THE FOURTH PHASE OF WATER
BEYOND SOLID, LIQUID, AND VAPOR
by GERALD H. POLLACK
"to Gilbert Ling
who taught me that water in the cell
is nothing like water in a glass;
whose courage has been a
continuing inspiration."
Our specific goal is to understand water. Water now seems complicated. The understanding of everyday phenomena often requires complex twists and non-intuitive turns — and still we fail to reach satisfying understandings. A possible cause of this unsatisfying complexity is the present foundational underpinning: an ad hoc collection of long-standing principles drawn from diverse fields. Perhaps a more suitable foundation — built directly from studying water — might yield simpler understandings. That’s the direction we’re headed.
To read this book, you needn’t be a scientist; the
book is designed for anyone with even the most
primitive knowledge of science. If you understand
that positive attracts negative and have heard of
the periodic table, then you should be able to get
the message. On the other hand, those who might
thumb their noses at anything that seriously
questions current dogma will certainly find the
approach distasteful, for threads of challenge
weave through the book’s very fabric. This book
is unconventional —a saga filled with steamy
scenes and unexpected twists, all of which
resolve into something I hope you will find
satisfying, and perhaps even fun to read.
I have restricted formal references to those
instances in which citations seemed absolutely
necessary. Where the point is generally known or
easily accessible, I’ve omitted them. The
overarching goal was to streamline the text for
readability.
Finally, let me admit to having no delusion that
all of the ideas offered here will necessarily turn
out to be ground truth. Some are speculative. I
have certainly aimed at producing science fact,
not science fiction. However, as you know, even
a single ugly fact can demolish the most beautiful
of theories. The material in this book represents
my best and most earnest attempt to assemble the
available evidence into a cohesive interpretational
framework. The framework is unconventional,
and I already know that some scientists do not
agree with all aspects. Nevertheless, it is a
sincere attempt to create understanding where
little exists.
So, as we plunge into these murky waters, let us
see if we can achieve some needed clarity.
THE FOURTH PHASE OF WATER
BEYOND SOLID, LIQUID, AND VAPOR
by GERALD H. POLLACK
(GHP)
Seattle, September 2012
Discovery consists of seeing what everybody has
seen and thinking what nobody has thought.
-- Albert Szent-Györgyi, Nobel laureate (1893-1986)
A BESTIARY
A reader's guide to the species that lurk within
the mysterious aqueous Domain.
Water Molecule: The familiar water molecule,
composed of two hydrogen atoms and one
oxygen atom.
Bulk Water : The standard collection of water
molecules, whose arrangement is still debated.
Ever wonder…
What mysteries lurk in the depths of a glass of
water? What makes the wispy clouds of vapor
rising from your cup of hot coffee? Or the puffy
white clouds hovering in the sky? Why do the
bubbles in your pop get bigger the longer you
wait? What keeps Jell-O’s water from oozing
out? Why does your tongue stick to something
frozen? And why don’t your joints squeak?
Questions such as those have remained
unanswered not only because they have seemed
complex, but also because they require that
scientists pursue a politically risky domain of
science: water research.
Scientists trying to understand the “social
behavior” of H20 do so at grave risk to their
reputations and livelihoods because water
science has suffered repeated fiascos. Water
scientists have been virtually tarred and feathered.
Undaunted, one scientist has navigated the perils
of water science by conducting dozens of simple,
carefully controlled experiments and piecing
together the first coherent account of water’s
three dimensional structure and behavior.
Professor Pollack takes us on a fantastic voyage
through water, showing us a hidden universe
teeming with physical activity that provides
answers so simple that any curious person can
understand. In conversational prose, Pollack
relentlessly documents just where some scientists
may have gone wrong with their Byzantine
theories, and instead lays a simple foundation for
understanding how changes of water structure
underlie most energetic transitions of form and
motion on Earth.
Pollack invites us to open our eyes and re-
experience our natural world, to take nothing for
granted, and to reawaken our childhood dream of
having things make sense.
Professor Gerald Pollack is Founding Editor-in-
Chief of the scientific journal, WATER and is
recognized as an international leader in science
and engineering.
The University of Washington Faculty chose
Pollack, in 2008, to receive their highest annual
distinction: the Faculty Lecturer Award. He was
the 2012 recipient of the coveted Prigogine
Medal for thermodynamics of dissipative
systems. He has received an honorary doctorate
from Ural State University in Ekaterinburg,
Russia, and was more recently named an
Honorary Professor of the Russian Academy of
Sciences, and Foreign Member of the Srpska
Academy. Pollack is a Founding Fellow of the
American Institute of Medical and Biological
Engineering and a Fellow of both the American
Heart Association and the Biomedical
Engineering Society. He recently received an
NIH Director’s Transformative R01 Award for
his work on water, and maintains an active
laboratory in Seattle.
Pollack’s interests have ranged broadly, from
biological motion and cell biology to the
interaction of biological surfaces with aqueous
solutions. His 1990 book, Muscles and
Molecules: Uncovering the Principles
of Biological Motion, won an “Excellence
Award” from the Society for Technical
Communication; his subsequent book,
Cells, Gels and the Engines of Life,
won that Society’s “Distinguished Award.”
Pollack is recognized worldwide as a dynamic
speaker and a scientist willing to challenge any
long-held dogma that does not fit the facts.
Water 'Exclusion Zone' (EZ): The “exclusion zone”
(EZ), the unexpectedly large zone of water that
forms next to many submersed materials, got its
name because it excludes practically everything.
The EZ contains a lot of charge, and its character
differs from that of bulk water. Sometimes it is
referred to as water’s fourth phase.
Electron and Proton : Electrons and protons are
the elementary units of charge. They attract one
another because one is positive and the other is
negative. Electrons and protons play central
roles in water’s behavior — more than you
might think.
Water Molecule Charge : The water molecule is
neutral. Oxygen has a charge of minus two, while
each of the hydrogen atoms has a plus one
charge. H2O net charge = 0
Hydronium Ion : Protons latch onto water
molecules to form hydronium ions. Imagine a
positively charged water molecule and you’ve
got a hydronium ion. Charged species like
hydronium ions are highly mobile and can
wreak much havoc. H3O+.
Interfacial Battery : This battery comprises the
exclusion zone and the bulk water zone beyond.
The respective zones are oppositely charged,
and the separation is sustained, as in an ordinary
battery.
Radiant Energy : Radiant energy charges the
battery. The energy comes from the sun and other
radiant sources. The water absorbs these energies
and uses them to charge the battery.
Honeycomb Sheet : The honeycomb sheet is the
EZ’s unitary structure. Sheets stack parallel to
the material surface to build the EZ.
Ice : The atomic structure of ice closely
resembles the atomic structure of the exclusion
zone. This similarity is beyond coincidence:
one transforms readily into the other.
Droplet : The water droplet consists of an EZ
shell that envelops bulk water. The two
components have opposite charges.
Bubble : The bubble is structured like the droplet,
except that it has a gaseous interior. Commonly,
that gas is water vapor.
Vesicle : Since droplets and bubbles are similarly
constructed, we introduce the generic label:
vesicle. A vesicle can be a droplet or a bubble,
depending on the phase of the water inside.
When a droplet absorbs enough energy, it can
become a bubble.
SECTION I
Water Riddles: Forging the Pathway
1 . Surrounded by Mysteries
Beaker in hand, two students rushed down the
hall to show me some thing unexpected.
Unfortunately, their result vanished before I
could take a look. But it was no fluke. The next
day the phenomenon reappeared, and it became
clear why the students had reacted with such
excitement: they had witnessed a water-based
phenomenon that defied explanation.
Water covers much of the earth. It pervades the
skies. It fills your cells — to a greater extent than
you might be aware. Your cells are two-thirds
water by volume; however, the water molecule is
so small that if you were to count every single
molecule in your body, 99% of them would be
water molecules. That many water molecules are
needed to make up the two-thirds volume. Your
feet tote around a huge sack of mostly water molecules.
What do we know about those water molecules?
Scientists study them, but rarely do they concern
themselves with the large ensembles of water
molecules that one finds in beakers. Rather, most
scientists focus on the single molecule and its
immediate neighbors, hoping to extrapolate what
they learn to larger-scale phenomena that we can
see. Everyone seeks to understand the observable
behavior of water, i.e., how its molecules act
“socially.”
Do we really understand water’s social behavior?
Since water is everywhere, you might reasonably
conclude that we understand it completely. I
challenge you to confirm that common
presumption. Below, I present a collection of
everyday observations, along with a handful of
simple laboratory observations. See if you can
explain them. If you can, then I lose; you may
stop reading this book. If the explanations remain
elusive even after consulting the abundant
available sources, then I ask you to reconsider
the presumption that we know everything there
is to know about water.
I think we don’t. Let’s see how you fare.
Everyday Mysteries
Here are fifteen everyday observations. Can you
explain them?
• Wet sand vs. dry sand. When stepping into dry
sand, you sink deeply, but you hardly sink into the
wet sand near the water’s edge. Wet sand is so
firm that you can use it for building sturdy castles
or large sand sculptures. The water evidently
serves as an adhesive. But how exactly does water
glue those sand particles together? (The answer is
revealed in Chapter 8.)
• Ocean waves. Waves ordinarily dissipate after
traveling a relatively short distance. However,
tsunami waves can circumnavigate the Earth
several times before finally petering out. Why do
they persist for such immense distances? (See Chapter 16.)
• Gelatin desserts. Gelatin desserts are mostly
water. With all that water inside, you’d expect a
lot of leakage (Fig. 1.1). However, none occurs.
Even from gels that are as much as 99.95% water,
[1] we see no dribbling. Why doesn’t all that
water leak out? (Read Chapters 4 and 11.)
(Fig. 1.1 What keeps the water from dribbling out
of the Jell-O?)
• Diapers. Similar to gels, diapers can hold lots of
water: more than 50 times their weight of urine
and 800 times their weight of pure water. How
can they hold so much water? (Look at Chapter 11.)
• Slipperiness of ice. Solid materials don’t usually
slide past one another so easily: think of your
shoes planted on a hilly street. Friction keeps you
from sliding. If the hill is icy, however, then you
must exercise great care to keep from falling on
your face. Why does ice behave so differently
from most solids? (Chapter 12 explains.)
• Swelling. Your friend breaks her ankle during a
tennis match. Her ankle swells to twice its normal
size within a couple of minutes. Why does water
rush so quickly into the wound? (Chapter 11
offers an answer.)
• Freezing warm water. A precocious middle-
school student once observed something odd in
his cooking class. From a powdered ice cream
mix he could produce his frozen treat faster by
adding warm water instead of cold water. This
paradoxical observation has become famous.
How is it that warm water can freeze more
rapidly than cold water? (See Chapter 17.)
• Rising water. Leaves are thirsty. In order to
through evaporation in plants and trees, water
flows upward from the roots through narrow
columns. The commonly offered explanation
asserts that the tops of the columns exert an
upward drawing force on the water suspended
beneath. In 100-meter-tall redwood trees,
however, this is problematic: the weight of the
water amassed in each capillary would suffice to
break the column. Once broken, a column can no
longer draw water from the roots. How does
nature avert this debacle? (Check out Chapter 15.)
• Breaking concrete. Concrete sidewalks can be
cracked open by upwelling tree roots. The roots
consist mainly of water. How is it possible that
water-containing roots can exert enough pressure
to break slabs of concrete? (Look through Chapter
12.)
• Droplets on surfaces. Water droplets bead up on
some surfaces and spread out on others. The
degree of spread serves, in fact, as a basis for
classifying diverse surfaces. Assigning a
classification, however, doesn’t explain why the
droplets spread, or how far they spread. What
forces cause a water droplet to spread? (Go to
Chapter 14.)
• Walking on water. Perhaps you’ve seen videos
of “Jesus Christ” lizards walking on pond
surfaces. The lizards scamper from one end to
the other. Water’s high surface tension comes to
mind as a plausible explanation, but if surface
tension derives from the top few molecular layers
only, then that tension should be feeble. What is
it about the water (or about the lizard) that
makes possible this seemingly biblical feat?
(Read Chapter 16.)
• Isolated clouds. Water vapor rises from vast
uninterrupted reaches of the ocean’s water. That
vapor should be everywhere. Yet puffy white
clouds will often form as discrete entities,
punctuating an otherwise clear blue sky (Fig.
1.2). What force directs the diffuse rising vapor
towards those specific sites? (Chapters 8 and 15
consider this issue.)
• Squeaky joints. Deep knee bends don’t
generally elicit squeaks. That’s because water
provides excellent lubrication between bones
(actually, between cartilage layers that line the
bones). What feature of water creates that
vanishingly small friction? (Take a look at
Chapter 12.)
• Ice floats. Most substances contract when
cooled. Water contracts as well — until 4 °C.
Below that critical temperature water begins
expanding, and very much so as it transitions to
ice. That’s why ice floats. What’s special about
4 °C; and, why is ice so much less dense than
water? (Chapter 17 answers these questions.)
• Yoghurt’s consistency. Why does yoghurt hold
together as firmly as it does? (See Chapter 8.)
Mysteries from the Laboratory
I next consider some simple laboratory
observations, beginning with the one seen by
those students rushing down the hall to show me
what they’d found.
(i) The Mystery of the Migrating Microspheres
The students had done a simple experiment. They
dumped a bunch of tiny spheres, known as
“microspheres,” into a beaker of water. They
shook the suspension to ensure proper mixing,
covered the beaker to minimize evaporation, and
then went home for a good night’s sleep.
The next morning, they returned to examine the
result.
By conventional thinking, nothing much should
have happened, besides possibly some settling at
the bottom of the beaker. The suspension should
have looked uniformly cloudy, as if you’d poured
some droplets of milk into water and shaken it
vigorously.
The suspension did look uniformly cloudy — for
the most part. However, near the center of the
beaker (looking down from the top), a clear
cylinder running from top to bottom had
inexplicably formed (Fig. 1.3). Clarity meant that
the cylinder contained no microspheres.
Some mysterious force had driven the micro-
spheres out of a central core and toward the
beaker’s periphery. If you’ve ever seen 2001: A
Space Odyssey, and the astonishment of the ape-
humans upon first seeing the perfect monolith,
you have some sense of just how our jaws
dropped. This was something to behold.
Fig. 1.3 Near-central clear zone
in microsphere suspension. Why
does the microsphere-free cylinder
appear spontaneously?
So long as the initial conditions remained within
a well-defined window, these clear cylinders
showed up consistently; we could produce them
again and again.[2] The question: what drives
the counterintuitive migration of the spheres
away from the center? (Chapter 9 explains.)
(ii) The Bridge Made of Water
Another curious laboratory phenomenon, the so-
called “water bridge,” connects water across a
gap between two glass beakers — if you can
imagine. Although the water bridge is a century-
old curiosity, Elmar Fuchs and his colleagues
pioneered a modern incarnation that has aroused
interest worldwide.
The demonstration starts by filling the two
beakers almost to their brims with water and then
placing them side-by-side, lips touching. An
electrode immersed in each beaker imposes a
potential difference on the order of 10 kV.
Immediately, water in one beaker jumps to the
rim and bridges across to the other beaker. Once
the bridge forms, the two beakers may be slowly
separated. The bridge doesn’t break; it continues
to elongate, spanning the gap between beakers
even when the lips separate by as much as
several centimeters. (Fig. 1.4).
( Fig. 1.4 The water-bridge.
A bridge made of water spans the gap
between two water-filled beakers.
What sustains the bridge?)
Astonishingly, the water-bridge hardly droops; it
exhibits an almost ice-like rigidity, even though
the experiment is carried out at room
temperature.
I caution you to resist the temptation to repeat
this high-voltage experiment unless you consider
yourself immune to electrocution. Better to
watch a video of this eye-popping phenomenon.
[w1] The question: what sustains the bridge
made of water? (See Chapter 17.)
(iii) The Floating Water Droplet
Water should mix instantly with water. However,
if you release water droplets from a narrow tube
positioned just above a dish of water, those
droplets will often float on the water surface for
a period of time before dissolving (Fig. 1.5).
Sometimes the droplets may sustain themselves
for up to tens of seconds. Even more
paradoxically, droplets don’t dissolve as single
unitary events; they dissolve in a succession of
squirts into the pool beneath.[3] Their
dissolution resembles a programmed dance.
Fig. 1.5 Water droplets persist on
water surface for some time. Why?
Floating water droplets can be seen in nature if
you know where to look. A good time is just after
a rainfall, when water drips from a ledge onto a
puddle or from a sailboat’s gunwales onto the
lake beneath. Even raindrops will sometimes
float as they hit ground water directly. The
obvious question: if water mixes naturally with
water, then what feature might delay the natural
coalescence? (Look at Chapters 13 and 16)
(iv) Lord Kelvin’s Discharge
Finally, Fig. 1.6 depicts another head-scratching
observation. Water drawn from an upside-down
bottle or an ordinary tap is split into two
branches. Droplets fall from each branch, passing
through metal rings as they descend into metallic
containers. The rings and containers are cross-
connected with electrical wires, as shown.
Metal spheres project toward one another from
each container through metallic posts, leaving
an air gap of several millimeters between the spheres.
Fig. 1.6, The Kelvin water-dropper
demonstration. Rising water levels
create a high-voltage discharge.
Why does this happen?
Originally conceived by Lord Kelvin, this
experiment produces a surprising result. Once
enough droplets have descended, you begin
hearing a crackling sound. Then, soon after, a
flash of lightning discharges across the gap,
accompanied by an audible crack.
Electrical discharge can occur only if a large
difference in electrical potential builds between
the two containers. That potential difference
can easily reach 100,000 volts, depending on gap
size. Yet, the massive separation of charge
needed to create that potential difference builds
from a single source of water.
Constructing one of these exotic devices at home
is possible[w2]; however, observing the discharge
on video is a lot simpler. A fine example is the
one produced by Professor Walter Lewin,[w3]
who demonstrates the discharge to a classroom
full of awe-struck MIT freshmen. He then invites
the students to explain the phenomenon as their
homework assignment. Can you explain how a
single source of water can yield this massive
charge separation? (Read about it in Chapter 15.)
Lessons Learned from These Mysteries
The phenomena presented in the foregoing
sections defy easy explanation. Even prominent
water scientists I know cannot come up with
satisfying answers; most cannot get beyond the
most superficial explanations. Something is
evidently missing from our framework of
understanding; otherwise, the phenomena
should be readily explainable — but they are not.
I want to reemphasize that we’re not dealing with
water at the molecular level; we’re dealing with
crowds of water molecules. We don’t yet
understand water molecules’ interaction with
other water molecules — water’s “social”
behavior.
Social behavior is the purview of social scientists
and clinicians, from whom we might learn. A
friend of mine, a psychiatrist, once told me that,
in order to understand human behavior, you
should focus on oddballs and weirdos. Their
behavioral extremes, the psychiatrist opined,
provide clues for understanding the subtler
behaviors of the rest of the population. That
same reasoning can apply here: the foregoing
cases describe some situations where water
exhibits extreme “social” behaviors; as such,
they provide clues for understanding the more
ordinary behaviors of water molecules.
Thus, rather than brushing aside our inability to
explain the phenomena above, we exploit them
for the clues they provide. We turn ignorance to
advantage. You’ll see many examples of this
process once we reach the book’s middle chapters.
The next chapter 2 , provides some helpful
background. It considers what we already know
about water’s social behavior and what we
don’t, but it focuses mainly on the surprising
reasons why we know so little about Earth’s
most common substance.
Chapter 2. The Social Behavior of H2O
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