What is the Difference Between a Transition State and an intermediate? Organic Chemistry > Reactivity: Kinetics, Ther... Understanding the difference between the transition state and an intermediate will help you in drawing the mechanisms, explaining the mechanistic differences, and understanding what exactly is going on in the reaction. So, let’s start by looking at the picture that, I'm sure, you have seen quite a few times by now:eo =Transition States —e Tot LO Intermediate PrA Products Reaction Coordinate 1 On this diagram we see: e the x-axis that is a reaction coordinate: a loosely defined term meaning the reaction progress in the general direction from the starting materials or reagents (SM) to the products (Pr).e the energy curve describing the energy states of the components at a certain point in the reaction. e the transition states (TS) and an intermediate (I). Among other things that you typically see in these diagrams are the change in energy and the activation energy, which are not too important for us at the moment. Let’s focus on the curve itself for right now. I've pointed out the transition states and the intermediate there, but what are those exactly?Definition of a Transition State Transition state is the highest point (or points) on the reaction coordinate diagram. Those are the “peaks” or the “hills” in the picture. A more strict definition is that a transition state is a molecular entity that has a lifetime no longer than a vibration that exhibits some structural characteristics of both the reactants and the products. As | couldn't find the “official” definition, so I've adapted this one from the Anslyn & Dougherty'’s Modern Physical Organic Chemistry book. | think, it describes the transition state the best:¢ it's neither the reactant nor it is a product « it resembles both to some extent, and « it's not something that can be isolated (exists only a vibration-long) The best analogy | can think to describe a transition state is this: imagine yourself merrily hopping down the alley in a park. That moment in time, when you're up in the air in the mid-jump is your transition state! You cannot “catch” that state when you're suspended in the midair, it's neither your right leg, nor it is your left leg step... it's something in between. Same applies to transition states: they are somewhere in between.Definition of an \ntermediate Intermediate is a comparatively long-lived species that can be experimentally detected and characterized. This means that an intermediate is an actual molecule or an ion that you can work with, sometimes even isolate. That's you freezing in space as you've landed on one foot while hopping in a park. It’s not the beginning of your journey (reactants), nor it is the end (products). Instead, it’s a relatively stable midpoint (intermediate).It is also very important to remember that a reaction doesn’t have to have an intermediate! You may or may not have one depending on the nature and the mechanism of the reaction. There are plenty of single-step reactions that have no intermediates at all. A typical first semester organic chemistry example is an SN2 reaction that involves no intermediate whatsoever (we'll see an example later in this post). You will always have a transition state though! Every reaction, no matter how simple it might be, has a transition state. For instance, let's consider the following bromine dissociation reaction giving us two bromine radicals:% hv “ * Br? —_—_—_——> :Br- + i Br: ] age Ber | Hy RE be: eG eG eo CHS CH watt Capa The first transition state is the process of the C-Br bond elongation that leads to the eventual bond dissociation and the formation of the carbocationic intermediate. This intermediate does exist long enough (although, still very briefly) so that we can “catch” it using experimental techniques and characterize it. The second step in this reaction has its own transition state:* CH A H,¢- of ma Hae Re ° WE ce ll _ oH © Sy be > “o, H-&% 4 om Ane k # 4 Nu 4 * In the second step above we have three different bonds in the “making-breaking” state. The H-O and C=C bonds are forming, while the C-H bond is breaking. Now, if | were to plot this reaction on the reaction coordinate vs energy plot, we'll get something like this: TI oe eens States Reaction Ceordinate 4.