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Proposed structure of polywater, from [122c]

 

proposed structure of polywater [Lippincott et al, Science 164 (1969) 1482], later proven mistaken

Polywater, 'Declustered Water' and Other Waters

An assessment of so-called polywater, declustered and anomalous water and other such waters claimed to have unusual properties.

 

V Polywater
V EZ water
V IE

V HHO
V Neowater
V Clustered and 'declustered' water

Polywater

'I regard this polymer as the most dangerous material on earth'

 

One of the difficulties in putting forward novel ideas for the structure of water is that the scientific press has been mistaken before and prefers to shuffle forward in the almost known rather than take big steps into the less well known.

 

 

Polywater in 25-µ capillary tube, from [122d]

 

 polywater in 25 micron capillary tube, from Everett et al Nature 226 (1970) 1033
The first water-related mischance, that the scientific literature fell into, concerned polywater (see left small droplets made in a similar manner, < 0.1 µg, in 25 µm diameter capillary tube, originally called anomalous water, modified water or super water) with a wave of over 500 publications between 1962 and 1974. The polywater was reported to be a dense (> 1.3 g cm-3), high boiling ~(200 °C) and viscous (20 ˣ increased) form of 'polymeric' water. It was first quietly reported by the Russian Fedyakin in 1962, to spontaneously form by condensation in narrow (< 20 μm) sealed capillaries even after great care had been made to keep the apparatus very clean and the water very pure [122]. It was not formed by simply placing the water in the tubes, even if the temperature is raised. Particularly remarkable properties were that the material was more stable than 'normal' water and could be removed from the glass capillaries and the eccentric properties continued even after further boiling and condensation. There were many scientific meetings, great media interest and widely published supporting papers on the phenomenon, including publications in the most prestigious journals Nature, and Science in 1969-1970. Also, the ideas had been given momentum from the populist media and continuing support of the well-respected, honorable and careful, scientists, the American Ellis Lippincott and the Russian Boris Deryagin.

 

'Good news: The U.S. has apparently closed the polywater gap, and the Pentagon is bankrolling efforts to push this country's polywater technology ahead of the Soviet Union's'

 

 

Polywater by Franks [122e]

 

Polywater by Franks
As only micrograms of material were available, it was challenging to chemically analyze the 'polywater', but when analyses became available it was shown to contain unforeseen impurities [123]. The New York Times then made unsubstantiated (and very unlikely concerning the original experiments but possible with later rushed preparations made solely for analysis) claims that human sweat contamination caused the effects. However, some samples contained just silica, dissolution of which was not anticipated at that time as quartz vessels were known to hold water without noticeable dissolution. d There were also delays in analyzing the polywater samples due to the minuscule volumes available (< μg) and consequentially low silica contents (< 10-4 μg as then determined). General recognition that the properties of anomalous water were due to impurities (and not a new compound of H and O) was not before it had generated a considerable theoretical literature, both for and, less embarrassingly particularly early on, against. As computers and theory became more powerful, it additionally became clear that there was no theoretical support for the hexagonal structuring proposed for 'polywater' (see top right). After it became clear that 'polywater' was not a polymer of water alone but also was not a product of careless experimental work, many scientists, who should have known better, offered their derisive hindsight.

 

'the concept of polywater is on its last legs'

 

There was a positive outcome to this work in that it did stimulate much work on water at that time and showed the importance of materials dissolved from water containers. However, the episode seems to be usually remembered with discomfiture and that has probably reduced the publications concerned with water structure over the subsequent few years with many young scientists avoiding the area to steer clear of any similar pitfall or ridicule. Since then, high-density liquid water has been verified to exist (at low temperatures [16]), but this is unrelated to any of the polywater samples. Polywater is still researched but on the basis of the properties of surfaces and concentrated electrolyte silica condensates.

 

Fourth phase of water

EZ water

 

Hexagonal structure

from Pollack's book

 

hexagonal structure fromPollacks book
Almost identical structures (see right) to 'polywater' (see top right of page) have recently been re-introduced as support for Pollack's self-published 'The fourth phase of water' and variously related exclusion zone (EZ) water papers [2077]. These, however, appear to be equally as unlikely as the original polywater and similarly disregard current basic and well accepted scientific concepts. See also for further information.

 

Likewise, an 'ice' (presented as pure water that is solid at ambient temperatures and pressures but with no structural information) prepared at room temperature by a substantial sequence of filtration through glass filters [2166], or by other similar methods from the same authors and also published in Pollack's journal, appears to be due to dissolved impurities, that apparently were not subjected to full and proper analyses. d [Back to Top to top of page]

IE

More recently than polywater, IE (ice formed by electric field forces) crystals (mm ˣ 100 nm diameter) have been proposed to form around ions due to their electric field [124, 125a c e]. It is also proposed that these 'spherically symmetrical crystals' can be broken by shaking to seed further crystal formation, although this seems more likely to cause the loss of water molecules from the surface (peeling) rather than the release of fragments. The ions must be dilute (< 10-5 M) to prevent ions 'interacting' (reducing the electric field gradient) before crystals have time to form. The crystals are proposed to have 20% lower dielectric than water. These IE crystals are now thought to be completely artifactual with the term 'crystals' now being replaced by 'water clusters'. Even with this change, these theories have not been confirmed [125b d] and are not generally accepted and no ice phase is formed above 0 °C below 632 MPa. The presence of extensive hydrogen-bonded clusters in less-than-pure water containing additional hydrophobic solutes, however, is quite reasonable. [Back to Top to top of page]

HHO

Also recently promoted is 'HHO' a material produced from water by electrolysis that is supposedly different of the expected electrolytic mixture. b This process supposedly breaks the (inviolable) laws of thermodynamics and is backed by a paper that is full of scientific and numerical errors [938]. The claims for this material (that is, HHO) should be examined with great care, and are now correctly reported as totally erroneous [938b], although this is disputed [938c]. [Back to Top to top of page]

Neowater

An interesting development was the sale of 'neowater' (water containing a minute amount of nano-sized, 10-50 nm, particles of barium titanate) for various biotechnological processes. It was suggested that the particles organize the surrounding water and stabilize gaseous nanobubbles (more properly called nanocavities) resulting in the change in the liquid's properties. Scientific support for this was beginning to appear [1129, 1172], when the company ceased trading. [Back to Top to top of page]

Clustered and 'declustered' water

 

Very recently there has been an explosion of Internet sites and sales outlets concerned with 'declustered' water and its production. Generally, these concern the promotion and sale of relatively expensive water preparations for their (supposed) health benefit. These appear to be related to Lorenzen's 'microclustered' water [164] or Hayashi's 'microwater' [111]. Lorenzen prepared such water by passing steam across a magnetic field a (using magnetite), exposing it to light/radiation with a wavelength between 610 nm and 1 mm (preferably monochromatic at 640 nm) and adding materials such as 3 - 4 ppm metasilicate, up to 1% yeast cells and gas under pressure. His patents claim such water may be diluted by between 103 and 1020 times. A similar product (Willards water) also uses silicates and surfactants [193], whereas 'Penta' water uses acoustical cavitation and oxygen saturation [496]. Hayashi prepared his water by electrolysis b using the reduced and oxidized streams for different purposes. Although cluster size can be determined from the shift in the 17O NMR resonance signal in line with its reduction with increasing temperature, in some cases it seems to have been determined by means of changes in the width (at half peak height) of the 17O NMR resonance signal from above 100 Hz to below 100 Hz. Other conditions being equal this width is expected to give a measure of the strength of the clustering as motionally-hindered water has faster relaxation kinetics and hence should give a greater 17O NMR resonance signal width (for example, the width also decreases with increasing temperature). However, these samples are not pure water samples as they have high (supersaturated) gas concentrations and may contain other additives. The widths do not appear to change reproducibly as Hayashi reports a width for impure water of 105 Hz but Lorenzen reports the width for distilled and triple distilled water as higher at 130 Hz and 115 Hz respectively.

 

Unfortunately, the data reported by Lorenzen and Hayashi is sparse and does not include any statistical data or precise experimental conditions. Also, there does not seem to be sufficient other data reported in the literature concerning the effect of solutes on the width of this resonance or its reproducibility. Other uncontrolled factors, such as pH, will also have a major effect. Independent NMR analysis [1516] fails to confirm any useful correlation with structure. Nor is there any unanimity on what cluster size any reduction in the width might indicate. Other unanswered questions concern (a) whether it is the strength or extent of the hydrogen bonding that is important, (b) if the extent is important, is it the mean number of hydrogen bonds that each water molecule participates in or the mean cluster size of fully satisfied hydrogen-bonded water molecules that is important? (c) if strength is important, is it the mean strength of all the bonds around a water molecule or only the strongest of these? (d) what is the effect of the distribution of hydrogen bond strengths (or extents)? and (e) how long do any effects last? c More importantly, controlled clinical trials are lacking so that all sales patter extolling the health-giving virtue of such water involves the (scientifically irrelevant and basically biased) use of testimonials.

 

In the light of the increased promotion of 'special' water preparations, it is important to take notice that there are definite and proven health benefits from simply drinking more water (within reason). [Back to Top to top of page]


Footnotes

a   It has been shown that a high magnetic field has an insignificant effect on the equilibrium content of dissolved oxygen (< 0.3 mM at 20 °C under atmospheric conditions) but does significantly enhance its dissolution rate [176]. High electric fields (E ~109 V m-1) reduce water's permittivity [616], which will increase the solubility of gases. Water may be supersaturated with oxygen (~3-6 mM; equivalent to less than a breath of air in each liter of supersaturated water) under pressure. It should be noted that, left by itself, degassed water may take days to re-equilibrate with atmospheric gases and as even small amounts of dissolved gases are reported to have relatively large effects on the structuring of water [560], it is not unreasonable to suppose that artificially induced metastable conditions with higher gas content may last for some time. Drinking of oxygenated water does give a transient moderate increase in serum ascorbyl radicals (with unknown consequences), an effect that disappears with regular consumption [422]. It will not, however, significantly add to the body's oxygen intake and has no apparent harmful or health-promoting effects [772]. Production of singlet oxygen (1O2;1Δg+, electrons paired in their π-antibonding molecular orbitals, compare 3O2, normal triplet oxygen, 3Σg-, where two electrons are in equivalent but separate π-antibonding orbitals with the same unpaired spin) during processing may cause the dissolved peroxide concentration to increase via the water-catalyzed reaction (x.1O2+2H2O->(1–x).3O2+2H2O2) [1199] with possible consequential pharmacological effects. Interestingly singlet oxygen takes part in antibody-catalyzed water oxidation similarly producing triplet oxygen and hydrogen peroxide [624]. However, as the lifetime of the singlet oxygen is expected to be in the μs range when dissolved upwards towards 45 min in the (low pressure) gas phase, singlet oxygen molecules are not expected to remain in the processed bottled water. [Back]

 

b   At the electrolytic electrodes, water molecules are oriented, hydrogen bonds are broken and water‘s reactivity is increased. Anodic water (oxidizing, from the positive electrode) is biocidal and acidic and may contain H2O2, ·O2-, ·OH, 1O2, plus HOCl and Cl2 if NaCl is present. Cathodic water (reducing, from the negative electrode) has been used for washing and sanitizing [1277] and may be alkaline and contain H2. Such H2 may form a supersaturated solution and be present in nanobubbles (10-1000 nm diameter nanocavities) stabilized by salts (for example, Na+ and Cl-) present [974]. Extensive electrolysis will also change the isotope ratio which may have an effect [424]. [Back]

 

c   There is one report that magnetically treated water (also from the same laboratory, electromagnetically treated water) retains a significantly changed effect on fungal spore germination for at least 24 hours [174]; however other parameters (for example, reduced dissolved oxygen levels) may be responsible for such effects. Mechanically-induced hydrogen bond breakage, caused by shaking (succussion) when producing homeopathic solutions, has been reported to last for weeks [336]. [Back]

 

d   We now understand that silica glasses may dissolve in water to a small extent (~µM) and that they cannot be washed clear of this dissolving material. Also, the presence of dissolved material seems to catalyze further dissolution. However, the extra solubility due to the presence of water vapor remains a puzzle. On partial drying, these solutions form water-containing silica glasses. Other highly hydrophilic polymers may also form gels containing high percentages (> 99%) of water. [Back]

 

 

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