Colligative Properties

Colligative properties refers to changes in the properties of a solution (compared to the pure liquid
solvent) based only on the total number of solute particles in the solution, and not the type or identity
of the solute.

Just for fun: Making Ice Cream at home in Zip-Lock Bags (taken from the Internet)

What you’ll need:

1 tablespoon sugar, 1/2 cup milk or half & half , 1/4 teaspoon vanilla, 6 tablespoons rock salt, 1 pint-
size plastic food storage bag (e.g., Ziploc), 1 gallon-size plastic food storage bag, ice cubes.

Question: What is all that salt for?

It is not to add to the ingredients, because then the ice cream would taste disgusting! The ice cubes go
into the bigger bag, and adding salt will melt the ice! The melting process causes energy in the
environment to be removed, causing a big temperature drop, possibly down to -20o C. The cream and
sugar go into the small bag, which is then placed into the cold ice/salt mixture. When the cream
freezes, you get ice cream!

The salt solute prevents the ice from existing in the solid phase. This is considered a colligative
property because the solute has changed the freezing properties of the water.

In our course, we will talk about 4 different colligative properties. In no particular order:

1. Vapour Pressure Lowering: Vapour pressure is defined as the pressure exerted by a vapour at
equilibrium with its liquid in a closed system.

Another way to think about vapour pressure is to think of it as the amount or extent of evaporation of
a liquid. The more a liquid is evaporating, the higher its vapour pressure will be. Vapor pressure is
proportional to temperature. As the temperature of a liquid goes up, so too does its vapour pressure
(since the extent of evaporation has increased)
But why would a solute in solution cause a lowering of vapor pressure? Let’s examine a cartoony
depiction of evaporation of water at room temperature:

We can’t see them, but water molecules are leaving the surface of the liquid at all times.

39
 However, when a non-volatile solute is dissolved in the solution, the extent of evaporation is reduced
(vapour pressure lowering).

Non-volatile: not
able to evaporate

Essentially, the solute interferes with the ability of the water molecules to leave the surface and
evaporate. The solutes do this in two main ways:

1. With solute present, there are simply less water molecules at the surface of the solution that can
escape into the gas phase compared to pure water.
2. The solute molecules attract the water molecules with greater force, “holding” them back from
evaporating into the gas state.

2. Boiling Point Elevation: Adding a solute to a pure liquid solvent creates a solution that will have a
boiling point higher compared to that of the pure liquid.
Boiling point is defined at the point where the vapour pressure of a substance equals the external
pressure, usually that of the atmosphere. So although water’s boiling point is commonly 100.0o C, it is
only this temp at sea level. At different elevations, the atmospheric pressure changes, and then so too,
the boiling point changes.

Since a solution’s vapour pressure

is lowered, it will take a higher
temp for a solution to generate
enough vapour pressure to match
that of the external atmosphere.

40
To calculate boiling temperature elevation, ΔTb (or the change in boiling temp), we use the equation:

ΔTb must always be a

positive value

- Where Kb is the boiling point elvation constant (for water it is 0.512o C/m) and m is the
molality of the solution.

- i is the vant Hoff factor. It represents the stoichiometry of particles produced when a compound
dissolves in solution under “ideal”, dilute conditions. In other words, it is how many particles a
compound will dissociate into when dissolved in water.

When 1 NaCl is dissolved in water, it produces 2 particles: one Na+ and one Cl-. This give sodium
chloride an i factor of 2.

When 1 Na2 CO3 is dissolved in water, it will produce 3 particles: two Na+ and one CO3 2-. This gives
sodium carbonate an i factor of 3.

Sucrose (C12 H22 O11 ) however is a molecular compound that does not dissociate, so its i factor is 1.

Weak acids and bases are tricky: they dissociate a little bit and have an i factor slightly greater than
1.

- If 100 CH3 COOH molecules are dissolved in water, only 1 out of the 100 molecules
dissociates into the ions CH3 COO- and H+. Therefore, 100 acetic acids in water produces
only 101 total particles. The i factor is technically ~1.01.

To calculate the boiling point of the solution, we add the temperature elevation change to the
regular boiling point of water.

Question: Calculate the boiling point of a solution of 1.50 m (molal) of aluminum chloride(aq).

AlCl3 breaks down into 1 Al3+ and 3 Cl-, giving a total of 4 particles, so its i factor is 4. Now we must
calculate the boiling point change, ΔTb.

ΔTb = 0.512o C/m x 1.50 m x 4 = 3.07o C. Now we add it to 100.0o C.

Boiling point of solution = 100.0o C + 3.07o C = 103.1o C

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3. Freezing Point Depression: Adding a solute to a pure liquid solvent creates a solution that will have a
freezing point lower compared to that of the pure liquid.

- To calculate freezing temperature depression, ΔTf (or change in freezing point):

ΔTf must always be a

positive value

- Where Kf is the freezing point depression constant (for water it is 1.86o C/m) and m is the
molality of the solution, and i once again is the vant Hoff factor.

Finally, to calculate the freezing point of the solution, we subtract the temperature depression change
to the regular freezing point of water.

Question: Calculate the freezing point of a solution of 1.50 m (molal) of aluminum chloride(aq). This
is the same solution as for the boiling point question above so…

ΔTf = 1.86o C/m x 1.50 m x 4 = 11.2o C. Now we subtract it from 0.0o C.

Freezing point of solution = 0.0o C - 11.2o C = -11.2o C

But why does a solute lower the freezing point of a solution? A simplified answer is that solutes will
interfere with the freezing process by getting in the way of the water molecules.

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 With solutes in solution,
even colder temperatures
are required before the
solution will reach solid
phase.

A Phase Diagram for Water (and most other substances)

A line on this graph represents a phase

boundary: the point at which the type
of matter being examined transitions
from one phase to another

The main thing to note in this graph is

how for a solution, the liquid phase
has boundary has widened.

4. Osmotic Pressure: Concentration differences in solution create a phenomenon called osmosis - the
spontaneous movement of water molecules through a semipermeable membrane from an area of low
concentration to high concentration of solute.
When osmosis occurs, it can generate a measure called osmotic pressure.

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Osmotic pressure is defined as the amount of pressure that would need to be applied (in this case to
the column on the left side of the U-tube) to prevent osmosis from taking place.

- The world’s most common semi-permeable membrane: the cell membrane. The cell
membrane separates the intracellular fluid of the cell from that of the surrounding fluid.

Some common terms used for concentrations of solution when compared to the concentration of
intracellular fluid:

- Isotonic (Isoosmotic): a solution having the same concentration of solute as the inside of a
cell.
- Hypertonic (Hyperosmotic): a soluton having a higher concentration of solute compared to
that of the inside of a cell.
- Hypotonic (Hypoosmotic): a solution having a lower concentration of solute compared to
that of the inside of a cell

It is vital that all the fluids inside our body that surround and contact our cells are isotonic!
Otherwise, cells could strivel up and die, or swell and burst!

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• To calculate osmotic pressure:

- Where π is osmotic pressure, M is concentration(molarity), R is the universal gas constant

(8.314 kPa.L.mol-1.K-1 ), T is the temperature in Kelvin, and i is the vant Hoff factor.

Eg. How much osmotic pressure can be generated by a solution of 1.50 M of aluminum chloride(aq) at
25.0o C?

You will need to convert the degrees Celcius to Kelvin by adding 273.15, and plugging everything else
into the formula above.

Answer = 14900 kPa

More Practice Questions: Molar Mass Determination From Colligative Properties: a "Reverse"
Calculation.

1.) 2.00 g of a salt is dissolved in 15.00 ml of water (assume density is 1.00 g/ml). This salt
solution freezes at -3.6o C, and the salt has an i factor of 3. What is the molar mass of this
salt? (Kf = 1.86o C/m)
First we need to solve for ΔTf. You can simply use intuition where you know if the freezing
point is now -3.6o C, that the change from 0.0o C must be +3.6o C. Otherwise, you can use the
formula: Tfsoltuion = 0.0o C - ΔTf.

Next, solve for molality, m by using ΔTf = Kf x m x i . Solving for m gives 0.65 mol/kg

We know that the mass of solvent is 0.0150 kg so we can solve for moles of the solute: 0.0098
mol. Finally, molar mass is the ratio of the grams of solute to the moles: 2.00 g/0.0098 mol = 2.0
x 102 g/mol

2.) 1.158 grams of a non-dissociating protein is dissolved in water to make a solution of

50.00 ml. This protein solution generates an osmotic pressure of 2.09 kPa at 25.0o C.
What is the molar mass of the protein?
To solve this question, we need to know that the term “non-dissociating“ means the i factor of
the solute (protein) is 1. Now we just plug into the osmotic pressure equation (π = MRTi) to
solve for molarity, M.

M = 8.43 x 10-4 mol/L. We know that the solution volume is 0.5000 L so we multiply to get
moles: 4.22 x 10-5 mol. Take the grams and divide by the moles = 27500 g/mol.

This value seems extremly large, but it is correct. Proteins are usually large molecules consisting
of hundreds to thousands of atoms.

45
 FYI on the i factor: In our course,
we will always assume "ideal"
dissociation of compounds into
ions. In reality, once a solution has
a reasonable concentration, the i
factor is actually lower than
expected. This is due to the fact
that ions in solution can actually
momentarily combine once in a
while to act as a single unit

Kinetics

Kinetics is the study of the change in concentrations of the reactants or products of a reaction over
time, which is the the rate of the reaction. In other words, it's the study of how fast a chemical reaction
occurs.

The first picture shows what happens when a highly exothermic reaction reacts “too fast” for its given
volume of space, causing an explosion. By understanding the chemical reaction, it might be possible
to control their speed as we wish. Rusting and aging are definitely reactions that we would like to
slow down as much as possible!

How do reactions occur in the first place? The “Collision Theory/Model”

The particles involved in a reaction must physically collide with each other with enough energy AND
in the proper orientation for a reaction to occur. The energy required during a collision is called the
activation energy.

46
 If reactant atoms/molecules do actually have to collide with enough energy to cause a reaction, what
kinds of things can we do increase the rate of a reaction?

• 4 “Things” That Can Be Done to Increase the Rate of a Reaction:

1.) Increase the concentration of reactants: If we have more particles of reactants, it should increase
the chances of having more effective collisions, causing an increase in rate of the reaction

2.) Changing the physical state (surface area): Certain physical states allow for greater mixing of the
reactants (due to increased surface area), thus increasing rate of reaction.

3.) Increasing temperature: Not all collisions result in a reaction. The energy of the collision must
surpass the activation energy. Increasing the temperature allows for more reactant collisions that can
surpass the activation barrier, thereby increasing the rate of reaction.

4.) Adding a catalyst: A substance that increases the rate of the chemical reaction but is not consumed
by the reaction. Catalysts can be homogeneous or heterogeneous.

Review: A Reaction Progress Diagram.

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In this diagram going from left to right (forwared reaction), A is the reactant, and in order to turn into
the product B, A must have enough enegy to surpass the activation energy/barrier (highest point on
graph). The highest energy point is called the transition state, where A is beginning to turn into B.
The molecular entity at the transitions state looks a bit like both A and B together.

Since A is higher in energy than B, the forward reaction will release energy and is called exothermic
(ΔHrxn is a negative value). However, if the reaction is reversible, B going to A (reverse reaction) will
require/absorb energy and is called endothermic. The value of ΔHrxn will be the same, but positive
in value. The activation energies will be different for the forward and reverse reaction.

Expressing Reaction Rate

Take the general reaction of A  B. How can one tell how fast this reaction is? In other words, what
is the rate of this reaction?

We will have to measure the change in concentration of a reactant or a product over time. This will
translate directly to the rate of the reaction.

Let’s say we decide to exame the change in A over time:

Say we start a reaction (at time = 0 seconds) with 60 M of A. After 30 seconds of reaction, we notice
that there is now only 30 M of A. To calculate the rate:

Δ[A] = 30 M – 60 M = -1.0 M/s Notice how the change in A over time has a negative
Δ [t] 30 s – 0 s value in front. However, when written in words, the
negative sign can be replaced by the words “disappears
at 1.0 M/s”.

However, the overal rate of the reaction translates directly into the rate of change of a reactant or
product based on stoichiometry. In this case:

48
- The overall rate of the reaction will always have a positive value. This is why there is a negative
sign in front of the change in A over time.

Alternatively, we could have also measured the rate of change in B. Through stoichiometry, we know
that the change in B over time will have the same value as rate of A, but since B is being produced, its
change is positive. Therefore, the rate of this reaction could also be:

Altogether, the rate of reaction can be written as one whole equation relating the changes in rate of all
the reactants and products:

What happens if the stoichiometry of the reaction changes? Say it’s A  2B, and it’s been determined
that that the rate of change of A = -1.0 M/s. Again, through stoichiometry, we should realize that B
will change at 2X the rate of A. Therefore, the rate of B = 2.0 M/s.

This means that the rate of change of A is only ½ that of B. Therefore, the rate of reaction equation
would be written as:

49
 Typical Expressing Rate Question:

Consider the reaction H2 O2 (aq) + 3 I-(aq) + 2 H+(aq)  I3 -(aq) + 2 H2 O(l)

It is measured that the I-(aq) is disappearing at a rate of 1.45 M/s.

A) What would be the rate of production of I3 -(aq)?

B) What would be the rate of disappearance of H+(aq)?
C) What is the rate of the overall reaction?

With the information given, we can translate the rate into symbols:

a) This can be solved with stoichiometry intuition/analysis. The fact that the coefficient in front of I- is 3
must mean that its change will be 3X as fast as I3 -, or the rate of I3 - will be 1/3 that of I-. But since I3 -
is a product, it will have a positive value.
Therefore 1.45 M/s / 3 = 0.48 M/s
Otherwise, you can write out the entire rate expression equation and isolate the variables that you need.

= = 0.48 M/s

b) Now that we know the rate of I3 -, we can use stoichiometry to realize that the rate of H+ must be 2X as
fast, but negative in value = -0.98 M/s
c) The overall rate of the reaction can be related to any of the terms we solved for. It’s either -1/3 of the
rate of I-, -1/2 the rate of H+, or exactly the same value as the rate of I3 -.

Some Real Kinetics Data and Graphing

In table form, the data is not nearly as

useful. More information can be
obtained by graphing the kinetics
data.

50
 The points are plotted and a smooth
curve connects the dots. Now it is
easier to see that the reaction rate is
slowing down as time goes on.

• Taking Average Rates from Graphical Data: The rate over a period of time

Say we want to know the average rate of this reaction over the first 60 seconds.

However, since the rate of the reaction is the negative value of the rate of O3 , the rate of the reaction is
positive 3.50 x 10-7 M/s.

However, when we take the change in concentration, we are really taking the change in the y-axis, or
Δy. And when we take the change in time, we are really taking the change in the x-axis, or Δx. When
we take the ratio of Δy/ Δx, this is otherwise known as the slope (of a line).

So this rate over the first 60 s of the reaction is also the slope of the line “b” on the graph.

• Taking an Instantaneous Rate from Graphical Data: The rate at a single time point

How can we take the rate at a single time point? Don't we need 2 time points to measure the change in
time?

If we pretend we are measuring an average rate at ever decreasing time differences, eventually, the two
time points overlap into one point! This results in the creation of a tangent line at the single time
point, and the slope of the tangent line will give us the instantaneous rate at that single time point.

The most important rate of all in the reaction: The initial rate. This is the instantaneous rate at time =
0. It is represented by the tangent line to the curve at time = 0 on the graph (line “a”).

51
 Summary of graphical analysis:

1. The average rate is the change in concentration over a certain period of time.
2. Connecting two points on the graph curve with a straight line and determining the slope of the line will
yield the average rate for that time period.
3. The instantaneous rate is the rate at a single time point. This type of rate is determined by drawing a
tangent line to the graph curve and determining the slope of the line.
4. The initial rate is the instantaneous rate at time = 0 for the reaction. It is typically the fastest possible
rate of the reaction.

The Rate Law:

How Concentration Affects the Rate of Reaction

The rate law expresses the rate of any reaction at a fixed temperature on the reactant concentration
AND the order of reaction. Rate law for an overall net reaction can only be determined from
experimental data.

Let's examine the simple general reaction of A  B

Without ever running the reaction and observing it, we already know a bit about how fast this reaction
could go in theory.

The rate law states that the rate of this reaction will be: Rate (of this reaction) = k[A]n

The main concept to grasp here is that the coefficient for the reactant(s) in the chemical reaction
DOES NOT automatically become the order in the rate law equation.

52
 Practice: Write general rate law equation for:

1.) 2 H2 (g) + 2 NO(g)  N2 (g) + 2 H2 O(g)

2.) H2 (g) + I2 (g)  2 HI(g) 2.) Rate = k[H2]n[I2]m

1.) Rate = k[H2]n[NO]m

More on Reaction Order:

- As a simple example, we will use the reaction of A  B

The rate law for the reaction will be: k[A]n

1. If the the order n = 0, the order with respect to [A] is zero, and overall, it will be a zero order
reaction.
When n = 0, the term [A]0 goes to 1. Therefore, the Rate = k.

The reaction would always proceed at

a constant rate independent of the
reactant concentration. A plot of [A]
vs time would be linear.

The units for k are variable, and depend on the overall order of the reaction. You must either
memorize the units, OR be able to use math logic to solve for the order (the latter is much more
useful!)

- Eg. We know that the units for Rate (of reaction) must be M/time (concentration change per
unit time).
- Since in zero order, since Rate = k, the rate constant k must also have units of M/time (or
mol L-1 time-1 )

But didn’t we say that concentration affects rate? How can the reaction rate be independent of the
concentration of reactants? Zero order reactions are rare, but they often occur when the reaction is
catalyzed.

For example, alcohol metabolism in your body is a zero order reaction since the break-down of the
alcohol is an enzyme-catalyzed process. The enzymes in your body can only break down the alcohol
at a constant rate, so even if you increase the concentration of alcohol in your bloodstream, the enzyme
cannot work any faster.
53
2. If the the order n = 1, the order with respect to [A] is 1, and overall, it will be a first order reaction.
Rate = k[A]

The rate of reaction will be directly proportional to the concentration of the reactant [A]. The higher
the concentration, the faster the rate

The k constant for a 1st order reaction has units of time -1 . Again, it is possible to solve for this
knowing that the units of Rate = M/time, and [A] has units of M. So what must k be to multiply into
M to result in units of M/time? Solving for k units gives time-1 .

In first order reactions, since the rate

is proportional to [A], as [A] is used
up the rate will slow down, producing
a curved graph

3. If the order n = 2, the order with respect to [A] is 2, and overall, it will be a second order reaction.
Rate = k[A]2

The rate of reaction will be proportional to the concentration of the reactant [A] squared. As the
concentration goes up, the rate increases exponentially.

The k constant for a 2nd order reaction has units of M -1 time -1 (or L mol-1 time-1 ). Again, it is possible to
solve for this knowing that the units of Rate = M/time, and [A]2 has units of M2 . So what must k be to
multiply into M2 to result in units of M/time? Solving for k units gives M-1 time-1 .

In second order reactions, since the as [A]

is used up the rate will slow down, also
producing a curved graph. It is impossible
to tell a 1st order reaction from a 2nd
order reaction from looking at the graph
alone

k unit calculation practice

Given that the actual rate law equation is Rate = k[A]2 [B][C], what is the overall order of this reaction?
What are the units of k?
Overall order = 4 Units of k = M-3time -1
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• How can we use experimental data to be able to solve for the rate law equation? How can we identify
the order and rate constant k for the reaction?

Method 1 for solving the variables in a rate law equation: Using initial rate information from the
reaction.

In this method, multiple experimental runs/trails of the same reaction are required, where the
concentration of starting reactants is altered between runs/trials and compared to see if there was an
effect on the initial rate. The most typical way in which the reactant is changed in a subsequent
reaction is to double the starting concentration.

Again, say we are studying the reaction of A  B. The general rate law is Rate = k[A]n

We go into the lab and run this reaction with a starting concentration of [A] = 0.10 M. We graph the
results, draw a tangent to the curve at time zero, and calculate the slope of the tangent line, which will
reveal the initial rate of the reaction. We then repeat the experiment for run 2, we double the starting
concentration of [A] to 0.20 M. Here is what the results might look like.

0.12 0.25
Run 1 with [A] @ 0.10 M Run 2 with [A] @ 0.20 M
0.1 0.2
0.08
0.15
0.06
[A] (M)

[A] (M)

0.1
0.04
0.05
0.02
0 0
0 1 2 3 4 5 6 7 8 9 10 11 12
-0.02 0 1 2 3 4 5 6 7 8 9 10 11 12 -0.05
Time (s) Time (s)

Eventually the results will be displayed in table form:

The fastest way to interpret this data is to use math intuition of the pattern of change in the initial rate.
We can see in this data that between trial 1 and trial 2, when the initial concentration of A was

55
doubled, the rate also doubled. The only way this is possible is if the reaction is first order (rate
directly proportional to [A]).

Therefore, we have solved for the order with respect to [A]. If we plug in our rate and concentration
data into the rate law equation, we can solve for k.

Eg. Take Trail 1: Rate = k[A] 0.015 M/s = k(0.10 M) Solving for k = 0.15 M/s

If you’d prefer to use math formulas to solve for the order, you need to take the ratio of 2 trials (divide
one trial by another). Take trial 2 vs. trial 1 for the first order reaction above.

To solve for this equation formally, take the log

of both sides of the equation. When you do this to the right side, the exponent comes down as a
multiplier.

If the reaction was not 1st order, there are only 2 other patterns to look for when interpreting initial
rates data.

With zero order, no matter how the With second order, the rate
concentration is changed, the rate of quadruples when the concentration is
reaction does not change. doubled.

Here’s one more practice with more than 1 reactant. To analyze this, you must compare trials where
one reactant has its concentration stay constant, but the other has been doubled.

56
Comparing trial 2 to 1 shows that the order with respect to [O2 ] is 1 (m=1). Comparing trial 3 to trail 1
shows that the order with respect to [NO] is 2 (n=2). The trials 4 and 5 are just extra that further
confirm the orders. The overall order of this reaction would be 1+2 = 3. The units for k would be M-
2 time-1

Integrated Rate Law

How Concentration Changes Over Time During a Reaction: The Second Method for Solving
Reaction Order

To obtain integrated rate law equations, we use calculus to derive equations for zero order, first order,
and second order reactions. These equations allow us to predict how the concentration of a reactant
will change over time as a linear relationship.

Again, we will use the simple reaction of A  B to illustrate.

Where n can be 0, 1 or 2. We use

d instead of Δ in calculus when we
talk about infinitesimal changes.

Next, we will use algebra to rearrange the differential equation a bit, and then we take the integral of
both sides of the equation. Now, if you know your integration rules (from Calculus 2), you can derive
3 different equations, depending on the value of n.

When n = 0 and we integrate, we get

an equation called the zero order
integrated rate law equation.

When n = 1 and we integrate, we will

get a different equation, called the first
order integrated rate law equation.

And of course, when n = 2, we get the

second order integrated rate law

The 3 integrated rate law equations do not need to be memorized, since we will provide them for you
on your information sheet at tests and the final exam.

57
- Zero Order Integrated Rate Law Equation:

This equation, as well as the other 2 integrated rate law equations, are all linear functions (straight line
equations). To see this better, we will rearrange the equation by putting the [A]0 term to the other side.

Since the slope of this line is a

negative value, the k will be (and
must be) a positive value.

- First Order Integrated Rate Law Equation:

58
- Second Order Integrated Rate Law Equation

59
1. Understanding that integrated rate law equations are linear functions allows us to determine the
variable k and the orders in the rate law of a reaction.

For Example: Decomposition of dinitrogen pentoxide

- Data: Monitoring N2 O5 (g) concentration during its decomposition reaction.

We can see that this graph is curved,

so that it could not be a zero order
reaction. However, we still don’t
know if it is 1st or 2nd order, and we
still don’t know k.

To figure out the variables, we transform the original data mathematically using a spreadsheet
program:
We will do an exercise with this type
of data in the lab, and possibly in
class using Microsoft Excel just to give
you an idea of how you would
actually analyze real kinetics data.

Once we have the 2 other columns,

we tell the program to make 2 new
graphs of ln[N2O5] vs time, and
1/[N2O5] vs time

The slope of the graph gives us –k, so

we have also determined what the k
value is (in units of min-1)

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 Here’s another example of a reaction with “real” kinetics data. You can enter the values into Excel
and try to graph the 3 different graphs to see which one produces the best straight line fit.

One more example: For the reverse

Haber process, ammonia decomposes
back into its elements under catalyzed
conditions according to the following
reaction equation:

2 NH3 (g)  N2 (g) + 3 H2 (g)

During a reaction, the concentration of

NH3 (g) is monitored over time to give
the following results.

If you plot this data, you should see immediately that the [ ] vs time graph is a straight line, telling
you it is a zero order reaction. No other graphs would be necessary to plot.

2. Understanding integrated rate law equations also allows us to calculate and predict the
concentration of reactants after a certain amount of time.

However, these are pretty simple 1 equation, 1 unknown calculations. You just have to know which
equation to use, and plug in the correct values into the correct variables.

Eg. The following reaction is a 2nd order reaction: 2 NO2 (g) → 2 NO(g) + O2 (g)

How long would it take for 4.64 M of the NO2 to be become 0.25 M given that the rate constant is
0.00935 M-1.s-1 ?
Answer: 410 s (to 2 sig figs)

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 Reaction Half-Life

- The half-life (t1/2 ) is the time required for the reactant concentration (or general quantity,
grams, moles, etc.) to reach half its initial value. In terms of symbols, the statement would
translate into the following:

- You must either memorize these equations, or be able to derive them by substituting the half-
life terms into the integrated rate law equation. For example, for zero order, the integrated
rate law equation is [A]t – [A]o = -kt. When we substitute in the half-life terms, the equation
becomes ½ [A]o - [A]o = -kt½
- Then, -½ [A]o = -kt½. And finally, rearranging to solve for t½ gives us ½ [A]o /k which is the
same as what is above.

The first order half-life equation is unique compared to the other two in that its half-life is
independent of the starting concentration of reactant. It doesn’t matter if it’s 20 M going to 10 M or
1.0 M going to 0.50 M. For the same reaction, reaching half the original concentration takes the
same amount of time for a 1st order reaction.

- Why use this term “half- life”? Half-life is always measured in time units, and typically
provides a more meaningful understanding of how fast a reaction occurs, and how much
more time is left until the reaction will be done. In nature, we seem to understand the
importance and significance of when something has reached its halfway point, especially
when it comes to our age and lifespan.

Sample Questions:

1. At 1000o C, the compound cyclopropane can be converted to propene: cyclopropane  propene. The
rate constant is 9.2 s-1 . What is the half-life for this reaction? (This is how long it takes for the initial
concentration of cyclopropane to become 50% of the original.)

- To do part a) we first need to know what is the order of this reaction so we can apply the
correct half-life equation. However, the question does not state the order, but there are 2
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 revealing pieces of information: the units of k is time-1 , which applies only to 1st order
reactions. Also, there is no initial concentration given, which is another indicator.

- When we use the equation, t1/2 = ln2/9.2 s-1 = 0.075 s. This means that the reaction is super
fast! It will likely be over in the blink of an eye. This is another example of how the half-life
is much more meaningful than the rate constant term of 9.2 s-1 .

The Effect of Temperature on Reaction Rate

- A plot of rate constant versus temperature (in K) shows an exponential increase.

- Taking the natural log of the Arrhenius equation gives a linear relationship of k and T,
which allows scientists to use experimental data to estimate the frequency factor and
activation energy of a particular reaction.

So by doing multiple trials of the same reaction and different temperatures and measuring the k
value, scientists can use this information to calculate the activation energy of a reaction when they
plot ln k vs. 1/T

Reaction Mechanism Multiple Steps in an Overall Reaction

- It is unlikely for many reactions to occur in one single step. Rather, it's more likely that
multiple smaller reaction steps occur to eventually convert the reactant(s) to the product(s) in
the overall reaction. These multiple steps are called the reactions “mechanism”.

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 - Each reaction step in an overall reaction is called an elementary step.

- Elementary reaction steps have predictable rate law equations, where the order with
respect to a reactant is the coefficient of the reactant.

Molecularity is a fancy word for "number of reactants" in a reaction.

Termolecular reactions are considered highly unlikely based on collision theory. For 3 particles to
simultaneously collide with correct energy and orientation is highly improbable.

An analogy for reaction mechanism: The “mechanism” to get from home to John Abbott. In terms of
symbolism, we can write this as: Home  JAC as an overall process. However, there are many different
ways that this overall process can be achieved, utilizing multiple steps along the way. And with certain
pieces of information, like where you live, and how long it took you to get to JAC, we can start to
hypothesize the “mechanism” of arrival. Say someone lives in Baie d’Urfe but it took them 30 minutes to
get to school. You might guess that their “mechanism” is to walk. Or, there’s someone who lives in
Pierrefonds but they get to school in 45 minutes. It’s likely he/she took multiple buses to get to school.

An example of a chemical mechanism: Overall Reaction: H2 (g) + 2 ICl(g)  2 HCl(g) + I2 (g)

This reaction likely happens in more than one step because it is a termolecular reaction. So a
scientist proposes a more likely 2-step mechanism for the reaction:

While the rate law for the overall

reaction must be determined from
Step 1: H2 (g) + ICl(g)  HI(g) + HCl(g) experimental data, we can write
exact rate law equations for the
Step 2: HI(g) + ICl(g)  HCl(g) + I2 (g)
elementary steps.
Overall: H2 (g) + 2 ICl(g)  2 HCl(g) + I2 (g)
Step 1: Rate 1 = k1[H2][ICl]

Step 2: Rate 2 = k2[HI][ICl]

The addition of the 2 elementary steps adds up (using Hess’ Law) to the overall reaction.

- However, notice that the chemical species HI(g), which is observed in the mechanism, is not
found in the overall equation. HI(g) is called an intermediate.

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Characteristics of an Intermediate:

1. It is not present at the start of a reaction, but is produced at some point during the mechanism.

2. It will then react again with something else and disappear.

3. It is not a reactant or a product in the overall equation.

Now that we have seen an example of a reaction mechanism, where do they come from?

- Reaction mechanisms are purely hypothetical, made up by scientists, but are based on chemical
evidence of intermediates and data from rate experiments.

Why would scientists want to propose mechanisms?

- The mechanism provides insight into how and why any given reaction has its characteristic
kinetics, and allows for the potential to modify reaction conditions in order to make the reaction
more efficient.

• A proposed mechanism must meet 3 criteria:

1. The elementary steps must add up to the overall balanced equation (Hess’ Law).

2. The elementary steps must by physically reasonable. This means that they should either be
unimolecular or bimolecular. Termolecular elementary step are unlikely to happen and rarely used in a
mechanism.

3. The rate law for the proposed mechanism must correlate with the actual experimentally
determined rate law for the overall reaction.

Rate-determining step (rate limiting step): The slowest elementary step of a reaction mechanism.
Since it limits how fast the overall reaction can proceed, the rate law for the rate-determining step
defines the rate law for the mechanism.

Although this is a chemistry term, “rate determining step” can be used to describe real-life situations
where someone or something slows down an entire process. If you had to do a group report for school
where every group member does a different part of the report, the person who finishes their section last
was the slowest, and determined the speed at which the entire report could be finished.

Example for examining if a proposed mechanism is reasonable/valid:

The following reaction was studied experimentally using the initial rates method, and it was
determined that the rate law is first order with respect to both reactants (2nd order reaction overall).

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 This actual rate law is evidence that the reaction likely happened in more than one step. Had the above
reaction actually occurred in a single step, the overall reaction would also be the elementary step,
where the rate law is known. The rate law would have then been: Rate = k[NO2 ]2 [F2 ]. But
experimental evidence shows that this is not the case, so the reaction could not occur in one step.

So instead, a scientist proposes a 2-step mechanism:

Now we go through the 3 criteria to check this mechanism’s validity:

1. Do the elementary steps add up to the overall reaction? Yes. When you use Hess’ Law, you should
indeed see that they add up to the overall reaction, where F(g) is an intermediate.
2. Is each elementary step physically reasonable? Yes. They are both bimolecular. There are no
termolecular steps.
3. Does the rate law for the mechanism match the actual rate law?

To examine criteria 3, we take the rate law for the slow, rate determining step, which is step 1.

For step 1, the rate law would be : Rate1 = k 1 [NO2 ][F2 ]

Yes, the orders of the reactants in rate law of the mechanism are the same as the orders in the actual
rate law. So the mechanism’s rate law does match that of the actual rate law where k 1 = k

- Now that the reaction mechanism has been deemed reasonable, a reaction progress diagram can be
created for the reaction Key Characteristics of a Multi-Step
Reaction Progress Diagram

1. Each peak represents an

elementary reaction step in the
mechanism.
2. At each "valley" (in-between the
peaks), an intermediate
chemical species has been
produced. (The valley does not
include the starting reactant and
product portion)
3. The peak of highest total
potential energy (the highest
peak) is the slowest, rate
determining step
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 It’s worth mentioning that sometimes, textbooks (or the internet) say that the rate determining step is
the one that has the highest Ea. This is an unresolved discrepancy, but usually the peak of highest
potential energy also has the highest Ea as well.

Practice:

1. Is the reaction exothermic or

endothermic?
2. How many elementary steps are
there in the reaction?
3. How many different
intermediates were created
during the reaction?
4. Which elementary step is the
rate determining step?

2 valleys. 4.) Step 2 because it has the highest total energy

1.) Exo 2.) 3 because there are 3 peaks. 3.) 2 because there are

• If the first elementary step is not the slowest step (rate determining), determination of the rate law
equation is more complicated, requiring a "substitution"

We will focus on the third criteria since it is easy to see that the first and second criteria hold, and it
can be seen that N2 O2 is an intermediate chemical species.

It is also important to note that the fast 1st step reaches equilibrium since it occurs before the slow step:
the N2 O2 builds up to a point that it must reverse its reaction since it “waits” for the slow step to occur.
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 When equilibrium is reached, the rate of the forward reaction equals the rate of the reverse reaction.

- Now we want to see it the rate law for the mechanism matches that of the actual rate law.

We take the rate law for the 2nd step, which is slow step: Rate2 = k 2 [H2 ][ N2 O2 ].

However, this rate law cannot be in this form since intermediates are not allowed in the rate law
equation, only reactants. We must now substitute out the [N2 O2 ].

To do this, we take the rate law equations of the 1st step for the forward and reverse reactions:
Rate1 = k 1 [NO]2 Rate-1 = k -1 [N2 O2]
Since at equilibrium the rates are equal to each other:
k 1 [NO]2 = k -1 [N2 O2]

Now we isolate the [N2 O2 ], which equals k 1 / k -1 [NO]2 , and we substitute this term into the rate law
equation for step 2:

Rate2 = k 2 [H2 ] k 1 / k -1 [NO]2 Rearranging: Rate2 = (k 2 k 1 )/ k -1 [H2 ] [NO]2

Now the mechanism’s rate law does indeed matche the actual rate law where
(k 2 k 1 )/ k -1 = k. The mechanism is valid.

Catalysis There are two types of catalysts: heterogeneous and homogeneous.

1. Heterogeneous Catalysts - The catalyst exists in a different phase than the reactant chemicals.

Eg. Hydrogenation reaction with palladium catalyst (this is the same reaction they use to create
hydrogenated and partially hydrogenated fats that appear in processed foods)

The hydrogen atoms get added onto a double bonded hydrocarbon molecule, but the mechanism is
unknown. It is believed that the H2 gas adheres to the surface of the metal, where the bond between
the 2 hydrogens becomes weakened. Then when the double bonded carbons approach, the H atoms
attach themselves to the carbons.

2. Homogeneous Catalysts - The catalyst exists in the same phase as the reactant chemicals.

Eg. The breakdown of ozone (O3 ) in the atmosphere

Normally, the breakdown reaction in the atmosphere would be O3 (g) + O(g)  2 O2 (g). However, this
is a slow, single step reaction with a high Ea. But the chemical chlorofluorocarbons (CFC’s) widely

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 used decades ago caused rapid ozone depletion. The CFC’s once they got into the atmosphere would
break down into Cl(g), which catalyses the ozone breakdown reaction into a 2-step mechanism.

(1) O3 (g) + Cl(g)  ClO(g) + O2 (g)

(2) ClO(g) + O(g)  Cl(g) + O 2 (g) The overall reaction is still the same.

Even though it is two steps, each step has very low Ea’s allowing for the reaction to happen much
more rapidly.

Observe that ClO(g) is an intermediate in the reaction, but Cl(g) is the catalyst and has an opposite
pattern than that of intermediates.

A homogeneous catalyst is present to start the reaction, but then disappears. However, it reappears by
the end of the reaction.

A catalyst speeds up a reaction by

lowering the reaction’s Ea. The Ea is
lowered because the catalyst has
changed the reaction’s mechanism.

Just for fun: A riddle with a “rate determining” aspect to it.

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