Okay, how are you guys doing? Good. All right, I'm glad to hear that. I'm doing awesome too. All right, we're going to talk about the final exam today. Let me remind you that it's Tuesday, not Monday. It's at 1.30 to 3.30. Okay, in this room. Now, I understand, is Stephen here? Maybe you know Jean-Marc. When the review session, I just checked Facebook and I didn't, right. So if you haven't weighed in on when you want the review to be, I think he's already settled on it being on Monday, but I don't think he's got the room nailed down yet and the time, all right? So if you haven't made your opinion known, you might want to do that, all right? And just stay tuned. It'll be posted, I presume, by the end of the day to day. Right, that, yes, thank you, it's wrong. The review is not on Saturday. Right now, the version of this lecture that's posted to the website says Saturday, it's not on Saturday. It's on Monday. Okay? So there's going to be, I wrote the exam yesterday. I know exactly what's on it, so I can tell you. There's four problems, 50 points. I don't know why. Okay, and here's what they are. There's a problem on Stack Mac that, I looked at this problem, I went and found it, it's similar to stuff that is in Chapter 13, it's stuff that's in Chapter 13. There's a thermal problem that's from Chapters 14 and 15, not so different from one that you saw on midterm one and then on midterm two and the quiz material. So you are really familiar with problems one and two. Problem three is enzyme connection. These last two problems are kinetics. We haven't had kinetics on a midterm exam yet, so we're going to focus this review on these last two problems and make sure that we review some of this stuff. All right, there's two extra credit problems that are worth a total of 20 points, each one. The first one is on transition state theory and solution. We barely talked about that. That was Wednesday, at the end of the lecture, we were rushing. All right, so we're going to go back and look at that again. We're going to try and get you this 10 points. To get this 10 points, you've got to get the answer exactly right. There isn't going to be any partial credit on these extra credit problems. There's also a Stack Mac problem that you've seen multiple times in different forms. I'm asking it in a slightly different way. This will not be something that catches you unprepared if you do any preparation. Okay, so that's what it's going to be. I don't think it'll take you a whole two hours to do this exam, honestly, but you'll have a whole two hours to do it. All right, you can relax, make sure you get everything right, double check your work. All right, there should be plenty of time to do this exam. Now, normal rules apply, open book, open notes. There will be no equations on the exam, no constants, no conversion factors. As usual, you need to be able to dig those out of your book. It's not open anything else. Computers, phones, iPads, solutions manuals, other books, no. All right, part of the problem is that this workspace gets kind of congested if everybody drags in a library worth of stuff. All right, so you've got your book. Any notes that you want are fine. Okay, that's it. No other books. I don't think we've enforced this on the previous midterms, but we're going to enforce it on Tuesday. Okay, any questions? Bring a ruler or some sort of straight edge. You're going to need to draw a straight line through data points on a graph. That's a hint. Okay, so what we want to do is we want to go back and look at the stuff that I threw at you in such haste on Wednesday. All right, because this is 10 points for everybody in this room if you can get this right. I put this on the exam because I think it's important. All right, transition state for ionic reactions in solution. Here are the three things that we want to understand. First of all, the first thing that we want to understand is that equilibrium itself in solution depends on whether ions are present even if those ions are not directly participating in the reaction. Okay, equilibrium is affected by the ionic strength of the solution. It's affected by ions that are not even reactants or products in the reaction that we care about. All right, that's the first thing to understand. The second thing to understand is transition state theory. So in transition state theory, one of the most important postulates is that there's an equilibrium between the reactants and a transition state. All right, and so that equilibrium, like every other equilibrium that involves ions, is perturbed by the presence of ions in the solution. All right, it's not a special case. All right, it's just another equilibrium, the transition state for equilibrium strength. All right, this is why the presence of ions can influence the rate of a reaction. So here we're talking about the equilibrium constant. Here we're talking about the rate of a reaction and the reason the rate is affected is because the equilibrium between reactants and the transition state, that equilibrium is perturbed. And if the transition state is favored, if the ionic content of the solution favors the transition state, you accelerate the reaction. It makes a perfect intuitive sense once you understand it that way. What did I write here? The rate of the reaction, so does this depend on the favor of the transition, so the rate is to accelerate, yes. Okay, so the main point is that we've got charge reactants. The charge on A is Z of A, charge on B is Z of B. The total charge on the transition state then is the sum of Z A plus Z B. All right? And what we're going to postulate is that this transition state exists and that it's an equilibrium with these reactants right here. Okay, and once you form this transition state, it's just a unimolecular reaction with rate constant K double dagger, not two pluses, to form products. So we're just going to call this thing AB double dagger. The rate of the reaction is just equal to that rate constant times the concentration of the transition state, yes. And this is the normal way that we would write the rate of the reaction, right? We would just, I don't know why I called it K2, but this is just the rate constant times the concentration of A times the concentration of B. This is just the normal way that we'd write the differential rate law for this reaction, isn't it? Okay, so we've got this. We're going to come back to it in a second. What we need to understand first, that first bullet that we have to understand is why ions in solution affect equilibrium, right? Why is that the case and how do we understand that? We talked briefly, I'll admit it, about activities, right? The activity of some molecule A, which can be an ion or a neutral, is given by this expression right here where that's the concentration of A and this is the activity coefficient, right? The activity coefficient. Now, obviously, if the activity coefficient is 1, the activity just equals the concentration. What we're interested in is cases where the activity coefficient is not equal to 1. And that turns out to be the case if A is charged. If A is charged, in general, the activity coefficient will not be equal to 1. It'll be less. So that's the activity. It just has units of concentration. That's the activity coefficient. It's got no units. It's dimensionless. Okay, so this activity coefficient, there's some math that we can use to calculate it. This is the simplest equation. There are equations that take up a whole screen, right? We're not going to pay attention to those. This is the only one we care about. That A is just a constant that's equal to 0.509 in water. That's the charge on the ion that we're calculating the activity coefficient for. And that is the ionic strength. The ionic strength is just a concentration of each ion in the solution multiplied by its charge squared. So if you had sulfate with a 2 minus charge, you'd be multiplying by 4. If you have sodium with a 1 plus charge, you'd be multiplying by 1. That's just a concentration. There's a term in this summation for each and every ion in the solution. You just take all of the ions that are in the solution, take their concentration, multiply by their charge, line them up, multiply by 1 half. That's the ionic strength. That's how it's defined. Okay, so this is called the Debye Huckle limiting law and it allows us to calculate this gamma. If you look at this equation, you can have zero intuition about gamma, right? This equation doesn't, it's not obvious what gamma is doing. But here let me show you what this equation predicts. What this equation, so what am I plotting? This is gamma on this axis right here. Notice that all of these curves are starting up here at 1 and on this axis right here, that's the ionic strength. Right, so at infinite dilution, we're here in pure water and gamma for everything, no matter what the ion is, gamma is equal to 1. Now as the ionic strength starts to increase, gamma becomes less than 1. All right, what are these different curves? This curve right here is for an ion, a cation or an anion that has a charge of 1, plus 1 or minus 1. All right, it's got a size of 9, right? That's its hydrated radius. We don't need to know in detail about that. But the main point is that bigger ions show larger gammas. See how this gamma over a whole range of ionic strength is higher than for this blue guy. This blue guy is a smaller ion that also has a charge of 1. All right, so there's a negative deviation from 1 as the ionic strength increases and if the charge goes up, this is 1, this is 1, this is 3, there's a huge effect. All right, there's a huge deviation from 1 that happens for highly charged ions. All right, di-cations or anions, things like sulfate, phosphate has a 3 minus charge, magnesium has a 2 plus charge. These ions have large activity effects if they are highly charged. Okay, so what do we want to know about this plot right here? Basically, the activity coefficient is always less than or equal to 1. It's never more than 1. As the ionic strength approaches 0, this should really be I because that's what we're calling it in this lecture. Gamma approaches 1 for any ion, yes. As the ionic strength approaches 0, gamma approaches 1. Okay, for neutrals, if the molecule has no charge, by definition, its gamma is equal to 1. All right, so whatever gamma is describing is an electrostatic effect, neutrals don't participate in it. Gamma decreases deviating more from 1 as the ion gets smaller. Yes, that's this difference right here. See how that's lower than that? That's what I'm talking about. The smaller the ion, the greater the negative deviation from 1. Usually you can tell just by looking at an equilibrium which direction will be favored by the addition of an inert salt. In other words, if you change the ion content of the solution, you change the ionic strength, what we as chemists want to be able to understand qualitatively is what's going to happen to some equilibrium that's in solution. Is the equilibrium going to shift to the right towards products as we add salt, for example? Is it going to shift to the left towards reactants when we add salt? As chemists, we need to have that intuition. Okay, so let's look, take this equilibrium right here. We already know that we can write the equilibrium constant for this equilibrium in terms of activities. If we do that, oops, I didn't write it here, that would be the activity of C, the activity of A, the activity of B. We take gamma to the C power, C to the C power, B to the B power, and so on. All right, we write each activity as an activity coefficient and a concentration. We don't forget these exponents. We can pull all of these gammas to one side, pull them out of the expression. Now we've just got concentrations here, and we can use this collection of gammas to write a concentration equilibrium constant. So there's two kinds of equilibrium constants, it turns out. What you look up in the back of your book is a thermodynamic equilibrium constant, this K right here. It doesn't depend on the ion concentration in the solution, it's constant, it really is constant. Then there's a K prime, that's a concentration equilibrium constant. That equilibrium constant applies specifically to a certain concentration of ions in the solution, a particular ionic strength. All right, and it includes the activity effects. So this is called the concentration equilibrium constant because what you've done is you've stripped all the gammas out, now your equilibrium constants written out in terms of concentrations. Well that's how we normally write it anyway, isn't it? But it turns out it's only strictly correct to do this. If you pull out all these gammas, then you take the thermodynamic equilibrium constant, multiply by these gammas, and you get the concentration equilibrium constant. Okay, so by comparing the thermodynamic equilibrium constant with the concentration equilibrium constant, you can tell what will happen if you change the ionic strength. All right, if K prime is bigger than K, if the concentration equilibrium constant is bigger than the thermodynamic equilibrium constant, that means that as you add salt, equilibrium shifts towards products. If the concentration equilibrium constant is less than the thermodynamic equilibrium constant, that means if you add salt, everything shifts towards reactants. Let's do an example. All we're trying to do here is qualitatively get the answer right. All right, I want to know, here's acetic acid. We're going to add salt to an acetic acid solution. I want to know if the pH is going to go up or down. You should be able to predict that with 100% accuracy every time. All right, there's no doubt about what will happen. It will not be a small change. It will be a change that you can measure with your pH meter. Your pH meter was going to, the digits are going to click as you add salt to this solution. So it's not a rounding error. All right, here's the equilibrium constant. Now I've pulled all these gammas out. They're gamma for hydronium. There's the gamma for acetate. There's the gamma for acetic acid and the gamma for water. Now I'm going to calculate the concentration equilibrium constant for this equilibrium. How do I do that? I just pull, so I take my thermodynamic equilibrium constant and I multiply by these two guys in the numerator. There they are, and I divide by these two guys. There they are. Now that's my concentration equilibrium constant. All right, and then I look at these gammas here and I can already guess how big they are. All right, notice these two guys in the numerator, what's special about them? They're neutral. All right, so their gammas are one by definition. Boom and boom. What about these bottom guys? They're charged. All right, their gammas are going to be less than one by definition, right? Okay, and so just this really crude thinking here, those are one, those are less than one. That means that this thing in the red box here is going to be greater than one. That means that the concentration equilibrium constant is greater than the thermodynamic equilibrium constant. That means if I add salt to this solution and these guys get smaller, right, when I add salt, these gammas are going to get smaller. Remember, because if we're here and we add more salt, we go down here. These gammas are getting smaller when we add salt in this direction right here. Okay, these two gammas are smaller when we add salt. So K prime we could look. All right, now we can go through and mathematically figure this out using this approach. For any equilibrium, you can do this. You can do the analogous thing. All right, now what happens if you have ions on both sides while you can't tell? In other words, if these guys were charged in the numerator, this would be less than one and this would be less than one, so you'd have less than one, less than one, less than one, less than one, you can't just do a back of the envelope prediction about what will happen. You'd have to actually calculate the numerical gammas using the Debye Huckle limiting law, then you could figure out what's happening. All right, here we're just doing sort of a meatball estimation. All right, which works fine, a lot of the time it turns out. Okay, so what we're going to predict is if we add salt to this solution, it's going to shift to the right. Solution is going to become more acidic. The hydronium concentration is going to go up. The pH is going to go down. That's what actually happens. What about this guy? Now notice something. I'm looking at this equilibrium here. What we just said is it's going to shift to the right. Look at these guys and look at these guys. Which state of the system is more ionic? Reactants or products? Products. The products are charged. The reactants are neutral. All right, it turns out that adding salt favors the more ionic state of the system. Here products are more ionic than reactants. And so if I add salt, equilibrium is going to shift to the right. If you just remember that, you'll get the right answer every time. All right, equilibrium favors the addition of salt to a system in equilibrium favors the most ionic state of the system. Yes? Yep. If it's the reactants, is it more basic? Yes. Look at this guy. All right, we're talking about the solubility of lead sulfide. Lead dissolves to give lead 2 plus sulfur, 2 minus. Which state of this system is more ionic? Products again. That's totally neutral. All right, what's going to happen if I add sodium chloride to this electrolyte? Amazingly, the lead sulfide is going to become more soluble. The solubility of the lead sulfide goes up by quite a bit. It's not a small effect. We neglect it in CAM 1, in O-CAM, in inorganic chemistry. We totally sweep these effects under the carpet, but they're not small effects. How do I know that that's true? I can work it out mathematically. Here are the two gammas for those two ions. Here's the KSP expression. All right? So that concentration equilibrium constant is going to be equal to the thermodynamic equilibrium constant divided by these two gammas. How big are those two gammas? Well, they're both going to be less than 1, because both of these species are charged. And so when I calculate, that means that this whole thing here is going to be greater than 1, and when I multiply, wait a second, right. This is greater than, sorry, brain lock. All right? So the concentration equilibrium constant is going to be greater than the thermodynamic equilibrium constant. Yes? And the solubility is going to go up. We call this salting in. All right? Hardly anybody calls it that anymore. All right? But old-time analytical chemists still know what this means. Salting in means you add an inert salt to a solution where you're trying to get some sparingly soluble salt that's on the bottom of your Erlemeyer. You're trying to get that into solution. It's not working. What are you going to do? If you can heat the solution up, of course, that's one option. Another option is just to add an inert salt. When you add an inert salt, these gammas go down. They become smaller. The solubility, this concentration equilibrium constant goes up. The solubility goes up. All right? It's a trick. That every old-timer knows. Absolutely. Yeah. Saturation concentration goes up. Yeah. That's actually what it means to say that the solubility goes up. Why? Why does this happen? Is this magic? All right? This is in some ways the most important thing to understand. All right? This is what Peter Debye understood when he derived the Debye-Huckl equation. Coulomb's law. What is this? This is the energy acting between two ions in the solution. This is the distance these two ions are from one another. They're center to center distance. Okay? As they get further and further apart, the energy goes to zero. Zero's up here at the top. All right? So as these ions move far apart, they have no Coulomb interaction. But as they come closer and closer together, the energy goes down. These two ions stabilize one another if they have an opposite charge.  All right? But the point is in solution, you've got ions. There's no barrier to these ions moving around. They can go wherever they want to. Wherever the energy is the lowest is where they choose to go. How do they arrange themselves? They automatically arrange themselves like this. Right? You see how cations are close to anions? Anions are close to cations. All right? There's few cases where anions are close to one another. They don't have to be so they're not. Now a solution is very flexional. Ions are moving around all over the place. But on average, if you take a snapshot, you'll see this loose ionic lattice exists even in liquid salt solutions. All right? There's an ionic lattice that exists even in liquid salt solutions. It's counterintuitive. All right? How could there be a lattice of ions in a liquid? All right? Well, it's not a precise lattice of ions, all right? But it's a very loose. So you see this, you don't see this. All right? The solution doesn't look like that. Otherwise, it would be electrostatically destabilized. Okay? So these physics exert an influence on every ionic reaction because ions want to join this ionic lattice. Why? Because they stabilize the whole system. The energy of the whole system goes down when they join the lattice. You add more ions, the lattice gets reinforced, all right? The energy goes down even more. That's why gamma keeps going down. All right? There's a greater and greater electrostatic effect acting as you increase the concentration because the ions are closer to one another. The solution looks like this, not like this. All right? If it looked like this, you'd get electrostatic destabilization, all right? So the ions, this is completely counterintuitive to me, all right? You've got these ions that can be anywhere they want to but they form a lattice, they organize themselves so that they lower their electrostatic energy, all right? And what that does is it changes the driving force for every reaction that involves ions. That's what we're trying to understand with these gammas, all right? The gammas allow us to predict the influence of this ionic lattice on equilibrium. Okay. So coming back to this picture, we can apply this logic now to this equilibrium, all right? So far we've just been talking about generic equilibria for reactions and solution. Now we can come back to the rate of this reaction which is going to be influenced by this equilibrium here, right? Because in transition state theory we postulate there's an equilibrium between the transition state and the reactants, okay? And so now I can write an expression for this equilibrium constant. Here's the activity of the transition state. Here's the activity of A and B. I can write each activity in terms of gamma times concentration. I can roll all these gammas up into a K gamma, this is what your book calls it, all right? So K gamma is the equilibrium constant for the activity coefficients, if you will. Very strange notation to use but this is what they chose to use. So that is just that collection of gammas there, okay? And if I solve for the transition state concentration here, all right, this is the expression that I get, this is the equilibrium constant here, this is that collection of gammas, all right? And then I've got A times B. And so the rate of the reaction is now going to be given by this expression right here, okay? This is your equation 2049A. So what this says, notice, very important, as this equilibrium constant gets larger, the reaction accelerates. What is that equilibrium constant? It's the equilibrium between the transition state and the reactants. As that gets bigger, the reaction goes faster. That's what transition state theory says, okay? And by putting this gamma in the denominator, we include now the effect of salt in the solution on this equilibrium. Now, we're not going to go through and derive all of these other equations here, but this turns out to be an important one, all right? What this says is the effective second-order rate constant of the reaction, the thing that we've been calling the rate constant all along, all right? That's equal to the rate constant at infinite dilution of salt, ionic strength equals zero. That's what that zero means. Minus log of K gamma and K gamma is this collection of, it's that, all right? That's K gamma. Okay, this is the master equation that describes this transition state theory in solution. What does this predict? Oh, yeah, that's those guys, yes, we can calculate them, yes, we can do some algebra, yes, we can derive this equation from that equation, this is a better equation and it actually explicitly says what the effect of K is on the ionic strength, that's 2051. Here's what's predicted, all right? This plot is kind of hard to understand. Let's make sure we understand it. What is on this axis? This is the rate constant K2, all right? Reaction going faster in this direction, slower in this direction. This is the square root of the ionic strength. So this is infinite dilution here and now I'm adding salt, adding salt, adding salt as I go in this direction. The point of this plot is to understand what happens to the reaction rate as we increase the ionic strength. All right, what happens to the reaction rate? It's a little counterintuitive, I think. Here's the reaction rate at infinite dilution. For every reaction, all right? If the reactant and the product have the same charge, the reaction rate gets accelerated. That's true here, that's true here, that's true here. The amount of acceleration depends on how charged the reactants are. The more charged they are, the more the reaction gets accelerated by adding salt. If they have an opposite charge, the reaction slows down, right? As I add salt, I slow the reaction down. That's bizarre. All right, the reason this happens, adding salt, is because in this case right here, look at this one, reactants both have plus 2 charge. The transition state, that will have a plus 4 charge, right? That plus 4 charge is a higher charge state than the 2 plus 2s. You might think plus 4 equals 2 plus 2. So isn't the amount of charge the same? No, 4 trumps 2 2s. All right, a higher magnitude has much stronger coupling with the ionic network in the solution than 2 2 plus ions. Okay?  So the more salt I add, the faster and faster and faster the reaction goes.  What's the charge on the transition state here? Zero. So now you're creating, you've got ions that are strongly coupled to this ionic network. Now you're creating a transition state that doesn't want to be in the network. It doesn't care. It's neutral. All right, the reaction gets slowed down by the addition of salt. Why? Because the reactants are stabilized. So equilibrium is shifting in the reactant direction. They are stabilized by the salt. The transition state is not. The reaction doesn't get accelerated. So if you can understand this plot qualitatively, you should be able to get 10 extra points on the final. Questions? Yes? 4 plus and a 2 minus. 4 plus and a 2 minus. Great question. Let's think about that. You've got reactants that are 4 plus and 2 minus. All right, what's going to happen to that reaction? Accelerated, deaccelerated or no effect? 2 plus, 4 minus, or 4 plus, 2 minus. All right, those are your reactants. 4 plus, 2 minus. How many people think that if I add salt to that solution, I will accelerate the reaction rate? How many people think if I add salt to that solution, I will deaccelerate the reaction rate? Right. 4 plus and 2 minus is 6 total charges in the reactants, the transition state is going to have a charge of what? 2 plus or minus. Right, 2, so you've got 6 total charges in the reactants and 2 for the transition state, so the reactants are going to be favored. The reactants are more ionic than the transition state. Okay, if the reactants have the same charge, then it's a little confusing because if you have 2 and 2 and they're both pluses, then the transition state is 4 and what you have to remember is 4 trumps 2 and 2. If they have opposite charges, that won't be the case. It'll be obvious, which one has, okay, everyone going to get those 10 points for a total score of 210. All right, so there's going to be a problem not dissimilar from this on your exam. Big piece of graph paper, concentration of some substrate velocity and we have to be able to figure out what's going on. We need to know, be able to calculate all of the relevant parameters, Km, Vmax, turnover number, catalytic efficiency, no, we didn't talk about it. No, that's not on your exam. All right, this picture keeps coming up in connection with everything that we do. We can't get away from it. All right, in this case, this is not the transition state, it's the enzyme substrate complex. This is the cartoon that applies. This is the rate constant for the reaction, the enzymatic reaction. All right, it's also the turnover number. It's also a constant called K subcat. All right, so if you're reading the literature on enzymes, they may say Kcat is this. They're just talking about that rate constant right there. All of those guys have units of seconds to the minus 1 because they're first order rate constants, first order in the enzyme substrate complex. Okay, so we worked out the mathematics for this using the steady-state approximation. This big Km here is the McHale's constant. It's this connection of rate constants right here related to those guys. This is what the generic enzyme reaction does. All right, this is the reaction rate on this axis. This is the substrate concentration here, not a time axis. This is the concentration of the substrate. Of course, if the substrate is zero, the reaction rate is zero. Now if I add substrate, the reaction looks first order at first, okay, but eventually when I fill up all the enzyme with substrate, I reach a Vmax. All right, this dashed line here represents what that is. Vmax is equal to K2 times the initial concentration of enzyme that I added at the beginning of the experiment, the total amount of enzyme that's present in the beaker. All right, that's its concentration there, so I can calculate Vmax if I know K2. We derived this equation, which is not called the line weaver-berk equation, but the plot that we make from it mysteriously is called the line weaver-berk plot. What is it? It's a plot of one over substrate versus one over the reaction rate. Okay? So if I'm given substrate and V information, I've got to calculate one over V and one over S before I can make a line weaver-berk plot. Once I've made it, this intercept here on the one over V axis is going to be one over Vmax. This intercept is one over, actually minus one over Km. All right, so I get Vmax and Km from those two intercepts right away. It's really easy. It's helpful if I can draw a straight line. That's why you need that ruler. Here's what your plot should look like, qualitatively. Okay? You've got to get these intercepts right. You've got to read them off the graph. You've got to be able to make a graph that looks, the graph is actually worth a lot of points. It's important to get it right, quantitatively right. So you'll have plenty of time to make it, don't worry. And then once you've got it, you can read 0.44, that's one over Vmax, 0.90, that's one over Km, K2 is Vmax over the concentration of enzyme. All right, I can calculate all this stuff. Make sure you get the units right. Units are going to be worth points, as always. Okay, here's an old exam. Here's an old exam question. Consider the following reaction mechanism, blah, blah, blah, assuming the steady-state approximation means you've got to derive an expression for the reaction rate. This is like the hardest steady-state problem I've ever asked on an exam. If you can do this one, you can do the one that's on the exam on Tuesday, I guarantee it. The one that could be on the exam Tuesday, I should say. All right, proton nitric acid, nitrous acid, sorry, reacts to protonate that. There's a plus sign there that's hard to see here. So that's H2NO2 plus, H2NO2 plus reacts with bromide to give ONBr, right here are the rate constants. Okay, so what do we have to know to get this right? First of all, we have to be able to pick out all the intermediates. What's an intermediate? Well, that guy looks like an intermediate. Look, he's here and here and he's not here. So he's definitely an intermediate. What else? ONBr, he's here and here and he's not here. Okay, so he's an intermediate. That's why this is hard. You've got to apply the steady-state approximation twice. You've got to apply it to every intermediate. Okay, so let's go through and do that. What do you do? I don't remember who my teaching assistant was in 2010, but they didn't have very good penmanship. This is not my handwriting. My handwriting is immaculate. So what do you do? The time rate of change of this guy, that's what this says right here. I know you can't read that. Time rate of change of H2NO2 plus, that's this. You set that equal to zero. That's the first thing that we're looking for. And then you've got to have each source and sink for that species represented by a term, right? This is the build-up of the H2NO2 plus from here, all right? Protons, HNO2, boom, boom, K1, boom. Then you've got K minus 1. You've got the second reaction here, boom. All right, so you've got three terms and now you solve for the concentration of the intermediate. You should really say H2NO2 plus steady-state to distinguish it from the general concentration for that species. That's what it's going to be equal to right there. All right, six points for getting that guy right. Then we've got to do the same thing with this guy, ONBR, here he is, set it equal to zero. You do exactly the same thing, source, sink of ONBR. In this case there's only two terms, one for that, one for that, okay? But when I write it out, this guy appears in this expression. And so once I've got this expression, I can substitute this whole mess here in for the H2NO2 plus. I get this monster equation here which happens to be correct, it is kind of monstrous. You should see what it looks like if you don't apply the steady-state approximation, total nightmare. So once I've got this guy, notice that that guy is the only one that appears in the rate expression for the product. That's the product we care about, that's the guy that appears in the rate expression, not this guy, but this guy appears indirectly because he appears in the expression for this guy, right there, okay? And so if I want to know the rate of the reaction, it's K3 times ONBR times C6H5 NH2, okay? And there it is, plug everything in, that's what the differential rate law is for this reaction in the steady-state approximation. Okay, now I can ask questions about this. I can say, look, what happens to the apparent rate law as a function of the bromide concentration? Well, there's bromide here and bromide here, right? If I increase, if I make bromide large, we expect this term in the denominator to dominate K minus 1, right? If that dominates, the bromide here will cancel, all right? And so I'm going to end up with, so at high BR, these BRs are going to cancel for us because this term K2BR dominates over K minus 1, BRs cancel, I get a reaction that has overall second order that doesn't depend on BR minus. At high BR minus, we shouldn't have any BR minus sensitivity to the rate, that makes sense. We've effectively isolated the reaction with respect to BR minus. You make BR minus big enough, all right, and the reaction doesn't care about it anymore. It cares about the ones that are not very, the reactants that are not very big. And at low BR minus, what happens, oops, at low BR minus, K minus 1 dominates, this term goes away, all right, we have a collection of rate constants here where we've got 1, 2, 3 concentrations, okay, and so the reaction has overall third order and it does depend on BR minus. So there's two limiting cases. You can tell there's going to be two limiting cases immediately because there's a plus sign in the denominator. Okay, so what else could we talk about, possibly? What other kinetic issues could be broached on this exam? I don't really know.  You have to be able to figure out what the units are on the rate constant, all right, you do that by just putting the units, writing the, first of all, writing the differential rate expression and then putting the units on the concentrations, putting the units on the reaction rate, which is always molar per second, and then just solving for the units of K. No matter what this thing looks like, you can always get the right units of K by doing that. Here's an example. Here's another example. We have three methods for determining what the reaction rate, what the differential reaction rate is, what the rate law is, we have three methods for doing that. One of them is the method of initial rates. You make everything, all the reactants in the mixture big except one, and if you do that, you've isolated the reaction with respect to that reactant. Let's say in this case it's A, and if you work out the math for doing that, this equation applies, log of the reaction rate equals log of the K prime, which includes the K and all the other concentrations, so you make everything big except one reactant, in this case A, did I just say that or did I say that wrong? Everything big except one reactant, you've isolated that one reactant in this case, it would be A, and then you can plot log of the reaction rate as function of log of A, and the slope is just the molecularity of the reaction with respect to A, right, the number of A's that are participating in the reaction. And you can pick the reaction mechanism apart reactant by reactant by doing that. Okay, what other options do you have? Well, you can use an integrated rate law. We talked about that, and you can fit your data to an integrated rate law, and there's the half-life. If you can measure the half-life of your reaction, here's an example of working out the integrated rate law for a reaction that has ordered three halves, that would be bizarre, but you could work it out if you had to, here's what that looks like. All right, and here's the half-life, and the half-life behaves, the half-life itself tells you absolutely nothing, but successive half-lives tell you a lot. All right, the successive half-life goes down by a factor of two, the reaction is first order. Half-life doesn't change, oh sorry, zero order. Half-life doesn't change, it's first order. Half-life gets doubled on each successive half-life, the reaction is second order, and so on. And you can derive the T1 half expression for more complicated mechanisms if you have to. Okay, and finally there's the Arrhenius equation that tells you about the temperature dependence of the reaction rate, all right, you have to know what the activation energy is, the temperature, and you have to know what this pre-exponential factor is, or you can determine the pre-exponential factor if you want from the data that you have because the pre-exponential factor is the intercept of this Arrhenius plot of log K versus 1 over T. I think that's everything. Now, I've located a website that you're going to be interested in, you guys are going to want this bumper sticker here, you're going to want a mug like this one, or it's possible, I don't think you're going to want it, but if, and I notice also that they have many of these in different colors and sizes in case you should want such, this is a terrible thing to say, but, okay, so everyone's going to do well on Tuesday, good luck.


There are several instances where an homocytic picture could deceive one into thinking that there is no abnormality in cytoplasmic maturation or nuclear maturation. And one of these instances is when you have had immune hemolysis. There is a strong reticulocytic response to an immune hemolysis, generating very large reticulocytes. And when you have increased numbers of these reticulocytes, then when you add up all the cells, although the majority are macrositic or nomocytic, these macrosites are not enough to give you a high MCV. The MCV remains within normal, but one needs to bear this in mind and look at the red cell distribution curve. The distribution curve will show telltale signs of a tail towards the larger cells. That will be the key and the reason for suspecting that there are a few large cells that are pushing the average to within normal. And it will only be a number, a question of time before you see a high MCV.


Welcome to JSA TV, the Newsroom for Tech and Telecom Professionals. I'm Jamie Scottokataya of JSA. Joining me here at ITW 2017, my friends, Jeff Graham, CEO of Consul Connect, and Terry Francis. She is the Chief Product Officer of Consul Connect. Thank you for joining us. Thank you. Nice to have you. So, Jeff, I'll start with you. You've been at the helm of Consul Connect now for the past nine months. Can you tell us about where Consul is today and where it's going tomorrow? Sure. Well, let's start out first with what happened before I came. So, Albergio, the CEO and founder of the company before I was there, basically built a software product, 1.8 million lines of code, and he also built a global network. And I came into scale with the company. So, I recruited an executive team, which Terry was one of them, but a CFO and a head of sales and so on, to build that team in place. And then what we've been doing since, essentially, is putting our go-to-market enterprise model in place, where we recruit cloud partners, SaaS providers, and enterprises to come on the platform. And phenomenal selection of your management team, may I say. Terry, a good friend of ours. So, Terry, you are here launching Cloud Nexus. Is that right? That's correct, Amy. Actually, we just launched Cloud Nexus yesterday. It was a press release that really extended on the platform that we have, which is the network and the software combined. And we're now able to automate and simplify for enterprises, cloud to cloud connectivity. So, Cloud Nexus virtualizes, it takes complexity out. It allows our customers to bypass the internet, be able to connect directly between their cloud providers. It reduces costs and complexity for them, and it reduces the risk of them actually putting traffic over the internet when they have multiple cloud providers. And most enterprises are operating under more than one cloud strategy now. So, they need that for disaster recovery, for redundancy, and hybrid clouds. So, Cloud Nexus is a tremendous solution. And we've had a really good response to our booth and to the press that has come out this week. Yeah, phenomenal announcement. So, what type of enterprises is this attractive for? Pretty much any enterprise that is operating in a public cloud, they would be able to utilize Cloud Nexus. Any of the network service providers, managed service providers, system integrators, many of the attendees here at ITW are seeing this as a tremendous benefit for their end enterprises. And they're able to get on our platform and solve that for their customers. And Jeff, there's a lot of talk today about bypassing the internet. How does Console Connect help with that? Well, we have a private network and our major value proposition is using that private network to go past the internet.  Well, you bypass it because you want better security and predictability than the internet provides. And so, if you want those things, you're going to find people like SD1 providers and ours and so on. What sets us apart is a one-click connect. So, when you come on the platform, you can connect to all the cloud partners that are there, all the SaaS providers that are there. So, it's a much easier platform to come on to if you want to do direct connect. And with automation and SDN developing every day, how does Console Connect stay ahead of that curve? Well, we offer more than a simple security and predictability of performance of the network. So, the things above that is this one connect, as I just mentioned, the ability to connect to all the partners you need to connect to, firstly. Also, doing routing automation where you don't need to speak border gateway protocols and autonomous system numbers and know those things in order to make a direct connection. We make that simple for you. And so, you can connect with a simple click of the button and we provide a network over the top of that where people can correspond with the people they deal with. So, instead of dealing with Amazon, they're dealing with Juliet Amazon or they're dealing with Fred at Microsoft. It makes it a much easier connection. That's the value of the proposition. Certainly very valuable for our network operators out there. So, for our viewers who want to learn more, where can they go, Terry? They can visit us at the Console booth. Please go online, consoleconnect.com. Follow us on Twitter, on Facebook, on LinkedIn as well. Consoleconnect.com. Thank you, Terry and Jeff, for joining us here. And thank you, viewers, for tuning in to JSA TV. Happy networking.


We're now going to look at the third conditional. Consider the same situation as we've been using for the first and second conditionals, but putting it into the past. We're looking at the past result of an imaginary situation that occurred in the past. So with that in mind, the sentence that we would produce from this, if I'd won in the past, what would be in the result in the past?  So it's a completely hypothetical situation, an imaginary situation in the past that didn't occur, and this would have been the result if it had occurred in the past. So let's have a look at the structure of this conditional. If I had won, we're looking at a past perfect clause, would have taken you on a cruise. Would, could be substituted, could. Also might have taken as a past participle. Students often ask, why is this not the present perfect? I have taken you. It would be a typical present perfect sentence. However, referring back to one of the previous conditionals, if we change the pronoun from I to she, in the absence of the modal would, could, or might, present perfect, she has taken you by introducing the modal have is always used regardless of the pronoun that is used in the sentence. Let's have a look at the usages. We're looking at regrets and also used for excuses. If I'd known it was your birthday, I would have bought you a present. Let's have a look at a teaching idea that could be used for the third conditional. A nice one that can be used, can be used for other conditionals as well is tennis. For example, two students or three can work in a group and they try to use the endings of the previous sentence for the start of another example. If I'd known it was your birthday, I would have taken you for a meal.  If we had gone for a walk afterwards, we might have seen the sunset and so on and so on until one of the students is unable to complete the sentence. And then the other student is the winner and set up different situations that are appropriate for third conditional.


I don't know what the story is with that once to go. It's desperately to go. I ended up getting out of that with the money yesterday, but after I went back and I looked at the SPCE and it fell back down to the low and I just, I said, that's it. We need a quick one today. Like a five minute biggie. Quick and big, whatever this is along. I really don't want this to break 120 and 120 is a long, long, long, long, long way away, but FYI, oh, spread is good. I wish we had done options into these earnings though. I did say I thought this capped up yesterday. Does anyone remember me saying that? I, if we had, I probably would have done the 120s, but I didn't do it. And again, that was nothing but a feeling, but, first it was down. I don't know if anyone watched this. It crashed. It's like a 113, 112, and then it flipped. We can talk about that later if we have time. I mean, I literally watched it go from one direction down big to the reverse. Okay, Disney, 12280. I'm gonna be very generous. Let's do 124 by 80. Here, hit it! Hit it right now! Hit it right now if you wanted it. Hit 124, you gotta be in it right now if you want it. Do it, stop, it's 12280. 12280, this is gonna just go. 125 is the first target here in Disney. Wow, this is a good gap. Here, you could still do it if you wanted. This isn't even too late right in here, but hopefully you got it at 124, here we go. I gave the numbers as fast as I could. We had to act quickly today, and in an ideal world, we'll be out of this by 935. Because really, the market is very, very much a mess. I don't wanna look away from this because this could go right this second to 125. But yeah, see, that is a total disaster. I can't even deal with that right now. Apple, Apple is up again today and now following. All right, Disney, we have to focus, focus, focus, focus, focus. Again, if you didn't hit it right at 124, you can still do it, but if you don't do it soon, it's gonna be too late. Dream target today, and this would be 130, and I don't think that happens without the market. I don't think that happens without the market, but who knows? 125, 126, maybe 127. Here, we're definitely gonna get up to 125. Here, Disney, Disney is a great call. Apple, I'll look at when we're done. The market, I'll look at when we're done. When was the Nothing Burger? I really did that even report, because it didn't look like it even reported. Nope, I do do do do do. Nope, I didn't call any options trades in this. I didn't do a thing in this, and, ooh, glad we didn't. That was a Nothing Burger, too. I'm gonna look at this. Did this really report? So strange, no volume, didn't move. It's just bizarre. I'm not sure why we are selling off here at this point, capped up selling off. I think it's sloppy, but we're selling off pretty fast here right now, and I don't have any indication why. I mean, it's almost like you have to have the news on 24-7 now while you're trading, which is really strange. I mean, it's kind of annoying, actually, because you can't really focus on what you're doing if you have the TV on in the background all the time, but it is almost kind of like that lately with everything that's been going on. But anyways, all these evictions are being served Thursday. Thursday, so like 14,000 in New York or something. So it'd be interesting to see if Trump has some kind of executive order today. Look at this market. I am not in that. Okay, so if you didn't do it, you can do it again. It looks great, it looks fabulous. Remember what's happening here, so you don't get scared out. Someone telling you what's really going on in this here. Somebody, anybody, I'm not gonna take any more because the price will be the same. You can go long at 124, here you can do it again, but you know, we didn't get out. What's really happening here? Somebody, anybody tell me, why did that have that big red barn come down so quick? No, not profit taking. Look at this chart, you would take profits here. If you were long, you wouldn't take profits. I'm so going on the options, thank you. Thank you very much. No, this is in profit taking. This is traders trying to short this as a gap fill because of the size of the gap up. And they will not even do a boot today. Trust me, when I say this, this is a very good gap, but that's why you just had those red bars. You might have had people that went long and into the earnings. You might have had that. Here, let me show you the flip. Yeah, Matthew got it. Matthew's on his game this month. Here's what this did. Actually, wait a minute, let me show you the one minute. Stay in this though, don't even touch this as it's going. Here, this you can see it. You couldn't really see it on there. That was the tail, oops, sorry. So this is what I watched. I was like, ooh, doo-doo-doo-doo. And then I looked away, came back and it was here. So, and then this is like from 10 minutes, from 4.06 to 4.16, it had completely reversed. It was down here, 1.1336. And then it was up here, 1.2048. So, I mean, people probably did go long here. Yeah, and maybe they got out some today, but you know you have these traders that believe the gap fills work, which they don't. So try to stay with us if you can. Again, that was really, that was unique to watch actually. Oh, Zen Trader Solid, here we go, Disney. The faster this goes, the better it goes. Why, we wanna be out of stuff early today. In fact, I'm just gonna set a buzzer. I'm gonna set a bell. There used to be sounds in here. General, do you know where those sounds are? There used to be sounds in this room. There you go, I don't know where are they? Where are the sounds? I never used them in 200 years. Where are the sounds? How'd you do that? There used to be sounds in here. I need like a buzzer to go off at a certain time. It looks like. I have it or I can't find it. That is a bummer. I don't see any, anything. On the bottom, just above, were you tight? Nope, I don't have it. Aww. We need a good one. Is there a happy one? How funny is that? I'll have to ask Kathy about it. Here we go, Disney, Disney. So now Disney is open. Is it open to everyone or only people that have the annual passes? I know you can't eat food and walk around. Now you have to wear a mask. Other than that, how are they doing down there being reopened? Yeah, you do. I really have to ask Kathy why I don't have it. But that's what I need. All right, 126, 126. Come on, you can do it. 939, woo. Let's take a look at the market here we go. We're gonna get through 126. Here, I mean, Disney really has a long way to go because of the fact that when you look at the market, here, here, come on Disney. Here it goes. It went through 126. Have to get out early. That is the best, where I just said what I wanted and we got it. I said, I declare that today we will have a big fast trade. So it be said and so it be done. There it was. That was probably the morning exit people. Yay. But the option looks amazing and couldn't get to 130 in the time that I called at least the second one.


Hey, welcome to the second form of Wing Chun, Chang Qiu in this form You're gonna learn about some more hand attacks, some kicks, waist movements and a lot of really cool stuff So Chang Qiu means seeking the bridge or seeking the gap or Bridging the hands so we're gonna talk about how to use those tactics in fighting So let's get started. We're gonna start with our Lu Chi position again Just like see them tell in the first form and drop Put our hands next to our chest flushed against the front of our chest pull back our elbows down and back Drop our knees slightly and feet together Now we're gonna open our toes 45 degrees out while pivoting on the heels Now we're gonna pivot on the balls of our cliff and then Swing our heels out about 30 degrees Now we're going to do a double cross block Double cross block should be in this position. There should be about a fist or a fist and a half space between the elbow and your body now rotate the left hand into the back of your right hand into a Back fist rolling back fist. So once again in here Down double gong sound We can roll the left hand behind right in the rolling back fist Then we're gonna pull it back to our chest From here, we're gonna do our yeti Chongkun again. So bring it to the center of the chest not co-facing your target Punch it out very co-fist open up town sound who's out and bring it back right hand Fist to the center of the chest and your sternum your sternum is where the lower ribs meet in the middle Punch it out for the whole vertical fist time cell in cell and bring it back now we're going to open up our hands and Do a double thumbs up So I'm sliding it like a console, but we're using the bottom part the edge of our forearms and Our hands to press down from here, we're going to Take our we're gonna pivot to the left so we're gonna pivot to our left What you want to do is have your feet point 45 degrees that way Your body will be facing 90 degrees this way and most of your weight will be on your back leg About 60 40 60% of the back leg 40% of the front leg So once again, we hear and Then let's not do the heart. Let's not do the hands. Let's just do the feet So we're here and we're gonna pivot this way. You see my right foot doesn't move ideally Okay, now they're both 45 degrees this way and my body is 90 degrees this way Okay, so ideally only your left foot needs to move and now my body is this way Now I feed a point this way you want to do three kitties. So one to the left One to the right and now your weight is shifted to the back leg again So your left leg is now your back leg now you have 60 percent 40 percent on the front now do another shift 60 percent 40 percent on the front, right? So the first part goes like this. You're in this position We're just doing the stance right now. You're gonna pivot To the left If it's to the right, I'm facing directly right If it's to the left, I'm facing directly left Now we add the hand movements. We have our double thumbs out. You're gonna bring our Left hand over our right. So we have a double line So your arms should be about your sternum level and your shoulders should be nice and relaxed So we combine it. We're gonna combine it by pivoting and Also doing the arm movement So we're here double thumbs out We're gonna do this and at the same time get to the left I'm facing directly to the left 90 degrees and my feet are pointing 45 degrees this way now We're going to shift to this way once again Wait is on the back leg Now the feet are pointing 45 degrees this way and I'm facing directly to my right And then here we go From here, we're going to do a double fox out. So we're going to fling it up I know your fingers should be about eye level and your arm should be nice and straight Now we're gonna sink the elbows and flip our hands upwards. So from here sink your elbows and flip your hand upwards Now you use your right hand Like you're closing a book Closing your book and slap it down to your into your forearm here close the book do the same thing close this book While turning the other hand slap into your right forearm Now close the book and slap it onto your left forearm Now we're gonna open up our palms do a right palm straight the left palm comes back into this position that palm and Then right palm from here. We're going to pivot to our right So our feet are gonna go like this Now our right arm is going to do a backwards elbow Okay, so this way it'll look like this. So this will be horizontal and you want to Go back to here Well, this one close and elbows backwards. So we ended up here. We're going to elbow back and Open up like this. So it expands your chest. Your chest will expand.  Now your center line is here facing this way Even though your body is facing 45 degrees this way Your center is now here. So we're going to do this and then this will be a Wusau protecting hand right about your Elbow right next to your elbow, but also on the center line. So here's the center. Here's the center. Here's the center Now we go back into the elbow position Back into the bonk cell Wusau elbow Bonk cell Wusau. That's the third time and the fourth time Now the fourth time you want to place your Wrist right over the other wrist and Then pull back with the other with your right arm to your chest and punch this out straight So now I'm still in this position. My feet is still pointing point five degrees But now my body is facing directly this way to the right And I have a vertical punch to my right From here, we go back up to our middle stance Our left hand doesn't box up up to the eye level and Then we're going to bring this elbow and form directly back into this position Wusau Wusau So here and bring it directly here Almost like you're chopping it back down But make sure you don't chop this way.  So scrape and pull At the same time while rotating Both your right and left this So fox out. I mean the to sell Will be a chop to the net We're going to open our palms Do a hoon sell and Pull it back Don't worry. There's a lot of stuff, but we can do it again on the right side. So we show you show you again You do a double thumbs up Now we're going to flip our Right on top of our left last time it was left over right this time It's going to be that right over left and we're going to pivot to the right Our feet will be 45 degrees this way and our bodies will be 90 degrees this way Give it to the left Give it to the right now do a fox out thinking about I Your fingers should be eye level stay to elbows Now do close the book with your left hand on your right hand now Close it onto your left and now close it to your right now do Palm chain palm to palm left right left now make an elbow and Pivot to the left and Elbow backwards this one also that was a elbows backward expands your chest We're going to give it to our right This becomes a bonk cell and who sell So bonk cell is like this Who sounds like this? You look from the top Here's the angles This will be straight is a hundred three five degrees is another hundred three five degrees and your fingers are pointed That way straight that way The boost up will be here right next to your elbow and right in your center line So we're going to do our second one. So this elbow again This is the fist and then we're gonna elbow that way.  What's out? I'll go this way. That's the third time also was out Not fourth time the fourth time. We're going to place on Wrists over the other wrist with a vertical punch. We do our vertical punch while pulling back with our other left hand From here Center center of stance to a five-cell up to the eyes Do a chums up so it leads with the elbow straight down here Place your left hand on the hook of your elbow scrape with your left Turn and twist and pull with your right and chop to the neck with your left hand To a time cell himself and so could So that's the first section. I'll tell you


The strength of my course is that we have an industry involvement in the delivery of the course. So we have CEOs, directors, deputy CEOs who come in and actually deliver the courses. The best thing about my course is that the institution resources and the facilities are really high standard. It trains you to think as a professional economist. It offers various pathways that you can take after completing the course. Staff is highly qualified and lectures are not one way and it's very interactive. My professors, they have pushed me to the level that I think I should be. So there's a lot of diversity in the development studies program offered at Melbourne Uni. Like I've taken subjects from global health to climate change and environment and human rights, which is definitely going to help me in my careers.


What is up Marvel Squad and welcome back to our channel. If you guys are new to me, you should go hit that subscribe button and turn on your post notifications so you can notify every single time we post. Also, we're doing an iPhone 11 giveaway. So if you want to be answered, all you have to do is make sure to follow me and Bill on Instagram. Make sure to subscribe. Make sure to show your love throughout all of our social medias. We'll be announcing the winner this Sunday. So we are really excited and we cannot wait for somebody to receive an iPhone 11. But as we rub with the title, today Bill is going to be experiencing his first period. Disclaimer, do not take it funds to anything that goes on this video. This is just for fun and Bill is going to basically experience a period for a day and act like, basically kind of reenact how I act on my period because I'm very emotional. I'm dramatic.  So keep in mind to experience all that through this video. I want to give a huge shout out to Madeline Steven. Madeline did this on Steven on their channel. They created this whole period of experiencing, boyfriend experience is a period for a day video. Basically what we're going to be doing in this video is I'm going to do a birth stimulator on him. So it's kind of basically like a period cramps except I don't really know how in depth these pains go in but he's basically going to experience how we experience, what we experience with our cramps. I don't think I want to see Bill in pain but I want Bill to have a better understanding on what girls have to go through each month because it's not fun.  Worse cramps in my entire life. Sorry Bill, but you're having an experience that today.  It's going to be up to 5,000 likes. Can we do that? Let's do this for Bill's pain because he's going to be feeling pain a little bit. Bill is currently not home. He's at work. He's going to be home in like 20 minutes. I got him some period essentials that he's going to need for his period. So I got at Walgreens because I got some pads because you need these for nighttime and some tampons.  So I got Bill some salted caramel ice cream, butter and dairy. This is super good. We really like this kind. That's basically what I got him. All right guys. So the gift bag is made. Bill should be home any minute. So when he gets home, he's going to open this up and the video is going to get going. I'm really excited. I think this video is going to be really funny. So this post notification show is going to go to somebody that's on TikTok. Their name is Names underscore five eight one. Thank you so much Names for being so supportive on our TikTok. We really do appreciate and love you. All right guys. So I'm going to get ready. And when Bill gets here, I will see you guys then. I'm so excited. All right Marvel Squad. So Bill's finally here. I have no idea what's going on. Can you guess what it is? All I know is there's a gift in front of me. Is this for me? Yeah. Can you guess what it is?  Like are these plane tickets? I don't know. You might want to open it up and see what it is. Where are we going? Are they actually plane tickets? What is this? What is it? Bill? This looks like some some pads. For girls. Okay. Oh there's ice cream. Thank you. Tampons? Tampons. Can you guess? You're pregnant. No you got your first period. You're going to experience a period. You're on your period? No you got it. This is stuff for a period. You got your first period. So I got you stuff to help you on your first day. This is the surprise? Yes. Yes. You're experiencing a period for the day. So you're going to go through a day with what girls go through. So you're going to have to go through. So what I brought down here was a birth simulator that is going to make the cramps like a period.  We used this two years ago. A year and a half ago. It's terrible. And you didn't even have it on the full setting.  You are not going full. Yes I am because I had a bad period last month and I need you to experience what girls go through. Wait wait wait.  I don't have a... You're going to go change your tampon. You need to put tampon up there because you just got your period. What?  No you need to put you have your period. You just got your first day. I don't have girl part. It doesn't matter but okay. So I have to be crabby and yelling all the time and angry and crying over nothing. Yes. I get to do that to you. Yes. Alright so I'm going to put this on you. You're putting them on me now? Yes because you're going to experience your first cramp and you have to go up to change your tampon. Wait so you're going to be pressing this thing the whole day? Well you're going to see.  It's about to start in a couple seconds so stay tuned. Alright marble squad here is the period stimulator. I put it right on his lower stomach and your period is about to begin. It doesn't just pop up. It pops up randomly. Yes it does. You're going to experience what we go through. I'd be able to handle it. Alright that's what you want to believe. You want to say that again? You want to say that again?  Wait so if you change your tampon I'm going to keep umping it.   We can't shut it off unless we take medicine. So how do you feel? It's not that bad. I'm going to open up a little bit more and show you how it really feels. Sometimes I get very excruciating pains where I have to go to the toilet and stay in the toilet for a few minutes. Now you get to experience that. Say that you feel their pain. Go back and turn it down till you say it. Say you feel your pain. Girls I really I'm being totally honest. Say it or I'm going to ump it up. Say it or I'm going to ump it up. Beards are not this bad. Stop. Okay reset I'm going to ump it up. Beards are not that bad. Bill yes they are. What do I do now? I'm in the bathroom. How do you even work these?  It doesn't feel good. It's hooked up right here. If you see it, it moves. It's vibrating. I want the blue one. How would you work a tampon? If that's the way you think we open them up that's totally the wrong way. Turn it down. No. Now stay on the toilet. The pains don't feel good do they? You say that we go yeah. The periods are literally not this bad. Like right now it's going boom. Bill this is what it feels like to have birth and have periods yes it does. The cramps don't go. Bill yeah it does. It literally feels like you're shocking me.  It doesn't feel good. Just teach me how to use this. I just snapped it. Is that good? Yeah I'm in a place here you know what you're doing. She turned it down. Okay I'll turn it down for a little bit but we don't get to just tell period and turn it down. Okay so what do I do with this?  My nose? How would you put a tampon? How do you apply it? I'm guessing you pull this string. No. How would you pull a string when you have an adapter like that? If you need to push it out. And it shoots up. What's the string for? The string is so when you take it out. Now don't worry about the string. And then you're done? Yes. It soaks up blood instantly. Raya. Ow. Now your nose is how I was the other day. Okay so how often do you have to change these? Every like depending on how heavy it is. Every three to six hours. Okay wow. Take it off in this setting. I don't like it. It's going like this. It's going like this. It's like someone is stabbing you. Okay come on.  So you're in a period. Right. I don't like this setting. No because it's just. Okay. Okay right. Uncalled for. Do you want to say that girls don't go through a hard time? No. Raya please stop. Turn it off.  Do you know how bad that hurts? Everyday. Okay if girls have to go through that I feel for you but there's no way that it's that bad. Yes it is. Can you give me my ice cream? That's all I want right now. I just want to cry. I'm a little baby. I need a spoon. I don't know go find me a spoon. You don't even do this stuff for me. You know how long it takes for you to get up on my periods to do stuff like this? You should be lucky. I always do stuff. I know exactly how it feels. It looks like I'm giving birth. Periods will go up to 0 to 100 real quick. So I'm going to put up to 100 real quick. No we were just there. Right please stop. Stop stop stop. Stop stop. That is actually not cool.  Don't turn it off. Periods don't fight back. Until you stop saying that I'm not going to keep pulling it up to full throttle. Don't put it to full. I'm literally going to puke everywhere. Stop. Okay then don't say it. Tell us a girl something. Stop. Turn it off. I can't talk. That is terrible. I just want you guys to know. If your periods are actually that bad I feel for you guys. They are bad. I can't even walk. We can't walk. I'll be laying in bed and I have to be in a ball. I can't move. Yes. Well at least you guys can get loving. So if you're a girl having a bad period. All I can take out from this is find yourself a loving man that will do anything for you. Because if I was on my period I would just want to lay here and do nothing. Right? Lay here and do nothing. Yeah that's what we go through. Imagine this once a month babe. Stop. Imagine it once a month. Stop. Once a month. Yes we get it once a month. Every month. Okay but why do you guys blame it on your period? Yes it's true. Oh I'm only mad because I'm getting my period in 10 weeks. That's literally you. I'm getting my period next week. That's why. Yeah we do. Because Bill you don't understand. Not only do we get period cramps not about the cramps it's about the PMS we get the week before. This is literally the worst surprise ever. Well you know what you have your first period for the day. You get to experience a period where us girls go through the next time and on my period you have a little better understanding of what I go through. I wish that, wait can we actually hook this machine up to you? No. Marvel Squad can we please? No. I want you to see if it actually works. No. No. No. No you're not doing that to me. Because if your period is actually that bad I feel for you I'm so sorry. Because I don't think any guy understands really how hard it is. And I still don't because there's no way that max level was any period. Yes it was. That max max level. I don't want to experience that. Please don't make me do that. Give me it. Give me it. Because I didn't know. Trust me it's not bad. I'm picking the speed because I don't want it. She'll see you right now. Are you ready? Oh my gosh. I don't like it. I don't like it. Here try this. I told you. Thank you so much for watching this video. I hope you guys found this amusing.  I told you it hurts. It hurts. I told you. And you did it on the intensity 10 times. Okay but I experienced those types of pain. Yeah I know. Maybe not exactly like swapping but scraping yes. So that was a real pain. I hope you guys loved the video. Make sure to give it a thumbs up. Let's try to give this video the 5000 likes for my pain because I was in pain. I was in pain too that was painful. I will give you that. Well thank you for just putting in on full speed. You go through some stuff. I don't understand why it hurts. I don't understand still why you are so moody. Why you are so annoying sometimes. Well funny. But we love you. You want to see more videos like this? Comment down below some more video ideas. Putting the birth stimulator on my girlfriend while she sleeps. No. Don't even do that. I'm hiding it from you. No. Alright guys we'll see you in the next video. See you then.


What's going on guys welcome back to the channel critical overload here So we're gonna be talking about the exorcist believer in this video once again here today So we know that the trailer for the film dropped yesterday We know over the last couple of days last week at this point or so we got in the poster got an updated plot synopsis Got a nice glimpse at the film and a lot of people myself included a lot of people did enjoy it for what it was me and a bunch of other people thought it was subpar to Just looks like your standard horror sequel that isn't up to par with a movie like the exorcist That came out back in the 70s. It's just hard to recreate that type of magic. Well for these for this creative team I would say that them doing Halloween. I could say is more believable than What they're planning to do with the exorcist is that supposed to be a trilogy? So what we're gonna discuss though primarily in this video is Linda Blair and her return or lack thereof as Reagan McNeil in the upcoming Exorcist believer sequel that's dropping in October. So earlier this year a Bloody discussing article came out stating that Jeff Snyder who if many of you know that name, you know that that's a scooper Insider Jeff Snyder Reported that Linda Blair will reprise her role as Reagan McNeil Above the line has exclusively learned Sources say that Blair was only on set for a few days So she's not in the film all that much but her return to the franchise should make fans headspin with the excitement Now it's important to note that Blumhouse spokesperson only confirmed to Snyder that Blair served as an advisor on the new movie Refusing to confirm or deny an on-screen appearance David Gordon Green just recently Confirmed that this advisor stuff is true yesterday when the trailer dropped for the exorcist believer During a recent interview with Entertainment Weekly when asked if Blair will appear in the exorcist believer or the subsequent sequels to the film Green sidesteps the question but reveals that the film alludes to her character in a number of ways The director does confirm the reports that Blair visited the set We were lucky and had Linda as a technical advisor She helped us bring excellent performances out of young actresses It was really valuable having a relationship with her and being able to get her as part of this conversation So I know the question I've seen over on Reddit Twitter a lot of other places down in my comment section is is Reagan in this movie or not is Linda back. Well, that's the thing. We'll have to wait and see in October However, Green saying that the film a loser character in a number of ways is true We all know this since her mother is back and basically filling in a role that many people would argue is far more believable for Reagan to be in and not her mother since Chris has written a book about her trauma and She's become kind of fascinated with the idea of exorcisms as much as That is still believable for Chris herself the fascination part and wanting to be informed on other cultures That relate to exorcisms and stuff that your daughter unfortunately went through as much as that's still a believable aspect of her arc There for her anyway It would have been far more believable for the character that went through it all in the first movie Which is none other than Reagan who was played brilliantly by Linda Blair so Reagan's name we also see in the trailer spotted being carved out at some point On on the bed. It looks like it is Here's what I know Test screening folks are backing up with Jeff Snyder reported earlier in this year and even prior to Jeff's own reports about Linda I was tipped off about Linda's return sometime in the later half of 2022 might have been a little bit earlier by a reliable individual But then the test screening folks just filled in the gaps by telling me her role and what she's present for So she was involved for the people who already saw this film for test purpose test purposes Reagan is in the movie Linda Blair did have a couple of scenes Jeff Snyder's report in this regard is true now Why is she in the trailer? Because as Snyder's reports claim Blair was only used briefly and according to the notes that I have from the test screening people It's not even enough to fill two lines on a piece of paper if I wanted to just to give an example of How little this return see seems to be in the overall story so Advertising her and marketing her return as Reagan only for her to have less than a minute of screen presence possibly That's just not worth it Taking the taking to keep it a surprise for most viewers approach like Tony Todd's return in Candyman That's more reasonable because her return is on the same playing field as Todd's return as Daniel in the Candyman Legacy sequel we got in 2021 Now back in that same year 2021 Blair did tweet this out about her potential return as Reagan She said to all of my fans asking about my involvement in the new exorcist reboot as of now There's not been any discussion about me participating or reprising my role I wish all of those involved the best and I appreciate the loyalty and passion the fans have for the exorcist and my character So clearly things change but likely not in a way that fans that wanted to see Reagan in a substantial role might have expected She's in the movie guys, but if she doesn't appear that's because it was cut That's how little she is in the movie these test folks. They're not lying about the film I know they are not lying because the trailer has confirmed a lot of their claims those of you follow me on Twitter You saw that I put out a tweet To associate one of the things that have come out publicly now that they told me about I lined that up with the Plot synopsis that came out so these folks are not lying people who saw this movie already They saw Reagan Reagan did appear But her role is so insignificant that Reagan could easily be cut from the final product that we now get in October But from what I know from the test screenings as well is that that was one of the more positive things from them So I don't know why it would get cut if anything Keep it in so it can have the same reaction or same response from the audiences Like how Tony Todd's brief appearance at the end of Candy Man had a very positive reaction from audiences If it's not cut Reagan's return that being it's just a return that will make those that want to see her happy But it is completely unnecessary and just another nostalgia tactic. I'm being quite honest She has that little significance to the story So she is in a cut of the film, but if she doesn't appear in October They just cut her out She's she's in the movie We might not even have them come out and confirm it if they cut her But chances are they are not going to cut her if they do not have her in the movie I'm telling you that's because her scenes were cut. She shot scenes for this movie She's just not very significant as much as it seems her mother is going to be because that's why her mother has highlighted more So in the trailer you guys can let me know what you think about this down the comment section below If you haven't already of course, make sure you go ahead and subscribe turn on post notifications that you never miss a video in the Description I will have links to all my social media accounts. I am on Facebook Twitter and Instagram You can message me there, of course, let me know is any movies news or if you'd like me to cover in the future And with all that in mind guys, I will see you in the next video


Well, if you think about the last two years, I'd say we've had one dominant headline across much of North Dakota, really, and that'd have to be grasshoppers. Grasshoppers, grasshoppers, grasshoppers, that's really been the focal point, especially if you live really from Highway 83 to the West. The last couple years, that has been the number one phone call I've really taken is grasshopper issues. They've really been a big deal. They can lead to some defoliation, especially early on in the growing season. As we get to this time of year, you know, we're having a later harvest, especially with many of our small grains. What we're seeing is some of these adult grasshoppers can even result in clipping or cutting off the top of the heads to some of those small grains. So really, they're impactful all year long, and they can have a yield impact all year long as a result of that. One of the big questions I've been getting over this last year is, you know, we've had a little bit more moisture this year, and doesn't usually moisture result in death of grasshoppers? Well, the simple answer to that is no. It's actually a little bit more complicated. When you think about grasshoppers as a whole and, you know, a lot of other insects drought tends to allow populations to explode. One, crops become more stressed out. That makes plants a little bit more vulnerable to insects like that of grasshoppers. Two, if you think about a normal growing season that has a little bit of moisture, that helps promote disease, not just in crops, but in insect populations as well. When you have a dry year like we saw in 2021, you really lose the impact of that disease in grasshopper populations. So as a result, that's one of those promotions of reduction in grasshopper populations that we really lost these last two years. So with that being said, moisture in 2022, we didn't really see impact or rebuilding of that disease impact. The main reason was the little bit of moisture we did get it interact with evaporated fairly quickly. The sun would come out in a pretty quick period of time to help dry that back out. So we continue to see this explosion of grasshopper building. If I think about Western North Dakota as a whole, there are really three different areas that I would say not just had high populations, but maybe even severe populations. That would, of course, be Southeast of Minot, looking through the Sawyer and Logan areas, looking near Southwest Ward County, Rider-McCody, and then pretty a large area really from Grenoia, North Dakota down to about Wofford City. Populations were very impactful. Some growers really resulted in three, four, maybe even five chemical applications at those field sites as economic threshold seemed to return very rapidly. One of the big questions I've been getting is what can we do to tackle this for next year? Can I go spray my fields or grass areas right now to control them? The answer is you could do that, but you may not get the response that you want. Really because populations are so high and they're so mobile, they really reinvest in area in a fairly short period of time. So my suggestion to you right now is take note of where the big populations are right now and also take note of where your late maturing crops are. Sunflowers are a great example of that, soybean, corn, just to name a few. As we are removing the early maturing crops from the field through harvest, those grass hoppers are moving to those later maturing crops and becoming more impactful. Those will become more sites where more egg laying can take place looking to next year. What populations will look like next year? We'll have a little bit of a bearing on what our winter looks like. If we could have a couple weeks of bitter cold before the snow, that may actually hurt populations going into the early season next year. However, any snow that falls will serve as a thermal blanket protecting some of those populations. So as we get to the early spring next year, border chemical control may be needed in some areas, especially if economic threshold is met. So what does 2023 hold for us? I guess time will tell along with the weather conditions.


Hey, so I'm Daniel Reitz of DIYBookScanner.org and this is the laser-cut book scanner that we're releasing under the GPL today. It's a joint project between myself and Dario de Mora. I created the original design and Dario documented it and made it into proper artwork. And the way it works is really simple.  Turn a page and you've captured both pages. And you just sort of do this ad nauseam until the book is over. It takes about one, you can get about 400 pages an hour. That's sort of the going rate. You can do more or less depending on the difficulty of the book itself. How hard it is to turn the pages and so on. If you have your own laser it costs you next to nothing. If you had to use a laser cutting service it would be different. The standard DIY book scanners are in the range of three to six hundred dollars with cameras and everything. This one, the plywood was 50 bucks and the cameras were 200 bucks. The miscellaneous hardware was another 50 bucks. So it sort of fell in the same range as my first one. That's because I have the laser. Everything is available at diybookscanner.org.


Going on everyone, Sam here with Layton Sports Cards. We're up in 23 tops, Chrome Black, baseball, hobby, 12 box, case number 9, pick your team style. It's up for Mars. Names of our list of names and teams, Allen H, Angels, Krispy, Cardinals, Di-K-O, Mariners, Darren R, Astros, Metz, Dugsy with the Royals, Dylan J, Braves, Eric L, White Sox, Greg M, Red Sox Dodgers, Marlins, Padres, Jason H with the Cubs, Jeremy H, Twins, John Thanh, Philly's, Jordan Nenrocky, Justin J, Pirates, Paul K, Ray's, Ryan B, Blue J, Scott J, Giant's Nets, Stephanie with the Reds, Steven J, Orioles, Guardians, Tigers, Athletics, Brewers, Timothy M with the Inks, Timothy H, D-Bax and Vaughn with the Rangers. So good luck everybody. Let's do it. We're like on Wednesday nights because you used to work Wednesday nights. Sean will come in and troll on channel 2 as Layton Sports Cards. Yeah. I don't know what I'm just thinking of this one, it's so funny, but Kevin Stone Rookie, 2-1-99 as Vinny Pasconzino, Refractor, and Brian Rathio Rookie. Nice, Ichiro Otto, congrats Mariners, wow dude, killing it right now. There you go, Di-K-O, congrats buddy, he just goes in and they're just, they're sitting there waiting for an order to come in, he just goes, do you two speak English? I think he was a battered Kyle, comes in on Layton Channel 2 and goes, yes we do. That is Zack Neto Rookie, oh boy, more, more, you can show them, 150 Bryce Harper and Emmanuel Valves. See some of them. Some of them you've already shown. All right, we're just going to show a couple Almanac Cards real quick. That's nasty, Vaughn Grissom, PSA 10, Levus we've seen, ooh Lamar, Power Surge Kaboom CMC, oh, okay, that is yeah, we saw the 8-in, Walter Payton 76 tops, nice one there, PSA 5, we saw the Halliburton, Luham, negative to 100, why is this slab so thick? Ah, CJ Stroud, Kenneth Walker, one of one, wow Chet, Jesus to 75, and then we saw the Pete Rose, so yeah, that's just some of the cards that are in that Almanac, we've showed like 20 of them, 20 of the 100, and another Mariano, nice one there for the Yanks, let's go dude, killing it right now. You know, like chew on this power button, where to go? Oh, it's like it's like in, right, yeah, A Shams with the O's and a couple of PYT cases, Thane with the Cubs, Candler picking up two random team spots, Fareed D with a Star Wars Masterwork, and John M. with a random team spot as well, so good luck everybody. Almanac will be Monday night remarks, Monday night, Personals, 100 cards, 169.99 a spot, Monday night with myself, Forrest and I are switching from Monday night and morning. Y'all know Star Wars tonight is going to be insane because it's marinating and didn't fill last night. Yup, it's going to be insane, Casey Schmidt, Shohei to 99 on the green, what's up Mitchell? Matt Mervis, yeah, you know what I thought about it, and Zekeal Doran to 150, refractor auto, nice one there Vaughn, got an orange coming up here, green Jordan Walker to 99, green wave, gold to 50, Chris Bryant for the Rockies, nice one there, and then Boba Shep base, orange Matthew Libertor, rookie auto, 3 of 25, congrats, Cardinals, there you go, STL, very nice, I have to say Jordan we got a pink as well, Magenta, Danny Machado, Jordan, and Raffy Devers, 3 of 10, that's on that Red Sox, on the Magenta, Magentas are clean in this man, and an orange of Gabby Moreno, 16 of 25 Super Futures, congrats Arizona, let's go D-backs, very nice, that's awesome dude, thank you Phillip, 3 spots in the 3 case break, appreciate you buddy of the Bowman 3 case break, the Choice Jumbo and Super Jumbo, right, Wander, refractor Joey Meneses to 199, and Luis Castillo, that is a Fernando Tates Jr. going to the Padres, let's go man, another great case we've got here, great case, who are the Padres in this one, that is going to be, I believe Greg, yep Greg, good stuff Greg, it's not an average giant, Brandon Fott, Variation, Jordan Walker, nice one there for the Cardinals, and then a blue Asturio Ruiz to 75 for the A's, that is a green Luis Castillo for the Mariners, 90 of 99, congrats Seattle, Seattle, as Waldo Cabrera rookie, refractor Vaughn Grissom to 199 for the Braves, and Shohei, that is a National Jeter Downs to 150, there you go Scott, congrats on that, two, one, 50, yes sir, short, still alive from the 30 case, yesterday it was a recovery day, for sure, yesterday was, played a lot of Grand Theft Auto yesterday, it was awesome, get ready for six, I can't wait dude, well they added a new update into five, it's a new business, the salvage yard which is a lot of fun, really perversions, it's been, the new update is good, I've had fun with the new update for sure, Jazz Chisel, that is a Yuri Perez, Gold Midi Diamonds to 50 for the Marlins, nice one there, and Riley Green, and we've got Bassado for the Red Sox, Big Poppy, David Ortiz, congrats on that, Boston, that will work Greg, congrats Greg, hi Steve, I'm feeling something man, I'm feeling something Steve, let's see it, come on, Rondo Cunha, Purple Midi Diamonds to 150, Luis Castillo, and Rafi Devers, and we've got Chipper Jones for the Braves, there we go man, congrats on that one, yeah the the graphics look insane, do you saw the trailer for it?