CEIC2005: Chemical Engineering Applications |Where We're Going Now... So far we've dealt with the bottom part of this graph Calculating internal energy, é free energy, and enthalpy differences between reactants and products - The top half is just as F important - if not more i This gives us information about the speed of the 4 A pti reaction — the rates and the energy required to at ofreion start a reaction - Activation energy Rents |The Big Picture This is a single step reaction which is reversible Reversibility, and by extension reaction equilibria, are governed by the kinetics of a reaction - Related to the rates of the reactions, reactant/product concentrations, temperature, pressure. - We'll see this later when we delve into thermodynamically controlled and kinetically controlled reaction systems XY + Z2=——X + YZ 4 AS potsSome Topics We'll Cover Rates of reactions ~ Arrhenius equation — determination of activation energies, how we measure them Rate laws — zeroth, pseudo-first, first, and second order rate law equations ~~ Isotope effect and its use in determining reaction mechanisms ~~ 7 Reaction mechanisms and kinetic equations ~~ Explosion reactions Transition state theory ~~ Enzyme and catalyst effect~” Complex reaction kinetics ~ - Chain reactions, polymerization reactions, thermodynamically and kinetically controlled reactionsRates of Reaction*” So, rate is just the formation or consumption of a substance with time As a substance is consumed/formed, the rate changes The rate is concentration, temperature, pressure, etc. dependent - The rate constant (k) independent of concentration, but dependent on T and p - Thus, the rate changes with concentration (conversion/extent of reaction), temperature, pressure... 42). ‘Molar concentration, (J A+ tics 0 404d AB, vee eae aie 2 Were <7Measuring Reaction Rates k XYZ eV: Movable Driving spectrometer syringes Ny Mixing chamber Here's a typical reaction (say in the liquid phase) We can directly monitor the reaction in real time - Flow method (shown here) + Rate of reaction is related to the flow (speed) of the solution and the distance traveled + Good for reaction rates in the second to millisecond timescale ~ Flashllaser photolysis Light pulses activate the reaction + Monitor reaction during the “dark” time and the pulse time + Effective for times in the femtosecond to nanosecond range (10° to 10°)Reaction Rate Laws and Order A + 2B—453C + D rae = 44). say ay For this reaction, we can write an idealized reaction rate law - The rate law usually depends on the reactant concentrations to some power (the order with respect to that substance) - The reaction order is the sum of the individual orders - The order is experimentally determined If the reverse reaction effects the reaction, then the oduct concentrations will appear in the reaction rate law (we'll see this later) But, before we get to the complex stuff, the basics first...Single Component Reactions and Rate Laws? A——>Products + Zeroth Order- very rare dA, [d= [A], - a> 4, = la a 2 « First Order — nuclear decay, thermal decomposition of radical initiators,, 4. ila Lae be she 4 « Second Order — ra molecules of th same material — — rxn) aw at lat > dd). nto gag a 0 1 2. ———— —Y Koat Alo315' Order Reactions asl, Nuclear Decay® OC +N) + B ST >™ Tht a Each radioactive isotope has its own ha When they decay, they emit a, b, or g radiation (along with positrons, neutrinos, ..) The material has an activity value (A,, in Bq) which is the number of decays per second - Orsimply, the rate constant times the number of molecules!! - We'll look at this more later... » oor (in af 5 i 4 bees «py. f{ MN ‘) ae uy sec1' Order Reaction Radical Initiators “ri” thst) NC. CHy —CH; H3C CN Typical free radical initiator for polymerization reactions Undergoes radical generation thermally, although can be done through g radiation as well The half-life for this material is given by the same 1 order reacti equations. eee - By knowing the hatt-life, we know how many radicals welll generate! The rate constant for this reaction is defined as ks due to the decomposi that the molecule undergoes ow eee - Due to the loss of an energetically stable nitrogen, the reaction is reversible ) - However, the radicals can recombine under certain conditions, thereby Téduting its effectiveness as an initiator for polymerization We'll discuss this more when we get into polymer kineticsConstructing the Rate Law’ Isolation method Holding one component constant and measuring the rate change in the other component Forcing it into a first order approximation to get the rate law Method of initial rates ‘Obtain the initial rate law equation by the ~ changes in the initial rate of the system as all but one component is held constant Doesn't take into account the effect of products on the rate law This method works to determine orders of each component as well None of the rate laws take into account the reverse reaction... M4. shafale eal = AAA) = ata 4, = MAY > when Bis held constant _4A_ atfReactions Approaching 4 Equilibruimtf First Order, reversible reaction 7 v= AA] v'=4[4] [A] . a ae -44. Ad A [A -Laa TAMA. at equilibria m, there is no net change in either ae products or reactants the reaction sill occurs he 4 but the concentrat ion of any substance is unchanged. 2 dA a crate = AA) 9 04 te = ‘ei o= Mal, 414A, 2 #1A, = Adal, Pet °0 Jee a ct Gre “Ye (k+k)t a tbihe Rm BAR. ad in**First Look at Complex Series*f AB) Se a=bo ath v= Mallat v= 47] rae = 44. _sayat +0) 0 = -{4k, [at + “UL, : Vi, _* labial, # . K= mall Ko eo Stoner, ke avd ice CEISA shiver he This equilibrium proof works for multiple steps, multiple components, and higher reaction orders In this step, the equilibrium is much much faster than the product formation step - Called a pre-equilibrium As before, the equilibrium is simply the ratio of the forward and reverse reaction step rate constants. Well come back to this reaction a bit later, but let's look at these rate constants.Rate Constants — Arrhenius Eqn.** The Arrhenius equation describes the temperature dependence of k This also has important implications - High E; values signify the rate constant depends strongly with temp (steeper slope) - E, can be negative in some cases - indicating the rate decreases with increasing temperature + This is not a typical occurrence * Signals the reaction has a complex mechanism We will not discuss when the plot is NOT linear (which can happen but has quantum chemistry implications) We know what kis, but what's A and E, b 4 me In4= In A-—_4 R crash, a psi Ina Slope=-E/R InkThe Arrhenius Eqn. and Collision Theory Molecules are constantly in motion In order for a reaction between two molecules to occur, the molecules need to: - Collide at the right energy to break/form bonds + Too low of energy and they don't react - Need to collide at the correct structural configuration Thus, not every collision will result in a reaction There is a kinetic energy AND a frequency factor component to successful reactionsThe Arrhenius Eqn. and Collision Theory k= Aer” So, the exponential term can be interpreted as the number of collisions with the minimum kinetic energy to result in a reaction - This is derived from Boltzmann distribution functions and a mix of collision theory and quantum chemistry The pre-exponential term, A, is the frequency factor and denotes the rate at which collisions occur, irrespective of energy Thus, the rate constant is the rate of successful collisions with the appropriate energy!!!\W Typical Arrhenius Parameters” wane 4). Aa Ist order reaction vere = AA. fa] 2nd ore wacton thnew th onde from te catds +E, is always in units of kJ mol (or cal mol) + Ahas the same units as k and is dependent on the overall order of the reaction - Since we're dealing with a rate of reaction which is the formation or consumption of a substance per unit time, the end rate should be mol L* s* - So, 1% order reactions, A and kare ins! and for 2" order reactions A and k are L mol" s*Arrhenius Eqn. and Half-Lives Half-life is independent of initial substance concentration for 1% order reactions — only dependent on the rate constant But rate constant depends on temperature - As the temperature increases, the rate constant increases Therefore, an increase in the rate constant would result in a decrease in the half-life of the substance - Radioactive decays are faster - Radical generation from thermal initiation is faster\*Tying Kinetics to Thermo**/ setthe temperature dependent tems equal 10 cach oer and the temperature INDEPENDENT Fora reversible reaction ems qa fo ach ober (Arforward reaction, and # reverse reaction) dictoue . deamin) Lage gale zB ££, -sH, #& a = chm lar bls,/a ar aa™ 4H,= £,-£, A yenye . jamie) pias) ae “4 é NG.=44,-™S,= TAG,~ JAG, ris = \H,= Y44,- YAH, ri = 4S, 5 S,- 5S,