Ace Your Next Organic Chemistry
Exam.

With these Downloadable PDF Study Guides

Our Study Guides

Free Radical Reactions

By James Ashenhurst

Free Radical Reactions

Last updated: June 14th, 2019 |

Free Radical Reactions – Chlorination of Methane

Alkanes are pretty boring, chemically speaking.  They don’t tend to undergo many reactions. However, when they are treated with Cl2 and light, a substitution of H for Cl occurs. As we hope to show here, this is NOT an acid-base reaction.  In  fact, it proceeds through a pathway we haven’t explored yet, called, “free radical substitution”. In this post we introduce the concepts  of homolytic bond breakage, single-barbed curved arrows, free radicals, and free-radical substitution through the example of  chlorination of  alkanes with Cl2 and light, which  will lay the  foundation for this series on free-radical chemistry.

Table of Contents

  1. Heterolytic Bond Cleavage Versus Homolytic Bond Cleavage
  2. Chlorination of Methane With Cl2 And Light () Breaks C–H and Forms C–Cl
  3. Why Chlorination of Methane With Cl2 Cannot Be An Acid-Base Reaction
  4. The Reaction Proceeds Through A Neutral  Intermediate
  5. The Chlorine-Chlorine Bond Is Weak. So How Does It Break?
  6. “Homolytic” Chlorine-Chlorine Bond Breaking Is Depicted With “Single-Barbed” Curved Arrows
  7. The Chlorine Atom Is Neutral And Has An Unpaired Electron
  8. Summary: “Free  Radicals”Are Highly Reactive Chemical Species Containing An Unpaired Electron

1. Heterolytic Bond Cleavage versus Homolytic Bond Cleavage

With rare exceptions, until now every reaction we’ve discussed (acid-base, substitution, elimination, addition) has involved the formation of bonds between an electron pair donor (Lewis base) and an electron pair acceptor (Lewis acid) or the breakage of bonds to generate the same [this is called “heterolytic” cleavage, by the way, since one bonding partner gets two electrons and the other gets zero].

In this series of posts we’ll take a detour into a corner of organic chemistry where bonds are formed by the combination of single electrons and bonds break through “homolytic” cleavage [that is, each bonding partner receives an equal number of electrons]. As we’ll see, these reactions are generally referred to as free radical reactions.

2. Chlorination Of Methane With Cl2 And “Light” Breaks C-H and Forms C-Cl

It all starts with a simple observation. Take an ordinary hydrocarbon gas – methane, for example, although any alkane hydrocarbon will be suitable here.  When we combine this hydrocarbon with chlorine gas, in the dark, nothing happens.

1-radical-dark

Here’s the interesting part. Flick a switch – or remove the cover – such that visible light can enter the flask, and suddenly our methane is consumed such that carbon-hydrogen bonds are replaced with carbon-chlorine bonds. The final product depends on the number of equivalents of chlorine gas – let’s use Cl2 in very small quantities to start with, to keep things simple.

2-radical-light

What’s going on here? Note that “hν” means “light”. [We can also do this reaction with heat alone, although it requires higher temperatures].

Before trying to understand why this happened, let’s make sure we’re clear on what has happened.

Let’s look at what bonds have formed and what bonds have broken. Notice that we’re breaking Cl-Cl, C-H, and forming C-Cl.

3. Why Chlorination of Methane With Cl2 Cannot Be An Acid-Base Reaction

What reactions have we seen so far that would be capable of such a transformation? Well, we’ve seen that all acid-base reactions involve the cleavage of a bond between H and some atom. So maybe, you might say, it’s possible that somehow a hydrogen is being pulled off the carbon by a strong base, and then the carbon attacks chlorine. But does that make sense here?

3-acid-base

Note that methane [CH4] would have to be the acid, and chloride ion [Cl- ] would have to be the base. As we’ve seen before, this makes NO sense as an acid base reaction, because we’d be going from a very weak acid [CH4] to a very strong acid [HCl] and likewise a weak base [Cl] to a strong base.

This is like trying to get Niagara Falls to flow in reverse. Not gonna happen!

4. The Reaction Proceeds Through A Neutral Intermediate

Furthermore, a second piece of evidence should give pause. If the reaction proceeded through some kind of charged intermediate like Cl- or CH3 , we would expect that the reaction would  proceed more quickly in polar solvents [that can stabilize charge] as opposed to nonpolar solvents [which do not stabilize charge]. Instead, we find that the rate of the reaction is almost completely independent of solvent polarity. It proceeds just about as quickly in [nonpolar] carbon tetrachloride as it does in a polar solvent such as methanol. 

4-solvent effects

So what does this mean? It is consistent with the reaction proceeding through neutral intermediates rather than polar ones.

Alright – so how, then, might we get a neutral intermediate?

5. The Chlorine-Chlorine Bond Is Weak. So How Does It Break?

Let’s think first about that chlorine-chlorine bond, which is relatively weak. Imagine that by heating it up or by shining light on it [recall that light is a form of energy!] it might break somehow. How might it break?

Option #1 would look something like this – “heterolytic” cleavage, where one atom receives both electrons from the bond, while the other does

5-cl-cl-solvent

However if this was the case, then we should expect to see a faster reaction in polar solvents, which is not the case.

So what else might happen here?

Recall that many of the molecules we’ve been discussing have a dipole. That is,  two atoms sharing a bond have unequal electronegativities, and thus unequal electron densities – one is electron rich and one is electron poor.

However here we have two chlorine atoms. They have equal electronegativity. So we would not expect that one chlorine should “win” the tug of war of electrons over the other.

6. “Homolytic” Chlorine-Chlorine Bond Breakage Is Depicted With “Single-Barbed” Curved Arrows

So we are left with this: What if the chlorine chlorine bond breaks such as to give each chlorine a single electron? 

6-homolytic cleaveage

Weird, when you first see it. One note – when using the arrow pushing notation, we modify it somewhat, such that we have single fishhooks showing where the electrons go. Note that we can use these to show a single electron going to each of the two chlorines.

But let’s look at this a bit more closely.

7. The Chlorine Atom Is Neutral And Has An Unpaired Electron

What would be the charge of the chlorine atom? It has seven valence electrons.

7-neutral

This species is neutral, which is consistent with the solvent data.

Would we expect such a species to be stable? If we think back to the octet rule, we see that  each chlorine atom bears less than a full octet of electrons.  In other words, it is electron-deficient.

8. Summary: Species With An Unpaired Electron Are Called “Free Radicals” And Are Highly Reactive

We would expect such a species to be highly reactive, since there will be a strong driving force to form the full octet.

The whole point of this article is to say that yes, such species do exist, and they are called “free radicals” [the etymology of this term is interesting, but a little old-fashioned and not crucial for us right now]

There are additional pieces of evidence collected over the past hundred-odd years to support the existence of free radicals. They aren’t crucial to understand, but if you’re curious you could try reading about EPR, CIDNP, or Moses Gomberg, the father of free radical chemistry.

In the next few posts we’ll go through the following topics:

  • What factors stabilize (or destabilize) free radicals ?
  • How do we “know” when a free radical reaction might be occurring?
  • What is the mechanism of free radical substitution reactions (such as that above?)
  • What useful reactions can we perform using free-radical chemistry?

See you next post!
Next Post: 3 Factors Which Stabilize Free Radicals

Comments

Comment section

7 thoughts on “Free Radical Reactions

  1. Hi, I was wondering if you could help me with my homework. Which reaction could easily produce a product: alkene plus HBR —–> antimarkivnov product or an alkene plus HCl——–>markivnov product? Thanks.

  2. Hi James,
    Free radical carbon atoms are electron deficient and they are stabilized by electron releasing groups next to it.
    But why aren’t they stabilized by solvation?

    1. They are neutral. In most polar reactions there is an activation barrier for forming a charged species such as a carbocation which can be reduced through solvation with a polar solvent. Not the case here.

Leave a Reply

Your email address will not be published. Required fields are marked *

This site uses Akismet to reduce spam. Learn how your comment data is processed.