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14829_kinetics ppt

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CHE 101:Chemistry

Chemical Kinetics
lecture no.8

Mr. Harminder Singh LSECA + LSTCA Chemical Kinetics

Kinetics
‡ Studies the rate at which a chemical process occurs. ‡ Besides information about the speed at which reactions occur, kinetics also sheds light on the reaction mechanism (exactly how the reaction occurs).
Chemical Kinetics

Outline: Kinetics
Reaction Rates Rate Laws Integrated Rate Laws Half-life Arrhenius Equation Mechanisms
How we measure rates. How the rate depends on amounts of reactants. How to calc amount left or time to reach a given amount. How long it takes to react 50% of reactants. How rate constant changes with T. Link between rate and molecular Chemical scale processes.
Kinetics

Factors That Affect Reaction Rates
‡ Concentration of Reactants 
As the concentration of reactants increases, so does the likelihood that reactant molecules will collide.

‡ Temperature 
At higher temperatures, reactant molecules have more kinetic energy, move faster, and collide more often and with greater energy.

‡ Catalysts 
Speed rxn by changing mechanism.
Chemical Kinetics

([A] vs (t Kinetics .Reaction Rates Rxn Movie Rates of reactions can be determined by monitoring the change in concentration of either reactants or products as a function of Chemical time.

The factors mentioned will affect the composition of the reaction mixture at any given time. aA + bB c + dD Chemical Kinetics . denoted by R. Therefore The change in composition of the reaction mixture with time is the rate of reaction. R is the same whether monitoring reactants or products Generally. r or Y.

R = -d[A]/dt = k [A]m [B]n Such an equation is called the rate law Chemical Kinetics . R E [A]m [B]n With the use of a proportionality constant k.Rate laws. rate constants. reaction order R= ([A][B]) And.). but dependent on temp. which is the rate constant (independent of conc.

The order of the reaction = m + n If m = n =1. but second-order overall. then the reaction is first-order in A and first-order in B. therefore: R = k [A][B] Hence. 3 1 R mol dm s k ! ! ! dm 3 mol [ A ][ B ] ( mol dm  3 ) 2 1 s 1 Units for rate constant for 2nd order reaction If first-order overall???? k! [ ] ! ol d ol d 3 s 1 3 ! s 1 Units for rate constant for 1st order reaction Chemical Kinetics .The exponents m and n are the order of the reaction with respect to reactant A and the order of the reaction with respect to reactant B respectively.

Lecture no.9-10 Chemical Kinetics .

017 y=1 x=1 rate = k [S2O82-][I-] Double [I-].08 0.08 M)(0.2 x 10-4 M/s rate k= = = 0.017 0.08 0.(aq) + 3I.16 0.034 M) Chemical Kinetics 13.2 x 10-4 1.1 x 10-4 2.08/M‡s 2-][I-] [S2O8 (0.2 x 10-4 1 2 3 0. rate doubles (experiment 2 & 3) 2.(aq) S2O82. rate doubles (experiment 1 & 2) Double [S2O82-].(aq) + I3.(aq) rate = k [S2O82-]x[I-]y Initial 2[I ] Rate (M/s) 2.Experiment [S2O8 ] Determine the rate law and calculate the rate constant for the following reaction from the following data: 2SO42.034 0.2 .

kt [A] = [A]0exp(-kt) A Chemical Kinetics .First-Order Reactions ([A] product rate = rate = k [A] (t rate k = [A] = M/s = 1/s or s-1 M [A] is the concentration of A at any time t ([A] = k [A] [A]0 is the concentration of A at time t=0 (t ln[A] = ln[A]0 .

kt t½ = t when [A] = [A]0/2 [A]0 t½ = 2k Chemical Kinetics .Zero-Order Reactions A product ([A] rate = (t rate = k [A]0 = k ([A] =k (t [A] is the concentration of A at any time t [A]0 is the concentration of A at time t=0 k = rate = M/s [A]0 [A] = [A]0 .

Second-Order Reactions A product ([A] rate = (t rate = k [A]2 ([A] = k [A]2 (t M/s rate k= = 2 = 1/M‡s 2 M [A] 1 1 = + kt [A]0 [A] [A] is the concentration of A at any time t [A]0 is the concentration of A at time t=0 t½ = t when [A] = [A]0/2 1 t½ = k[A]0 Chemical Kinetics .

the rate law is: rate = k [A]m Order (m) Zero (0) 1st (1) [A] by a factor of: 2.Reaction Orders For the reaction: A B. etc. 15. 4. 2 3 2 2nd (2) 3 ½ Effect on rate None 2X 3X 4X 9X ¼X Chemical Kinetics . ½.

Chemical Kinetics .First-Order Processes If a reaction is first-order. a plot of ln [A]t vs. So. use graphs to determine rxn order. t will yield a straight line with a slope of -k.

CH3NC CH3CN How do we know this is a first order rxn? Chemical Kinetics .First-Order Processes Consider the process in which methyl isonitrile is converted to acetonitrile.

First-Order Processes CH3NC This data was collected for this reaction at 198. Does rate=k[CH3NC] for all time intervals? CH3CN Chemical Kinetics .9rC.

 k is the negative slope: 5.First-Order Processes ‡ When ln P is plotted as a function of time. a straight line results. Chemical Kinetics .1 v 10-5 s-1.  The process is first-order.

integrate: also in the form y = mx + b Chemical Kinetics . integrating the rate law for a process that is second-order in reactant A: Rearrange.Second-Order Processes Similarly.

t will yield a straight line with a slope of k.Second-Order Processes So if a process is second-order in A. Chemical Kinetics . a plot of 1/[A] vs. First order: If a reaction is first-order. t will yield a straight line with a slope of -k. a plot of ln [A]t vs.

Half-Life ‡ Half-life is defined as the time required for one-half of a reactant to react. [A]t = 0. Chemical Kinetics .5 [A]0. ‡ Because [A] at t1/2 is one-half of the original [A].

Chemical Kinetics . set [A]t=0.5 [A]0 in integrated rate equation: NOTE: For a first-order process. the half-life does not depend on [A]0.Half-Life For a first-order process.

set [A]t=0. Chemical Kinetics .2nd order For a second-order process.5 [A]0 in 2nd order equation.Half-Life.

Lecture no. 11 Chemical Kinetics .

a reaction cannot occur unless the molecules possess sufficient energy to get over the activation energy barrier. ‡ Just as a ball cannot get over a hill if it does not roll up the hill with enough energy.Activation Energy ‡ In other words. there is a minimum amount of energy required for reaction: the activation energy. Ea. Chemical Kinetics .

so does the reaction rate.Temperature and Rate ‡ Generally. Chemical Kinetics . as temperature increases. ‡ This is because k is temperature dependent.

Chemical Kinetics .Maxwell-Boltzman Distribution ‡ At higher temperatures. ‡ This increases the reaction rate. more molecules will have adequate energy to react.

The Collision Model ‡ In a chemical reaction. bonds are broken and new bonds are formed. Chemical Kinetics . ‡ Molecules can only react if they collide with each other.

The Collision Model Furthermore. Chemical Kinetics . molecules must collide with the correct orientation and with enough energy to cause bond breakage and formation.

Chemical Kinetics .Reaction Coordinate Diagrams It is helpful to visualize energy changes throughout a process on a reaction coordinate diagram like this one for the rearrangement of methyl isonitrile.

Chemical Kinetics .Reaction Coordinate Diagrams ‡ It shows the energy of the reactants and products (and. therefore. (E). ‡ The energy gap between the reactants and the activated complex is the activation energy barrier. ‡ The species present at the transition state is called the activated complex. ‡ The high point on the diagram is the transition state.

a number that represents the likelihood that collisions would occur with the proper orientation for Chemical reaction. Kinetics .Arrhenius Equation Svante Arrhenius developed a mathematical relationship between k and Ea: where A is the frequency factor.

Chemical Kinetics . the equation becomes 1 RT y = mx + b When k is determined experimentally at several temperatures. 1/T.Arrhenius Equation Taking the natural logarithm of both sides. Ea can be calculated from the slope of a plot of ln k vs.

Outline: Kinetics First order Rate Laws Integrate d Rate Laws Second order Second order complicated Half-life complicated k(T) Chemical Kinetics .

Lecture no.12 Chemical Kinetics .

Chemical Kinetics .Reaction Mechanisms The sequence of events that describes the actual process by which reactants become products is called the reaction mechanism.

Chemical Kinetics .Reaction Mechanisms ‡ Reactions may occur all at once or through several discrete steps. ‡ Each of these processes is known as an elementary reaction or elementary process.

The rate law for an elementary step is written directly from that step. Chemical Kinetics .Reaction Mechanisms ‡ ‡ The molecularity of a process tells how many molecules are involved in the process.

rate-determining step. ‡ The overall reaction cannot occur faster than this slowest.Multistep Mechanisms ‡ In a multistep process. Chemical Kinetics . one of the steps will be slower than all others.

but the rate of the reaction does not depend on its concentration. ‡ This suggests the reaction occurs in two steps.Slow Initial Step NO2 (g) + CO (g) €€p NO (g) + CO2 (g) ‡ The rate law for this reaction is found experimentally to be Rate = k [NO2]2 ‡ CO is necessary for this reaction to occur. Chemical Kinetics .

it does not appear in the rate law. Chemical Kinetics . ‡ As CO is not involved in the slow. rate-determining step.Slow Initial Step ‡ A proposed mechanism for this reaction is Step 1: NO2 + NO2 €€p NO3 + NO (slow) Step 2: NO3 + CO €€p NO2 + CO2 (fast) ‡ The NO3 intermediate is consumed in the second step.

Chemical Kinetics .Fast Initial Step ‡ The rate law for this reaction is found (experimentally) to be ‡ Because termolecular (= trimolecular) processes are rare. this rate law suggests a two-step mechanism.

Fast Initial Step ‡ A proposed mechanism is Step 1 is an equilibriumit includes the forward and reverse reactions. Chemical Kinetics .

‡ The rate law for that step would be ‡ But how can we find [NOBr2]? Chemical Kinetics .Fast Initial Step ‡ The rate of the overall reaction depends upon the rate of the slow step.

Fast Initial Step ‡ NOBr2 can react two ways: With NO to form NOBr By decomposition to reform NO and Br2 ‡ The reactants and products of the first step are in equilibrium with each other. ‡ Therefore. Chemical Ratef = Rater Kinetics .

Fast Initial Step ‡ Because Ratef = Rater . k1 [NO] [Br2] = kí1 [NOBr2] Solving for [NOBr2] gives us k1 [NO] [Br2] = [NOBr2] kí1 Chemical Kinetics .

Fast Initial Step Substituting this expression for [NOBr2] in the rate law for the rate-determining step gives Chemical Kinetics .

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