Showing posts with label peroxide. Show all posts
Showing posts with label peroxide. Show all posts

Tuesday, February 16, 2010

The Strangest Liquid





Understanding what water is doing has been problematic forever.  This article outlines the full range of the anomalies.

I would like to throw another conjecture into this mix that is supported by the hard data that I have had to work with.  My conjecture is that all water is contaminated with biologically modified water that most likely takes the form of a ring molecule weakly bonded having the form H3 O3.   I have written on this before on this blog but also in my manuscript ‘Paradigm’s Shift’.  The molecule allows oxygen retention in biologically active water and explains the oxygen cycle available to marine life and land based wet environments.  It appears to run around one percent contained oxygen, but the extreme difficulty in measuring it has made it all but invisible.

It explains needle like crystals in freezing pond water.

It explains general oxygen availability in the marine environment that is not explained by seven parts per million at all.  The problem was recognized early on but appears to have been largely forgotten or at least ignored if not forgotten.

It explains the high noise threshold in spectrographic analysis which should otherwise reflect that of water.

It is chemically neutral unlike hydrogen peroxide, although easily unbound to release free oxygen and a spare hydrogen atom.

We have discovered that it is a powerful medical agent.

My conjecture is that the weirdness of water can be resolved once this molecular form is taken into account.

Inquiries are welcome from researchers who want samples to work with.


The strangest liquid: Why water is so weird

03 February 2010 by Edwin Cartlidge


We are confronted by many mysteries, from the nature of dark matter and the origin of the universe to the quest for a theory of everything. These are all puzzles on the grand scale, but you can observe another enduring mystery of the physical world - equally perplexing, if not quite so grand - from the comfort of your kitchen. Simply fill a tall glass with chilled water, throw in an ice cube and leave it to stand.
The fact that the ice cube floats is the first oddity. And the mystery deepens if you take a thermometer and measure the temperature of the water at various depths. At the top, near the ice cube, you'll find it to be around 0 °C, but at the bottom it should be about 4 °C. That's because water is denser at 4°C than it is at any other temperature - another strange trait that sets it apart from other liquids.
Water's odd properties don't stop there (see "Water's mysteries"), and some are vital to life. Because ice is less dense than water, and water is less dense at its freezing point than when it is slightly warmer, it freezes from the top down rather than the bottom up. So even during the ice ages, life continued to thrive on lake floors and in the deep ocean. Water also has an extraordinary capacity to mop up heat, and this helps smooth out climatic changes that could otherwise devastate ecosystems.

Yet despite water's overwhelming importance to life, no single theory had been able to satisfactorily explain its mysterious properties - until now. If we can believe physicists Anders Nilsson at Stanford University, California, and Lars Pettersson of Stockholm University, Sweden, and their colleagues, we could at last be getting to the bottom of many of these anomalies.

Their controversial ideas expand on a theory proposed more than a century ago by Wilhelm Roentgen, the discoverer of X-rays, who claimed that the molecules in liquid water pack together not in just one way, as today's textbooks would have it, but in two fundamentally different ways.

Key to the understanding of water's mysteries is the way its molecules - made up of two hydrogen atoms and one oxygen atom - interact with one another. The oxygen atom has a slight negative charge while the hydrogen atoms share a compensating positive charge. As such, the hydrogen and oxygen atoms of neighbouring molecules are attracted to one another, forming a link called a hydrogen bond.
Hydrogen bonds are far weaker than the bonds that link the atoms within molecules together, and so are continually breaking and reforming, but they are at their strongest when molecules are arranged so that each hydrogen bond lines up with a molecular bond (see diagram). The shape of a water molecule is such that each H2O molecule is surrounded by four neighbours arranged in the shape of a triangular pyramid - better known as a tetrahedron.

At least, that's the way the molecules arrange themselves in ice. According to the conventional view, liquid water has a similar, albeit less rigid, structure, in which extra molecules can pack into some of the open gaps in the tetrahedral arrangement.
That explains why liquid water is denser than ice - and it seems to fit the results of various experiments in which beams of X-rays, infrared light and neutrons are bounced off samples of water.
True, some physicists had claimed that water placed under certain extreme conditions may separate into two different structures (see "Extreme water"), but most had assumed it resumes a single structure under normal conditions.

Then, 10 years ago, a chance discovery by Pettersson and Nilsson called this picture into question. They were using X-ray absorption spectroscopy to investigate the amino acid glycine. The peaks in the X-ray absorption spectrum can shed light on the precise nature of the target substance's chemical bonds, and hence on its structure. Importantly, the researchers had got hold of a new, high-power X-ray source with which they were able to make more sensitive and accurate measurements than had ever been possible. They soon realised that the water containing their glycine sample was producing a far more interesting spectrum than the amino acid. "What we saw there was sensational," Nilsson recalls, "so we had to get to the bottom of it."
What we saw in the water was sensational, so we had to get to the bottom of it

Dramatic implications

 


The feature that sparked their interest was a peak in the absorption spectrum that is not predicted by the traditional model of liquid water. In fact, in a paper published in 2004 they concluded that at any given moment 85 per cent of the hydrogen bonds in water must be weakened or broken, far more than the 10 per cent predicted by the textbook model (Science, vol 304, p 995).

The implications of this finding are dramatic: it suggests that a total rethink of the structure of water is needed. So Nilsson and Pettersson turned to other X-ray experiments to confirm their claims. Their first move was to enlist the help of Shik Shin of the University of Tokyo, Japan, who specialises in a technique called X-ray emission spectroscopy. The key thing about these spectra is that the shorter the wavelength of the X-rays in a substance's emission spectrum are, the looser the hydrogen bonding must be.

The team struck gold: the spectrum of emitted X-rays included two peaks that might correspond to two separate structures. The spike of the longer-wavelength X-rays, the researchers argued, indicates the proportion of tetrahedrally arranged molecules, while the shorter-wavelength peak reflects the proportion of disordered molecules.
Importantly, the shorter-wavelength peak in the X-ray emissions was the more intense of the two, suggesting that the loosely bound molecules must be more prevalent within the sample - an assertion that fitted the team's previous models. What's more, they also found that this peak shifts to an even shorter wavelength as the water is heated, while the other peak remains more or less fixed (Chemical Physics Letters, vol 460, p 387).

That suggests that the hydrogen bonds connecting molecules arranged in a disordered way are more likely to loosen upon heating than those linking the more regularly arranged molecules - which again is what the team had predicted. They then reanalysed older experimental data that had seemed to support the traditional picture of water - and now argue that these results, too, are consistent with the new model.
If the team is right, another question arises: how large are the different structures within the liquid? To find out, they turned to the high-power X-rays generated at the Stanford Synchrotron Radiation Lightsource in California, this time measuring how water scatters rays arriving from various angles. The results, they say, reveal that water is dotted with small regions of tetrahedrally arranged molecules, each region being 1 to 2 nanometres across (Proceedings of the National Academy of Sciences, vol 106, p 15214).

Combined with further measurements carried out by Uwe Bergmann at Stanford University, they concluded that the ordered structures consisted of roughly 50 to 100 molecules, on average, surrounded by a sea of the more loosely bound molecules. These regions are not fixed, however. In less than a trillionth of a second, water molecules are thought to fluctuate between the two states as the hydrogen bonds break and reform.

Explaining the inexplicable

 


The changing balance between Nilsson and Pettersson's two types of water provides an explanation for the way water's density peaks at 4 °C. In the disordered regions, water molecules are more closely packed, making them denser than regions where the molecules are arranged in a tetrahedral structure. At 0 °C these disordered regions should be relatively uncommon, but as the water is warmed the extra heat energy tends to shake the more ordered structure apart, so molecules spend less time in the tetrahedral structure and more time in the disordered regions, making it more dense on average.
Counterbalancing this, the loosely bound molecules will move around more vigorously as the temperature rises, gradually forcing them further apart from each other. Once enough of the molecules become loosely bound - at 4 °C - this expansion effect will dominate, and the density will fall with increasing temperatures.
According to Pettersson, the theory offers equally tidy explanations for many of water's other previously inexplicable anomalies - something they say that no other theory can yet achieve (see "Water's mysteries"). Martin Chaplin, a chemist at London South Bank University, agrees. Explanations based on the conventional one-component system have to "go round the houses" to try to accommodate the maxima and minima in various properties as the temperature of water changes, he says. "The dual-structure idea is strongly supported by experiment and can explain water's anomalies far more readily than the conventional picture," Chaplin says.

Nilsson and Pettersson's 2004 paper in Science has now been cited over 350 times by other researchers. Yet many remain sceptical. One criticism is that the team's explanation of their X-ray spectroscopy results is based on simulations of at least 50 interacting water molecules - an immensely complex model that can only be resolved approximately. "We need a much more accurate theory in order to make such drastic claims," says Richard Saykally at the University of California, Berkeley.

He claims that minor adjustments to the arrangement of the hydrogen bonds in the conventional structure are enough to explain Nilsson and Pettersson's X-ray results.

One member of their group, Michael Odelius of Stockholm University, even left the collaboration because he disagreed with their interpretation of the X-ray emission data.

One detail that alienated many sceptics was an assertion in the 2004 paper that the more loosely bound molecules form rings and chains - and indeed Nilsson and his colleagues are now less specific about the structure of the disordered molecules. Eugene Stanley of Boston University, however, does not believe that this fatally damages the team's case. "I don't think they should be condemned forever," he says. Though their argument is not yet watertight, the X-ray scattering results provide "one more piece of supporting evidence", he says.

There is no doubt that Nilsson and Pettersson still face stiff opposition, but the rewards of a comprehensive understanding of the structure of liquid water could be considerable. It could lead to a better understanding of how drugs and proteins interact with water molecules within the body, for example, and so provide more effective medicines. And by giving us a better idea of how water behaves around narrow pores, it might improve water desalination attempts and so increase access to clean water.
"Our understanding of water is an evolving picture," Pettersson says. "Further research by many different groups is needed before this exciting and important journey can end." With so much to gain, who could disagree?

Extreme water

 

The dual structure of water proposed by Anders Nilsson of Stanford University, California, and Lars Pettersson of Stockholm University in Sweden may be a ghostly echo of the strange properties of "supercool" water - water that has been cooled to below 0 °C without freezing.
Eugene Stanley of Boston University and his colleagues have long claimed that at temperatures below about -50 °C and pressures of more than 1000 times atmospheric pressure, distinct high and low-density forms of supercool water should exist. Several research groups claim they have found evidence for these two structures.
Stanley, however, believes there should be small but discernible traces of this behaviour at higher temperatures too - seen as fluctuations in water's density. Sure enough, the size of the fleeting high and low-density regions seen in Nilsson and Pettersson's X-ray scattering experiments are consistent with his theory's predictions.
However, physicist Alan Soper at the Rutherford Appleton Laboratory in Oxfordshire in the UK is not convinced that these density differences are anything other than the density fluctuations that can occur in any liquid.

The crux of this dispute concerns the precise statistical distribution of regions of different density. According to Nilsson and Pettersson's model, there should be two peaks at two distinctly different densities, but Soper believes only one continuous distribution is possible.
Edwin Cartlidge is a journalist based in Rome, Italy. To enjoy more stunning images of water in motion by Shinichi Maruyama, visit his website:



Scientists Freeze Water with Heat
By Charles Q. Choi, LiveScience Contributor

posted: 11 February 2010 08:30 am ET

Imagine water freezing solid even as it's heating up. Such are the bizarre tricks scientists now find water is capable of.

Popular belief contends that water freezes at 32 degrees Fahrenheit (0 degrees Celsius). Surprisingly, if water lies in a smooth bottle and is free of any dust, it can stay liquid down to minus 40 degrees F (minus 40 degrees C) in what's called "supercooled" form. The dust and rough surfaces that water is normally found in contact with in nature can serve as the kernels around which ice crystals form.

Now researcher Igor Lubomirsky at the Weizmann Institute of Science in Rehovot, Israel, and his colleagues have discovered another way to control the freezing point of water — via what are called quasi-amorphous pyroelectric thin films. These surfaces change their electrical charge depending on their temperature.

When pyroelectic surfaces are positively charged, water becomes easier to freeze, and when they have a negative charge, it becomes harder to freeze.

The researchers saw that supercooled water could freeze as it's being heated, as long as the temperature changes the surface charge as well. For instance, when supercooled water is on a negatively charged lithium tantalate surface, it will freeze solid immediately when the surface is heated to 17.6 degrees F (minus 8 degrees C) and its charge switches to positive.

Curiously, positively charged surfaces inspire supercooled water to freeze from the bottom up, while negatively charged surfaces cause it to freeze from the top down. This likely has to do with how water molecules orient themselves — the negatively charged oxygen atoms in water molecules naturally point toward positively charged surfaces, while the reverse is true with hydrogen atoms.

"The difference between the positive and negative charge was unexpected," Lubomirsky said.

The ability to better control the freezing temperature of supercooled water could be critical for a variety of applications, including the survival of cold-blooded animals, the cryo-preservation of cells and tissues, the protection of crops from freezing, and the ability to understand and trigger cloud formation.

The scientists detailed their findings in the Feb. 5 issue of the journal Science.

Wednesday, April 8, 2009

Hydrogen Breakthrough

This is a major development in the hydrogen story. Suddenly we can use solar energy to directly produce both hydrogen and oxygen from water while keeping them separate. Plants are unable to do this because they produce the oxygen by consuming the hydrogen. Up to now, when the question of producing hydrogen came up at all we were treated to a hand wave because we had no satisfactory solution protocols that did not entail huge energy expenditures.

This breakthrough needs a quick work up on a practical production tool, just to get a handle on the practical issues involved. It sounds extremely promising at this point.

The light step is using very little energy to succeed in producing free oxygen that can then be removed. The concentrated hydrogen is liberated by the solution been heated to 100C. so the energetics of the system calls for a solution circulating between room temperature and 100C in concert with a heat exchanger while absorbing sunlight to release the oxygen. It is efficient on paper but sounds a lot like refrigeration.

However, it surely will be massively efficient compared to the cost of electrolysis that has crippled the use of hydrogen from the beginning.

Having a simple and cheap mechanism for the production of both hydrogen and oxygen from water is a huge boon to industrial process. Metallurgy particularly will be revolutionized as pure oxygen substitutes the present regimes. We are going to see factories using this technology to produce the two gases on a massive scale.

Even if we never use hydrogen as a transportation fuel and there is good reason not to, we can use massive amounts in industry itself were transporting the cgas is not an issue.

Unique Approach For Splitting Water Into Hydrogen And Oxygen

http://www.energy-daily.com/reports/Unique_Approach_For_Splitting_Water_Into_Hydrogen_And_Oxygen_999.html

http://www.energy-daily.com/images/hydrogen-bonding-water-h2o-molecule-bg.jpg



The new approach that the Weizmann team has recently devised is divided into a sequence of reactions, which leads to the liberation of hydrogen and oxygen in consecutive thermal- and light-driven steps, mediated by a unique ingredient - a special metal complex that Milstein's team designed in previous studies.


by Staff Writers
Rehovot, Israel (SPX) Apr 07, 2009

The design of efficient systems for splitting water into hydrogen and
oxygen, driven by sunlight is among the most important challenges facing science today, underpinning the long term potential of hydrogen as a clean, sustainable fuel.

But man-made systems that exist today are very inefficient and often require additional use of sacrificial chemical agents. In this context, it is important to establish new mechanisms by which water splitting can take place.

Now, a unique approach developed by Prof. David Milstein and colleagues of the Weizmann Institute's Organic Chemistry Department, provides important steps in overcoming this challenge. During this work, the team demonstrated a new mode of bond generation between oxygen atoms and even defined the mechanism by which it takes place.

In fact, it is the generation of oxygen gas by the formation of a bond between two oxygen atoms originating from water molecules that proves to be the bottleneck in the water splitting process. Their results have recently been published in Science.

Nature, by taking a different path, has evolved a very efficient process:
photosynthesis - carried out by plants - the source of all oxygen on Earth.

Although there has been significant progress towards the understanding of photosynthesis, just how this system functions remains unclear; vast worldwide efforts have been devoted to the development of artificial photosynthetic systems based on metal complexes that serve as
catalysts, with little success. (A catalyst is a substance that is able to increase the rate of a chemical reaction without getting used up.)

The new approach that the Weizmann team has recently devised is divided into a sequence of reactions, which leads to the liberation of hydrogen and oxygen in consecutive thermal- and light-driven steps, mediated by a unique ingredient - a special metal complex that Milstein's team designed in previous studies.

Moreover, the one that they designed - a metal complex of the element ruthenium - is a 'smart' complex in which the metal center and the organic part attached to it cooperate in the cleavage of the water molecule.

The team found that upon mixing this complex with water the bonds between the hydrogen and oxygen atoms break, with one hydrogen atom ending up binding to its organic part, while the remaining hydrogen and oxygen atoms (OH group) bind to its metal center.

This modified version of the complex provides the basis for the next stage of the process: the 'heat stage.' When the water solution is heated to 100 degrees C, hydrogen gas is released from the complex - a potential source of clean fuel - and another OH group is added to the metal center.

'But the most interesting part is the third 'light stage,'' says Milstein. 'When we exposed this third complex to light at room temperature, not only was oxygen gas produced, but the metal complex also reverted back to its original state, which could be recycled for use in further reactions.'

These results are even more remarkable considering that the generation of a bond between two oxygen atoms promoted by a man-made metal complex is a very rare event, and it has been unclear how it can take place. Yet Milstein and his team have also succeeded in identifying an unprecedented mechanism for such a process.

Additional experiments have indicated that during the third stage, light provides the energy required to cause the two OH groups to get together to form hydrogen peroxide (H2O2), which quickly breaks up into oxygen and water. 'Because hydrogen peroxide is considered a relatively unstable molecule, scientists have always disregarded this step, deeming it implausible; but we have shown otherwise,' says Milstein.

Moreover, the team has provided evidence showing that the bond between the two oxygen atoms is generated within a single molecule - not between oxygen atoms residing on separate molecules, as commonly believed - and it comes from a single metal center.

Discovery of an efficient artificial catalyst for the sunlight-driven splitting of water into oxygen and hydrogen is a major goal of renewable clean energy research.

So far, Milstein's team has demonstrated a mechanism for the formation of hydrogen and oxygen from water, without the need for sacrificial chemical agents, through individual steps, using light. For their next study, they plan to combine these stages to create an efficient catalytic system, bringing those in the field of alternative energy an important step closer to realizing this goal.

Participating in the research were former postdoctoral student Stephan Kohl, Ph.D. student Leonid Schwartsburd and technician Yehoshoa Ben-David all of the Organic Chemistry Department, together with staff scientists Lev Weiner, Leonid Konstantinovski, Linda Shimon and Mark Iron of the Chemical Research Support Department.

Prof. David Milstein's research is supported by the Mary and Tom Beck-Canadian Center for Alternative Energy Research; and the Helen and Martin Kimmel Center for Molecular Design. Prof. Milstein is the incumbent of the Israel Matz Professorial Chair of Organic Chemistry.