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 --> 00:00:26 PROFESSOR: OK, so we're going to leave off where we were last 10 00:00:26 --> 00:00:28 time talking about buffers. 11 00:00:28 --> 00:00:33 And I'm a big fan of buffers, actually, and buffers are 12 00:00:33 --> 00:00:38 extremely useful in my research because they keep the p 13 00:00:38 --> 00:00:39 h of things constant. 14 00:00:39 --> 00:00:42 So if you're going to do any kind of biology research or 15 00:00:42 --> 00:00:46 biochemistry research, you need to know about buffers. 16 00:00:46 --> 00:00:51 And as I'll mentioned later, also your body needs to be 17 00:00:51 --> 00:00:55 buffered appropriately, you don't want a large changes in 18 00:00:55 --> 00:00:59 p h in your body or things won't function properly. 19 00:00:59 --> 00:01:02 So buffering is very important. 20 00:01:02 --> 00:01:06 So let's go over buffers. 21 00:01:06 --> 00:01:09 So if we talk about an acid buffer, that's something that's 22 00:01:09 --> 00:01:13 buffering on the acidic side of the p h range. 23 00:01:13 --> 00:01:18 And in that, you want to have play on both sides. 24 00:01:18 --> 00:01:21 So if you have a strong acid, it can be neutralized, 25 00:01:21 --> 00:01:22 the p h stays the same. 26 00:01:22 --> 00:01:24 If you had a strong base, that would be neutralized 27 00:01:24 --> 00:01:26 so the p h stays the same. 28 00:01:26 --> 00:01:29 So what happens, you have to have an acid and its conjugate 29 00:01:29 --> 00:01:32 base in the mixture to have a good buffer. 30 00:01:32 --> 00:01:36 So what the weak acid is going to do is it will transfer 31 00:01:36 --> 00:01:41 protons or hydrogen ions to hydroxide ions that are 32 00:01:41 --> 00:01:45 supplied by the strong base to neutralize that strong 33 00:01:45 --> 00:01:46 base that was added. 34 00:01:46 --> 00:01:49 So you need to have an acid in there that's capable of giving 35 00:01:49 --> 00:01:54 up a proton to neutralize the hydroxide ion that was added. 36 00:01:54 --> 00:01:57 You also need to have a conjugate base. 37 00:01:57 --> 00:02:00 The conjugate base is going to accept protons if an acid is 38 00:02:00 --> 00:02:06 added, thereby neutralizing the effect of that added acid. 39 00:02:06 --> 00:02:09 So again, you need a weak acid and its conjugate base, you 40 00:02:09 --> 00:02:12 need both to have a good buffer. 41 00:02:12 --> 00:02:15 So I've been talking about weak acids and weak conjugate bases, 42 00:02:15 --> 00:02:22 so why would a strong acid and the salt of its conjugate 43 00:02:22 --> 00:02:27 base not make a good buffer? 44 00:02:27 --> 00:02:29 What do strong acids do? 45 00:02:29 --> 00:02:34 They dissociate almost completely, and that's not 46 00:02:34 --> 00:02:35 going to do you any good. 47 00:02:35 --> 00:02:39 You want to be able to shift that equation both directions. 48 00:02:39 --> 00:02:42 So a strong acid goes to completion is going to drive it 49 00:02:42 --> 00:02:46 to the right, and for a good buffer you want to be able to 50 00:02:46 --> 00:02:49 switch things around that if you add a strong acid, then you 51 00:02:49 --> 00:02:52 neutralize that, you add a strong base, you neutralize it. 52 00:02:52 --> 00:02:56 So you need the conjugate to be effective as a base, 53 00:02:56 --> 00:02:59 and a strong acid has an ineffective conjugate base. 54 00:02:59 --> 00:03:04 It's not good as a base at all, so that won't work. 55 00:03:04 --> 00:03:07 So buffers are made up of weak acids and their conjugate 56 00:03:07 --> 00:03:11 bases, or weak bases and their conjugate acids. 57 00:03:11 --> 00:03:13 They need to be in the weak range or there's 58 00:03:13 --> 00:03:17 no buffering capacity. 59 00:03:17 --> 00:03:21 So let's look at a base buffer example. 60 00:03:21 --> 00:03:24 The only difference here is that a basic buffer is going 61 00:03:24 --> 00:03:28 to buffer on the basic end of the p h range. 62 00:03:28 --> 00:03:29 So here's an equation. 63 00:03:29 --> 00:03:33 We have a base in water forming a conjugate of that weak 64 00:03:33 --> 00:03:35 base and hydroxide ions. 65 00:03:35 --> 00:03:39 So let's think about what happens if a strong 66 00:03:39 --> 00:03:41 acid is added. 67 00:03:41 --> 00:03:46 Well if a strong acid is added, then this base, n h 3, can 68 00:03:46 --> 00:03:50 accept protons from the incoming acid and make more n h 69 00:03:50 --> 00:03:55 4 plus, thereby removing the strong acid from the solution 70 00:03:55 --> 00:03:58 and neutralizing the p h. 71 00:03:58 --> 00:04:02 If on the other hand a strong base is added, n h 4 plus or 72 00:04:02 --> 00:04:06 ammonium ions can donate the proton forming its conjugate 73 00:04:06 --> 00:04:11 base in water, and again, the p h remains about the same. 74 00:04:11 --> 00:04:16 So the base and its conjugate acid can both react, 75 00:04:16 --> 00:04:21 neutralizing the p h. 76 00:04:21 --> 00:04:25 So in the base buffer acid, a weak base, b, will accept 77 00:04:25 --> 00:04:28 protons supplied by the strong acid, removing a strong 78 00:04:28 --> 00:04:30 acid from the solution. 79 00:04:30 --> 00:04:34 The conjugate acid of that weak base, which again, would be a 80 00:04:34 --> 00:04:40 weak acid, can transfer protons to the hydroxide ions added 81 00:04:40 --> 00:04:45 by the strong base, again, neutralizing the effect there. 82 00:04:45 --> 00:04:50 So a buffer is a mixture of a weak acid base conjugate pair 83 00:04:50 --> 00:04:54 that will stabilize the p h serving as a source or a 84 00:04:54 --> 00:04:59 sink for the added protons. 85 00:04:59 --> 00:05:03 So that's how a buffer works. 86 00:05:03 --> 00:05:06 So, I mentioned buffering is very important. 87 00:05:06 --> 00:05:09 It's very important in your blood. 88 00:05:09 --> 00:05:13 Your blood is buffered in the range of p h 7 . 89 00:05:13 --> 00:05:15 35 to 7 . 90 00:05:15 --> 00:05:22 45, and you have a buffering pair and a conjugate acid 91 00:05:22 --> 00:05:25 base pair that's in your blood that does to work. 92 00:05:25 --> 00:05:30 So nature has its own buffering system design to keep the p 93 00:05:30 --> 00:05:33 h of your blood constant. 94 00:05:33 --> 00:05:37 Well what happens if the p h of your blood changes? 95 00:05:37 --> 00:05:43 So let me just tell you about one disease that can change 96 00:05:43 --> 00:05:45 the p h of your blood. 97 00:05:45 --> 00:05:47 This is from a vitamin B12 dependent enzyme called 98 00:05:47 --> 00:05:54 methylmalonic coa mutase, and this enzyme is your friend. 99 00:05:54 --> 00:05:57 I think that most of you are excited about the idea of 100 00:05:57 --> 00:06:00 having all your fat go to energy, so you should be 101 00:06:00 --> 00:06:02 all fan of this enzyme. 102 00:06:02 --> 00:06:07 So it breaks down from fatty acids -- you get methylmalonyl 103 00:06:07 --> 00:06:11 coa, which is converted to succinyl coa and goes into 104 00:06:11 --> 00:06:12 the citric acid cycle. 105 00:06:12 --> 00:06:16 But if this step is blocked, if there's some kind of genetic 106 00:06:16 --> 00:06:19 disease associated with that particular enzyme, you 107 00:06:19 --> 00:06:22 get a condition called methylmalonic aciduria. 108 00:06:22 --> 00:06:25 So this is excreted in the body, it can't be converted to 109 00:06:25 --> 00:06:29 the succinyl coa, so it has to be excreted from the body, 110 00:06:29 --> 00:06:31 and it has an acidic p h. 111 00:06:31 --> 00:06:35 And so when it's excreted, it will actually, there's a large 112 00:06:35 --> 00:06:38 amount of it, and it can change the p h of blood. 113 00:06:38 --> 00:06:41 So even though you have this buffering system, it can 114 00:06:41 --> 00:06:45 overwhelm the buffering system and cause a change in the p h, 115 00:06:45 --> 00:06:51 which can lead to neurological disorders and sometimes death. 116 00:06:51 --> 00:06:55 So they can look for this in newborns, they can do a test, 117 00:06:55 --> 00:07:00 and I was -- one of the tests is -- it's not in every state, 118 00:07:00 --> 00:07:03 but it is in Massachusetts, so my daughter, Samantha, 119 00:07:03 --> 00:07:06 had this test. 120 00:07:06 --> 00:07:09 But they can simply look at the urine of a newborn and look at 121 00:07:09 --> 00:07:13 the p h and whether any of this is being excreted. 122 00:07:13 --> 00:07:16 And some infants that have this condition can excrete like 123 00:07:16 --> 00:07:18 a gram of this acid a day. 124 00:07:18 --> 00:07:22 So it's really large quantities of acid that are excreted 125 00:07:22 --> 00:07:26 and it goes beyond the buffering capacity. 126 00:07:26 --> 00:07:29 So, I'm going to tell you a little story and it sort of 127 00:07:29 --> 00:07:32 emphasizes some of the importance of genetic research. 128 00:07:32 --> 00:07:36 So before the human genome project, scientists were trying 129 00:07:36 --> 00:07:38 to find the gene to figure out what was wrong with these 130 00:07:38 --> 00:07:40 patients that had this condition. 131 00:07:40 --> 00:07:45 And here are all the amino acids translated from the gene. 132 00:07:45 --> 00:07:50 This is not a small protein, that's a lot of amino acids. 133 00:07:50 --> 00:07:53 And they found that the problem was right here, or one of the 134 00:07:53 --> 00:07:54 main problems is right here. 135 00:07:54 --> 00:07:57 There's a glycine residue, which glycine is the smallest 136 00:07:57 --> 00:08:00 amino acid and that had been changed to something else and 137 00:08:00 --> 00:08:02 that led to the disease. 138 00:08:02 --> 00:08:06 Now I want you to imagine if you were parents of a small 139 00:08:06 --> 00:08:10 child and you found out your child had this condition and 140 00:08:10 --> 00:08:12 then you had heard that there were advances, they now know 141 00:08:12 --> 00:08:15 what caused it, and so, they went to the doctor and the 142 00:08:15 --> 00:08:21 doctor said, yes, your child, the DNA is wrong, and so let's 143 00:08:21 --> 00:08:27 substitute a different amino acid for glycine here. 144 00:08:27 --> 00:08:29 OK. 145 00:08:29 --> 00:08:30 What does that do for you? 146 00:08:30 --> 00:08:32 Like why is that a problem? 147 00:08:32 --> 00:08:35 Well, they didn't know why it was a problem, they just knew 148 00:08:35 --> 00:08:38 that it had the wrong amino acid in there. 149 00:08:38 --> 00:08:43 And so, the next step was to try to understand what 150 00:08:43 --> 00:08:45 was actually going on. 151 00:08:45 --> 00:08:49 So what happened in this case was that the vitamin B12 152 00:08:49 --> 00:08:53 cofactor had changed its conformation when it 153 00:08:53 --> 00:08:54 bound to the protein. 154 00:08:54 --> 00:08:58 And instead of having this sort of loop structure here, 155 00:08:58 --> 00:09:00 it had more of a tail. 156 00:09:00 --> 00:09:05 So this base here had moved down, and so there was a 157 00:09:05 --> 00:09:10 different shape to the vitamin than had been expected. 158 00:09:10 --> 00:09:14 So when the first structure was solved of one of these enzymes, 159 00:09:14 --> 00:09:18 it found that here's kind of what the vitamin B12 looked 160 00:09:18 --> 00:09:20 like, it had this extended region which no one was 161 00:09:20 --> 00:09:24 expecting, and so that had to fit into the protein. 162 00:09:24 --> 00:09:27 So this is the domain of the protein that binds the vitamin, 163 00:09:27 --> 00:09:31 and it had a large hole, and you put these together and 164 00:09:31 --> 00:09:35 that's great, it fits and you have happy enzyme. 165 00:09:35 --> 00:09:40 Well, how do you create a hole -- nature supposedly abhors 166 00:09:40 --> 00:09:43 a vacuum, so how do you have this hole? 167 00:09:43 --> 00:09:47 Well, what nature did was it put the smallest amino acids 168 00:09:47 --> 00:09:51 there are, glycines, right along here to make room 169 00:09:51 --> 00:09:53 for this to fit together. 170 00:09:53 --> 00:09:58 So, what was happening in this genetic case is that the switch 171 00:09:58 --> 00:10:02 of a glycine to an argenine did this to the hole. 172 00:10:02 --> 00:10:07 So, what people were trying to do is treat these patients with 173 00:10:07 --> 00:10:10 extra B12, you give them injections of it, you have a 174 00:10:10 --> 00:10:14 lot more B12, and you want to the B12 to bind and get the 175 00:10:14 --> 00:10:16 activity back going again. 176 00:10:16 --> 00:10:20 But really, no matter how much vitamin B12 you added to it, it 177 00:10:20 --> 00:10:22 wasn't really going to do much good, it just wasn't 178 00:10:22 --> 00:10:24 going to fit. 179 00:10:24 --> 00:10:27 So instead, there was a suggestion that instead of 180 00:10:27 --> 00:10:30 giving the whole vitamin, perhaps you could just give a 181 00:10:30 --> 00:10:33 truncated version of the vitamin, which was commercially 182 00:10:33 --> 00:10:39 available, and that that might bind and restore activity 183 00:10:39 --> 00:10:41 of the protein. 184 00:10:41 --> 00:10:44 So this is what was suggested once you knew what the 185 00:10:44 --> 00:10:47 problem actually was. 186 00:10:47 --> 00:10:51 So this is just an example of a genetic disease, and it's not 187 00:10:51 --> 00:10:54 that common, but as I said, it is tested for here 188 00:10:54 --> 00:10:55 in Massachusetts. 189 00:10:55 --> 00:11:00 And how knowing something about what the problem is can lead 190 00:11:00 --> 00:11:02 to a potential solution. 191 00:11:02 --> 00:11:06 But for most of you, your blood is doing just fine, you don't 192 00:11:06 --> 00:11:09 have a genetic condition which is pumping too much acid into 193 00:11:09 --> 00:11:13 your bloodstream, so that nature's buffering capacity 194 00:11:13 --> 00:11:18 is working quite well. 195 00:11:18 --> 00:11:23 So buffers are important. 196 00:11:23 --> 00:11:29 It's great to have my important statements emphasized up there. 197 00:11:29 --> 00:11:32 We've been rehearsing at home. 198 00:11:32 --> 00:11:33 OK. 199 00:11:33 --> 00:11:36 So let's do a sample buffer problem. 200 00:11:36 --> 00:11:41 All right, suppose we have an acid, 0.1 moles of an acid, and 201 00:11:41 --> 00:11:46 0.5 moles of its conjugate base added in the form of a salt. 202 00:11:46 --> 00:11:50 And so they're put into water and diluted to 1.0 liter. 203 00:11:50 --> 00:11:54 And you're given information about the k a of the acid, 1 . 204 00:11:54 --> 00:11:58 77 times 10 to the minus 4, and you're asked 205 00:11:58 --> 00:12:00 to calculate the p h. 206 00:12:00 --> 00:12:02 So what do you do? 207 00:12:02 --> 00:12:05 All right, first, it's always good to write the equation 208 00:12:05 --> 00:12:06 that you're talking about. 209 00:12:06 --> 00:12:11 And so you have acid in water forming hydronium ions 210 00:12:11 --> 00:12:14 and the conjugate base. 211 00:12:14 --> 00:12:19 So here, the acid is giving up a proton to the water, forming 212 00:12:19 --> 00:12:24 h 3 o plus and it's conjugate base. 213 00:12:24 --> 00:12:28 Now we want to think about what happens at equilibrium. 214 00:12:28 --> 00:12:30 So we know how many moles we have and we know what 215 00:12:30 --> 00:12:32 the total volume is. 216 00:12:32 --> 00:12:35 And in this table we should be using molarity, but the math 217 00:12:35 --> 00:12:40 here is pretty easy because we have 1 mole and 1 liter or 1, 218 00:12:40 --> 00:12:46 and 0.5 moles in 1 liter or 0.5 for molarity. 219 00:12:46 --> 00:12:50 And now at equilibrium what's going to happen, well, when 220 00:12:50 --> 00:12:54 this equilibrates some of this will go away and more of these 221 00:12:54 --> 00:12:56 are going to be formed. 222 00:12:56 --> 00:13:01 So we have minus x over here, plus x and plus x over there, 223 00:13:01 --> 00:13:05 and we add it all together you get 1 minus x plus 224 00:13:05 --> 00:13:08 x and 0.5 plus x. 225 00:13:08 --> 00:13:10 So the important thing to remember is in buffering 226 00:13:10 --> 00:13:14 problems, you have the acid and the conjugate. 227 00:13:14 --> 00:13:17 So we're used to seeing these tables where we only have 228 00:13:17 --> 00:13:21 something over here and it's all zero on the other side. 229 00:13:21 --> 00:13:24 But in a buffering problem, you have things on both sides 230 00:13:24 --> 00:13:25 from the very beginning. 231 00:13:25 --> 00:13:28 And that's a really important point, and that alone, if you 232 00:13:28 --> 00:13:31 can remember that, will get you a long way through this unit. 233 00:13:31 --> 00:13:35 So you remember that in a buffer you got to have both an 234 00:13:35 --> 00:13:39 acid in its conjugate base or a base in its conjugate acid. 235 00:13:39 --> 00:13:42 So here we're talking about an acid in water, it's an acidic 236 00:13:42 --> 00:13:47 buffer, and so we can use our k a value -- we want to know what 237 00:13:47 --> 00:13:49 the concentrations are at equilibrium to 238 00:13:49 --> 00:13:51 calculate our p h. 239 00:13:51 --> 00:13:57 So we can use our k a and we can set it up, so we have 240 00:13:57 --> 00:14:01 on the top products over reactants, and we we're not 241 00:14:01 --> 00:14:05 including water in this because it's dilute in solution and so 242 00:14:05 --> 00:14:06 it's not changing very much. 243 00:14:06 --> 00:14:10 And now we can plug in our values, so we have 0.5 244 00:14:10 --> 00:14:15 plus x, x over 1 minus x. 245 00:14:15 --> 00:14:19 All right, now this is just written again from the last 246 00:14:19 --> 00:14:24 slide, we can try an approximation, which is it 247 00:14:24 --> 00:14:28 that x is small compared to 1 molar or 0.5 molar. 248 00:14:28 --> 00:14:32 And so we can get rid of the plus x and the minus x down 249 00:14:32 --> 00:14:37 here and just have one x term, which makes it simpler to 250 00:14:37 --> 00:14:39 solve, but we'll have to go back and check that 251 00:14:39 --> 00:14:42 approximation in a few minutes. 252 00:14:42 --> 00:14:46 So making that approximation, we can calculate x as 3 . 253 00:14:46 --> 00:14:51 54 times 10 to the minus 4 molar, and now we need to 254 00:14:51 --> 00:14:52 check that assumption. 255 00:14:52 --> 00:14:56 Well, you can probably guess it's going to be OK, because 256 00:14:56 --> 00:15:01 something times 10 to the minus 4 compared to 0.5 and 1, that's 257 00:15:01 --> 00:15:03 probably going to be OK that it's small. 258 00:15:03 --> 00:15:07 But our assumption here is that it needs to be less 259 00:15:07 --> 00:15:11 than 5%, and here it's 0.1%. 260 00:15:11 --> 00:15:14 So you could just take this value of x, divide it by the 261 00:15:14 --> 00:15:20 smaller of the two, 0.5 , times 100, and calculate 262 00:15:20 --> 00:15:21 the percent ionization. 263 00:15:21 --> 00:15:26 If it's less than 5% you're OK, if it's more you need to use 264 00:15:26 --> 00:15:30 the quadratic equation to solve the problem. 265 00:15:30 --> 00:15:35 So x here is our concentration of hydronium ion, which is 266 00:15:35 --> 00:15:39 great, because then we can easily calculate the p h. 267 00:15:39 --> 00:15:42 So p h again is minus log of the hydronium ion 268 00:15:42 --> 00:15:47 concentration, and so the p h here is 3 . 269 00:15:47 --> 00:15:48 45. 270 00:15:48 --> 00:15:51 And again, significant figures, we'll be talking about 271 00:15:51 --> 00:15:53 this as we go through. 272 00:15:53 --> 00:15:55 The volume had two, it was 1 . 273 00:15:55 --> 00:16:00 0 liters, and so we're going to have two significant figures 274 00:16:00 --> 00:16:03 after the decimal point, because the volume was limiting 275 00:16:03 --> 00:16:08 insignificant figures. 276 00:16:08 --> 00:16:14 All right, now let's consider what happens if some strong 277 00:16:14 --> 00:16:17 acid had been added in the solution. 278 00:16:17 --> 00:16:20 So the volume is still going to be 1 liter, because the acid 279 00:16:20 --> 00:16:28 was added in before we went up to the 1 liter mark. 280 00:16:28 --> 00:16:32 So strong acids, they go to completion. 281 00:16:32 --> 00:16:37 So, if we added 0.1 moles of that strong acid, it will react 282 00:16:37 --> 00:16:41 with equal number of moles of the conjugate base to 283 00:16:41 --> 00:16:44 form the conjugate acid. 284 00:16:44 --> 00:16:47 So we can just do subtractions here. 285 00:16:47 --> 00:16:49 We don't have to worry about setting up any kind of 286 00:16:49 --> 00:16:52 equilibrium, we assume it goes completely. 287 00:16:52 --> 00:16:58 So for the conjugate base we had 0.5 moles before, and it's 288 00:16:58 --> 00:17:03 going to be reacting then with a strong acid, so 0.1 of those 289 00:17:03 --> 00:17:08 will react, leaving us with 0.4 moles of the conjugate, 290 00:17:08 --> 00:17:10 and that's in 1 liter. 291 00:17:10 --> 00:17:13 So now we have 0.4 molar. 292 00:17:13 --> 00:17:17 For the acid, we had 1 mole to begin with, but now we formed 293 00:17:17 --> 00:17:24 more as they reaction has taken place, and so we have 0.1 more. 294 00:17:24 --> 00:17:25 Now we have 1 . 295 00:17:25 --> 00:17:29 1 moles again in 1 liter. 296 00:17:29 --> 00:17:33 So now we can do the same thing again. 297 00:17:33 --> 00:17:36 So after this has happened, after we have added the strong 298 00:17:36 --> 00:17:40 acid, then a new equilibrium is going to be reached. 299 00:17:40 --> 00:17:46 And so we can plug in this table as well. 300 00:17:46 --> 00:17:47 So we have 1 . 301 00:17:47 --> 00:17:55 1 now over here, and 0.4 on the other side. 302 00:17:55 --> 00:17:59 As equilibrium is approached, you lose some of the acid as it 303 00:17:59 --> 00:18:05 reacts with water and ionizes and you form more of the h 3 o 304 00:18:05 --> 00:18:08 plus and more of the conjugate. 305 00:18:08 --> 00:18:09 So we have 1 . 306 00:18:09 --> 00:18:14 1 minus x, x, and 0.4 plus x. 307 00:18:14 --> 00:18:18 So again, the trick here is just to remember that there is 308 00:18:18 --> 00:18:21 a reaction with a strong acid that has been added, and you 309 00:18:21 --> 00:18:25 need to figure out the new molarities, and then go back 310 00:18:25 --> 00:18:33 to your equilibrium table with those new molarities. 311 00:18:33 --> 00:18:37 So here we can set up with a k a again, and do the same 312 00:18:37 --> 00:18:42 problem that we did before. 313 00:18:42 --> 00:18:45 And so, we can make the assumption again that x 314 00:18:45 --> 00:18:49 is small, try it out and see if it works. 315 00:18:49 --> 00:18:52 X turns out to be 4 . 316 00:18:52 --> 00:18:55 87 times 10 to the minus 4 molars -- so again, 317 00:18:55 --> 00:18:57 it's a small number. 318 00:18:57 --> 00:19:03 And so, it turns out to be 1 . -- less than 1% of 0.4 . 319 00:19:03 --> 00:19:06 If it's less than 5% of the smaller number, you don't have 320 00:19:06 --> 00:19:10 to worry about the bigger number, and so your assumption 321 00:19:10 --> 00:19:13 is OK, you don't need to use the quadratic equation. 322 00:19:13 --> 00:19:17 And so, then we can calculate at the end 323 00:19:17 --> 00:19:19 that the p h is now 3 . 324 00:19:19 --> 00:19:22 31, again, two significant figures after the decimal 325 00:19:22 --> 00:19:24 place because of the volume. 326 00:19:24 --> 00:19:27 So addition of 0.1 moles of a strong acid changed 327 00:19:27 --> 00:19:29 our p h from 3 . 328 00:19:29 --> 00:19:32 45 to 3 . 329 00:19:32 --> 00:19:33 31. 330 00:19:33 --> 00:19:34 So we buffered pretty well. 331 00:19:34 --> 00:19:38 There was a change in p h, we added acid and the p h did go 332 00:19:38 --> 00:19:41 down, but not by an enormous amount. 333 00:19:41 --> 00:19:45 And so, that's because this turned out to be a pretty 334 00:19:45 --> 00:19:48 decent buffer here, so we didn't have a really 335 00:19:48 --> 00:19:54 huge effect. 336 00:19:54 --> 00:20:07 So, those are -- that's an example of a buffer problem. 337 00:20:07 --> 00:20:10 So, let's think for a minute about designing a buffer. 338 00:20:10 --> 00:20:17 Suppose you wanted to create a buffer at a particular p h, 339 00:20:17 --> 00:20:19 what do you need to think about? 340 00:20:19 --> 00:20:22 Well, you need to think about the ratio of your acid to the 341 00:20:22 --> 00:20:26 conjugate, and you need to think about the p k a of the 342 00:20:26 --> 00:20:32 acid, and the p h that's desired. 343 00:20:32 --> 00:20:38 So here is a generic equation for an acid in water, so we 344 00:20:38 --> 00:20:41 have our acid, h a, in water forming hydronium ions 345 00:20:41 --> 00:20:44 and our conjugate base. 346 00:20:44 --> 00:20:47 And now we're going to do a little derivation to come up 347 00:20:47 --> 00:20:50 with an equation that would be useful to you in thinking about 348 00:20:50 --> 00:20:53 buffers and designing buffers. 349 00:20:53 --> 00:20:57 So, we can write a generic term for k a. 350 00:20:57 --> 00:21:01 K a equals products over reactants, and so we have our 351 00:21:01 --> 00:21:05 hydronium ions are conjugate base over our acid. 352 00:21:05 --> 00:21:09 And now we can take this term and rearrange it. 353 00:21:09 --> 00:21:14 So we can pull a hydronium ion concentration over to one side. 354 00:21:14 --> 00:21:19 And now we're going to take the logs of both sides, so we get 355 00:21:19 --> 00:21:23 the log of hydronium ion concentration, the log of k 356 00:21:23 --> 00:21:27 a, and the log of h a concentration over a minus 357 00:21:27 --> 00:21:31 concentration, and now we're going to multiply everything by 358 00:21:31 --> 00:21:36 negative sign, so we have minus logs of things. 359 00:21:36 --> 00:21:40 And I'm just going to move this now up to the top of the 360 00:21:40 --> 00:21:43 screen, and we have this equation. 361 00:21:43 --> 00:21:49 So what is minus log of hydronium ion concentration? 362 00:21:49 --> 00:21:49 P h. 363 00:21:49 --> 00:21:53 What's minus log of k a? 364 00:21:53 --> 00:21:55 P k a. 365 00:21:55 --> 00:22:00 So, we have p h equals p k a minus the log of a 366 00:22:00 --> 00:22:03 concentration of your acid over the concentration 367 00:22:03 --> 00:22:05 of your conjugate base. 368 00:22:05 --> 00:22:08 And these are equilibrium concentrations for that, 369 00:22:08 --> 00:22:10 because remember, we derived it from our equilibrium 370 00:22:10 --> 00:22:13 expression for k a. 371 00:22:13 --> 00:22:16 But a lot of times when you're working buffer problems, you 372 00:22:16 --> 00:22:19 know the concentrations that you added of these things, not 373 00:22:19 --> 00:22:23 necessarily the concentrations of equilibrium. 374 00:22:23 --> 00:22:27 And if we rewrite this expression in terms of the 375 00:22:27 --> 00:22:31 initial concentrations or original or o concentrations, 376 00:22:31 --> 00:22:36 then we have p h is approximately equal to p k a 377 00:22:36 --> 00:22:40 minus log of the initial concentrations of your acid 378 00:22:40 --> 00:22:41 over your conjugate base. 379 00:22:41 --> 00:22:45 And this is known as a Henderson Hasselbalch equation. 380 00:22:45 --> 00:22:48 And people love the Henderson Hasselbalch equation, and it 381 00:22:48 --> 00:22:51 can be incredibly useful to you in solving these problems. 382 00:22:51 --> 00:22:55 But I'm going to emphasize when it's OK to use it and when it's 383 00:22:55 --> 00:22:58 not OK to use it, because people try to apply it to 384 00:22:58 --> 00:23:02 everything, and it's for buffer problems, and people apply it 385 00:23:02 --> 00:23:05 to all sorts of things that are not buffer problems. 386 00:23:05 --> 00:23:07 So I want to make sure that it's clear when you can use it 387 00:23:07 --> 00:23:10 and when you can't use it. 388 00:23:10 --> 00:23:13 And it's fine to use it and you should use it when 389 00:23:13 --> 00:23:17 it's acceptable, but not at other times. 390 00:23:17 --> 00:23:19 It's one of the few equations in acid base, so people 391 00:23:19 --> 00:23:22 get very excited by it. 392 00:23:22 --> 00:23:26 All right, so remember that it's really equal when they're 393 00:23:26 --> 00:23:29 at equilibrium concentrations, and this is just an 394 00:23:29 --> 00:23:32 approximation that we're saying that those are initial 395 00:23:32 --> 00:23:34 concentrations. 396 00:23:34 --> 00:23:39 So when is it OK to say well, the equilibrium concentration 397 00:23:39 --> 00:23:43 is more or less the same as the initial concentration. 398 00:23:43 --> 00:23:47 And that's true when x, which is in this particular example 399 00:23:47 --> 00:23:50 your hydronium ion concentration, is small 400 00:23:50 --> 00:23:54 compared to your initial concentration of the acid and 401 00:23:54 --> 00:23:57 the conjugate base that you added to the buffer. 402 00:23:57 --> 00:24:01 So, and when x is small, then pretty much, the equilibrium 403 00:24:01 --> 00:24:04 concentration equals the initial concentration. 404 00:24:04 --> 00:24:07 So there's not really very much change if x is a 405 00:24:07 --> 00:24:10 really small number. 406 00:24:10 --> 00:24:13 So, a lot of the time this is true. 407 00:24:13 --> 00:24:15 Remember, we're making buffers from weak acids and weak 408 00:24:15 --> 00:24:19 conjugate bases, and the definition of a weak acid is 409 00:24:19 --> 00:24:22 that it only loses a tiny fraction of its protons. 410 00:24:22 --> 00:24:26 It only ionizes slightly in water. 411 00:24:26 --> 00:24:29 And a weak base typically only accepts a fraction of the 412 00:24:29 --> 00:24:31 protons it can accept. 413 00:24:31 --> 00:24:36 It's a weak base, so it's not doing a whole lot 414 00:24:36 --> 00:24:37 of chemistry there. 415 00:24:37 --> 00:24:41 So this approximation is good a lot of the time. 416 00:24:41 --> 00:24:44 So just you know when you can and can not use it, we're going 417 00:24:44 --> 00:24:47 to give a rule and say it's the same rule as before. 418 00:24:47 --> 00:24:52 When we say when x is small or your hydronium ion 419 00:24:52 --> 00:24:55 concentration is small compared to the acid or the conjugate 420 00:24:55 --> 00:24:58 base, when it's less than 5%, that's what we're going to call 421 00:24:58 --> 00:25:03 small, so the same rule we've been using all along. 422 00:25:03 --> 00:25:06 When x is small, this approximation 423 00:25:06 --> 00:25:08 works pretty well. 424 00:25:08 --> 00:25:11 And you can plug in your concentrations right there -- 425 00:25:11 --> 00:25:14 your initial concentrations not your equilibrium 426 00:25:14 --> 00:25:19 concentrations. 427 00:25:19 --> 00:25:22 All right, so let's use Henderson Hasselbalch and 428 00:25:22 --> 00:25:26 design a buffer system if we want a p h of 4 . 429 00:25:26 --> 00:25:27 6. 430 00:25:27 --> 00:25:32 And a good rule to remember is that a buffering solution is 431 00:25:32 --> 00:25:38 most effective when it's plus or minus 1 away from the p k a. 432 00:25:38 --> 00:25:40 So that's a good thing too I keep in mind 433 00:25:40 --> 00:25:43 for research as well. 434 00:25:43 --> 00:25:46 If you're really far away from the p k a, it's not going to be 435 00:25:46 --> 00:25:49 a good buffering system, and this is a mistake the people 436 00:25:49 --> 00:25:52 make in the lab sometimes, so you may run into that in some 437 00:25:52 --> 00:25:55 of your laboratory courses. 438 00:25:55 --> 00:25:59 So we want a buffer about p h 4 . 439 00:25:59 --> 00:26:00 6. 440 00:26:00 --> 00:26:03 So we can look at our ionization constants of acid, 441 00:26:03 --> 00:26:05 and of course, we're always doing everything at room 442 00:26:05 --> 00:26:09 temperature in this unit, and so we can look at what p k a's 443 00:26:09 --> 00:26:14 are of some weak acids, and acetate, acetate is an easy 444 00:26:14 --> 00:26:19 buffer to get your hands on, acetate is quite available, and 445 00:26:19 --> 00:26:21 it has a good p k a 4 . 446 00:26:21 --> 00:26:22 75. 447 00:26:22 --> 00:26:27 So that's great, we can use that in designing our buffer. 448 00:26:27 --> 00:26:32 So, acetic acid has the right p k a, and we're all set, 449 00:26:32 --> 00:26:34 we can prepare a buffer. 450 00:26:34 --> 00:26:38 But we'll need to add the acid and the conjugate, and we need 451 00:26:38 --> 00:26:42 to know how much acid and how much of the conjugate to add. 452 00:26:42 --> 00:26:46 So we can use Henderson Hasselbalch equation for this. 453 00:26:46 --> 00:26:49 We're creating a buffer, and so this is an equation 454 00:26:49 --> 00:26:51 we can use for buffers. 455 00:26:51 --> 00:26:55 We know what p h we want, we know the p k a of the thing 456 00:26:55 --> 00:26:58 we're going to use, and we want to figure out how much of the 457 00:26:58 --> 00:27:01 acid to use and how much of the conjugate to use. 458 00:27:01 --> 00:27:05 We need to know the ratio of one to the other to set 459 00:27:05 --> 00:27:07 up our buffer ideally. 460 00:27:07 --> 00:27:12 So we can plug our numbers in and calculate that. 461 00:27:12 --> 00:27:15 So, we can rearrange this if you want so that the unknown is 462 00:27:15 --> 00:27:18 on one side and we have to p k a and the p h on 463 00:27:18 --> 00:27:21 the other side. 464 00:27:21 --> 00:27:26 And so, we have here our p k a minus our p h and we get 0 . 465 00:27:26 --> 00:27:27 15. 466 00:27:27 --> 00:27:32 Now we need to inverse log and come up with the ratio, and 467 00:27:32 --> 00:27:34 the ratio that we want is 1 . 468 00:27:34 --> 00:27:35 4. 469 00:27:35 --> 00:27:38 So we want to have a ratio from our acid to the 470 00:27:38 --> 00:27:40 conjugate of 1 . 471 00:27:40 --> 00:27:40 4. 472 00:27:40 --> 00:27:43 Well how much exactly are we going to add them, we know 473 00:27:43 --> 00:27:46 the ratio now, how much are we going to add? 474 00:27:46 --> 00:27:48 Well, you could use 1 . 475 00:27:48 --> 00:27:53 4 molar and 1 molar, for example, that would have 476 00:27:53 --> 00:27:54 the correct ratio. 477 00:27:54 --> 00:27:59 But how do you know if that's going to be good? 478 00:27:59 --> 00:28:02 Well, the ratio is more important than the exact 479 00:28:02 --> 00:28:07 amounts, however, the amounts get to this issue of sort of 480 00:28:07 --> 00:28:10 the capacity of the buffer -- how resistant it is to 481 00:28:10 --> 00:28:12 changes in the p h. 482 00:28:12 --> 00:28:15 So if you use too low concentrations of both, it 483 00:28:15 --> 00:28:17 won't be all that resistant. 484 00:28:17 --> 00:28:22 So if you need to have a better buffering capacity, the higher 485 00:28:22 --> 00:28:24 concentrations that you should use. 486 00:28:24 --> 00:28:27 And you can use Henderson Hasselbalch then to calculate 487 00:28:27 --> 00:28:31 what sort of the minimum amount you use, the minimum amount 488 00:28:31 --> 00:28:35 to have that 5% rule work. 489 00:28:35 --> 00:28:39 So in the example I told you about this condition, the 490 00:28:39 --> 00:28:43 buffer in the blood was pretty good, but the acid with so much 491 00:28:43 --> 00:28:46 that it overwhelmed buffering capacity. 492 00:28:46 --> 00:28:48 So if there had been larger concentrations of the buffer, 493 00:28:48 --> 00:28:52 that would have certainly helped in that case. 494 00:28:52 --> 00:28:55 So the higher the concentrations you use, the 495 00:28:55 --> 00:28:57 more resistant to change. 496 00:28:57 --> 00:29:02 And that's the idea of buffering capacity. 497 00:29:02 --> 00:29:04 So, and if you use too low concentrations, then your 498 00:29:04 --> 00:29:08 Henderson Hasselbalch equation won't even be valid. 499 00:29:08 --> 00:29:12 So we can go back and calculate what is sort of the minimum 500 00:29:12 --> 00:29:16 concentrations we need to use for Henderson Hasselbalch to be 501 00:29:16 --> 00:29:18 valid to meet that 5% rule. 502 00:29:18 --> 00:29:20 So for a p h of 4 . 503 00:29:20 --> 00:29:24 6, a hydronium ion concentration is a 2 . 504 00:29:24 --> 00:29:26 5 times 10 to the minus 5. 505 00:29:26 --> 00:29:31 And so then if we work our equation backwards, we want to 506 00:29:31 --> 00:29:35 be less than 5%, so we have this over the concentration of 507 00:29:35 --> 00:29:39 either one of those times 100% gives you 5%. 508 00:29:39 --> 00:29:42 So the concentrations need to be greater than 5 times 10 to 509 00:29:42 --> 00:29:46 the minus 4 moles or you won't meet this 5% rule. 510 00:29:46 --> 00:29:48 So at least to be greater than that and they need 511 00:29:48 --> 00:29:50 to be in the right ratio. 512 00:29:50 --> 00:29:55 Other than that you're somewhat free to decide what you're 513 00:29:55 --> 00:29:56 going to do with that, and there may be other 514 00:29:56 --> 00:30:01 considerations involved if you're working with a certain 515 00:30:01 --> 00:30:04 concentration of protein, you might not want your buffer 516 00:30:04 --> 00:30:07 concentration to be too high, it might start interfering with 517 00:30:07 --> 00:30:10 enzyme assay, for example. 518 00:30:10 --> 00:30:14 And often buffers are somewhere around 100 millimolar, that's a 519 00:30:14 --> 00:30:19 pretty common concentration for buffers. 520 00:30:19 --> 00:30:24 All right, so this slide we're doing really well. 521 00:30:24 --> 00:30:28 So we talked about weak acids in water, weak bases in water, 522 00:30:28 --> 00:30:31 and I'm trying to convince you that these are the same as 523 00:30:31 --> 00:30:33 the salt and water problems. 524 00:30:33 --> 00:30:35 So we're going to talk much more about salt and 525 00:30:35 --> 00:30:36 water in a few minutes. 526 00:30:36 --> 00:30:39 And I told you about buffers, so we only have 527 00:30:39 --> 00:30:40 2 more things to go. 528 00:30:40 --> 00:30:43 We need to talk about strong acids in water, and strong 529 00:30:43 --> 00:30:47 bases in water, and then you'll have all of the 5 types of 530 00:30:47 --> 00:30:50 problems to do the problem-set. 531 00:30:50 --> 00:30:55 And as I mentioned last time, it looks deceivingly short, 532 00:30:55 --> 00:30:58 the number of questions on them, but the titration 533 00:30:58 --> 00:31:00 problems are long. 534 00:31:00 --> 00:31:04 So don't leave those to the last minute or there will 535 00:31:04 --> 00:31:06 not be a whole lot of sleep involved. 536 00:31:06 --> 00:31:10 So just a word of warning from the past. 537 00:31:10 --> 00:31:12 Everyone looks and go, "Oh, this is an easy problem-set, 538 00:31:12 --> 00:31:19 there aren't many problems." So, titration problems 539 00:31:19 --> 00:31:20 do take a lot of time. 540 00:31:20 --> 00:31:24 So let's talk about titration, so that as soon as class is 541 00:31:24 --> 00:31:27 over today, you can go work on those questions on 542 00:31:27 --> 00:31:28 the problem-set. 543 00:31:28 --> 00:31:29 All right. 544 00:31:29 --> 00:31:31 So acid base titrations. 545 00:31:31 --> 00:31:37 How many of you in high school titrated an acid with a base? 546 00:31:37 --> 00:31:42 Large fraction of you, OK. 547 00:31:42 --> 00:31:47 So usually what titration problems are meant to do, that 548 00:31:47 --> 00:31:52 you have something known about an acid or a base, base say of 549 00:31:52 --> 00:31:58 known concentration, and and acid of unknown concentration 550 00:31:58 --> 00:32:01 or maybe unknown molecular weight, and you're titrating 551 00:32:01 --> 00:32:04 them out, titrating them together to find 552 00:32:04 --> 00:32:06 missing information. 553 00:32:06 --> 00:32:08 So you can determine concentration, sometimes 554 00:32:08 --> 00:32:11 you can determine a molecular weight. 555 00:32:11 --> 00:32:14 All right, so here's what a plot looks like and some 556 00:32:14 --> 00:32:19 of the key terms involved in acid base titrations. 557 00:32:19 --> 00:32:24 So you have a p h on one side, and then volume of either base 558 00:32:24 --> 00:32:26 or acid added on the other side. 559 00:32:26 --> 00:32:28 So p h versus a volume. 560 00:32:28 --> 00:32:33 And the actual experiment here, you have a base that you're 561 00:32:33 --> 00:32:37 dripping, one drip at a time supposedly into 562 00:32:37 --> 00:32:40 your strong acid. 563 00:32:40 --> 00:32:44 And then you're looking to figure out when you're going to 564 00:32:44 --> 00:32:48 reach the either equivalence point or the end point, these 565 00:32:48 --> 00:32:49 are basically the same terms. 566 00:32:49 --> 00:32:53 It's also called the stoichiometric point, and often 567 00:32:53 --> 00:32:58 equivalence point is used as a more theoretical amount of 568 00:32:58 --> 00:33:01 volume is added, where as end point is the 569 00:33:01 --> 00:33:03 experimentally measured. 570 00:33:03 --> 00:33:06 So we're going to be talking a lot about equivalence points, 571 00:33:06 --> 00:33:09 because we have no lab associated with this course, so 572 00:33:09 --> 00:33:12 everything will be theorectical in terms of these, but 573 00:33:12 --> 00:33:15 they should be the same. 574 00:33:15 --> 00:33:19 So, many times you will measure p h with the p h meter -- 575 00:33:19 --> 00:33:21 this just shows a p h meter. 576 00:33:21 --> 00:33:25 And for those of you who have done these experiments, 577 00:33:25 --> 00:33:26 this should look familiar. 578 00:33:26 --> 00:33:30 And for those of you who haven't, often what you're 579 00:33:30 --> 00:33:32 doing when you're dripping something in, you're waiting 580 00:33:32 --> 00:33:36 for an indicator dye to change color as an indication that you 581 00:33:36 --> 00:33:39 have reached the end point, and often you're adding, and it's 582 00:33:39 --> 00:33:44 clear, clear, clear for what seems to be forever, and 583 00:33:44 --> 00:33:46 just as you get incredibly impatient, you start adding it 584 00:33:46 --> 00:33:49 faster and you go all the way to this dark color. 585 00:33:49 --> 00:33:55 And what you want is this very, very, very light changed color 586 00:33:55 --> 00:33:57 that indicates the end point. 587 00:33:57 --> 00:34:02 So you usually go too slow and then go too fast and then have 588 00:34:02 --> 00:34:03 to do the experiment over again. 589 00:34:03 --> 00:34:06 Those of you who know how to calculate theoretical values 590 00:34:06 --> 00:34:09 could sit down and do a calculation first and then go 591 00:34:09 --> 00:34:13 really fast right until you get around this point and add it 592 00:34:13 --> 00:34:16 really slowly, and be done with lab sooner. 593 00:34:16 --> 00:34:20 So, we'll talk about how you do the theoretical value, which 594 00:34:20 --> 00:34:24 could save you a lot of time if you ever run across these 595 00:34:24 --> 00:34:30 labs in any future class. 596 00:34:30 --> 00:34:34 So, here are the two curves that you would see for either a 597 00:34:34 --> 00:34:36 strong acid with a strong base, or strong base with 598 00:34:36 --> 00:34:38 a strong acid. 599 00:34:38 --> 00:34:41 So if you're titrating a strong acid with a strong base, you're 600 00:34:41 --> 00:34:45 going to start down being very acidic, because all you 601 00:34:45 --> 00:34:47 have is your strong acid. 602 00:34:47 --> 00:34:51 And then as you add in base, the p h will go up. 603 00:34:51 --> 00:34:55 You'll reach this point -- s is for the stoichiometric point, 604 00:34:55 --> 00:34:58 we also call this, again, the equivalence point, and then 605 00:34:58 --> 00:35:01 it'll continue to go up and then start to level off 606 00:35:01 --> 00:35:03 a bit more up here. 607 00:35:03 --> 00:35:06 If you're going the other direction, you're starting with 608 00:35:06 --> 00:35:10 strong base, your p h is going to be high, and the p h will 609 00:35:10 --> 00:35:12 decrease as you add the acid. 610 00:35:12 --> 00:35:14 And then you get to the stoichiometric or equivalence 611 00:35:14 --> 00:35:20 point in the middle of this curve here. 612 00:35:20 --> 00:35:23 And then as you go down farther, more acidic, it 613 00:35:23 --> 00:35:24 starts to level off. 614 00:35:24 --> 00:35:29 So those are what the titration curves look like. 615 00:35:29 --> 00:35:32 So let's do an example. 616 00:35:32 --> 00:35:35 We're going to have a strong base being titrated with 617 00:35:35 --> 00:35:38 a strong acid first. 618 00:35:38 --> 00:35:47 And our strong base is n a o h, and our strong acid is h c l. 619 00:35:47 --> 00:35:56 So let's calculate the p h at the equivalence point. 620 00:35:56 --> 00:36:01 Well, let's just calculate the p h at 5 mils -- I don't know 621 00:36:01 --> 00:36:03 whether it's equivalence point, actually. 622 00:36:03 --> 00:36:08 5 mils of this have been added to the amount of base. 623 00:36:08 --> 00:36:12 So we have 25 mils of our strong base at 0.15 molar 624 00:36:12 --> 00:36:21 concentration, and we're adding 5 mils of our 0.34 molar acid. 625 00:36:21 --> 00:36:25 So what we want to do is figure out how many moles of base 626 00:36:25 --> 00:36:28 we had to start with. 627 00:36:28 --> 00:36:33 So how many moles of o h minus -- again, n a o h is a strong 628 00:36:33 --> 00:36:37 base, so however much n a o h you add, is the amount of o h 629 00:36:37 --> 00:36:42 minus you get, and so we just put in the number of liters 630 00:36:42 --> 00:36:44 times the concentration to get moles. 631 00:36:44 --> 00:36:48 We don't need any equilibrium table here. 632 00:36:48 --> 00:36:52 So then we want to figure out the amount of acid added when 633 00:36:52 --> 00:36:55 you're adding 5 mils of it. 634 00:36:55 --> 00:36:59 So again, h c l is a strong acid, so the amount of h c l 635 00:36:59 --> 00:37:05 added equals the amount of h 3 o plus, that's formed, goes to 636 00:37:05 --> 00:37:09 completion, and so we added 5 mils, the concentration was 637 00:37:09 --> 00:37:12 0.34 molar, so we have 1 . 638 00:37:12 --> 00:37:17 7 times 10 to the minus 3 moles. 639 00:37:17 --> 00:37:21 So now, the strong acid is going to react with the strong 640 00:37:21 --> 00:37:25 base, and we want to figure out how much of the base is left, 641 00:37:25 --> 00:37:28 how much hydroxide ion is left after it reacts with 642 00:37:28 --> 00:37:31 the hydronium ions. 643 00:37:31 --> 00:37:35 So it'll react 1:1, so we had 6 . 644 00:37:35 --> 00:37:41 25 times 10 to the minus 3 moles, and we added 1 . 645 00:37:41 --> 00:37:45 7 times 10 to the minus 3 moles of the acid, so 646 00:37:45 --> 00:37:47 we're going to have 4 . 647 00:37:47 --> 00:37:53 55 times 10 the minus 3 moles left. 648 00:37:53 --> 00:37:59 And now we can calculate the molarity here, so we have the 649 00:37:59 --> 00:38:03 number of moles and the new volume, so we had 25 mils 650 00:38:03 --> 00:38:04 to the base to begin with. 651 00:38:04 --> 00:38:09 We've added 5 mils to the acid, so our new volume is 30, and so 652 00:38:09 --> 00:38:12 we have our new concentration. 653 00:38:12 --> 00:38:15 And now we can calculate p h. 654 00:38:15 --> 00:38:19 First we'll calculate p o h, and then use 14 minus 655 00:38:19 --> 00:38:23 to get the new p h. 656 00:38:23 --> 00:38:29 So if you were making your own little titration curve, we 657 00:38:29 --> 00:38:34 could have volume of acid on one side and p h on the other 658 00:38:34 --> 00:38:39 side, and you have a point of 13 . 659 00:38:39 --> 00:38:40 18. 660 00:38:40 --> 00:38:49 That's how much we have after you have 5 mils added. 661 00:38:49 --> 00:38:52 So we didn't, in this curve, we have not measured the zero 662 00:38:52 --> 00:39:00 point, but we know what one point after 5 mils of the 663 00:39:00 --> 00:39:02 acid has been added. 664 00:39:02 --> 00:39:06 So now let's go right to the equivalence point -- so the way 665 00:39:06 --> 00:39:09 I draw it should indicate that was not an equivalence point. 666 00:39:09 --> 00:39:13 So we want to figure out how much we need to add of the acid 667 00:39:13 --> 00:39:15 to reach the equivalence point. 668 00:39:15 --> 00:39:18 So the equivalence point or the stoichiometric point means that 669 00:39:18 --> 00:39:23 you add the same amount of moles of your titrate as you 670 00:39:23 --> 00:39:26 had, and so they're going to be equal to each other. 671 00:39:26 --> 00:39:30 So if you're adding acid to a strong base, you've added 672 00:39:30 --> 00:39:33 enough acid that you now have equal number of moles to the 673 00:39:33 --> 00:39:36 number of moles of base that you had to begin with. 674 00:39:36 --> 00:39:37 So we know we have 6 . 675 00:39:37 --> 00:39:42 25 times 10 to the minus 3 moles of the base were present. 676 00:39:42 --> 00:39:46 So at the equivalence point, you need to have that exact 677 00:39:46 --> 00:39:49 same number of moles of acid. 678 00:39:49 --> 00:39:53 So we know the concentration of the acid we have and the number 679 00:39:53 --> 00:39:57 of moles we need, and so we can calculate the volume, 680 00:39:57 --> 00:39:59 which is 18 . 681 00:39:59 --> 00:40:04 4 millimeters, or 0.0184 liters. 682 00:40:04 --> 00:40:12 So what would the p h then be of the equivalence point? 683 00:40:12 --> 00:40:15 We're titrating a strong acid with a strong base, 684 00:40:15 --> 00:40:19 what should the p h be? 685 00:40:19 --> 00:40:22 The p h should be 7. 686 00:40:22 --> 00:40:27 So somewhere around here we're going to be at 18, so you can 687 00:40:27 --> 00:40:36 just try to draw a curve, and here we have a p h of 7 when 688 00:40:36 --> 00:40:39 we've gone to about 18 . 689 00:40:39 --> 00:40:44 4 milliliters added. 690 00:40:44 --> 00:40:47 So when you titrate a strong acid with a strong base, you 691 00:40:47 --> 00:40:49 form a salt that's neutral. 692 00:40:49 --> 00:40:52 Because the conjugates of a strong acid and a strong base 693 00:40:52 --> 00:40:53 are not basic or acidic. 694 00:40:53 --> 00:40:56 They're ineffective as acids or bases, so you're going 695 00:40:56 --> 00:40:58 to get a neutral salt. 696 00:40:58 --> 00:41:01 So if you're doing a problem with a strong acid and strong 697 00:41:01 --> 00:41:04 base, it's not a lot of calculations that need to be 698 00:41:04 --> 00:41:06 done at this point, you just need to recognize that your 699 00:41:06 --> 00:41:09 salt should be neutral. 700 00:41:09 --> 00:41:12 So now, we can talk about what happens if you add an extra 701 00:41:12 --> 00:41:17 milliliter of your acid, after you've reached that equivalence 702 00:41:17 --> 00:41:20 point, which is something that people probably have done in 703 00:41:20 --> 00:41:24 doing these titrations not meaning to, gone well beyond 704 00:41:24 --> 00:41:27 the equivalence point. 705 00:41:27 --> 00:41:31 So first we can find out the number of moles of the strong 706 00:41:31 --> 00:41:36 acid that we've added extra, so we added one mil of the strong 707 00:41:36 --> 00:41:39 acid, and so again, it goes to completion. 708 00:41:39 --> 00:41:43 The concentration, the acid, is 0.34 molar times our 1 709 00:41:43 --> 00:41:45 mil, so we've added 3 . 710 00:41:45 --> 00:41:52 4 times 10 to the minus 4 extra moles of our acid, and so let's 711 00:41:52 --> 00:41:55 calculate then what the molarity is that we have 712 00:41:55 --> 00:42:03 added that was extra. 713 00:42:03 --> 00:42:05 And even if you don't have a calculator, 714 00:42:05 --> 00:42:41 we've helped you out. 715 00:42:41 --> 00:43:05 Let's just take 10 more seconds. 716 00:43:05 --> 00:43:10 I think this is a first, isn't it? 717 00:43:10 --> 00:43:15 Did I mention it's a good idea to start the problem-set early. 718 00:43:15 --> 00:43:20 So the trick here was about the volume. 719 00:43:20 --> 00:43:25 So we had 25 mils to begin with, then we added 18 . 720 00:43:25 --> 00:43:30 4 to get to the equivalence point, and then we're 1 mil 721 00:43:30 --> 00:43:32 beyond the equivalence point. 722 00:43:32 --> 00:43:36 And the tricks to these parts of the problems are to remember 723 00:43:36 --> 00:43:39 all the things that have been added to get to the volume. 724 00:43:39 --> 00:43:43 So the problem itself is not very tricky of having just an 725 00:43:43 --> 00:43:47 acid in water, but the one trick is in calculating the 726 00:43:47 --> 00:43:50 molarity, remembering all of the things that were added 727 00:43:50 --> 00:43:52 to get to this point. 728 00:43:52 --> 00:43:56 And so by the end of the problem-set this should be 729 00:43:56 --> 00:43:59 pretty familiar to you, but it's also something that you 730 00:43:59 --> 00:44:02 want to make sure that you check on an exam that you're 731 00:44:02 --> 00:44:06 not making any volume mistakes. 732 00:44:06 --> 00:44:10 So again, here are the things that you want to remember to 733 00:44:10 --> 00:44:13 add in in calculating this. 734 00:44:13 --> 00:44:17 And then, if you calculate the p h of that, you 735 00:44:17 --> 00:44:19 get a p h of 2 . 736 00:44:19 --> 00:44:24 1106, so that's down somewhere in here. 737 00:44:24 --> 00:44:33 We've added 1 more mill, and we're at a p h of 2 . 738 00:44:33 --> 00:44:38 1106, and this can be a check as well. 739 00:44:38 --> 00:44:40 If you forgot to add some of your volume, you might 740 00:44:40 --> 00:44:43 get a p h that doesn't make a lot of sense. 741 00:44:43 --> 00:44:45 So that can be a double check. 742 00:44:45 --> 00:44:49 Always ask yourself when you have a strong base and you're 743 00:44:49 --> 00:44:51 adding acid, before you've added very much, your 744 00:44:51 --> 00:44:53 p h should be basic. 745 00:44:53 --> 00:44:56 At the equivalence point of a strong acid, strong base 746 00:44:56 --> 00:44:58 titration, it'll be 7. 747 00:44:58 --> 00:45:01 And if you continue to add acid, then you should have 748 00:45:01 --> 00:45:03 a pretty low p h, you'll notice the curve drops 749 00:45:03 --> 00:45:05 off pretty fast. 750 00:45:05 --> 00:45:07 So it should be a dramatic change in p h by adding 751 00:45:07 --> 00:45:09 extra of your acid. 752 00:45:09 --> 00:45:11 So always check your work. 753 00:45:11 --> 00:45:14 OK, so let's stop there, and we're going to weak acid, weak 754 00:45:14 --> 00:45:17 base titrations next time. 755 00:45:17 --> 00:45:18