When Cl, Br, I turn into Cl+, Br+ and I+?

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Discussion Overview

The discussion revolves around the conditions under which chlorine (Cl), bromine (Br), and iodine (I) can lose electrons to form their respective cations (Cl+, Br+, I+). Participants explore theoretical scenarios, chemical processes, and the behavior of these elements in various environments, including plasma and electrochemical reactions.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested
  • Chemical reasoning

Main Points Raised

  • Some participants question the conditions necessary for Cl, Br, and I to donate electrons and form cations, seeking clarification on the chemical term for losing electrons.
  • One participant suggests that creating an arc lamp with these elements could lead to the formation of positive ions, although they express uncertainty about its feasibility.
  • Another participant notes that Cl+ ions can be formed in Cl2–Ar based plasmas used for semiconductor treatment.
  • There is a discussion about the oxidation process required to convert halides (Cl-, Br-, I-) into their respective neutral forms or cations, with some participants asserting that oxidation is necessary.
  • One participant proposes that Cl+ can be generated through reactions with more electronegative elements, such as fluorine, but emphasizes that free Cl+ cannot exist independently.
  • Another participant mentions that hypochlorite can oxidize chloride to chlorine under certain conditions, but clarifies that the resulting Cl+ is bonded to oxygen in the hypochlorite anion.
  • Some participants discuss the electrolytic dissociation of iodine monochloride and the conditions under which iodine can lose electrons, noting that extreme conditions are required for the formation of I+.

Areas of Agreement / Disagreement

Participants express multiple competing views on the formation of Cl+, Br+, and I+, with no consensus on the specific conditions or processes that would allow for their existence as free cations. The discussion remains unresolved regarding the feasibility and mechanisms of generating these cations.

Contextual Notes

Limitations include the dependence on specific chemical environments, the need for powerful oxidants, and the ambiguity surrounding the existence of free cations in various states. The discussion also highlights the complexity of reactions involving these halogens and their interactions with other elements.

HCverma
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As we know that Cl, Br and I are highly electronegative elements, the receive electrons and become Cl-, Br- and I-. But my question is in which situation, they start donating electrons and become Cl+, Br+, and I+?
 
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This is sort of a guess on my part, because I have never seen an arc lamp with these elements,(=I don't think there's any reason why it couldn't be done=it would just require higher voltages). If you were to make an arc lamp (arc discharge lamp=e.g. the same kind of arc that is used in fluorescent lamps) with the gas of any of these diatomic molecules, it would necessarily create positive ions. ## \\ ## Additional item: I do believe it is likely the atomic spectrum has been studied in detail for these elements and ions in such a discharge. ## \\ ## See also: http://rspa.royalsocietypublishing.org/content/136/830/585
 
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HCverma said:
But my question is in which situation, they start donating electrons and become Cl+, Br+, and I+?
What is the chemical term for losing electrons?
 
Cl+ ions are, e.g., formed in Cl2–Ar based plasmas which are used for plasma etching in semiconductor treatment.
 
TeethWhitener said:
What is the chemical term for losing electrons?
Cations
 
HCverma said:
Cations
No, cations are positively charged species. But Cl- can lose an electron to become neutral chlorine, for example:

$$\textrm{2Cl}^- \longrightarrow \textrm{Cl}_2 + \textrm{2e}^-$$

What is the term for the process above, when a chemical undergoes a reaction which specifically causes a loss of electrons?
 
Cl(I), Br(I) and I(I) are mildly acidic species. In aqueous environment, they are likely to occur as HClO, HBrO and HIO, which have a weakly acidic character and in strong base form ClO-, BrO- and IO- anions.
But in acidic environment? Cl2/AlCl3 reacts like the reaction had been
Cl2+AlCl3⇔Cl++AlCl4-. But from the behaviour of the mixture, it appears that the Cl-Cl bond does not quite break and Cl+ does not appear as a free cation at these conditions.
Are there any conditions where it does?
 
TeethWhitener said:
No, cations are positively charged species. But Cl- can lose an electron to become neutral chlorine, for example:

$$\textrm{2Cl}^- \longrightarrow \textrm{Cl}_2 + \textrm{2e}^-$$

What is the term for the process above, when a chemical undergoes a reaction which specifically causes a loss of electrons?
The term is called oxidation.
But here 2Cl^- forms Cl2 by sharing two electrons through the .covalent bond. So how do Cl^- lose electron rather than sharing a pair of electrons? Could you explain it, please?
 
HCverma said:
But here 2Cl^- forms Cl2 by sharing two electrons through the .covalent bond. So how do Cl^- lose electron rather than sharing a pair of electrons? Could you explain it, please?

Turns out that free Cl+ and even I+ cannot quite be made.
The approach would be:
React Cl with an element even more electronegative than Cl. Such as F, forming, for example, ClF.
Cl would have the positive charge. ClF is a polar covalent compound, though - the electron pair is still partially shared with Cl.
Then bond F to some ligand whose empty orbital gives a strong covalent bond to F-, forming a weakly basic anion. Like:
ClF+BF3→Cl++BF4-
But Cl+ is too strongly polarizing cation to be dissociated in that way. Even I+ cannot be made - compounds with strongly electronegative groups are still covalent unless the positive charge is spread across ligands.
 
  • #10
HCverma said:
The term is called oxidation.
This was the point I was trying to make. You'd need to oxidize the halogen to get a halonium.
HCverma said:
But here 2Cl^- forms Cl2 by sharing two electrons through the .covalent bond.
No, simply sharing the electrons would give you Cl22-. To get rid of the electrons requires an oxidizer (something that accepts electrons).
snorkack said:
Turns out that free Cl+ and even I+ cannot quite be made.
I'm assuming that the OP was talking about formal halonium. Free H+ can't be made in solution either (apart from briefly upon exposure to something like high energy radiation), but it's useful to talk about acid-base chemistry as if free protons did exist in solution.
 
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  • #11
TeethWhitener said:
This was the point I was trying to make. You'd need to oxidize the halogen to get a halonium.

No, simply sharing the electrons would give you Cl22-. To get rid of the electrons requires an oxidizer (something that accepts electrons).

I'm assuming that the OP was talking about formal halonium. Free H+ can't be made in solution either (apart from briefly upon exposure to something like high energy radiation), but it's useful to talk about acid-base chemistry as if free protons did exist in solution.
Could you name the oxidizer please and could you mention the reaction where we can get neutral Cl2?
 
  • #12
HCverma said:
Could you name the oxidizer please and could you mention the reaction where we can get neutral Cl2?
I'm a bit confused by your question. Do you want to know how to oxidize chloride (Cl-) to chlorine (Cl2)? The easiest way to do that is electrochemically (electrolyze an aqueous solution of NaCl, for example, and adjust the pH so that free Cl2 is released). You can also oxidize HCl with potassium permanganate, for example.
 
  • #13
TeethWhitener said:
I'm assuming that the OP was talking about formal halonium. Free H+ can't be made in solution either (apart from briefly upon exposure to something like high energy radiation), but it's useful to talk about acid-base chemistry as if free protons did exist in solution.

If that's sufficient, then a lot of things count.
Like iodine monochloride. The liquid (freezes at 27 Celsius, boils at 97) conducts electricity, and is thereby electrolyzed to I2 and Cl2.
It is therefore useful to talk about iodine monochloride as dissociating:
ICl⇔I++Cl-
The actual ions in the liquid are more associated, more like
3ICl⇒I2Cl++ICl2-
You do not even need to use an electronegative element to take an electron from iodine. Element iodine itself can easily be molten (triple point pressure 120 mbar, melts at 114 Celsius, boils at 184 Celsius with liquid range of 70 Celsius - just because iodine vapour is so conspicuously coloured does not mean that iodine will sublimate without melting from a closed vessel). And molten iodine conducts electricity. You can simplify it as a spontaneous electrolytic dissociation with dismutation:
I2⇔I++I-
though the actual reaction is, again, more like
3I2⇔I3++I3-
 
  • #14
To answer the original question, you'd need extreme conditions to oxidize a Cl atom to a Cl+ (chloronium) ion. Powerful oxidants like elemental fluorine can pull electrons from chlorine, but there's no chemical process that can generate free Cl+, as it will always be bonded in some way to whatever atoms or molecules happen to be present. I suspect that you can only find isolated Cl+ ions in an ionized plasma, as noted above.
The same goes for bromine and iodine. There are commercially available reagents, such as bis(pyridine)iodonium tetrafluoroborate, that contain iodonium ions in a complexed state, but to my knowledge there are no simple salts containing isolated I+ ions.

Hypochlorite (bleach) will oxidize chloride to chlorine if you lower the pH (this is why you should never add acid to bleach.) Formally, it's
Cl+ + Cl- → Cl2
but the "positive" chlorine is actually bonded to oxygen, in the form of a hypochlorite anion, ClO-.
 
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