Why Does Oxidation Release Energy?

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Mission Medical

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My book is saying that as we oxidize methane to methanol, then oxidize further to formaldehyde, oxidize even further to formic acid and finally to carbon dioxide, there is a decrease in free energy each time. Why is this?

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Compounds with lots of bound highly energetic electrons have more energy, aka, highly reduced compounds. When you oxidize these compounds, energy is released.

Think of ATP vs. AMP, NADH vs. NAD+, FADH2 vs. FAD+. These compounds either serve as electron carriers or have highly energetic bonds due to the surplus of electrons. When oxidized, they release that energy.
 
Are you sure about that? I think C-H bonds are stronger than C-O bonds. Which is the reason why C-H bonds stretches further down in the IR spectra than C-O bonds.
 
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Are you sure about that? I think C-H bonds are stronger than C-O bonds. Which is the reason why C-H bonds stretches further down in the IR spectra than C-O bonds.

Ah a good point! It turns out you're right, but when we oxidize methane to methanol, we replace the C-H bond not only with a less stable C-O bond but also a more stable (than both) O-H bond, so there is a net increase in stability of the molecule.

This page explains this well: http://www.wou.edu/las/physci/GS361/Energy_From_Fossil_Fuels.htm
 
Wait, I would think that the C-O bond is in fact stronger than C-H, like you initially said. That explanation made sense, that a stronger bond will have lower energy since it's harder to break and therefore more stable. The C-O bond is polar covalent, and the C-H bond is non-polar covalent. A polar covalent bond is going to be stronger because of the partial positive and partial negative charge. Carbon and hydrogen have very similar electronegativities.
 
Wait, I would think that the C-O bond is in fact stronger than C-H, like you initially said. That explanation made sense, that a stronger bond will have lower energy since it's harder to break and therefore more stable. The C-O bond is polar covalent, and the C-H bond is non-polar covalent. A polar covalent bond is going to be stronger because of the partial positive and partial negative charge. Carbon and hydrogen have very similar electronegativities.

Technically they're both polar covalent and just google the bond energies yourself, C-H is stronger than C-O.
 
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Technically they're both polar covalent and just google the bond energies yourself, C-H is stronger than C-O.

Wikipedia: "Using Pauling's scale—C (2.55) and H (2.2)—the electronegativity difference between these two atoms is 0.35. Because of this small difference in electronegativities, the C−H bond is generally regarded as being non-polar."

I mean, Wikipedia's not always the best source, but the reasoning here is exactly right. I'm pretty surprised that a non-polar covalent C-H bond is actually stronger than a polar covalent C-O bond.
 
Wikipedia: "Using Pauling's scale—C (2.55) and H (2.2)—the electronegativity difference between these two atoms is 0.35. Because of this small difference in electronegativities, the C−H bond is generally regarded as being non-polar."

I mean, Wikipedia's not always the best source, but the reasoning here is exactly right. I'm pretty surprised that a non-polar covalent C-H bond is actually stronger than a polar covalent C-O bond.
I was just making a technical point; the only strictly non-polar covalent bonds are homonuclear diatoms (and, I guess, homonuclear complexes, like S8 or something).

And here's the bond energies: http://www.cem.msu.edu/~reusch/OrgPage/bndenrgy.htm

And yes, it seems unintuitive given the generalization about covalent bond polarity and strength.
 
maybe a simple answer would be that oxygen is more electronegative than carbon so it stabilizes the molecule by withdrawing electron density from carbon?
 
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In response to why a C-H bond is stronger than a C-O bond, I would think that the discussion of electronegativity is slightly irrelevant.

C-H bond is shorter than a C-O bond (periodic trends), meaning that the electrons involved in the bond are closer to the nuclei of the two atoms. this attraction is what stabilizes the bond and therefore makes it stronger than C-O.
 
In response to why a C-H bond is stronger than a C-O bond, I would think that the discussion of electronegativity is slightly irrelevant.

C-H bond is shorter than a C-O bond (periodic trends), meaning that the electrons involved in the bond are closer to the nuclei of the two atoms. this attraction is what stabilizes the bond and therefore makes it stronger than C-O.

Yeah, this makes a lot of sense. The internuclear distance allows a much lower electrostatic potential energy to be achieved through the bonding.
 
Simple answer is because C-O bonds are stronger than C-H bonds. More stable bonds formed means net release of energy.

Kind of confused me with the stability thing. I guess the way I see it is that energy is absorbed to break a bond and energy is released to form a new bond. In the reaction of methane to methanol you break 1 bond and form 2 bonds. As you further oxidize it you form even more bonds so there should be a net release of energy. Is that a good enough reasoning to use for the mcat? Or should we really go in depth by being familar with those bond energy numbers? I am far from taking the mcat but my classes really didn't go in this depth lol. Also how do you know all this? Is this the level of comprehension we should know for all subjects while studying for mcat?

One last thing, did they mean total energy in general? Or Gibb's free energy? I just finished two semesters of thermodynamics and no where in the course did we use the terms "free energy."
 
Kind of confused me with the stability thing. I guess the way I see it is that energy is absorbed to break a bond and energy is released to form a new bond. In the reaction of methane to methanol you break 1 bond and form 2 bonds. As you further oxidize it you form even more bonds so there should be a net release of energy. Is that a good enough reasoning to use for the mcat? Or should we really go in depth by being familar with those bond energy numbers? I am far from taking the mcat but my classes really didn't go in this depth lol. Also how do you know all this? Is this the level of comprehension we should know for all subjects while studying for mcat?

One last thing, did they mean total energy in general? Or Gibb's free energy? I just finished two semesters of thermodynamics and no where in the course did we use the terms "free energy."

You won't need to memorize bond energy values for the MCAT. They would be provided if a question required them. I learned about this in a summer biochemistry course and was curious about the reasoning, although it wouldn't hurt to understand for the MCAT since these concepts (oxidation/reduction, changes in free energy, bond stability, etc.) deal with topics that would be found on the MCAT. I wouldn't worry about this specific question though. I didn't come across this while studying for the MCAT or anything like that. As for the level of comprehension required for most topics, I would say your best bet is to just work hard to get good grades in all your classes and then use review books for practice questions and going over areas you're weaker in. That will give you the best sense of how in-depth you need to understand concepts. Lastly, I was referring to "Gibb's free energy" when I simply said "free energy." I think those terms are used interchangeably pretty often.

This thread has confused me. So what's the conclusion?

Here's my conclusion:
A compound that gets oxidized loses electrons. When we talk about oxidation of hydrocarbons, which is usually the case in organic chemistry and biochemistry, we are usually talking about a C-H bond changing to a C-O bond. The loss of electrons is essentially due to the fact that when carbon was bonded to hydrogen, carbon was slightly more electronegative than hydrogen and therefore holding on to hydrogen’s electron a little bit more tightly, but when carbon became bonded to oxygen, the oxygen is much more electronegative, and oxygen pulls much more tightly on the electrons involved in the C-O bond, essentially taking away the electrons from carbon. Recall from general chemistry and physics that electrons exist at certain energy levels in atoms. Electrons possess stored, potential energy that is capable of doing work, so the “loss of electrons” accompanying oxidation leads to a release of free energy. Another way of understanding why oxidation leads to release of free energy is to consider how the type of bonding changes with oxidation. Stronger bonds are being made with oxidation. For example, initially we might mainly have C-H bonds. Strangely enough, a C-O bond is actually weaker (Look at the bonding energies). This is due to the fact that hydrogen is much smaller than oxygen, so the hydrogen is much closer to carbon in a bond than is oxygen, and consequently, the electrons can be shared more effectively, allowing for a stronger bond. However, oxidation of a hydrocarbon often also forms O-H bonds, as in oxidation of methane to methanol. O-H bonds are very strong polar covalent bonds with higher bonding energies (more energy needed to break them) than C-H bonds. Additionally, oxidation often results in C=O bonds. Double bonds are much stronger than single C-H bonds. In other words, the bonds being formed are harder to break and therefore more stable. Stability is associated with lower free energy, so the stronger bonds resulting from oxidation must be causing a release of free energy. If you also remember from general chemistry, combustion reactions, in which a hydrocarbon is in the presence of oxygen and subjected to oxidation, are highly exothermic, releasing large amounts of energy. These more reduced molecules, such as hydrocarbons, that get oxidized are referred to as fuel molecules. Oxidation of fuel yields free energy, which can be used to add phosphate to ADP to produce ATP. That ATP can then be hydrolyzed to ADP, releasing free energy in the process, which can be used for active transport, etc.

Someone let me know if I'm missing anything or if this explanation has any errors.
 
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That was a great explanation! I did well in Biochem but always sort of missed the big picture in cellular respiration but this sort of cleared everything up.
 
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