Chapter 12 Chemical Kinetics Chemica l Kinetics Chemical Kinetics Studies the rate(Speed) at which a chemical process occurs. Speed of a reaction is measured by the change in concentration over time. Different from Thermodynamics: which determines if a reaction take place.

Our goal is to understand chemical reactions at the molecular level.(mechanics of the reaction) Chemica l Kinetics Outline: Kinetics Reaction Rates How we measure rates. Rate Laws How the rate depends on concentration

of reactants. Integrated Rate Laws How to calc amount left or time to reach a given amount. Half-life How long it takes to react 50% of reactants. Arrhenius Equation

How rate constant changes with T. Mechanisms Link between rate and molecular scale processes. Chemica l Kinetics Reaction Rates We define the reaction rate as the change in concentration of a reactant or product per unit time. For the reaction A

measuring rate: B there are two ways of (1) the speed at which the reactants disappear (2) the speed at which the products appear Chemica l Kinetics Reaction Rates Rates of reactions can be determined by

monitoring the change in concentration of either reactants or products as a function of time. Chemica l 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. Surface area More area for reactants to be in contact with each other. Pressure of gaseous reactants or Products. Increased number of collisions Chemica l Kinetics Chemica

l Kinetics Chemical Kinetics Most Common Units Rate = M/s (RememberMolarity (M) = moles/Liter) Reaction rate is the change in the concentration of a reactant or a product with time (M/s). A [A]A] rate = t [A]B] rate =

t B [A]A] = change in concentration of A over time period t [A]B] = change in concentration of B over time period t Because [A]A] decreases with time, [A]A] is negative. AVERAGE Reaction Rates C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq) [C4H9Cl] M

In this reaction, the concentration of butyl chloride, C4H9Cl, was measured at various times, t. Chemica l Kinetics AVERAGE Reaction Rates C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq) Average Rate, M/s

The average rate of the reaction over each interval is the change in concentration divided by the change in time: Chemica l Kinetics Reaction Rates C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

Note that the average rate decreases as the reaction proceeds. This is because as the reaction goes forward, there are fewer collisions between reactant molecules. Chemica l Kinetics Reaction Rates and Stoichiometry

C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq) In this reaction, the ratio of C4H9Cl to C4H9OH is 1:1. Thus, the rate of disappearance of C4H9Cl is the same as the rate of appearance of C4H9OH. Rate = -[A]C4H9Cl] = t

[A]C4H9OH] t Chemica l Kinetics Reaction Rates and Stoichiometry What if the ratio is not 1:1? H2(g) + I2(g) 2 HI(g) Only 1/2 HI is made for each H2 used. Chemica

l Kinetics Reaction Rates and Stoichiometry To generalize, for the reaction aA + bB Reactants (decrease) cC + dD Products (increase)

Chemica l Kinetics THE RATE LAW USING INITIAL CONCENTRATIONS Each reaction has its own equation that gives its rate as a function of reactant concentrations. Chemica l Kinetics

Calculating The Initial Rate Law The rate law expresses the mathematical relationship of the rate of a reaction to the concentrations of the reactants. The products play no role in the calculations. aA + bB products Rate = k [A] x [B] y Rate = Molarity /sec k= rate constant and it varies with each reaction, temperature dependent. [A] [B] = Concentrations of reactants in M (moles/liter)

x and y = Values for the reaction order. They tell us how important each of the reactants is in regard to speed.The higher the number the more value it has to overall speed. x does not equal a and y does not equal b aA + bB products Trial [A]A] M/S [A]B] M/S

Rate M/S 1 0.100 .100 2.00 x10-3 2 0.200

.100 4.00 x 10 -3 3 0.200 .200 16.00 x 10 -3 Concentration and Rate

Homework Compare Experiments 1 and 2: when [A]NH4+] doubles, the initial rate doubles. Chemica l Kinetics ZERO ORDER The rate of change is independent of the concentration of the reactant. A products

Rate = k [A]A] 0 Rate = k Ex: Decomposition of ammonia over tungsten Chemica l Kinetics Concentration and Rate Homework Likewise, compare Experiments 5 and 6: when [A]NO2-] doubles, the initial rate doubles.

Chemica l Kinetics INTEGRATED RATE LAWS Chemica l Kinetics Zero Order Integrated Rate Law The rate of change is independent of the concentration of the reactant. [A]t = - kt + [A]0

Y = mx + b This means that we can graph the concentration as a function of time and it should create a straight line that will give a slope and then you can find the value of -k! Chemica l Kinetics First Order Integrated Rate Law The rate is proportional to the concentration of a single reactant raised to the first power Using calculus you get the following equation: ln[A]t = - kt + ln [A]A]0 Y = mx + b

If a reaction is first-order, a plot of ln[A]t vs t will give a straight line with a slope of -k. So, use graphs to determine rxn order. Chemica l Kinetics Second Order Integrated Rate Law The rate is proportional to a either the concentration of a single reactant raised to the second power or two reactants each raised to the first power. also in the form

y = mx + b Chemica l Kinetics How are these equations helpful? You now have a technique for determining the order of a reaction by observing graphs created from experimental data of concentration vs time. If a simple graph of concentration vs time is a straight line then you know that it is a zero order reaction.

If the natural log of concentration vs time is a straight line then you know that it is a first order reaction. If the reciprocal concentration vs time is a straight line then you know that it is a second order. Chemica l Kinetics The conclusion: In all cases, once you get a straight line fit , you can then get the rate constant from calculating the slope of the line. Slope (m) = Y X

Chemica l Kinetics Chemica l Kinetics Zero Order Integration 2NH3(g) N2 + 3 H2 (g)

[A]t = - kt + [A]0 Chemica l Kinetics First-Order Integration When lnCH3NC is plotted as a function of time, a straight line results. The reaction is first-order, a plot of ln [A]A]t vs. t will yield a Chemica straight line with a slope of -k. l

Kinetics . Second-Order Integration So if a reaction is second-order in A, a plot of vs. t will yield a straight line with a slope of k. Chemica l Kinetics Determining rxn order The decomposition of NO2 at 300C is described by

the equation 2NO2 (g) 2NO (g) + O2 (g) and yields these data: Time (s) 0.0 50.0 100.0 200.0 300.0 [A]NO2], M 0.01000

0.00787 0.00649 0.00481 0.00380 ln [A]NO]2 1/ [A]NO2] Chemica l Kinetics [A]NO2] vs Time

The plot is not a straight line, so the process is not zero-order. Chemica l Kinetics Determining rxn order Graphing ln [A]NO2] vs. t yields: The plot is not a straight line, so the process is not first-order in [A]A]. Time (s)

0.0 50.0 100.0 200.0 300.0 [A]NO2], M 0.01000 0.00787 0.00649 0.00481 0.00380 ln [A]NO2]

-4.610 -4.845 -5.038 -5.337 -5.573 Does not fit: Chemica l Kinetics Second-Order Processes A graph of 1/[A]NO2] vs. t

gives this plot. Time (s) 0.0 50.0 100.0 200.0 300.0 [A]NO2], M 0.01000 0.00787 0.00649 0.00481

0.00380 1/[A]NO2] 100 127 154 208 263 This is a straight line. Therefore, the process is secondorder in [A]NO2]. k= 0.543

Chemica l Kinetics Chemica l Kinetics Half-Life Half-life is defined as the time required for one-half of a reactant to react. Half-Life is also defined as the rate of decay of a radioactive substance. A radioactive substance is one that will slowly decay into

a more stable form as time goes on. Chemica l Kinetics Determining a Half Life To determine a half life, t, the time required for the initial concentration of a reactant to be reduced to one-half its initial value, we need to know: The order of the reaction or enough information to determine it. The rate constant, k, for the reaction or enough information to determine it.

In some cases, we need to know the initial concentration, [A]Ao] Substitute this information into the equation for the half life of a reaction with this order and solve for t. Chemica l Kinetics Half-Life For a first-order reaction the formula is as follows and it is also found on the AP Reference sheet in the Kinetics section. A Products Chemica

l Kinetics 1st Order reactions Half-life is constant Chemica l Kinetics Half-Life for a Second- Order Reaction A A+B

products products Chemica l Kinetics 2nd order reaction half-life is variable. It increases with decreasing concentration. Chemica l Kinetics Chemica

l Kinetics Finding the Overall Rate Law by Utilizing Reaction Mechanisms Chemica l Kinetics Reaction Mechanisms Not all reactions occur in one step. The step by step sequence of 2 or more

simple reactions that combine to form the overall reaction. A chemical mechanism describes in detail exactly what takes place at each stage of an overall chemical reaction. Chemica l Kinetics Reaction Mechanism Terms Complex reaction- overall reaction elementary steps- series of simpler reactions that combine to form the complex reaction.

Intermediate-a substance produced in one elementary step and consumed in another. Catalyst-increases the rate but not consumed by the reaction.It remains unchanged. Chemica l Kinetics Multistep Mechanisms In a multistep process, one of the steps will be slower than all others. The slowest step is called the ratedetermining step.It will be the one used to find the rate law for the overall reaction. The overall reaction cannot occur faster

than this slowest, rate-determining step Chemica l Kinetics Hypothetical Reactions #1 1)P + Q B (SLOW) 2) B + Q 2R (FAST) What is the overall rate law for this reaction?

What is the complex equation for this reaction? Chemica l Kinetics Hypothetical Reactions # 2 1)P + Q 2) B + Q B (SLOW) P + 2R(FAST) What is the overall rate law for this reaction?

What is the complex equation for this reaction? Chemica l Kinetics Practice Reactions 1. 2NO 2.N2O2 + H2 3.N2O + H2 N2O2 (slow) N2O + H2O (fast)

H2O +N2(fast) a.)Which is the rate determining step? b.)Does this reaction have a catalyst? c.)What is the complex equation for this reaction? d.) What is the rate law? Chemica l Kinetics Answers to practice problem A.) Step one is the rate determining step B.) No catalyst

C.) 2NO + 2H2 N2 + 2H2O D.) rate = k [A]NO]2 Chemica l Kinetics Please Remember!!!! YOU CAN ONLY USE THE COEFFICIENT METHOD TO DETERMINE THE RATE LAW OF ELEMENTARY STEPS. YOU CANNOT USE THE COEFFICIENTS FROM THE COMPLEX EQUATION AND

DO THE SAME THING. Chemica l Kinetics