[ Header here ] Kaushal Is Awesome :D :D

1. recall that rates of reaction may be expressed by empirical rate equations of the form: rate = k[A]m[B]n, where m and n are 0, 1 or 2 2. define the terms rate constant and order of reaction and understand that these are experimentally determined 3. deduce rate equations from given experimental initial rate data 4. recall that reactions with a large activation energy will have a small rate constant 5. students will be expected to be familiar with the Arrhenius equation but not to recall it 6. understand that many reactions take place in several steps, one of which will be the rate-determining step 7. understand that it is sometimes possible to deduce information regarding the mechanism of a chemical reaction from kinetic data 8. understand that many reactions proceed through a transition state 9. select and describe a suitable experimental technique for following a given reaction 10. present and interpret the results of kinetic measurements in graphical form 11. define the term half-life and recall that this is constant for any given first-order reaction. Rate equations A + B Products If the rate of reaction depends upon the conc. of A and B: m[B]n Reaction Rate = k[A] (m and n are 0, 1 or 2) Term : rate equation Definition : An expression relating the rate of a reaction to the centrations of species present in the reaction mixture. Rate constant and order of reaction If the reaction Rate = k[A]m[B]n then reaction is of order m with respect to A and of order n with respect to B. The overall order of reaction is (m+n). The proportionality constant k is called the rate constant for the reaction. The rate constant and order of reaction are experimentally determined. Rate equations from experimental data Rate equations are of the form rate = k[A]m where k is a proportionality constant. A graph of rate of reaction against [concentration] m is plotted and the gradient of the graph will give you the constant of the reaction k. A data table may yield a rate equation. E.g. A reacts with B to form C. From the table below find the rate equation and calculate the rate constant. [A]/mol [B]/mol initial rate/ dm-3 dm-3 mol dm-3 s-1 1.00 2.00 1.00 1.00 1.00 2.00 4.00 8.00 16.0

experiment 1 2 3

In experiment 1 and 2 doubling [A] multiplies rate by 2 so rate proportional to [A] In experiment 1 and 3 doubling [B] multiplies rate by 22 so rate proportional to [B]2 so rate = k[A][B]2. k = [A][B]2/rate = 1.00mol dm-3 * (1.00mol dm-3)2 /4.00mol dm-3 s-1 k = 0.250 mol dm-3 s

1|Page

Rates, How Fast - Checklist

[ Header here ] Kaushal Is Awesome :D :D

Activation energy and rate constant Some bonds in a molecule must break before it can react and form new bonds. Energy is needed to break these bonds is called the activation energy. Reactant molecules must be given enough energy to pass the activation energy barrier to react. The activation energy and the rate constant are linked by the Arrhenius equation. k=Ae-Eact/RT where k=rate constant, e = the base of natural logarithms, A is a constant for any given reaction, Eact = the activation energy, R = the gas constant, T = the temperature in K. The Arrhenius equation shows that the rate constant (k) decreases if the activation energy (Eact) increases. A reaction will have a small rate constant if it has a large activation energy. The activation energy for a reaction can be calculated as follows.

If k is calculated for different values of T then a plot of log k against 1/T gives a line of gradient = - Eact/2.3R.

The rate determining step in a reaction Reactions often occur in several steps, one of which, the rate determining slow step, is likely to control the overall rate of reaction. e.g. for an SN1 reaction two steps are involved RX -------> R+ + X- step 1 slow R+ + OH- -----> ROH step 2 fast The rate depends on the slow step 1. rate = k[RX] first order E.G. RX=(CH3)3CBr For an SN2 reaction there is a rate determining slow step involving two species RX + OH- ------> HO--R--X rate = k[RX][OH-] second order E.G. RX = CH3Br

2|Page

Rates, How Fast - Checklist

[ Header here ] Kaushal Is Awesome :D :D

Mechanisms and kinetic data The mechanism for a reaction can be proposed with help from kinetic data but some speculation is needed. 1. The rate equation gives us information about what reacts in the rate determining step. 2. Sensible products must be suggested for the rate determining step. 3. If more molecules of reactant remain and more product molecules are still to be formed more steps must be proposed. e.g. What is the mechanism for the following reaction CH3CH2I + NH3 -----> CH3CH2NH2 + HI if rate = k[CH3CH2I] CH3CH2I is a halogenoalkane so likely to take part in a nucleophilic substitution. NH3 is a nucleophile because of its lone pair of electrons on the nitrogen atom. The rate equation shows that it is first order so the slow step in the mechanism must involve only CH3CH2-I. CH3CH2---I -----> CH3CH2+ + IA nucleophilic attack by ammonia is now possible in a fast step; NH3 + CH3CH2+ -----> CH3CH2NH3+ a final fast step might be loss of hydrogen ion; CH3CH2H2N----H+ -----> CH3CH2NH2 + H+ For the reaction 2ICl(g) + H2(g) ----> 2HCl(g) + I2(g) Experiments show that rate = k[ICl(g)][H2(g)] so the rate determining step involves 1 molecule of ICl and one of H2 ICl(g) + H2(g) ----> products possible products are HCl because it is a product of the overall reaction and HI because the elements hydrogen and iodine are left over. ICl(g) + H2(g) ----> HCl(g) + HI(g) slow step check full equation to see what is unaccounted for one molecule of ICl still has to react so ICl(g) + HI(g) ----> HCl(g) + I2(g) fast step The kinetic data has led to a 2 step mechanism for the reaction. The transition state When particles collide the breaking of bonds and the formation of new bonds may take place at the same time. Half way through the process an intermediate called the transition state is formed. The transition state has more energy than the the reactants. The transition state has more energy than the products. e.g. for the reaction between a hydrogen molecule and a chlorine radical. H-H + Cl. <=> H- - - H - - - Cl ----> H. + H-Cl reactants energy = E transition state energy > E products energy < E for exothermic reaction Experimental techniques for following reactions Reactions can be followed by * sampling, quenching and titrating (suitable for acid base reactions) * measuring gas volumes (suitable for reactions involving a change in gas volume) * polarimetry (suitable for reactions involving optically active substances) * measuring conductivity (suitable for reactions producing or consuming ions)

3|Page

Rates, How Fast - Checklist

[ Header here ] Kaushal Is Awesome :D :D

* colorimetry (suitable for reactions involving coloured substances) * dilatometry (suitable for reactions involving reactions in which liquids change volumes) Presenting and interpreting kinetics graphs From a graph of concentration against time the initial slope of the graph is the initial rate of reaction. A graph of rate against concentration will be a straight line through the origin if the rate is proportional to the concentration. Half-life The time taken for the reaction to go to half completion is called the half-life of the reaction t1/2. The half life of a 1st order reaction is independent of the initial concentration. 1st order reactions have a constant half life. t1/2 = 0.69/k where k = the rate constant for the reaction

4|Page

Rates, How Fast - Checklist