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Symmetric and asymmetric stretching

How symmetric and asymmetric stretching of two identical groups can lead to two distinct signals in IR spectroscopy. Created by Jay.

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  • blobby green style avatar for user Adam Roth
    Why does the C-H bond have a higher intensity in the IR than the N-H bond, if the dipole moment for N-H bond is greater?
    (14 votes)
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  • male robot hal style avatar for user the ULTIMATE GEEK
    why can't the secondary amine stretch asymmetrically ?
    (6 votes)
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    • leafers tree style avatar for user Bobbie Dinkins
      Because there is only one hydrogen that gives only one possibility of stretching (out and in). With primary amines, there are two hydrogen, giving two possiblities of stretching: the same direction (both out/both in) or opposite directions (one out, one in).
      (9 votes)
  • blobby green style avatar for user Nguyen Nguyen
    Hi guys,
    At , the peak at 3300 cm-1 could also be C-H (sp hybridized), how do we know which is which?
    Thank ;)
    (7 votes)
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  • piceratops seedling style avatar for user Nandan Sheernaly
    As there is nitrogen in the amine there must be hydrogen bonding between any two amine molecules. So we must get broad signals, right?
    (4 votes)
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  • blobby green style avatar for user rizwangiki
    In the last example, at , why are we observing the symmetric and asymettric stretch for the carbonyl group. We have two different carbonyl groups on two different carbon atoms.So from my understanding, both of these double bonds should stretch individually, giving us a single peak.
    (3 votes)
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    • female robot amelia style avatar for user rozema
      Note: That is a really good question, I am not sure if my answer is correct, but I think its generally the right idea....
      Answer: The electron withdrawing/donating effect of functional groups can be seen throughout a molecule. They are strongest on directly bound atoms, but continue to have an effect on atoms adjacent to those they are directly bonded to, and beyond. Thus in the case of an anhydride, the bond characteristics of each carbonyl bond are somewhat impacted by the stretching of the other carbonyl bond.
      This results in a differential energy of stretching for symmetric vs asymmetric stretching.
      I hope this was helpful.
      (3 votes)
  • aqualine seedling style avatar for user Soheila Fallah
    we see the C-O bond in 1100, but why this signal is so broad?
    (3 votes)
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  • blobby green style avatar for user JMHusky53
    In general, if you have a double-tipped peak like that, is it indicative of the asymmetric and symmetric streching?
    (2 votes)
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    • male robot hal style avatar for user Slider
      I would say it really depends on the structure of your molecule, if you have only one functional group like the acid anhydride in the video, than its obvious the signal belongs to the symm. and asymm. stretch vibration.
      But you could also have two carbonyl groups in your molecule with different environment, which results in two different signals. Then it would be not obvious if two signals belong to a sym. and asym. stretch or two different carbonyl groups. Maybe take a look at the next video.
      (4 votes)
  • blobby green style avatar for user Kartikeya Dixit
    At why asymmetric stretch is taking more energy than symmetric stretch ?
    (4 votes)
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    • spunky sam blue style avatar for user Ernest Zinck
      Here's my guess:
      Consider a CH₂ group.
      In a symmetric stretch, the two H atoms are going in the same direction. The group dipole moment changes considerably because both bonds are going in and out at the same time.
      In an asymmetric stretch, they are going in opposite directions. One bond gets longer as the other gets shorter, so the change in dipole moment is much less.
      It takes energy to separate positive and negative charges from each other, so the symmetric vibration has a higher frequency (energy).
      (0 votes)
  • leafers seed style avatar for user Aaron
    So it seems in and out with one N-H makes one signal. With two N-Bonds he says the signals are not because of the two N-Hs but because of the combination where they could both be going out symmetrically. I see three possibilities for energy level in that case. one and and one out which averages to the same in/out of the signal carbon. Out/Out would be a symmetric stretch and create a signal. But I am having a hard time wrapping my head around in/in not creating a third signal. If there is a difference between in/out and out/out then it seems there must be a energy difference between in/out, out/out, and in/in. How does it boil down to two things?
    (1 vote)
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    • spunky sam blue style avatar for user Ernest Zinck
      In/in and out/out are opposite extremes of the same symmetric vibration. They are not different vibrations.
      In the same way, in/out and out/in are opposite extremes of the same asymmetric vibration.
      Hence there are only two types of vibrations.
      (2 votes)
  • blobby green style avatar for user Natalie Bata
    In trying to combine all of the concepts, how would I relate the Kinetic Energy of the electrons? Is it correct to say that a stronger bond that requires more energy (from photon of light) will have an increase in KE of the electrons, thus an increase in vibrations?

    Or am I just trying to combine way too many concepts?
    (1 vote)
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    • female robot grace style avatar for user tyersome
      I'm pretty sure that you must have things backwards — a strong bond is more stable and that should mean it has lower energy — so I would guess that if kinetic energy is relevant that the electrons would have lower kinetic energy in a stronger bond ...

      However, to be honest, I'm not really sure if talking about the KE of bonding electrons is helpful ...

      As for the vibrations, I believe that most of the movement is of the nuclei rather than the electrons.
      (1 vote)

Video transcript

- [Voiceover] Before we get into symmetric and asymmetric stretching, let's look at the IR spectrum for dibutylamines. So here's our dot structure for a dibutylamine. And we start by drawing a line about 3,000, and we know to the right of that, we expect to find the signal for the carbon-hydrogen bond stretch, where we're talking about an SP3 hybridized carbon. So this is the bond to hydrogen region on the IR spectrum. And notice we have another signal right here, so a signal that is at a higher wave number than the carbon-hydrogen bond stretch. So if we drop down here, we can estimate the wave number. It's approximately, this'll be 31, 32, 33. So at approximately 3,300 wave numbers, we get another signal, so another bond of an atom to hydrogen. This is the bond stretch for nitrogen-hydrogen, so that's this bond stretching right there. So in magenta, this is the nitrogen-hydrogen bond stretch. Let's compare the strength of that bond to a carbon-hydrogen bond where the carbon is SP3 hybridized. We know that the wave number is dependent on two things from an earlier video. We know it's dependent upon the force constant, k, or the spring constant k, and the reduced mass. Well, the reduced mass for these two bonds is approximately the same. So if you did a calculation for the reduced mass for nitrogen-hydrogen and for carbon-hydrogen, you're gonna get approximately the same value for the reduced mass. And so that's not what's affecting the different wave numbers for these signals here. So it must be the force constant. It must be k. And since the nitrogen-hydrogen bond has a greater wave, the signal shows up at a higher wave number, that must mean it's a stronger bond, because if you increase the force constant, increase the strength of the bond, you increase the wave number. You increase the frequency. And so the nitrogen-hydrogen bond is stronger than the carbon-hydrogen bond, where the carbon is SP3 hybridized. And if it's stronger, it takes more energy to cause that bond to stretch. So let's really quickly talk about energy. Energy is equal to h, which is Planck's constant, times the frequency, so when you're talking about the energy of a photon, it's equal to h nu. And nu is our frequency, and we know that relates to wave number. So the frequency is equal to the wave number times the speed of light. We talked about this in an earlier video. So if you take this and plug it into here, you can see the energy is directly proportional to the wave number, so this would be E is equal to h times the wave number times the speed of light. And this is one of the reasons why you see IR spectrum done in wave numbers, because you can also think about energy, right? So if you increase the wave number, if you're talking about increased wave number, you're talking about increased energy. So as you go this way, as you increase in wave number, you're also talking about increasing in energy. So you can think about it takes more energy, more energy is needed to stretch a stronger bond. And so it takes more energy to stretch this nitrogen-hydrogen bond. So again, think about a bond as a spring. If you have a really stiff or strong spring, it takes more energy to stretch that spring out as compared to a looser spring. And so that's thinking about energy, and also looking at a typical IR spectrum here for a secondary amine. So this nitrogen here is bonded to two carbons, so this is a secondary amine. And in a secondary amine, you're going to get one signal approximately 3,300 here. So let's compare this IR spectrum of a secondary amine with another amine, so this is a primary amine. Let's compare it to butylamine. So over here, this is a primary amine. The nitrogen is bonded to one carbon, so we're talking about a primary amine now. And let's analyze the IR spectrum. So once again, we're gonna draw a line around 3,000, and we know that this in here is talking about the carbon-hydrogen bond stretch for an SP3 hybridized carbon. Alright, once again, let's look at just past that, right in the bond to hydrogen region, and we get two signals this time, right? So if we look over here, there are two signals. This signal, let's drop down, this is approximately 3,300, so we have one signal approximately 3,300. And then we have another signal. Let me go ahead and make that green here. So we've got another signal right here, which is a little bit higher in terms of the wave number. So we drop down, this signal is approximately 3,400. So we know this is where we would expect to find the nitrogen-hydrogen bond stretch. We get two signals, and we need to figure out what's going on here. Well, this has to do with symmetric and asymmetric stretching. So let's look at two generic amines here, and let's talk about what the difference is between symmetric and asymmetric stretching. If you have symmetric stretching, so these bonds are stretching in phase, if you will. You can think about the hydrogens stretching away from the nitrogen at the same time. So this is called symmetric stretching. This is symmetric stretching. And this one over here, let me go ahead and draw what's happening over here. So this time these two nitrogen-hydrogen bonds are stretching out of phase. So if that hydrogen is stretching this way, this hydrogen might be contracting here, so that's an asymmetric stretch. Let me go ahead and write that. So we're talking about an asymmetric stretch here. So this is what's happening. This is why we get these two different signals. It turns out it takes less energy to do the symmetric stretching. So if it takes less energy to do the symmetric stretching, this is the one that we find at a lower wave number. Remember, wave numbers correspond to energy. So it takes less energy to do a symmetric stretching, and so that's this signal. It takes a little more energy to do asymmetric stretch. And so that's this signal, right up here. So we get two different signals here for our primary amine. Two signals, right? And it's tempting to say, "Oh, we get two signals "because we have two nitrogen-hydrogen bonds. "So here's a nitrogen-hydrogen bond, "and here's a nitrogen-hydrogen bond." But that's not really what's happening. Some of the molecules are having a symmetric stretch, and some of the molecules are having an asymmetric stretch. And so that's why you see these two different signals. Once again, let's just really quickly compare these two different amines. A secondary amine is going to give you only one signal on your IR spectrum, whereas a primary amine is going to give you two signals, right? These two different signals, here. That's something to look out for. Also, we can think about the carbon-hydrogen SP3 stretching here. For example, if you have a CH2 here, so a CH2, let me go ahead and draw two different situations here, so a CH2 in a molecule, you can have the same thing. You can have a symmetric stretch and an asymmetric stretch. So if these hydrogens are both stretching at the same time, that's a symmetric stretch. You could also have an asymmetric stretch like this. And, once again, you'll find the asymmetric stretch, so this one, actually takes a little bit more energy. So you're gonna find this signal at a slightly higher wave number. It's a pretty small difference, but it is a slightly higher wave number for this stretch. And that's one of the reasons why you get such a hard to interpret signal in here, so less than 3,000 there's a lot of stuff going on. It's too difficult to worry about in great detail. Just understand that that's where you would expect to find your carbon-hydrogen bond stretch, where I'm talking about an SP3 hybridized carbon. Finally, let's look at one more example of a symmetric and asymmetric stretch, and that's an acid and hydride. So let's look at an IR spectrum, just a generic IR spectrum for an acid and hydride. Let's draw a line around 1,500. To divide our two regions, we draw a line around 3,000 here. So we know this is our carbon-hydrogen in here. And then we get these two very intense signals, right? So let's figure out where these are, approximately. This signal right in here, let me use a different color for right here. We drop down, so where is that, approximately? Well, if this is 1,500, 1,600, 1,700, so that's pretty close to, let's say, 1,760 here for this signal. So, 1,760 wave numbers for that signal. And then this other signal, we drop down here. This is just a tiny bit past 1,800. We'll say approximately 1,800 here. So we get these two different, strong signals for an acid and hydride, and once again, we're talking about symmetric and asymmetric stretching. So a symmetric stretch, let me go down here, so this carbonyl, of course, is what we're talking about. We're talking about this really strong absorbence in the double bond region, right? So in here is the double bond region on our IR spectrum. We get these two strong signals, and the signal at a lower wave number is due to symmetric stretching. So this carbonyl could be stretching in phase with this carbonyl, so that's our symmetric stretch signal. So that's this one, down here. And then once again, we could get an asymmetric stretch. So we could have one of these, we could have this one stretching and this one contracting for our spring. It takes more energy to do an asymmetric stretch, and so that's this higher signal here. So if you see an IR spectrum, and you see these two really intense signals, we're talking about the carbonyl. So right in here, this is our double bond region. We're talking about the carbonyl stretch, with a large dipole moment, so a large change in dipole moment when it stretches. So that's why we see such an intense signal here. And then we see two of them, because we have symmetric and asymmetric stretching. There are other examples of symmetric and asymmetric stretching, but hopefully this gives you an idea about what to look for on your IR spectrum.