1 00:00:00,000 --> 00:00:00,016 The following content is provided under a Creative 2 00:00:00,016 --> 00:00:00,022 Commons license. 3 00:00:00,022 --> 00:00:00,038 Your support will help MIT OpenCourseWare continue to 4 00:00:00,038 --> 00:00:00,054 offer high quality educational resources for free. 5 00:00:00,054 --> 00:00:00,072 To make a donation or view additional materials from 6 00:00:00,072 --> 00:00:00,088 hundreds of MIT courses, visit MIT OpenCourseWare at 7 00:00:00,088 --> 00:00:00,110 ocw.mit.edu. 8 00:00:00,110 --> 00:00:23,990 PROFESSOR: OK, I want to take 10 more seconds now the 9 00:00:23,990 --> 00:00:27,670 clicker slide. 10 00:00:27,670 --> 00:00:31,680 This is giving us one more try on the vsper geometries, 11 00:00:31,680 --> 00:00:37,100 because it didn't go so well on Wednesday. 12 00:00:37,100 --> 00:00:38,150 All right, excellent. 13 00:00:38,150 --> 00:00:40,320 So that is a very good job. 14 00:00:40,320 --> 00:00:43,880 Let's quickly go over why. 15 00:00:43,880 --> 00:00:45,620 We have p h 3. 16 00:00:45,620 --> 00:00:50,040 We told you that phosphorous has 5 valence electrons plus 3 17 00:00:50,040 --> 00:00:52,390 from each of the hydrogens, so we have a total 18 00:00:52,390 --> 00:00:54,860 of 8 valence electrons. 19 00:00:54,860 --> 00:00:57,300 How many do we need to get full valence shells 20 00:00:57,300 --> 00:00:58,100 everywhere? 21 00:00:58,100 --> 00:01:00,340 STUDENT: [INAUDIBLE] 22 00:01:00,340 --> 00:01:00,620 PROFESSOR: 14. 23 00:01:00,620 --> 00:01:03,330 So, we need 14 minus 8. 24 00:01:03,330 --> 00:01:09,380 That leaves us with 6 bonding electrons. 25 00:01:09,380 --> 00:01:15,330 And if we put that in our bond here, we have 1, 2, 3 bonds, 26 00:01:15,330 --> 00:01:18,630 plus we have one lone pair left over. 27 00:01:18,630 --> 00:01:21,000 So this is our Lewis structure here. 28 00:01:21,000 --> 00:01:24,940 If these bonds were all completely of equal distance 29 00:01:24,940 --> 00:01:28,300 apart, whether is was a lone pair or bonding electrons, the 30 00:01:28,300 --> 00:01:29,990 angles would be 109 . 31 00:01:29,990 --> 00:01:31,130 5 degrees. 32 00:01:31,130 --> 00:01:34,640 But because there's this lone pair here, it's pushing down 33 00:01:34,640 --> 00:01:38,270 on the other bonds, so we end up with an angle of 34 00:01:38,270 --> 00:01:40,080 less than 109 . 35 00:01:40,080 --> 00:01:40,970 5 degrees. 36 00:01:40,970 --> 00:01:44,630 All right, so let's switch over to notes for today. 37 00:01:44,630 --> 00:01:46,710 So we're going to finish talking about molecular 38 00:01:46,710 --> 00:01:50,410 orbital theory, and then we'll switch over to discussing 39 00:01:50,410 --> 00:01:54,180 bonding in larger molecules, even larger than diatomic, so 40 00:01:54,180 --> 00:01:59,690 we'll move on to talking about valence bond theory and 41 00:01:59,690 --> 00:02:00,010 hybridization. 42 00:02:00,010 --> 00:02:01,510 So, clearly you don't have your notes in front of you 43 00:02:01,510 --> 00:02:04,230 yet, so you can just listen, take it all in. 44 00:02:04,230 --> 00:02:07,650 What I'll do is I'll post the notes filled in to the point 45 00:02:07,650 --> 00:02:10,420 where you actually get your class notes today. 46 00:02:10,420 --> 00:02:13,930 So, this will be a little bit more like a seminar to start 47 00:02:13,930 --> 00:02:17,460 with, and a little bit less like a lecture in class. 48 00:02:17,460 --> 00:02:20,550 But let's go ahead and start our discussion in terms of 49 00:02:20,550 --> 00:02:23,910 molecular orbital theory. 50 00:02:23,910 --> 00:02:27,650 So where we had left off with was we'd fully discussed up to 51 00:02:27,650 --> 00:02:31,000 the point of considering homonuclear diatomic 52 00:02:31,000 --> 00:02:34,370 molecules, so molecules that both have the same nucleus. 53 00:02:34,370 --> 00:02:37,990 And where we had left off was we were going to start one 54 00:02:37,990 --> 00:02:41,400 example of thinking about now where we have a heteronuclear 55 00:02:41,400 --> 00:02:47,080 diatomic molecules, so two different atoms in terms of 56 00:02:47,080 --> 00:02:48,590 forming the molecule. 57 00:02:48,590 --> 00:02:50,760 But first, I just want to remind you when we're talking 58 00:02:50,760 --> 00:02:53,440 about molecular orbital theory, this is treating 59 00:02:53,440 --> 00:02:56,350 electrons as waves, so what we're actually able to do is 60 00:02:56,350 --> 00:03:00,370 either constructively or destructively combine atomic 61 00:03:00,370 --> 00:03:01,970 orbitals to form molecular orbitals. 62 00:03:01,970 --> 00:03:06,080 So you should remember that any time we combine 2 s 63 00:03:06,080 --> 00:03:09,290 orbitals, what we're going to find is if we constructively 64 00:03:09,290 --> 00:03:11,420 interfere those two orbitals, we're going to 65 00:03:11,420 --> 00:03:13,220 form a bonding orbital. 66 00:03:13,220 --> 00:03:16,250 And that's going to be lower in energy than the two 67 00:03:16,250 --> 00:03:18,350 individual atomic orbitals. 68 00:03:18,350 --> 00:03:21,850 And we call that, for this case, our sigma 2 s orbital. 69 00:03:21,850 --> 00:03:26,740 In contrast, if we have destructive interference, what 70 00:03:26,740 --> 00:03:30,300 we're going to form is a sigma 2 s star, and what does the 71 00:03:30,300 --> 00:03:31,630 star designate? 72 00:03:31,630 --> 00:03:32,830 STUDENT: [INAUDIBLE] 73 00:03:32,830 --> 00:03:33,630 PROFESSOR: Anti-bonding, yup. 74 00:03:33,630 --> 00:03:35,440 So it's an Anti-bonding orbital. 75 00:03:35,440 --> 00:03:38,320 It's going to be higher in energy than the individual 76 00:03:38,320 --> 00:03:38,950 atomic orbitals. 77 00:03:38,950 --> 00:03:41,300 All right, great. 78 00:03:41,300 --> 00:03:43,860 So, I think we have these molecular orbital energies 79 00:03:43,860 --> 00:03:46,140 down, so let's move on to talking about 80 00:03:46,140 --> 00:03:48,390 more complex molecules. 81 00:03:48,390 --> 00:03:51,520 And to do this we're going to introduce valence bond theory, 82 00:03:51,520 --> 00:03:56,270 and the idea of hybridization of orbitals. 83 00:03:56,270 --> 00:03:59,420 So the idea behind valence bond theory is very easy to 84 00:03:59,420 --> 00:04:00,090 understand. 85 00:04:00,090 --> 00:04:03,330 Essentially what you have is bonds resulting from the 86 00:04:03,330 --> 00:04:05,880 pairing of unpaired electrons. 87 00:04:05,880 --> 00:04:09,910 So the simplest case we can think of is with h 2 where we 88 00:04:09,910 --> 00:04:14,550 have two unpaired electrons, each in a 1 s orbital of a 89 00:04:14,550 --> 00:04:16,570 separate h atom. 90 00:04:16,570 --> 00:04:20,120 And if we picture those two coming together, we form the h 91 00:04:20,120 --> 00:04:21,620 2 molecule. 92 00:04:21,620 --> 00:04:25,110 And again, we have the pairing of the unpaired electrons, and 93 00:04:25,110 --> 00:04:28,170 we have two orbitals coming together. 94 00:04:28,170 --> 00:04:31,350 So in molecular orbital theory, what we did was we 95 00:04:31,350 --> 00:04:33,920 named orbitals based on their symmetry. 96 00:04:33,920 --> 00:04:37,310 In valence bond theory, the focus is on discussing the 97 00:04:37,310 --> 00:04:40,210 bonds, but it should look very familiar to you, because 98 00:04:40,210 --> 00:04:43,040 there's two types of bonds that we want to discuss here. 99 00:04:43,040 --> 00:04:46,570 We want to discuss sigma bonds and pi bonds. 100 00:04:46,570 --> 00:04:49,340 So this is very similar to what we saw in terms of sigma 101 00:04:49,340 --> 00:04:51,160 orbitals and pi orbitals. 102 00:04:51,160 --> 00:04:53,470 So in this first case here, what we're 103 00:04:53,470 --> 00:04:55,770 seeing is a sigma bond. 104 00:04:55,770 --> 00:04:59,010 And a sigma bond forms any time you have two orbitals 105 00:04:59,010 --> 00:05:02,250 coming together and interacting on that 106 00:05:02,250 --> 00:05:05,150 internuclear axis. 107 00:05:05,150 --> 00:05:08,830 So we talk about a sigma bond as being cylindrically 108 00:05:08,830 --> 00:05:11,980 symmetric about the bond axis, and it's important to point 109 00:05:11,980 --> 00:05:15,950 out that it has no nodal plane across this bond axis. 110 00:05:15,950 --> 00:05:17,840 This is in direct contrast to when we're 111 00:05:17,840 --> 00:05:20,000 thinking about pi bonds. 112 00:05:20,000 --> 00:05:25,520 So pi bonds have electron density both above and below 113 00:05:25,520 --> 00:05:29,560 the bond axis, but they actually have a nodal plane at 114 00:05:29,560 --> 00:05:31,940 this z, this bond axis here. 115 00:05:31,940 --> 00:05:34,990 And remember for this class, we always define z as the 116 00:05:34,990 --> 00:05:37,570 internuclear or the bond axis. 117 00:05:37,570 --> 00:05:40,700 So it might look like here, if you don't understand about p 118 00:05:40,700 --> 00:05:42,950 orbitals, which I know all you do, but if someone else was 119 00:05:42,950 --> 00:05:45,100 just looking and seeing, it kind of looks like there's two 120 00:05:45,100 --> 00:05:46,090 bonds here. 121 00:05:46,090 --> 00:05:49,320 There's not two bonds, that's one pi bond, and the reason is 122 00:05:49,320 --> 00:05:52,440 because it's 2 p orbitals coming together, and remember 123 00:05:52,440 --> 00:05:55,805 p orbitals have electron density above and below the 124 00:05:55,805 --> 00:05:58,290 axis, so when they come together, it kind of looks 125 00:05:58,290 --> 00:06:00,670 like one bonds, but essentially what we have here 126 00:06:00,670 --> 00:06:03,270 is one pi bond. 127 00:06:03,270 --> 00:06:07,330 So let's think about how we can classify single and double 128 00:06:07,330 --> 00:06:09,360 and triple bonds, which is what we're really used to 129 00:06:09,360 --> 00:06:11,920 dealing with in terms of these sigma bonds 130 00:06:11,920 --> 00:06:13,750 and these pi bonds. 131 00:06:13,750 --> 00:06:16,340 So, if we take a look at what a single bond is, and let me 132 00:06:16,340 --> 00:06:19,720 grab some molecules here. 133 00:06:19,720 --> 00:06:22,570 If we're talking about a single bond, we're talking 134 00:06:22,570 --> 00:06:27,070 about 2 orbitals overlapping in the internuclear axis. 135 00:06:27,070 --> 00:06:29,860 So if we have a single bond here, would you consider that 136 00:06:29,860 --> 00:06:33,300 a sigma bond or a pi bond? 137 00:06:33,300 --> 00:06:33,830 STUDENT: [INAUDIBLE] 138 00:06:33,830 --> 00:06:35,510 PROFESSOR: Right, it's a sigma bond. 139 00:06:35,510 --> 00:06:38,020 Essentially what we're seeing is overlapping 140 00:06:38,020 --> 00:06:40,450 in this z axis here. 141 00:06:40,450 --> 00:06:44,130 In contrast, if we talk about a double bond, what we're now 142 00:06:44,130 --> 00:06:47,450 talking about is having both a sigma bond 143 00:06:47,450 --> 00:06:49,750 and also one pi bond. 144 00:06:49,750 --> 00:06:53,210 And I apologize, I intended to set this up right before 145 00:06:53,210 --> 00:06:55,840 class, but that didn't happen today. 146 00:06:55,840 --> 00:06:59,760 All right, so what we see here is we have our sigma bond 147 00:06:59,760 --> 00:07:03,470 that's along the internuclear axis here, but we also have a 148 00:07:03,470 --> 00:07:07,210 pi bond, because each of these atoms now has electrons in 149 00:07:07,210 --> 00:07:09,510 it's in a p orbital, so we're going to overlap of electron 150 00:07:09,510 --> 00:07:13,540 density above and below the bond. 151 00:07:13,540 --> 00:07:16,900 So that's exactly what our definition of a pi bond is, so 152 00:07:16,900 --> 00:07:20,160 we have one sigma bond, and one pi bond. 153 00:07:20,160 --> 00:07:22,310 So now let's think about a triple bond. 154 00:07:22,310 --> 00:07:26,400 A triple bond, again is going to have one sigma bond on the 155 00:07:26,400 --> 00:07:28,130 internuclear axis. 156 00:07:28,130 --> 00:07:29,930 How many pi bonds would you expect? 157 00:07:29,930 --> 00:07:31,410 STUDENT: [INAUDIBLE] 158 00:07:31,410 --> 00:07:32,670 PROFESSOR: Two, great. 159 00:07:32,670 --> 00:07:34,460 So, we're going to see two pi bonds. 160 00:07:34,460 --> 00:07:38,120 The first one will be above and below the bond axis is 161 00:07:38,120 --> 00:07:40,650 where we'll see the electron density, and the second will 162 00:07:40,650 --> 00:07:44,050 be perpendicular to that, so it will be a density in front 163 00:07:44,050 --> 00:07:45,860 of and behind the bond axis. 164 00:07:45,860 --> 00:07:48,680 So we can kind of flip it this way -- this will be one pi 165 00:07:48,680 --> 00:07:50,690 bond, this will be another interacting 166 00:07:50,690 --> 00:07:51,740 between these p orbitals. 167 00:07:51,740 --> 00:07:56,040 All right, so that's really all there is to thinking about 168 00:07:56,040 --> 00:07:58,400 valence bond theory in terms of the most 169 00:07:58,400 --> 00:08:00,160 simple explanation here. 170 00:08:00,160 --> 00:08:02,500 But what we're going is we're going to start trying to apply 171 00:08:02,500 --> 00:08:05,200 it to a molecule, and I actually picked a molecule 172 00:08:05,200 --> 00:08:07,630 that it's not going to work for, even though it would work 173 00:08:07,630 --> 00:08:10,410 even just at this level for many, many molecules. 174 00:08:10,410 --> 00:08:13,510 And I picked looking at methane so we could see if 175 00:08:13,510 --> 00:08:16,470 there are other factors that we're not considering, that we 176 00:08:16,470 --> 00:08:19,920 need to maybe tweak our model a little bit, and I think 177 00:08:19,920 --> 00:08:24,150 we'll find that we do if we take a look at a polyatomic 178 00:08:24,150 --> 00:08:27,660 molecule, methane, so c h 4. 179 00:08:27,660 --> 00:08:32,560 So let's think about methane using valence bond theory. 180 00:08:32,560 --> 00:08:36,010 So, using our simple valence bond theory, what we would 181 00:08:36,010 --> 00:08:40,790 expect is that we want to pair up any unpaired electrons in 182 00:08:40,790 --> 00:08:44,580 methane with unpaired electrons from hydrogen and 183 00:08:44,580 --> 00:08:46,280 form bonds. 184 00:08:46,280 --> 00:08:49,410 But what we see we have is that we only have two unpaired 185 00:08:49,410 --> 00:08:51,000 electrons here. 186 00:08:51,000 --> 00:08:55,180 Because we have paired set in a 2 s orbital, so all we're 187 00:08:55,180 --> 00:08:58,360 left essentially is two electrons that are available 188 00:08:58,360 --> 00:08:59,200 for bonding. 189 00:08:59,200 --> 00:09:01,780 So this should immediately look like a problem because we 190 00:09:01,780 --> 00:09:04,850 know, in fact, that methane is tetravalent, and this is 191 00:09:04,850 --> 00:09:07,130 telling us it's only divalent. 192 00:09:07,130 --> 00:09:10,380 Essentially it would only allow for us to bond to two 193 00:09:10,380 --> 00:09:14,650 hydrogen atoms. So if it did this, it now looks like, from 194 00:09:14,650 --> 00:09:17,610 looking at the paired electrons that we have a 195 00:09:17,610 --> 00:09:21,930 stable structure here, and our structure is not c h 4, it's a 196 00:09:21,930 --> 00:09:25,740 stable structure of c h 2, and it will actually predict, 197 00:09:25,740 --> 00:09:29,740 also, what this h c h bond angle it is. 198 00:09:29,740 --> 00:09:32,510 So according to this model what is that bond angle? 199 00:09:32,510 --> 00:09:35,660 STUDENT: [INAUDIBLE] 200 00:09:35,660 --> 00:09:37,760 PROFESSOR: One more time. 201 00:09:37,760 --> 00:09:39,250 OK, I hear a mix. 202 00:09:39,250 --> 00:09:42,630 So, according to this model, what we're seeing is a bond 203 00:09:42,630 --> 00:09:44,150 angle of 90 degrees. 204 00:09:44,150 --> 00:09:48,060 What do you know the bond angle should be? 205 00:09:48,060 --> 00:09:49,270 It's 109 . 206 00:09:49,270 --> 00:09:51,370 5 is what we would expect for methane because it's 207 00:09:51,370 --> 00:09:54,370 tetravalent, but here we're just seeing something that's 208 00:09:54,370 --> 00:09:56,740 divalent, and they're both in p orbitals that are 209 00:09:56,740 --> 00:09:58,290 perpendicular to each other. 210 00:09:58,290 --> 00:10:01,620 So what we're predicting is a bond angle of 90 degrees. 211 00:10:01,620 --> 00:10:05,790 This is totally wrong, this is the wrong picture altogether. 212 00:10:05,790 --> 00:10:07,950 If you had your notes, you could do some fun scribbling 213 00:10:07,950 --> 00:10:10,110 right now, so you can do that at home. 214 00:10:10,110 --> 00:10:14,320 We're going to need to tweak our explanation here, and take 215 00:10:14,320 --> 00:10:17,970 into account another factor, and that factor is the fact 216 00:10:17,970 --> 00:10:21,460 that we know that we must have four unpaired electrons in 217 00:10:21,460 --> 00:10:24,400 carbon if we're going to form four bonds. 218 00:10:24,400 --> 00:10:26,580 So the way that we can explain this is through something 219 00:10:26,580 --> 00:10:28,580 called electron promotion and 220 00:10:28,580 --> 00:10:30,460 hybridization of atomic orbitals. 221 00:10:30,460 --> 00:10:34,440 So let's take a look at what we mean by this. 222 00:10:34,440 --> 00:10:39,160 So if we take our carbon atom here, which has two electrons 223 00:10:39,160 --> 00:10:44,130 in the 2 s orbital, and we promote one of these electrons 224 00:10:44,130 --> 00:10:49,090 into a 2 p orbital, what we see now is that yes, we do, we 225 00:10:49,090 --> 00:10:50,460 have four unpaired electrons. 226 00:10:50,460 --> 00:10:53,450 So, looking at this, this might not 227 00:10:53,450 --> 00:10:54,440 look so good for you. 228 00:10:54,440 --> 00:10:58,610 What we're proposing here is that you take a nice low 229 00:10:58,610 --> 00:11:01,090 energy s electron and move it into a 230 00:11:01,090 --> 00:11:02,790 higher energy p orbital. 231 00:11:02,790 --> 00:11:05,750 And the truth is that yes, this costs energy, we're going 232 00:11:05,750 --> 00:11:07,740 up to a higher energy state. 233 00:11:07,740 --> 00:11:10,300 But it doesn't actually cost as much energy as you might 234 00:11:10,300 --> 00:11:13,350 think, because in this s orbital here we have a paired 235 00:11:13,350 --> 00:11:16,530 electron situation where we're moving up to a p orbital where 236 00:11:16,530 --> 00:11:19,040 the electron is no longer paired, so it won't feel quite 237 00:11:19,040 --> 00:11:22,050 as much electron repulsion, but nonetheless, this is going 238 00:11:22,050 --> 00:11:23,140 to cost us energy. 239 00:11:23,140 --> 00:11:25,210 So we'll have to think about where that energy is going to 240 00:11:25,210 --> 00:11:27,530 come from and we'll see that in just a minute. 241 00:11:27,530 --> 00:11:30,440 But let's assume that this is, in fact, going to happen. 242 00:11:30,440 --> 00:11:33,760 So now what we have is four unpaired electrons. 243 00:11:33,760 --> 00:11:36,510 That's great, but it's still not quite the picture we need, 244 00:11:36,510 --> 00:11:39,430 because actually, all the electrons are not in equal 245 00:11:39,430 --> 00:11:43,040 orbitals -- one's in an s orbital, and 3 are in p. 246 00:11:43,040 --> 00:11:46,270 But what we need to remember is the fact that we're talking 247 00:11:46,270 --> 00:11:47,990 about electrons which are waves. 248 00:11:47,990 --> 00:11:50,490 When we're talking about orbitals, we're talking about 249 00:11:50,490 --> 00:11:51,350 wave functions. 250 00:11:51,350 --> 00:11:53,750 So we can actually constructively and 251 00:11:53,750 --> 00:11:57,320 destructively combine these waves, these atomic orbitals 252 00:11:57,320 --> 00:11:59,620 to make a hybrid. 253 00:11:59,620 --> 00:12:02,410 So if we go ahead and hybridize our p orbitals and 254 00:12:02,410 --> 00:12:06,130 our s orbitals, we'll switch from having these original 255 00:12:06,130 --> 00:12:10,170 orbitals to having something called hybrid orbitals. 256 00:12:10,170 --> 00:12:13,810 And hybrid orbitals are all going to be completely equal, 257 00:12:13,810 --> 00:12:16,690 and you'll notice that they're higher in energy than the s 258 00:12:16,690 --> 00:12:20,400 orbital, and lower in energy than the p orbital. 259 00:12:20,400 --> 00:12:23,540 That should make sense because they come from combining s 260 00:12:23,540 --> 00:12:25,360 orbitals and p orbitals. 261 00:12:25,360 --> 00:12:28,080 And specifically, when we give them a name it's very clear 262 00:12:28,080 --> 00:12:30,690 exactly which orbitals they come from combining, we're 263 00:12:30,690 --> 00:12:34,540 calling these s p 3 orbitals -- that's because they come 264 00:12:34,540 --> 00:12:38,230 from combining 1 s orbital and 3 p orbitals. 265 00:12:38,230 --> 00:12:41,070 You should never get the names of hybrid orbitals wrong 266 00:12:41,070 --> 00:12:42,720 because it's very straightforward. 267 00:12:42,720 --> 00:12:46,770 If it has 1 s and 3 p's, we call it s p 3. 268 00:12:46,770 --> 00:12:49,200 Naming doesn't always make sense in chemistry, so I like 269 00:12:49,200 --> 00:12:51,320 to point out this is a place where naming does 270 00:12:51,320 --> 00:12:52,490 make a lot of sense. 271 00:12:52,490 --> 00:12:56,200 All right, so let's consider our methane situation now that 272 00:12:56,200 --> 00:12:58,850 we have our hybrid orbitals. 273 00:12:58,850 --> 00:13:01,650 So I want to mention also, these are exactly equivalent, 274 00:13:01,650 --> 00:13:04,540 they're equivalent in energy, they're equivalent in shape. 275 00:13:04,540 --> 00:13:06,420 The only thing that is different about these orbitals 276 00:13:06,420 --> 00:13:08,540 is their orientation in space. 277 00:13:08,540 --> 00:13:10,500 So actually, first let's take a look at how 278 00:13:10,500 --> 00:13:11,890 we got these orbitals. 279 00:13:11,890 --> 00:13:14,710 We got them from combining again, 1 s 280 00:13:14,710 --> 00:13:17,310 orbital and the 3 p orbitals. 281 00:13:17,310 --> 00:13:21,040 If we hybridize these, what we end up seeing are these four 282 00:13:21,040 --> 00:13:22,080 hybrid orbitals. 283 00:13:22,080 --> 00:13:24,780 You'll notice the shape is the same, all that's different is 284 00:13:24,780 --> 00:13:26,360 their orientation. 285 00:13:26,360 --> 00:13:29,510 So essentially, each of these orbitals come from linear 286 00:13:29,510 --> 00:13:33,330 combinations of all of the original orbitals, and it's 287 00:13:33,330 --> 00:13:36,260 hard to picture exactly how that happens, but one that you 288 00:13:36,260 --> 00:13:38,350 can at least start to get an idea is if you think about 289 00:13:38,350 --> 00:13:42,000 combining the 2 s and the 2 p z here, which is not quite 290 00:13:42,000 --> 00:13:44,290 accurate because of course, we're combining all of them. 291 00:13:44,290 --> 00:13:45,530 But it would just give you a little bit 292 00:13:45,530 --> 00:13:46,580 of an idea of shape. 293 00:13:46,580 --> 00:13:50,050 You can see if we combine the s with the top lobe of the p, 294 00:13:50,050 --> 00:13:51,810 they're going to constructively interfere 295 00:13:51,810 --> 00:13:53,720 because they have the same sign. 296 00:13:53,720 --> 00:13:57,090 So you see in the hybrid orbital we actually have a 297 00:13:57,090 --> 00:14:01,340 larger lobe on top where they constructively interfered. 298 00:14:01,340 --> 00:14:04,250 If you compare the s orbital with the bottom lobe, these 299 00:14:04,250 --> 00:14:05,830 have a different sign so they're going to 300 00:14:05,830 --> 00:14:07,580 destructively interfere. 301 00:14:07,580 --> 00:14:10,900 So what you see is actually a diminished lobe on the back 302 00:14:10,900 --> 00:14:12,960 part of this s p 3 orbital. 303 00:14:12,960 --> 00:14:16,580 So s p 3 orbitals always have one huge lobe and one really 304 00:14:16,580 --> 00:14:17,410 little lobe. 305 00:14:17,410 --> 00:14:20,140 A lot of times when people draw them, they even only draw 306 00:14:20,140 --> 00:14:22,710 the big lobe just to keep their paper looking nicer, but 307 00:14:22,710 --> 00:14:27,290 there is that little tiny lobe on the other side. 308 00:14:27,290 --> 00:14:30,470 All right, so in terms of s p 3 hybrid orbitals, let's 309 00:14:30,470 --> 00:14:34,690 combine all four together on one axis, because this is 310 00:14:34,690 --> 00:14:37,680 what's going to happen in an s p 3 carbon atom. 311 00:14:37,680 --> 00:14:39,480 So in this case, what would you say that 312 00:14:39,480 --> 00:14:40,650 the angle is here? 313 00:14:40,650 --> 00:14:43,320 STUDENT: [INAUDIBLE] 314 00:14:43,320 --> 00:14:43,770 PROFESSOR: Right, great. 315 00:14:43,770 --> 00:14:45,750 So, we've achieved the angle that we observed, which is 316 00:14:45,750 --> 00:14:47,260 good, which is a 109 . 317 00:14:47,260 --> 00:14:48,600 5. 318 00:14:48,600 --> 00:14:52,170 So we can think about now doing bonding, and now we have 319 00:14:52,170 --> 00:14:56,130 four equal orbitals with one electronic each. 320 00:14:56,130 --> 00:14:58,940 So we can bring in four hydrogen atoms, which will 321 00:14:58,940 --> 00:15:01,500 each contribute another unpaired electron. 322 00:15:01,500 --> 00:15:05,360 So now what we have is four bonds. 323 00:15:05,360 --> 00:15:08,000 And we can think about where we did get that energy for 324 00:15:08,000 --> 00:15:10,370 electron promotion that I mentioned before where we 325 00:15:10,370 --> 00:15:13,460 moved the electron from the 2 s to the 2 p. 326 00:15:13,460 --> 00:15:14,490 We get that from bonding. 327 00:15:14,490 --> 00:15:16,510 We're going to release a lot of energy for bonding, it's 328 00:15:16,510 --> 00:15:18,760 going to more than make up for the fact that we actually had 329 00:15:18,760 --> 00:15:22,540 to spend some energy to promote that electron. 330 00:15:22,540 --> 00:15:26,400 So, we can think about now how do we describe this bond in 331 00:15:26,400 --> 00:15:28,050 valence bond theory. 332 00:15:28,050 --> 00:15:30,890 So the way that you describe a bond is you describe the 333 00:15:30,890 --> 00:15:33,350 orbitals that the bond comes from, and also the 334 00:15:33,350 --> 00:15:34,740 symmetry of the bond. 335 00:15:34,740 --> 00:15:37,080 So would you expect this to be a pi bond or 336 00:15:37,080 --> 00:15:38,340 a sigma bond here? 337 00:15:38,340 --> 00:15:41,210 STUDENT: [INAUDIBLE] 338 00:15:41,210 --> 00:15:43,630 PROFESSOR: OK, so I'm hearing some mixed answers. 339 00:15:43,630 --> 00:15:45,820 It turns out that it's a sigma bond. 340 00:15:45,820 --> 00:15:49,350 The reason that it's a sigma bond is because the s p 3 341 00:15:49,350 --> 00:15:52,090 hybrid orbital is directly interacting with the 1 s 342 00:15:52,090 --> 00:15:55,810 orbital of the hydrogen atom, and that's going to happen on 343 00:15:55,810 --> 00:15:58,070 the internuclear axis, they're just coming together. 344 00:15:58,070 --> 00:16:01,550 Any time two orbitals come straight on together in that 345 00:16:01,550 --> 00:16:05,690 internuclear axis, you're going to have a sigma bond. 346 00:16:05,690 --> 00:16:09,120 So if we go ahead and name this bond, what we're going to 347 00:16:09,120 --> 00:16:15,750 name it is sigma, because that's the -- basically the 348 00:16:15,750 --> 00:16:17,620 shape of the bond or that's how our 349 00:16:17,620 --> 00:16:19,100 bond is coming together. 350 00:16:19,100 --> 00:16:21,330 And then we're going to name the atomic orbitals that make 351 00:16:21,330 --> 00:16:26,050 it up, and it's being made up of a carbon 2 s p 3 orbital, 352 00:16:26,050 --> 00:16:30,090 and a hydrogen 1 s orbital. 353 00:16:30,090 --> 00:16:32,570 All right, so let's think of a case now that's getting a 354 00:16:32,570 --> 00:16:33,720 little bit more complicated. 355 00:16:33,720 --> 00:16:36,090 We were talking about methane, which has 356 00:16:36,090 --> 00:16:37,780 only one central atom. 357 00:16:37,780 --> 00:16:40,750 We can also talk about atoms that have two or more central 358 00:16:40,750 --> 00:16:44,540 atoms. So let's talk about ethane now, which is c h 2. 359 00:16:44,540 --> 00:16:48,580 So let's take our carbon s p 3 hybridized carbon and just 360 00:16:48,580 --> 00:16:53,490 move it around here so we can make the z inter- bonding axis 361 00:16:53,490 --> 00:16:56,080 between the two carbons right here. 362 00:16:56,080 --> 00:16:58,840 So if we still have an angle of a 109 . 363 00:16:58,840 --> 00:17:03,200 5 degrees, and again, we still have four unpaired electrons 364 00:17:03,200 --> 00:17:06,850 available for bonding, we can make one of those bonds with 365 00:17:06,850 --> 00:17:10,550 another s p 3 hybridized carbon, so we're going to make 366 00:17:10,550 --> 00:17:13,830 up one pair here. 367 00:17:13,830 --> 00:17:16,320 If we think about that, that's a sigma bond, right, they're 368 00:17:16,320 --> 00:17:22,730 coming together along the nuclear axis. 369 00:17:22,730 --> 00:17:25,810 We also have six spots available to form hydrogen 370 00:17:25,810 --> 00:17:28,260 bonds, so we can go ahead and fill in those 371 00:17:28,260 --> 00:17:30,750 electrons as well. 372 00:17:30,750 --> 00:17:33,950 So in terms of thinking about ethane, we actually have two 373 00:17:33,950 --> 00:17:38,680 bond types that we're going to be describing just in terms of 374 00:17:38,680 --> 00:17:42,730 the carbon-carbon bond and then the carbon h bonds. 375 00:17:42,730 --> 00:17:45,660 So let's talk about ethane and how we would actually write 376 00:17:45,660 --> 00:17:47,180 these bonds. 377 00:17:47,180 --> 00:17:52,250 If we have the molecule ethane, then what we're going 378 00:17:52,250 --> 00:17:55,810 to have first is our sigma bond that we described between 379 00:17:55,810 --> 00:17:57,670 the two carbons. 380 00:17:57,670 --> 00:18:00,000 So it's going to be carbon, and then what's the 381 00:18:00,000 --> 00:18:01,160 hybridization here? 382 00:18:01,160 --> 00:18:05,500 STUDENT: [INAUDIBLE] 383 00:18:05,500 --> 00:18:06,410 PROFESSOR: All right, start again, what's the 384 00:18:06,410 --> 00:18:07,530 hybridization of the carbon atom? 385 00:18:07,530 --> 00:18:10,190 STUDENT: [INAUDIBLE] 386 00:18:10,190 --> 00:18:14,820 PROFESSOR: OK, so it's 2 s p 3, and our second carbon is 387 00:18:14,820 --> 00:18:17,250 also 2 s p 3. 388 00:18:17,250 --> 00:18:21,560 All right, so this is our first type of bond here. 389 00:18:21,560 --> 00:18:24,420 Our second bond is going to be between the carbon and the 390 00:18:24,420 --> 00:18:28,380 hydrogen atoms. Is that a sigma or a pi bond? 391 00:18:28,380 --> 00:18:28,830 STUDENT: [INAUDIBLE] 392 00:18:28,830 --> 00:18:30,050 PROFESSOR: Sigma, good. 393 00:18:30,050 --> 00:18:35,000 So again, our carbon is going to be 2 s p 3. 394 00:18:35,000 --> 00:18:37,300 And what will our hydrogen be? 395 00:18:37,300 --> 00:18:40,050 1 s -- we don't have to hybridize it, it already has 396 00:18:40,050 --> 00:18:43,290 only one unpaired electron in a 1 s orbital. 397 00:18:43,290 --> 00:18:47,060 All right, so that's how we describe ethane. 398 00:18:47,060 --> 00:18:49,540 We don't have to just stick with carbon, we can think 399 00:18:49,540 --> 00:18:52,960 about describing other types of atoms as well using this 400 00:18:52,960 --> 00:18:54,170 hybridization. 401 00:18:54,170 --> 00:18:57,260 For example, we can talk about nitrogen, and nitrogen has 402 00:18:57,260 --> 00:19:00,100 five valence electrons shown here. 403 00:19:00,100 --> 00:19:03,410 Would you expect to see electron promotion in nitrogen 404 00:19:03,410 --> 00:19:05,300 where we pull one of these 2 s electrons into 405 00:19:05,300 --> 00:19:06,950 one of the 2 p orbitals? 406 00:19:06,950 --> 00:19:08,640 STUDENT: [INAUDIBLE] 407 00:19:08,640 --> 00:19:09,330 PROFESSOR: No, good. 408 00:19:09,330 --> 00:19:12,770 So, electron promotion does not happen in terms of 409 00:19:12,770 --> 00:19:15,250 nitrogen, because it would not increased our number of 410 00:19:15,250 --> 00:19:16,670 unpaired electrons. 411 00:19:16,670 --> 00:19:19,380 No matter what we do in terms of promotion, we're always 412 00:19:19,380 --> 00:19:22,460 going to have three unpaired electrons. 413 00:19:22,460 --> 00:19:25,700 We can still hybridize all these orbitals, however, so we 414 00:19:25,700 --> 00:19:31,290 can still form four hybrid orbitals, which are again, 2 s 415 00:19:31,290 --> 00:19:35,060 p 3 hybrid orbitals. 416 00:19:35,060 --> 00:19:38,150 So if we take a look at nitrogen here, what you'll 417 00:19:38,150 --> 00:19:40,400 notice is we have thre available for bonding, and we 418 00:19:40,400 --> 00:19:42,890 already have our lone pair -- one of our orbitals is 419 00:19:42,890 --> 00:19:45,210 already filled up. 420 00:19:45,210 --> 00:19:49,010 So we can add three hydrogen atoms here, and fill in our 421 00:19:49,010 --> 00:19:50,900 other orbitals right here. 422 00:19:50,900 --> 00:19:54,230 So if we do this and we form the molecule ammonia, let's 423 00:19:54,230 --> 00:19:57,040 switch to a clicker question, and have you tell me what the 424 00:19:57,040 --> 00:19:59,510 bond angle is going to be in ammonia -- 425 00:19:59,510 --> 00:20:02,490 the h n h bond angle. 426 00:20:02,490 --> 00:20:05,520 Actually, let me draw it on the board as you look -- 427 00:20:05,520 --> 00:20:08,220 actually, can you put the class notes on, since you 428 00:20:08,220 --> 00:20:10,000 don't actually have your notes to refer to. 429 00:20:10,000 --> 00:20:11,710 So there's the class notes there. 430 00:20:11,710 --> 00:20:17,830 All right, this should be a pretty quick thing for you to 431 00:20:17,830 --> 00:20:32,640 figure out, so let's just take 10 seconds on this. 432 00:20:32,640 --> 00:20:33,270 OK, great. 433 00:20:33,270 --> 00:20:36,060 Even thinking quickly, most of you got it correct. 434 00:20:36,060 --> 00:20:40,410 So what we see is on ammonia here, we know that it's less 435 00:20:40,410 --> 00:20:41,730 than a 109 . 436 00:20:41,730 --> 00:20:46,400 5, it's actually 107, so it's less than a 109 . 437 00:20:46,400 --> 00:20:48,810 5, because of that lone pair pushing down 438 00:20:48,810 --> 00:20:50,430 in the bonding electrons. 439 00:20:50,430 --> 00:20:52,460 And what is the shape, for one more 440 00:20:52,460 --> 00:20:59,450 clicker question on ammonia? 441 00:20:59,450 --> 00:21:14,790 Let's take 10 seconds again, this should be pretty quick. 442 00:21:14,790 --> 00:21:15,810 All right, pretty good. 443 00:21:15,810 --> 00:21:17,090 So, 70% of you. 444 00:21:17,090 --> 00:21:19,180 We'd like to get this up higher. 445 00:21:19,180 --> 00:21:21,740 The shape is actually trigonal pyramidal. 446 00:21:21,740 --> 00:21:23,940 And you need to just remember your shapes. 447 00:21:23,940 --> 00:21:26,460 If they're not obvious to you what they're called, you need 448 00:21:26,460 --> 00:21:28,170 to just study them and learn them. 449 00:21:28,170 --> 00:21:31,780 So it's trigonal because we have these three atoms that 450 00:21:31,780 --> 00:21:35,330 are bound to the central atom here, and if you picture it, 451 00:21:35,330 --> 00:21:37,060 it's actually shaped like a pyramid. 452 00:21:37,060 --> 00:21:38,700 So it's trigonal pyramidal. 453 00:21:38,700 --> 00:21:42,490 That's what we call when we have three bonding atoms and 454 00:21:42,490 --> 00:21:46,860 one lone pair. 455 00:21:46,860 --> 00:21:47,190 All right. 456 00:21:47,190 --> 00:21:50,630 So we can switch all the way back to our notes here. 457 00:21:50,630 --> 00:21:53,200 And the last thing we can think about is how do we name 458 00:21:53,200 --> 00:21:56,030 this n h bond, and again, we just name 459 00:21:56,030 --> 00:21:57,380 it based on it symmetry. 460 00:21:57,380 --> 00:22:01,380 It's a sigma bond, and it's going to be -- no. 461 00:22:01,380 --> 00:22:05,860 OK, it's going to be nitrogen 2 s p 3, because it's a 462 00:22:05,860 --> 00:22:09,930 nitrogen atom, and then hydrogen 1 s. 463 00:22:09,930 --> 00:22:11,520 So, I don't even have to worry because you're not writing 464 00:22:11,520 --> 00:22:14,040 this down, so I can just fix it when I post the notes and 465 00:22:14,040 --> 00:22:17,160 no one will ever know, except that this is not 466 00:22:17,160 --> 00:22:17,410 OpenCourseWare. 467 00:22:17,410 --> 00:22:22,500 So let's switch to thinking about oxygen 468 00:22:22,500 --> 00:22:23,990 hybridization here. 469 00:22:23,990 --> 00:22:27,570 So in oxygen we have a similar situation where, in fact, we 470 00:22:27,570 --> 00:22:30,050 are not going to promote any of the electrons because we 471 00:22:30,050 --> 00:22:33,680 have two lone pair electrons no matter what we do. 472 00:22:33,680 --> 00:22:37,460 So when we hybridize our orbitals, we're going to end 473 00:22:37,460 --> 00:22:42,840 up with again, four hybrid orbitals, 4 s p 3 orbitals, 474 00:22:42,840 --> 00:22:45,890 and what we'll see is that two of these are already going to 475 00:22:45,890 --> 00:22:49,590 be filled up with a paired electrons, so we're only going 476 00:22:49,590 --> 00:22:51,750 to have 2 orbitals with an unpaired electron available 477 00:22:51,750 --> 00:22:53,780 for bonding. 478 00:22:53,780 --> 00:22:56,750 So let's think about water here as our simplest example 479 00:22:56,750 --> 00:22:57,970 with oxygen. 480 00:22:57,970 --> 00:23:02,260 So we can have our two hydrogen atoms come in here, 481 00:23:02,260 --> 00:23:05,260 and what we will find is now that we have all of our 482 00:23:05,260 --> 00:23:08,870 orbitals filled up -- so thinking about what this angle 483 00:23:08,870 --> 00:23:13,120 is here, would you expect it to be less than or greater 484 00:23:13,120 --> 00:23:16,770 than what we saw for ammonia before? 485 00:23:16,770 --> 00:23:17,730 STUDENT: Less than. 486 00:23:17,730 --> 00:23:18,810 PROFESSOR: Good, good, it's going to be less than, and 487 00:23:18,810 --> 00:23:20,320 it's going to be less than because now we 488 00:23:20,320 --> 00:23:22,470 have two lone pairs. 489 00:23:22,470 --> 00:23:24,220 So since we have two lone pairs, we're going to be 490 00:23:24,220 --> 00:23:27,210 pushing down even further on the bonding electrons, so 491 00:23:27,210 --> 00:23:29,900 we're going to smoosh those bonds even closer together. 492 00:23:29,900 --> 00:23:31,980 The bond, it turns out, is 104 . 493 00:23:31,980 --> 00:23:36,040 5 degrees, that h o h bond. 494 00:23:36,040 --> 00:23:40,590 So in terms of naming our o h bond, good, it's right here. 495 00:23:40,590 --> 00:23:45,610 So it's going to be a sigma bond, and we have oxygen 2 s p 496 00:23:45,610 --> 00:23:51,770 3 and hydrogen 1 s. 497 00:23:51,770 --> 00:23:54,650 And the geometry, which I didn't ask you, is going to be 498 00:23:54,650 --> 00:23:56,030 bent for this molecule. 499 00:23:56,030 --> 00:23:59,300 All right, so that's s p 3 hybridization, but those 500 00:23:59,300 --> 00:24:02,300 aren't the only type of hybrid orbitals that we can form. 501 00:24:02,300 --> 00:24:04,800 Let's take a look at what happens if instead of 502 00:24:04,800 --> 00:24:07,940 combining all four orbitals, we just combine three of those 503 00:24:07,940 --> 00:24:10,660 orbitals, and what we'll end up with is s p 2 504 00:24:10,660 --> 00:24:12,120 hybridization. 505 00:24:12,120 --> 00:24:16,920 So in s p 2 hybridization, instead of combining all four, 506 00:24:16,920 --> 00:24:18,460 we're just combining two of the p 507 00:24:18,460 --> 00:24:20,540 orbitals with the s orbital. 508 00:24:20,540 --> 00:24:22,630 So what we're going to end up with now is 509 00:24:22,630 --> 00:24:24,480 three hybrid orbitals. 510 00:24:24,480 --> 00:24:28,240 And what happens to this last p orbital is nothing at all, 511 00:24:28,240 --> 00:24:29,540 we just get it back. 512 00:24:29,540 --> 00:24:32,990 So we end up with 1 p orbital completely untouched, and 513 00:24:32,990 --> 00:24:36,960 three hybrid s p 2 orbitals. 514 00:24:36,960 --> 00:24:39,550 So again, we can think of an example here. 515 00:24:39,550 --> 00:24:44,170 So let's take boron, for example, and this has -- it 516 00:24:44,170 --> 00:24:46,690 starts off with three valence electrons. 517 00:24:46,690 --> 00:24:49,350 Would you expect to see electron promotion for boron? 518 00:24:49,350 --> 00:24:50,790 STUDENT: Yes. 519 00:24:50,790 --> 00:24:53,890 PROFESSOR: Yeah, absolutely. if we move up one of our 520 00:24:53,890 --> 00:24:56,150 electrons into an empty p orbital, what were going to 521 00:24:56,150 --> 00:24:56,440 see is now we have three unpaired electrons that are 522 00:24:56,440 --> 00:24:57,910 ready for bonding. 523 00:24:57,910 --> 00:25:05,880 So, if we hybridize just these three orbitals, what we're 524 00:25:05,880 --> 00:25:10,240 going to end up with is our s p 2 hybrid orbitals. 525 00:25:10,240 --> 00:25:12,860 Again, the name is very straightforward, it comes from 526 00:25:12,860 --> 00:25:17,130 1 s and 2 p orbital, so it will be s p 2. 527 00:25:17,130 --> 00:25:20,250 And again, you might be thinking well, why didn't we 528 00:25:20,250 --> 00:25:23,010 actually hybridize this 2 p y orbital. 529 00:25:23,010 --> 00:25:26,180 It doesn't actually have an electron in it, so we don't 530 00:25:26,180 --> 00:25:28,720 have to worry about whether it's very high in energy or 531 00:25:28,720 --> 00:25:30,720 not, we don't care that it's high in energy. 532 00:25:30,720 --> 00:25:33,930 What we do care about is the energy of our orbitals that 533 00:25:33,930 --> 00:25:37,680 have electrons in them, and if we combined all four of the 534 00:25:37,680 --> 00:25:40,480 orbitals, then our hybrid orbitals would have more p 535 00:25:40,480 --> 00:25:43,930 character to them, so they'd actually be higher in energy. 536 00:25:43,930 --> 00:25:46,240 So if we don't have to hybridize one of the p 537 00:25:46,240 --> 00:25:49,150 orbitals, we can actually end up with a lower energy 538 00:25:49,150 --> 00:25:53,320 situation, because now these s p 2 orbitals are 1/3 s 539 00:25:53,320 --> 00:25:59,660 character, and only 2/3 p character, instead of 3/4. 540 00:25:59,660 --> 00:26:04,690 So we end up with 3 s p 2 hybrid orbitals, so we can 541 00:26:04,690 --> 00:26:09,420 think about what would happen here in terms of bonding, and 542 00:26:09,420 --> 00:26:14,880 if we think about how to get our bonds as far away as 543 00:26:14,880 --> 00:26:16,860 possible from each other, what we're going to have is the 544 00:26:16,860 --> 00:26:18,600 trigonal planer situation. 545 00:26:18,600 --> 00:26:21,950 So if you picture, for example, b h 3, it's going to 546 00:26:21,950 --> 00:26:23,750 look like this. 547 00:26:23,750 --> 00:26:26,610 All of our electrons are in our bonds, we want to got them 548 00:26:26,610 --> 00:26:29,960 a 120 degrees away from each other, that's as far away as 549 00:26:29,960 --> 00:26:31,220 we can get them. 550 00:26:31,220 --> 00:26:34,310 Keep in mind we do have this p orbital here and it's coming 551 00:26:34,310 --> 00:26:35,620 right out at us. 552 00:26:35,620 --> 00:26:38,350 And this p orbital is here, but it's empty, it doesn't 553 00:26:38,350 --> 00:26:41,220 have any electrons in it, that's why we don't have to 554 00:26:41,220 --> 00:26:43,720 worry about it in terms of getting our electrons as far 555 00:26:43,720 --> 00:26:45,810 away from each other as possible. 556 00:26:45,810 --> 00:26:49,060 So what we'll have here is a trigonal planar case, and you 557 00:26:49,060 --> 00:26:52,330 can see that we only have three electrons that are set 558 00:26:52,330 --> 00:26:55,950 for bonding, so we'll add three hydrogens, and for b h 559 00:26:55,950 --> 00:26:58,650 3, we'll get a stable structure here. 560 00:26:58,650 --> 00:27:02,070 So, remember, boron was one of those exceptions to our Lewis 561 00:27:02,070 --> 00:27:04,780 structure rules where it was perfectly happy not having a 562 00:27:04,780 --> 00:27:05,760 full octet. 563 00:27:05,760 --> 00:27:09,660 So this can tell you why it's so happy with only having six 564 00:27:09,660 --> 00:27:10,830 electrons around it. 565 00:27:10,830 --> 00:27:16,830 All right, so if we think about b h bond here, again, 566 00:27:16,830 --> 00:27:20,000 it's the sigma bond, and we're going to say it's a boron 2 s 567 00:27:20,000 --> 00:27:26,470 p 2 hybrid orbital interacting with a hydrogen 1 s orbital. 568 00:27:26,470 --> 00:27:29,400 So let's take a look at another case where we have s p 569 00:27:29,400 --> 00:27:31,510 2 hybridization, we can actually also have 570 00:27:31,510 --> 00:27:33,190 it happen in carbon. 571 00:27:33,190 --> 00:27:35,970 So if we think about having it happen in carbon, we're 572 00:27:35,970 --> 00:27:38,630 starting with the situation where we've already promoted 573 00:27:38,630 --> 00:27:42,500 our electron into a 2 p orbital here, and what we're 574 00:27:42,500 --> 00:27:46,340 going to do is just combine the s and two of the p's, so 575 00:27:46,340 --> 00:27:50,470 we'll end up with electrons in one of each three 576 00:27:50,470 --> 00:27:52,090 s p 2 hybrid orbitals. 577 00:27:52,090 --> 00:27:55,890 But unlike the case with boron where we had an empty p 578 00:27:55,890 --> 00:27:59,520 orbital, we're actually going to have an electron in the p 579 00:27:59,520 --> 00:28:02,920 orbital of carbon as well. 580 00:28:02,920 --> 00:28:05,790 So again, if we think about that shape of that carbon 581 00:28:05,790 --> 00:28:08,110 atom, it's going to be trigonal planar, it's going to 582 00:28:08,110 --> 00:28:12,500 have bond angles of 120 degrees, because we have this 583 00:28:12,500 --> 00:28:16,350 set up of having three hybrid orbitals. 584 00:28:16,350 --> 00:28:18,790 So let's take a look at what actually happens if we're 585 00:28:18,790 --> 00:28:22,990 talking about a carbon-carbon double bond, such as in 586 00:28:22,990 --> 00:28:27,060 ethene, c 2 h 4, we're going to have a double bond. 587 00:28:27,060 --> 00:28:30,310 If we have a double bond, we know we need to have only one 588 00:28:30,310 --> 00:28:33,180 sigma bond, and we're also going to have one pi bond. 589 00:28:33,180 --> 00:28:35,080 So it already should make sense why we have that p 590 00:28:35,080 --> 00:28:37,350 orbital there, in order to form a pi bond, we're going to 591 00:28:37,350 --> 00:28:38,770 need a p orbital. 592 00:28:38,770 --> 00:28:42,740 So if you picture this as our s p 2 carbon atom where we 593 00:28:42,740 --> 00:28:47,510 have three hybrid orbitals, and then one p y orbital 594 00:28:47,510 --> 00:28:49,090 coming right out at us. 595 00:28:49,090 --> 00:28:51,840 So again, we picture the same thing as we pictured with the 596 00:28:51,840 --> 00:28:53,770 boron there. 597 00:28:53,770 --> 00:28:57,600 If we have, coming along this z axis, another carbon atom, 598 00:28:57,600 --> 00:29:00,060 we can actually form one bond between the two 599 00:29:00,060 --> 00:29:01,670 carbon atoms there. 600 00:29:01,670 --> 00:29:07,850 So if we picture how this happens, what we have here if 601 00:29:07,850 --> 00:29:19,680 these are our 2 s p 2 carbon atoms -- so here we have s p 2 602 00:29:19,680 --> 00:29:25,410 hybrid carbon, and here we have s p 2 hybrid carbon atom. 603 00:29:25,410 --> 00:29:29,180 These 2 are going to come together like this, and the 604 00:29:29,180 --> 00:29:31,450 first bond that we're going to form is going to be a sigma 605 00:29:31,450 --> 00:29:32,950 bond, right, so we see that here. 606 00:29:32,950 --> 00:29:36,020 If we're looking head on, we see they form a sigma bond. 607 00:29:36,020 --> 00:29:38,440 We can also look at them coming in from the side, and 608 00:29:38,440 --> 00:29:40,770 that's what I tried to depict here where you can actually 609 00:29:40,770 --> 00:29:43,250 see in pink is the p orbital. 610 00:29:43,250 --> 00:29:45,850 So we can also show them coming together this way, so 611 00:29:45,850 --> 00:29:48,460 now you're looking at it where you can see the p orbital, and 612 00:29:48,460 --> 00:29:52,430 maybe just see well one of the hydrogen atoms. 613 00:29:52,430 --> 00:29:57,630 So we can have four total hydrogens bonding here, and we 614 00:29:57,630 --> 00:29:59,340 can think about how to describe these 615 00:29:59,340 --> 00:30:01,000 carbon-carbon bonds. 616 00:30:01,000 --> 00:30:05,050 So in the first case of this first bond here that I've put 617 00:30:05,050 --> 00:30:07,460 in a square, what type of a bond is this, is 618 00:30:07,460 --> 00:30:08,650 the sigma or pi? 619 00:30:08,650 --> 00:30:10,210 STUDENT: Sigma. 620 00:30:10,210 --> 00:30:11,210 PROFESSOR: Yup, it's a sigma bond. 621 00:30:11,210 --> 00:30:12,870 We're having two orbitals coming 622 00:30:12,870 --> 00:30:15,530 together on the bond axis. 623 00:30:15,530 --> 00:30:20,210 So we'll call this sigma, and it's between two s p 2 hybrid 624 00:30:20,210 --> 00:30:26,560 carbon atoms. So it's stigma carbon s p 2, carbon s p 2. 625 00:30:26,560 --> 00:30:29,750 What about this second bond here where we're going to have 626 00:30:29,750 --> 00:30:32,470 interaction of 2 p orbitals, is that sigma or pi? 627 00:30:32,470 --> 00:30:34,140 STUDENT: Pi. 628 00:30:34,140 --> 00:30:34,820 PROFESSOR: Pi, great. 629 00:30:34,820 --> 00:30:38,040 So our second bond is going to be a pi bond. 630 00:30:38,040 --> 00:30:40,990 And again, this is between the p orbitals, these are not 631 00:30:40,990 --> 00:30:43,940 hybrid orbitals, so when we name this bond we're going to 632 00:30:43,940 --> 00:30:47,770 name it as a pi bond here, because it's between two p 633 00:30:47,770 --> 00:30:51,150 orbitals, and it's going to be between the carbon 2 p y 634 00:30:51,150 --> 00:30:54,280 orbital, and the other carbon 2 p y orbital. 635 00:30:54,280 --> 00:30:57,740 Remember, we didn't hybridize the 2 p y orbital, so that's 636 00:30:57,740 --> 00:31:00,490 what we have left over to form these pi bonds. 637 00:31:00,490 --> 00:31:03,430 All right. 638 00:31:03,430 --> 00:31:07,160 So in addition to having these two carbon bonds, we actually 639 00:31:07,160 --> 00:31:11,890 also have four carbon hydrogen bonds in addition to our 640 00:31:11,890 --> 00:31:13,370 carbon-carbon bonds. 641 00:31:13,370 --> 00:31:17,280 So why don't you tell me what the valence bond description 642 00:31:17,280 --> 00:31:19,520 would be of these carbon hydrogen bonds? 643 00:31:19,520 --> 00:31:45,280 So let's take 10 seconds on that. 644 00:31:45,280 --> 00:31:45,880 OK, great. 645 00:31:45,880 --> 00:31:48,660 So most and you got it, so we can switch to the notes and 646 00:31:48,660 --> 00:31:50,860 let's talk about this here. 647 00:31:50,860 --> 00:31:55,230 So in terms of the carbon hydrogen bond, it's a sigma 648 00:31:55,230 --> 00:31:59,520 bond, because we define it -- any time we are bonding to an 649 00:31:59,520 --> 00:32:01,940 atom, we have to keep redefining our bond axis to 650 00:32:01,940 --> 00:32:04,040 whatever two atoms we're talking about. 651 00:32:04,040 --> 00:32:07,540 So it's along the bond axis and it's between a carbon s p 652 00:32:07,540 --> 00:32:10,950 2 hybrid, and then the hydrogen is just a 1 s orbital 653 00:32:10,950 --> 00:32:12,680 that we're combining here. 654 00:32:12,680 --> 00:32:17,290 So those are our three types of bonds in ethene. 655 00:32:17,290 --> 00:32:19,340 One thing that I want to mention that is really 656 00:32:19,340 --> 00:32:22,690 important is once you have double bonds, what happens 657 00:32:22,690 --> 00:32:25,900 between those two atoms in the molecule is they can no longer 658 00:32:25,900 --> 00:32:28,380 rotate in relation to each other. 659 00:32:28,380 --> 00:32:29,950 So you can think about why that is. 660 00:32:29,950 --> 00:32:33,170 When we have just a single bond in them molecule, you 661 00:32:33,170 --> 00:32:35,780 have all the free rotation you want, you can just spin it 662 00:32:35,780 --> 00:32:37,930 around, there's nothing keeping it in place. 663 00:32:37,930 --> 00:32:41,010 But once you have a double bond here, we have our pi 664 00:32:41,010 --> 00:32:43,050 bond, as well as our sigma bond. 665 00:32:43,050 --> 00:32:46,710 So there's electron density above the bond 666 00:32:46,710 --> 00:32:47,940 and below the bond. 667 00:32:47,940 --> 00:32:51,310 So if I try to rotate my 2 atoms, you see that I have to 668 00:32:51,310 --> 00:32:54,470 break that pi bond, because they need to be lined up so 669 00:32:54,470 --> 00:32:56,680 that the electron density can overlap. 670 00:32:56,680 --> 00:33:00,550 So in order to rotate a double bond, you have to actually 671 00:33:00,550 --> 00:33:02,980 break the pi bond, so essentially what you're doing 672 00:33:02,980 --> 00:33:04,420 is breaking the double bond. 673 00:33:04,420 --> 00:33:07,880 So really, you can not ever rotate a double bond, it makes 674 00:33:07,880 --> 00:33:09,820 your molecule very rigid. 675 00:33:09,820 --> 00:33:13,470 This is incredibly important because if you picture having 676 00:33:13,470 --> 00:33:16,780 a double bond in a very large molecule, you could have all 677 00:33:16,780 --> 00:33:19,920 sorts of other atoms off this way and all sorts of other 678 00:33:19,920 --> 00:33:22,710 atoms off this way, and you can picture the shape would be 679 00:33:22,710 --> 00:33:26,300 very different if you have one confirmation versus another 680 00:33:26,300 --> 00:33:27,600 confirmation. 681 00:33:27,600 --> 00:33:31,280 So it's very important that the double bond locks it in a 682 00:33:31,280 --> 00:33:32,610 particular conformation. 683 00:33:32,610 --> 00:33:35,980 This completely could change if you were to flip from one 684 00:33:35,980 --> 00:33:37,350 to the other conformation which can 685 00:33:37,350 --> 00:33:39,240 happen in chemical reactions. 686 00:33:39,240 --> 00:33:41,550 If you were to make that change you would find that the 687 00:33:41,550 --> 00:33:44,460 molecule now has completely different biological and 688 00:33:44,460 --> 00:33:46,390 chemical properties. 689 00:33:46,390 --> 00:33:48,880 So it's very important to be keeping in mind that any time 690 00:33:48,880 --> 00:33:51,650 you see a double bond, you have a pi bond there, so 691 00:33:51,650 --> 00:33:56,160 you're not going to see any rotation around the bond axis. 692 00:33:56,160 --> 00:33:59,620 All right, so let's think of a more complicated example of 693 00:33:59,620 --> 00:34:01,590 having a double bond, and maybe a more interesting 694 00:34:01,590 --> 00:34:03,960 example, and this is talking about benzene. 695 00:34:03,960 --> 00:34:06,380 I think most and you have talked a little bit about 696 00:34:06,380 --> 00:34:09,550 benzene over this past week in recitation. 697 00:34:09,550 --> 00:34:13,520 Benzene is a ring that's made up of six carbon atoms and six 698 00:34:13,520 --> 00:34:16,760 hydrogen atoms. So let's picture what this looks like 699 00:34:16,760 --> 00:34:18,660 here, and we'll start with four and we'll 700 00:34:18,660 --> 00:34:19,430 add in our last two. 701 00:34:19,430 --> 00:34:23,480 So essentially, we have two ethene or ethylene molecules 702 00:34:23,480 --> 00:34:28,690 here to start with where these blue are our 2 s p 2 hybrid 703 00:34:28,690 --> 00:34:32,000 orbitals, so you can see that for each carbon atom, one is 704 00:34:32,000 --> 00:34:35,150 already used up binding to another carbon atom. 705 00:34:35,150 --> 00:34:39,160 If we think about bringing in those last two carbons, what 706 00:34:39,160 --> 00:34:43,220 you can see is that for every carbon, two of its hybrid 707 00:34:43,220 --> 00:34:48,500 orbitals are being used to bond to other carbons. 708 00:34:48,500 --> 00:34:50,750 So that leaves each carbon with only one 709 00:34:50,750 --> 00:34:53,370 hybrid orbital left. 710 00:34:53,370 --> 00:34:56,320 And if we think about the six hydrogens, now each of those 711 00:34:56,320 --> 00:34:59,380 are going to bind by combining one of the carbon hybrid 712 00:34:59,380 --> 00:35:03,160 orbitals to a 1 s orbital of hydrogen. 713 00:35:03,160 --> 00:35:07,400 So, if we think about what bonds are in this molecule, we 714 00:35:07,400 --> 00:35:11,960 actually have six of these sigma carbon s p 2, 715 00:35:11,960 --> 00:35:14,160 carbon s p 2 bonds. 716 00:35:14,160 --> 00:35:18,660 We also have carbon s p 2 hydrogen 1 s bonds. 717 00:35:18,660 --> 00:35:21,370 How many of those do we have? 718 00:35:21,370 --> 00:35:23,980 Yup, we also have six of these, because we have six 719 00:35:23,980 --> 00:35:25,770 carbon hydrogen bonds. 720 00:35:25,770 --> 00:35:28,900 So that's two of our types of bonds in benzene, and we have 721 00:35:28,900 --> 00:35:31,610 one type left, and that's going to actually be the 722 00:35:31,610 --> 00:35:35,570 double bond or the pi bond that forms between some of 723 00:35:35,570 --> 00:35:37,140 these p orbitals. 724 00:35:37,140 --> 00:35:41,400 So we can have one bond here between this carbon's p 725 00:35:41,400 --> 00:35:43,410 orbital and this carbon's p orbital. 726 00:35:43,410 --> 00:35:46,180 So let's have a clicker question here on how many 727 00:35:46,180 --> 00:35:50,980 total pi bonds do you expect to see in benzene? 728 00:35:50,980 --> 00:35:56,950 Oh good, so it's left up -- the notes are left up on this 729 00:35:56,950 --> 00:35:57,690 screen right now. 730 00:35:57,690 --> 00:36:16,980 All right, so let's take 10 seconds on that. 731 00:36:16,980 --> 00:36:17,530 All right, great. 732 00:36:17,530 --> 00:36:20,920 So, most of you saw that what we would expect to see is a 733 00:36:20,920 --> 00:36:22,540 three bond, some of you thought six. 734 00:36:22,540 --> 00:36:25,010 So let's take a look at why three is correct. 735 00:36:25,010 --> 00:36:29,305 So, what we end up having is three of these pi -- 736 00:36:29,305 --> 00:36:32,930 2 p y 2 p y bonds, we can have one between 737 00:36:32,930 --> 00:36:34,130 these two carbons here. 738 00:36:34,130 --> 00:36:36,260 Can we have one between these two carbons here 739 00:36:36,260 --> 00:36:37,310 if we have one here? 740 00:36:37,310 --> 00:36:38,280 STUDENT: No. 741 00:36:38,280 --> 00:36:38,670 PROFESSOR: No, we can't. 742 00:36:38,670 --> 00:36:42,230 We're already using it up in this pi bond here, so that 743 00:36:42,230 --> 00:36:45,130 means we're limited to only two other spots on the 744 00:36:45,130 --> 00:36:47,250 molecule, so we have three. 745 00:36:47,250 --> 00:36:49,810 But, of course, what you saw in recitation, and hopefully, 746 00:36:49,810 --> 00:36:53,240 what you can now think very quickly by looking at this, is 747 00:36:53,240 --> 00:36:56,720 that this is not the only configuration of pi bonds that 748 00:36:56,720 --> 00:36:58,670 we could have in benzene. 749 00:36:58,670 --> 00:37:00,770 There's absolutely no reason I couldn't have switched it 750 00:37:00,770 --> 00:37:04,710 around and said that instead the pi orbitals form between 751 00:37:04,710 --> 00:37:08,120 these atoms instead of those first atoms I showed. 752 00:37:08,120 --> 00:37:11,390 So, let's look at this in a more simple structure here 753 00:37:11,390 --> 00:37:15,110 where we have the two possible forms of benzene, and the 754 00:37:15,110 --> 00:37:17,250 reality is is that it's going to be some 755 00:37:17,250 --> 00:37:18,410 combination of the two. 756 00:37:18,410 --> 00:37:21,830 This is resonance, this is a case of a resonance structure. 757 00:37:21,830 --> 00:37:25,260 So what we see is that those six pi electrons are actually 758 00:37:25,260 --> 00:37:29,620 going to be de-localized around all six of those atoms. 759 00:37:29,620 --> 00:37:33,330 So if you think about any one of these carbon-carbon bonds, 760 00:37:33,330 --> 00:37:36,000 what type of a bond would you expect that to be? 761 00:37:36,000 --> 00:37:38,460 What would the bond order be for this bond? 762 00:37:38,460 --> 00:37:40,360 STUDENT: [INAUDIBLE] 763 00:37:40,360 --> 00:37:41,320 PROFESSOR: Yup, it's going to be a 1 and 1/2 bond. 764 00:37:41,320 --> 00:37:45,510 It's a 1 and 1/2 because it's halfway between a double bond 765 00:37:45,510 --> 00:37:46,590 and a single bond. 766 00:37:46,590 --> 00:37:49,080 So, of course, this is resonance so we can go ahead 767 00:37:49,080 --> 00:37:51,980 and put our resonance notation in there to indicate that 768 00:37:51,980 --> 00:37:53,680 benzene is a resonance structure. 769 00:37:53,680 --> 00:37:55,420 All right. 770 00:37:55,420 --> 00:37:58,530 So let's quickly talk about our last type of hybridization 771 00:37:58,530 --> 00:38:00,710 that we're going to discuss today, which is s p 772 00:38:00,710 --> 00:38:01,160 hybridization. 773 00:38:01,160 --> 00:38:06,640 So s p hybridization comes now from when we're combining an s 774 00:38:06,640 --> 00:38:08,180 orbital now with only one p orbital. 775 00:38:08,180 --> 00:38:11,700 So let's take a look at this with carbon. 776 00:38:11,700 --> 00:38:15,450 And if we hybridize these orbitals in carbon, what we 777 00:38:15,450 --> 00:38:19,060 end up with is having two hybrid orbitals, and then 778 00:38:19,060 --> 00:38:21,750 we're going to be left with two of our p orbitals that are 779 00:38:21,750 --> 00:38:25,770 each going to have an electron associated in them. 780 00:38:25,770 --> 00:38:28,350 So again, looking at the shapes, now we're just 781 00:38:28,350 --> 00:38:32,720 combining two, we've got these two equal hybrid orbitals plus 782 00:38:32,720 --> 00:38:34,540 these 2 p orbitals here. 783 00:38:34,540 --> 00:38:38,830 So let's take the case of acetylene where we have two 784 00:38:38,830 --> 00:38:41,430 carbon atoms that are going to be triple bonded to each 785 00:38:41,430 --> 00:38:43,420 other, each are bonded to a carbon 786 00:38:43,420 --> 00:38:45,290 and then to one hydrogen. 787 00:38:45,290 --> 00:38:47,660 So this is a little bit trickier to look at and see 788 00:38:47,660 --> 00:38:50,290 what it means, but essentially we have two hybrid orbitals, 789 00:38:50,290 --> 00:38:53,870 which are shown in blue here, and then we have one p orbital 790 00:38:53,870 --> 00:38:56,590 that's left alone that's going up and down on the page. 791 00:38:56,590 --> 00:38:58,820 And then that second p orbital's actually coming 792 00:38:58,820 --> 00:39:01,650 right out at you, it's coming out of the screen at you. 793 00:39:01,650 --> 00:39:05,070 So, if we think about this z bonding axis between the two 794 00:39:05,070 --> 00:39:09,170 carbon atoms, we can picture overlap of those s p hybrid 795 00:39:09,170 --> 00:39:13,400 orbitals, and then we can also picture bonding to hydrogen. 796 00:39:13,400 --> 00:39:19,380 So, in a settling, what is the bond angle here? 797 00:39:19,380 --> 00:39:21,700 This is the easiest question all day, what is the bond 798 00:39:21,700 --> 00:39:24,760 angle between all of these? 799 00:39:24,760 --> 00:39:26,130 Great, so it's 180 degrees. 800 00:39:26,130 --> 00:39:30,800 So, if we think about the bonds that are forming -- oh I 801 00:39:30,800 --> 00:39:33,870 see our TAs are here, so you can start handing them out, 802 00:39:33,870 --> 00:39:37,530 because we have two minutes left to go. 803 00:39:37,530 --> 00:39:44,530 So, as they're very quietly handing out your class notes, 804 00:39:44,530 --> 00:39:47,670 let's think about what this bond is here, this boxed bond, 805 00:39:47,670 --> 00:39:50,380 is it a pi bond or a sigma bond? 806 00:39:50,380 --> 00:39:51,860 It's going to be a sigma bond. 807 00:39:51,860 --> 00:39:56,120 So, we have sigma 2 s p, carbon 2 s p. 808 00:39:56,120 --> 00:39:59,070 So they're two s p bonds combining. 809 00:39:59,070 --> 00:40:01,740 Now let's think about this first pi bond, which will be 810 00:40:01,740 --> 00:40:04,500 above and below the bonding axis. 811 00:40:04,500 --> 00:40:07,330 Is this pi or sigma? 812 00:40:07,330 --> 00:40:08,540 This is pi. 813 00:40:08,540 --> 00:40:13,080 So we're talking about pi carbon 2 p x, because it's the 814 00:40:13,080 --> 00:40:17,720 x axes combining to carbon 2 p x. 815 00:40:17,720 --> 00:40:22,830 And the last bond that we have here is a carbon-carbon bond, 816 00:40:22,830 --> 00:40:25,530 and this is our last p orbitals 817 00:40:25,530 --> 00:40:26,470 that are coming together. 818 00:40:26,470 --> 00:40:29,200 These are the ones that are coming right out at you, so 819 00:40:29,200 --> 00:40:32,470 this is going to be on a second pi orbital. 820 00:40:32,470 --> 00:40:36,580 So this will be pi carbon 2 p y, carbon 2 p y. 821 00:40:36,580 --> 00:40:38,880 All right. 822 00:40:38,880 --> 00:40:42,000 So, we'll stop here today. 823 00:40:42,000 --> 00:40:44,520 Just stay in your seats for another 30 seconds as they're 824 00:40:44,520 --> 00:40:46,040 handing out your notes. 825 00:40:46,040 --> 00:40:48,830 I want to mention that you're going to get problem-set five 826 00:40:48,830 --> 00:40:52,060 is posted today, and I'll write which ones you can 827 00:40:52,060 --> 00:40:55,430 already do so far, because you don't have class on Monday. 828 00:40:55,430 --> 00:40:58,760 But remember that you do have recitation on Tuesday, so that 829 00:40:58,760 --> 00:41:02,660 could be very helpful with the problem-set, so be sure to go 830 00:41:02,660 --> 00:41:06,090 to recitation on Tuesday, and have a great long weekend.