The potential of water

[pioneer]

I would like to bounce an idea off my fellow chemists. I am going to stay simple and avoid extrapolating, until this basic relationship is settled.

 

Premise: In molecular water, the hydrogen are at higher potential than the oxygen.

 

Observations and logic for support:

 

If you look at a molecule such as HCl, this has a dipole moment, where the H is positive and the Cl is negative. Inspite of this having an equal and opposite dipole charge, this is considered an acid, because the H side carries the highest potential. The reason; Cl is highly electronegative and gains stability by completing its octet to become Cl-. By forming the octet, the Cl- creates orbitial stability to cancel out some negative charge potential. It is still negative, but it becomes a weak base making it inert compared to the H side, which is a very strong acid, i.e., higher potential.

 

If we look at H2O, one also has a highly electronegative atom in O. It too will try to gain octet stability. Its negative charge is also depotentiated, sort of like the Cl-. The result is the plus charge of H has more potential. Both sides of the water's dipole have potential but the H side has a little extra. When a hydrogen bond forms it is the hydrogen lowering potential more than the oxygen, because the oxygen would prefer an octet.

 

Part 2

 

If one assumes both the hydrogen and oxygen have the same potential, one can still explain most of the observations of hydrogen bonding. One thing one can't explain, with this assumption, is the pH affect. If you look at the pH=7 affect in neutral water, what you have are moderately strong secondary bonding forces, able to overcome strong covalent bonding, as reflected by the equation 2H2O---> OH- + H3O+.

 

The only way to explain this is using the high electronegativity of the oxygen and it ability to accommodate even more negative charge than its dipole charge. This makes the -OH stable enough for the H+ to leave. But the H+ does not exist freely in water, but becomes part of H3O+. In this state, all three hydrogen are partially positive and not full positive.

 

Another observation; as we add hydrogen bonding water to a chain or cluster of water, the last added water molecule shows higher hydrogen bonding potential. One way to explain this is, when the H hydrogen bond to O, that O will take it out on its own hydrogen to recoup some of its loss. The result will be its own H gaining potential, making the next hydrogen bond stronger.

 

I have often asked myself, how could chemistry not see this relationship. If it existed, than one would expect it would have been picked up. One way to explain this is, water is the gold standard of pH comparision. It is used as the zero point with respect to relative acidity and basicity. By definition pH of 7 is it called neutral. But in reality, the 10-7 of neutral water is a reflection of the stability of the O and the resultant H potential expressed by neutral liquid water. If the dipole was equal and opposite, the 10-7 should actually be much closer to zero, or weak hydrogen bonds should not be able to break strong covalent bonds that easily.

 

We either need for the chemistry experts to refute this with data, or we need to start changing the chemistry books, so students can learn truth. There are a lot of good applications, especially in the living state, which are being given the bum's rush, by experts who don't understand water.

 

Part 3

 

If we go back to the pH affect 2H2O--> OH- + H3O+, if you look at -OH, the oxygen goes from a partial negative charge to a full negative charge. What this means is the O is, loosely acting like it is positive , in the sense it is able to accommodate more negative charge than within the H2O dipole. The O in water in H2O --> OH- + H+, acts like it is a double acid with the O in -OH gaining electron density relative to H2O. The other aspect or H2O + H+ --> H3O+ acts like an acid-base. The three acid to one base, is due to the high electronegativity of oxygen. The result is the hydrogen is induced to carry the primary burden of the potential.

 

The reason this occurs is connected to magnetic addition. Electron orbitals shapes are charge in motion, which generates a magnetic field. The octet allows the magnetic fields of O's electrons to attract in a way that helps overcome the negative charge repulsion. This allows an extra electron.

 

The dipole explanation does not take into consideration the entire EM force. Where this problem may have come from, are the orbital wave equations. Electrons are treated like waves, which is fine. But these waves reflect charge in motion, which is the definition of magnetism. The total EM force is the the sum of the two allowing lopsided chemical potentials. To close the loop, if we come back to HCl, this is a charge dipole that will show a very lopsided affect relative to the EM orbtial affects of chemistry.

[John Cuthber]

Define what you mean by "potential". It doesn't seem to be any of the normal uses of the word.

[Sayonara]

I have often asked myself, how could chemistry not see this relationship. If it existed, than one would expect it would have been picked up.

 

I think you may have hit the nail right on the head there.

[pioneer]

If you look at HCl, the business end of that molecule is the H side. The Cl side will just absorb the shared electrons within the molecule and become more or less inert. The H end needs to go outside the original molecule's electrons to lower its potential. This is what I call higher potential.

 

If we look at water, the oxygen is also highly electronegative. It can stabilize the slight negative dipole end, since this completes its octet. The H end does not gain any stability by becoming partially positive. The H has the primary burden of potential, since the higher electronegativity of O would actually allow it to gain even more electron density toward -OH. This is exactly what the O tries to do during the pH affect. But since this will amplify the potential of H even further, the equilibrium stops at 10-7. With H replaced by Na+ or K+, the O can go all the way to O-2.

 

If you look at H20, both sides of the dipole are electrophilic. Or both sides are able to accommodate electron density, with O of water going to -OH. The mistake chemistry has made is due to looking at only charge. One also needs to take into consideration the entire EM force, which includes magnetism. The p-orbitals of O allows excellent magnetic addition. This is what allows it to gain more electrons than it has positive charges.

 

A simple physics experiment that demonstrates this, is to take two wires and run electricity through them, but in opposite directions. All this movement of negative charge should be repulsive, yet the wires attract. It has to do with the magnetic fields that result, causing an attraction. The octet of the oxygen is sort of like wires with opposite current in 3-D, causing all the electrons to stay attracted even with extra negative charge. If the oxygen tried to share its negative dipole, it may lose the partial negative charge, but it will also lose some of its magnetic addition. The hydrogen on the other hand, can gain both when it shares electrons. This is what I referred to as the H having higher EM potential than the O.

 

When we form a hydrogen bond, the H lowers it potential both ways. The oxygen lowers its charge potential but loses magnetic addition. The way the oxygen compensates is via the partial covalent nature of H-bonds. This occurs to restore a more favorable magnetic addition for the O. This way the O can assert its higher electronegativity once again. The result is the H is once again induced to retain a slight electrophilic potential.

 

The way to understand why the hydrogen retains electrophilic potential, in minimum energy H-bonds, is to consider the situation the H places itself in. It is a sharing two electrons with its own O, and two more electrons with the other O. So we have one hydrogen trying to share four electrons, i.e., partially. This is possible due to the sp3 hybrid orbitals of the oxygen of water. The H ends up with one time average electron, that is a sort of a time averaged orbital state, that is not 1S. It is sort of partially ionized.

 

If you look at oxidation of metals in water using O2, the water will increase the rate of oxidation relative to O2 in dry air. It has to do with the electrophilic nature of the both ends of the water's dipole. The O takes its share internally, while the H gains potential and tries to excite the metals electrons. This makes it easier for the O2 to scoop them up.

[John Cuthber]

Just as soon as you define what you mean by potential we might be able to answer the original question. "The H end needs to go outside the original molecule's electrons to lower its potential." doesn't seem to me to mean anything.

OTOH Sayonara's point is valid enough that defining what you mean by potential may not contribute greatly to the world of chemistry.

[pioneer]

Applications;

 

The idea of hydrogen bonding hydrogen carrying the burden of potential, due to the covalently bonded, highly electronegative atom, being able to accommodate extra electron density, so it can complete the octet, for favorable magnetic addition, has some very important applications.

 

The easiest to see is the DNA double helix. This forms due to hydrogen bonding between base pairs. If you look closely, every base pair also contains one or two extra hydrogen bonding hydrogen, which can not form a stable hydrogen bond; they have to share with their neighbor H. What this means is the DNA double helix is quite electrophilic. It looks very stable, using conventional wisdom, but is a very busy molecule. Sort of reminds one of water, which is very stable but very powerful.

 

What the extra H potential in the DNA brings to the table, is the incentive for the double helix to separate. The separation of the DNA double helix is movement up an activation energy hill, with the hope all the H can lower their potential by sliding down the energy hill to lower energy. The rest of the DNA is fine, it is only the H that have residual potential. There is an H potential advantage due to the formation of RNA on the DNA relative to the DNA double helix. But the RNA has its own hydrogen problems, which creates a disadvantage to it. The RNA needs to leave the DNA to lower its H potential and the DNA has to reset to the moderate energy default. I can detail this but it is beyond the scope of this discussion.

 

This analysis does not discount the enzymes that make all this possible. But enzymes are also rich in H bonds. If these are not perfect in length and angle, they will result in residual electrophilic potential. This is how the enzymes are able to get the DNA double helix up its energy hill. The electrophilic potential stored within enzymes excite electrons for their own needs. In doing, so they cause the DNA to move up the activation hill. Without the H potential analysis, we can still get the job done. This works for smaller systems, but tends to require blackbox statistics during scale-up. This is the default result, when we ignor the integrated H potential.

[Paralith]

I agree, pioneer - you keep stepping around the issue of defining your use of the word "potential" for us. You can't use the word itself in the definition of that word.

 

Now, I understand that a hydrogen atom in a water molecule has a relatively weak positive charge since the oxygen atom, being more electronegative, has a greater pull on the electrons it shares with hydrogen, so that those electrons spend more time closer to the oxygen than to the hydrogen. I think we all understand that. So you're saying that in this situation, hydrogen has a greater potential to do what?? Electrons in a higher orbital shell have more potential to fall to a lower orbital shell, water at the top of a hill has a more potential to flow to the bottom of the hill. So what are you saying that hydrogen is more likely to do than oxygen? You need to be more explicit if we're going to understand you. Are you saying that a hydrogen ion, aka a free proton, is more reactive than an oxygen ion? Then yes, that is true, because the oxygen has a full electron octet, but the proton is still electron hungry. If that's what you're saying, then I can sort of loosely follow your OP up to this point:

 

Another observation; as we add hydrogen bonding water to a chain or cluster of water, the last added water molecule shows higher hydrogen bonding potential. One way to explain this is, when the H hydrogen bond to O, that O will take it out on its own hydrogen to recoup some of its loss. The result will be its own H gaining potential, making the next hydrogen bond stronger. (emphasis mine - paralith)

 

um, citation please? how do you know with such certainty that one hydrogen bond can be stronger than others? As far as I know there is no such phenomenon that occurs to any significant degree. But if you can prove me wrong with an independent confirming source, then please do.

[pioneer]

Experiment: What I contend is neutral water is electrophilic due to the H potential created on the positive side of the dipole, because the high electronegativity of O stabilizes the negative dipole charge.

 

One experiment/observation is Fe corrosion in and out of, water. When the pH goes up above neutral, Fe and steel becomes more resistant to corrosion. As the pH drops below neutral, the rate of corrosion increases.

 

If we compare this data, to Fe corrosion data without water, the slower rate of waterless Fe corrosion, equates with the slower rate analogous to Fe in water with pH higher than 7. Neutral water, by accelerating the rate of corrosion is acting with a relative acid affect.

 

If the oxygen end interacted for corrosion, relative to waterless corrosion, it should be showing an affect more in line with higher pH. Or the rate of corrosion should be falling in water relative to the waterless corosion. If both ends had the same impact, the rate of corrosion should be the same.

 

This data indicates that the H potential of the water is dominant.

 

Hydrogen bonds getting stronger with the number in a chain

 

for both statistical [11] and energetic reasons. Hydrogen bonded chains (that is, O-H····O-H····O) are cooperative [379]; the breakage of the first bond is the hardest, then the next one is weakened, and so on (see the cyclic water pentamer).

 

Such cooperativity is a fundamental property of liquid water where hydrogen bonds are up to 250% stronger than the single hydrogen bond

 

http://www.lsbu.ac.uk/water/hbond.html

 

The O just keeps passing on the burden due to its high electronegativty.

 

Defining hydrogen potential

 

Hydrogen potential is the electro-magnetic potential difference between the highly electronegative atom and the attached H, with the H being at higher potential due to its lower electronegativity, i.e., more ionized. The electromagnetic potential is the sum of the electrostatic, and the orbital magnetic potentials.

 

If we look at HCl, although H+ and Cl- have equal and opposite charge, the EM potential is not the same for both. The H+ is a strong acid while the Cl- is a weak base. This is due to the magnetic contributions having more of an impact than the charge. Looking at charge alone does not allows us to determine relative potential. CH3- has more potential than Cl-even though both have -1 charge. The same is true of, molecular dipoles like H2O, with the H at higher EM potential than the stable O.

[John Cuthber]

Can you supply any evidence for the claim that "This is due to the magnetic contributions having more of an impact than the charge"?

 

As far as I'm aware the magnetic effects of H, H+ , Cl and Cl- can all generally be ignored. OK there's NMR spectroscopy but you need a magnetic feild that will just about pull your fillings out to get an energy difference that's markedly less than the typical thermal energy at room temperature.

 

From the point of view of a positice test charge the H in HCl is at a higher electric potential than the Cl. From an equally arbitrarily chosen negative test charge's point of view the reverse is true.

[pioneer]

One way to look at this EM affect is to compare the beginning and the final state. A free hydrogen proton may have little magnetic affect, but if it can secure a spot among the orbitals of a molecule, the magnetic affect plays a role in stablizing the final charge. The stability difference between the initial and final state is the potential. I will need to go to the physics section of the forum to iron out the wave-particle nature of the electron in orbitals. That is a very formal way to look at this.

 

But in less formal chemical terms, in neutral water, the H20 has the affect of increasing the oxidation rate of O2, relative to O2 in air. The H2O is causing the O2 to become more affective at taking electrons. The water is acting like a catalyst, that is helping the O2 and Fe, climb the activation energy hill, leading to the oxidation. Irregardless of the mechanism, this implies the water is exerting an electrophilic affect. This is how one pulls things up the activation energy hill.

 

If we increase the pH, the rate of oxidation falls. What we are adding is -OH which is nucleophilic, which cancels out the electrophilic catalyst. It does not change the affect of the negative dipole of H2O, but adds to this affect. It only takes away the potential of the positive or H side of the H2O. If we decrease the pH, we are adding extra electrophilic H+, thereby making the H2O catalysts far more affective, due to the addition of H3O+.

 

The amount of O2 that can dissolve in water will increase with increasing pH. While the amount of O2 that can dissolve in water will decrease with decreasing pH. With an acid, although the amount of O2 is lower, the corrosion rate is higher. While with a base, although the amount of O2 is higher, the corrosion rate is lower. The corrosion affect is inversely dependant on the amount of O2. So it is not the O2 concentration that is of primary importance. It how we tweak the electrophilic potential of neutral H2O, which implies the hydrogen. This data provides a way to calculate the H-potential (electrophic) of liquid water.

 

If the catalytic potential was equally distributed over the dipole of water, it should not matter whether we add acid or base. The base should have the advantage of the higher O2 concentration, but the opposite occurs. The catalytic affect of neutral water (electrophilic) is connected to the H.

 

I seem to be knit picking but the implications of H2O, having a lopsided potential within its dipole, which is electrophilic, i.e., H-potential, has a lot of very important implications. The life science theory needs total update. The observational data is still good, but it needs total reinterpretation. One is not looking at some charge neutral affect, when dealing with H-bonds, but with a lopsided electrophilic affect. One can not honestly look at DNA, RNA and proteins in the same way again. The extra H along the DNA double helix are not there for decorations. They generate potential.

 

Addendum

An EM explanation may be more complicated than is needed. The idea of H being induced to have a electrophilic potential by the O of water may be sufficient. The O does not end up with an equal/opposite nucleophilic potential, since the high electronegativity of O allows the O to stabilize its electrons. This lopsided potential is evident in the cataylic affect of H2O on liquid phase oxidation using O2.

 

The reason this oxidation analysis is important, is that it deals with the very atoms that are used as the standards of chemical analysis. Oxidation and reduction are based on the O and H standard, as are pH. Water is then used as our standarized reference media. Neutral water still acts as an electrophilic catalyst. It is not a neutral affect that one would expect from balanced potential, where one affect cancels the other.

 

If you look at liquid water, it is highly hydrogen bonded. A neutral dipole affect has the means to neutralize potential. But inspite of hydrogen bonding, the water still acts with an electrophilc affect. Even with H-bonds, the neutral pH affect still occurs. This is due to the O also displaying an electrophilic affect for the electrons in its water molecule. For simplicity, if we normalize the electrophilic affect of water, relative to the O and H, the net affect is what I refer to as the H-potential.

 

If we look at H bonding H, as a first approximation, the H carries the burden of an electrophilic potential for the electronegative atom-H (EA-H) combo. The H needs to H-bond to another highly electronegative atoms, to reduce that potential. But it can never really zero out, since these bonds will display partial covalent character, allowing the more electronetative atom to reassert its higher electronegativity and then pass some of the burden back. The H-bonding within water, causes the H-bond energy to get stronger and strong due to this pass the buck affect.

 

When we start to retranslate the life science data, if one assumes the H is essentially on its own, trying to its lower it electrophilic potential, in a world of highly electronegative atoms, who will try to shift the burden back, we end up with life molecules maintaining electrophilic potential. The dipole does not cancel out, but shifts the burden to the H.

 

Water is a poor conductor of electrons. The O is too electronegative. The way water conducts potential is through the potential in the H. The electrophilic potential of the H is everywhere. They are all on their own, but are also connected, so that the overall H-potential is minimized. The potential can never really go away 100%. The living state keeps trying, leading to a dynamic steady state that is trying to do the impossible.

 

If we just look at the H and its burden of potential, ignorring everything else for the time being, life minimizes H potential when it forms C-H bonds. The H is finally in a state, on in own energy scale, close to zero. H2 would be even better for the needs of the H, but the H still has to deal with the highly electronegative O, which makes the C-H bond about it. But this is short lived in the cell, due to the electrophilic nature of the water-O2, causing corrosion/metabolism back to higher H-potential. The cell stays in a constant state of recycle between high and low H-potential.

 

This may seem like a tiny potential to be able to be a driving force for life. One way to put this into perspective is to look at lightning. This is due to the electrophilic potential of the H and cloud/rain/hail hydrogen bonds. All the hydrogen work together causing affects in the 100M volt range. They can pull electrons from the earth with the same ferocious potential. That is a lot of combined electrophilic potential. In life, the little H ants can make the larger DNA double helix worm wiggle for genetic expression. We only need to change the mindet from one H one H-bond, to residual potential and a community affect, where the H work as a team to create affects where the sum of the parts become stronger than the parts, i.e., sort of the lighting within the cell organized by bio-structures.

[John Cuthber]

Am I missing some profound point, or is stuff like this

"When we start to retranslate the life science data, if one assumes the H is essentially on its own, trying to its lower it electrophilic potential, in a world of highly electronegative atoms, who will try to shift the burden back, we end up with life molecules maintaining electrophilic potential. "

the sort of gibberish I normally only see in shampoo adverts ("Here's the science bit").

 

Stuff like this "Water is a poor conductor of electrons. The O is too electronegative. The way water conducts potential is through the potential in the H. " leaves me wondering if Pioneer knows anything about ionic conduction as opposed to electron bands. I mean, sure water is a poor conductor of electrons but, since hydrogen is too, it can't be down to electronegativity. At the other end of the scale; silver is one of the least electropositive metals but it's the best conductor.

 

Oh, and by the way, lightning is driven by the sun. Plenty of power there without invoking new exciting theories based on very little.

[Sayonara]

I have often asked myself, how could chemistry not see this relationship. If it existed, than one would expect it would have been picked up.

 

I think you may have hit the nail right on the head there.

 

Quoted for emphasis.