1 00:00:00 --> 00:00:01 2 00:00:01 --> 00:00:02 The following content is provided under a Creative 3 00:00:02 --> 00:00:03 Commons license. 4 00:00:03 --> 00:00:06 Your support will help MIT OpenCourseWare continue to 5 00:00:06 --> 00:00:10 offer high-quality educational resources for free. 6 00:00:10 --> 00:00:13 To make a donation or view additional materials from 7 00:00:13 --> 00:00:15 hundreds of MIT courses, visit MIT OpenCourseWare 8 00:00:15 --> 00:00:17 at ocw.mit.edu. 9 00:00:17 --> 00:00:23 PROFESSOR: OK, it's time to get started. 10 00:00:23 --> 00:00:25 Pay attention to the clicker questions. 11 00:00:25 --> 00:00:59 All right, I'll give you 10 more seconds. 12 00:00:59 --> 00:01:09 Not bad, we seem to be in the 70's. 13 00:01:09 --> 00:01:10 All right. 14 00:01:10 --> 00:01:14 So if you didn't have time to click in, let's consider 15 00:01:14 --> 00:01:18 what's going on here. 16 00:01:18 --> 00:01:28 What's true about the relationship of q and k here? 17 00:01:28 --> 00:01:31 So is q less than or greater than k? 18 00:01:31 --> 00:01:34 Less than. 19 00:01:34 --> 00:01:38 And so you have to think about what that means in terms of 20 00:01:38 --> 00:01:41 where we are now in the reaction and where the reaction 21 00:01:41 --> 00:01:44 is at equilibrium, and I like to think about it in terms of 22 00:01:44 --> 00:01:46 products -- are there more products now, or are there more 23 00:01:46 --> 00:01:48 products at equilibrium. 24 00:01:48 --> 00:01:52 So if q is less than k, then there are more products at 25 00:01:52 --> 00:01:56 equilibrium, and so the reaction will shift 26 00:01:56 --> 00:01:58 toward products. 27 00:01:58 --> 00:02:02 So it's going to move in the direction to reach equilibrium, 28 00:02:02 --> 00:02:05 since k is a bigger number than q, and both of these terms are 29 00:02:05 --> 00:02:08 products over reactants, there'd mean there's more 30 00:02:08 --> 00:02:11 product at equilibrium then there are now, and so the 31 00:02:11 --> 00:02:14 reaction is going to shift toward products. 32 00:02:14 --> 00:02:17 All right, so we're at 73%. 33 00:02:17 --> 00:02:21 Let's see if by the end of today, we can get up to 90 on 34 00:02:21 --> 00:02:22 these kinds of questions. 35 00:02:22 --> 00:02:29 All right, so we're going to continue to consider external 36 00:02:29 --> 00:02:32 effects on k in today's class. 37 00:02:32 --> 00:02:38 I also wanted to mention that on each of the handouts for the 38 00:02:38 --> 00:02:42 lectures, I have the corresponding reading material 39 00:02:42 --> 00:02:47 listed on the handout, and I've listed it as section numbers in 40 00:02:47 --> 00:02:50 the chapters rather than page numbers, so that's a little 41 00:02:50 --> 00:02:51 bit of a difference. 42 00:02:51 --> 00:02:54 And the reason why I've done that is that we've had many 43 00:02:54 --> 00:02:58 different versions of the book in this class, and they don't 44 00:02:58 --> 00:03:02 seem to change the section titles or the section numbers, 45 00:03:02 --> 00:03:06 but they do change the page numbers associated with them. 46 00:03:06 --> 00:03:09 So if I give you section numbers then you should be able 47 00:03:09 --> 00:03:12 to use of whichever version of the book is available to you. 48 00:03:12 --> 00:03:17 So that's how I have it listed now, and the reading assignment 49 00:03:17 --> 00:03:21 is also listed on each problem-set as well. 50 00:03:21 --> 00:03:24 So when you're going over the handouts later studying for the 51 00:03:24 --> 00:03:29 exam, you can see where in the book this particular lecture, 52 00:03:29 --> 00:03:32 the material is, so you can go and do that reading. 53 00:03:32 --> 00:03:36 All right, so we talked at the end of the class last time 54 00:03:36 --> 00:03:42 about the Le Chatelier's principle, and this is a 55 00:03:42 --> 00:03:45 principle that you can use to predict the direction of change 56 00:03:45 --> 00:03:47 of a reaction -- whether it'll shift to the right or 57 00:03:47 --> 00:03:49 shift to the left. 58 00:03:49 --> 00:03:54 And simply stated, that systems tend to respond in such a 59 00:03:54 --> 00:03:56 way to minimize the stress. 60 00:03:56 --> 00:03:59 So if something is added to the reaction, the reaction will 61 00:03:59 --> 00:04:03 shift in a way to minimize that stress caused by the thing 62 00:04:03 --> 00:04:06 that's added to the system. 63 00:04:06 --> 00:04:11 So, we talked about adding reagents and removing products 64 00:04:11 --> 00:04:15 last time, and now we're going to go on and talk about 65 00:04:15 --> 00:04:18 what happens when you change the volume. 66 00:04:18 --> 00:04:21 So if you have a system at equilibrium and you change the 67 00:04:21 --> 00:04:24 volume of it, and here in particular we're talking about 68 00:04:24 --> 00:04:28 a gaseous system, what's going to happen? 69 00:04:28 --> 00:04:35 So what do we know about volumes when it comes to gases? 70 00:04:35 --> 00:04:37 We say that a decrease in volume of the gaseous 71 00:04:37 --> 00:04:41 system causes an increase in total pressure. 72 00:04:41 --> 00:04:48 What equation leaps to your mind when I say those words? 73 00:04:48 --> 00:04:53 Exactly, p v equals n r t. 74 00:04:53 --> 00:04:55 Yes. 75 00:04:55 --> 00:04:59 So there's a relationship between pressure and volume -- 76 00:04:59 --> 00:05:04 n is the number of moles, r is our gas constant, and 77 00:05:04 --> 00:05:05 t is our temperature. 78 00:05:05 --> 00:05:09 This is one of the things that usually sticks from high 79 00:05:09 --> 00:05:13 school, and if you haven't seen it before, it's pretty easy to 80 00:05:13 --> 00:05:18 get up to speed with this equation. 81 00:05:18 --> 00:05:21 So Le Chatelier's principle then predicts that the system 82 00:05:21 --> 00:05:26 will respond if possible in a way to reduce the 83 00:05:26 --> 00:05:27 total pressure. 84 00:05:27 --> 00:05:30 So if you decrease the volume and you cause an increase in 85 00:05:30 --> 00:05:33 total pressure, Le Chatelier says wait a minute, the system 86 00:05:33 --> 00:05:37 wants to respond to minimize that stress, so that it's going 87 00:05:37 --> 00:05:41 to respond in such a way to reduce that total pressure. 88 00:05:41 --> 00:05:44 So let's look at some examples of this. 89 00:05:44 --> 00:05:48 So we have an example of a reaction where we have two 90 00:05:48 --> 00:05:52 moles of p 2 gas going to one mole going to p 4 gas. 91 00:05:52 --> 00:05:56 And I have a little cartoon here to show this. 92 00:05:56 --> 00:06:02 So we have our p 4 gas up here, and our p 2 gas. 93 00:06:02 --> 00:06:05 All right, so what's going to happen if we're going to change 94 00:06:05 --> 00:06:07 the volume of this system? 95 00:06:07 --> 00:06:13 So if we're going to decrease the volume of the system, 96 00:06:13 --> 00:06:15 then the reaction should shift toward products. 97 00:06:15 --> 00:06:16 So let's think about that. 98 00:06:16 --> 00:06:26 So here in the middle we have our sort of system, and then on 99 00:06:26 --> 00:06:30 one side what happens when you decrease the volume and 100 00:06:30 --> 00:06:32 on the other side we're expanding the volume. 101 00:06:32 --> 00:06:35 So first, let's consider our system when we're going to 102 00:06:35 --> 00:06:39 compress that volume, decrease that volume. 103 00:06:39 --> 00:06:42 So what would be true is that the system's going to respond 104 00:06:42 --> 00:06:47 in such a way to minimize that stress that has been put 105 00:06:47 --> 00:06:50 forward by decreasing the volume, and you're going to try 106 00:06:50 --> 00:06:57 to compensate for that, and in this case you can compensate by 107 00:06:57 --> 00:06:58 a shift toward products. 108 00:06:58 --> 00:06:58 Why is that? 109 00:06:58 --> 00:07:01 Well, it all has to do with the stoichiometry of 110 00:07:01 --> 00:07:02 this equation up here. 111 00:07:02 --> 00:07:05 So for every two moles of reactants, you get 112 00:07:05 --> 00:07:08 one mole of products. 113 00:07:08 --> 00:07:14 So if you shift from the two to the one, that will cause a 114 00:07:14 --> 00:07:18 decrease in pressure, and so that will help compensate for 115 00:07:18 --> 00:07:21 the increase in pressure caused by the switch in volume. 116 00:07:21 --> 00:07:24 So you're going to respond in such a way to compensate 117 00:07:24 --> 00:07:26 for that stress. 118 00:07:26 --> 00:07:29 So a shift to the reaction to the right decreases 119 00:07:29 --> 00:07:31 the total pressure. 120 00:07:31 --> 00:07:33 So now let's think more about why this is true. 121 00:07:33 --> 00:07:36 Let's think about it from a math perspective and also just 122 00:07:36 --> 00:07:40 this qualitative perspective. 123 00:07:40 --> 00:07:45 So let's consider it in terms of q and k. 124 00:07:45 --> 00:07:49 So suppose our volume is decreased by a factor of 2, 125 00:07:49 --> 00:07:54 let's just make it easy, and we have constant temperature here. 126 00:07:54 --> 00:07:58 So this change will increase the partial pressure of both 127 00:07:58 --> 00:08:01 gases, the reacting gas and the product gas, and it's going 128 00:08:01 --> 00:08:05 to increase them both by the same amount, by 2 initially. 129 00:08:05 --> 00:08:09 So let's look at our equation for q, the reaction quotient. 130 00:08:09 --> 00:08:12 We have partial pressure of products over the partial 131 00:08:12 --> 00:08:16 pressures of the reactants, a raise to the coefficient 132 00:08:16 --> 00:08:17 to the equation. 133 00:08:17 --> 00:08:21 So initially you're going to increase the pressure, partial 134 00:08:21 --> 00:08:25 pressure of both gases by 2 -- then your product by 2, the 135 00:08:25 --> 00:08:28 reactant by 2 -- but here it's 2 squared. 136 00:08:28 --> 00:08:33 So overall, q becomes 1/2. 137 00:08:33 --> 00:08:36 So q decreases by a factor of 2, and so q 138 00:08:36 --> 00:08:39 becomes less then k. 139 00:08:39 --> 00:08:41 And so, in the clicker question, we talked about what 140 00:08:41 --> 00:08:47 happens when q becomes less than k, and what happens there 141 00:08:47 --> 00:08:51 is you're going to shift toward products until q 142 00:08:51 --> 00:08:54 equals k again. 143 00:08:54 --> 00:08:57 So you can think about this in terms of q and k, and you can 144 00:08:57 --> 00:08:59 also just think about it how many moles of gas are on one 145 00:08:59 --> 00:09:03 side, how many mold of gas on the other side, and how are you 146 00:09:03 --> 00:09:06 going to correspond, how are you going to decrease or 147 00:09:06 --> 00:09:08 minimize the stress on the system. 148 00:09:08 --> 00:09:14 All right, so let's think about what happens if we increase the 149 00:09:14 --> 00:09:17 volume, so here is our system and now we're going 150 00:09:17 --> 00:09:19 to expand it. 151 00:09:19 --> 00:09:22 If we're going to increase the volume, what's going to happen 152 00:09:22 --> 00:09:30 to the total pressure? 153 00:09:30 --> 00:09:33 I'm hearing it, but I want everyone to answer. 154 00:09:33 --> 00:09:36 Thank you. 155 00:09:36 --> 00:09:38 All right, so it will decrease the pressure. 156 00:09:38 --> 00:09:43 And what that's going to do is shift toward reactants, because 157 00:09:43 --> 00:09:47 we want to compensate for that decrease in pressure, and to do 158 00:09:47 --> 00:09:50 that, we can increase the pressure by switching or 159 00:09:50 --> 00:09:53 shifting the reaction toward the reactants. 160 00:09:53 --> 00:09:58 So again, we're going from one mole of product on one side 161 00:09:58 --> 00:10:00 to two of the reactants. 162 00:10:00 --> 00:10:06 So here, we see a shift toward the reactants. 163 00:10:06 --> 00:10:11 And so, this shift to the left is going to increase the total 164 00:10:11 --> 00:10:15 pressure to compensate for the decrease in pressure that was a 165 00:10:15 --> 00:10:20 result of this applied force to the system. 166 00:10:20 --> 00:10:28 And we could do this again in terms of q and k. 167 00:10:28 --> 00:10:33 Now we're going to get a little trickier. 168 00:10:33 --> 00:10:39 What happens if we add an inert gas to a system increasing 169 00:10:39 --> 00:10:44 the total pressure at constant temperature? 170 00:10:44 --> 00:10:46 So we're not adding one of the reactants or one of the 171 00:10:46 --> 00:10:49 products, we're adding an inert gas, and we're increasing 172 00:10:49 --> 00:10:51 the total pressure. 173 00:10:51 --> 00:10:58 What's going to happen? 174 00:10:58 --> 00:11:05 There's a couple of options, what do you think? 175 00:11:05 --> 00:11:09 How about nothing. 176 00:11:09 --> 00:11:13 Why would nothing happen? 177 00:11:13 --> 00:11:17 Well, q depends on the partial pressure of the reactant 178 00:11:17 --> 00:11:19 gas and the product gas. 179 00:11:19 --> 00:11:23 And in this particular example, the partial pressures 180 00:11:23 --> 00:11:25 are not changing. 181 00:11:25 --> 00:11:27 We are changing the total pressure of the system 182 00:11:27 --> 00:11:30 by adding an inert gas, but we're not changing 183 00:11:30 --> 00:11:33 the partial pressure. 184 00:11:33 --> 00:11:38 So let's take this opportunity to review partial pressures, or 185 00:11:38 --> 00:11:40 if you haven't seen it before, I'm going to tell you 186 00:11:40 --> 00:11:43 everything you need to know about partial pressures. 187 00:11:43 --> 00:11:49 So here's a little review, or for the first time, description 188 00:11:49 --> 00:11:51 of partial pressure. 189 00:11:51 --> 00:11:53 So what is the definition? 190 00:11:53 --> 00:11:57 The partial pressure is the pressure that each gas would 191 00:11:57 --> 00:12:03 exert if it were present alone in the container. 192 00:12:03 --> 00:12:06 So in this example, we have oxygen in a container, and 193 00:12:06 --> 00:12:09 we have one atmosphere of pressure. 194 00:12:09 --> 00:12:12 In the second one there's nitrogen in the container with 195 00:12:12 --> 00:12:15 one atomosphere of pressure. 196 00:12:15 --> 00:12:18 If you put this amount of oxygen and this amount of 197 00:12:18 --> 00:12:22 nitrogen together in a container, then you would have 198 00:12:22 --> 00:12:26 two atmospheres of total pressure, but you're still 199 00:12:26 --> 00:12:31 going to have one atmosphere of partial pressure for oxygen, 200 00:12:31 --> 00:12:35 and one atmosphere of partial pressure for nitrogen. 201 00:12:35 --> 00:12:39 So it's as if the gas is alone in the container. 202 00:12:39 --> 00:12:43 That's the definition of partial pressure. 203 00:12:43 --> 00:12:48 So let's look at some equations. 204 00:12:48 --> 00:12:52 So the partial pressure of a gas, p to sub a, is equal to 205 00:12:52 --> 00:12:57 the number of moles of that gas, and we also have in this 206 00:12:57 --> 00:13:00 equation, r, our gas constant, t, our temperature, 207 00:13:00 --> 00:13:02 and v, our volume. 208 00:13:02 --> 00:13:05 The total pressure on the system, which is what this two 209 00:13:05 --> 00:13:10 atmospheres is, is equal to the partial pressure of gas a, 210 00:13:10 --> 00:13:13 which would be the partial pressure of the oxygen at one 211 00:13:13 --> 00:13:16 atmosphere, the partial pressure of the nitrogen at one 212 00:13:16 --> 00:13:18 atmosphere, that's all we have here. 213 00:13:18 --> 00:13:21 So the partial pressure of those two, of one plus one, 214 00:13:21 --> 00:13:24 we have two for a total. 215 00:13:24 --> 00:13:29 And that's equal to the total number of the moles. 216 00:13:29 --> 00:13:32 So in these problems, we're going to be considering partial 217 00:13:32 --> 00:13:34 pressure, and the question you're going to be asking 218 00:13:34 --> 00:13:37 yourself in all of these different wordings of the 219 00:13:37 --> 00:13:41 question is is the partial pressure of the gas changing? 220 00:13:41 --> 00:13:43 That's a very important question to ask because 221 00:13:43 --> 00:13:50 that'll help you answer the questions correctly. 222 00:13:50 --> 00:13:54 So let's go back to the original question, what happens 223 00:13:54 --> 00:13:59 if an inert gas is added to the container, increasing the total 224 00:13:59 --> 00:14:02 pressure at constant temperature? 225 00:14:02 --> 00:14:07 And the answer is nothing, because q is not affected, 226 00:14:07 --> 00:14:10 because q depends on the partial pressures, and the 227 00:14:10 --> 00:14:12 partial pressure isn't changing. 228 00:14:12 --> 00:14:15 We aren't changing the number of moles of the gas in 229 00:14:15 --> 00:14:20 question, we're just changing the total pressure of the 230 00:14:20 --> 00:14:22 system, we're adding an inert gas. 231 00:14:22 --> 00:14:25 And because partial pressures don't change, q doesn't change, 232 00:14:25 --> 00:14:27 and if q doesn't change, there's no response 233 00:14:27 --> 00:14:30 from the system. 234 00:14:30 --> 00:14:34 So a lot of the questions in this unit, they're not actually 235 00:14:34 --> 00:14:37 very difficult, but the wording can be tricky. 236 00:14:37 --> 00:14:40 And so when you're doing these problems, you have to be 237 00:14:40 --> 00:14:45 thinking about what is changing and what isn't changing to 238 00:14:45 --> 00:14:47 be able to get these questions correct. 239 00:14:47 --> 00:14:50 And if you do that, then these are some nice questions for you 240 00:14:50 --> 00:14:54 to get right on the exams -- they're short, they're good 241 00:14:54 --> 00:14:59 questions to go after. 242 00:14:59 --> 00:15:00 All right. 243 00:15:00 --> 00:15:03 Let's see how you're doing with this. 244 00:15:03 --> 00:15:07 What happens if an inert gas is added to the container, but the 245 00:15:07 --> 00:15:11 total pressure is now kept constant, temperature 246 00:15:11 --> 00:15:14 is also constant. 247 00:15:14 --> 00:15:15 So let's think about this. 248 00:15:15 --> 00:15:57 OK, let's take 10 more seconds. 249 00:15:57 --> 00:16:01 OK, we're going down into the 60's -- again, we're heading 250 00:16:01 --> 00:16:04 toward the 90's by the end, but this is actually new 251 00:16:04 --> 00:16:07 material, so that's fine. 252 00:16:07 --> 00:16:09 All right, so let's think about it. 253 00:16:09 --> 00:16:13 So the reaction's going to shift toward reactants. 254 00:16:13 --> 00:16:15 Let's think about why, let's break it down. 255 00:16:15 --> 00:16:19 And what was important is that hint that for the pressure to 256 00:16:19 --> 00:16:22 be kept constant, the volume of the container must 257 00:16:22 --> 00:16:23 have increased. 258 00:16:23 --> 00:16:27 So let's take a look at that. 259 00:16:27 --> 00:16:31 So if the total pressure was kept constant, if the total 260 00:16:31 --> 00:16:35 pressure didn't change when you added an inert gas, the 261 00:16:35 --> 00:16:37 volume must have changed. 262 00:16:37 --> 00:16:38 Let's look at this. 263 00:16:38 --> 00:16:41 Say oxygen is our gas of interest, and n 264 00:16:41 --> 00:16:43 2 is an inert gas. 265 00:16:43 --> 00:16:47 If we added an inert gas to our system, the total 266 00:16:47 --> 00:16:48 pressure should go up. 267 00:16:48 --> 00:16:52 If it doesn't, then something else must have changed, and 268 00:16:52 --> 00:16:55 what must have changed is the volume. 269 00:16:55 --> 00:17:01 Otherwise the total pressure would not have stayed the same. 270 00:17:01 --> 00:17:05 So the volume of the container must have increased if 271 00:17:05 --> 00:17:09 the pressure is the same. 272 00:17:09 --> 00:17:16 So then we asked the question, if you increase the volume, 273 00:17:16 --> 00:17:19 what happens to the reaction, how does it shift? 274 00:17:19 --> 00:17:25 If you increase the volume, if you expand the volume, then 275 00:17:25 --> 00:17:29 you're going to shift from, in this case where you have one 276 00:17:29 --> 00:17:34 mole to two moles toward reactants, you will, as the 277 00:17:34 --> 00:17:38 volume increases, then you're going to have a change in the 278 00:17:38 --> 00:17:41 partial pressure of the gas -- all of a sudden the gas has a 279 00:17:41 --> 00:17:46 lot more room, and its pressure is going to decrease, the 280 00:17:46 --> 00:17:48 partial pressure will decrease. 281 00:17:48 --> 00:17:51 It has a lot more space for itself -- it's like it's 282 00:17:51 --> 00:17:53 in there all by itself. 283 00:17:53 --> 00:17:56 Partial pressure, you can think of it as selfish gas molecules, 284 00:17:56 --> 00:17:57 they don't care what else is there. 285 00:17:57 --> 00:18:00 They're only thinking about how they're fairing 286 00:18:00 --> 00:18:02 in this environment. 287 00:18:02 --> 00:18:06 So then we want to shift in a way that compensates for that 288 00:18:06 --> 00:18:08 stress that increases the pressure, so we move from one 289 00:18:08 --> 00:18:12 molecule to two molecules. 290 00:18:12 --> 00:18:17 So it's all about the partial pressure q and k. 291 00:18:17 --> 00:18:19 So again in these questions you have to dissect 292 00:18:19 --> 00:18:20 what's going on. 293 00:18:20 --> 00:18:22 What has changed? 294 00:18:22 --> 00:18:25 The questions are often phrased in such a way, something's kept 295 00:18:25 --> 00:18:28 constant, but if something's kept constant, you have to ask 296 00:18:28 --> 00:18:31 the question, to keep it constant, did something have to 297 00:18:31 --> 00:18:33 change for that to be true. 298 00:18:33 --> 00:18:35 So again, the wordings of these can be tricky. 299 00:18:35 --> 00:18:36 Do you have a question? 300 00:18:36 --> 00:18:39 STUDENT: [INAUDIBLE] 301 00:18:39 --> 00:18:47 PROFESSOR: So, the question is is it necessary for it to 302 00:18:47 --> 00:18:48 try to increase pressure. 303 00:18:48 --> 00:18:50 This is just the predictive tool of Le Chatelier. 304 00:18:50 --> 00:18:54 Le Chatelier would predict that if the system has changed in 305 00:18:54 --> 00:18:56 such a way, such as volume increases so the partial 306 00:18:56 --> 00:18:59 pressure decreases, that the system will shift in a way 307 00:18:59 --> 00:19:01 to minimize that stress. 308 00:19:01 --> 00:19:05 And to minimize that stress, you would increase the partial 309 00:19:05 --> 00:19:07 pressure by doing the shift from one mole to two. 310 00:19:07 --> 00:19:12 So again, this is Le Chatelier's predictive, how you 311 00:19:12 --> 00:19:15 would predict the direction of the shift based on the simple 312 00:19:15 --> 00:19:18 idea that a system where a stress is applied, the system 313 00:19:18 --> 00:19:22 will respond in a way to minimize the stress. 314 00:19:22 --> 00:19:26 And again, I talked about last time that this concept of 315 00:19:26 --> 00:19:30 minimizing stress is difficult for some MIT students, but you 316 00:19:30 --> 00:19:33 just sort of have to memorize that in this case we're 317 00:19:33 --> 00:19:43 predicting how a system will shift to minimize that stress. 318 00:19:43 --> 00:19:45 OK. 319 00:19:45 --> 00:19:48 So if you need a review of partial pressure, go over this. 320 00:19:48 --> 00:19:51 This part, it looks a little challenging at first, and some 321 00:19:51 --> 00:19:54 of the questions you really have to sit down and dissect 322 00:19:54 --> 00:19:57 what's going on, and for most people, once they get there, 323 00:19:57 --> 00:20:00 that part, those are good questions, you look forward 324 00:20:00 --> 00:20:04 to them on the exam. 325 00:20:04 --> 00:20:07 So now, we've talked about adding reagents, we've talked 326 00:20:07 --> 00:20:11 about removing reagents, removing products, adding 327 00:20:11 --> 00:20:17 products, shifts in volume, and now we're going to talk about 328 00:20:17 --> 00:20:20 changing the temperature. 329 00:20:20 --> 00:20:23 So here, Le Chatelier's principle, it's a little 330 00:20:23 --> 00:20:28 bit more fuzzy, but it still basically works. 331 00:20:28 --> 00:20:32 So if you talk about raising the temperature of a mixture 332 00:20:32 --> 00:20:37 at equilibrium, then Le Chatelier's principle would 333 00:20:37 --> 00:20:41 suggest that the system is going to respond in such a 334 00:20:41 --> 00:20:42 way to minimize that stress. 335 00:20:42 --> 00:20:47 So if you're adding heat, the system wants to respond in a 336 00:20:47 --> 00:20:50 way to absorb some of the heat, to counterbalance 337 00:20:50 --> 00:20:54 that change to the system. 338 00:20:54 --> 00:20:57 So let's take a look at this. 339 00:20:57 --> 00:21:01 So let's think about raising the temperature of an 340 00:21:01 --> 00:21:07 exothermic reaction. 341 00:21:07 --> 00:21:09 So what's going to happen here? 342 00:21:09 --> 00:21:14 Raising the temperature of an exothermic reaction, favors the 343 00:21:14 --> 00:21:18 formation of reactants, would shift toward reactants. 344 00:21:18 --> 00:21:20 Well, why would this be true. 345 00:21:20 --> 00:21:24 Well, you can think about this very simplistically that in an 346 00:21:24 --> 00:21:29 exothermic reaction, you're going to be producing heat in 347 00:21:29 --> 00:21:33 the forward direction and absorbing heat in the 348 00:21:33 --> 00:21:35 reverse direction. 349 00:21:35 --> 00:21:38 So if it's an exothermic reaction, that means it's 350 00:21:38 --> 00:21:41 exothermic in the forward direction, which would mean 351 00:21:41 --> 00:21:45 it was endothermic in the reverse direction. 352 00:21:45 --> 00:21:49 So if you raise the temperature of an exothermic reaction, 353 00:21:49 --> 00:21:53 you're adding heat, the system wants to respond in such a way 354 00:21:53 --> 00:21:58 to absorb that heat, so it would shift toward the 355 00:21:58 --> 00:22:02 endothermic direction of the reaction, which is the reverse 356 00:22:02 --> 00:22:05 direction toward reactants. 357 00:22:05 --> 00:22:09 So add heat, system wants to shift to absorb 358 00:22:09 --> 00:22:10 some of that heat. 359 00:22:10 --> 00:22:13 So in this part you think about the direction of the reaction, 360 00:22:13 --> 00:22:16 whether it's exothermic or endothermic, and then think 361 00:22:16 --> 00:22:19 about compensating for that stress. 362 00:22:19 --> 00:22:25 Endothermic reaction, again, they say it's an endothermic 363 00:22:25 --> 00:22:27 reaction, it means it's endothermic in the 364 00:22:27 --> 00:22:29 forward direction. 365 00:22:29 --> 00:22:32 So heat is being absorbed in the forward direction -- again 366 00:22:32 --> 00:22:35 this is just sort of a very simplistic way to 367 00:22:35 --> 00:22:37 think about it. 368 00:22:37 --> 00:22:41 So if you raise the temperature then, you want to absorb that 369 00:22:41 --> 00:22:44 heat, according to Le Chatelier's principle, and 370 00:22:44 --> 00:22:51 so that would favor a shift toward products. 371 00:22:51 --> 00:22:56 So let's look some more at this. 372 00:22:56 --> 00:23:01 The predictive tool here is delta h. 373 00:23:01 --> 00:23:04 So delta h, whether the reaction is exothermic or 374 00:23:04 --> 00:23:08 endothermic, is going to be a predictive tool in thinking 375 00:23:08 --> 00:23:13 about the direction of change, when heat is added to a system 376 00:23:13 --> 00:23:21 or heat is removed from a system. 377 00:23:21 --> 00:23:24 So let's try this out. 378 00:23:24 --> 00:23:27 Heat is added to a system. 379 00:23:27 --> 00:23:30 You're given information about your predictive tool, delta h. 380 00:23:30 --> 00:23:49 Which direction will the reaction go? 381 00:23:49 --> 00:24:06 All right, 10 seconds. 382 00:24:06 --> 00:24:42 Why don't you discuss with your friends and vote again. 383 00:24:42 --> 00:24:55 All right, 10 more seconds. 384 00:24:55 --> 00:24:58 Yes! 385 00:24:58 --> 00:25:02 I knew we could get into the 90's. 386 00:25:02 --> 00:25:05 All right, so what type of reaction is this, 387 00:25:05 --> 00:25:07 endo or exothermic? 388 00:25:07 --> 00:25:08 Exothermic. 389 00:25:08 --> 00:25:13 And so we're adding heat to an exothermic reaction, so it 390 00:25:13 --> 00:25:17 wants to shift to absorb that heat, so it wants to go in 391 00:25:17 --> 00:25:20 endothermic direction, which is the reverse direction or 392 00:25:20 --> 00:25:24 toward the reactants. 393 00:25:24 --> 00:25:26 And that's how it's supposed to work too, more people 394 00:25:26 --> 00:25:30 get the right answer after the group discusses. 395 00:25:30 --> 00:25:34 All right. 396 00:25:34 --> 00:25:39 So we've been talking about the equilibrium constant so far in 397 00:25:39 --> 00:25:43 terms of it being a constant, it's called the equilibrium 398 00:25:43 --> 00:25:46 constant, but it's only constant at a given 399 00:25:46 --> 00:25:47 temperature. 400 00:25:47 --> 00:25:53 So the equilibrium constant changes with temperature. 401 00:25:53 --> 00:25:56 It's also true that rates of reaction change 402 00:25:56 --> 00:25:58 with temperature. 403 00:25:58 --> 00:26:01 And kinetics is our last unit in this course, and we'll be 404 00:26:01 --> 00:26:04 discussing that quite a bit. 405 00:26:04 --> 00:26:08 So how does the equilibrium constant change 406 00:26:08 --> 00:26:09 with temperature? 407 00:26:09 --> 00:26:12 Let's consider that. 408 00:26:12 --> 00:26:15 So let's look at some of the equations that we know that 409 00:26:15 --> 00:26:19 have delta h in them -- delta h, again, is our predictive 410 00:26:19 --> 00:26:23 factor when we're talking about changes in temperature. 411 00:26:23 --> 00:26:28 We know that delta g nought is minus r t natural log of k, so 412 00:26:28 --> 00:26:31 the relationship with our standard free energy, our gas 413 00:26:31 --> 00:26:35 constant temperature, and our equilibrium constant. 414 00:26:35 --> 00:26:38 We also know that delta g nought equals delta h nought 415 00:26:38 --> 00:26:40 minus t delta s nought. 416 00:26:40 --> 00:26:44 If those equations don't look familiar, then you should go 417 00:26:44 --> 00:26:48 back and review the material on thermodynamics because you're 418 00:26:48 --> 00:26:51 going to need it in this unit, the next unit, the unit after 419 00:26:51 --> 00:26:54 that, and then the next two units, and they we're 420 00:26:54 --> 00:26:55 done with the class. 421 00:26:55 --> 00:26:59 All right, so good to get familiar with this now. 422 00:26:59 --> 00:27:04 All right, so we can rearrange these in terms of solving for 423 00:27:04 --> 00:27:07 our equilibrium constant. 424 00:27:07 --> 00:27:10 And so we see the natural log of the equilibrium constant 425 00:27:10 --> 00:27:15 minus delta h nought over r t, plus delta s nought over r. 426 00:27:15 --> 00:27:19 And so, it's reasonable to assume that for the things 427 00:27:19 --> 00:27:24 we're talking about, that delta h nought and delta s nought are 428 00:27:24 --> 00:27:26 pretty much independent of temperatures. 429 00:27:26 --> 00:27:29 That would be true for pretty much any temperature we 430 00:27:29 --> 00:27:30 would be talking about. 431 00:27:30 --> 00:27:36 So that means that k, or the natural log of k, is going to 432 00:27:36 --> 00:27:38 change depending on the temperature. 433 00:27:38 --> 00:27:41 It won't change -- these other ones are constant at all the 434 00:27:41 --> 00:27:44 temperatures, so there's a relationship between 435 00:27:44 --> 00:27:50 equilibrium constant and temperature. 436 00:27:50 --> 00:27:54 So you can consider an equilibrium constant at one 437 00:27:54 --> 00:27:57 temperature, and an equilibrium constant at another 438 00:27:57 --> 00:27:58 temperature. 439 00:27:58 --> 00:28:03 So we can talk about the natural log of a k 2, of an 440 00:28:03 --> 00:28:07 equilibrium constant 2, equal to minus delta h over r 441 00:28:07 --> 00:28:12 t temperature 2, plus delta s nought over r. 442 00:28:12 --> 00:28:17 We can do the same thing for another temperature, another 443 00:28:17 --> 00:28:23 temperature 1, equilibrium 1, and if we subtract these two, 444 00:28:23 --> 00:28:26 delta s is going to cancel out, and we're going to get this 445 00:28:26 --> 00:28:30 equation, which you know is important because it has a 446 00:28:30 --> 00:28:34 name, so this is the van't Hoff equation. 447 00:28:34 --> 00:28:37 And at some point later in the course, I'll be asking you to 448 00:28:37 --> 00:28:40 come up with this name, so I always get very excited when 449 00:28:40 --> 00:28:43 people can tell me it's a van't Hoff equation later on, not 450 00:28:43 --> 00:28:46 that that's on a test, but there are very few 451 00:28:46 --> 00:28:48 equations that have names. 452 00:28:48 --> 00:28:50 So here we go. 453 00:28:50 --> 00:28:51 So what does this do? 454 00:28:51 --> 00:28:54 Well, we can talk about the natural log of one equilibrium 455 00:28:54 --> 00:28:58 constant over another, an equilibrium constant k 2, which 456 00:28:58 --> 00:29:01 is the equilibrium at temperature 2, equilibrium 457 00:29:01 --> 00:29:03 constant k 1, which is the equilibrium constant at 458 00:29:03 --> 00:29:08 temperature 1, is going to be equal to minus delta h nought 459 00:29:08 --> 00:29:11 over r, and then it depends on the temperature. 460 00:29:11 --> 00:29:14 So you bracket 1 over temperature 2 minus 1 461 00:29:14 --> 00:29:15 over temperature 1. 462 00:29:15 --> 00:29:19 And this just comes from subtracting those 2 equations. 463 00:29:19 --> 00:29:23 So again, you can think about how the equilibrium constant's 464 00:29:23 --> 00:29:26 going to change with temperature -- that's what 465 00:29:26 --> 00:29:30 this equation does for you. 466 00:29:30 --> 00:29:34 So let's look at some of the things that fall out of 467 00:29:34 --> 00:29:39 this particular equation. 468 00:29:39 --> 00:29:43 Let's think first about a case where this delta h nought 469 00:29:43 --> 00:29:45 is less than zero. 470 00:29:45 --> 00:29:49 What type of reaction is that? 471 00:29:49 --> 00:29:50 Exothermic. 472 00:29:50 --> 00:29:54 All right, so now let's consider a case for this 473 00:29:54 --> 00:29:59 exothermic reaction where we're going to increase the 474 00:29:59 --> 00:30:04 temperature, and so that means that t 2 will be greater than t 475 00:30:04 --> 00:30:08 1 -- we've increased the temperature. 476 00:30:08 --> 00:30:12 So now let's think about what sign the natural log of k 477 00:30:12 --> 00:30:19 2 over k 1 will have if these things are true. 478 00:30:19 --> 00:30:21 So there's a minus in the equation, let's put 479 00:30:21 --> 00:30:23 the minus down here. 480 00:30:23 --> 00:30:27 Delta h nought is negative, it's exothermic reaction, so 481 00:30:27 --> 00:30:29 that's another negative sign. 482 00:30:29 --> 00:30:33 And if we're increasing the temperature, and t 2 is greater 483 00:30:33 --> 00:30:37 than t 1, then this temperature term will also have 484 00:30:37 --> 00:30:39 and negative sign. 485 00:30:39 --> 00:30:42 So if you have negative times negative times negative, you're 486 00:30:42 --> 00:30:47 going to get a negative for your net result over here. 487 00:30:47 --> 00:30:52 And what that will mean in terms of k 2 and k 1, is that 488 00:30:52 --> 00:30:57 k 1 will be greater than k 2. 489 00:30:57 --> 00:31:00 So you can think about this mathematically by running 490 00:31:00 --> 00:31:02 through this argument. 491 00:31:02 --> 00:31:06 You can also sort of think about it in terms of what you 492 00:31:06 --> 00:31:12 would expect if you increase the temperature in terms of 493 00:31:12 --> 00:31:15 what's the relative ratio of products to reactants 494 00:31:15 --> 00:31:20 at equilibrium for an exothermic reaction. 495 00:31:20 --> 00:31:24 So if you're increasing the temperature of an exothermic 496 00:31:24 --> 00:31:29 reaction, the reaction would want to shift in the direction 497 00:31:29 --> 00:31:33 to absorb that heat in the endothermic direction. 498 00:31:33 --> 00:31:38 So you would expect that the equilibrium constant that was 499 00:31:38 --> 00:31:41 at the lower temperature would be larger than the higher 500 00:31:41 --> 00:31:44 temperature one, that there'd be less products at this 501 00:31:44 --> 00:31:47 new higher temperature. 502 00:31:47 --> 00:31:50 So again, you can think about it in terms of Le Chatelier's 503 00:31:50 --> 00:31:53 principle, or you can run through with this equation and 504 00:31:53 --> 00:32:02 do the math and think about the relative size of k 1 and k 2. 505 00:32:02 --> 00:32:04 So now let's think about what happens when you decrease the 506 00:32:04 --> 00:32:09 temperature where t 2 is less than t 1. 507 00:32:09 --> 00:32:14 So we can do the same thing, we have a negative sign here, we 508 00:32:14 --> 00:32:16 also have a negative sign for delta h, it's an 509 00:32:16 --> 00:32:18 exothermic reaction. 510 00:32:18 --> 00:32:22 But now we have a positive sign for this temperature term. 511 00:32:22 --> 00:32:25 So overall we're going to have a positive sign for the natural 512 00:32:25 --> 00:32:30 log of k 2 over k 1, which mathematically is going to mean 513 00:32:30 --> 00:32:35 that k 1 is less than k 2 or that you would expect more 514 00:32:35 --> 00:32:41 products in the equilibrium constant at higher temperature. 515 00:32:41 --> 00:32:49 All right, so that's an exothermic reaction. 516 00:32:49 --> 00:32:52 So if you're ever having problems with Le Chatelier, you 517 00:32:52 --> 00:32:55 can go and use the van't Hoff equation to think about what 518 00:32:55 --> 00:32:58 you would expect in terms of this shift, what you would 519 00:32:58 --> 00:33:01 expect if you change the temperature of an exothermic 520 00:33:01 --> 00:33:05 reaction in terms of the magnitude of the new 521 00:33:05 --> 00:33:06 equilibrium constants. 522 00:33:06 --> 00:33:12 All right, now you can do the same for me in terms 523 00:33:12 --> 00:33:18 of this delta h nought is greater than zero. 524 00:33:18 --> 00:33:22 Which of the following are going to be true, and notice 525 00:33:22 --> 00:33:27 there's a possibility that all of them are true or that just 526 00:33:27 --> 00:33:30 some of them are true or that one of them is true. 527 00:33:30 --> 00:34:46 All right, take 10 more seconds. 528 00:34:46 --> 00:34:49 See, actually people did very well, because e is also true, 529 00:34:49 --> 00:34:53 all of those are true, but d was also true. 530 00:34:53 --> 00:34:58 So if we add the 30 and the 58 together, I'm very happy. 531 00:34:58 --> 00:35:03 All right, so let's look at this -- we'll keep the 532 00:35:03 --> 00:35:06 questions up and let's consider all of them in order. 533 00:35:06 --> 00:35:12 So the first one is that the reaction was endothermic, 534 00:35:12 --> 00:35:16 I think everybody saw that as being correct. 535 00:35:16 --> 00:35:19 OK, the second one talked about the equilibrium constant is 536 00:35:19 --> 00:35:21 higher at higher temperatures. 537 00:35:21 --> 00:35:22 So let's look at the first one. 538 00:35:22 --> 00:35:27 We increased the temperature here, and we see that if you 539 00:35:27 --> 00:35:31 work out the math or just think about it, k 2 is larger than k 540 00:35:31 --> 00:35:35 1, so the second equilibrium constant is greater than the 541 00:35:35 --> 00:35:39 first when you increase the temperature. 542 00:35:39 --> 00:35:42 So that would favor then, in an endothermic direction, if 543 00:35:42 --> 00:35:44 you're increasing the temperature, it favors the 544 00:35:44 --> 00:35:47 endothermic direction of the reaction, so you could think 545 00:35:47 --> 00:35:52 about the ratio having more products at that new 546 00:35:52 --> 00:35:55 equilibrium constant at that higher temperature. 547 00:35:55 --> 00:35:57 So that one was also true. 548 00:35:57 --> 00:36:00 Then let's think about when you decrease the temperature, when 549 00:36:00 --> 00:36:05 temperature 1 is greater than temperature 2. 550 00:36:05 --> 00:36:09 And so this would favor, then, the exothermic direction. 551 00:36:09 --> 00:36:14 So you would expect less products at this 552 00:36:14 --> 00:36:16 newer temperature. 553 00:36:16 --> 00:36:20 So, this part asked about k 1 versus k 2, and we see 554 00:36:20 --> 00:36:22 k 1 is greater than k 2. 555 00:36:22 --> 00:36:26 And then d says there's fewer products and equilibrium when 556 00:36:26 --> 00:36:30 the temperature is decreased, and that's just the word way 557 00:36:30 --> 00:36:33 of saying the same thing. 558 00:36:33 --> 00:36:36 So all of those are true. 559 00:36:36 --> 00:36:42 But again, people did very, very well with this question. 560 00:36:42 --> 00:36:45 All right. 561 00:36:45 --> 00:36:50 So now we're going to combine what we learned on Friday with 562 00:36:50 --> 00:36:55 what we learned today, and think about ways that 563 00:36:55 --> 00:36:57 that can be applied. 564 00:36:57 --> 00:37:01 So why should you care about Le Chatelier's principle? 565 00:37:01 --> 00:37:04 Well, for two reasons -- one I think Le Chatelier had sort of 566 00:37:04 --> 00:37:08 a good life plan that when stress is applied to the 567 00:37:08 --> 00:37:12 system, one should respond in a way to minimize that stress. 568 00:37:12 --> 00:37:15 I think that is an important life lesson. 569 00:37:15 --> 00:37:19 But also, it's very useful in terms of thinking 570 00:37:19 --> 00:37:22 about maximizing a yield of a reaction. 571 00:37:22 --> 00:37:26 So if you were going to create an industrial process and make 572 00:37:26 --> 00:37:31 lots of money and give some of it back to MIT to improve 573 00:37:31 --> 00:37:36 things in terms of teaching chemistry at MIT, then you 574 00:37:36 --> 00:37:39 would want to think about these principles, because you would 575 00:37:39 --> 00:37:40 want to maximize your yield. 576 00:37:40 --> 00:37:42 If you're going to be making a product, you want to make a lot 577 00:37:42 --> 00:37:45 of that product, and so you want to be thinking 578 00:37:45 --> 00:37:47 about these things. 579 00:37:47 --> 00:37:51 So we've talked about the reaction with nitrogen 580 00:37:51 --> 00:37:54 and hydrogen making ammonia last time. 581 00:37:54 --> 00:37:58 And this is an exothermic reaction. 582 00:37:58 --> 00:38:03 So, there are a lot of people who want to make ammonia -- 583 00:38:03 --> 00:38:06 it's for fertilizer, and as some of you have heard in terms 584 00:38:06 --> 00:38:11 of terrorism, it also can be used as an explosive, so there 585 00:38:11 --> 00:38:16 are a lot of people who want to make a lot of this. 586 00:38:16 --> 00:38:19 So how do you maximize this yield? 587 00:38:19 --> 00:38:22 It's an exothermic reaction. 588 00:38:22 --> 00:38:25 So you can think about temperature. 589 00:38:25 --> 00:38:32 So here, low temperature would favor product, which is good. 590 00:38:32 --> 00:38:35 We haven't talked about kinetics yet, but low 591 00:38:35 --> 00:38:39 temperature also slows the rate, which is bad. 592 00:38:39 --> 00:38:41 Because you not only want to make a lot of your product, you 593 00:38:41 --> 00:38:45 want to make it in a reasonable time frame and sell it and make 594 00:38:45 --> 00:38:47 lots of money and retire early. 595 00:38:47 --> 00:38:51 So you care about how fast the reaction is going as well. 596 00:38:51 --> 00:38:55 So for an exothermic reaction then, you have to balance out 597 00:38:55 --> 00:38:58 what's thermodynamically favorable and what's 598 00:38:58 --> 00:39:00 kinetically favorable. 599 00:39:00 --> 00:39:04 So thermodynamically, you would want a low temperature, but 600 00:39:04 --> 00:39:08 kinetically in terms of the rate, that's not so good. 601 00:39:08 --> 00:39:12 So they use a compromised temperature, which is 500 602 00:39:12 --> 00:39:15 degrees c, so that's pretty high actually 603 00:39:15 --> 00:39:18 for this reaction. 604 00:39:18 --> 00:39:21 So what are other things that you could do to drive this 605 00:39:21 --> 00:39:26 reaction toward products? 606 00:39:26 --> 00:39:27 So yeah, what's something else you could do? 607 00:39:27 --> 00:39:31 STUDENT: Increase the volume. 608 00:39:31 --> 00:39:31 PROFESSOR: Right. 609 00:39:31 --> 00:39:33 So you could think about volume here. 610 00:39:33 --> 00:39:39 So here we have four molecules of gas on one side, and two 611 00:39:39 --> 00:39:42 molecules of gas on the other side. 612 00:39:42 --> 00:39:48 So you can think about changing that to favor your products. 613 00:39:48 --> 00:39:49 What is something else you could do? 614 00:39:49 --> 00:39:51 STUDENT: Enzymes. 615 00:39:51 --> 00:39:56 PROFESSOR: Enzymes, we'll talk about that in a minute. 616 00:39:56 --> 00:39:58 If you can't use the enzymes, what's something else 617 00:39:58 --> 00:39:59 that you could do? 618 00:39:59 --> 00:40:02 STUDENT: You could remove ammonia from the system. 619 00:40:02 --> 00:40:04 PROFESSOR: Yup, so you could remove ammonia from the 620 00:40:04 --> 00:40:07 system, which would also shift the direction. 621 00:40:07 --> 00:40:10 So let's just put those two things down. 622 00:40:10 --> 00:40:11 Remove products. 623 00:40:11 --> 00:40:14 So if you remove ammonia from the system, and they actually 624 00:40:14 --> 00:40:17 do this in the industrial process, so they'll stop -- 625 00:40:17 --> 00:40:21 they'll, at a certain time points, they will remove the 626 00:40:21 --> 00:40:23 product and they'll say hey, let's shift the 627 00:40:23 --> 00:40:24 reaction to make more. 628 00:40:24 --> 00:40:28 You just changed q versus k, you removed your product, so 629 00:40:28 --> 00:40:31 now we want to shift to minimize that stress 630 00:40:31 --> 00:40:33 and make more product. 631 00:40:33 --> 00:40:37 And the first response, compress the volume, so we go 632 00:40:37 --> 00:40:41 from four molecules to two molecules, and that would be 633 00:40:41 --> 00:40:44 favor -- again, the system would want to respond, you 634 00:40:44 --> 00:40:49 compressed the volume, you increased the pressure, so you 635 00:40:49 --> 00:40:53 want to respond in such a way that compensates for that 636 00:40:53 --> 00:40:56 increased pressure, which is decrease the pressure by going 637 00:40:56 --> 00:40:59 from the four molecules to two. 638 00:40:59 --> 00:41:01 So both of those are great, and both of those 639 00:41:01 --> 00:41:03 are, in fact, used. 640 00:41:03 --> 00:41:06 Sometimes when you study chemistry you'll realize that 641 00:41:06 --> 00:41:11 some of the -- people made a lot of money on this, and 642 00:41:11 --> 00:41:13 that some of the principles are actually very simple. 643 00:41:13 --> 00:41:16 You are learning principles in this class that, applied 644 00:41:16 --> 00:41:19 correctly, could make you a lot of money. 645 00:41:19 --> 00:41:21 Some of the scientific discoveries are actually 646 00:41:21 --> 00:41:23 not all that complicated. 647 00:41:23 --> 00:41:26 All right. 648 00:41:26 --> 00:41:29 So someone said use enzymes. 649 00:41:29 --> 00:41:32 I love that answer, I want to use enzymes to do a lot of 650 00:41:32 --> 00:41:35 those things, and people are trying to do this. 651 00:41:35 --> 00:41:39 Now, why would you want to use an enzyme? 652 00:41:39 --> 00:41:42 Well, there is a lot of nitrogen in the air, but 653 00:41:42 --> 00:41:47 there's not a lot of usable nitrogen, because n 2 gas is 654 00:41:47 --> 00:41:49 in the air, but it's very difficult to break it 655 00:41:49 --> 00:41:52 apart to form ammonia. 656 00:41:52 --> 00:41:55 And when you think about bonding, you can probably tell 657 00:41:55 --> 00:42:00 me why it's hard to break n 2 apart, and if you consider how 658 00:42:00 --> 00:42:04 many bonds would be between those two nitrogens. 659 00:42:04 --> 00:42:08 So it's there but it's hard to do. 660 00:42:08 --> 00:42:11 So the industrial process that's used now pretty much is 661 00:42:11 --> 00:42:14 the same industrial process that's been used for quite a 662 00:42:14 --> 00:42:18 while, the Haber-Bosch process, which does not use enzymes. 663 00:42:18 --> 00:42:22 And here are some pictures of these folks. 664 00:42:22 --> 00:42:28 This resulted in two Noble prizes, the development of 665 00:42:28 --> 00:42:32 the industrial process here, and it's still being used. 666 00:42:32 --> 00:42:37 On a historic note, these were German scientists, and so, 667 00:42:37 --> 00:42:40 working out this process was important to the Germans 668 00:42:40 --> 00:42:42 during World War II. 669 00:42:42 --> 00:42:47 It's still the process going on today. 670 00:42:47 --> 00:42:49 So what about enzymes. 671 00:42:49 --> 00:42:52 Maybe enzymes could do a bit better than this process. 672 00:42:52 --> 00:42:54 It's not true yet. 673 00:42:54 --> 00:42:58 Still the Haber-Bosch industrial process is the 674 00:42:58 --> 00:43:02 one that's being used, but enzymes can do it. 675 00:43:02 --> 00:43:07 So, some of the problems of a lot of the common industrial 676 00:43:07 --> 00:43:10 reactions are that you use high temperatures -- remember we 677 00:43:10 --> 00:43:12 said the compromised temperature was 500 678 00:43:12 --> 00:43:14 degrees celsius. 679 00:43:14 --> 00:43:17 We were talking about compressing the volume, so 680 00:43:17 --> 00:43:21 you want to put in energy to compress that volume. 681 00:43:21 --> 00:43:24 And so that is expensive. 682 00:43:24 --> 00:43:27 And you might want to think about a way, could you do that 683 00:43:27 --> 00:43:33 reaction at normal ambient temperature without applying 684 00:43:33 --> 00:43:34 energy to the system. 685 00:43:34 --> 00:43:39 Well, enzymes can do this reaction at ambient 686 00:43:39 --> 00:43:42 temperatures and they don't have to have high pressure 687 00:43:42 --> 00:43:45 associated with them, and the way the enzymes do this, and 688 00:43:45 --> 00:43:48 here's a little cartoon of a space-filling model of 689 00:43:48 --> 00:43:52 a particular enzyme called nitrogenase. 690 00:43:52 --> 00:43:56 So for nitrogen, and the ase means it's an enzyme. 691 00:43:56 --> 00:44:00 And the secret to this enzyme, how it can do what Haber and 692 00:44:00 --> 00:44:04 Bosch got two Nobel prizes for -- this enzyme has received 693 00:44:04 --> 00:44:08 no Nobel prizes, and it can do the same thing. 694 00:44:08 --> 00:44:11 Its secret are metals. 695 00:44:11 --> 00:44:15 It uses these clusters of metals in the context of the 696 00:44:15 --> 00:44:20 protein environment to do this chemistry, and they have iron, 697 00:44:20 --> 00:44:24 and they have also inorganic sulfide, and molybdenum, and so 698 00:44:24 --> 00:44:29 these combinations of metals can do this chemistry. 699 00:44:29 --> 00:44:31 And a number of scientists have been working for decades 700 00:44:31 --> 00:44:35 now trying to understand how the enzyme works. 701 00:44:35 --> 00:44:37 It's actually quite complicated and it's been pretty 702 00:44:37 --> 00:44:39 controversial. 703 00:44:39 --> 00:44:42 So let me just kind of show you at the heart of the enzyme, 704 00:44:42 --> 00:44:46 here all the atoms of the enzyme, but if you rotate the 705 00:44:46 --> 00:44:50 enzyme around and go in, the secret was that those 706 00:44:50 --> 00:44:52 combinations of metals. 707 00:44:52 --> 00:44:54 And one of the units that we're going to have second to last in 708 00:44:54 --> 00:44:58 this courses is about transition metals, that metals 709 00:44:58 --> 00:45:00 can do a lot of really important things in biological 710 00:45:00 --> 00:45:03 systems, and also in industrial processes and other 711 00:45:03 --> 00:45:06 things as well. 712 00:45:06 --> 00:45:10 So I do also like to mention research is 713 00:45:10 --> 00:45:11 going on here at MIT. 714 00:45:11 --> 00:45:16 I've mentioned Dick Schrock before, he won a Nobel Prize in 715 00:45:16 --> 00:45:21 chemistry a few years back, but not for his work on sort of 716 00:45:21 --> 00:45:28 nitrogenase systems, but he was able to design a small catalyst 717 00:45:28 --> 00:45:31 that can do this chemistry, that can catalyze this 718 00:45:31 --> 00:45:34 reduction of nitrogen to ammonia at a defined 719 00:45:34 --> 00:45:36 molybdenum center. 720 00:45:36 --> 00:45:38 Again, we'll talk about transition metals 721 00:45:38 --> 00:45:39 later in the course. 722 00:45:39 --> 00:45:43 And so his laboratory is very interested in coming up with 723 00:45:43 --> 00:45:49 better ways to split nitrogen than the industrial processes 724 00:45:49 --> 00:45:50 that are currently used. 725 00:45:50 --> 00:45:53 Some people are studying enzymes, other people are 726 00:45:53 --> 00:45:56 trying to use some of the tools that come out the enzymes, 727 00:45:56 --> 00:46:00 thinking about the enzymes and come up with other 728 00:46:00 --> 00:46:01 catalysts as well. 729 00:46:01 --> 00:46:04 So this work is going on here at MIT. 730 00:46:04 --> 00:46:11 All right, so let's give one more example of Le Chatelier 731 00:46:11 --> 00:46:15 from a biological perspective, and this has to do with 732 00:46:15 --> 00:46:17 the following reaction. 733 00:46:17 --> 00:46:23 The combination of oxygen with hemoglobin in your blood. 734 00:46:23 --> 00:46:27 And the reaction here, we have hemoglobin plus oxygen has 735 00:46:27 --> 00:46:33 oxyhemoglobin, so the oxygen is now bound to be hemoglobin. 736 00:46:33 --> 00:46:36 This reaction is very important for you. 737 00:46:36 --> 00:46:40 None of us would be alive if this was not happening. 738 00:46:40 --> 00:46:46 We need to get the oxygen from our lungs to our cells. 739 00:46:46 --> 00:46:49 So what happens if you decide to climb Mount 740 00:46:49 --> 00:46:51 Everest, for example. 741 00:46:51 --> 00:46:55 You may be thinking how hard can that be after a first 742 00:46:55 --> 00:46:57 semester freshman year at MIT. 743 00:46:57 --> 00:47:02 Really, I can think more broadly about it. 744 00:47:02 --> 00:47:06 All right, how many of you have climbed a mountain so far? 745 00:47:06 --> 00:47:07 Woah, a lot of people. 746 00:47:07 --> 00:47:10 OK, something about going to MIT and climbing big mountains 747 00:47:10 --> 00:47:12 seems to be connected. 748 00:47:12 --> 00:47:15 How many people feel like after surviving the first year, why 749 00:47:15 --> 00:47:17 not, go ahead and climb a mountain? 750 00:47:17 --> 00:47:18 Any more people? 751 00:47:18 --> 00:47:20 OK, no. 752 00:47:20 --> 00:47:24 So you gotta -- you've been through the hard part now, 753 00:47:24 --> 00:47:26 you don't want to risk anything anymore. 754 00:47:26 --> 00:47:29 All right, so this slide seems to be cutting off some stuff, 755 00:47:29 --> 00:47:31 so let's look over here. 756 00:47:31 --> 00:47:34 So what happens to this reaction? 757 00:47:34 --> 00:47:38 Well, as you go up higher and higher, the partial 758 00:47:38 --> 00:47:40 pressure of oxygen changes. 759 00:47:40 --> 00:47:47 So you're going to drop in partial pressure 0.2 to 0.14 . 760 00:47:47 --> 00:47:51 So what happens to this reaction if this 761 00:47:51 --> 00:47:54 value decreases? 762 00:47:54 --> 00:47:59 What happens, what direction does it shift? 763 00:47:59 --> 00:48:03 For products or reactants? 764 00:48:03 --> 00:48:03 Right. 765 00:48:03 --> 00:48:08 So, if this is going down, then some of your oxygenated 766 00:48:08 --> 00:48:12 hemoglobin is going to a release its oxygen. 767 00:48:12 --> 00:48:15 So it'll respond in such a way to compensate 768 00:48:15 --> 00:48:20 for that added stress. 769 00:48:20 --> 00:48:23 So what can you do to switch it back the other way? 770 00:48:23 --> 00:48:26 Again, we want our blood to be oxygenated. 771 00:48:26 --> 00:48:30 What happens to compensate for this if you're going 772 00:48:30 --> 00:48:34 to climb a mountain? 773 00:48:34 --> 00:48:37 What happens in the body? 774 00:48:37 --> 00:48:37 Yeah. 775 00:48:37 --> 00:48:41 STUDENT: The body can produce more hemoglobin. 776 00:48:41 --> 00:48:41 PROFESSOR: The body can produce more hemoglobin. 777 00:48:41 --> 00:48:44 So you often go to another altitude and hang out 778 00:48:44 --> 00:48:47 for a while before you start going way up. 779 00:48:47 --> 00:48:51 And what's happening during that time is your body realizes 780 00:48:51 --> 00:48:54 there is a problem, it knows about the Le Chatelier's 781 00:48:54 --> 00:48:58 principle, and so it's going to make more hemoglobin. 782 00:48:58 --> 00:49:02 And if you add more hemoglobin to this reaction, what 783 00:49:02 --> 00:49:06 direction does it go? 784 00:49:06 --> 00:49:10 Toward products, right. 785 00:49:10 --> 00:49:11 OK. 786 00:49:11 --> 00:49:18 So I wanted to mention significant figures, and there 787 00:49:18 --> 00:49:22 is -- I have to make a confession that when I first 788 00:49:22 --> 00:49:26 started teaching this course, I had never really paid attention 789 00:49:26 --> 00:49:28 to the rules of significant figures for logs. 790 00:49:28 --> 00:49:31 In this unit, the next unit, the unit after, you get the 791 00:49:31 --> 00:49:34 idea, there are going to be a lot of logs, and they 792 00:49:34 --> 00:49:38 have special rules for significant figures. 793 00:49:38 --> 00:49:40 So in the bottom of your handout, these rules 794 00:49:40 --> 00:49:43 are explained, it's also in your book. 795 00:49:43 --> 00:49:44 Pay attention to this. 796 00:49:44 --> 00:49:48 It's going to help you on all the problem-sets 797 00:49:48 --> 00:49:49 and in the course. 798 00:49:49 --> 00:49:54 So I just wanted to point out special rules about 799 00:49:54 --> 00:49:56 significant figures for logs. 800 00:49:56 --> 00:50:01 All right, that's it for today, see you on Wednesday. 801 00:50:01 --> 00:50:02