Van der Waals radius of hydrogen deuteride

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Discussion Overview

The discussion centers around the Van der Waals radius of hydrogen deuteride (HD) and its implications for molecular interactions. Participants explore the nature of bonding in HD, the existence of Van der Waals interactions, and the prevalence of HD versus D2 in the universe.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant seeks references for the Van der Waals radius of hydrogen deuteride and questions how closely the atoms can approach each other while maintaining stability.
  • Another participant confirms that most deuterium exists as hydrogen deuteride rather than D2, attributing this to statistical likelihoods related to isotope abundance.
  • Some participants discuss the implications of the mass difference between protons and deuterons on bond strength and molecular behavior, noting that deuterons may have stronger binding due to their larger reduced mass.
  • There is a mention of the lack of dipole moment in H2 and D2, which may prevent these molecules from forming under certain conditions, while HD possesses a dipole moment that allows for photon emission and potential molecular formation.
  • One participant acknowledges a mistake in their earlier reasoning about bond strengths and suggests that the equilibrium constant for the reaction D + D -> D2 would need to be significantly larger than that for D + H -> HD for D2 to be prevalent.

Areas of Agreement / Disagreement

Participants generally agree on the statistical prevalence of HD over D2, but there is ongoing debate regarding the nature of bonding in HD, the existence of Van der Waals interactions, and the implications of mass differences on molecular behavior.

Contextual Notes

Some assumptions regarding the nature of Van der Waals interactions and the specifics of molecular bonding in HD remain unresolved. The discussion reflects differing interpretations of how mass affects molecular interactions and bond strengths.

Salman2
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Does anyone have a reference for experimental and/or estimated Van der Waals radius for the molecule hydrogen deuteride ? Symbolically, this would be a proton {(p)e-} + {(np)e-} deuterium.

I would like to know how closely the two atoms can approach each other to maintain the stable state of a hydrogen deuteride molecule, and the Van der Waals radius should help provide the answer..?

==

EDIT: OK, is it possible there is NOT any Van der Waals interaction for HD...that the two atoms within the molecule only have a covalent sharing of the two e- to close the 1s electronic orbital for each atom ?

==

Also, it is my understanding that most of the deuterium (D) in the universe exists in the form of hydrogen deuteride (HD) and not D2 molecule, would this be correct ?

Thanks for any help provided.
 
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Salman2 said:
Also, it is my understanding that most of the deuterium (D) in the universe exists in the form of hydrogen deuteride (HD) and not D2 molecule, would this be correct ?

This is correct and follows from simple statistics. As deuterium is a minority isotope of H, it's unlikely to have a molecule with two deuterium atoms, especially as a D atom binds no more strongly with another D atom than it does with regular hydrogen.
 
hilbert2 said:
This is correct and follows from simple statistics. As deuterium is a minority isotope of H, it's unlikely to have a molecule with two deuterium atoms, especially as a D atom binds no more strongly with another D atom than it does with regular hydrogen.

Not sure about that.
Deuteron is more massive than proton.

It follows that an electron in deuterium possesses a bigger reduced mass and is more strongly bound to a deuteron than to a proton.

Not sure how it effects the strength of molecular bond, but I would be surprised if the enthalpy difference were exactly zero.

But there is another important effect.
A diprotium molecule possesses no dipole momentum.

It follows that if two protium atoms encounter each other, they cannot emit photons. And since they have no way of emitting their energy, they cannot form a molecule - they can only bounce off each other.

The same reasoning - no dipole momentum - would apply to two deuterons, even though they have more energy to dispose of.

But HD is different. Since deuteron is more massive, it is slightly more electronegative than proton. It follows that HD possesses a small dipole moment and the ability to emit photons, which H2 and D2 both lack.

This would enable H and D, on their encounter, to dispose of their energy by emitting photons and form HD molecules, while the encounters between two H or two D merely lead to elastic bouncing.
 
^ Yeah, I noticed the mistake in my reasoning, there obviously is a difference in H-D and D-D bond strengths because of the mass difference affecting the moment of inertia of the molecule. However, the equilibrium constant for the reaction D + D -> D2 would have to be hugely larger than the one for D + H -> DH reaction if there were to be any significant fraction of D2 molecules in a sample of natural hydrogen at thermodynamic equilibrium.
 

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