Chapter 14

Chemical Kinetics

The Rate of a Reaction

Chemical Kinetics is the area of chemistry concerned with the speeds, or rates, at which a chemical reaction occurs. The reaction rate is the change in the concentraiton of a reactant or a product with time (M/s). Reactions have very different rates at which they occur. Some processes, such as the initial steps in photosyntesis and nuclear chain reactions, take place on a time scale as short as 10-12 seconds to 10-6 seconds. Others, like the conversion of graphite to diamond, take years or millions of years to complete. Industrial chemists often focus on how to speed up a rate of a reaction rather than maximizing its yield.

We know that any reaction can be represented by the general equation: Reactants -> Products This states that as products are formed, reactants are consumed. So we can follow the progress of a reaction by monitoring either the decrease in concentration of the reactants or the increase in concentration of the products. When A molecules are converted to B molecules: A -> B The decrease in the number of A molecules and the increase in the number of B molecules can be measured with time. In general, it is more convenient to express the reaction rate in terms of the change in concentration with time. Therefore, for the reaction A -> B, we can express the rate as: rate = - D[A] / Dt or rate = D[B] / Dt Notice the only difference between the equations is that A has a negative concentration because it decreases with time (therefore the concentration would be a negative value and the rate is not negative, we need to add a negative sign in order to make the overall rate positive!) and B has a positive concentration because it increases with time. These are average rates because they occur over a certain time period, Dt.

Experimentally Determining Average Reaction Rates

For reactions in solutions, the concentration of a species can be measured by spectroscopic means. Or, if ions are involved, the change in concentration can be measured by electrical conductance. Gas reactions are most easily followed by pressure measurements. Reaction of Molecular Bromine and Formic Acid In aqueous solutions, molecular bromine reacts with formic acid (HCOOH) as follows:
Br2 (aq) + HCOOH (aq) -> 2Br- (aq) + 2H+ (aq) + CO2 (g) Molecular bromine is reddish-brown in color. All the other species in the reaction are colorless. As the reaction progresses, the concentration of Br2 steadily decreases and its color fades. This loss of color and hence concentration can be monitored easily with a spectrometer, which registers the amount of visible light absorbed by bromine.

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Experimentally Determining Average Reaction Rates

Measuring the change (decrease) in bromine concentration at some initial time and then at some final time allows us to determine the average rate of the reaction during that interval: Average rate = - D[Br2] / Dt Average rate = - [Br2]final - [Br2]initial / tfinal - tinital Using the following data: Time (s) [Br2] (M) 0.0 0.0120 50.0 0.0101 100.0 0.00846 We can calculate the average rate over the first 50 sec time interval as follows: Avg rate = - (0.0101 0.0120)M / 50.0 sec = 3.80 x 10-5 M/s If we had chosen the first 100 sec as our time interval, the average rate would then be: Avg rate = - (0.00846 0.0120)M / 100.0 sec = 3.54 x 10-5 M/s These calculations show us how the avg rate of the rxn depends upon the time interval that we choose.

Rate of at a specific instant in Time

If we calculate the average rate of a reaction over shorter and shorter intervals, we can obtain the rate for a specific instant in time, which gives us the instantaneous rate of the reaction at that time. If we plot the previous data as concentration versus time, we can find the instantaneous rate at any point in time by taking the slope of the tangent to the curve of the graph at that point. Unless otherwise stated, the instantaneous rate will be referred to as just the rate. An example between instantaneous and average rate is if you were to take a trip somewhere and you found the average speed to be 65 miles per hour for the whole trip. This does not mean that you were going 65 miles every second of the trip, you may have been doing 100 mph or 0 mph at any instant in time. This is considered an instantaneous speed.

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The graph in the next slide shows the rate vs. concentration of the Bromine and Formic Acid reaction. The fact that the graph is a straight line shows that the rate is directly proportional to the concentration, the higher the concentration, the higher the rate. rate a [Br2] rate = k [Br2] k is known as the rate constant, a proportionality constant rate = k [Br2] k = rate / [Br2] Since reaction rate has the units M / s, and [Br2] is in M, the unit of k is 1/s, or s-1 in this case (k has varying units and will not always equal s-1). Using the previous information in the data table, we can calculate the rate constant for t = 50 sec: k = (3.52 x 10-5 M/s) / 0.0101 M k = 3.49 x 10-3 s-1

The Rate Law

The rate law expresses the relationship of the rate of a reaction to the rate constant and the concentrations of the reactants raised to some powers. For the general reaction aA + bB -> cC + dD The rate law takes the form: rate = k[A]x[B]y Where x and y are numbers that must be determined experimentally. Note that, in general, x and y are not equal to the stoichiometric coefficients a and b. The exponents x and y specify the relationships between the concentrations of reactants A and B and the reaction rate. Adding together, they give us the overall reaction order, x + y. But note that you would say that the reaction order is xth order in A and yth order in B.

Determining the rate law of a reaction

Let us consider the reaction: F2 (g) + 2ClO2 (g) -> 2FClO2 (g) The data of the concentrations of the reactants and the initial rate (which is the rate that depends on the starting concentrations of the reactants) was: [F2] (M) [ClO2] (M) Initial Rate (M/s) (a) 0.10 0.010 1.2 x 10-3 (b) 0.10 0.040 4.8 x 10-3 (c) 0.20 0.010 2.4 x 10-3 Looking at the three rate measurements for the formation of FClO2, we see that (a) and (c) values have [ClO2] the same while [F2] and the rate doubles. Also notice that (a) and (b) values show [ClO2] and the rate quadrupling while [F2] remains constant. rate = k[F2]x[ClO2]y (c) 2.4 x 10-3 = k [0.20]x[0.010]y (a) 1.2 x 10-3 = k [0.10]x[0.010]y
2 = [0.20 / 0.10]x Therefore, x and y = 1 and x and y are both called first order and the overall order of the reaction = 2: rate = k [F2] [ClO2]

We can use the final rate law of the previous reaction in order to determine the rate constant for the reaction, k.

rate = k [F2][ClO2]
k = rate / [F2][ClO2] k = (1.2 x 10-3 M/s) / (0.10 M)(0.010M) k = 1.2/ M x s Also note that ClO2 was raised to the first power even though the stoichiometric coefficient for ClO2 in the reaction was 2. This is because the orders of the reactants do not depend upon the stoichiometric coefficients. F2 (g) + 2ClO2 (g) -> 2FClO2 (g) For future calculations always remember that any number raised to the power of 1 = that number, (example: 21 = 2), and any number raised to the power of 0 equals 1, (example: 20=1).

Summary of Rate Law Rules

1. Rate laws are always determined experimentally. From the concentrations of the reactants and the initial reaction rates we can determine the reaction order and then the rate constant of the reaction. 2. Reaction order is always defined in terms of reactant (and not product) concentrations. 3. The order of the reactant is not related to the stoichiometric coefficient of the reactant in the overall balanced equation. 4. The overall order of the reaction is equal to the sum of the orders of all of the individual reactants. 5. If the order to a reactant is zero, then it tells us that the rate of the reaction is independent of the concentration of that reactant. 6. The reaction order can be a fraction.

First Order Reactions

A first-order reaction is a reaction whose rate depends on the reactant concentration raised to the first power. The reaction: A -> product Has the rate: rate = - D[A] / Dt From the rate law we also know that: rate = k[A] If we combine these two rates we get: D[A] / Dt = k[A] Using calculus we get the following, which is used to solve most problems: ln ([A] / [A]0) = -kt [A]0 = initial concentration of A [A] = concentration at time = t Rearranging the equation gives us the linear equation y = mx + b : ln [A] = -kt + ln [A]0 If we plot ln [A] as y and t as x, the slope = -k, is a straight line. This is an important characteristic of a first order reaction that should be memorized!

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Solving First Order Rxn Problems

The conversion of cyclopropane to propene in the gas phase is a first order reaction with a rate constant of 6.7 x 10-4 s-1 at 500 degrees Celsius. (a) If the initial concentration of cyclopropane was 0.25 M, what is the concentration after 8.8 min? (b) How long will it take for the concentration of cyclopropane to decrease from 0.25 M to 0.15 M? (c) How long will it take to convert 74% of the starting material? Remember when solving the problem ln can be canceled out by using ex and whatever you do to one side of an equal sign, you must also do to the other side! (a) 0.18 M (b) 13 min (c) 33 min = 1/k ln (1.0 / 0.26)

Using Pressure for a first order Rxn

The gas producing rxn: 2N2O5 -> 4NO2(g) + O2(g) In order to get the [A] and [A]0 for N2O5 we use the results of the pressure from an experiment and the ideal gas law: PV = nRT n/V = [A] = P/RT We plug this into the first order rxn equation to get: ln ([A]/[A]0) = ln [(P/RT)/(P0 /RT)] = ln P / P0 = -kt Now we get the linear eqn: ln P = -kt + ln P0 We use the graph of ln P vs. time in order to find the straight line slope = -k.

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Half-Life of a First Order Rxn

Another measure for the rate of a reaction is the half-life, t1/2. This is the time required for the concentration of a reactant to decrease to half of its initial concentration. For the first order rxn the half-life is found from rearranging the previous equation into: t = (1/k) ln ([A]0/[A]) We know that the half life is when t = t1/2 which has [A] = [A]0/2 ...The final conc. @ half life = (initial concentration) t1/2 = (1/k) ln ([A]0/([A]0/2))
(Notice every rxn life is independent of initial concentration, it only depends upon the rate constant, k).

t1/2 = (1/k) ln 2 = 0.693 / k

Second Order Reactions

A second-order reaction is a reaction whose rate depends on the concentration of one reactant raised to the second power or on the concentrations of two different reactants, each raised to the first power. For the reaction: A -> product Has the rate: rate = - D[A] / Dt From the rate law we also know that: rate = k[A]2 If we combine these two rates we get: D[A] / Dt = k[A]2 Using calculus, we get: 1/[A] = (1/[A]0) + kt [A]0 = initial concentration of A [A] = concentration at time = t
For the reaction: A + B -> product rate = k[A][B] This type is too complex to discuss!!

Has the rate:

Half-Life of a Second Order Rxn

Another measure for the rate of a reaction is the half-life, t1/2. This is the time required for the concentration of a reactant to decrease to half of its initial concentration. We know that the half life is when t = t1/2 which has [A] = [A]0/2 ...The final conc. @ half life = (initial concentration)
Therefore, rearranging the previous equation and using the above information, we get:

(Notice every rxn life for a second order rxn is dependant upon the initial concentration and the rate constant, k).

1 / ([A]0/2) = 1 / [A]0 + kt1/2 t1/2 = 1/k[A]0

Zero Order Reactions

Reactions with zero orders are rare. For a zero order rxn: A -> Product The rate law is given by: rate = k[A]0 rate = k This means that the rate of a zero order reaction is a constant, independent of concentration.

What effects the Rate of a Reaction?

The Type of the Reactants. Activation Energy. Orientation Factor Catalysis The number of collisions of the reactant. The Concentration of the reactants. The Temperature of the reactants. For gas reactions (PV = nRT, so pressure will also effect the rate). As pressure increases, reaction rate increases. Because pressure is inversely proportional to volume so as pressure goes up, volume goes down, which makes concentration mol/L increase. The Surface Area of Reactants. The more surface area reactants expose to one another, the greater the number of reactant molecular collisions and therefore, the faster the reaction rate. Only solids and liquids can have their surface area changed. We can increase solids by breaking it up or grinding it into a powder. We can increase liquids by spraying it out as a mist of fine droplets.

The Type of the Reactants

The Strength of the bond the stronger the bond, the harder it is to break and the longer the reaction. The weaker the bond, the easier it is to break and the faster the reaction. Except when you look at dissolved ionic compounds (which are strong bonds, but they are dissociated in water). Ionic compounds react faster because when dissociated, the charges are attracted to one another and collide often. Therefore double displacement reactions occur quickly. Electron transfers and bond rearrangement reactions take longer. Typically molecular compounds and single displacement reactions and oxidation-reduction reactions take longer to react than ionic compounds because they must break their bonding and rearrange the electron clouds between atoms to create new bonds.

Activation Energy, Ea
When molecules collide, they need enough energy from their collision to break the bonds in order for a chemical reaction to occur. If there is little amount of energy held in their kinetic energy from motion, then the bonds will not break and the molecules will simply bounce off one another. We postulate that in order to react, the colliding molecules must have a total kinetic energy that is greater than or equal to the activation energy, Ea, which is the minimum amount of energy required to initiate a chemical reaction. When molecules collide, they form an activated complex (also known as the transition state), which is a temporary species formed by the reactant molecules as a result of the collision before they form the product.

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Exothermic Reaction

Endothermic Reaction

Orientation Factor
Sometimes the way in which the molecules collide when they react is important. For example, in the reaction between potassium and methyl iodide, the reaction
occurs only when the potassium hits the Iodine part.

Catalysis
Catalysis a substance that increases a reaction rate without being permanently changed is called a catalysis. A catalyst lowers the activation energy of the activated complex so that the reaction can occur faster and with less energy. A homogeneous catalyst means the reactants and the catalyst are in the same phase. Enzymes in the body are examples of homogeneous catalysts. Where enzymes are used for a variety of body functions. One example is to break down hydrogen peroxide, H2O2 into water and oxygen inside the body so that it does not harm us. A heterogeneous catalyst means the reactants and the catalyst are in different phases. Usually the catalyst is a solid and the reactants are either gases or liquids. For example, a solid piece of iron (catalyst) can be placed into a vessel with N2 and H2. The N2 and H2 molecules will attach to the surface of the catalytic iron and therefore weaken the bonding between the N-N and H-H molecules. Once this bond is weaker, the activation energy for the reaction is lower and the following reaction occurs (Known as the Haber process): N2(g) + 3H2(g) g 2NH3(g)

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Catalytic Converters in Cars

At high temperatures inside a running cars engine, nitrogen and oxygen gases react to form nitric oxide: N2(g) + O2(g) g 2NO(g) When released into the atmosphere, NO rapidly combines with O2 to form NO2. Nitrogen dioxide and other gases emitted by an automobile, such as carbon monoxide (CO) and unburned hydrocarbons make automobile exhaust a major source of air pollution. Most new cars are equipped with catalytic converters. These converters serve as 2 purposes: It oxidizes CO and unburned hydrocarbons to CO2 and H2O, and it reduces NO and NO2 to N2 and O2. These catalytic converters are an example of a heterogeneous catalysts. They are usually made of platinum, palladium, and rhodium, which catalyze the combustion of CO and hydrocarbons.

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Collision Theory of Chemical Kinetics

We all know that as temperature increases, the rate of a rxn increases. But, why? The Collision Theory states that chemical rxns occur as a result of collisions between reacting molecules. This means that we expect the rate of a rxn to be directly proportional to the number of molecular collisions per second: Rate a (number of collisions / second) This explains why reaction rates are dependant upon concentrations. If you increase the number of molecules, then the number of collisions per second will increase. Note that collisions alone do not explain the rates of all reactions! In some cases, collisions do not guarantee that a reaction will take place.

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Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

What effects the Rate of a Reaction?

The Type of the Reactants. Activation Energy. Orientation Factor Catalysis The number of collisions of the reactant. The Concentration of the reactants. The Temperature of the reactants. For gas reactions (PV = nRT, so pressure will also effect the rate). As pressure increases, reaction rate increases. Because pressure is inversely proportional to volume so as pressure goes up, volume goes down, which makes concentration mol/L increase. The Surface Area of Reactants. The more surface area reactants expose to one another, the greater the number of reactant molecular collisions and therefore, the faster the reaction rate. Only solids and liquids can have their surface area changed. We can increase solids by breaking it up or grinding it into a powder. We can increase liquids by spraying it out as a mist of fine droplets.

Reaction Mechanisms
In many cases, the total reaction occurs in several elementary steps, or elementary reactions, where a series of simple reactions create the overall reaction. The term for the sequence of elementary steps that leads to the product formation is reaction mechanism. For example the overall rxn is: 2NO(g) + O2(g) -> 2NO2(g) Occurs in steps: (1) 2NO(g) -> N2O2(g) (2) N2O2(g) + O2(g) -> 2NO2(g) N2O2(g) is said to be an intermediate because they appear in the mechanism but do not appear in the overall balanced equation. If you are going on a trip, the origin and destination addresses are similar to the reactants and production in the overall balanced reaction equation. The directions of turning left at a particular street after going 2.3 miles is an example of the reaction mechanism.

The slowest elementary step is the rate-determining step!

Example- in a traffic jam on a narrow road, the rate at which the cars travel is governed by the slowest-moving car in the front (remember if 5 or more cars are following you-pull over and let them pass!)

Rules for postulating a plausible reaction mechanism: 1. The sum of the elementary steps must give the overall balanced equation for the reaction. 2. The rate-determining step should predict the same rate law as is determined experimentally even if it involves an intermediate as part of the rate law!

Arrhenius Equation
The dependence of the rate constant of a reaction on temperature can be expressed by the Arrhenius Equation: k = Ae-Ea/RT A = collision frequency-treat as a constant. Shows k a A. Shows k a 1/Ea. Shows k a T. Rearranging for a linear Equation: ln k = (-Ea/R)(1/T) + ln A y = m x + b

Slope = -Ea/R

When two temperatures and rate constants are used a new equation is obtained from subtracting two separate arrhenius eqns:

ln (k1/k2) = (Ea/R)[(T1 T2)/(T1T2)]