Polywater—A search for alternative explanations

Polywater~A Search for Alternative Explanations ~ E L L I S R. L I P P I N C O T T

AND G E R A L D

L. C E S S A C

Department of Chemistry, University of Maryland, College Park, Maryland 207~2

AND ROBERT

R. S T R O M B E R G

A~D W A R R E N

H. G R A N T

Institute for Materials Research, National Bureau of Standards, Washington, D. C. 20234

Received December 21, 1970 The case for the existence of"polywater" has been re-examined. Studies were made of the method of preparation of this material. It was determined that surface creep is a factor in the transport of "polywater" into the capillary tubes used for its preparation. It was found possible to reproduce approximately the infrared spectrum previously attributed to "polywater" by synthetic mixtures of salts of carboxylie acids, particularly acetic acid. The inclusion of lactates and pyruvates was also considered. It was established both by infrared and microprobe analyses of "polywater", that neither silicon nor silicon compounds were present in significant quantities. Several impurity elements were detected by microprobe analysis, but the very thin films did not permit quantitative interpretation of the data. Carbon was not detected in the microprobe analysis. Although several mass spectrographic analyses of"polywater" preparations were made no peaks characteristic of multiple water units were ever observed. Attempts to reproduce the Raman spectrum previously reported have been unsuccessful. It was concluded that there is reason to seriously question the concept that water exists in a stable polymeric condition and that contaminants, both inorganic and organic, may account for a number of the physical properties and other phenomena associated with "polywater". INTRODUCTION The details of preparation and properties of a material proposed to be a new form of water has been reported by Deryagin et al. (1-17). The initial preparation by Fedyakin (1) consisted of condensation from normal water in a capillary sealed at both ends. Subsequently, the material was prepared by condensation of water vapor at relative vapor pressures between 0.93 and 0.98 in open capillary tubes of glass oi" fused quartz up to 20 p in radius, as well as on fiat plates (9). i This paper was presented at the 44th National Colloid Symposium, Lehigh University, June 1970. This paper was taken in part from a Dissertation submitted by G. L. C. in partial fulfillment of the requirements for the PhD degree from the University of Maryland (1970).

T h e properties of this material, as rep o r t e d b y D e r y a g i n et al., consisted of a low v a p o r pressure, density of 1.01 to 1.4 g i n / em 3 (9, 12), a refractive index as high as 1.48 to 1.50 (13), boiling point above 200°C, viscosity 15-20 times t h a t of normal water, a n d a considerably altered t h e r m a l expansion below 0°C. Because of these unusual properties, the material has been called " a n o m a l o u s w a t e r " or more recently, "water I I " b y this group. One of the most irapressive properties is its reported stability in the liquid and v a p o r phases (17). N o change in properties were observed at t e m peratures up to 400°C, nor for long storage. H e a t i n g and distilling the material at temperatures of 259-300°C resulted in no change in properties; however, h e a t i n g to t e m p e r a -

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tures of 700-800°C resulted in a condensate with properties of normal water. These results were interpreted as proof that "water I I " consists only of polymeric molecules and eontains no significant impurities. Thermal expansion has probably been most frequently used as a means of characterization of the material, its deviation from normal behavior being used as an indication of the fraction of "water I I " in the sample. The thermal behavior has been verified by Willis et al. (18) and by Bellamy et at. (19). The high refractive index has been corroborated by Castellion et al. (20) who measured the refractive index of the material in the capillary tubes, reporting a maximum value of 1.51. Bellamy et al. (19) stated that the material appeared to be a polymeric form of water that was stable to distillation, using this method to concentrate the contents of many small tubes into a larger one. No residue was observed after distillation. They measured the near infrared spectrum of "anomalous water" in capillary tubes and found a reduction in the intensities of the normal water bands at 6900 and 5150 cm -1. The Raman spectrum exhibited a shift of the 3400 em-~ band to 3440 cm-~. They concluded that anomalous water consisted of polymer units of tetramers or higher molecular weight. Collection of larger samples of the material by distillation from a bundle of capillary tubes has also been reported by Fabuss et al. (21). They reported the successful reuse of these bundles after heating to 300°C, as well as the production of "anomalous" water using columns of quartz powder. Proton nuclear-magnetic-resonance spectra have been reported by Page et al. (22) and by Petsko (23). In addition to the normal water band both of these groups found a new broad resonance approximately 300 Hz downfield, and pointed out that the shift is consistent with a bound proton. Lippincott et al. (24) reported the midinfrared spectrum of "anomalous water" that had been removed from the tubes onto a diamond platelet. In this method of preparation, all normal water would evaporate, leaving the anomalous component. A Raman Journal of Colloid and Interface Science, Vol. 36, No. 4, August. 1971

spectrum was also obtained on a highly viscous sample of "anomalous water" in a quartz capillary tube, normal water having been removed by pumping. The infrared spectrum showed no OH absorption between 4000 and 3000 em-1 and strong bands near 1600 and 1400 em-I. The Raman spectrum showed a strong band near 620 em-I. Both spectra showed some other absorption peaks, but all were small. Similar infrared spectra have also been reported by Page et al. (22) and by Rousseau and Porto (25). The vibrational frequencies observed were very similar to those for systems with very strong symmetric hydrogen bonds. We had eoncluded that strong symmetrical hydrogen bonding oeeurred among water molecules, and several structures were proposed (24). One consisted of a network of hexagonal units, with an O-tI-O distance of 2.3 A. Such a structure is consistent with the formation of hexagonal rings of water molecules as proposed by Hertl and Hair (26) for the adsorption of water on quartz surfaces at high vapor pressures. A number of theoretical treatments have been reported (27-35) which propose a variety of structures, primarily polymeric, if a new form of water were to exist. On the other hand, the possibility that the properties and spectra which have been reported are caused by contaminants must be given eareful consideration. Several papers reporting such impurities have been published (25, 36, 37) and their findings will be discussed below. The investigation reported here was directed to a search for materials, other than a new form of water, which could account for the behavior described above. If such substances are found, their occurrence in the capillary tubes must be explained. We have studied the possibility of creep into the capillary tubes, reexamined material that has been called "polywater" by microprobe analysis in an attempt to identify contaminants, and have prepared synthetic mixtures in an attempt to reproduce the midinfrared spectrum. Sample Preparation. We have prepared the material for both this and the previous study (24) by the vapor e~ndensation of distilled

POLYWATEK

water at a relative vapor pressure of approximately one (18). The capillaries were prepared by drawing Speetrosil (38) fused quartz or Pyrex (38) glass tubes into capillaries usually varying from 10 to 50 u in diameter, although occasionally tubes as large as 150 u in diameter were used. The tubing used to form capillaries as well as any other glassware used in the systems, was cleaned with hot I-INO3 and thoroughly rinsed with hot and then room-temperature distilled water. The capillaries were not further cleaned after drawing in an oxygennatural gas flame. Capillaries were used immediately after dra~4ng. Although the capillaries and apparatus were prepared in the laboratory and not in an enclosed system, precautions were used to prevent contamination during handling, such as plastic gloves, degreased and flamed forceps, etc. Depending on the experiment, the capillaries were placed in a vessel such as a cleaned Pyrex petri dish, on a fused quartz plate, or on a platinum wire screen. The capillaries, supported on the appropriate substrate were placed in a glass, fused quartz, or plastie vessel. Glass or plastic desiccators were frequently used. Contact between the capillary support and the walls of the desiccator or other vessel was kept low by suspending the support on cleaned fused quartz rods. A high-quality distilled water (consumption of available oxygen <<2 N 10-7 gm/liter, conductivity 1.0 to 1.2 mho/em NH3 no greater than 0.1 ppm) was also placed in the vessel, not in contact with the capillaries or their support. The system was evacuated with a mechanical pump until the air above the water was practically removed. Liquid nitrogen and molecular sieve traps were used to prevent contamination by pump oil. The system was then sealed and allowed to stand for time periods varying from 18 hr to several days. The desiccator or other vessel was then opened, and the capillary tubes examined under a microscope. Those containing liquid columns were placed in an empty desiccator and the system was evacuated for approximately 15 rain. Frequently the entire column would disappear. In other eases the size of the column would decrease in length,

445

often about 50%, with an increase in refractive index. To obtain specimens for examination outside the capillary, the open tube was inserted into a hypodermic needle, sealed along the capillary wall with beeswax, and the sample forced out onto the appropriate surface with air, using a syringe. Possible Sources of Contami~ants. Two possible sources of contaminants are the water used to generate the appropriate vapor pressure and the surfaces in contact with this water or with the condensed water vapor. Most investigators, including ourselves, have not used saturated salt solutions extensively for vapor pressure, since this might present a possible source of contaminants. The water used to obtain water vapor has been of extremely high purity, ~4th negligible impurities. However, it has been suggested that the reservoir water in contact with the container for extended periods of time could dissolve or pick up constituents which would then be transported along the walls of the container and into the capillary tubes. The water reservoir does not appear to be a source of contamination in our studies. We obtained essentially identical results using the base of an ordinary desiccator as the container, fused quartz vessels in desiccators to contain the water, or plastic desiccators, which should have different surface contaminants. In the ease of the plastic desiccator, there is a barrier to surface creep from the reservoir. From time to time we observed small birefringent crystals both in the fused quartz capillaries as well as in materials that had been transferred from the capillaries to other surfaces. These crystals were identified by means of Raman spectroscopy and X-ray diffraction analysis (39) as NaNO~. The source of the "contaminant" appeared to be the result of the cleaning by the nitric acid, although very thorough rinsing procedures were followed. (In one ease a crystal of NaF was identified by X-ray-diffraction analysis (39) in a tube that had been cleaned ~dth HF.) The sodium content of the fused quartz tubing, as reported by the manufacturer, was too low (0.04 ppm) (38), to account for the NaHO3. Therefore, it appears

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that the NaNOs was formed outside the capillary and that creep, the transport of a liquid film (together with available contaminants) across a surface, indeed, was a factor in the preparation of "anomalous water." In order to determine the importance of Pyrex in the creep, about one hundred fused quartz capillaries were prepared at one time and divided randomly into two equal groups. One set was placed in a Pyrex dish, the other on a flamed platinum wire screen, and both were set on quartz rods and positioned very close to one another in the same desiccator. The purpose of the platinum screen was to provide a low number of contact points between the support and the capillaries and thus minimize creep. After exposure as described earlier, the tubes were evacuated for 15 min. About 50 % of the tubes in contact with the Pyrex contained liquid while none of the tubes which had been in contact with the screen contained liquid. After additional exposure to water vapor for an extended period of time only one Or two tubes in this latter set contained any material, but the amount present was too small to characterize. Similar experiments were performed using fused quartz plates or rods to hold the capillary tubes. Again, the yields were very low compared to yields when Pyrex holders were used. The use of an all fused quartz system never produced enough material to ascertain if any "anomalous water" was prepared, we, as well as others, have observed large unexplained variations in yields among runs made under presumably identical conditions. Therefore, a certain amount of caution must be exercised in interpreting negative results. It should be pointed out that these results are in contrast to those reported by Deryagin et al. (17) who formed "anomalous water" in fused quartz systems, Page and Jakobsen (40) who suspended capillaries from wires, and Brummer et al. (41) who placed fused quartz capillaries on plastic and slotted quartz supports. However, they are consistent with results reported by Rousseau and Porto (25) and by Rabideau and Florin (26). It should also be pointed out that any investigation of creep is subject to question Journal of Colloid and Interface Science, Vol. 36, No. 4, August 1971

in that it was usually not established that the material was identical to specimens used for infrared or other methods of characterization. For example, in the study reported here it was frequently impossible to obtain samples that collectively would give a film adequate for infrared analysis. Our results would indicate, therefore, that the materials or impurities are formed in the process of vapor condensation on "clean" Pyrex glass surfaces outside of the highpurity fused quartz capillary tubes, flowing into the position of minimum free energy by surface creep. As a further indication of this, for a stack of tubes in a Pyrex dish, the lower tubes in direct contact with the Pyrex surface showed higher yields than the upper tubes with only a few contact points. This was also consistent with higher yields for capillaries prepared from Pyrex rather than fused quartz tubing. The experience in our laboratory has been that high-purity quartz surfaces are not necessarily sufficient for the formation of "polywater," and that the capillaries are merely containers and are not necessary for its formation. This does not necessarily mean, however, that "anomalous water" is comprised only of dissolved impurities. Consideration must be given to the possibility that other ions available from the Pyrex surface are required for initiation of the growth process of "anomalous water "or that an ion such as sodium is required for a stable structure. As will be seen below, sodium was almost always present in any sample we analyzed. Although the location and requirements for the formation of the material are certainly important, the critical concern is its chemical composition. Spectroscopic Results. The mid-infrared spectrum has been previously published by Lippincott et al. (24) and is shown in Fig. la. Additional spectra have been obtained which retain the principal features, i.e. strong bands near 1600 and 1400 cm-I; however, some sample-to-sample variation is observed. Other published spectra by Page et al. (22) and by Rousseau and Porto (25) also show some variation. Possibly the greatest sample-to-sample changes occur in the band at 1100 cm-1.

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FIG. 1. Infrared spectrum of aged "polywater" sample on Type II diamond, a. Spectrum of "polywater" (reproduced from reference 24). b. Spectrum of sampIe used to obtain Fig. la, after 11 months. As shown in Fig. la, the band at 1100 cm -1 is relatively weak. The specimen was allowed to age in laboratory air, protected only from dust, and spectra were obtained from time to time. This band at 1100 em -1 was attributed to S04=. The band in the original spectrum split with time into three bands, and this is consistent with the change in environment of this anion. A spectrum of the sample after aging for a period of 11 months is shown in Fig. lb. Page et al. (22) published a spectrum with a strong absorption at 1100 em -~, but stated t h a t subsequently a spectrum was obtained with no 1100 cm -~ band. Rousseau and Porto (25) also concluded t h a t this band was caused b y S O C and in fact, found t h a t its intensity varied with the sulfate concentration. I n our own material the sulfate is believed to be a minor component. I t would appear t h a t sulfate is a contaminant t h a t is not a p r i m a r y source for the properties of " p o l y w a t e r . " The bands near 1600 and 1400 cm -1 are considerably reduced in intensity as a result of aging. The b a n d at 1380 cm -~ m a y be caused b y Izitrate in the originM m a t e r i a l This is consistent with the detection of NAN03 b y R a m a n spectroscopy and X - r a y diffraction, as described above. We have observed some differences in the location of the b a n d near 1600 em -~ v a r y -

ing from approximately 1590 to 1620 cm -1, and some differences in the s h a p e of the band near 1400 em -~. Inasmuch as the formation of the material is always associated with fused quartz or glass surfaces, it might be expected that, if the properties are not due to a new form of water, but rather to an extraneous material, the only, or at least principal component would be a compound of silica. This view has been advanced b y Cherkin (42) who suggested t h a t "anomalous water" is asilicic acid dispersion resulting from the interact,ion of water with the quartz surface. E v e r e t t et al. (43) were led to the tentative conclusion t h a t the anomalous component is a polydisperse silica polymer which forms a sol and coagulates to a gel. T h e y find m a n y of ther poperties of "anomalous water" consistent with a silicic acid sol. The spectra of compounds of silica are characterized b y a very strong absorption near 1000 em-L We have been unable to agree with the correlation between the spectra obtained b y Lippineott et al. (24) and the spectra given for silica and water or porous glass and water as given b y E v e r e t t et al. (43). As the b a n d at 1100 cm -1 in Fig. l a is probably due to SO4=, it is apparent t h a t none of the strong bands normally associated with the spectrum Journal of Colloid and Interface Science, V o I . 36, N o . 4, A u g u s ~ 197i

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was inconclusive. Microscopic examination of the sample after heating indicated t h a t a considerable portion of the sample had volatilized. The infrared spectrum of this heated sample was rerun and is shown in Fig. 2b. The bands near 1400 and 1600 em -1 have been diminished considerably. After heating to 800°C in a muffle furnace in air, the infrared spectrum, shown in Fig. 2c, showed no absorption other t h a n t h a t of the diamond. I t was estimated t h a t less than 5 % of the original sample remained after heating. An electron microprobe examination of this small remaining residue showed it to consist primarily of NaC1. This will be discussed in more detail below.

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FIG. 2. Infrared spectra of heated "polywater" sample on Type I diamond platelet. The spectra were obtained using multiple scans on a Fourier Transform Spectrometer. There is a background shift among the three spectra which is probably due to instrument variations and small signal level. Scatter and dispersion effects caused by sample size changes may also contribute to the background drift. Bands marked with an asterisk are due to diamond platelet. The diamond bands near 1200 cm-~ are due to the Type I diamond used. Type I I diamonds do not absorb in this region, a. Before heating; b. After heating in a mass spectrometer to 400°C; c. After heating in air to 800°C. of "polywater" arise from silica. Any silica would be present only in trace amounts. A t t e m p t s were made to study the changes in the infrared spectrum as a result of heating. The sample was prepared in fused quartz capillary tubes in a plastic desiccator, as described earlier, and transferred to a diamond platelet. The spectrum is shown in Fig. 2a, and is v e r y similar to the spectrum shown in Fig. la, although there is a small shift in the band near 1600 em -I. As mentioned above, we have observed some sampie-to-sample shift in this band. This sample was then heated to 400°C in a mass spect r o m e t e r (44). Due to the small size of the sample, the analysis of the volatile products Journal of Colloid and Interface Science,

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associated with "polywater" or "anomalous water" there are strong bands at 1600, 1400, and in some cases 1100 cm -1. As described above, the 1100 cm -1 band can be attributed to a sulfate impurity. Some sample-tosample variability in the bands at 1600 and 1400 em -1 has been observed. Salts of earboxylic acids have the same general features in their infrared spectra. T h e spectra of single salts do not m a t c h any of the spectra associated with "polywater." However, if these salts are p a r t of a complex mixture of other salts, the frequencies of bands can shift, the intensity and band shape can change dramatically, and weaker bands can disappear entirely. Solutions (1 gin/100 ml H20) were made up from the following salts: CH3COONa, H C O O N a , NaNO~, KNO3, Ca(NO~)2, A12(SO4)3, Na2S04. These salt solutions were then mixed in varying ratios and small quantities allowed to evaporate on a zinc sulfide or diamond platelet. I n Fig. 3a, an infrared spectrum is shown of a mixture of acetates, formates, sulfates, and nitrates which closely resembles the spectrum shown in Fig. la, obtained from water condensed in capillary tubing. The spectrum shown in Fig. 3b represents another formulation in which the 1600 and 1400 cm -1 bands are the most prominent features. Although A12(SO4)3 was used to alter the band shape of the high-frequency component of sodium acetate so

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FIG. 3. I n f r a r e d s p e c t r a of s y n t h e t i c m i x t u r e s . T h e s p e c t r a were o b t a i n e d b y e v a p o r a t i n g small

quantities of various mixtures of salt solutions on platelets. Stock solutions of each salt consisting of 1 gm/100 mi were prepared and mixed in various ratios prior to evaporation, a. Spectrum of a complex mixture of salts on a ZnS platelet, closely resembling the spectrum shown in Fig. la. This mixture consisted of 2 parts by volume of A12(SO4)a, 10 parts CI-I3COONa, 5 parts (CH3COO)2Ca, 0.5 parts I-ICOONa, 2.5 parts KNO3, and 1 part NaC1. b. Spectrum of a mixture of salts on a Type II diamond vs. diamond showing shift of the acetate peak from 1575 to 1595 cm-~ caused by presence of aluminum salts. This mixture consisted of 12 parts CH3COONa, 10 parts HCOONa, 10 parts A1(NO3) 3 and I part A12(SO4)3. t h a t the synthetic spectrum matched t h a t of

"polywater," the use of other carboxylic salts, such as lactate or p y r u v a t e has not been successful in adequately reproducing the infrared spectrum shown in Fig. ta, even with the addition of inorganic salts. I t should be noted t h a t the mixture used to obtain the spectra shown in Figs. 3a and 3b caused the acetate band, shown in the spectrum of sodium acetate in Fig. 4b, at 1050 to be completely suppressed. The acetate b a n d at 600 cm -1 is shown to be suppressed in Fig 3b. I n addition, the C H b a n d at 2900 cm - I is also completely removed in the spectrum shown in Fig. 3a. The formulations used to obtain the spectra shown in Fig. 3 are given in the caption. Several pyrolysis experiments were carried out with known compounds to compare

the changes in a synthetic spectrum with t h a t from the aged or heated materials. Equal quantities of two solutions, each consisting of 1 gm CH3COONa/100 ml I-I20 and 1 gm Na2SO4/100 ml H20, were mixed. Several drops of this solution were allowed to evaporate on a ZnS surface, and the infrared spectrum obtained this mixture was then heated to 300°C and the infrared spectrum was rerun. (The heating was carried out only to observe changes in spectra and not to accurately measure the pyrolysis of the materials.) New bands appeared at 1400 and 880 em - I due to Na2CO3, and at 1630, 1330, and 780 era-1 due to Na2C204. Changes in the spectrum of sodium acetate up on heating are shown in Fig. 4. I n general, the pyrolysis of alkali earboxylates yields alkali carbonates. CarbonJournal of Cdloid and Interface Science, Vol. 36, No. 4, August 1971

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Fie. 4. Change in the infrared spectrum of CH3COONa as a result of heating, a. After heating to 300°C, showing the presence of carbonate bands, b. Spectrum of sodium acetate showing bands at 1050, 600 and 2900 cm-1 that have been suppressed by the mixture used to obtain Fig. 3a.

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a result of heating, a. Mixture before heating, b. Mixture after heating to approximately 400°C. a t e s are easily i d e n t i f i a b l e in t h e i n f r a r e d s p e c t r u m b y a b r o a d b a n d a t 1430 c m -1 a n d a s h a r p b a n d a t 880 c m -1. O x a l a t e s are int e r m e d i a t e p r o d u c t s w h i c h can b e i d e n t i f i e d b y b a n d s a t 1630, 1335, a n d 790 c m - t B y 400°C t h e o x a l a t e s a r e c o n v e r t e d to t h e c a r b o n a t e s . T h e c a r b o n a t e s are g e n e r a l l y Journal of Colloid and Interface Science, V o l . 36, N o . 4, A u g u s t

1971

s t a b l e u p to 800°0 or higher. T h e s a m p l e o b t a i n e d b y v a p o r c o n d e n s a t i o n in c a p i l l a r y t u b e s b e h a v e d differently u p o n h e a t i n g . N o c a r b o n a t e was o b s e r v e d in t h e s p e c t r a shown in Fig. 2b. T h e o n l y e a r b o x y l a t e s w h i c h we h a v e f o u n d t o b e h a v e in t h i s m a n n e r a r e t h e a m m o n i u m salts. F i g u r e 5

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F z e . 6. I n f r a r e d s p e c t r a of c a l c i u m l a c t a t e , s o d i u m p y r u v a t e , a n d a s y n t h e t i c m i x t u r e , T h e s p e c t r a

were obtained on a ZnS platelet: a. calcium lactate; b. sodium pyruvate; e. the spectrum was obtained by evaporating a mixture of salt solutions on a ZnS platelet. The mixture consisted of saturated salt solution in the following amounts: 0.5 ml NaNOa, 0.15 mI Na~SO4, 5.0 ml NaC1, and 10 ml of a 1.5% solution of sodium lactate. shows the result of heating a synthetic sample (similar to the above but substituting CH3COONH4 for CII3COONa) to 45fl°C. This result indicates t h a t if enough ammonium ions are present the earboxylate anion is sufficiently volatized to prevent the formation of carbonate detectable in the infrared spectrum. Therefore., the disappear-

ance of the 1600 and 1400 cm -1 bands on heating can be accounted for on the basis of ammonium salts of carboxylie acids, but not on the basis of sodium salts of earboxylic acids. Synthetic mixtures of other salts can Mso be used in attempts to obtain spectra similar to that shown in Fig. la. Lactates have been Journal of CoUoid and Interface Ncievuze, Vol. 86, No. 4, August 1971

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suggested as a possible source of contamination (45). Given in Fig. 6a and b are infrared spectra of calcium lactate and sodium pyruvate. The curve shown in Fig. 6c represents the spectrum obtained from a formulation made up from sodium lactate, sodium nitrate, sodium chloride, and sodium sulfate. The absorption bands at low frequencies seen in Figs. 6a and 6b have not been sufficiently suppressed to obtain a plausable match with the infrared spectrum given in Fig. la. It should be noted that all of these spectra show the presence of a definite absorption in the OH region which is missing in the spectrum given in Fig. la. The results described earlier with respect to the spectra of material obtained from capillary tubes can be regarded as typical for our studies. However, from time to time, atypical results were obtained. The infrared spectrum of one such atypical sample, in this case on a ZnS platelet, is shown in Fig. 7a. Although the spectrum is considerably different from that shown in Fig. la, it does have very strong absorption bands in the 1600 and 1400 cm-1 region of the spectrum. In the spectrum shown in Fig. 7a, the relative intensities of these two bands are reversed, compared to Fig. la, and a weak band which is absent in Fig. la, occurs at 880 cm-1. From the bands at 1400 and 880 cm-1 it appears that CO8- must be present in relatively high concentrations. Microprobe analysis, to be described later, indicated the presence of carbon in part of the sample. The center portion, however, showed only a strong oxygen signal. Attempting to obtain an infrared spectrum of this center portion alone resulted in it being touched by the mask and disturbed. A subsequent microprobe analysis of this center portion then showed a high concentration of sodium, coming either from the outer portions of the sample, from the surface below the sample, or~ from the mask. This center portion was then transferred to a high-pressure infrared diamond cell and an infrared spectrum obtained. This is shown in Fig. 7b. It is in approximate agreement with the spectrum of Na2B4OT. 10H20, shown in Fig. 7c. It would appear then, that from time to Journal of Colloid and Interface Science, ¥ol. 36, No. 4, August 1971

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FIG. 7. Infrared spectra of an atypical sample. a. Entire sample using 400 tL aperture on a ZnS platelet.b. Center portion, transferred to a Type I ! diamond pressure cell. The dashed line represents the spectrum of the empty cell. c. Nujol mull of Na2B4OT. 10 H~O, showing similarities with Fig. 6b. The asterisk represent Nujol bands.

time other contaminants can be obtained in the capillary tubes. In this case, however, the material could be relatively easily iden2 tiffed by its infrared spectrum. We (Io not believe that borates account for the typical spectra obtained from our samples. Attempts to Synthesize the Raman Spectrum. Raman spectroscopy would normally be ideal as a method for directly characterizing samples in capillary tubing. In an earlier experiment the Raman spectrum of "polywater" was obtained with relative ease (24). Since then, we have not been able to reproduce that Raman spectrum. Most of the samples prepared for the present study fluoresced so strongly that all Raman lines were obscured. A number of the samples charred badly when exposed to a high-powered focused laser beam, indicating the presence of some carbon-containing compounds. Charring has also been reported by Rousseau and Porto (25). Although the Raman spectrum has not been reproduced with any synthetic mixture of compounds that can reproduce the infra-

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FIG. 8. E l e c t r o n microprobe area s c a n s o f a " p o l y w a t e r " sample on a beryllium substrate, showing elem e n t s found a n d d i s t r i b u t i o n in sample: a. M i c r o g r a p h of sample o b t a i n e d from the t a r g e t c u r r e n t ; b. oxygen (or sodium); e. silicon.

red spectrum, we have nearly duplicated it with a dry mixture of NaF and N a F H F . This mixture yielded one intense line in the R a m a n spectrum at 630 em -1. The sample used to obtain the Raman spectrum reported in Ref. (24), however, was very viscous, but still liquid and nonbirefringent. However, concentrated aqueous solutions of N a F H F and N a F do not behave in an analogous manner due to limited solubility of each in water. In addition, the source of a fluoride impurity would be unexplainable as H F was not used for cleaning purposes. Microprobe Analysis. Analyses of several of our samples of "polywater" were carried out with an electron microprobe (46). Usu* ally the samples were prepared in the manner described earlier and transferred from the capillary tubes to a beryllium or aluminum surface. The films were so thin that

they were completely penetrated by the beam. However, some determination of relative amounts could be made as well as distribution of elements within the sample. Microprobe area-scan photographs are shown in Fig. 8 for a sample of "polywater" that had been forced from a capillary tube onto a beryllium substrate. Shown in Fig. 8a is a micrograph obtained from the target current. This is essentially the same as a scanning electron micrograph. As the analysis is made under vacuum at a pressure of approximately 6 X 10.3 N / m 2, all volatile components would have been lost. Typically, the sample has a definite outline, with relatively sharp borders. In this ease a center portion is essentially free of sample, and thicker and thinner portions can be delineated. For all samples, a search was made for all elements of atomic number 6 (carJournal of Colloid and Interface Science, Vol. 36, No. 4, August 1971

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FIG. 9. E l e c t r o n microprobe area scans of " p o l y w a t e r " sample on b e r y l l i u m s u b s t r a t e , showing elem e n t s found a n d d i s t r i b u t i o n in sample: a. M i c r o g r a p h of sample o b t a i n e d from t h e t a r g e t c u r r e n t ; b. sodium; c. silicon; d. oxygen.

bon) and higher. For the sample shown, only three elements could be detected--oxygen, sodium, and silicon. The distribution of oxygen is shown in Fig. 8b and that of silicon in Be. The distribution of sodium was essentially identical to that of oxygen. Both oxygen and sodium are distributed in a manner almost identical to that of the sample itself, as shown in Fig. 8a, i.e., absent where there is no sample, such as in the center of the circle, and thicker or thinner where the sample is thicker or thinner. The silicon, however, is more randomly distributed with no correlation with holes or thick and thin portions of the sample. I t appears to be particulate and is concentrated somewhat at the edges of the sample, as would be expected from a drying pattern. The low intensity and distribution of silicon in this and other samples indicate that silicon is not a major component of these specimens. Because of the thinness of the film, a Journal of Colloid and Interface Science,

Vol. 36, No. 4, August 1971

quantitative analysis could not be made of this sample. No quantitative significance can be attributed to the intensity of the signal, as this is a function of the specific X-ray emitted, length of exposure, etc. as well as amount. However, because oxygen is such a weak emitter, it is obvious that oxygen is present in large quantities. Carbon, nitrogen, sulfur, and halogens were not detected in this sample. As carbon is relatively difficult to detect in small quantities, and as these very thin films present additional difficulties, we prepared a dilute mixture (0.25% each) of Na2CO3, NaC1, N a N Q , Na2SO~, and Na2SiO3.9H~O, transferring small quantities to the beryllium substrate from capillary tubes in the same manner as was used for the "polywater." Carbon, oxygen, sulfur, sodium, and chlorine were easily detected; however, nitrogen was not. Although nitrogen can be easily detected for thick samples stable under the beam, it

POLYWATEIZ appears that for these thin films the beam causes decomposition and loss of the nitrate. Therefore, one can state that the residue of the sample of Fig. 8 contained no significant amount of carbon, halogens, or sulfur, but may have contained nitrates. A similar microprobe analysis for another sample is shown in Fig. 9. The appearance of the sample in Fig. 9a gives indication of some volatilization, although one cannot determine whether this oceurred as a result of drying, evacuation, or action by the beam. The only elements detected were oxygen, sodium, and silicon. The location of this analysis at the edge of the sample permits a comparison of the signal from the sample with that of the background. The same limitations discussed above for a thin film apply, however, with respect to the intensities for the elements. In this case the silicon did not appear to be particulate. Although it was associated with the sample, it was present only in trace quantities. Again no carbon was detected and the negative results for nitrates may be inconclusive. The results shown in Figs. 8 and 9 arc typical of a number of samples analyzed by the electron microproble. A described earlier, a sample of "polywater" was transferred to a diamond platelet and heated. The infrared spectra before and after heating are shown in Fig. 2. After heating to 800°C a microprobe analysis was obtained. The maior components of this small residue (estimated to be less than 5 % of the original sample) were sodium and chlorine. It could be shown that the distribution of the sodium matched that of the chlorine, i.e., the major component was NaC1. A few particles containing an association of Si, Ca, and S were found. Although the diamond substrate prevented analysis for carbon, as all of the sodium was associated with chlorine, it is possible to state that Na2CO3 was not present in any significant amount. Given in Fig. i0 are the microprobe analyses for the sample on a zinc sulfide crystal, whose spectrum is given in Fig. 7. The micrograph (target current) of the sample is shown in Fig. i0. Also shown are lille scans for silicon, carbon, potassium, sodium, and oxygen taken along the horizontal marker. The sample consisted of an exceptionally

455

thick center portion, hexagonally shaped, surrounded by a thin film. All of the components, with the possible exception of oxygen, were present in the thin film. Oxygen was the only eomponen~ found in any significant quantity in the thick center portion. Sodium was present at a fairly high signal level in the area surrounding the thiek portion. In this case, the center portion of the sample was suffieiently thick to mask the zinc sulfide substrate as well as any sodium or other elements on the underside of this portion. After touching the specimen with a mask, as described earlier, the microprobe analysis did show sodium as a major constituent in large parts of the center portion. It is not known whether this sodium was transferred from the mask or from thg underside of the portion or from the outer portions of the sample. The similarity of the infrared spectrum of this sodium-containing material with Na2B4OT10H20 has been shown in Fig. 7. Although the microprobe analysis did not detect boron, the use of an electron beam of 15 kv does not permit a sensitive test for boron. DISCUSSION OF RESULTS To date, "polywater" or "anomalous water" has been prepared only in very small amounts, most frequently in microgram quantities. It is to be expected that some contamination would occur, and the small quantities prepared make purification very difficult, if not impractical. In many ana. lyrical techniques, the handling, transfer, and other procedures carried out on the specimen provide the opportunity for loss of volatile components. Thus, a loss of the low molecular weight components of any polymeric forms of water if present, is to be expected, as well as a concentration of nonvolatile contamination such as many of the inorganic salts. Reeognizing these limitations, certain conclusions, although some of them are tentative, can be made. It was shown above that the infrared spectrum (Fig. la) of the material obtained from the condensation of water in capillary tubes can be nearly reproduced from a mixture of sodium acetate and inorganic salts (Fig. 3a). If the spectrum given in Fig. la is caused

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FIG. 10. Electronmicroprobeanalysisof anatypicalsampleof"polywater"ona ZnS substrateshowing line scans for elements found. The white line shown in the target current micrograph, Fig. 10a, gives the focus for the elemental scan. The sample consisted of a thick center portion surrounded by a thin film. The only element detected in any significant amount in this central portion was oxygen, a. Micrograph of sample obtained from the target current; b. oxygen; c. silicon; d. carbon; e. potassium; f. sodium. b y materials other than oxygen and hydrogen, then it is apparent that carboxyl groups must be responsible, at least in part, for the bands at 1600 and 1400 cm -~. The formulation used for the spectrum shown in Fig. 3a permits suppression of formate and acetate bands, which are missing from the spectrum shown in Fig. la. We do not suggest that the mixture used to obtain the spectrum shown in Fig. 3a represents the mixture formed in the capillary tubes by the condensation of water. However, it does appear that some formulation similar to the one given is required to both retain the principal bands and suppress others. This formulation must, of course, be reconciled with any analytical results obtained

on "polywater." I t is not possible, in our judgment, to reproduce the spectrum represented in Fig. l a by salts of mixtures of sulfates, nitrates, a n d / o r borates. We have not detected carbon in our microprobe analyses, although carbon was easily detected in very thin films made from dilute solutions of sodium carbonate or sodium lactate and inorganic salts. An explanation for this would be that the samples studied on metallic substrates by the electron microprobe were different in composition from those on which infrared spectra were obtained, although this would seem unlikely in view of the number of samples examined b y both techniques. The use of a diamond substrate did not permit an analysis for carbon

Journal of Colloid and Interface Science, Vol. 36, No. 4, August 1971

POLYWATER on samples characterized by infrared spectroscopy, although it did permit an examination for most other dements. However, others have found carbon in their samples, e.g., Page and aakobsen (40) reported carbon contents as high as 12% in their sampies, which gave infrared spectra similar to that shown in Fig. la. In addition, Deryagin et al. (17) reported the detection of carbon "impurities" by mass spectrometric analysis. However, in further work, the same group (17) found that the mass of organic content was less than 1% of the content of "water II." The change in the spectrum as a result of degradation provides another means of comparing the synthetic mixture with the materiaI collected from the capillary tubes. As shown in Figs. 1 and 2, either aging or heating a sample of material collected from the capillary tubes results in a simultaneous decrease in the intensities of the two bands at 1600 and 1400 cm -1. No new bands, such as carbonates, are formed. The heating of sodium acetate or mixtures containing sodium acetate, however, results in the formation of oxalates or carbonates, as shown in Fig. 4. The use of the less stable ammonium salts, however, results in the simultaneous loss of the principal bands, x~,qthout the appearance of any oxalate or carbonate bands, as shown in Fig. 5. It would appear that the only way to explain the infrared spectra at the present time is to postulate the presence of ammonium salts of earboxylie adds as well as sodium salts, since sodium salts of earboxylic acids alone cannot explain the disappearance of the 1600 and 1400 era-* bands on heating to 400°C or higher without leaving any other characteristic absorption bands. Attempts to detect nitrogen by electron microprobe from a very thin film of ammonium sulfate were unsuccessful, probably due to decomposition of the material by the beam, as was the ease for sodium nitrate. (Nitrogen was detected in thin films of more stable ammonium salts such as NH4C1.) Thus, it is possible that our samples contained appreciable quantities of NH4 +, undetected by the microprobe, atthough analyses by others (25, 36) using different techniques have detected nitrogen in their samples only in trace quantities.

457

In ally discussion of substances that may be responsible for the reported unusual properties of"polywater," compounds of silicon must be considered, as fused quartz or glass have always been used for its preparation. We have never found any evidence for silicon-containing compounds in the infrared spectra. Unlike nitrogen or some of the light elements, silicon is easy to detect with the electron microprobe. It has been shown to be either particulate and not. directly associated with the sample (Fig. 8e) or present only in trace amounts (Fig. 9c). If silieon plays a role in the properties ascribed to "anomalous water," it must do so for extremely low concentrations. Rousseau and Porto (25) also reported no significant quantity of silicon in their samples. If then the material collected in capillary tubes consists of mixtures containing carbon, such as that shown in Fig. 3a or Fig. 6e, one can speculate about the source of the contamination. One should immediately suspeer contamination from pump oils, greases, etc. Although precautions such as traps and speeial handling procedures were used to prevent contamination of the surfaces, it is possible that some organic contamination occurs. For example, lactic acid (a earboxylic acid) and sodium lactate are secreted by the skin. Cystine, a component of the skin, can be broken down by a series of complicated reactions oceurring in the skin to inorganic sulfates and carboxylie acids (47). Attempts to prepare "anomalous" alcohols by the same methods yielded infrared spectra resembling long-chain esters or triglycerides. Sebaceous glands lying within the skin secrete a complex lipid mixture. The secreted lipids contain free cholesterol, waxes, triglycerides, and free fatty acid~. These substances are soluble in alcohols and insoluble in H20 and as a consequence would not be found in the H20 preparation. On the other hand, compounds such as salts of carboxylic acids, Na2SO4, and NaC1 are not very soluble in alcohols and thus would not and are not found in the alcohol preparations. One possible source of carbon-containing compounds in the "polywater" preparations is the gas-oxygen flame used in drawing the capillary tubes. For instance, it is well

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known that the radical HCO. is present in results shown in Figs. 7 and 10. The fact that such flames, and this, after adsorption on the attempts to prepare large quantities of "polyglass surface, might be a source of formate water" have been unsuccessful further raises ion. If this is indeed a source of formate ion the suspicion that the amount formed is dein "polywater" preparations, it is clear from pendent on the quantity of available surthe fact that "polywater" forms when Pyrex face impurity. is the substrate, but does not form when At the present time, it does not appear essentially sodium-free fused quartz is used that the spectrum for "polywater" given in as the substrate, that it would have to be Fig. la is due to a lactate. Attempts to match postulated that HCO. (or the formate de- the infrared spectrum of lactates with the rived therefrom) needs a positive ion to spectrum given in Fig. la have not been release it into soluble form so that the surface successful, even with the use of a wide creep carries it into the capillary. variety of inorganic salts. In addition, the In addition to these considerations, (mr pyrolysis of sodium lactate leaves a residue experience is that very low or no yields were of sodium carbonate which is readily identiobtained when the capillary tubes were pre- fiable in the infrared spectrum, but has not vented from contacting a Pyrex surface, been identified in our "polywater" samples using either fused quartz or platinum gauze after heating. If lactates, arising from consupports. Organic contamination should tamination from the skin, were the source of have been approximately equal for fused the infrared spectrum, the major quantities quartz or Pyrex substrates. It would appear of sodium chloride which would have been then that some reaction of an organic con- expected were not found in our samples. Finally, mass-spectrometer studies of taminant with a material leached from the surface of the Pyrex would be required for a samples of "anomalous" water have never decrease in quantity of material with in- shown any mass peaks that could be atcreasing purity of the fused quartz container. tributed to large water molecules (17, 18). We have been unable to prepare any Although alternate explanations have been specimens of polywater using DyO. Realizing given (17), it is reasonable to expect that a that negative results can be misleading, if material able to withstand distillation would surface contamination is the source of the yield mass numbers for some multiple nummaterial, one might expect yields to be ap- ber of water molecules. Although extensive proximately the same, whether I-IyO or DyO effort was put forth to analyze our samples is used, although the transport of films of with mass spectrometry (42), we were unHyO and D20 may be very different. Rous- able to obtain any results that would confirm seau (48) has reported the preparation of the presence of"polywater." From the variety material using DyO which had essentially and number of samples analyzed, it would the same infrared spectrum as that prepared seem likely that peaks characteristic of from HyO, i.e., no frequency shift was ob- multiple water units would have been observed if such a substance were present. served. I t appears, then, that alternate explanaCONCLUSIONS tions may be given for at least some of the In summary, we conclude that there is evidence attributed to a new form of water. The capillary tubes may be merely con- reason to seriously question the concept that tainers for materials which arrive from their water exists in a stable polymeric condition. near environment by a surface creep. Some It appears that contaminants, both inorganic of this material, surprisingly, may be or- and organic, may account for most of the ganic, and relatively reproducible among physical properties or other phenomena several laboratories. Some is inorganic, con- which have been associated with the material sisting of minor impurities such as nitrates called anomalous water (9), water II (17), or sulfates and is dependent on the method polywater (24), superwater (33), cyclimetrie of cleaning, etc. Other impurities occur more water (34), etc. This has been shown in part erratically, and are specific to a given labora- by Everett et al. (43) in their examination tory or a given preparation, such as the of some of the physical properties and in Journal of Colloid and Interface Science, ¥oi. 36, No. 4, August]1971

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459 I{EFERENCES

this paper by our examination of some of the spectroscopic properties. In addition to the a n a l y t i c a l r e s u l t s p r e s e n t e d here, a n u m b e r

of other authors, e.g., Rousseau and Porto (25), Rabideau and Florin (36), Davis (49), have shown that foreign materials not involving oxygen and hydrogen are present. The fact that the specific constituents vary a m o n g l a b o r a t o r i e s is p r o b a b l y i n d i c a t i v e of t h e i m p o r t a n c e of t r a c e i m p u r i t i e s in s y s t e m s j u d g e d " c l e a n or p u r e " b y m o r e c o n v e n t i o n a l s t a n d a r d s a n d is p r o b a b l y r e l a t e d to different cleaning a n d h a n d l i n g p r o c e d u r e s . W e h a v e n o t a t t e m p t e d in this p a p e r to a n s w e r t h e b a s i c q u e s t i o n : D o e s a n e w f o r m of w a t e r exist? A l t h o u g h we h a v e p r e s e n t e d o u r reasons for q u e s t i o n i n g t h e existence of " p o l y w a t e r , " s o m e of t h e p h e n o m e n a s u c h as d i s t i l l a t i o n r e p o r t e d b y D e r y a g i n et al. (17) a n d some of t h e t e c h n i q u e s e m p l o y e d b y t h a t g r o u p a p p e a r to b e i n c o n s i s t e n t w i t h

the types of impurities discussed here. It is apparent that larger quantities and additional analytical data would resolve this question unambiguously. ACKNOWLEDGMENTS The authors wish to thank Dr. Leslie E. Smith for carrying out some of the creep measurements. They also wish to thank Dr. John D. Hoffman for discussions and for his suggestions regarding tICO. as a possible source of carbon contamination. This work was supported in part by the Office of Saline Water and The National Science Foundation. ADDENDUM Since submission of this manuscript, several pertinent papers in areas discussed in this paper have been published or have come to the attention of the authors. All result in negative conclusions regarding the existence of a stable polymer of water. These include an article by Davis, Rousseau, and Board (59) which discusses the use of electron spectroscopy for chemical analysis to identify ions found in "polywater." This is a~ extension of the work reported in Ref. (49). Rousseau (51) has described the similarities between the infrared spectrum of "polywater" and that of sodium lactate. This contains the details of the information given as a private communication in (45). Allm~ and Kollman (52) have distributed a copy of a manuscript which describes the results of quantum-mechanical calculations.

1. FEDYAKIN, N. N., KoIloid Zh. 24, 497 (1962); translation in J. Coll. USSR 24,425 (1962). 2. FI~DYAKIN,N. N., Russ. J. Phys. Chem. 36, 776 (1962). 3. FEDYAKIN, N. N., DERY~GIN, B. V., NOVIKOW% A. V., ~ND TALXEV, M. V., Dokl. Akad. Nauk SSSR 165, 878 (1965); transl. Dokl. Phys. Chem. 165,862 (1965). 4. I)I~RYAGIN,B. V., TAk4.EV, M. V., AND FEDYAxxJ, N. N., Dokl. Akad. Nauk SSSR 165, 597 (1965); transl. DokI. Phys. Chem. 165, 807 (1965). 5. DERYAGIN, B. V., ERSEIOVA, I. O., ZIIELEZNYI, B. V., ~ND CHURAEV, N. V., Dold. Al~ad. Naul~ SSSR 170, 876 (1966); transl. Dokl. Phya. Chem. 170,635 (1966). 6. DEI%YAGIN, B. V., FEDYAKIN, N. N., AND TALAEV, M. V., Dok,1. Al~ad. Nauk SSSR 167, 376 (1966); transl. Doll. Phys. Chem. 167, (1966). 7. DERYAGIN~ B. V., EEDYAKIN~ N. ~., AND TAL£EV, M. V., J. Colloid Interface Sci. 24, 132 (1967). 8. ZHELEZNYI,B. V., Kolloid. Zh. 29, 493 (1967); transl. Colloid J. USSR 29, 367 (1967). 9. DERYAGIN, B. V., ~ND CttURAEY, N. V., Priroda (Moscow), 16-22 (1968); transl, in Joint Publications Research Service No. 45, p. 989 (1968). 10. K~RASEV,V. V., AND LUZIINOV,YU. M., Russ. J. Phys. Chem. 42, 1255 (1968). 11. SAVlTSXlI, A. N., Koll. Zh. 30, 119 (1968); translation in Colloid J. USSR 30, 90 (1968). 12. DERY~kGIN, B. V., LYOHNIKOV, D. S., MERZIIANOV~ ~ . i~/[.~ RA.BINOVICIt, YA. I., AND CHURAEV, N. V., Dokl. Akad. N a u k SSSR 181, 823 (1968); transl. Soy. Phys. Dokl. 13, 763 (1969); see also Mansfield, Trans. Faraday Soc. 66,341 (1970) and Ref. (17). 13. DEI~YAGIN,B. V., ZORIN, Z. M., ANI)CHURAEV, N. V., Dold. Al~ad. Nauk SSSR 182, 811 (1968); transl. Soy. Phys. Dokl. 13, 1030 (1969). 14. DERYAGIN, ]~. V., ZORIN, Z. M., I~AR.~SEV, V. V., SOBOLEV, V. D., KHROMOVA, E. N., AND CtIURAEV, N. V., Dokl. Akad. Naul~ SSSR 187, 605 (1969); transl. Dolcl. Chem. 187,496 (1969). 15. DERY.4.GIN,B. V., ZORIN, Z. M., RABINOVICH, YA. I., TALAEV,M. V., AND CI-IURAEV,N. V., Dokl. Akad. Naulc SSSR 191,859 (1970). 16. DERYAGIN, B. V., ZIIELEZNY,V. B., RAeINOVICIt, YA. I., SII~{ONOVA,V. KH., TALAEV, M. V., AND CHURAEV, N. V., Dokl. Akad. Naul~ SSSR 190,372 (1970).

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17. DERY~.INN, B. V., AND CHUR.(EV, N. V., " I n vestigation of the Properties of Water I I , " presented at ]~4th Nat. Colloid Syrup., Lehigh Univ. (1970); to be published in J. Colloid Sur. Chem. This paper presents a summary and review of the work by B. V. Deryagin et al., together with references to a number of their previous publications. 18. WILLIS, E., ]:~ENNIE, G. K., SMART, C., AND PET~ICA, B. A., Nature (London) 222, 159 (1969). 19. BELLAMY, L. J., OSBORN, A. E., LIPPINCOTT, E. R., AND BANDY, A. R., Chem. Ind. (London), 686 (1969). 20. CASTELLION,G. A., GRABAR,D. G., HESSION, J., AND BURK~ARD, H., Science 167, 865 (1970). 21. FABVSS, B. M., DOLMAN, A., SUSL±VICH, R., AND KEKIS, D., "Investigation of Anomalous Water," Office of Saline Water Res. and Develop. Report 558, Supt. Documents, U. S. Govt. Printing Office, Washington, D.C. 22. PAGE, T. A., JAKOBSEN, R., AND LIPPINCOTT, E. R., Science 167, 51 (1970). 23. PETSKO, G. A., Science 167,171 (1970). 24. LIPPINCOTT,E. R., STROMBERG, R. R., GRANT, W. H., A.NDCESSAC, G. L., Science 164, 1482

(1969). 25. RovssE~V, D. L., AND PORTO, S. P. S., Science 167, 1715 (1970). 26. HERTL, W., AND HAIR, IV[.L., Nature (London) 223, 1150 (1969). 27. MESSMER, 1~. P., Science 168,479 (1970). 28. BATES, J. D., LIPPINCOTT, E. R., MIKAWA, Y., AND JAKOBSEN, R. J., J. Chem. Phys. 52, 3731 (1970). 29. BOLA.NDER,R. W., KASSNER, J. L., A.NDZUNG, J. T., Nature (London) 221, 1233 (1969). 30. DONOHUE, J., Science 166, 1000 (1969). 31. LINNETT, J. W., Science 167, 1719 (1970). 32. 0'KONSKI, C. T., Science 168, 1089 (1970). 33. ElCLANDER, S. 1~., Phys. Rev. Lett. 22, 177 (1969) ; Phys. Rev. Abstr. 1 (1970). 34. ALLEN, L. C., AND KOLLMAN, P. A., Science 167, 1443 (1970). 35. ALLEN, L. C., AND KOLLMAN, P. A., J . Amer. Chem. Soc. 92, 4108 (1970).

36. RABIDEAU,S. W., AND FLORIN, A. E., Science 169, 48 (1970). 37. I~URTIN, S. L., MEAD, C. A., MUELLER, W. A., KURTIN, B. C., AND WOLF, E. D., Science 167, 1720 (1970). 38. Spectrosil is registered trademark of the Thermal American Fused Quartz Co., and Pyrex is a registered trademark of the Corning Glass Co. The use of such materials does not imply an endorsement by the National Bureau of Standards. The designation of the commercial product is given only to acquaint the reader with the specific nature of the materials used. 39. The authors thank A. Perloff and S. Block, National Bureau of Standards, for their X-ray analyses. 40. PAGE, T. F., AND JAKOBSEN, R. J., Battelle MeT. Inst., "Polywater and Polyorganics," Presented at $$th Nat. Colloid Syrup,, Lehigh Univ. (1970). 41. BRUMMER, S. B., COCKS, F. m., ENTINE, G., AND BRADSPIES, J. I., Paper presented at ]~th Nat. Colloid Symp. Lehigh Univ. (1970). 42. CHERKIN, A., Nature (London) 224, 1293 (1969). 43. EVERET% D. H., HAYNES, J. M., AND MCELnOY, P. J., Nature (London) 226, 1033 (1970). 44. The authors thank E. E. Hughes, National Bureau of Standards, for the mass-spectrometer analyses. 45. ROVSSEAU,D. L., private communication. 46. The authors thank K. F. Heinrich and R. L. Myklebust for the microprobe analyses and for the interpretation of the results. 47. WHITE, A., HANDLER, P., AND SMITH, E. L., "Principles of Biochemistry," 3rd Ed., pp. 707, 823. McGraw-Hill, 1964. 48. ROUSSEAU, D. L., Paper presented at ~$th Nat. Colloid Syrup. Lehigh Univ. (1970). 49. DAvis, R. L., Paper] presented at 4~th Nat. Colloid Syrup., Lehigh Univ. (1970). 50. DAvis, n. E., ROUSSEAU, D. L., AND BOARD~ R. D., Science 171,167 (1971). 51. ROUSSEAU, D. L., Science 171,170 (1971). 52. ALLEN, L. C., AND KOLLMAN, P. A., private communication.

Journal of Colloidand Interface Science, Vol. 36, No. 4, August 1971