Chemical Kinetics

Molecular View of Kinetics

We will begin our study of kinetics by moving from the particulate level to the macroscopic level. Recall that temperature (along with concentration of reactants, surface area, and catalysts) affects the rate of a chemical reaction. GENERALLY, the rate of a chemical reaction increases by a factor of 2 or 3 for each 10C increase in temperature. But, why?

Collision Theory
Collision theory states:
The rate of a reaction is proportional to the number of EFFECTIVE collisions per second among the reactant molecules EFFECTIVE collisions result in the formation of product molecules Anything that can increase the frequency of effective collisions should increase the reaction rate. Its all based on probability.

Collision Theory, Cont.

Orientation of molecules
Molecules of reactants must line up just right in order for a reaction to occur.

Kinetic Energy
When reactant molecules line up, they must collide with enough energy to cause bonds to break and bonds to reform.

Activation Energy, Ea
The minimum kinetic energy that must be possessed by the reactants in order to result in an effective collision Is generally quite large, but we can get over it. Ha!

Energy Diagrams
Like what Mrs. Freeman talked about.

http://www.youtube.com/watch?v=VbIaK6PLrRM&feature=player_embed ded

Energy Diagrams
Potential energy is plotted on the y-axis. Reaction coordinate (or progress or time) is plotted on the x-axis. The hump, or hill, represents activation energy. The difference between reactants and products still represents H and will differ for an exothermic or endothermic reaction.

Quantifying Reaction Rates

Recall that reaction rates are represented as concentration / time Units for reaction rates are usually mol/L s Or mol L-1 s-1 Reaction rates are represented as positive values whether the rate was measured as the increase in product concentration or decrease in reactant concentration. Be careful!

Stoichiometry and Kinetics

Coefficients from balanced equations can be used to find relative rates. For example: C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (g) Oxygen must react five times as fast as propane. Carbon dioxide must form three times as fast as propane is used up. Water vapor must form four times as fast as propane is used up.

Example 1
Butane, the fuel in cigarette lighters, burns in oxygen to give carbon dioxide and water. If the butane concentration is decreasing at a rate of 0.20 mol L-1 s-1, what is the rate at which the oxygen concentration is decreasing? Carbon dioxide concentration increasing? Water concentration increasing?

Your turn
The iodate ion reacts with sulfite ions in the reaction: IO3- + 3SO32- I- + 3SO42At what rate are the iodide and sulfate ions being produced if the sulfite ion is disappearing at a rate of 2.4 x 10-4 mol L-1 s-1?

Your Turn 2
Hydrogen sulfide burns in oxygen to form sulfur dioxide and water. If sulfur dioxide is being formed at a rate of 0.30 mol L-1 s-1, what are the rates of disappearance of hydrogen sulfide and oxygen?

 Because you now see that the rates of reactants and products are all related (by good ol stoichiometry), it doesnt matter which species we choose to follow concentration changes over time. If we know one, we know them all.

Relative Rates of a Reaction

We can express the speed of a reaction in a way that is independent of which reactant or product is monitored. This is called the rate of reaction and is accomplished by dividing the relative rate of reaction by the coefficient of the substance in the balanced chemical equation.

Relative Rates of a Reaction

C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (g)
Rate = -1 [C3H8] = -1 [O2 ] = 1 [CO2] = 1 [H2O] 1 t 5 t 3 t 4 t

Relative Rates of a Generalized Reaction

For aA + bB cC + dD
Rate = -1 [A] = -1 [B ] = 1 [C] = 1 [D] a t b t c t d t

Reaction Rates vs. Time

Reaction rates are rarely constant throughout the reaction. GENERALLY, rates slow down as reactants are used up.
Less effective collisions

Data can be graphed (time vs. concentration) to determine reaction rates.

2HI (g) H2 (g) + I2 (g)

[HI]

0.100 0.0716 0.0558 0.0457 0.0387 0.0336 0.0296 0.0265

Time (s) 0 50 100 150 200 250 300 350

0.1 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 0 50 100 150 200 250 300 350

Graphical Analysis
Graphing the concentration vs. time for a reaction allows us to see the average rate of the reaction. What about instantaneous rate?
Calculate the slope of a tangent line to the curve at a particular time. See pages 702-704 in text.

Homework
Pg. 744 #1-5 You can graph by hand or with your calculator.

Rate Equations a.k.a. Rate Laws

We know how to write relative rates and graphically determine average rates and instantaneous rates. Thats baby stuff according to the AP folks. We also need to be able to consider a rate expression that includes all reactants and can give us the rate for any set of concentrations.

Rate Laws
The rate of a reaction at any instant is proportional to the product of the molar concentrations of the reactants, each molarity raised to some exponent that has been experimentally determined. Exponents can be positive, negative, zero, or fractional. Sometimes, catalysts are included in the rate law even though theyre not written directly in the balanced equation. In other words

For A + B products
Rate = k[A]m[B]n Where k is the rate constant [A] is the molar concentration of a reactant m is the experimentally determined exponent (not to be confused with the stoichiometric coefficient) [B] is the molar concentration of a reactant n is the experimentally determined exponent (not to be confused with the stoichiometric coefficient)

 Once we know values for k, m, and n, we can calculate the rate of the reaction at any set of known concentrations.

Example 1
In the stratosphere, molecular oxygen can be broken into two oxygen atoms by UV radiation from the sun. If one of these oxygen atoms strikes an ozone molecule with sufficient energy, two oxygen molecules are created: O (g) + O3 (g) 2O2 (g) The rate law for this reaction is: Rate = 4.15 x 105 L mol-1 s-1 [O3][O] What is k? What is the rate of ozone destruction if [O3] = 1.2 x 10-8 M and [O] = 1.7 x 10-14 M?

Your Turn
2NO (g) + 2H2 (g) N2 (g) + 2H2O (g) The rate law for the reaction is: Rate = k[NO]2[H2] If the rate of reaction is 7.86 x 10-3 mol L-1 s-1 when the concentration of NO and H2 are both 2 x 10-6 mol L-1, what is the value of the rate constant?

Your Turn 2
The rate law for the decomposition of HI to I2 and H2 is Rate = k[HI]2 At 508C, the rate of reaction of HI was found to be 2.5 x 10-4 mol L-1 s-1 when [HI] = 0.0558 M. What is the value of k?

Pitfall Warning!
While this stuff seems like simple algebra, you must remember the coefficient business. Just because the exponents of a rate law sometimes happen to match the stoichiometric coefficients, THIS IS NOT HOW WE DETERMINE THEM! IT IS PURELY COINCIDENCE! Exponents in rate laws are experimentally determined. Accept this and lets move on.

Orders of Reaction
So, what about those exponents? Exponents in rate laws are called orders of the reaction WITH RESPECT TO THE CORRESPONDING REACTANT.

Example
2N2O5 (g) 4NO2 (g) + O2 (g) Has the rate law Rate = k[N2O5] The exponent of [N2O5] is 1. Therefore, this reaction is said to be first order WITH RESPECT TO N2O5.

Your Turn
The rate law for the decomposition of HI to I2 and H2 is Rate = k[HI]2 What is the order of the reaction with respect to HI?

Your Turn 2
2NO (g) + 2H2 (g) N2 (g) + 2H2O (g) The rate law for the reaction is: Rate = k[NO]2[H2] What is the order of the reaction with respect to NO? To H2?

Overall Order of A Reaction

Is the sum of the orders with respect to each reactant IN THE RATE LAW (not necessarily in the equation). Rate = k[H2SeO3][I-]3[H+]2 First, find order with respect to each reactant in the rate law: H2SeO3 = 1, I- = 3, H+ = 2 Then, add them up: 1 + 3 + 2 = 6 This reaction has an overall order of 6.

Your Turn
BrO3 - + 3SO32- Br- + 3SO42Rate = k[BrO3-][SO32-] What is the overall order for this reaction? What are the units of k?

Important Concepts
The rate constant, k, regardless of its units, indicates how fast a reaction will proceed. If k is large, the reaction proceeds rapidly. If k is small, the reaction proceeds slowly.

Homework
Pg. 744-745 #7, 8, 9a,10a

Obtaining Rate Laws From Experimental Data

Yesterday, we figured out how to determine the order of a reaction when we were given the rate law. It was pretty easy to add exponents, but Where do those exponents come from? Hopefully, you remember that those exponents are not simply the coefficients from the balanced equation, but are experimentally determined. Therefore, if we are given experimental data, we should be able to write our own rate laws. Right? Right?

 To do this, we will study how changes in concentration affect the rate of the reaction. A + B products We know the rate law will look something like this: Rate = k[A]m[B]n

Initial Concentrations Experiment 1 2 3 4 5 [A] mol/L 0.10 0.20 0.30 0.30 0.30 [B] mol/L 0.10 0.10 0.10 0.20 0.30 Initial rate of formation of products (mol/L/s) 0.20 0.40 0.60 2.40 5.40

 If we look at the rate law, we see that the rate is affected by both [A] and [B]. In the data, we see that [B] has been held constant in experiments 1, 2, and 3. That means that any change in the rate must be due to the change in [A].

Lets Pause Here for A Word From Our Guest Lecturer, Dr. Ian Prado.

 When [A] is doubled between experiments 1 and 2, the rate also doubles. This SIMPLIFIED relationship can be represented as 2.0 = 2.0m When [A] is tripled between experiments 1 and 3, the rate also triples. This SIMPLIFIED relationship can be represented as 3.0 = 3.0m When [A] is multiplied by 1.5 between experiments 2 and 3, the rate is also increased by a factor of 1.5. This SIMPLIFIED relationship can be represented as 1.5 = 1.5m

 So if 2.0 = 2.0m 3.0 = 3.0m 1.5 = 1.5m

Whats m? m=1 Therefore, the reaction is first order with respect to A. But, what about B?

 If we look at the rate law, we see that the rate is affected by both [A] and [B]. In the data, we see that [A] has been held constant in experiments 3, 4, and 5. That means that any change in the rate must be due to the change in [B].

 When [B] is doubled between experiments 3 and 4, the rate is increased by a factor of 4. This SIMPLIFIED relationship can be represented as 4.0 = 2.0n When [B] is tripled between experiments 3 and 5, the rate is increased by a factor of 9. This SIMPLIFIED relationship can be represented as 9.0 = 3.0n When [B] is multiplied by 1.5 between experiments 4 and 5, the rate is increased by a factor of 2.25. This SIMPLIFIED relationship can be represented as 2.25 = 1.5n

 So if 4.0 = 2.0n 9.0 = 3.0n 2.25 = 1.5n

Whats n? n=2 Therefore, the reaction is second order with respect to B. Now what?

Rate =

1[B]2 k[A]

Can we now solve for k? Substitute any rate and corresponding concentration terms into the rate law (complete with exponents) and solve! Rate = k[A]1[B]2 0.20 mol/L/s = k[0.10 mol/L][0.10 mol/L]2 k = 200 L2 mol-2s-1

Alternative Approach to Writing the Rate Law

Your Turn
Sulfuryl chloride, SO2Cl2, is used to manufacture antiseptic chlorophenol. The following data were collected on the decomposition of sulfuryl chloride SO2Cl2 (g) SO2 (g) + Cl2 (g)
[SO2Cl2] 0.100 Initial rate of formation of SO2 (mol/L/s) 2.2 x 10-6

0.200
0.300

4.4 x 10-6
6.6 x 10-6

What is the rate law and rate constant for this reaction?

Homework
Pg. 745 #11-16

Try This!
2H2 (g) + 2NO (g) N2 (g) + 2H2O (g) Initial [H2] 0.10 0.20 0.10 Concentrations [NO] Rate of Formation of H2O (mol/L/s) 0.10 1.23 x 10-3 0.10 2.46 x 10-3 0.27 8.97 x 10-3

What is the rate law for the reaction?

Logs, Your New Best Friend

Used when the value of the exponents are not super-obvious. Ratex = [A]xm Ratey [A]ym Is equivalent to:

Now Try This!

2H2 (g) + 2NO (g) N2 (g) + 2H2O (g) Initial [H2] 0.10 0.20 0.10 Concentrations [NO] Rate of Formation of H2O (mol/L/s) 0.10 1.23 x 10-3 0.10 2.46 x 10-3 0.27 8.97 x 10-3

What is the rate law for the reaction?

Homework
Rate Laws Review Worksheet Read and outline section 15.4 on pgs. 712-716 (through zero-order reactions) Quiz tomorrow!

Quiz
1.) Did you do your outline? 2.) Are you good at calculus?

Integrated Rate Laws

Use calculus to quantitatively give concentration as a function of time. Calculus and function should terrify you, but its really not that bad. The form of the integrated rate law depends on the overall order of the reaction. Remember those?

Integrated Rate Laws for First Order Reactions

Rate = k[A] ln[A]t = -kt [A]0
Where ln is the natural log [A]t is the concentration of A at time t [A]0 is the initial concentration of A k is still the rate constant t is the amount of time that has elapsed USE WHEN WE ARE GIVEN BOTH CONCENTRATIONS! WATCH YOUR UNITS OF k AND t!

Rearranged
We can obtain the concentration at time t directly as a function of time. [A]t = [A]0e-kt Where e is the base of ln ~ 2.718 USE WHEN WE NEED TO FIND ONE OF THE CONCENTRATIONS!

Example 1
2N2O5 2N2O4 + O2 The rate law is: Rate = k[N2O5] At 45C, the rate constant for the reaction is 6.22 x 10-4s-1. If the initial concentration of N2O5 at 45C is 0.500 M, what will its concentration be after exactly one hour?

Your Turn 1
C12H22O11 + H2O C6H12O6 + C6H12O6 The reaction is first order with respect to sucrose with a rate constant of 6.17 x 10-4s-1. Suppose the initial sucrose concentration was 0.40 M. What will the concentration be after exactly 2 hours?

Integrated Rate Laws for Second Order Reactions

Rate = k[A]2 1 1 = kt [A]t [A]0

Example 2
2HI (g) H2 (g) + I2 (g) Rate = k[HI]2 Where k = 30.0 L mol-1 min-1 How much time does it take for the concentration of HI to drop from 0.010 M to 0.0050 M?

Your Turn 2
Using the rate constant from the previous problem, calculate the concentration of HI after 12 minutes if [HI]0 is 0.010 M.

Integrated Rate Laws for Zero Order Reactions

Rate = k[A]0 [A]0 [A]t = kt

Homework
Pg. 746 #17, 19, 20, 21, 22 Outline pg. 716-722

Recall the Integrated Rate Law for First Order Reactions

ln[A]t = -kt [A]0

Solve this for [A]t

Calculating the Rate Constant for First Order Reactions

We should get ln[A]t = -kt + ln[A]0 Which resembles slope-intercept form (y=mx + b) from algebra class. Whats your y? Whats your m? Whats your x? Whats your b?

Graphing First Order Reactions

Plotting ln[A]t on the y-axis vs. time on the x axis should give a straight line with a slope = -k We can use this graphical method to determine whether a reaction is first order. If a plot of the natural logarithm of the concentration vs. time produces a straight line, it is a first order reaction.

Recall the Integrated Rate Law for Second Order Reactions

1 1 = kt [A]t [A]0

Solve this for 1 [A]t

Calculating the Rate Constant for Second Order Reactions

We should get 1 = kt + 1 [A]t [A]0 Which also resembles slope-intercept form (y=mx + b) from algebra class. Whats your y? Whats your m? Whats your x? Whats your b?

Graphing Second Order Reactions

Plotting the reciprocal of [A]t on the y-axis vs. time on the x axis should give a straight line with a slope = +k We can use this graphical method to determine whether a reaction is second order. If a plot of the reciprocal of the concentration at time t vs. time produces a straight line, it is a second order reaction.

Recall the Integrated Rate Law for Zero Order Reactions

[A]0 [A]t = kt Solve this for [A]t

Calculating the Rate Constant for Zero Order Reactions

We should get Which also resembles slope-intercept form (y=mx + b) from algebra class. Whats your y? Whats your m? Whats your x? Whats your b?

Calculating the Rate Constant for Zero Order Reactions

We should get [A]t = -kt + [A]0 Which again resembles slope-intercept form (y=mx + b) from algebra class. Whats your y? Whats your m? Whats your x? Whats your b?

Graphing Zero Order Reactions

Plotting [A]t on the y-axis vs. time on the x axis should give a straight line with a slope = -k We can use this graphical method to determine whether a reaction is zero order. If a plot of the concentration at time t vs. time produces a straight line, it is a zero order reaction.

Homework
Complete Rate Cheat Sheet Pg. 747 #33, 35, 37, 39

Half-Lives
A reactants half-life is the amount of time required for half of the reactant to disappear. Equations for half-lives depend on the order of the reaction.

Half-Lives of First Order Reactions

t1/2 = (ln2)/(k) Once we know k, we can refer back to the integrated rate law to find the initial concentration or the concentration at time t.

Example 1
A patient is given a certain amount of radioactive iodine-131 which has a half-life of 8.02 days based on a first order reaction . What percent of iodine-131 would be present in the patient after 25 days?

Your Turn 1
The radioactive isotope, phosphorus-32, has a half-life of 14.26 days in a first order reaction. What percent of phosphorus-32 will remain after 60 days?

Half-Lives of Second Order Reactions

For a second order reaction, half-life depends on the initial reactant concentration. t1/2 = 1 k[A]0

Example 2
A reaction has the rate law, rate = k[HI]2 with k = 0.079 L mol-1 s-1. What is the halflife for this reaction when the initial HI concentration is 0.10 M?

Your Turn 2
The rate law for a reaction is, rate = k[NO2]2. What is the half-life if the initial concentration of NO2 is 6.54 x 10-4 mol L-1 and the reaction rate is 4.42 x 10-7 mol L-1 s-1?

Homework
Pg. 746 #25, 29

Combustion of Propane
C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (g) In terms of effective collisions, this reaction is theoretically impossible. The stoichiometry shows that, in order for this reaction to occur, one molecule of propane must simultaneously and effectively collide with 5 molecules of oxygen. Have you ever played billiards?

 Clearly, the combustion of propane occurs otherwise youd never be able to have a backyard BBQ.* There must be some alternative explanation for how this happens. We call it mechanisms!

Mechanisms of Reactions
Are the series of individual steps that add up to the overall observed reaction Each individual step is called an elementary process. Usually, these elementary processes cannot be observed. We only see the net reaction which is the sum of all elementary processes with the intermediates (think spectator atoms or molecules from electrochem) canceled out. Therefore, the mechanism of a reaction is really just a theory which cannot be proven.

Elementary Processes
Each have their own activation energy, Ea, and rate constant, k Must add up to give the balanced equation for the overall reaction Can be:
Unimolecular = only one molecule as the reactant (A products) Bimolecular = two molecules as the reactants (A + A products or A + B products) Termolecular = three molecules as the reactants (3A products, 2A + B products, or A + B + C products) We usually dont go above termolecular elementary processes because of good ol probability.

Confession
Remember how I drilled it into your head that the coefficients from the OVERALL balanced equation have nothing to do with the exponents for the rate law? And remember how Ian had to teach us how to experimentally determine those exponents? Well, I lied sort of.

 FOR ELEMENTARY PROCESSES ONLY: THE RATE LAW FOR AN ELEMENTARY STEP IS DEFINED BY THE INTERMEDIATE REACTION STOICHIOMETRY.

Example
2NO (g) + 2H2 (g) N2 (g) + 2H2O (g) Rate = k [NO]2[H2] Could this reaction occur in a single step where two NO molecules collide perfectly with two H2 molecules? Probably not. This reaction likely occurs in a series of elementary steps. Can you figure out what they might be?

Example, Continued
The elementary processes might look something like this: 2NO (g) + H2 (g) N2O (g) + H2O (g) N2O (g) + H2 (g) N2 (g) + H2O (g) Looks good, right? Would it be likely for 2 molecules of NO and one molecule of H2 to collide perfectly as is written in the first step? Probably not.

Example, Continued
The actual mechanism for this reaction looks like this: 2NO (g) N2O2 (g) (fast) N2O2 (g) + H2 (g) N2O (g) + H2O (g) (slow) N2O (g) + H2 (g) N2 (g) + H2O (g) (fast) Howd they get that? It doesnt matter. Who cares? Not us.

Good News and Bad News

The good news is that we dont have to worry about writing mechanisms. The bad news is that we do have to be able to answer certain questions about them:
Given a proposed reaction mechanism, can you write the overall reaction? Given a proposed reaction mechanism, can you identify the rate-determining step? Given a proposed reaction mechanism, can you write the rate law for each elementary process?

Example 1
Step 1: Br2 (g) + NO (g) Br2NO (g) Step 2: Br2NO (g) + NO (g) 2BrNO (g)

Write the overall reaction. Write the rate law for each elementary step.

Your Turn 1
Step 1: ClO (aq) + ClO (aq) ClO2 (aq) + Cl- (aq) Step 2: ClO2 (aq) + ClO (aq) ClO3 (aq) + Cl (aq) Write the overall reaction. Write the rate law for each elementary step.

What About the Rate-Determining Step?

Like dealing with sig figs, look for the weakest link. A reaction can only proceed as quickly as its slowest step. Think about a slow worker on an assembly line. The rate law for the rate-determining step is RELATED to the rate law for the OVERALL reaction, but it cant include any intermediates.

Example 2
The decomposition of NO2Cl is proposed to occur by the following mechanism: Step 1: NO2Cl NO2 + Cl (fast) Step 2: NO2Cl + Cl NO2 + Cl2 (slow) Write the overall reaction. Identify the rate-determining step. Predict the rate law for the OVERALL reaction.

 AN INTERMEDIATE CANNOT BE INCLUDED IN YOUR RATE LAW. WE DONT EVEN KNOW IF IT REALLY EXISTS! REPLACE YOUR INTERMEDIATE WITH ITS SOURCE. YOU MIGHT END UP WITH A DENOMINATOR, BUT THATS PERFECTLY OKAY. VERY COMMON FOR MECHANISMS THAT INVOLVE EQUILIBRIUM!

Your Turn 2
A mechanism is proposed as: Step 1: NO2 + F2 NO2F + F (slow) Step 2: NO2 + F NO2F (fast) Write the overall reaction. Identify the rate-determining step. Predict the rate law for the overall reaction.

Homework
Pg. 748-749 # 47, 49, 51, 53 (try part b)

Bringing it all home

So, were talking about graphical analysis to find rate constants and the overall order of the reaction. Is there anything else we can determine graphically? The answer is yes. Its activation energy. Remember that?

Back to Activation Energy

Activation energy is the energy hump that reactants must get over to form products. For this exothermic reaction, its relatively small (compared to the activation energy of the reverse reaction).

The Arrhenius Equation

Arrhenius (the acid guy) found a link between activation energy and the rate constant, k. k = Ae-Ea/RT Where k is the rate constant A is called the frequency factor e is the base of the natural log system Ea is activation energy R is the universal gas constant (8.314 J mol-1 K-1) T is the temperature in Kelvin

The Useful Arrhenius Equation

ln k = (-Ea/R) (1/T) + ln A This should resemble slope-intercept equation of a line. Whats your y? Whats your m? Whats your x? Whats your b?

Graphical Determination of Ea
Graphing ln k on the y-axis and 1/T on the x-axis should produce a graph where the slope is equal to Ea/R. We know R is equal to 8.314 J mol-1 K-1 so we can easily solve for Ea.

Example 1
Graphically determine the Ea for the following data set: 2NO2 (g) 2NO (g) + O2 (g) k (mol L-1 s-1) 7.8 9.9 14 18 24 Temperature (C) 405 415 425 435 445

Your Turn 1
The reaction CH3I + HI CH4 + I2 was observed to have rate constants: k = 3.2 L mol-1 s-1 at 355C k = 23 L mol-1 s-1 at 405C What is the order of the reaction? What is the value of Ea expressed in kJ/mol?

Homework
Pg. 748 # 41, 43