Transcript: Honors Chemistry

Chemical Reactions: Reaction Rates

Scene 1
Carbon monoxide is a poisonous gas that is formed in automobile engines and released in their
exhaust. When a car idles in an enclosed area, such a garage, the concentration of carbon monoxide
can quickly become dangerous, or even lethal. Carbon monoxide reacts with molecular oxygen present
in the air of the garage and produces a far less toxic gas, carbon dioxide. From an energy standpoint,
carbon dioxide is a greatly favored reaction, and given enough time, essentially all of the carbon
monoxide reacts with the oxygen and is converted into carbon dioxide. This might lead you to think that
carbon monoxide should not present a health risk, since there is plentiful oxygen in the air to react with
carbon monoxide. However, this is not the case. In spite the fact that carbon monoxide is eventually
converted into carbon dioxide, the rate of reaction is so slow that the carbon monoxide concentration in
the garage can quickly build to a toxic level. When the exhaust of the car is run through a catalytic
converter, however, the reaction rate is much faster, and most of the carbon monoxide quickly reacts
with oxygen and is converted into carbon dioxide. The reasons carbon monoxide and oxygen react so
slowly with each other, the role of the catalytic converter in speeding up the reaction, and other topics
relating to reaction rates are covered in this program.

Scene 2
Before introducing reaction rates, it is important to understand what a rate is. A rate is defined
as the amount of change per unit time. A rate you are probably familiar with is rate of travel, or speed.
Suppose you are in a plane that travels from London to New York in six hours, and the distance from
London to New York is 5,585 kilometers. You can easily set up an equation that gives you the rate of
travel. Simply divide the distance traveled, or change in position in this case, 5,585 kilometers by
the time, which is six hours. In this example, the rate is 931 kilometers per hour. In contrast, a sailboat
on a calm day travels at a much lower rate, perhaps only eight kilometers per hour.

Scene 3
Speed is only one example of a rate. Here are two more rates. At a ski resort, you might be able
to rend a snowboard at the rate of $25 per day. The number of vibrations a guitar string makes per
second determines the note produced by the guitar. Notice that in each of the three examples, the unit
of time is different. The time unit for the airplane speed is hours; the snowboard rental is days, and the
vibration of the guitar string is measured in seconds. The unit of time selected for a specific rate is
usually based on convenience. For example, it is easier to comprehend that a car is moving at a rate of
60 kilometers per hour, which is 37 miles an hour, than the equivalent speed in seconds, which is 0.017
kilometers per second, or 0.010 miles per second.

Scene 4
Since many chemistry and physics problems involve a conversion in the time unit, it is important
to understand how to convert units of time. It is fairly simple to make these conversions. Say you want
to know how many kilometers the plane in the previous scenes travels in one second. In this case, set
up the equation by multiplying the speed 931 kilometers per hour by the conversion factors. One
hour equals 60 minutes, and one minute equals 60 seconds. Remember to cancel units. Arriving at the
correct units in your final answer is a sign that you are doing things correctly. Performing the calculation
shows the plane travels 0.259 kilometers per second.

Page 1 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 5
Since you are now familiar with rates, we can move on to discuss the rates of chemical
reactions. Chemical reactions can be extremely fast, as when a balloon full of hydrogen gas quickly
reacts with oxygen and bursts into flame in the presence of a spark. Reactions can be much slower as
well. The reactions that converted compressed plant matter into coal took many thousands of years.
The careful study of reaction rates, including the factors that influence them and the mechanisms by
which they occur, is known as kinetics. Understanding the kinetics of a reaction can help chemists
devise methods for speeding up important industrial processes, such as petroleum refining, which
produces gasoline and oil. A detailed understanding of reaction rates also gives chemists a picture of
what is going on at the atomic level during chemical reactions.

Scene 6
The following scenes follow the progress of the decomposition, or break down, of the colorless
gas dinitrogen pentoxide to show how the rates of chemical reactions are measured. If a sample of
dinitrogen pentoxide gas is placed in a sealed container, it decomposes, or breaks down, into brown
nitrogen dioxide gas and molecular oxygen. The balanced equation for this reaction is shown on your
screen. This reaction does not occur instantaneously, so at a given time, only a certain fraction of the
dinitrogen pentoxide has decomposed. For example, suppose 0.050 moles of the reactant are placed in
a previously empty one liter container. The initial concentration of dinitrogen pentoxide is 0.050 moles
per liter. Square brackets around a chemical formula indicate a concentration. The dinitrogen pentoxide
immediately starts decomposing, so there are less molecules of the reactant in the same volume. This
means there is a lower concentration of the reactant after a given time. A sample taken after one
minute reveals that the concentration of dinitrogen pentoxide has gone down to 0.033 moles per liter.
What has happened to the concentrations of nitrogen dioxide and oxygen? Since the decomposition of
the reactant leads to the formation of the product, the concentrations of these two gases increase.

Scene 7
In the last scene, you saw the change in concentration of dinitrogen pentoxide over a one
minute period. Although the data were given in terms of the concentration of dinitrogen pentoxide, this
did not have to be the compound that was actually measured. Often it is easiest to measure the
concentration of one particular reactant or product during the course of a reaction, but this may not
necessarily be the substance one is studying. For example, in the reaction from the last scene, it is
relatively easy to measure the concentration of nitrogen dioxide, which is a brown gas, by using a
device that determines the concentration of the gas by how brown it becomes. Even when you are
investigating the breakdown of dinitrogen pentoxide, it may be easier to measure the concentration of
nitrogen dioxide and use the measurement obtained to calculate the concentration of dinitrogen
pentoxide. In the previous scene, it was noted that as the concentration of dinitrogen pentoxide
decreases, the concentrations of nitrogen dioxide and oxygen increase. If you know the change in
concentration of one reactant or product, you can determine the changes in concentrations of all the
others, based on the stoichiometric relationships of the balanced equation. In this reaction, the
balanced equation shows every two moles of dinitrogen pentoxide that breaks down produces four
moles of nitrogen dioxide and one mole of molecular oxygen.

Page 2 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 8
For an example on how to calculate changes in concentration from stoichiometric relationships,
look at the following data from the production of nitrogen dioxide. The initial concentration of nitrogen
dioxide in the one liter container was 0 moles per liter, and after one minute the concentration of
nitrogen dioxide was 0.034 moles per liter. Since the concentration of nitrogen dioxide s 0.034 moles
per liter and the volume of the container is one liter, there is a total of 0.034 moles of nitrogen dioxide.
The experimental data that you have are for nitrogen dioxide, but the compound under investigation is
dinitrogen pentoxide. How many moles of dinitrogen pentoxide must have decomposed to produce
0.034 moles of nitrogen dioxide? As you can see from the balanced equation, for every two moles of
dinitrogen pentoxide broken down, there are four moles of nitrogen dioxide created. Multiplying 0.034
moles of nitrogen dioxide times the conversion factor of two moles of dinitrogen pentoxide for every four
moles of nitrogen dioxide shows that 0.017 moles of reactant decomposed.

Scene 9
Now that you can determine the concentration of all the reactants and products, you can learn
to calculate reaction rate. The reaction rate of a given product or reactant is the change in the
concentration of that reactant or product per unit of time. In mathematical terms, the reaction rate for a
given reactant or product equals the change in its concentration divided by the change in time. Change
in concentration is equal to the concentration of a reactant or product at time2, which is the time the
second measurement is made, minus its concentration at time1, the time the first measurement is
made. The change in time is simply time2 minus time1. The uppercase Greek letter delta is used to
signify change, so the equation can be rewritten as delta concentration divided by delta time. The
concentration of reactants becomes smaller as they are used up to form products, so the concentration
of reactants at time2 will be smaller than the concentration at time1. This means that for reactants, the
overall expression for the reaction rate will be negative. Since it is conventional to report reaction rates
as positive numbers, simply multiply the value found for reactants by negative one. When finding the
reaction rate for products, the negative sign is not necessary, since products are being formed and the
concentration at time2 will be greater than at time1. It is also important to clearly note the product or
reactant for which you are determining the rate, since the rate of formation or disappearance depends
on the stoichiometric ratio in the balanced equation. For example, hydrogen will be consumed twice as
fast as oxygen in the reaction 2H2 plus O2 yields 2H2O, because the ratio is two moles of hydrogen per
mole of oxygen.

Scene 10
In the last scene, you learned how to determine the rate at which a specific reactant or product
reacts. You also learned that the reaction rate for different products or reactants differs based on their
stoichiometric coefficients. To determine the overall rate for the entire reaction, simply divide the rate of
each of the reactants and products by its stoichiometric coefficient. Doing this normalizes the reaction.
In other words, it gives you only one reaction rate for the overall reaction. As an example, consider the
reaction of nitrogen and hydrogen gases, which produces ammonia gas. The reaction rate for a given
reactant say, hydrogen is the change of its concentration divided by time, and multiplied by negative
one, since hydrogen is a reactant. To get the overall reaction rate, divide the rate by its stoichiometric
coefficient, which for hydrogen is three. If you had measured the reaction rate of ammonia, what would
you do to find the overall rate? Do you see why you divide by two, which is the stoichiometric
coefficient? In this case, you do not multiply by negative one, since ammonia is a product and the rate
is already positive. The normalized rates equal each other, and normalizing gives you one reaction rate
for the entire reaction, so you dont have separate rates for each reactant and product. In the next
scene, you will see a numerical example of how to determine the reaction rate of a specific reactant,
and how to use stoichiometric coefficients to obtain the overall reaction rate.

Page 3 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 11
Using the equation from the last scene, you can calculate the average reaction rate of dinitrogen
pentoxide in the first minute of experiment shown in previous scenes. Substitute the known values into
the rate equation shown on the screen, subtracting the concentration at time1 0.050 moles per liter
from the concentration at time2 0.033 moles per liter gives a difference of -0.017 moles per liter.
This is divided by the change in time, which is time2 60 seconds - minus time1 0 seconds. This
means the change in time equals 60 seconds. The change in the concentration of the reactant
dinitrogen pentoxide over the first minute of the reaction is -2.8 x 10-4 moles per liter-second. Since a
reaction rate cannot be negative, multiply by negative one, which gives you a reaction rate of 2.8 x 10-4
moles per liter-second. Many reaction rates are given in moles per liter second, but slower reactions
may be given in terms of minutes, hours, or even days. To normalize the reaction, divide 2.8 x 10-4
moles per liter-second by the stoichiometric coefficient of dinitrogen pentoxide, which is two. This gives
an overall reaction rate of 1.4 x 10-4 moles per liter-second. Earlier, you saw when 0.017 moles of
dinitrogen pentoxide decomposed in the first minute, 0.034 moles of nitrogen dioxide were created.
Using this data to solve for the reaction rate of nitrogen dioxide gives the value 5.7 x 10-4 moles per
liter-second. Note that in this case you do not multiply by negative one, since nitrogen dioxide is a
product. Dividing 5.7 x 10-4 moles per liter-second by the coefficient of nitrogen dioxide, which is four,
yields an overall reaction rate of 1.4 x 10-4 moles per liter-second. This is the same value obtained
earlier when the rate of decomposition of dinitrogen pentoxide was normalized, which is the reason for
normalizing the reaction.

Scene 12
Now assume the reaction discussed in the previous scene continues and measurements are
made at one minute intervals. The chart shown on your screen shows the concentrations of dinitrogen
pentoxide at the first three time intervals. Do you notice anything about the differences in
concentration? The size of the difference in concentration gets smaller each minute, meaning that less
dinitrogen pentoxide is breaking down, and therefore the reaction rate is decreasing. For example, in
the first minute 0.017 moles of dinitrogen pentoxide decompose; in the second minute, 0.011 moles
decompose, and in the third minute, only 0.007 moles decompose. From the last scene, you know the
rate that dinitrogen pentoxide decomposes over the first minute is 2.8 x 10-4 moles per liter-second.
Substituting values from the chart in the rate equation shows that the average rate of dinitrogen
pentoxide decomposition over the second minute is 1.8 x 10-4 moles per liter-second, and over the third
minute it is 1.2 x 10-4 moles per liter-second. In other words, as the concentration of dinitrogen
pentoxide decreases, the reaction goes slower.

Scene 13
The data from the last scene, along with further measurements, have been plotted on this
graph. Time is measured along the horizontal, or x, axis, and the concentration of the reactant is
measured along the vertical, or y, axis. In the previous scenes, the average reaction rates were
determined for three one minute periods. However, these are average rates, and the rate at any instant
of these given periods known as the instantaneous rate is not likely to be the same as the average
rate. While this program will not go into the math involved in determining the instantaneous rate, it is
important to realize that the instantaneous rate at a given time is related to the slope of the line that is
tangent to the curve at the time the rate is measured. The tangent line for a point on the curve is the
line that touches the curve at only that point. The slope of a line is equal to rise over the run, or the
distance the line travels along the y axis divided by the distance it travels along the x axis. As a reaction
proceeds, the rate of reaction decreases, so the slope of the tangent line becomes flatter. Just as a
skier will go slower if she starts at a less steep part of the hill, the rate of reaction is slower in less steep
portions of the curve. The reaction rates given in the remainder of the program will be instantaneous
rates.

Page 4 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 14
The rates of chemical reactions depend on several factors, some of which may already be
familiar. You may have noticed that food cooks faster at a higher temperature, or that it is easier to
start a fire by lighting twigs and other small pieces of wood than it is to light a large branch. Among the
factors that influence reaction rate are: the concentration of the reactants, the temperature at which a
reaction is conducted, the surface area of solid or liquid reactants, the presence of catalysts, and the
nature of the reactants. Each of these factors will be addressed in the next section of the program.

Scene 15
The nature meaning the identity and state of the reactants themselves affects reaction rates.
At one extreme, alkaline metals, such as metallic potassium, will react quickly when exposed to air,
water, and many other substances. At the other extreme, a Noble gas, such as argon, does not react
under normal circumstances. Another important factor is the physical state of the reactants. In general,
a substance in the gas phase reacts faster than that substance in the liquid phase, which reacts faster
than that substance in the solid phase. This is because particles in the gas phase move more freely
than particles in the liquid phase, and particles in a liquid move more freely than particles in a solid.
Particles that move more freely are able to collide more often, and as you will see later in the program,
more collisions lead to a faster reaction rate.

Scene 16
Almost all reactions are slower at lower temperatures and faster at higher temperatures. For
many chemical reactions, the reaction rate doubles for every 10 degree Celsius rise in temperature,
though this is a crude approximation. An example of a reaction that takes place faster at higher
temperatures is the hardening of glue. This means you have less time to work with the glue at higher
temperatures before it hardens. Another example of the effect of temperature on reaction rates is the
activity level of insects. Insects do not maintain a constant internal temperature. Since the temperature
inside the insect is essentially the same as the outside temperature, the reactions occurring inside the
insect occur more slowly at lower temperatures, and the insect tends to move more slowly. This is why
you can accurately estimate the temperature by counting the number of times a cricket chirps in one
minute. Since the activity of the cricket decreases at lower temperatures, it chirps at a lower rate when
it is cold.

Scene 17
At the beginning of the program, you learned that carbon monoxide from car exhaust reacts
slowly with atmospheric oxygen. Inside a cars catalytic converter, the temperature and concentration of
reactants are similar to the rest of the exhaust system, yet the reaction takes place much more quickly
in the catalytic converter. This is because in the catalytic converter, metals such as platinum and
palladium act as catalysts. A catalyst is a substance that increases the rate of a reaction and is not
changed at the end of the reaction. Since a catalyst is unchanged by a reaction, it can continue to
facilitate the conversion of reactants into products. This allows a small amount of a catalyst to catalyze
a large number of reactions. Hydrogen peroxide decomposes very slowly into water and oxygen at
room temperature, but if a small amount of manganese dioxide is added, the reaction will occur quite
rapidly. When the reaction has run its course, all of the manganese dioxide can be recovered.

Page 5 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 18
A large variety of catalysts affect many different reactions. Living organisms possess a class of
catalysts called enzymes, which are large molecules that increase the rate of biologically important
reactions. A granule of sugar can sit unchanged on a table for a long period of time without reacting
with oxygen. However, if an ant eats it, the sugar will rapidly react in the presence of oxygen, producing
carbon dioxide and water, and providing energy to the ant. The breakdown of sugar in the ant is
catalyzed by a series of enzymes that increases the overall reaction rate, even at room temperature.
The enzymes are the same at the end of each reaction as they were at the start, and are therefore
available to catalyze the breakdown of more sugar molecules.

Scene 19
Another factor that increases reaction rate is increasing the surface area of a solid or liquid
reactant. This is why, as mentioned earlier, it is easier to light small pieces of wood than it is to light one
large piece that has the same mass. Each time a large object is broken up into smaller pieces, the
surface area increases. For example, a cube with a volume of eight cubic centimeters has a surface
area of 24 centimeters. If it is cut three times to make eight cubes, each with a volume of one cubic
centimeter, the total volume is still eight cubic centimeters, but the surface area increases to 48 square
centimeters. The same effect means the fine spray of gasoline from the fuel injector of a car has a
greater surface area than a large stream of gasoline, so the fine spray reacts more quickly with oxygen.
A dramatic example of the effect of surface area can be seen in this demonstration, using the spores of
the lycopodium plant. Spores in a pile are hard to ignite, but as you can see from the video, when the
surface area of the spores is increased by blowing on them, they ignite readily.

Scene 20
You have already seen that dinitrogen pentoxide decomposes more quickly at higher
concentrations. In general, the higher the concentration of reactants, the faster the reaction rate. The
following demonstration illustrates the relationship between changes in concentration and the number
of potential reactions. Each pool table on your screen is the same size, so the table on the left with 15
balls on it has a higher concentration of balls than the one on the right, which has two balls. A cue ball
shot at random is much more likely to hit a ball at the table having a higher concentration of balls than it
is on the table having a lower concentration of balls. This is analogous to varying the concentration of
reactants. A higher concentration can lead to more reactions.

Scene 21
As you have just seen, increasing the concentration of reactants increases the reaction rate.
The demonstration with the pool tables showed there are more collisions occurring among molecules at
higher concentration, but does every collision lead to a reaction? The answer for the majority of
reactions is no. In a typical sample of gas at standard temperature and pressure, a single oxygen
molecule makes over one billion collisions per second. If all collisions lead to reactions, then reactions
between gases would be nearly instantaneous. However, you have seen that many of these reactions
are quite slow. Clearly the mere fact that two gas molecules collide is not sufficient to cause them to
react. A theory known as collision theory distinguishes between effective collisions that lead to
reactions, and ineffective collisions, which do not. The two factors determining the effectiveness of a
collision are the energy of the colliding particles and the orientation of the particles when they collide.
These factors will be explored in the next few scenes.

Page 6 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 22
For a collision to be effective, the colliding particles must have enough kinetic energy. Kinetic
energy is the energy related to motion. The more kinetic energy a particle possesses, the faster it
travels. To understand why the kinetic energy of the reactants is important, consider the reaction in
which two molecules of hydrogen iodide collide and react to form one molecule of hydrogen and one of
iodine. In order for these reactants to be converted into products, the bond between the hydrogen atom
and the iodine atom in each hydrogen iodide molecule first must be broken. It requires a certain amount
of energy to break the bond between hydrogen and iodine, and that energy comes from the collision of
the reactant molecules. Only molecules that collide with sufficient energy are capable of breaking
bonds. Notice that when these two toy cars collide at low speed, the driver stays in place. But when
they collide at high speed, the driver flies out. In this demonstration, the ejection of the driver is
analogous to the breaking of a chemical bond, because sufficient energy is required for either event to
occur.

Scene 23
In the last scene, you learned that only collisions of particles with sufficient kinetic energy have
the ability to produce a reaction. Raising the temperature of a sample of gas increases the average
kinetic energy of the molecules in the sample. This explains why reaction rates increase at higher
temperatures. Not all of the molecules in the sample have the same kinetic energy. For a given sample
of molecules, there is a distribution of kinetic energies, which means that only a fraction of the
molecules will have sufficient kinetic energy to react. The graph on the screen shows the fraction of the
molecules in the sample plotted against their kinetic energies at a given temperature. Notice that as you
move to the right on the graph, kinetic energy increases, so the molecules in this portion of the graph
have greater kinetic energy. Observe what happens when the temperature increases by ten degrees;
the curve flattens out and shifts to the right. This means at a higher temperature, more molecules have
a higher kinetic energy. You can see this when the two curves are superimposed. The colored portions
under the curves show the fraction of molecules that have at least a given kinetic energy. Do you see
why the percentage of high energy molecules is greater at higher temperatures?

Scene 24
In addition to kinetic energy, molecules also have potential energy. Potential energy is stored
energy. Within molecules, energy is stored in chemical bonds. This graph portrays the energy change
that occurs during the course of a reaction. The horizontal axis of the graph represents the course of
the reaction over time, and the vertical axis represents potential energy. The reaction shown is
exothermic, meaning it releases energy. In an exothermic reaction, the reactants have higher potential
energy than the products. If little energy is required to break chemical bonds in the reactant molecules
prior to forming the products, the graph is drawn like this, with only a slight hump in the curve. However,
in most cases, substantial energy is needed to break bonds among reactants during the reaction
process, and a larger hump is created. This hump represents the extra amount of energy required to
make the reaction occur, which is referred to as the activation energy of the reaction. Bonds are being
broken and reformed during the course of the reaction, which results in potential energy increasing until
it reaches a peak, which is the activation energy. When molecules collide with sufficient kinetic energy,
existing bonds can be broken, allowing the formation of new bonds. Each reaction has a characteristic
activation energy, and higher activation energies act to make reaction rates slower, as you will see in
the next scene.

Page 7 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 25
In this demonstration, the marbles on the table represent the molecules taking part in an
exothermic reaction. When marbles are on the table, they represent the reactants at a high potential
energy. When they are on the floor, they represent the products at a lower potential energy. Shaking
the table gives the marbles energy, and this represents the kinetic energy imparted to the particles in a
system by raising the temperature. At first there is no lip around the table, a situation analogous to a
reaction with no activation energy. Notice that with even with a little bit of energy, marbles fall onto the
floor. The marbles that fall off the table onto the floor represent molecules that have been converted to
products. Now a medium sized lip is placed around the edge of the table, representing a low activation
energy. The table must be shaken harder for any marbles to fall off. Lastly, a tall lip is placed around
the table, representing a high activation energy. At a low or medium degree of shaking, corresponding
to a low or moderate temperature, no marbles fall off. Even with energetic shaking, only a small fraction
of the marbles has enough energy to make it over the lip and leave the table. The situation is similar for
molecules in a reaction. If the activation energy is high, as it is when the lip around the table is high,
only a few of the reactants have enough energy to get over the hump and react. Since only a few of the
reactants have the energy to make it over the hump corresponding to activation energy in a given time,
it is analogous to having a slower reaction rate. Just as you would have to gently shake the table for a
long time to get all of the marbles to fall onto the floor, it takes a long time for reactants to be converted
to products at a low temperature.

Scene 26
Putting your understanding of reaction energy together with the concept of kinetic energy
distribution allows you to understand how increasing the temperature of most reactions increases their
rates. Here is a kinetic energy distribution at 298 Kelvin, or 25 degrees Celsius. This vertical line
represents the activation energy, or the minimum energy necessary for the reaction to occur. Notice
that only a small fraction of the molecules, shaded in blue, has enough energy to react. Now look at the
distribution of kinetic energy at 308 Kelvin. The activation energy necessary for the reaction stays the
same, so at the higher temperature, the number of molecules equals or exceeds the activation energy.
This portion is shaded in red. Logically, if a higher fraction of molecules at a higher temperature has
enough energy to react, the proportion of collisions that can lead to reactions will be higher and the
reaction rate will increase. This is why many reactions, such as the hardening of glue, occur faster at a
higher temperature.

Scene 27
Not all collisions with sufficient kinetic energy result in reactions. The way in which the
molecules strike each other is also important in bringing about a reaction. Think about a batter in a
baseball game. The rapid movement of the bat and the ball are analogous to two particles meeting with
enough kinetic energy to react. When the bat contacts the ball, the ball can go in a number of
directions. It can go straight down or straight up, to the left or to the right, depending on how the bat
strikes it. If the bat strikes the ball in just the right way and with sufficient energy, the batter hits a home
run. When molecules strike each other with the correct orientation, they form what is called an
activated complex. This is an extremely unstable short-lived structure in which bonds are in the
process of breaking and reforming and which quickly breaks apart. During the period of time in which
the activated complex exists, it is referred to as being in the transition state, which corresponds to the
highest potential energy. Just as it takes a certain bat speed and orientation to produce a home run, it
also takes enough kinetic energy and the correct molecular orientation to form a activated complex.

Page 8 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 28
Earlier in the program, you learned that a catalyst is a substance that increases the rate of a
reaction, but is unchanged at the end of the reaction. Catalyzing a reaction is similar to driving a car
home versus walking home. You will end up in the same place, but driving the car will get you there
faster. In an earlier scene, you saw how manganese dioxide catalyzed the breakdown of hydrogen
peroxide into oxygen and water. The final amounts of products and reactants will be the same, whether
the decomposition of hydrogen peroxide is catalyzed or uncatalyzed, but the catalyzed reaction occurs
much more rapidly.

Scene 29
A catalyst works by providing a new pathway for the reaction, lowering the activation energy. If
the activation energy is viewed as a wall that the reactants must have enough energy to get over, a
catalyst can be viewed as knocking off the top of the wall. This means that a greater fraction of reactant
molecules at a given temperature has enough kinetic energy to react, and the reaction rate will be
higher. As you can see in the accompanying graphs, lower activation energy means that the fraction of
molecules with energy sufficient to react will be greater. Because catalysts act by lowering the
activation energy of a reaction, they can only increase the rate of a reaction, but they cannot cause a
reaction to occur that will not happen under the reaction conditions.

Scene 30
Earlier in the program, you saw that the rate at which dinitrogen pentoxide decomposes to form
nitrogen dioxide and water is related to its concentration. At a high concentration, dinitrogen pentoxide
breaks apart at a faster rate. As you learned earlier, most reactions proceed faster when the
concentration of the reactants is higher. Chemists have determined that for the majority of reactions,
the reaction rate is proportional to each reactants concentration raised to an experimentally derived
power and multiplied together. The power to which each concentration is raised can be fractional,
negative, zero, or a positive whole number. For ease of understanding, this program only deals with
whole number powers. You cannot determine from the balanced equation for the reaction the power to
which a concentration is raised; it can only be determined by experiment. This is an important point to
keep in mind.

Scene 31
In the last scene, you found out that the reaction rate is proportional to the product of the
concentrations of each reactant raised to an experimentally derived exponent. At any given
temperature, the proportion can be changed into an equation by multiplying the expression by a
constant, symbolized by k. The term k is called the rate constant for the reaction. The rate constant
is different for each reaction and changes with temperature. This equation in which the rate equals k
times the concentration of each reactant raised to a power is called the rate law for the reaction.
Knowing a reactions rate law is valuable to chemists, because it allows them to determine how quickly
a given product will be produced from known concentrations of reactants. As you will see in the section
of the program on reaction mechanisms, the rate law also helps chemists understand what happens on
the molecular level during a reaction.

Page 9 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 32
If you know the rate law for a reaction, it is possible to use the concentrations of the reactants
and the rate of the reaction to determine the value of k, the rate constant. In these calculations, the
concentrations used are generally those at the beginning of the experiment, called the initial
concentration. Look at the reaction in which nitrogen dioxide and molecular fluorine combine, forming
the explosive gas nitryl fluoride. The rate law for this relation is rate equals k times the concentration of
nitrogen dioxide times the concentration of fluorine. The experimentally derived exponent for both
nitrogen dioxide and fluorine is one, and an exponent of one is not written. When the initial
concentration of both reactants is 0.020 moles per liter, the rate of the reaction is 0.016 moles per liter-
second. Given these data, it is a straightforward procedure to calculate the rate constant. First,
substitute the known values into the rate law equation, and then solve for k. Performing the calculation
gives you a numerical value of 40, but what are the units? The rate is in moles per liter-second, and
each concentration is in moles per liter. When the concentrations in the denominator are multiplied, the
resulting unit is moles squared per liter squared. When you invert and multiply the units, the result is
liter per mole-second. So the rate constant for this reaction is 40 liters per mole-second. The units of
the rate constant can vary, as you will see in the next scene.

Scene 33
Here is another example of how to determine a rate constant, this time for the decomposition of
dinitrogen pentoxide, a compound studied earlier in the program. At a temperature of 328 Kelvin, which
is 55 degrees Celsius, the reaction rate for the breakdown of 0.30 moles per liter of dinitrogen
pentoxide is 4.5 times 10-4 moles per liter-second. The rate law for the decomposition of dinitrogen
pentoxide is rate equals k times the concentration of dinitrogen pentoxide. Notice that the power to
which the concentration is raised, one, is not the same as the coefficient in the balanced equation,
which is two. It is important to remember that the powers in a rate law expression are not necessarily
the same as the coefficients in the balanced equation, but are determined by experiment. To find the
value of the rate constant, substitute the known values into the rate law equation. Solving for k and
canceling units gives you a value of 1.5 times 10-3 per second. Once you know the value of k, you can
use it to determine the rate of decomposition of any concentration of dinitrogen pentoxide at 328 Kelvin.

Scene 34
Did you notice that the rate constants in the two examples had different units? In the first case,
the units are liters per mole-seconds, and in the second case they are per second. The unit of the rate
constant depends on what is known as the reaction order. The order of a reaction is equal to the sum of
the powers of the concentrations in the rate law expression. For example, the reaction that forms nitryl
fluoride is a second order reaction because the concentration of each reactant is raised to the first
power, and one plus one is two. The decomposition of dinitrogen pentoxide is first order, because its
concentration is raised to the first power. Here is the rate law for the reaction of nitric oxide and
molecular hydrogen. Do you see why this is a third order reaction? The individual reactants are
described by their individual order as well. The order of a given reactant equals the power to which its
concentration is raised. For example, the reaction of nitric oxide and hydrogen is second order with
respect to nitric oxide and first order with respect to hydrogen. Since one plus two equals three, the
reaction is third order overall.

Page 10 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 35
The order of the individual reactants can be determined using experimental data for
concentration and rate. For example, look at the data collected for three experiments on the breakdown
of sulfuryl chloride. For each initial concentration of sulfuryl chloride, the initial rate of decomposition
was measured. To determine the order of the reactant, start by writing the general rate law for the
reaction, which in this case is rate equals k times the concentration of sulfuryl chloride raised to some
power x. To determine the power to which the concentration is raised, observe the relationship between
the increase in concentration and the increase in rate. When the initial concentration is doubled, as it is
between the first and second experiment, the reaction rate doubles. When the initial concentration is
tripled, as it is between the first and the third experiment, the reaction rate also triples. Because of the
one to one relationship between the change in concentration and the change in rate, the reaction is first
order in sulfuryl chloride and first order overall. Therefore, the rate law expression is rate equals k times
the concentration of sulfuryl chloride to the first power, or just k times the concentration of sulfuryl
chloride.

Scene 36
Now look at data collected for the decomposition of hydrogen iodide gas into molecular
hydrogen and molecular iodine. In this case, when the initial concentration is doubled, as it is between
the first and second experiment, the initial reaction rate increases by a factor of four. Between the first
and third experiment, the initial concentration is tripled and the initial rate increases by a factor of nine.
This shows that the reaction rate is proportional to the square of the concentration, since two squared is
four, and three squared is nine. The rate law, therefore, is rate equals k times the square of the
concentration of hydrogen iodide. Can you see that the reaction is second order in hydrogen iodide and
second order overall? Now that you know the rate law, you can determine the value of the rate constant
by using any set of values for rate and concentration from the chart in the rate law equation. For
example, substituting the values at time1 into the rate law equation gives the equation 8.0 times 10-6
moles per liter-second equals k times the square of 0.010 moles per liter. Solving for k gives the answer
0.080 liters per mole-second.

Scene 37
It is also possible to determine the rate law for reactions having more than one reactant. To see
how this is done, take a look at the reaction of nitric oxide and molecular oxygen, which produces
nitrogen dioxide. To determine the rate law for this reaction, start by writing the general form of the rate
law rate equals k times the concentration of nitric oxide to the unknown power x times the
concentration of oxygen to the unknown power y. Now examine the data that were collected for the
reaction. When you are presented with data on two variables in this case, the concentration of nitric
oxide and the concentration of oxygen compare situations where only one variable changes at a time.
For example, in the first two experiments, only the concentration of oxygen changes. This allows you to
determine the effect of changing the concentration of oxygen. In this case, when the concentration of
oxygen is doubled, the rate also doubles. This means that the reaction is first order in oxygen. In the
second and third experiments, only the concentration of nitric oxide changes, so you can use this data
to determine the effect of changing the concentration of nitric oxide. As you can see, doubling the
concentration increases the reaction rate by a factor of four, which means the reaction is second order
in nitric oxide. Thus the rate law is written as rate equals k times the square of the concentration of
nitric oxide times the concentration of oxygen. This reaction is second order in nitric oxide, first order in
oxygen. Adding the exponents shows that the reaction is third order overall.

Page 11 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 38
You have seen that in order to react, molecules must collide with a certain minimum energy and the
proper orientation. Even with the incredibly large number of collisions that occurs among gas molecules
every second, the collision of two molecules with the correct orientation and sufficient kinetic energy to
react is still relatively infrequent in all but instantaneous reactions. Now look at the balanced equation
for the combustion of heptane, which is a component of gasoline. One molecule of heptane reacts with
11 molecules of oxygen and forms seven molecules of carbon dioxide and eight molecules of water. If it
is so unlikely for two molecules to come together with the correct orientation and energy to react, how is
it possible for a heptane molecule to collide effectively with 11 oxygen molecules at the same time? The
answer is, it is not. The reaction of heptane with oxygen, as well as many less complicated reactions,
goes through a series of steps called a reaction mechanism. While the reaction mechanism for the
reaction of heptane and oxygen is far too complex for the scope of this program, the following scenes
show reaction mechanisms for several, simpler reactions.

Scene 39
Each of the steps in a reaction mechanism is known as an elementary process. The
elementary processes in the hypothetical reaction mechanism on your screen show the progress of the
reaction from reactants to products through intermediate steps, much as this map shows the progress
of a passenger flying from San Francisco to Detroit through Dallas. Elementary processes are inferred
from experiments and observations and generally cannot be proven. When all of the elementary
processes of a reaction mechanism are added, they produce the overall balanced equation. This is
because a substance on one side of an elementary process cancels the same substance on the
opposite side of another elementary process. In a similar way, the layover in Dallas is cancelled when
the legs of the flight are added to give the overall trip from San Francisco to Detroit.
An intermediate is a substance thought to be present in some steps in the reaction mechanism
but which is not part of the overall balanced equation. An intermediate disappears by the end of the
reaction, so it is cancelled when the elementary processes are added. The intermediates in a reaction
mechanism are believed to exist for such a short time that they are usually undetectable, although
some have been detected.

Scene 40
Here is the proposed reaction mechanism for the decomposition of nitryl chloride into nitrogen
dioxide and molecular chlorine. In the first elementary process of the reaction mechanism, one
molecule of nitryl chloride loses its chlorine atom, forming nitrogen dioxide and a chlorine atom. In the
second elementary process, the chlorine atom reacts with another nitryl chloride molecule, forming
nitrogen dioxide and molecular chlorine. The chlorine atom is an intermediate in this reaction. The
chlorine atom created in the first step of the decomposition of nitryl chloride cancels the chlorine atom
on the reactant side of the second step. The presence of an uncombined chlorine atom might be
somewhat surprising to you, since you may have learned that chlorine is found as a diatomic molecule,
not as a free atom. The chlorine atom is an intermediate in this reaction mechanism, and exists for a
very short period of time, since it is an extremely reactive form of the element.

Page 12 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 41
As you learned in the previous scene, the overall balanced equation of the decomposition of
nitryl chloride does not reflect what is happening at the molecular level during the reaction. At the
molecular level, it is not the collision of two nitryl chloride molecules that causes the reaction, which it
might seem from the overall equation, but it is a series of steps that starts when a nitryl chloride
molecule loses its chlorine atom. In contrast to the overall equation, each elementary process in a
reaction mechanism is an attempt to reflect what happens at the molecular level. Since an elementary
process portrays what happens at the molecular level, a rate law can be written using the coefficient of
each reactant as the exponent. An example of how this is done is shown at the bottom of your screen.
It is important to note that this is in contrast to the balanced equation for the overall reaction, for which
the rate law can only be determined by experiment.

Scene 42
In the reaction mechanism for the decomposition of nitryl chloride discussed in previous scenes,
there are two elementary processes. A separate rate law can be written for each one, based on the
coefficients of the reactants. This is in contrast to the overall balanced equation. Remember, if you are
given the balanced equation for a reaction, you have no way of determining the rate law without
experimental data. For the elementary processes in a reaction mechanism, however, rate laws can be
derived using the coefficients. The rate law for the first elementary process is rate equals k1 times the
concentration of nitryl chloride raised to its coefficient, which is one. For the second elementary
process, the rate law is equal to k2 times the concentration of nitryl chloride times the concentration of
chlorine atoms, each raised to the power of its coefficient, in each case one. In these equations, k1 and
k2 are the rate constants for each elementary process. Again, remember that you can only derive rate
laws for elementary processes, not the balanced equation.

Scene 43
In most reaction mechanisms, there is one elementary process that takes place at a far slower
rate than the others. Since the reaction cannot proceed any faster than the slowest step, this is known
as the rate-determining or rate-limiting step. The rate-determining step can be compared to a slow
ticket taker at a theater. People can arrive at the door at any rate, but they can only get through the
door at the rate that the employee takes their tickets. The fact that the slowest step determines the rate
of the reaction means that the rate law for the slowest elementary process is the rate law for the overall
reaction. In the first step of the reaction mechanism for the decomposition of nitryl chloride, a chlorine
atom splits off of a nitryl chloride molecule. The first elementary process has been determined to be
very slow compared to the second one, which involves the highly reactive chlorine atom. This means
that the first step is rate-determining. This means that the rate law for the overall reaction will be the
same as the rate law for the first elementary process, which is k times the concentration of nitryl
chloride. Notice that this is the same result that was found experimentally in an earlier scene.

Scene 44
When evaluating the plausibility of a proposed reaction mechanism, there are three crucial
factors to consider, two of which have already been discussed. The first factor is that when the
elementary processes of the reaction mechanism are added, the intermediates cancel, and the result is
the overall balanced equation. The second factor to consider is that the rate law derived from the rate-
limiting step is consistent with the experimentally determined rate law for the reaction. The third factor is
that no elementary process involves more than three reactant molecules. In fact, elementary processes
with more than two reactant molecules are relatively rare, and chemists never propose an elementary
process with more than three reactant molecules. This is because it is extremely unlikely that more than
two, and at most three, molecules will collide at the same instant with enough kinetic energy and at the
correct orientation to react.

Page 13 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 45
Using the guidelines given in the last scene, you can evaluate a proposed reaction mechanism.
Consider the combination reaction of nitrogen dioxide and fluorine gases, which produces nitryl fluoride
gas. Experiments have shown that the rate law for this reaction is k times the concentration of nitrogen
dioxide times the concentration of fluorine. Now, examine a proposed reaction mechanism. In the first
step, one molecule of nitrogen dioxide and one molecule of fluorine collide and produce one molecule
of nitryl fluoride and a fluorine atom. In the second step, the fluorine atom reacts with a molecule of
nitrogen dioxide, producing a second nitryl fluoride molecule. Do the elementary processes add up to
the balanced equation? As you can see, when the two steps are added, the intermediate fluorine atoms
cancel, and the result is the balanced equation. In this reaction mechanism, the rate of the first
elementary process has been determined to be slow, while the second is much faster. Which is the
rate-determining step? Since the first elementary process is the slowest, it is the rate-determining step,
and the reactants of that step are used to determine the rate law. The rate law derived from this step is
k times the concentration of nitrogen dioxide times the concentration of fluorine. This is the same as the
rate law that was determined experimentally. Since the elementary processes add up to the balanced
equation, the rate law for the rate-determining step is the same as the experimental rate law, and no
elementary step contains more than three reactant molecules, this is a plausible reaction mechanism.

Scene 46
Think back to the reaction discussed at the beginning of the program in which toxic carbon
monoxide gas from a cars exhaust reacts with oxygen in the air, producing carbon dioxide. Even
though essentially all of the carbon monoxide will eventually be converted to carbon dioxide, the
reaction takes place very slowly at normal temperatures. By applying what you have learned in this
program, you can understand why this reaction takes place so slowly. One reason this is such a slow
reaction is the relatively low concentrations of the reactants. At standard temperature and pressure, the
concentration of molecular oxygen in the air is 9.0 times 10-3 moles per liter. If the concentration of
carbon monoxide emitted from a car in a garage builds up to only 5.0 times 10-5 moles per liter, it can
be lethal. You know from collision theory that at lower concentrations of reactants, there are fewer
collisions, which lead to fewer reactions per second and thus a slow reaction rate. In addition, the
activation energy for this reaction has been experimentally determined to be high. As you know from
collision theory, few molecules at room temperature have sufficient energy to overcome a large
activation energy barrier. Now you can understand why the reaction of carbon monoxide and oxygen is
so slow in the garage, even though the products are favored energetically. You have also learned
enough to understand why catalytic converters are used on cars. The platinum and palladium in a
catalytic converter increase the rate of the reaction by lowering the reactions activation energy. This
means that more molecules have sufficient energy to react at a given temperature. The metals in a
catalytic converter are finely divided, which increases the surface area and therefore the reaction rate.
You can see why carbon monoxide emission from motor vehicles is a potential problem which has been
address by use of catalytic converters.

Page 14 of 15
 Transcript: Honors Chemistry
Chemical Reactions: Reaction Rates
Scene 47
This program has introduced you to reaction rates. You have learned the concept of rate, and
specifically how rates of chemical reactions are determined. You saw that some reactions, like the
combining of oxygen and hydrogen, happen almost instantaneously, while other reactions, such as the
combination of carbon monoxide and oxygen, take considerably longer. You also learned the effects
factors such as concentration, temperature, and surface area have on reaction rate. Collision theory
and reaction mechanisms allow you to picture at the particle level what is occurring during a reaction
and how this affects the rate of the reaction. Rate law expressions allow mathematical calculations of
rate and relate to reaction mechanisms. Understanding reaction rates provides both practical and
theoretical information to chemists. On the practical side, understanding the factors influencing rate
allows chemists to manipulate the rates of important industrial reactions. On the theoretical side,
understanding rate laws allows chemists to derive reaction mechanisms, which allows them to
understand what is happening on the molecular level.

Page 15 of 15