Why does the reactivity of halogens decrease down the group?

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Discussion Overview

The discussion revolves around the reactivity of halogens, specifically why reactivity decreases down the group from chlorine to bromine. Participants explore theoretical explanations, bond strength, and the role of equilibrium in acid strength.

Discussion Character

  • Debate/contested
  • Conceptual clarification
  • Technical explanation

Main Points Raised

  • Some participants express confusion about the relationship between bond strength and reactivity, questioning why chlorine is more reactive than bromine despite the Cl-Cl bond being stronger than the Br-Br bond.
  • One participant suggests that as you go down the halogen group, the average distance of the outer p-electrons increases, leading to decreased electron affinity and thus lower reactivity.
  • Another participant argues that the stability of the product must be considered, indicating that Cl- is less reactive than Br-, which relates to the strength of HCl compared to HBr.
  • There is a mention of equilibrium constants and their relevance to the reactivity of Cl2 versus Br2, with a claim that Cl2 is more reactive due to the relative stability of Cl- compared to Br-.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the reasons behind the differences in reactivity among halogens. Multiple competing views and uncertainties remain regarding the influence of bond strength, electron affinity, and equilibrium on reactivity.

Contextual Notes

Limitations include unresolved assumptions about bond energies and the definitions of stability and reactivity. The discussion does not clarify how these factors interact in the context of halogen reactivity.

sgstudent
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It is stated that for the halogens reactivity decreases down the group. Buy why is this so? Since they would form elements so since they should be stable hence eg chlorine being more reactive than bromine won't the bonds be stronger making it even less reactive? So I'm quite confused about this part here. Thanks for the help!
 
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sgstudent said:
It is stated that for the halogens reactivity decreases down the group. Buy why is this so? Since they would form elements so since they should be stable hence eg chlorine being more reactive than bromine won't the bonds be stronger making it even less reactive? So I'm quite confused about this part here. Thanks for the help!

As you go down the halogen group the average distance of the outer p-electrons increases and so does the screening of the nuclear charge. As a result the affinity for gaining another electron is decreased.
 
But aren't the bonds between Cl and Cl stronger than Br and Br. So why is chlorine more reactive than bromine since it should be harder to break those bonds? Since the explanation of the distance of valence electrons increases works only for atoms of the molecule of the elements meaning Cl and Br. Or am I wrong here, thanks so much for the help!
 
The reason that HCl is a stronger acid than HBr is that Cl- is less reactive than Br-. You have to consider the stability of the product, not just the bond energy. Equilibrium constants exist for a reason.
 
aroc91 said:
The reason that HCl is a stronger acid than HBr is that Cl- is less reactive than Br-. You have to consider the stability of the product, not just the bond energy. Equilibrium constants exist for a reason.

Um sorry I don't quite understand the equilibrium concept. I guessing its another factor to reactivity? Because what I'm thinking is that the Cl-Cl bond is stronger than Br-Br bond due to the reactivity of the chlorine atom. So won't it be harder to break the Cl-Cl bond and make it react? So why is Br2 less reactive than Cl2? Thanks for the help!
 
Last edited:
Cl2 is more reactive because Cl- is more stable than Br-. Bond energy is not the only factor. You have to consider the relative stability of reactants and products. In the case of Cl2 and Br2, Cl2 is more reactive because Cl- is more stable and there's not as much pressure (where the equilibrium concept comes into play) to remain as Cl2.
 

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