Comments on: Initiation, Propagation, Termination https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/ Mon, 23 Sep 2024 17:56:04 +0000 hourly 1 https://wordpress.org/?v=6.6.2 By: TINA https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-650800 Fri, 24 Mar 2023 11:59:32 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-650800 Thank you so much for this, really helpful.

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-556518 Wed, 19 Jun 2019 16:59:59 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-556518 In reply to Rodgers.

You can do it. Use this as a template.

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-556517 Wed, 19 Jun 2019 16:59:36 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-556517 In reply to Britney.

The methyl radical and chlorine radical are present in very low concentrations (relative to CH4 and Cl2) and the rate should be low for most of the reaction since rate is proportional to concentration. If these radicals do meet each other, they will react of course, it’s just that it’s quite unlikely.
The reaction of the alkyl radical with Cl2 is more favored simply because the concentration of cl2 is much, much higher than that of the Cl radical.

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-556516 Wed, 19 Jun 2019 16:56:36 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-556516 In reply to Subhan Bihan.

Examine the radical formed through homolytic cleavage of the C2 C-H bond, compared to the radical formed through homolytic cleavage of the C3 C-H bond. What do you notice about its neighbor?
Although this isn’t the best example, you might find this interesting: https://en.wikipedia.org/wiki/Captodative_effect

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-556515 Wed, 19 Jun 2019 16:53:42 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-556515 In reply to Oosman Beekawoo.

The unpaired electron of Cl interacts with the s orbital of the hydrogen and there is a transition state where there are partial bonds between Cl and H and carbon. The H-Cl bond is comparable in strength (102 kcal/mol) to the H-C bond in methane (105 kcal/mol) so the process is reasonably favorable. The resulting carbon-based radical then reacts with leftover Cl2. C-H bond dissociation energies in methane are quite high relative to other alkanes, so in other alkanes it will be even more favorable.

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-556513 Wed, 19 Jun 2019 16:47:10 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-556513 In reply to stephnie okwuonu.

Same as written here, just use propane instead of methane. The complication is that you will have two different monochlorination products. 1-chloropropane and 2-chloropropane.

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-556512 Wed, 19 Jun 2019 16:46:06 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-556512 In reply to noonoowhale.

This is for free-radical halogenation of alkanes, although the reaction of CFCs with ozone also proceeds through initiation, propagation and termination steps.

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By: James https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-535527 Mon, 16 Jul 2018 19:40:59 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-535527 In reply to Rome.

The way to look at it is to compare bond enthalpies and calculate the difference in energy going from starting material to product.

The bond strength of H-Cl is about 106-107 kcal/mol whereas the bond strength of H-CH3 is about 104 kcal/mol. Therefore the “gain” in energy is about 3kcal/mol from the chlorination of methane.

(The C-Cl bond does not factor into this reaction, except as a possible termination step).

That at least gives you an idea of whether or not the process will be energetically favorable overall.

We don’t cover free-radical fluorination because the H-F bond is even stronger than C-H, and furthermore the reaction is so exothermic that combustion tends to take place.
On the other hand free-radical iodination generally fails because H-I bonds are so weak, relative to C-H .

So, in summary: bond strengths are a good guide.

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By: Rome https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-535398 Fri, 13 Jul 2018 22:38:29 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-535398 Hello! Thanks for all the info, the website is really great.
I have one question if I may. Why in the first place does the Cl* radical “take” the hydrogen from, for example, the methane? Is the H-C bond in methane weaker than the Cl-C bond? Or should I ask if the Cl* radical least stable than the H3C* radical? Which one is the right question? And are there other basic thing to take into account?

Thank you!

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By: noonoowhale https://www.masterorganicchemistry.com/2013/09/06/initiation-propagation-termination/#comment-531674 Sun, 29 Apr 2018 20:14:22 +0000 https://www.masterorganicchemistry.com/?p=7528#comment-531674 how does it work
for chlorofluorocarbons?

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