How Chemistry Narrowly Avoids Negating Quantum-Mechanics

According to Quantum-Mechanics, the ultimate solution to the question, of Wave-Particle Duality, no matter how deeply this solution is buried, lies in the idea, that Particles cause Waves. Hence, the particles are more-ultimately real, and waves are not. In certain cases such as phonons, this even extends beyond waves-in-a-vacuum, to sound waves, that can be modeled as quasi-particles.

One rule which this evokes is the notion, that if (A) causes (B) with certainty, then it cannot be true that (B) causes (A). And to my mind, this has presented the greatest challenge with Chemistry.

The way Chemistry is understood to work today, the electrons that were loosely stated to be orbiting the nucleus, are actually occupying Quantum-Mechanical states around the nucleus, thus merely being attached to the nucleus, and they occupy shells, which are subdivided into orbitals. Further, these orbitals have known wave-functions, that follow from QM. Hence, the s2 -orbitals are spherical, the p6 -orbitals are perpendicular, and the d10 and f14 -orbitals have the more-complex geometries, which are possible modes of resonance. If all the orbitals belonging to a shell are filled, then indeed the shell becomes spherical itself, and this is best exhibited with inert gasses, which therefore also have ideal cancellation of the nuclear charge at close distance, and which therefore also lack electronegativity. (:1)

The main point of confusion which is possible here, is in the fact that these orbitals and their wave-functions seemingly define the chemical and physical properties of the element, except for anything related to its mass. The suggestion follows, that since the electrical field of the nucleus is strong enough to manipulate the wave-functions, it can also end up displacing where the particle ultimately occurs. In so doing, this action on the orbital would seem to suggest that the wave-function can also be said to change the particle-parameters, thereby creating a contradiction with the way in which QM is currently taught.

There is a specific observation which we can make about this subject, which causes Chemistry to avoid contradicting QM by the width of a hair.

These s, p, d and f -orbital geometries are only thought to exist, if their electrons are unpaired. Each orbital is capable of holding up to 2 electrons, and an orbital which only holds 1 electron is said to be “half-filled”. It has these formally-defined properties when half-filled.

There has never been a precedence in Chemistry, in which a half-filled orbital can be shared by two atoms. But some sort of entity needs to be shared between 2 or 3 atoms, in order actually to form a bond, and in order to change position around either atom. (:2)

When orbitals are filled by 2 electrons each, these two electrons perform a dance which electrons are already famous for, in which both their spin-vector and their magnetic dipole moment pair up, to cancel out. This is also known as “spin-spin decoupling”, and causes the electron to resemble a Fermion less, resulting in some quasi-particle that resembles a fluid more – i.e. a massive Bose particle.

The same affinity causes electron-pairs to form Cooper Pairs, which ultimately result in superconductivity. But in Chemistry, it forms charge-droplets, which are able to change position on an atom or molecule, and which can be shared between 2 or 3 atoms, thus forming either the sigma-bond or the pi-bond known.

The important fact to understand, is that This quasi-particle does not represent a wave-function, and so its mutability also does not represent the mutability of a wave-function. This charge-droplet has mass.

What is typical about this subject in a negative way however, is that Chemistry teaches us that the single-atom state is also the original state of an element. This is not true in practice. When most elements are gained on an industrial scale, they are dug out of the ground already-bound to other elements, and chemical reactions are used to purify them. Even when they do form the only element in a quantity, the atoms are still usually bound to others of the same element, thus forming O2, N2, Cl2, etc.. (:3)

Only, in an abstract way, it is still the desire of the atom from its single-atom state, to complete its orbitals, thus completing an octet ideally, that forms the best first-approximation of how it will react. Many other behaviors are known, in which some of the electrons remain unpaired, thus resulting in paramagnetism, or in which the completed valence shell ends up with a higher number of completed orbitals, than 4. And these frequent exceptions make Chemistry harder to study, than ‘Chem 101′ would have taught it.

Dirk

1:) Unlike reactive elements, the inert gasses commonly do occur in the single-atom state.

2:) The way I was taught the meaning of the phrase ‘Multi-Centered Bonds’, 3-center bonds are already extremely rare, and the main examples I know are certain hydrides – where the hydrogen atom can also be related to an unshielded nucleus, such as in Beryllium Hydride. In this example, each hydrogen atom shares a bond with 2 beryllium atoms, resulting in a chain.

Another example I know, involves the Pi bond from a double-bond, where double or triple bonds exist as Sigma bonds – which form an axis between two atoms – plus 1 or 2 Pi bonds, which stand out from the Sigma bond as mirror-images at 90⁰ angles in 3D. This involvement of Pi bonds is also what makes quadruple bonds between two atoms impossible. Well, the Pi bond can become attracted to a 3rd atom, acting as a cation or an oxidizer, thus forming another kind of 3-center bond.

By default, a covalent bond is an electron-pair shared by only 2 nuclei, while electron-pairs attached to a single nucleus do not form a bond, but nevertheless exist, and contribute to satiating the electronegativity of the atom in question.

Further, those single-centered electron-pairs are often available, for ‘coordinate covalency’ to form, starting from an atom that is not coordinate yet, and that so far has a formal charge of zero. Once coordinate, its valence will have changed, and it will acquire the corresponding formal charge.

3:) It can happen that when a quantity of atoms belongs to the same element, each atom is bound to more than one other atom. Hence, covalent solids can form, out of one element, as opposed to the molecular solids. In this way, Sulfur can consist of the molecular solid S8. But when we heat it, shortly after melting, it will want to form the polymer Sn. And in other examples, the 3-dimensional structure of the solid is too complex to be stated fully in this notation, so that notations like Al(m) and B(s) are often written, to refer to the metal or the solid form, without being more specific.

This generally does happen, if in the abstract single-atom representation, an element has fewer than 4 valence electrons. Hence, this will happen to most of the elements in the periodic table – when pure – even though practical chemistry often tends to focus on the atypical, well-behaved elements, towards the upper-right corner, that are also the basis for life-forms.

(Edited 12/16/2017 : )

Beryllium:

The only way metallic beryllium could complete its octet – and thereby, its valence shell – would be by forming a crystal with as many electron-pairs, as there are beryllium atoms, to balance the charge. But I think that in such crystals, as soon as 1 electron pair would be shared by 4 or more atoms, this may no longer be called a covalent bond.

In practice, metallic beryllium has a “close-packed hexagonal structure“.

(Edit 12/19/2017 : )

When spheres are hexagonally close-packed, as the WiKi-article states, the order in which their layers fill empty positions, one layer ‘up’ or ‘down’, each new sphere should be positioned within one out of two triangular cusps, that formed between 3 spheres belonging to the previous layer, so that each sphere of the first layer, is also positioned at a cusp, between 3 spheres of the new layers. But there are actually different reasons for which a hexagonal structure could form. One such structure misses an atom at the center of each hexagon. And in case they are close-packed, there are actually 2 available ways in which this can progress to each new layer. When this progresses to yet another layer, only 1 out of the 2 available arrangements actually corresponds to that of the first layer.

hex_d-svg

And so to distinguish what the exact, hexagonal configuration of an unknown substance is, in general, the ordering of layers should be determined, as possibly being AA, or ABA, or ABCBA, or just plain random… But the only other element I was aware of, which actually does this, would be helium in its solid state.

Because helium is completely non-reactive, it only solidifies when liquid and put under approximately 10 atmospheres of pressure, and the vulgarization would then be correct, to say that ‘Helium atoms only stay packed together, because they have been forced to do so, due to high pressure and very low temperature.’ And in that case, helium neither prefers the ABA nor the ABCBA order, of the close-packed configuration… Its ordering is random.

If that situation was also to describe metallic beryllium, then the result would be, that beryllium has no tensile strength ! But we know factually, that real beryllium has good tensile strength, which suggests to the contrary, that it shares electron-pairs in fixed positions. Based on that observation, it might be a bit safer to speculate, that the ordering of the hexagonal close-packed structure of beryllium, is actually ‘ABA’.

In that case, the atoms no longer truly correspond to spheres either.


 

And if this is true, then 3-dimensionally, a configuration would be plausible, in which each of its electron-pairs would be shared by 5 beryllium atoms, and each beryllium atom would conversely be connected to 5 electron-pairs, that correspond simultaneously to the 3 atoms in the hexagonal layers above and below, plus corresponding to the 2 positions directly above and below the current layer’s atoms.

If the (stressed) ‘vertical’ bond in such a scenario, from one layer to the next, did not belong to the atoms’ valence shell, then the physical properties of the solid would more-closely resemble that of layered materials, such as clays or micas. But we also know that true beryllium has approximately as much strength to hold its successive layers to each other, as it does to hold each layer together.

And this would also be why, I find the WiKiPedia diagram of the hexagonal structure, in the article just about beryllium, so hard to understand.

This would give beryllium in its pure form, a so-called ‘extended octet’ (of 10 electrons). It would only be possible, due to the highly electrophilic nature of beryllium ions, and would be spectacular.


 

 

But alternatively, an electron-configuration would be plausible, in which pure beryllium only has ‘a regular octet’ of 8 electrons. This configuration would be easiest to visualize, as if it was a “Wurtzite crystal“, tetrahedral. The difference would be in the fact that true Wurtzite crystals are binary compounds, and that in visualizing beryllium, we’d need to substitute the shared electron-pairs, as corresponding to 1 of the 2 elements in a Wurtzite crystal.

This scenario would suggest that alas, each electron-pair is shared by 4 beryllium atoms, and that each atom shares 4 electron-pairs.

After much contemplation, I’ve concluded, that I should believe in the electron-configuration, which breaks the fewest rules.


 

(Updated 10/30/2018, 7h50 : )

Periodic Table:

I have removed some extensive content in this part of the posting, because a mistake which I made did not agree with confirmed facts about the periodic table. I would recommend that my readers read other articles, if they need to know the specifics about the periodic table. The subject is well-researched, and the electron configuration of all the conventional elements, including the lanthanides, is known by today.

What had tripped me up, was the fact that Chemists use the term ‘Electronegativity’, in reality, to refer to two similar but distinct properties of an element:

  1. The potential with which a neutral atom of an element attracts electrons, from neighboring atoms, and
  2. The resistance against which a neutral atom of the same element, loses an electron which it already has.

Without making this distinction, it’s possible to run into some confusion, let’s say, about the Group (2) elements such as Be, Mg, Ca, etc.. These elements all have completely-filled s -orbitals, and so the question can arise, as to why they’re even Chemically reactive. The completed s -orbital is spherical by definition, so that its negative electrostatic field will in fact cancel the positive electrostatic field of the nucleus, equally in all directions.

The behavior that results is, that negative ions such as Be-1, Mg-1, Ca-1, etc., will just not form. However, it’s still easy for neighboring atoms to pull electrons out of this s -orbital, resulting in Be+2, Mg+2, Ca+2 ions, etc.. The true inert elements, including Helium, which also possess a completed s -orbital, will be resistive to either ion forming as a result of Chemical reactions. And then, why Helium is inert, while Beryllium is not, is no longer such a trivial question to answer.

(Update 11/03/2018, 18h20 : )

I could extend my line of speculation further, to reach the conclusion, that what applies to the p, d and f -orbitals – according to what I wrote above – applies in reverse to the s -orbital. And my reason would be the observation that, although Chemists sometimes refer to ‘the probability cloud’ of the electron, for sure, they also refer to its wave-function. And the other wave functions are stated to be resonances, in which one region in space may be positive, while another region in space would be negative, and vice-versa. Well the spherical, half-filled s -orbital would be degenerate, in appearing as a region in space, which simply resonates on-the-spot. At the very least this defies common sense, unless space is also just assumed to have added dimensions which we cannot observe or account for.

I would say that where and when the probability of the electron is (+1), the electrical charge is (-1), and I believe in conservation of charge…

But what would work for me, is that the s -orbital could be completely filled, and therefore occupied by two electrons, each of which just does the opposite of whatever the other does, at any instant in time, in the same region of space. And so according to that, the completely-filled s -orbital could be spherical, have some similarities with the electron-pair I described above, and with the charge-droplet, that can reposition itself as a whole.

(End of Update, 11/03/2018. )


 

Slicing a Hexagonal Close-Packing in 3D:

A hexagonal close-packing may have as desirable feature, that if sliced along a plane inclined by 60⁰ in 3D to the original plane, doing so may reveal an equivalent plane, in which the spheres are packed efficiently, in 2D again, and with the same scaling. If this was fulfilled, then it would indicate ‘good 3D symmetry’, even though some elements and compounds form crystals, which lack this symmetry.

(Edit 12/20/2017 :

In order for this to be possible, the layering-order must be ABC in each chosen plane.

hex_f-svg

One limitation of the above diagram is, that it assumes that the view has just been inclined 60⁰. In reality, we’d need to consider what happens, when the view is inclined 60⁰ and rotated 30⁰. Yet, this does not change the fact that the ordering of the spheres would need to repeat itself exactly, every 2nd layer, as seen in 2D. Otherwise, we’d see a row of spheres that’s shifted with respect to the newly-defined plane. Every second row of spheres would need to be, as if shifted in alternating directions.

hex_h2-svg

Therefore, If solidified helium exhibits poor adherence to ABC ordering in one plane, then it will also exhibit poor 2D packing in another, inclined plane. But, because the helium atoms themselves do not exhibit any preferred directional properties, this would also mean, poor 2D packing in whatever plane the description started in. )

And this should mean in practice, that any success to get helium to solidify in a cryogenic lab, can at best be a partial success.


 

 

Print Friendly, PDF & Email

2 thoughts on “How Chemistry Narrowly Avoids Negating Quantum-Mechanics”

Leave a Reply

Your email address will not be published. Required fields are marked *

You may use these HTML tags and attributes: <a href="" title=""> <abbr title=""> <acronym title=""> <b> <blockquote cite=""> <cite> <code> <del datetime=""> <em> <i> <q cite=""> <strike> <strong>

This site uses Akismet to reduce spam. Learn how your comment data is processed.