometers.

The substance resulting from Dr. Derjaguin's preparation had a density of 1.4, an index of refraction of 1.49, and a vaselinelike consistency. These prop­erties along with an early hypothesis that anomalous water consisted of com­plexes of associations of common water molecules led the Soviet scientists to name anomalous water "water II." A hypothesis advanced by several U.S. scientists was that the substance was a true high polymer consisting of H2O monomer units—hence "poiywater."

The problem surrounding all the hy­potheses was that no one of them seemed to fit all the data. Some 25 dif­ferent experimental measurements had been made on the anomalous substance and no model satisfied all of these. But then, neither could scientists be sure that the measurements had all been made on the same phenomenon.

Dr. Derjaguin describes the problem and the reasoning that went on in his laboratory. He and his associates, he

July 16, 1973 C&EN 13

says, believed from the beginning that if contamination during condensation in the quartz capillaries were the most important factor, then anomalous water also would form on introduction of nor­mal water into the same capillaries. This would be the case whether the contami­nants had arisen from quartz leaching or from some outside source, such as oil vapors from the vacuum pump. How­ever, all attempts by the Soviet scien­tists to produce typically anomalous water in this way, including prolonged heating, had failed.

It was only in the process of condensa­tion, Dr. Derjaguin says, that anomalous water formed. Moreover, he says, anom­alous water didn't appear in capillaries or on flat quartz surfaces if constant undersaturation of water vapor was maintained. Regular variation of rela­tive vapor pressure, including periods of supersaturation, was required. This phenomenon, he says, could hardly be explained by the contamination hypoth­esis only.

Analysis of the conditions required for water II to form added further to the assurance of the Soviet scientists. They had developed a method making it possible to avoid contamination both from the gaseous phase and through the film creep along the quartz surface. The quartz surface, Dr. Derjaguin ex­plains, was cleaned by the most efficient methods they could devise, including

steam and glow discharge treatments. Anomalous water still continued to form, provided that an indispensable condition of pulsed condensation was satisfied. This convinced Dr. Derjaguin's group that a specific phenomenon had been discovered.

These considerations, however, still weren't outright proof of the existence of water II. And the contradictory re­sults of experiments and analyses by others left the phenomenon an open question.

The basic question, Dr. Derjaguin points out, was whether there existed water II molecules containing nothing but oxygen and hydrogen. One approach taken by him and his associates to an­swer the question involved neutron ac­tivation analysis to determine concen­trations of silicon, sodium, and potas­sium atoms in anomalous water. And there was also the possibility that com­pounds not detected by the method, perhaps organic, were involved.

But even after such analysis, ques­tions still remained. The next approach, described by Dr. Derjaguin in "Recent Advances in Adhesion," was to use an electron probe method to determine silicon, sodium, potassium, sulfur, and carbon atoms relative to oxygen atoms.

These further studies showed the Soviet scientists that samples of anoma­lous water, prepared under the most clean conditions, contain silicon atoms

YOUR INVITATION TO ATTEND

International Conference O N

Molybdenum Chemistry and Biochemistry

UNIVERSITY OF READING, ENGLAND

September 17-21, 1973

The Conference is sponsored by the Dalton Division of the Chemical Society and Climax Molybdenum Co. Ltd. The object is to bring together academic and industrial research workers to discuss and relate fundamental and applied aspects of molybdenum chemistry and biochemistry. Because the chemistry of molybdenum is so extensive and varied it is anticipated that the conference will be of wide interest to chemists generally. It is intended that papers will be printed and circulated beforehand and ultimately published in book form as part of the Conference Proceedings. Some sessions of the Conference will be organized on the rapporteur principle.

Over 120 papers have been received. For full particulars, including very nominal attendance and accommodation fees, contact:

Dr. E. R. Braithwaite c/o Climax Molybdenum Co. Ltd.

Villiers House 41 /47 Strand

London WC2N 5JS. England

Telephone: 01 930 0255

Dr. R. E. Anderson c/o Climax Molybdenum Co.

One Greenwich Plaza Greenwich, Conn 06830

USA Telephone: 203-661-3000

in amounts to indicate dissolution of quartz when water is condensing on it. This dissolution occurs to a greater ex­tent than when quartz is in contact with liquid water. The result is probably a gel or sol of silicate acid. When sodium atoms wind up in the condensate along with silicon atoms, the melting point of anomalous water decreases.

"Consequently," Dr. Derjaguin says, "these experiments do not support the hypothesis of anomalous or polymeric water. The formation of the anomalous water is probably attributable to an enhanced dissolving power of condens­ing vapors."

NIH seeks antifertility compounds At the end of this month, the Center for Population Research, National Insti­tute of Child Health and Human De­velopment, National Institutes of Health, will again issue a request for proposals in its program for synthesizing and testing antifertility compounds. The contract program's objective is to stimulate synthetic chemical and bio­logical investigations of new or existing compounds for fertility regulation. The center hopes to develop a variety of new contraceptive methods that are effica­cious, safe, economical, and of broad acceptability to various populations.

The center isn't limiting proposals but is primarily interested in several areas: compounds for potential use as antiprogestational agents, compounds for potential use as luteolytic agents, compounds that interfere with post-ovulatory events leading to and includ­ing implantation, compounds that in­terfere with postspermatogenic matura­tion and those potentially useful as anti-spermatogenic agents (excluding alkyl­ating and antimitotic agents), unusual nonsteroidal and unusual steroidal com­pounds with potential antifertility ac­tivity, and active principles, excluding plant estrogens, that have been isolated from natural sources and that have demonstrated antifertility activity (ex­cluding broad programs of extraction, isolation, and screening of unknown chemical entities).

The investigator isn't required to have capabilities for conducting biological testing on proposed compounds, al­though such testing may ultimately be carried out. The investigator may pro­pose to have the Contraceptive Develop­ment Branch conduct biological testing. The center says it is prepared to support clinical trials on acceptable compounds.

Requests for proposals (RFP-NICHD-CD-74-2) are available in writing or by telephone from: Grants and Con­tracts Management Branch, National Institute of Child Health and Human Development, Landow Building, Room A609, 7910 Woodmont Ave., Bethesda, Md. 20014, (301) 496-4611. Proposals must be received by end of day Oct. 15.

14 C&EN July 16, 1973