Why are almost all polyatomic ions negative?

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Discussion Overview

The discussion centers on the prevalence of negative polyatomic ions compared to positive polyatomic ions, exploring the reasons behind this observation and the mechanics of atomic structure that may contribute to it. Participants examine examples of both types of ions and consider their stability and commonality in various contexts.

Discussion Character

  • Exploratory
  • Debate/contested
  • Conceptual clarification

Main Points Raised

  • Some participants question the assertion that "almost all" polyatomic ions are negative, suggesting that this may be based on personal impression rather than established fact.
  • Others point out that while there are examples of positive polyatomic ions, such as CO+, CH4+, and N2+, these are often less stable than their negative counterparts.
  • A participant notes that many common polyatomic anions contain oxygen and suggests that the abundance of these oxyanions may be linked to the presence of oxygen in Earth's atmosphere, although this connection is debated.
  • Another participant expresses skepticism about the idea that the presence of oxygen explains the dominance of oxyanions, proposing that the observed distribution may reflect a broader trend in chemistry rather than being solely influenced by Earth's conditions.
  • The discussion also touches on the existence of various ammonium and phosphonium compounds, indicating that there are indeed positive polyatomic ions, but their prevalence may vary depending on the specific area of chemistry being considered.
  • One participant admits a lack of formal education on the topic, relying instead on personal observation to inform their understanding.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the reasons for the predominance of negative polyatomic ions, with multiple competing views and ongoing debate regarding the influence of oxygen and the stability of different ion types.

Contextual Notes

Some claims about the stability and commonality of certain ions are not fully substantiated, and the discussion reflects a variety of perspectives without resolving the underlying questions.

Cram Namlyts
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or, Why are there so few polyatomic cations? What about the mechanics of an atom makes it so?
 
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Welcome to PF;
The first three I thought of, off the top of my head, are all positive: CO+ , CH4+ , N2+ ... where do you get the idea that "almost all" molecular ions are negative? Is this something you have seen written down or an impression you have formed?
 
Simon Bridge said:
Welcome to PF;
The first three I thought of, off the top of my head, are all positive: CO+ , CH4+ , N2+ ... where do you get the idea that "almost all" molecular ions are negative? Is this something you have seen written down or an impression you have formed?

All of the ions that you listed are radial cations that are not very stable. The OP is talking about commonly encountered polyatomic ions found in ionic salts.

If you look at the list of common polyatomic anions (which is much larger than the list of common polyatomic cations), you'll see that many contain oxygen and are oxyanions. Perhaps the prevalence of these oxyanions is a consequence of life on Earth: Living organisms have made Earth's atmosphere rich in a relatively reactive substance, oxygen gas, that has reacted with many substances to produce the wide variety of oxyanions we see.
 
My understanding is that the OP asks why there are plenty of ions like CO32-, PO43-, MnO4- and so on, but only a few like VO2+ or UO22+.

I am not convinced presence of oxygen on Earth explains that - I have a feeling it is not that these are the oxyions we observe, rather these are "oxyions" that exist in general. And oxyions seem to be dominated by oxyanions, with a relatively low number of oxycations.
 
How many mono-, di-, tri-, tetra- (alkyl/alkenyl/aryl/etc.) ammonium/phosphonium compounds are there?

Edit

Tropylium, carbonium, diazonium, oxonium, sulfonium, pyridinium --- just a matter of digging around a bit, and the difference in populations may not vanish, but become a matter of which areas of chemistry one wishes to focus upon.
 
Last edited:
That's actually a great question! I don't know what it says about my education/studies, but it was never explained to me nor shown. I'm banking on simple observation...
 

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