On Saturday, December 26, 2015 at 2:52:05 PM UTC-8, James McGinn wrote:
Hydrogen Bonding as The Mechanism That Neutralizes H2O Polarity:
A Unique Perspective on The Transition Between The Liquid and Solid States of Water
James McGinn
Solving Tornadoes
solvingtornadoes at gmail dot com
Significance:
This paper introduces a theoretical breakthrough: H2O molecules collectively neutralize their own polarity through hydrogen bonding. Dual (symmetric) bonds fully neutralize polarity, allowing for the low viscosity (high fluidity) of liquid water.
Singular (asymmetric) bonds neutralize only one half. Thus, situational factors that remove or inhibit the attachment of one of the duo of weak bonds associated with symmetrically coordinated hydrogen bonds effectively activates the polarity that
underlies the structural rigidity and electromagnetic forces evident in ice and surface tension.
Abstract
In an attempt to theoretically reconcile the tensional forces that are apparent along the surface of liquid water (surface tension) with those in ice, a radical notion is considered: might the relationship between H2O polarity and hydrogen bonding be
involved but in a manner that is the inverse of the manner that is normally considered? Accordingly, the tetrahedral coordinated state would be the structurally weak form of hydrogen bonding underlying the liquid state of water. The strong form of
hydrogen bonding would be associated with situational factors that restricted or reversed the comprehensiveness of hydrogen bonds, effectively activating (or failing to neutralize) H2O polarity, causing the remaining bonds to be strong. The precise
mechanism thereof is sought through an explicit examination of the theory underlying molecular polarity. A larger theory is developed to explain surface tension, subsurface low-density anomalies, and the freezing process, culminating in the comparing and
contrasting of the freezing process with the antithesis of the freezing process that produces supercooled water. An argument is presented that this new understanding provides the foundations of a larger consensus.
Keywords: hydrogen bonding, polarity, liquid water, surface tension, ice, electronegativity differences, symmetrically coordinated bond, asymmetric bond, low-density anomalies, mechanical matrix, freezing process, supercooled water, PRPA, PNSA, PISD,
PMPD.
Introduction
Premise
In an attempt to explain the molecular basis of the structure that is apparent in atmospheric vortices (which will not be discussed here) it is proposed that the surface tension associated with liquid water might, somehow, be involved if some mechanism
can be found in the atmosphere that maximizes its surface area, the simple logic being that maximization of surface area should maximize surface tension. Although its relatedness was far from clear in my own mind when it was originally formulated, within
this premise was the overarching assumption that H2O polarity and hydrogen bonding might be the causative factors underlying such a mechanism. But the more I considered it the more it seemed I was confronted with a major quandary: if we assume that this
hypothetical maximization of surface tension in the atmosphere is some kind of consequence of H2O polarity and hydrogen bonding then we have to explain how the forces associated with polarity are absent in the liquid state. In other words, we have to
explain how H2O polarity is dormant or neutralized in the liquid state and activated or de-neutralized under conditions that maximize surface area. And the only way I could envision this all working would be if H2O polarity is neutralized in liquid water
as a direct consequence of being more comprehensively hydrogen bonded (most of its H2O molecules having hydrogen bonds with four other H2O molecules, two acceptor bonds and two donor bonds) and activated again in the context of situational factors that
cause the breaking of some but not all of its hydrogen bonds (resulting in many or most of its H2O molecules having one acceptor and one, or possibly two, donor bonds).
Background and Approach
Examination of the literature very rapidly brought me to the realization that this hypothesis is diametrically incompatible with conventional thinking.1 This incompatibility was most plainly apparent with respect to how these competing hypotheses
characterize ice and the freezing process. Indisputably, if the conventional model of ice and freezing is correct then this new hypothesis couldn’t possibly be correct in that the freezing process associated with the conventional model involves H2O
molecules forming into a more highly organized, symmetrically coordinated network of polarized H2O molecules.2 In contrast, with the model that I am proposing any such increase in symmetric coordination could only further neutralize polarity. With
respect to which, it is important to understand that both of these competing models depend on polarity to explain why the freezing/melting temperature of H2O is at 0 degrees Celsius and not at a much lower temperature, around -170 degrees Celsius,
predicted by comparison to other similar but non-polar molecules (methane). So, there was no getting around it. The freezing process associated with this new hypothesis required the inclusion of situational factors that reduce the relative number of
symmetrically coordinated bonds in water and increase the relative number of asymmetric bonds. Because otherwise it lacks the polarity required to explain the hardness of ice.
And so, the challenge at hand was becoming clear. Firstly, the mechanism by which polarity is activated by the breaking of some but not all hydrogen bonds, producing structurally strong hydrogen bonds, needed to be explicated. Secondly, the ensuing
theory had to reconcile the freezing process, including an explanation of the lower density of ice. But I had some reservations as to whether this would be convincing. The conceptualization of ice and the freezing process associated with the conventional
model had been in place for a long time and had been considered by a large number of researchers and, therefore, had a lot of tacit support behind it. In an effort to find something definitive to distinguish my model from the conventional model I came
across supercooled water, the tendency for water to remain unfrozen even at temperatures well below 0 degrees Celsius.3
Although the process underlying the origins of supercooled water—what we might describe as the antithesis of the freezing process—seemed to not have been adequately explained by the conventional model this was not the main reason my attention was
drawn to it. Rather, it was the fact that the situational circumstances associated with its origins seemed to directly contradict what is predicted by the conventional model. Specifically, since the freezing process associated with the conventional model
indicates an increase in the polar alignment of H2O molecules during the transition from liquid to ice it seems reasonable that one would predict chaotic or agitated conditions as the underlying root cause, but exactly the opposite is the case.
Supercooled water is associated with situational factors in which water is cooled very gradually under placid, calm conditions.3 To me this indicated that the underlying mechanism involves the comprehensiveness of symmetrically coordinated bonds being
locked in, forming a threshold that inhibits the breaking of bonds without which, in accordance with my hypothetical thinking, polarity remains dormant, preventing the formation of ice. And so, lastly, I hope to distinguish this new model by
demonstrating that it engenders an elegant explanation as to why the conditional factors underlying supercooled water involve gradual cooling and placid, calm conditions.
Theoretical Presentation
Molecular Basis of H2O Polarity
There are two requirements for a molecule to be polar (dipole moment). Firstly, there must be electronegativity differences between its covalently bonded atoms.4 (These are, sometimes, referred to as “polar” bonds. In my opinion this designation is
the source of a lot of confusion. Herein polarity is considered an attribute of a molecule in its entirety, not just its bonds.) The H2O molecule has electronegativity differences of 1.34 between its oxygen atom and any one of its two hydrogen atoms.4
Electronegativity differences between the atoms of any molecule do not change regardless of circumstances. Therefore, any purported variability of H2O polarity cannot be solely a consequence of electronegativity differences between its atoms.
The second requirement for a molecule to be polar is that electronegativity differences between its atoms must be structurally lopsided, asymmetrically distributed. This can be better understood with comparison to CH4, the methane molecule. Between the
carbon atom and any one of the four hydrogen atoms of the methane molecule is an electronegativity difference (.45) that is one third of that (1.34) between the oxygen and any one of the two hydrogen atoms of the water molecule (.45 / 1.34 = .34).4 From
this one might, at first, assume that the methane molecule would possess one third the polarity of the water molecule, but it has zero polarity. (And, in comparison to water, this lack of polarity is the reason it is a gas at room temperature, with a
boiling point at -164 Celsius and a freezing point at -182 Celsius.) This is because the electronegativity differences of the methane molecule are structurally symmetric.
The distinction between the symmetry of the methane molecule and the asymmetry of the water molecule might be better understood with respect to the fact that their respective base molecules, carbon and oxygen, share the same structural template as the
underlying factor that dictates the arrangement of their covalent bonds, a tetrahedron.5 Having four unshared electrons in its outer shell, the symmetry of the methane molecule is a consequence of the fact that the carbon atom can, and in the case of
methane does, form covalent bonds on all four of the four corners of the tetrahedron. Oxygen possesses only two unshared electrons in its outer shell. Consequently it can only form covalent bonds on two of the four corners of the tetrahedron, as is the
case with the water molecule. This results in the electronegativity differences of the water molecule being structurally lopsided (asymmetric), making the water molecule a polar molecule.
The convention that is generally used to represent the strength of the electromagnetic forces associated with polarity is the ∂ symbol.6 Although it is not intended to be a precise attribution, its magnitude is generally considered to produce a
binding force that is a fraction of that associated with a covalent bond, possibly one twentieth. Being positively charged, each of the two hydrogen atoms on a H2O molecule is attributed a positive charge of +1∂ for a total of +2∂. Each of the two
unbonded pair electrons on the oxygen atom is attributed a negative charge of -1∂ for a total of -2∂. Accordingly, the H2O molecule is hereby considered to have a polarity coefficient (a net difference in charges from one end of the molecule (-2∂)
to the other (+2∂) of 4∂.
The Mechanism
In the context of this understanding we can ask ourselves two rhetorical questions in regard to completing the corners of the tetrahedron of the oxygen atom. Must the bonds be covalent? Would hydrogen bonds not be equally effective as covalent bonds in
regard to completing the corners of the tetrahedron to, thereby, effectuate symmetry? I believe the answers to these rhetorical questions are, respectively, no and yes. Accordingly, I believe completion of the tetrahedron with hydrogen bonds effectively
establishes symmetry. It becomes a molecule with perfectly balanced electronegativity differences, identical to those of a nonpolar molecule like methane. Accordingly, when a H2O molecule is symmetrically bonded it’s polarity coefficient drops from 4∂
to zero. Removing only one of these bonds (leaving one attached) cuts its polarity in half, giving it a polarity coefficient (-1∂ to +1∂) of 2∂.
This is all very confusing, but it is even more confusing when you consider that polarity determines the strength of any remaining hydrogen bonds. Accordingly, when a water molecule is symmetrically bonded (having two acceptor bonds [two positively
charged “donor” hydrogen atoms from each of two other H2O molecules] attached on its negatively charged “acceptor” oxygen atom]) its polarity is neutralized (it’s polarity coefficient is zero) and, therefore, the force that created the bonds is
neutralized. Consequently, the hydrogen atoms just float alongside the oxygen atom. The only thing holding them is that if they move away the charge returns. This is why liquid water is so fluid. We can think of the molecules in liquid water as being in
a perpetual state of trying to become a gas and being unsuccessful in that as the hydrogen atom moves away from the oxygen atom polarity reemerges preventing it from escaping. (This functionality is also the basis for the pendulumic aspect of
symmetrically coordinated bonds, which is discussed more explicitly further along.)
The H2O molecule has the strongest polarity when both bonds are broken, as in gaseous H2O. (This phrase “gaseous H2O” refers to steam, not evaporate.7 In some less rigorous disciplines, meteorology and climatology for example, it is common to
conflate the concepts of steam, a genuine gas that only occurs above the known boiling temperature/pressure of H2O, with evaporate, not a genuine gas but a form of liquid H2O that is suspended in air [often completely invisible] and that only occurs at
temperatures below the known boiling temperature/pressure of H2O.) Then, and only then does the H2O molecule have full polarity (its polarity coefficient is restored to 4∂). This explains why the boiling point of water is so high in that it requires
having enough energy to break the very strong attraction of the full polarity of the H2O molecule.
When bonds are asymmetric (having only one acceptor bond [one positively charged “donor” hydrogen atom from an adjacent H2O molecule attached on its negatively charged “acceptor” oxygen atom]) one half of the polarity is restored or, depending
on perspective, one half of its polarity remains un-neutralized (its polarity coefficient is 2∂) producing a strong hydrogen bond. Therefore, situational factors that prevent or reverse the formation of the second of the two acceptor bonds associated
with weak symmetrically coordinated bonds (dual) will allow or cause the formation of a strong asymmetric bond (singular).
Addressing Explanatory Challenges
Since the attachment of a hydrogen atom (a donor from an adjacent H2O molecule) to its oxygen atom (the acceptor) is the mechanism that neutralizes or de-activates the polarity of that H2O molecule; and since the removal of the same is the mechanism
that activates or de-neutralizes it; and since it can accept up to two hydrogen atoms (a donor from each of two adjacent H2O molecules) producing three variants: 1) no attachment at all; 2) one accepted, being a strong asymmetric bond; or 3) two accepted,
being two very weak (floating) symmetrically coordinated bonds; there is huge potential for explanatory confusion. It would appear that this potential for confusion mostly has to do with how we differentiate between the process of attaching and
detaching bonds to go back and forth between the weaker and stronger bonding states and the duo of bonds associated with a symmetrically coordinated bond which can also be described as “weaker” and “stronger”. It becomes quite precarious. For
example, we might, at first, designate the “weaker” of the duo of bonds as always being the last hydrogen atom accepted or the first one detached and the “stronger” one as always being the first one accepted or the last one detached. But that
becomes confusing further along because it, unavoidably, creates the impression that one of the duo is “strong” and the other is “weak”, which is certainly not the case. It gets even more confusing when you consider that whether or not one or the
other is attached or detached is relative and not absolute—the closer either or both of them come to the oxygen atom the more they neutralize the polarity that maintains the bond and the farther either or both of them move away from the oxygen atom the
more the polarity that underlies the strength of the bonds is reactivated. And, therefore, for all of these reasons, referring to either one of them as “weaker” or “stronger” doesn’t make a lot of sense accept in the context of the process of
them becoming fully attached or fully detached.
In order to circumvent the potential for confusion between the processes that produce them and the hydrogen bonded variants themselves, I hereby designate the following with respect to encapsulating the different processes associated with hydrogen
atoms becoming attached or detached:
PRPA Polarity Reducing Primary Attachment: The attachment of one hydrogen atom, a donor from an adjacent H2O molecule, to an unattached oxygen atom of an accepting H2O molecule to create a (singular) strong asymmetric bond.
PNSA Polarity Neutralizing Secondary Attachment: The attachment of an additional hydrogen atom, a donor from another adjacent H2O molecule, to create two (dual) weak (polarity neutralized [floating]) symmetrically coordinated bonds.
PISD Polarity Increasing Secondary Detachment: The removal (breaking) of either of the two hydrogen atoms associated with (dual) weak symmetrically coordinated bonds to create a (singular) strong asymmetric bond.
PMPD Polarity Maximizing Primary Detachment: The removal (breaking) of a (singular) strong asymmetric bond.
Starting from different states, steam and liquid water, PRPA and PISD produce the same end result, a singular, strong asymmetric bond. PRPA and PNSA both neutralize one half of the polarity of a H2O molecule, but they produce very different end results.
PRPA involves a transition from steam to a singular, strong asymmetric bond. PNSA involves a transition from a singular, strong asymmetric bond to the dual, weak symmetrically coordinated bonds of liquid water. PRPA and PMPD involve transitions to and
from steam and will not be discussed through the rest of this paper. PISD and PNSA involve transitions to and from the singular, strong asymmetric bond associated with the structural properties of water and the dual, weak (floating) symmetrically
coordinated bonds associated with the high fluidity of liquid water, both of which are highly relevant through the rest of this theoretical presentation.
Surface Tension Explained
The two dimensions of a surface restricts the completion of hydrogen bonds that would normally occur in the less restricted three dimensions below the surface of liquid water, producing PISD events and inhibiting PNSA events for the molecules along the
surface. This explains surface tension of liquid water. In calm water its existence is very stable.
Subsurface, Low-Density Anomalies Explained
Although its occurrence is considerably more brief in comparison to that of surface tension, another situational factor that causes the formation of the strong, asymmetric bonds actually does occur within the unrestricted three dimensions below the
surface of liquid water. These are generally referred to as low-density anomalies.8 In accordance with the understanding being presented here, these subsurface low-density anomalies are, hereby, hypothesized to be a collective consequence of the
geometric limitations of H2O molecules in that they don’t quite pack into a 100% symmetrically bonded matrix. Between 3% and 10% (unknown) are collectively excluded and, therefore, can only form asymmetric bonds. (This percentage will, most likely,
vary depending on temperature/pressure.) Moreover, this collective inability to form fully symmetric bonds can and will itself be spread between many or even all of the molecules within a body of water. Thus within liquid water (under normal, ambient,
conditions) there will always be a small percentage of the structurally strong and electromagnetically active asymmetric bonds. And, since asymmetric bonds are intrinsically lower in density these “anomalies” will be associated with lower density.
However, unlike those associated with surface tension, their existence is usually very brief in that as soon as they come into existence they create the tensional forces (polarity) that reestablish higher density, weak symmetrically coordinated bonds.
And so, a PISD event creates the conditions that initiate a corresponding PNSA event. And a PNSA event, working through the matrix, will contribute to initiating another PISD event in the general neighborhood. In other words, there is constant interplay
between PISD events and PNSA events. And these reverberate, by way of the matrix, through the body of water. So, in addition to being a small percentage of the bonds within the greater matrix these “low-density anomalies” exist for very short periods
of time (Consequently, they can only be detected using sophisticated equipment.9) and will, over time, be averaged out over many of the symmetrically coordinated bonds within the greater body of the liquid.
Ice and the Freezing Process Explained
As indicated in the previous paragraph, any PISD event that occurs within liquid water will produce a lower density, strong asymmetric bond that will exist for only a brief instant in time before it is reversed by a corresponding PNSA event. However,
at and below 0 degrees Celsius the rules change. At these lower temperatures the same occurrence can initiate a chain reaction of PISD events that produce a network of strong asymmetric bonds that instantaneously inhibit corresponding PNSA events
resulting in the structurally strong form of water, ice. This process is commonly referred to as freezing. And so, like surface tension and subsurface, low-density anomalies, the H2O freezing process also involves PISD events, but, as will be explained,
it is more complicated because it involves an additional situational factor that causes both a chain reaction of cascading PISD events and inhibition of corresponding PNSA events. Properly conceptualizing this additional situational factor involves, for
the most part, getting a better understanding of how the molecules in liquid water collectively comprise a mechanical matrix that itself dictates ensuing implications.
Mechanical Matrix: Understanding the mechanical matrix and its implications to the freezing process that produces ice, as well as its implications to the antithesis of the freezing process that produces supercooled water, depends on understanding three
concepts and their interrelationships:
1) How the pendulumic relationship that exists between the duo of hydrogen atoms and the oxygen atom in each of the symmetrically coordinated bonds within a body of liquid water collectively dictates the transfer of kinetic energy (spreads energy)
throughout the liquid (which also, arguably, goes a long way into explaining the high heat capacity of water [attributable to the conservation of energy aspect of the pendulum] and high heat conductivity [attributable to the high degree of connectivity
between the H2O molecules in that over 90 percent of them have bonds with four of their neighbors]);
2) How the collective of symmetrically bonded H2O molecules tends to become more interconnected over time, balancing out kinetic energy and electromagnetic charges (balancing out polarity) throughout the greater body of the liquid, effectuating a
larger mechanical matrix and therefore having a higher threshold of resistance to change in that greater momentum is required to move the gears of a larger mechanical matrix; and
3) How the displacement of one of the duo of hydrogen atoms (a PISD event) on at least one of the symmetrically coordinated bonds in the greater matrix causes the remaining hydrogen atom of that symmetrically coordinated bond to move to a more central
position on its oxygen atom in order to balance out electronegativity differences and how this movement turns the gears of the mechanical matrix causing additional PISD events, causing their remaining hydrogen atoms to move to more central positions on
their oxygen atoms, further turning the gears and causing more of the same, producing a cascade of PISD events that produces a network of strong asymmetric bonds that instantaneously inhibit (block) corresponding PNSA events and that, therefore, are
highly stable. (Another factor that might power the turning of the gears of the mechanical matrix during PISD events is a shift in the bond angle of the covalently bonded hydrogen atoms of the H2O molecule from 109.5 degrees to 107 degrees. As with the
shifts in polarity being hypothesized here, this too is a result of shifts in electronegativity that are an implication of PISD events.)
Comparing and Contrasting The Freezing Process With Its Antithesis
Consider two scenarios of water being cooled below 0 degrees Celsius. Both involve a sealed, one liter plastic container filled with pure H2O at normal atmospheric pressure. Scenario A involves the container being placed in a room that is -5 degrees
Celsius. Its temperature drops gradually and it does not freeze. It continues to exist as supercooled water all the way down to -5 degrees Celsius. In scenario B the water is cooled both more rapidly and more unevenly. It involves the container having
its bottom one quarter suspended in liquid nitrogen. Its temperature drops rapidly and as soon as any part of it drops below 0 degrees it begins to freeze. Why did scenario B produce freezing whereas scenario A did not?
In scenario A the pendulumic process has more time to process the distribution of changes in energy to all of the molecules in the body of water before its average temperature crosses below 0 degrees. More specifically, the collective, pendulumic
process of the mechanical matrix has more time to become one large matrix and to stay as such with gradual reductions in temperature. Therefore there is less variance in the swings of the pendulum of the different symmetrically coordinated bonds therein.
Additionally, since the matrix is larger, greater momentum is required to overcome the threshold resistance in order to turn the collective gears of the mechanical matrix. Consequently, for both of these reasons, the chain reaction of cascading PISD
events cannot be initiated. And/or (unknown) corresponding PNSA events are not blocked, and the water remains supercooled, unfrozen.
In contrast, in scenario B the rapid and unequal removal of energy makes achieving the same degree of temperature distribution to all of the molecules in the body of water impossible. More specifically, the pendulumic process has less time to process
and become a larger matrix. Instead there exists, in a sense, many different matrices at different energy levels. And, therefore, there is much greater variance in the swings of the pendulums of the various symmetrically coordinated bonds in the body of
water. Consequently there is a greater probability that one of the duo of hydrogen atoms associated with at least one of the many symmetrically coordinated bonds in the body of water will swing away from its oxygen atom to initiate a PISD event. And,
since the mechanical matrices thereof are smaller there is less threshold resistance to overcome and, therefore, less momentum is required to turn the collective gears of any one matrix, thus a cascade of PISD events has a higher probability of being
initiated. Once initiated, the turning of the gears of the highly interconnected matrix causes the ensuing emergence of a network of strong asymmetric bonds that instantaneously inhibit (block) corresponding PNSA events, and the water begins to freeze.
The end result, ice, is less dense simply because asymmetric bonds are intrinsically less dense than symmetrically coordinated bonds.
Discussion
Addressing Anticipated Objections
The Mechanism: The only objection I can anticipate to the validity of the mechanism being suggested here—the notion that hydrogen bonds neutralize polarity and their removal, breaking of hydrogen bonds, activates it—are arguments based on dogmatic
interpretations of what is a molecule or what is polarity. Us humans tend to emplace absolutistic interpretations on our definitions and subsequently forget that nature doesn’t necessarily always conform with this absolutistic aspect. Along these lines,
I would like to suggest a change in perspective. Instead of looking at it from the outside in, look at it from the inside out. Specifically, consider this notion from the perspective of an electron on the oxygen atom of a H2O molecule that maintains (
dual) symmetrically coordinated bonds. When it looks up into each of the four corners of the oxygen molecule’s tetrahedron it will see the same thing, a positively charged hydrogen atom. Is there any reason to assume it would be more or less attracted
to the hydrogen atoms on the corners that are covalently bonded than it is to those that are hydrogen bonded? If there is, I don’t know what this would be.
Freezing and its Antithesis: As for the description of the freezing process and its antithesis that is presented herein there is, in my opinion, much more potential for it to be incomplete, partially wrong, or even (though much less likely in my
opinion) fully mistaken. My concerns in this regard involve the assertion that this hypothesis appears not to predict the increase in density that occurs with drop in temperature between 4 degrees Celsius and 0 degrees Celsius. My guess is that something
distinctive is happening with the mechanical matrix over this transition, something that has not been adequately explained. It might even indicate that the notion that the, purported, repositioning of the extant hydrogen atom that, purportedly, turns the
gears of the mechanical matrix to initiate a cascade of PISD events is either wrong or superfluous. I also think an alternative hypothesis should be considered with respect to the barrier associated with the the antithesis of the freezing process being
something other than the threshold momentum requirements of the mechanical matrix. Might, for example, the actual barrier have something to do with a larger and more synchronized mechanical matrix having an increases in its mean collective ability to
absorb perturbation as it goes below 4 degrees, preventing an initial PISD event, but only when it gets below 0 degrees does it lose its ability to block corresponding PNSA events, due to some unexplained mechanical implication? I am curious as to
whether a clue leading to a resolution might be found through more in depth analysis of low-density anomalies in the context of comparing and contrasting the freezing process to the antithesis of the freezing process over the course of this transition.
Some Resolution to The Strangeness of Water
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