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Kinetic And Thermodynamic Control Of Reactions Pdf

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14.3: Kinetic vs. Thermodynamic Control of Reactions

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Current timeTotal duration Google Classroom Facebook Twitter. Video transcript In this video, I want to go ahead and talk about thermodynamics and kinetics.

I remember that when I was first learning about these two things in the context of chemical reactions, I used to hear phrases like, oh, this chemical reaction-- let's say hypothetically A going to B-- is kinetically favorable, so it must proceed. But then the next day when I go to class, I'd hear another statement that said, oh, well this reaction A going to B is thermodynamically favorable, so it must proceed. So to get it started, I've already drawn two plots so that we can plot out the free energy change that occurs for the forward reaction-- we'll do that on the left side-- and the reverse reaction, which we'll do on the right side.

So before we get into that, let's go ahead and label our axes. Our y-axis in both cases will be measuring free energy, which is in units of joules. Then our x-axis will be an abstract dimension called the reaction coordinate, which essentially allows us to monitor the progress of a reaction. So now I'm going to go ahead and say that the forward reaction we'll draw out in this teal color. And the reverse reaction we'll go ahead and draw out in this pink color.

So let's go ahead and start with the forward reaction. So I'm just going to go ahead and say that the forward reaction has a negative delta G value.

So remember that means it's spontaneous, and visually that means that our reactants start off at a higher free energy than our products. Now, this of course means that the reverse reaction, which will have the same magnitude of delta G, that is the free energy change, will be at the same numerical value. But of course, since the reaction is going the opposite direction, the sign of delta G will be now positive. And visually, we're saying essentially that our reactant, which in this case is B, starts our at a lower free energy than our product, which is A.

Now thus far in drawing this free energy diagram, we've just been talking about thermodynamics. But it turns out that there is also a kinetic energy barrier for the conversion of reactants to products, regardless of whether the reaction is spontaneous or non-spontaneous. This kinetic barrier of energy is referred to as the free energy of activation, or simply activation energy. So I'm going to go ahead and put in parentheses E sub A, which we'll say stands for activation energy.

And remember that delta G of course is talking about thermodynamics. With that said, let's go ahead and add this kinetic energy barrier to our diagrams. And we can do this by understanding that the activation energy is defined as the amount of energy that is required to form a high-energy intermediate during the course of the reactions.

In other words, in our hypothetical reaction of A going to B, it proceeds through an intermediate, that is a high-energy chemical product that won't last very long, but is important in the conversion of A to B or vice versa.

So in our diagrams here, we can go ahead and indicate that there is some intermediate, so in between our reactants and our products, that is at much higher energy than everything else. And we can go ahead and then connect the dots. So go ahead and essentially draw a line from reactants to products that includes our high-energy intermediate. And this ultimately allows us to see the presence of the activation energy as well as the change in free energy.

So let's go ahead and actually label these things. So on the left side here, remember our change in free energy, which is looking at our reactants compared to our products-- we're ignoring this little bump. The change in free energy, which I'm going to indicate with the green line, extends between these two points. And the same on the right side, just again extending between the start and endpoints of our reactions. So I'll go ahead and indicate that this green line in both cases refers to our delta G values.

And in a different color, let's say red, I'm going to go ahead and indicate the activation energy, which takes into account the change in energy between the high-energy intermediate and the reactants. So in the case on the left, that change is indicated here with red. And on the right side, the change between the intermediate and the reactant is a bit longer, so we'll go ahead and indicate that here.

Now, activation energy is an important quantity to take into account, because in order for molecules to react, they must have enough energy to overcome this activation energy barrier. Essentially, in the case of a spontaneous reaction for example, I think of it like the energy one needs to get a ball to start rolling down a hill.

We all know that gravity will make a ball roll down a hill, which is like a negative delta G value, it's telling us that the reaction is very thermodynamically favorable. But we need to sometimes give the ball push in order for the reaction to occur.

And so that's kind of this little help that it needs to go over before it can actually proceed. For a non-spontaneous reaction, the idea is essentially the same. We still need to have some activation energy.

But in addition, because it requires an input of energy, we can think about it as rolling ball up a hill instead of down a hill. Now in general, the idea is that the lower this free energy change, the faster a reaction will occur. And remember I'm saying faster, so I'm talking about kinetics. I'm talking about the rate of a reaction. So just to write that out, the activation energy, the smaller it is, the faster the reaction will proceed.

Now in biochemistry in particular, it's really important to distinguish between these two terms of thermodynamics and kinetics, which we've drawn out in our diagrams as the change in delta G over the change in activation energy.

Because many biochemical reactions in our body are kinetically unfavorable, that is to say they have a very high energy of activation even if they are thermodynamically favorable. This is why our bodies have enzymes, which essentially lower the activation energy of a reaction. So I went ahead and drew a dotted white line that's a little bit lower, so you can see that when an enzyme is present, the height of the barrier has decreased.

And if it's decreased, the reaction will proceed faster. Now, there's one analogy that my chemistry professor used to tell us all the time that really helped me understand the interplay between kinetics and thermodynamics as they apply to whether or not a reaction will occur.

So I'm going to go ahead and scroll down so we can briefly talk about this analogy, which is I think a fun way to think about all of this. So let's say you went to a dating website, because you were looking for your perfect match. And this dating website told you that your perfect match lived halfway across the globe.

And this is such a perfect match, and they have all these algorithms. And if this match were a chemical equation, we would say that you had a very, very negative delta G value. That means you would be very, very spontaneous. But you live halfway around the world, so in terms of chemistry language, we might say that you are kinetically limited. That is to say, you don't have any way of actually travelling halfway across the world to meet your special someone.

So we might say that you have a very high activation energy. So from this discussion, perhaps the biggest take-away is that neither kinetics nor thermodynamics solely determines whether a reaction will proceed. It's important to take both into account. Now one of the applications of this, in biochemistry especially, is remember that enzymes lower the activation energy of a reaction.

So we can think of enzymes as light switches. They can regulate whether a reaction will proceed or won't proceed. But, of course, a light switch only works if the light bulb itself is working. And so the metaphor for the working light bulb is saying that a reaction has a negative delta G value. Or if light bulb is not working, we're saying that the delta G value is positive. That is, it requires a new battery or energy for the reaction to proceed.

Thermodynamics vs kinetics

Thermodynamic reaction control or kinetic reaction control in a chemical reaction can decide the composition in a reaction product mixture when competing pathways lead to different products and the reaction conditions influence the selectivity or stereoselectivity. The distinction is relevant when product A forms faster than product B because the activation energy for product A is lower than that for product B , yet product B is more stable. In such a case A is the kinetic product and is favoured under kinetic control and B is the thermodynamic product and is favoured under thermodynamic control. The conditions of the reaction, such as temperature, pressure, or solvent, affect which reaction pathway may be favored: either the kinetically controlled or the thermodynamically controlled one. Note this is only true if the activation energy of the two pathways differ, with one pathway having a lower E a energy of activation than the other.

The potential outcome of a reaction is usually influenced by two factors:. This will be the faster reaction since it has a lower energy more stable transition state, and therefore a lower activation barrier. Therefore, product 1, P1 is the kinetic product the product that forms the fastest. Reaction 2 via pathway 2 blue generates product 2 P2 via transition state 2 TS2. P2 is the more stable product since P2 is at a lower energy than P1.

While we are building a new and improved webshop, please click below to purchase this content via our partner CCC and their Rightfind service. You will need to register with a RightFind account to finalise the purchase. As part of these celebrations, we are offering free access to the virtual issue of PAC: 60 seminal papers published in PAC over the past 60 years. Pure and Applied Chemistry is the official monthly Journal of IUPAC, with responsibility for publishing works arising from those international scientific events and projects that are sponsored and undertaken by the Union. The policy is to publish highly topical and credible works at the forefront of all aspects of pure and applied chemistry, and the attendant goal is to promote widespread acceptance of the Journal as an authoritative and indispensable holding in academic and institutional libraries.

Thermodynamic and Kinetic Products

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Reactions of Dienes: 1,2 and 1,4 Addition. More On 1,2 and 1,4 Additions To Dienes. First, an explanation. My dad died. Life is now returning to normal.

Because thermodynamics deals with state functions, it can be used to describe the overall properties, behavior, and equilibrium composition of a system. It is not concerned with the particular pathway by which physical or chemical changes occur, however, so it cannot address the rate at which a particular process will occur. Although thermodynamics provides a significant constraint on what can occur during a reaction process, it does not describe the detailed steps of what actually occurs on an atomic or a molecular level. Thermodynamics focuses on the energetics of the products and the reactants, whereas kinetics focuses on the pathway from reactants to products. Table

Thermodynamic versus kinetic reaction control

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Like nonconjugated dienes, conjugated dienes are subject to attack by electrophiles. In fact, conjugated electrophiles experience relatively greater kinetic reactivity when reacted with electrophiles than nonconjugated dienes do. Upon electrophilic addition, the conjugated diene forms a mixture of two products—the kinetic product and the thermodynamic product—whose ratio is determined by the conditions of reaction.


At low temperature, the reaction is under kinetic control (rate, irreversible conditions) and the major product is that from the fastest reaction. · At high temperature.


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Kurchatov Sq. Rovisco Pais, Lisbon , Portugal E-mail: max mail. Therefore, a very rare and unexpected example of full kinetic and thermodynamic control in the Diels—Alder reaction is reported in this paper. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes. Information about reproducing material from RSC articles with different licences is available on our Permission Requests page. Fetching data from CrossRef.

Стратмор сидел наверху с береттой в руке. Он перечитал свою записку и положил на пол возле. То, что он собирался сделать, несомненно, было проявлением малодушия.

Этот фонд был для Стратмора постоянной головной болью.

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