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AP* Chemistry

CHEMICAL KINETICS:
THE RATES AND MECHANISMS OF CHEMICAL REACTIONS

Chemical kinetics is the study of the speed or rate of a reaction under various conditions. Thermodynamic
favorability is also important AND a thermodynamically favorable reaction does NOT imply a rapid reaction.
The changing of diamond into graphite is thermodynamically favorable, but so slow that it is not detectable
even in a lifetime. Why? It has an enormous activation energy that must be overcome before the reaction may
proceed. We must also consider the mechanism of the reaction which is a sequence of events at the molecular
level that controls the speed and outcome of the reaction. Dust off all those algebraic rate skills youve been
acquiring, they will come in mighty handy in this unit.
FACTORS THAT AFFECT REACTION RATES (loads of multiple choice points lurk within this section)
1.

Nature of the reactantsSome reactant molecules react in a hurry, others react very slowly. Why? The
phase of matter comes into play; solids will react much more slowly than liquids or aqueous solutions.

Physical state matters a great deal. Consider gasoline() vs. gasoline(g).


K2SO4(s) + Ba(NO3)2(s) no rxn.; while the reaction is rapid in aqueous solution.

Chemical identity - What exactly is reacting? Usually ions of opposite charge react very rapidly. Also,
the more bonds between reacting atoms in a molecule, the slower the reaction rate. Why? More energy
is required to separate the molecule into its bits. Substances with strong bonds (larger bond energies)
will react much more slowly. Examples: metallic sodium reacts much faster with water than metallic
calcium. Oxidation of methane can be increased with an increase in temperature; photosynthesis is very
slow and changes very little with an increase in temperature simply because there are so many
intermediate steps often requiring specific catalysts.

2. Concentration of reactantsThe more molecules present, the more collisions occur, the faster reaction
proceeds, the greater its rate. Simple enough. Its much like the crowded halls during the passing period!
3. TemperatureHeat em up & speed em up!; the faster molecules move, the more likely they are to
collide and the more energetic the collisions become. (Were back to the passing period analogy.) In other
words, the more likely molecular damage will occur. Bonds will be broken and new bonds will form.

4.

An increase in temperature produces more successful collisions that are able to overcome the needed
activation energy, therefore, a general increase in reaction rate with increasing temperature.

In fact, a general rule of thumb is that a 10C increase in temperature will double the reaction rate.

This actually depends on the magnitude of the activation energy, Ea* and the temperature range.

Surface area of reactants--exposed surfaces affect speed.

Except for substances in the gaseous state or solution, reactions occur at the boundary, or interface,
between two phases. In other words, at the exposed surface of the substance.

Therefore, the greater surface area exposed, the greater chance of collisions between particles, hence, the
reaction should proceed at a much faster rate. Ex. coal dust is very explosive as opposed to a piece of
charcoal. Aqueous solutions are ultimate exposure!

*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
2013 by Ren McCormick. All rights reserved.

5. Adding an inert gas has NO EFFECT on the rate [or equilibrium] of the reaction since it is NOT in the
reaction mechanism! This is a classic ruse with regard to test questions.
6. Catalysis is the increase in rate of a chemical reaction due to the participation of a substance called a
catalyst. (Sounds like a circular argument, huh?) Unlike other reagents in the chemical reaction, a catalyst is
not consumed, therefore it can be used again and again. A catalyst may participate in multiple chemical
transformations. The effect of a catalyst may vary due to the presence of other substances known as
inhibitors (which reduce the catalytic activity) or promoters (which increase the activity).

Biological catalysts are proteins called enzymes. They are very shape specific to their substrate and
have an active site that attracts the substrate using intermolecular forces. You may have studied the
lock and key enzyme analogy in a prior biology class. Since their shape is mostly determined by IMFs
(as opposed to actual chemical bonds), which are very temperature sensitive. Altering the pH or heating
the enzyme easily disrupts the IMFs and causes the enzyme to denature (lose its three dimensional
shape).

A catalyst is a substance that changes the rate of reaction by altering the reaction pathway. Most
catalysts work by lowering the activation energy needed for the reaction to proceed, therefore, more
collisions are successful and the reaction rate is increased.

Remember! The catalyst is not part of the chemical reaction and is not used up during the reaction.
Usually, the catalyst participates in the rate-determining or slowest step.

Catalysts may be homogeneous or heterogeneous catalysts. A homogeneous catalyst in the same phase
as the reactants. So, go ahead, guess what heterogeneous means in this context. Yep. A heterogeneous
catalyst is in a different phase than the reactants. Heterogeneous catalysis offers the advantage that
products are readily separated from the catalyst, and heterogeneous catalysts are often more stable and
degrade much slower than homogeneous catalysts.
Example: H2O2 decomposes relatively slowly into H2O and O2; however; exposure to light accelerates
this process AND with the help of MnO2, it goes extremely FAST!! Note: Since a catalyst lowers the
activation energy barrier, the forward and reverse reactions are both accelerated to the same degree.

Homogeneous catalysts actually appear in the rate law because their concentration affects the reaction.

THE COLLISION THEORY OF REACTION RATES


The collision theory states that when suitable particles of
the reactant hit with each other, only a certain
percentage of the collisions cause any noticeable or
significant chemical change; these successful changes
are called successful collisions. The successful collisions
have enough energy, also known as activation energy, at
the moment of impact the coulombic attractions between
each bonded atom and the shared electrons is overcome
in the reactant molecules thereby breaking the
preexisting bonds and form all new bonds. This results
in the products of the reaction. Increasing the
concentration of the reactant particles or raising the
temperature, thus bringing about more collisions and therefore many more successful collisions, increases the
rate of reaction.
Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

Essential Components of the Collision Theory

Particles must collide.


Most often, only two particles may collide at one time.
Proper orientation of colliding molecules is essential so
that molecule come into contact with each other to
form products.
The collisions must occur with enough energy to overcome
the electron/electron repulsion of the valence shell electrons of
the reacting species and must have enough energy to transform
translational energy into vibrational energy in order to penetrate
into each other so that the electrons can rearrange and form new
bonds. We speak of such collisions as effective collisions.
This new collision product is at the peak of the activation
energy hump and is called the activated complex or the transition
state. At this point, the activated complex can still either fall to
reactants or fall back to the products.

With all of these criteria met, the reaction may proceed in the
forward direction. Its amazing that we have reactions occurring at all!
You can mark the position of activation energy Ea, on a
Maxwell-Boltzmann distribution to get a diagram
like the one shown right. If the temperature is increased, the
molecules speed up and collide more frequently with more
energetic collisions.
Only those particles represented by the area to the right of the
activation energy mark will react when they collide. The great
majority don't have enough energy, and will simply bounce
apart.
If we increase the temperature from T1 to T2, more molecules
are energetic enough to achieve the Ea, thus more molecules
react and the overall reaction rate increases. Notice how many
more molecules are to the right of the activation energy and
thus will react when they collide.
A general rule of thumb is that reaction rate doubles for
each 10 C rise in temperature!

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

TYPES OF CHEMICAL REACTION RATES


The speed of a reaction is expressed in terms of its rate which is equal to some measurable quantity that is
changing with time.
The rate of a chemical reaction is measured by the decrease in concentration of a reactant or an increase in
concentration of a product in a unit of time.
change in concentration of a species [reacants]
Generally speaking, Rate

time interval
t
When writing rate expressions, they can be written in terms of
reactant disappearance or product appearance.
* Rate is not constant, it changes with time. Graphing the data
of an experiment will show an average rate of reaction.
Time
(s)
0
50
100
150
200
250
300
350
400
1.

[NO2]

[NO]

[O2]

0.1000
0.0079
0.0065
0.0055
0.0048
0.0043
0.0038
0.0034
0.0031

0.0000
0.0021
0.0035
0.0045
0.0052
0.0057
0.0062
0.0066
0.0069

0.0000
0.0011
0.0018
0.0023
0.0026
0.0029
0.0031
0.0033
0.0035

Instantaneous Reaction Rate which is simply the rate


at a given instant of time, hence its name! You probably know how to do this from math classespecially
if you are currently enrolled in Pre-Calculus or Calculus. Go ahead; its OK to show off! Examine the graph
on the previous page. Note the shapes of the curves in relation to the concentration data presented for each
substance. Note the slope of each of the lines drawn
tangent to a given curve.
To determine the value of the rate at a particular instant
of time, known as the instantaneous rate, simply
compute the slope of a line tangent to the curve at that
point in time. Be particular with regard to your
vocabulary when describing how to do this process.
Writing, take the tangent earns no points. Why
not?
Shall we practice?
Use this technique to determine the instantaneous rate
for the reactant at 10 s and at 20 s.
Use this technique to determine the instantaneous rate
for the product at 10 s and at 20 s.
What has happened to this system at 60 seconds? Practice determining the instantaneous rate for both
substances at 20 minutes and 30 minutes.

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

2.

Relative Reaction Rate is expressed as the change in concentration of a reactant per unit time or

A
time

You should focus either on the disappearance of reactants or the appearance of products
rate of of a reactant is always negative
rate of of a product is always positive
Also, the word relative here doesnt refer to family members, it refers to terms that relate to each other in
the context of a given chemical system.
Consider the reaction for the decomposition of nitrogen dioxide once again:
2 NO2(g) O 2(g) + 2 NO(g)
A cursory analysis of the stoichiometry of the equations reveals that oxygen gas can appear only half as
rapidly as the nitrogen dioxide gas disappears while NO gas appears twice as fast as oxygen appears.
The simplest way to obtain relative rate expressions is to place a one over each coefficient in the balanced
equation (if a coefficient is missing, it is understood that its coefficient is 1).
Next, apply the appropriate algebraic sign () for reactants since they are disappearing as time goes by, (+)
for products since they are appearing as time goes by. Always respect the algebraic sign AND respect the
stoichiometry.
Thus,

O2
1 NO 2
1 NO
= +
= +
2
t
t
2 t
Of course you can change these once the ratio is set if you have an aversion to fractions. Simply multiply
ALL the terms by the same factor to eliminate the fractions. In this case, multiply each term by 2. So, you
might prefer 1 : +2 : +1

Initial Rate of Reaction =

Shall we try another? Consider this reaction and write all the relative rate terms for the reactants and
products.
4 PH3(g) P4(g) + 6 H2(g)
Rate =

1 PH 3
4
t

P4
t

1 [ H 2 ]
6 t

Its OK to shorten initial rate of reaction to simply rate. Its OK to leave the + off a coefficient. We are
doing it here for emphasis! Again, you may prefer to multiply through to eliminate the fractions, but you should
work on your prejudices against them! (I still campaign that using the fractions is easier.)
Rate =

which becomes

3 [ PH 3 ]
12 t

Rate = 3

[ PH 3 ]
t

12 P4
12 t

= 12

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

P4
t

2 [ H 2 ]
12 t

= 2

[ H 2 ]
t

Exercise 1
Write the relative rates of change in concentration of the products and reactant in the decomposition of nitrosyl
chloride, NOCl?
2 NOCl(g) 2 NO(g) + Cl2(g)

Initial rate rxn. =

3.

1 [NOCl]
2
t

1 [NO]
2 t

[Cl 2 ]
t

DIFFERENTIAL Rate Law or Rate Expression (often referred to without the differential)
Reactions are reversible. So far, weve only considered the forward reaction. The reverse is equally
important. When the rate of the forward is equal to the rate of the reverse we have EQUILIBRIUM! To
avoid this complication we will discuss reactions soon after mixing, before things get too messy. So, we
will deal with initial reactions rates, thus we need not worry too much about the buildup of products and
how that starts up the reverse reaction.
The Method of Initial Reaction Rates--begin with pure reactants, mix thoroughly, then measure speed of
rxn. over time. How? Count number of bubbles, measure mass of precipitate, use spectroscopy to measure
color change, etc.
The presence of products can alter results dramatically and lead to confusing results. Well be talking
initial reaction rates throughout our discussions!
[NO 2 ]
Rate = k[NO2]n =

t
The rate expression or rate law expression is the relation between reaction rate and the concentrations of
reactants given by a mathematical equation. Be on the lookout for either symbolism for rate and never,
ever forget rate is equal to a change in some measurable quantity per unit time.
Analyzing CONCENTRATION--RATE data allows us to determine the differential rate law
expression. Its time to master the lingo!
Rates generally depend on reactant concentrations. To find the exact relation between rate and
concentration, we must conduct experiments, collect data and subsequently interpret the data. Youll get
your crack at the data in just a bit. First, examine the generic reaction below:

aA +bB

xX

C is a catalysts, the rate expression will always have the form:


Initial rxn rate = k[A]m[B]n[C]p
*note the catalyst is included only if it is homogenous (in the same phase of matter as the reactants)

k = rate constant
[A] = molar concentration of reactant A & [B] = molar concentration of reactant B
[C] = molar concentration of the catalystwont see this too often in AP
m = order of reaction for reactant A
n = order of reaction for reactant B
p = order of reaction for the catalyst C
We call the exponents orders and they can be zero, whole numbers or fractions which MUST BE
DETERMINED BY EXPERIMENTATION!!
Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

THE RATE CONSTANT, k

k is most definitely temperature dependent & must be evaluated by experiment


Example: rate = k[A]
Example: Suppose k is determined to be 0.090/hr, when [A] = 0.018 mol/L
Then, rate = k(0.0090/hr)[0.018 mol/L] = 0.00016 mol/(L hr) = 1.6 104 mol/(L hr)
Yeah, I knowthose units look frightful! Have faith, we have a way to simplify determining them.

THE SCOOP ON ORDERS


The order with respect to a certain reactant is simply the exponent on its concentration term in the
rate expression. We must analyze concentration & rate data to make this determination.
(Patience, its coming)
The overall order of the reaction is simply the sum of all the exponents on all the concentration
terms in the expression.

1. Zero order: The change in concentration of reactant has no effect on the rate. These are not very common.
General form of rate equation: Rate = k
2. First order: Rate is directly proportional to the reactants concentration; doubling [rxt], doubles rate.
These are very common! Nuclear decay reactions usually fit into this category. General form of rate
equation: Rate = k [A]1 = k[A]
3. Second order: Rate is quadrupled when [rxt] is doubled and increases by a factor of 9 when [rxt] is tripled
etc. These are common, particularly in gas-phase reactions. General form of rate equation: Rate = k [A]2
or Rate = k[A]1[B]1 which has an overall order of two (second order).
4. Fractional orders are rare, but do exist!
Recall our general rate expression: Rate = k[A]m[B]n
If m = 0 ; Say, The reaction is zero order with respect to A.
If m = 1 ; Say, The reaction is 1st order with respect to A.
If m = 2 ; Say, The reaction is 2nd order with respect to A.
If n = 0 ; Say, The reaction is zero order with respect to B.
If n = 1 ; Say, The reaction is 1st order with respect to B.
If n = 2 ; Say, The reaction is 2nd order with respect to B.
Again, summing all of the orders for each reactant gives the overall order of the reaction.
NOW, you know enough to work some examples! Try to contain your excitement

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

Example: Ponder the following experimental data for the reaction A + B Product
Experiment Number

Initial Rate
mol/(L hr)

Initial concentration
[A]o

Initial concentration
[B]o

0.50 102

0.50

0.20

0.50 102

0.75

0.20

0.50 102

1.00

0.20

1.00 102

0.50

0.40

1.50 102

0.50

0.60

Method 1: TABLE LOGIC

1. Examine the data with an analytical eye. Look for two trials where the concentration of a reactant was
held constant. Why? Its good experimental design! Meanwhile, you want a comparison where the other
reactants value changed by a factor of 2, 3, 4, , etc. For example, Experiments # 1 & 4 make a good
choice. [A] was held constant and [B] was doubled. This allows you to focus solely on the effect
manipulating the concentration of [B] has on the overall rate.
2. Next, focus on the other reactant. Ask yourself how its concentration changed for the same two trials.
Was it doubled? Was it tripled? Was it halved? Doubling is my personal favorite since even on my
worst day; I can multiply by 2, divide by 2, square 2 and even cube 2 in my head, sans calculator.
Once you have determined the factor by which the concentration of the other reactant was changed,
determine how that affected the rate for those same two trials. Expect easy math!
In our example using trials 1 & 4 [A] is held constant at 0.5 M while [B] is doubled from
trial 1 [0.2] trial 4 [0.4]. Ask yourself, What effect did that have on the rate?
Well, the respective rates increased from 0.50 102 M h1 to 1.00 102 M h1 (since the
102 M h1 part is the same for both, its just plain simpler to think 0.50 1.0) which is a doubling,
so the rate increased by (2)?. Well the only way to double the rate is to multiply it by (2)1, so the
exponent we seek is 1, thus we say it is first order with respect to reactant B.
Which so far, makes our rate law expression rate = k[A]?[B]2
3. What if changing the concentration of a given reactant had zero effect on the rate? In other words the
rate was unaffected, if so, then the reaction is zero order for that reactant. Why? (any number)0 = 1
which, as a multiplier is code for unaffected.

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

SUMMARY
Upon selecting two trials where the concentration of one (or more) reactants concentration was held
constant, ask yourself
Did the rate double (2)1 when the concentration of the other reactant was doubled?
If so, it is first order for that reactant.
Did the rate quadruple (2)2 when the concentration of the other reactant was doubled?
If so, it is second order for that reactant.
Did the rate increase by a factor of eight (2)3 when the concentration of the other reactant was
doubled? If so, it is third order for that reactant.
Did the rate remain constant (2)0 when the concentration of the other reactant was doubled?
If so, it is zero order for that reactant.

Still dont get it? THINK of the concentration doubling as the number two.
So, rate = k[reactant] becomes, rate = k[2]m and you are trying to determine the value of m.
If the rate doubled think (2 rate) = k[2]m and more simply, since the k is constant you can ignore it for
now, and think 2 = [2]m m = 1 or else we just broke the 11th commandment!
If the rate quadrupled, then think simply, 4 = [2]m m must equal 2 to make that a true statement.
By the way, if youve never listened to a screencast of your AP Chemistry notes, now may be the time!
Go to www.apchemistrynmsi.wikispaces.com, find a quiet place and your favorite beverage.

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

4. Finally, examine the data table again. Same song, second verse! This time, with feeling.
Look for trials where the concentration of the reactant you just determined the order for is held constant
and repeat the steps above with the reactant whose concentration is being varied.
Experiment Number

Initial Rate
mol/(L hr)

Initial concentration
[A]o

Initial concentration
[B]o

0.50 102

0.50

0.20

0.50 102

0.75

0.20

0.50 102

1.00

0.20

1.00 102

0.50

0.40

1.50 102

0.50

0.60

Examine trials 1-3. The concentration of [B] is held constant AND the rate remains the same regardless
of the concentration of [A]. What gives?
The reaction it is zero order with respect to A.
Double check all results by examining trials 3-5. The rate doubles with a doubling of [B] and triples
with a tripling of [B]. This indicates the rate is first order with respect to [B].
Summary: Initial reaction rate k A 0 B0 k B0 k B
0

(the superscript outside and above the molarity brackets indicates the order of that reactant, the subscript
outside and below the molarity bracket means at time zero or original concentration if you prefer)

The overall reaction rate order = 1 + 0 = 1st order overall.

Calculating the Value of the Rate Constant, k

Select a set of the data to calculate k ,gasp! Im choosing Experiment 1 (for lack of imagination).
Get started by writing your newly determined rate law expression:
Rate k B

Rate

mol
2.5 10 2
L hr
1
0.025 hr
or 2.5 10 2 h 1
h
mol
0.20
L

0.0050

You should get the same value with any line of data! Test it, Im sure youre still skeptical

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

10

Method 2: UGLY ALGEBRAIC METHOD

Sometimes, the Ugly Algebraic Method is necessary. Some folks actually like this better, we here at NMSI
dont judge! Make getting started with this method easy on yourself. Select a trial where one reactant
concentration is held constant SO THAT IT CANCELS, and lucky for you, the ks will also cancel greatly
simplifying the math.
Use the general set-up below and substitute data from the data table. Im choosing trails 1 & 4 since [A] is held
constant at 0.50 M:

rate1 k1 reactant reactant


0.50 102 k1 0.50 0.20
becomes

rate2 k2 reactant m reactant n


1.00 102 k2 0.50m 0.40n
m

Commence canceling like terms!


0.50 102
1.00 102

k1 0.50

0.20
m
n
k2 0.50 0.40
m

0.50 0.20
1 1

becomes
which simplifies to n 1
n
1.00 0.40
2 2
n

Its just the long-hand version of table logic. Either way works, employ the method you like best.
If you have a case where one reactant is never held constant, then you can either add an expect column to the
table since you usually can determine the order of at least one reactant and can predict the expected change in
the rate. Then proceed as usual and compare your expected rate to the actual rate for doubling the
concentration of the other reactant. (Screencast time again!) OR just plug into ugly algebra. Again, employ the
method that makes you both quick and accurate!
Exercise 2
In the following reaction, a CoCl bond is replaced by a CoOH2 bond.

[Co(NH3)5Cl]+2 + H2O [Co(NH3)5H2O]+3 + Cl


Initial rate = k{[Co(NH3)5Cl]+2}m
Using the data below, find the value of m in the rate expression and calculate the value of k.
Experiment

1
2
3

Initial Concentration
of [Co(NH3)5Cl]+2
(mol/L)
1.0 103
2.0 103
3.0 103

Initial rate
mol/(L min)
1.3 107
2.6 107
3.9 107
m = 1; k = 1.3 104 min1

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

11

Exercise 3
The reaction between bromate ions and bromide ions in acidic aqueous solution is given by the equation

BrO3-(aq) + 5 Br (aq) + 6 H+(aq) 3 Br2() + 3 H2O()


The table below gives the results of four experiments. Using these data, determine the orders for all three
reactants, the overall reaction order, and the value of the rate constant. What is the value of k? What are the
units of k?
Experiment
1
2
3
4

Initial
[BrO3]
0.10
0.20
0.20
0.10

Initial
[Br]

Initial
[H+]

0.10
0.10
0.20
0.10

0.10
0.10
0.10
0.20

Measured initial rate


(mol/Ls)
8.0 10-4
1.6 10-3
3.2 10-3
3.2 10-3

rate = k[BrO3][Br ][H+]2 ; overall order = 4; k = 8.0 L3/mol3s

What weve explored thus far is termed differential rate law or simply rate law, its the method we use when the
data presented is concentration & time data. IF the data presented is concentration and rate data, we need a new
method!
So, there are TWO TYPES OF RATE LAW which implies to different approaches are needed. Hey,
youre half-way there!
Differential rate lawdata table contains concentration and rate data. Use table logic or ugly algebra to
determine the orders of reactants and the value of the rate constant, k.
Integrated rate lawdata table contains concentration and time data. Use graphical methods to determine
the order of a given reactant. The value of the rate constant k is equal to the absolute value of the slope of
the best fit line which is decided by performing 3 linear regressions and analyzing the regression correlation
coefficient r. Not nearly as hard as it sounds! Fire up your graphing calculator.
INTEGRATED RATE LAW: CONCENTRATION-TIME DATA

When we wish to know how long a reaction must proceed to reach a predetermined concentration of some
reagent, we can construct curves or derive an equation that relates concentration and time.
Set up your axes so that time is always on the x-axis. Plot the concentration of the reactant on the
y-axis of the first graph. Plot the natural log of the concentration (ln[A], NOT log[A]) on the y-axis of the
second graph and the reciprocal of the concentration on the y-axis of the third graph.

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

12

You are in search of linear data! Here comes the elegant part If you do the set of graphs in this order with the
y-axes being concentration, natural log of concentration and reciprocal concentration, the alphabetical
order of the y-axis variable leads to 0, 1, 2 orders respectively for
that reactant.

First order
k = negative slope

Zero order
k = negative slope

Second order
k = the slope

You can now easily solve for either time or concentration once you know the order of the reactant.
Just remember y = mx + b. Choose the set of variables that gave you the best straight line (r value closest to 1)
and insert them in place of x and y in the generalized equation for a straight line.
A is reactant A and Ao is the initial concentration of reactant A at time zero [the y-intercept].
zero order
first order
second order

y
[A]
ln[A]
1/[A]

= mx
= kt
= kt
= kt

+
+
+
+

b
[Ao]
ln [Ao]
1/[Ao]

Also recognize that slope = k, since the rate constant is NEVER negative. If you are asked to write the rate
expression [or rate law] it is simply Rate = k[A]order you determined from analyzing the graphs

Graphing Calculator Tutorial Set up your calculator so that time is always in L1.
Use L2, L3 and L4 to display the y-variables. Remember the list for what is placed on the y-axis is alphabetical
(concentration, natural log of concentration and reciprocal concentration).
L1 = time (x-variable throughout!)
L2 = concentration
L3 = ln concentration
L4 = reciprocal concentration

[A]
ln [A]
1/[A]

straight line infers zero order


straight line infers first order
straight line infers second order

Use this system to set up the data given in the following exercise:
We are going to perform 3 linear regressions to determine the order of the reactant. They will be L1,L2; L1,L3;
L1,L4. Next, we will determine which regression has the best r-value [linear regression correlation coefficient
in big people language!] We will also paste the best regression equation Y=
so that we can easily do other calculations commonly required on AP Chemistry Exam problems.

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

13

Turn on your calculator and lets start draining those batteries!


IF you need a calculator tutorial on entering data into lists, batch transforming list, graphing data, running a
linear regression, graphing the regression equation and subsequently using the equation to solve integrated rate
problems in a flash, go here: https://vimeo.com/14866721 If that is blocked, try the links from
www.apchemistrynmsi.wikispaces.com

Exercise 4
The decomposition of N2O5 in the gas phase was studied at constant temperature.

2 N2O5(g) 4 NO2(g) + O2(g)


The following results were collected:
[N2O5]
0.1000
0.0707
0.0500
0.0250
0.0125
0.00625

Time (s)
0
50
100
200
300
400

(a) Determine the rate law and calculate the value of k.

(b) Determine the concentration of N2O5(g) at 250 s. Does your calculated answer make sense? Justify your
answer.

(c) Determine the concentration of N2O5(g) at 600 s. Does your calculated answer make sense? Justify your
answer.

(d) At what time is the concentration of N2O5(g) equal to 0.00150 M ? Explain how you know your answer is
correct.

Ans: rate = k[N2O5] ; k = slope of graph of ln [N2O5] vs. time = 6.93 103 s1; 0.0177 M; 0.00156 M; 606 s
Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

14

Exercise 5
For the reaction of (CH3)3CBr with OH,

(CH3)3CBr + OH (CH3)3COH + Br
The following data were obtained in the laboratory.
TIME (s)
0
30.0
60.0
90.0

[(CH3)3CBr]
0.100
0.074
0.055
0.041

(a) Determine the order of this reaction. Sketch your graph.

(b) Determine the value of the rate constant and include proper units.

(c) At what time is the concentration of (CH3)3CBr equal to [0.086]? Justify your answer.

(d) At what time is the concentration of (CH3)3CBr equal to [0.025]? Justify your answer.

(e) What is the concentration of (CH3)3CBr after 2 minutes? Justify your answer.

(a) A straight line with a negative slope; 1st order since plot of ln[(CH3)3CBr] vs. time is linear;
(b) k = 9.9 103 s1; (c) 15.0 s; (d) 140 s; (e) 0.0304 M

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

15

DETERMINING HALF-LIFE (t1/2)

Half-life is defined as the time required for one half of one of the reactants to disappear. Well, that seems
logical enough. Finally, a concept with a simple name! You probably remember dealing with half-life in the
context of 14C and using it to approximate the age fossils and such. Or, you may have heard it in a medical
sense such as injecting 131I which is an important radioisotope of iodine into a patient. It has a radioactive decay
half-life of about eight days and is associated with nuclear energy, medical diagnostic and treatment procedures,
especially those involving the thyroid gland.
We will focus on the half-life for first order reactions only. Be thankful! Since you are all smart students, you
will need to be able to analyze this verbally, graphically and algebraically. Which sounds worse than it is.
Again, you already know most of this!
Concept

Numerical Interpretation of Concept

The data points plotted on the graph pictured right represent


concentration-time data collected for the radioactive decay of
Element Q. Your task is to supply the graph with an
appropriate title and answer the following questions:
1. While you may at a glance be unable to determine the
order of this reaction, you can definitely determine
which order it is NOT! So, which order is not the order
for this reaction?
2. What is the half-life of Element Q?
3. What is the molar concentration of Element Q
after a second half-life has elapsed?
4. At what time has 75% of the original sample decayed?

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

16

Why do we care about half-lives of only 1st order reactions? Because they are the only reactions for which
the length of the half-life is constant and this course is equivalent to a first-year university chemistry course so
Calculus is not required, thus we focus on the chemical situation where the math is simple.
I still cant resist the comparison, though! Examine the Concentration vs. Time Graphs below:
Zero Order Reaction
A products & rate = k

First Order Reaction


A products & rate = k[A]:

Second Order Reaction


2A products or A + B products
rate = k[A]2 or Rate = k[A][B]

What is alike about each graph?


What is different about each graph?
What is the significance of the lengths of the horizontal red lines associated with each half-life?
Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

17

Indulge me in a derivation. (That means you can skip this unless youre in Calculusyou might actually find it
interesting!)
The half-life, t 1 is a timescale by which the initial population (reactants in our case) is decreased by half of its
2

original value. We can represent the relationship by the following equation:

A 0
ln
kt
A

where A0 means concentration at time = zero

By definition, when t t 1 ,

Substitute, and we arrive at

A 0
ln
A 0

A 0
2

A0
ln
A
0
2

kt 1 ; clean it up a bit
2

kt 1 which then becomes ln 2 kt 1


kt 1 becomes ln
1

2
2
2
2

Rearrange once again to solve for t 1 and arrive at whats on the formula sheet for the AP Chemistry Exam:
2

ln 2 0.693
which is almost downright friendly!
t1 =

k
k
2

Notice that, for first-order reactions, the half-life is independent of the initial concentration of reactant, which is
a unique aspect to first-order reactions.

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

18

Exercise 6
Butadiene reacts to form its dimer according to the equation

2 C4H6(g) C8H12(g)
The following data were collected for this reaction at a given temperature:
[C4H6]
0.01000
0.00625
0.00476
0.00370
0.00313
0.00270
0.00241
0.00208

Time ( 1 s)
0
1000
1800
2800
3600
4400
5200
6200

(a) Determine is the order of this reaction? Write the rate law expression. Justify your answer. Sketch a
graph as part of your explanation.

(b) Determine the value of the rate constant for this reaction?

(c) Determine the half-life for the reaction under the conditions of this experiment?

2nd since plot of 1/[C4H6] vs. time yields a straight line with a |slope| = k = 6.14 102 M/s; 1630 s

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

19

Exercise 7
A certain first-order reaction has a half-life of 20.0 minutes.

a. Calculate the rate constant for this reaction.

b. How much time is required for this reaction to be 75% complete?

3.47 102 min1; 40 minutes

Exercise 8
The rate constant for the first order transformation of cyclopropane to propene is 5.40 102 hr1. Calculate the
half-life of this reaction. What fraction of the cyclopropane remains after 51.2 hours? What fraction remains after
18.0 hours?

12.8 hr; 0.063; 0.38

INTEGRATED RATE LAWS FOR REACTIONS WITH MORE THAN ONE REACTANT
Must [still] be determined by experiment! But we use a technique called swamping.
Flood the reaction vessel with high concentrations of all but one reactant and perform the experiment.
The reactants at high concentrations like say, 1.0 M compared to the reactant with a low concentration
say, 1.0 103 M, stay the same.

In Englishthe rate is now dependent on the concentration of the little guy since the big guys
arent changing, therefore the rate = k [little guy]

We now re-write the rate as a pseudo-rate-law and k is a pseudo-rate-constant

This is what is happening in the Crystal Violet lab!

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

20

SUMMARY:
Note k = |slope| for ANY linearized graph.
ORDER

Rate law:
Units of rate constant:

Zero

First

Second

Rate = k

Rate = k[A]

Rate = k[A]2

M time1 or M/time

time1 or 1/time

M1 time1 or

1
M time

[A] = -kt + [A]0

ln[A] = kt + ln[A]0

1
1
kt
A
A0

Relationship of rate constant to slope


of straight line:

Slope = k

Slope = k

Slope = k

Plot needed to give a straight line:

[A] versus t

ln[A] versus t

1
versus t
A

Integrated rate law:

Half-life:

t1

[A]0

2k

t1
2

0.693
k

t1
2

1
k [A]0

REACTION MECHANISMS
A mechanism represents the sequence of bond-making and bond-breaking steps that occurs during the
conversion of reactants to products.

1. Must be determined by experiment!


2. Must agree with overall stoichiometry!
3. Must agree with the experimentally determined rate law!
The vocabulary of mechanisms involves elementary steps & molecularity which describes the number of
molecules that participate in an atomic rearrangement. Add these terms into your explanations.

unimolecular: involves one reactant molecule that collides with a solvent or background molecule
thereby becoming collisionally activated. In this state the reactant molecule is thermodynamically
favorable for converting into product

bimolecular: involves a collision between two reactant molecules

termolecular: simultaneous collision between three reactant molecules [very rare!]*

RATE EXPRESSIONS FOR ELEMENTARY STEPS--the rate expression cannot be predicted from
overall stoichiometry. The rate expression of an elementary step is predicted from the stoichiometry of
the elementary step as per the table below:

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

21

ELEMENTARY
STEP

MOLECULARITY

RATE EXPRESSION

A products

unimolecular

rate = k[A]

A + B products

bimolecular

rate = k[A][B]

A + A products

bimolecular

rate = k[A]2

2 A + B products*

termolecular*

rate = k[A]2[B]

THE PHYSICAL SIGNIFICANCE OF RATE EXPRESSIONS FOR ELEMENTARY STEPS


- the more molecules the more collisions, the faster the rate
- the faster the molecules are moving, the more likely they will collide, the faster the rate

MOLECULARITY AND ORDER


- an elementary step is a reaction whose rate law can be written from its molecularity
- NOT true of the overall reaction order!

Exercise 9
Nitrogen oxide is reduced by hydrogen to give water and nitrogen,
2 H2(g) + 2 NO(g) N2(g) + 2 H2O(g)
and one possible mechanism to account for this reaction is
2 NO(g) N2O2(g)
N2O2(g) + H2(g) N2O(g) + H2O(g)
N2O(g) + H2(g) N2(g) + H2O(g)

What is the molecularity of each of the three steps? Show that the sum of these elementary steps yields the net
reaction.
bimolecular; unimolecular; unimolecular

REACTION MECHANISMS AND RATE EXPRESSIONS


are determined by experiment and MUST agree with the experimentally determined rate law
the slowest step is the rate determining step
the rate of the overall reaction is limited by, and is exactly equal to, the combined rates
of all elementary steps up to and including the slowest step in the mechanism
reaction intermediate--produced in one step but consumed in another
catalyst--goes in as a reactant, comes out as an unharmed product and DOES NOT show up in
the final overall rxn.

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

22

Exercise 10
The balanced equation for the reaction of the gases nitrogen dioxide and fluorine is
2 NO2(g) + F2(g) 2 NO2F(g)

The experimentally determined rate law is


Rate = k [NO2][F2]
A suggested mechanism for the reaction is
NO2 + F2 NO2F + F

Slow

F + NO2 NO2F

Fast

Is this an acceptable mechanism? That is, does it satisfy the two requirements? Justify your answer.
Yes. It is bimolecular in the first step which is the slow step, which yields a rate law expression that agrees
with the experimentally determined rate law that was given.
CATALYSIS

Catalysis is the increase in rate of a chemical reaction due to the participation


of a substance called a catalyst. Unlike other reagents in the chemical
reaction, a catalyst is not consumed. Catalysts function by lowering the
activation energy of an elementary step in a reaction mechanism, and by
providing a new and faster reaction mechanism. The effect of a catalyst may
vary due to the presence of other substances known as inhibitors (which
reduce the catalytic activity) or promoters (which increase the activity).
Important classes in catalysis include acid-base catalysis, surface catalysis,
and enzyme catalysis.
How do they do their job? They alter the mechanism so the activation
energy barrier can be lowered, thus speeding up the reaction by offering a
different pathway for the reaction.
Collisions must be effective which is code for having enough Umph! or
sufficient energy AND for having the correct orientation.
The overall E is NOT changed for the process, BUT the activation
energy IS lowered.
Biological catalysts are called enzymes which are proteins with specific
shapes. ATP synthetase is the most important enzyme in the human
body! Death occurs when an organism runs out of ATP.

You need to interpret graphs such as the one above left in terms of kinetics and thermodynamics!
You also need to be able to label the REVERSE rxns.
Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

23

HOMOGENEOUS CATALYSTSexists in the same phase as the reacting molecules.

Freons or chlorofluorocarbons [CFCs] were used until recently as refrigerants and as propellants in aerosol
cans. Freon-12 (CCl2F2) is relatively inert and thus remains in the environment for a long time. Eventually
they migrate upward into the upper atmosphere and are decomposed by high-energy light. Among the
decomposition products are chlorine atoms:
CCl2F2(g)

light

CClF2(g)

+ Cl(g)

These chlorine atoms can catalyze the decomposition of ozone by forming a new reaction intermediate, thus
thinning the atmospheric ozone layer that protects Earth from harmful UV rays :
Cl(g) + O3(g) ClO(g) + O2(g)
O(g) + ClO(g) Cl(g) + O2(g)
2 O2(g)

O(g) + O3(g)

HETEROGENEOUS CATALYSTexists in a different phase than reactants,


usually involves gaseous reactants adsorbed on the surface of a solid catalyst

adsorptionrefers to the collection of one substance on the surface of


another
absorptionrefers to the penetration of one substance into another; water
is absorbed by a sponge
Hydrogenation of unsaturated hydrocarbonsespecially important in
converting unsaturated fats [oils] into saturated fats [solids like Crisco]
C=C bonds are converted into C-C bonds by adding a pair of hydrogens
across the double bond.

A simple example of hydrogenation involves ethylene:


H

H
C=C

H
ethene (ethylene)

+ H2(g)

H
H
ethane

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

24

Acid-Base Catalysis is an acceleration of a chemical reaction by the addition of an acid or a base, the acid or
base itself not being consumed in the reaction. The catalytic reaction may be acid-specific (acid catalysis), as
in the case of decomposition of the sugar sucrose into glucose and fructose in sulfuric acid. This is also an
example of a dehydration reaction.

Mixing sucrose with dilute sulfuric acid in a beaker (a, right) produces a simple solution. Mixing the same amount of sucrose
with concentrated sulfuric acid (a, left) results in a dramatic reaction (b) that eventually produces a column of black porous
graphite (c) and an intense smell of burning sugar.
Taken from: http://2012books.lardbucket.org/books/general-chemistry-principles-patterns-and-applications-

v1.0/section_18_01.html

Wanna see? (You have no idea how bad this smells!) http://www.youtube.com/watch?v=GzQDdrcJEBE
The reaction pictured right uses a solid catalyst in the form of Pt, Pd, or Ni.
The hydrogen and ethylene adsorb on the catalyst surface where the reaction occurs. The
catalyst allows for metal-hydrogen interactions that weaken the strong H-H bonds
stabilizing the transition state.
Typically involves 4 steps:
1.
2.
3.
4.

Adsorption and activation of the reactants


Migration of the adsorbed reactants on the surface
Reaction of the adsorbed substances
Escape, or desorption, of the products

Catalytic converters are also heterogeneous catalysts. They contain platinum and have
been placed in automobiles since 1974. [I know! You werent born yet! Dont rub it in.]
Gasoline containing lead RUINS the catalytic converter in your car!

Chemical Kinetics: The Rates and Mechanisms of Chemical Reactions

25

AP* Kinetics Free Response Questions

page 1

Essay Questions
1983
Graphical methods are frequently used to analyze data and obtain desired quantities.
2 HI(g) H2(g) + I2(g)
The following data give the value of the rate constant at various temperatures for the gas phase reaction
above.
k (liter/mol sec)
T (K)
647
8.58 105
666
2.19 104
683
5.11 104
700
1.17 103
716
2.50 103
(a) Describe, without doing any calculations, how a graphical method can be used to obtain the
activation energy for this reaction.
A(g) B(g) + C(g)
The following data give the partial pressure of A as a function of time and were obtained at 100C for
the reaction above.
t (sec)
PA (mm Hg)
348
0
247
600
185
1200
105
2400
58
3600
(b) Describe, without doing any calculations, how graphs can be used to determine whether this
reaction is first or second order in A and how these graphs are used to determine the rate constant.
1985

PCl3(g) + Cl2(g) PCl5(g)


In the equation above, the forward reaction is first order in both PCl3 and Cl2 and the reverse reaction is
first order in PCl5.
(a) Suppose that 2 moles of PCl3 and 1 mole of Cl2 are mixed in a closed container at constant temperature.
Draw a graph that shows how the concentrations of PCl3, Cl2, and PCl5 change with time until after
equilibrium has been firmly established.
(b) Give the initial rate law for the forward reaction.
(c) Provide a molecular explanation for the dependence of the rate of the forward reaction on the
concentrations of the reactants.
(d) Provide a molecular explanation for the dependence of the rate of the forward reaction on temperature.
(1) AP is a registered trademark of the College Board. The College Board was not involved in the production of and does not endorse this product. (2) Test
Questions are Copyright 1984-2008 by College Entrance Examination Board, Princeton, NJ. All rights reserved. For face-to-face teaching purposes,
classroom teachers are permitted to reproduce the questions. Web or Mass distribution prohibited.

AP* Kinetics Free Response Questions

page 2

1990
Consider the following general equation for a chemical reaction.
A(g) + B(g) C(g) + D(g)

H reaction = 10 kJ

(a) Describe the two factors that determine whether a collision between molecules of A and B results in
a reaction.
(b) How would a decrease in temperature affect the rate of the reaction shown above? Explain your
answer.
(c) Write the rate law expression that would result if the reaction proceeded by the mechanism shown
below.
A + B p [AB]
(fast)
[AB] + B C + D

(slow)

(d) Explain why a catalyst increases the rate of a reaction but does not change the value of the
equilibrium constant for that reaction.

1992
H2(g) + I2(g) 2 HI(g)
For the exothermic reaction represented above, carried out at 298 K, the rate law is as follows.
Rate = k[H2][I2]
Predict the effect of each of the following changes on the initial rate of the reaction and explain your
prediction.
(a) Addition of hydrogen gas at constant temperature and volume.
(b) Increase in volume of the reaction vessel at constant temperature.
(c) Addition of catalyst. In your explanation, include a diagram of potential energy versus reaction
coordinate.
(d) Increase in temperature. In your explanation, include a diagram showing the number of molecules as
a function of energy.

AP* Kinetics Free Response Questions

page 3

1995

(I) A2 + B2 2 AB
(II) X2 + Y2 2 XY
Two reactions are represented above. The potential energy diagram for reaction I is shown below. The
potential energy of the reactants in reaction II is also indicated on the diagram. Reaction II is endothermic, and
the activation energy of reaction I is greater than that of reaction II.

(a) Complete the potential energy diagram for reaction II on the graph above.
(b) For reaction I, predict how each of the following is affected as the temperature is increased by 20C.
Explain the basis for each prediction.
(i) Rate of reaction
(ii) Heat of reaction
(c) For reaction II, the form of the rate law is rate = k[X2]m[Y2]n. Briefly describe an experiment that can
be conducted in order to determine the values of m and n in the rate law for the reaction.
(d) From the information given, determine which reaction initially proceeds at the faster rate under the
same conditions of concentration and temperature. Justify your answer.
1996
The reaction between NO and H2 is believed to occur in the following three-step process.
NO + NO p N2O2

(fast)

N2O2 + H2 N2O + H2O


N2O + H2 N2 + H2O

(slow)
(fast)

(a) Write a balanced equation for the overall reaction.


(b) Identify the intermediates in the reaction. Explain your reasoning.
(c) From the mechanism represented above, a student correctly deduces that the rate law for the
reaction is rate = k[NO]2[H2]. The student then concludes that (1) the reaction is third-order and (2)
the mechanism involves the simultaneous collision of two NO molecules and an H2 molecule. Are
conclusions (1) and (2) correct? Explain.
(d) Explain why an increase in temperature increases the rate constant, k, given the rate law in (c).

AP* Kinetics Free Response Questions

page 4

2003
The decay of the radioisotope I-131 was studied in a laboratory. I-131 is known to decay by beta
( 01e ) emission.
(a) Write a balanced nuclear equation for the decay of I-131.
(b) What is the source of the beta particle emitted from the nucleus?
The radioactivity of a sample of I-131 was measured. The data collected are plotted on the graph below.

(c) Determine the half-life, t1/2 , of I-131 using the graph above.
(d) The data can be used to show that the decay of I-131 is a first-order reaction, as indicated on the graph below.

(i)

Label the vertical axis of the graph above.

(ii) What are the units of the rate constant, k, for the decay reaction?
(iii) Explain how the half-life of I-131 can be calculated using the slope of the line plotted on the graph.
(e) Compare the value of the half-life of I-131 at 25C to its value at 50C.

AP* Kinetics Free Response Questions

page 5

Problems
1981

A(aq) + 2 B(aq) 3 C(aq) + D(aq)


For the reaction above, carried out in solution of 30C, the following kinetic data were obtained:
Initial Conc. of
Reactants
Experiment
1
2
3
4
5
6

(mole.liter1)

Ao
0.240
0.240
0.360
0.120
0.240
0.0140

Initial Rate of
Reaction

(mole.liter1.hr1)

Bo
0.480
0.120
0.240
0.120
0.0600
1.35

8.00
2.00
9.00
0.500
1.00
?

(a) Write the rate-law expression for this reaction.


(b) Calculate the value of the specific rate constant k at 30C and specify its units.
(c) Calculate the value of the initial rate of this reaction at 30C for the initial concentrations shown
in experiment 6.
(d) Assume that the reaction goes to completion. Under the conditions specified for experiment 2, what
would be the final molar concentration of C?
1984
For a hypothetical chemical reaction that has the stoichiometry 2 X + Y Z, the following initial rate
data were obtained. All measurements were made at the same temperature.

(a)
(b)
(c)
(d)

Initial Rate of
Formation of Z, Initial [X]o, Initial [Y]o,
(mol.L1)
(mol.L1)
(mol.L1.sec1)
7.0 104
0.20
0.10
3
1.4 10
0.40
0.20
3
2.8 10
0.40
0.40
3
4.2 10
0.60
0.60
Give the rate law for this reaction from the data above.
Calculate the specific rate constant for this reaction and specify its units.
How long must the reaction proceed to produce a concentration of Z equal to 0.20 molar, if the initial
reaction concentrations are [X]o = 0.80 molar, [Y]o = 0.60 molar and [Z]0 = 0 molar?
Select from the mechanisms below the one most consistent with the observed data, and explain your
choice. In these mechanisms M and N are reaction intermediates.
(1) X + Y M
(slow)
X+MZ
(fast)
(2) X + X p M
(fast)
Y+MZ
(slow)
(3) Y M
(slow)
M+XN
(fast)
N+XZ
(fast)

AP* Kinetics Free Response Questions


1987

page 6

2 HgCl2(aq) + C2O42 2 Cl + 2 CO2(g) + Hg2Cl2(aq)

The equation for the reaction between mercuric chloride and oxalate ion in hot aqueous solution is shown
above. The reaction rate may be determined by measuring the initial rate of formation of chloride ion, at
constant temperature, for various initial concentrations of mercuric chloride and oxalate as shown in the
following table
Experiment
1
2
3
4

Initial
[HgCl2]

Initial
[C2O42]

Initial Rate of
Formation of Cl

0.0836
0.0836
0.0418
0.0316

0.202
0.404
0.404
?

0.52 104
2.08 104
1.06 104
1.27 104

(mol.L1.min1)

(a) According to the data shown, what is the rate law for the reaction above?
(b) On the basis of the rate law determined in part (a), calculate the specific rate constant. Specify the units.
(c) What is the numerical value for the initial rate of disappearance of C2O42 for Experiment 1?
(d) Calculate the initial oxalate ion concentration for Experiment 4.
1991

2 ClO2(g) + F2(g) 2 ClO2F(g)


The following results were obtained when the reaction represented above was studied at 25C.

Experiment

Initial [ClO2],

Initial [F2],

Initial Rate of
Increase of [ClO2F],

1
2
3

0.010
0.010
0.020

0.10
0.40
0.20

2.4 103
9.6 103
9.6 103

(mol.L1)

(mol.L1)

(mol.L1.sec1)

(a) Write the rate law expression for the reaction above.
(b) Calculate the numerical value of the rate constant and specify the units.
(c) In experiment 2, what is the initial rate of decrease of [F2]?
(d) Which of the following reaction mechanisms is consistent with the rate law developed in (a).
Justify your choice.
I.

II.

ClO2 + F2 p ClO2F2

(fast)

ClO2F2 ClO2F + F
ClO2 + F ClO2F
F2 2 F
2 (ClO2 + F ClO2F)

(slow)
(fast)
(slow)
(fast)

AP* Kinetics Free Response Questions

page 7

2003
5 Br(aq) + BrO3(aq) + 6 H+(aq) 3 Br2(l) + 3 H2O(l)
In a study of the kinetics of the reaction represented above, the following data were obtained at 298 K.

(a) From the data given above, determine the order of the reaction for each reactant listed below.
Show your reasoning.
(i) Br
(ii) BrO3
(iii) H+
(b) Write the rate law for the overall reaction.
(c) Determine the value of the specific rate constant for the reaction at 298 K. Include the correct
units.
(d) Calculate the value of the standard cell potential, E, for the reaction using the information in the
table below.

(e) Determine the total number of electrons transferred in the overall reaction.

AP* Kinetics Free Response Questions

page 8

2004
The first-order decomposition of a colored chemical species, X, into colorless products is monitored with
a spectrophotometer by measuring changes in absorbance over time. Species X has a molar absorptivity
constant of 5.00 103 cm1 M 1 and the path length of the cuvette containing the reaction mixture is
1.00 cm. The data from the experiment are given in the table below.

(a) Calculate the initial concentration of the colored species.


(b) Calculate the rate constant for the first-order reaction using the values given for concentration and
time. Include units with your answer.
(c) Calculate the number of minutes it takes for the absorbance to drop from 0.600 to 0.075.
(d) Calculate the half-life of the reaction. Include units with your answer.
(e) Experiments were performed to determine the value of the rate constant for this reaction at various
temperatures. Data from these experiments were used to produce the graph below, where T is
temperature. This graph can be used to determine the activation energy, Ea, of the reaction.

(i) Label the vertical axis of the graph.


(ii) Explain how to calculate the activation energy from this graph.

AP* Kinetics Free Response Questions

page 9

2004B
2 H2O2(aq) 2 H2O(l) + O2(g)
Hydrogen peroxide decomposes according to the equation above.
(a) An aqueous solution of H2O2 that is 6.00 percent H2O2 by mass has a density of 1.03 g mL1. Calculate
each of the following.
(i) The original number of moles of H2O2 in a 125 mL sample of the 6.00 percent H2O2 solution
(ii) The number of moles of O2(g) that are produced when all of the H2O2in the 125 mL sample

decomposes
(b) The graphs below show results from a study of the decomposition of H2O2 .

(i)
(ii)
(iii)
(iv)

Write the rate law for the reaction. Justify your answer.
Determine the half-life of the reaction.
Calculate the value of the rate constant, k. Include appropriate units in your answer.
Determine [H2O2] after 2,000 minutes elapse from the time the reaction began.

AP* Kinetics Free Response Questions

page 10

2005B

X
2Y + Z
The decomposition of gas X to produce gases Y and Z is represented by the equation above. In a certain
experiment, the reaction took place in a 5.00 L flask at 428 K. Data from this experiment were used to
produce the information in the table below, which is plotted in the graphs that follow.

(a) How many moles of X were initially in the flask?


(b) How many molecules of Y were produced in the first 20. minutes of the reaction?
(c) What is the order of this reaction with respect to X? Justify your answer.
(d) Write the rate law for this reaction.
(e) Calculate the specific rate constant for this reaction. Specify units.
(f) Calculate the concentration of X in the flask after a total of 150. minutes of reaction.

AP* Chemistry
PROPERTIES OF SOLUTIONS
IMPORTANT TERMS
Solutiona homogeneous mixture of two or more substances in a single phase.
Does not have to involve liquids. Air is a solution of nitrogen, oxygen, carbon dioxide etc.;
solder is a solution of lead, tin etc.

solutecomponent in lesser concentration;


dissolvee
solventcomponent in greater
concentration; dissolver

solubilitymaximum amount of material that


will dissolve in a given amount of solvent at a
given temperature to produce a stable solution.
In other words, the solution is saturated.
Study the solubility rules!!
molar solubilitythe number of moles of solute that dissolves in exactly 1.0 L of solvent,
expressed in units of molarity, M or the use of square brackets.
Saturated solution a solution containing the maximum
amount of solute that will dissolve under a given set of
pressure and temperature conditions. Saturated solutions are
at dynamic equilibrium with any excess undissolved solute
present. Solute particles dissolve and recrystallize at equal
rates.
Unsaturated solution a solution containing less than the
maximum amount of solute that will dissolve under a given
set of conditions. (more solute can dissolve)
Supersaturated solutionoxymorona solution that has
been prepared at an elevated temperature and then slowly
cooled. It contains more than the usual maximum amount of
solution dissolved. A supersaturated solution is very
unstable and agitation (stirring, pouring, etc.) or the
addition of a seed crystal will cause all excess solute
to crystallize out of solution leaving the remaining
solvent saturated. (rock candy is made this way as are
those liquid hand warmer packets of sodium acetate
solution, pictured at left, folks use hunting, at football
games, skiing, etc.)

*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
2008 by Ren McCormick. All rights reserved.

miscibleWhen two or more liquids mix (ex. Water and food coloring)
immiscibleWhen two or more liquids DONT mix.they usually layer if allowed to set
for a while. (ex. Water and oil)

Concentration Units
Molarity (M) = # of moles of solute per liter of solution; IS temperature dependent.
The liquid solvent can expand and contract with changes in temperature. Thus, not a constant
ratio of solute:solvent particles. Most molar solutions are made at 25 C so this point is subtle
and picky, but important none the less!!

M =

moles of solute
liters of solution

Mass percent (weight percent) = percent by mass of the solute in the solution

Mass percent =

grams of solute
100%
grams of solution

Mole fraction () = ratio of the number of moles of a given component to the total number
of moles of present.

Mole fractiona = a

Mole Fraction a = a =

na
na + nb +"

Molality (m) = # of moles of solute per kilogram of solvent; NOT temperature dependent.
Represents a ratio of solute:solvent molecules at all times.

m =

Properties of Solutions

moles of solute
kilograms of solvent

Exercise 1

Various Methods for Describing Solution Composition

A solution is prepared by mixing 1.00g ethanol (C2H5OH) with 100.0g water to give a final volume
of 101 mL. Calculate the molarity, mass percent, mole fraction, and molality of ethanol in this
solution.

molarity = 0.215 M
mass percent = 0.990% C2H5OH
mole fraction = 0.00389
molality = 0.217 m

Exercise 2

Calculating Various Methods of Solution Composition


from the Molarity

The electrolyte in automobile lead storage batteries is a 3.75 M sulfuric acid solution that has a
density of 1.230 g/mL. Calculate the mass percent, molality, and normality of the sulfuric acid.

mass percent = 29.9% H2SO4


molality = 4.35 m
normality is 7.50 N

THE SOLUTION PROCESS


Energies involved in solution formation
When a solute is dissolved in a solvent, the attractive forces between solute and solvent
particles are great enough to overcome the attractive forces within the pure solvent and
within the pure solute. The solute becomes solvated (usually by dipoledipole or
iondipole forces). When the solvent is water the solute is hydrated.

Substances with similar types of intermolecular forces dissolve in each other. Like
dissolves like.
Polar solvents dissolve polar or ionic solutes.
Nonpolar solvents dissolve nonpolar solutes.

Properties of Solutions

Water dissolves many salts because the stronger iondipole attractions water forms with
the ions of the salt are very similar to the strong attractions between the ions themselves.
The same salts are insoluble in hexane (C6H14) because the weaker London dispersion
forces their ions could form with this nonpolar solvent are much weaker than the
attraction between the ions of the salt.
Oil does not dissolve in water. Oil is immiscible in water due to the fact that any weak
dipole-induced dipole attractions that form between oil and water cannot overcome the
stronger dipole-dipole hydrogen bonding that water molecules have for each other.
Solubilities of alcohols in water: As the hydrocarbon portion of the alcohol increases in
length, the alcohol becomes less soluble. (More of the molecule is nonpolar; the dipole
moment is diminished.)
Solubilities of alcohol in nonpolar solvents: As the hydrocarbon portion of the alcohol
increases in length, the alcohol becomes more soluble in a nonpolar solvent such as
hexane.

Enthalpy of solution (Hsoln) = the enthalpy change associated with the formation of a
solution (just the sum of all of the steps involved!)

3 steps: Hsoln = H1 + H2 + H3

Hsoln can be positive (endothermic) or negative (exothermic).

Step 1 (H1)
Separating the solute into individual components of the solute (expanding the solute).
This requires E be added to the system, therefore endothermic. The magnitude of the
value is high in ionic and polar solutes, low in nonpolar solutes.
Hsolute = Hlattice energy
Step 2(H2)
Overcoming IMFs in solvent to make room for the solute (expanding the solvent).
Requires that E be added to the system, therefore endothermic. The magnitude of the
value is high in polar solvents, low in nonpolar solvents.

Properties of Solutions

Step 3 (H3)
Interaction of solute and solvent to form the solution. Energy must be released here, else
the solution would never form since nature always tends toward a lower energy state,
therefore exothermic. The magnitude of this value is high in polar solutepolar solvent
interactions, low in other types of interactions.

H2 + H3 = enthalpy of hydration (Hhyd)


Enthalpy of hydration is more negative for small ions and highly charged ions.

Some heats of solution are positive (endothermic). The reason that the solute
dissolves is that the solution process greatly increases the entropy (disorder) which
overrides the cost of the small positive heat of solution. This makes the process
spontaneous. The solution process involves two factors; the change in heat and the
change in entropy, and the relative magnitude of these two factors determine whether
a solute dissolves in a solvent.

Hot and cold packs:


These often consist of a heavy outer pouch containing water and a thin inner pouch
containing a salt. A squeeze on the outer pouch breaks the inner pouch and the salt
dissolves. Some hot packs use anhydrous CaCl2 (Hsoln = 82.8 kJ/mol) whereas
many cold packs use NH4NO3 (Hsoln = +25.7 kJ/mol). We discussed other hot packs
earlier that function on the principle of a supersaturated solution crystallizing,
releasing the heat of crystallization. Other hot packs contain iron filings and the
process of rusting is sped up thus, producing heat energy.

Exercise 3

Differentiating Solvent Properties

Decide whether liquid hexane (C6H14) or liquid methanol (CH3OH) is the more appropriate solvent
for the substances grease (C20H42) and potassium iodide (KI).

hexane grease
methanol KI
Properties of Solutions

FACTORS AFFECTING SOLUBILITY


Molecular Structure:

Fat soluble vitamins, (A,D,E,K) nonpolar (can be stored in fatty body tissues)
Water soluble vitamins, (B&C) polar (are not stored, wash away and must be consumed
regularly)
Hydrophobic water fearing (nonpolar)
Hydrophilic water loving (polar)

The Effect of Increasing Pressure

The solubility of a gas increases with


increasing pressure. Increasing
pressure has very little effect on the
solubility of liquids and solids.
(carbonated beverages must be
bottled at high pressures to ensure a
high concentration of carbon dioxide
in the liquid)

Henrys Law the amount of a gas dissolved in a solution is directly proportional to the
pressure of the gas above the solution. Henrys Law is obeyed best for dilute solutions of
gases that dont dissociate or react with the solvent.

Henrys Law: C = kP
P = partial pressure of the gaseous solute above the solution
k = constant (depends on the solution)
C = concentration of dissolved gas

Properties of Solutions

Exercise 4

Calculations Using Henrys Law

A certain soft drink is bottled so that a bottle at 25C contains CO2 gas at a pressure of 5.0 atm over the liquid.
Assuming that the partial pressure of CO2 in the atmosphere is 4.0 104 atm, calculate the equilibrium
concentrations of CO2 in the soda both before and after the bottle is opened. The Henrys law constant for
CO2 in aqueous solution is 0.031 mol/L atm at 25C.

before = 0.16 mol/L


after = 1.2 105 mol/L

The Effect of Increasing Temperature

The amount of solute that will dissolve usually increases with increasing temperature
since most solution formation is endothermic. Solubility generally increases with
temperature if the solution process is endothermic (Hsoln > 0). Solubility generally
decreases with temperature if the solution process is exothermic (Hsoln < 0). Potassium
hydroxide, sodium hydroxide and sodium sulfate are three compounds that become less
soluble as the temperature rises. This can be explained by LeChateliers Principle.

Remember, the dissolving of a solid occurs


more rapidly with an increase in temperature,
but the amount of solid may increase or
decrease with an increase in temperature. It
is very difficult to predict what this solubility
may beexperimental evidence is the only
sure way.

The solubility of a gas in water always


decreases with increasing temperature.

There are all types of environmental issues


involved with the solubility of a gas at higher
temperatures. Thermal pollution water
being returned to its natural source at a higher
ambient temperature has killed much wildlife
as less oxygen is dissolved in the water.
Boiler scale is another problem. This is
where a coating builds up on the walls of
containers such as industrial boilers and pipes
causing inefficient heat transfer and blockage.

Properties of Solutions

COLLIGATIVE PROPERTIES
Colligative Properties properties that depend on the number of dissolved particles; not on the
identity of the particle. Intermolecular forces of the solvent are interrupted when the solute is added.
This changes the properties of the solvent. These properties include: vapor pressure lowering,
boiling-point elevation, freezing-point depression, and osmotic pressure.
Vapor Pressure Lowering The presence of a
nonvolatile solute lowers the vapor pressure of a
solvent. This is because the dissolved nonvolatile
solute decreases the number of solvent molecules
per unit volume. (Nonvolatile solute dilutes the
solution and interferes with the IMFs of the solvent).
There are fewer solvent molecules on the surface to
escape. This can be mathematically expressed by

Raoults Law:

Psolution = (solvent) (Posolvent)

Psolution = observed vapor pressure of the solvent in the solution


solvent = mole fraction of solvent
Posolvent = vapor pressure of the pure solvent
i = vant Hoff factor (moles of electrolyte must be multiplied by this)
number of moles particles in solution/number of moles particles dissolved

The vapor pressure of a solution is directly proportional to the mole fraction of solvent
present. If the solute ionizes the number of ions further affects (lowers) the vapor
pressure. The moles of solute must be multiplied by the number of ions the given solute
breaks into. For instance, if we had 1 mole of NaCl as the solute, we would use 2 moles
of particles for our mole fraction calculations, AlCl3 would yield a vant Hoff factor
of 4 and so on.
For nonelectrolytes, i = 1. For electrolytes, i = the number of particles formed when one
formula unit of the solute dissolves in the solvent.
The experimental value of i is often less than the expected value of i because of a
phenomenon called ion pairing. Especially in concentrated solutions, oppositely
charged ions can pair up and thus, we have fewer particles than expected. Conversely,
nonelectrolytes may also pair up forming dimers (2 units bound together).

Properties of Solutions

An ideal solution is a solution that obeys Raoults Law. There is no such thing. In very
dilute solutions, Raoults Law works fairly well. Solutions are most ideal when the
solute and the solvent are very similar. If hydrogen bonding occurs between solute and
solvent, vapor pressure is less than expected. We call this a negative deviation from
Raoults law. This can often be predicted when the enthalpy of solution formation is
large and negative (highly exothermic)
A great example of this negative deviation is acetone and
water.

EXAMPLE: Calculate the vapor pressure caused by the addition of 100.g of sucrose,
C12H22O11, to 1000.g of water if the vapor pressure of the pure water at 25oC is 23.8 torr.

100 g sucrose

1000 g water

water =

1 mol sucrose
= 0.292 mol
342.0 g sucrose
1 mole water
= 55.6 mol water
18.0 g water

55.6
= 0.995
0.292 + 55.6

Psoln = 0.995 23.8 = 23.7 torr


Exercise 5

Calculating the Vapor Pressure of a Solution

Calculate the expected vapor pressure at 25C for a solution prepared by dissolving 158.0 g of
common table sugar (sucrose, molar mass = 342.3 g/mol) in 643.5 cm3 of water. At 25C, the
density of water is 0.9971 g/cm3 and the vapor pressure is 23.76 torr.

= 23.46 torr
Properties of Solutions

Exercise 6

Calculating the Vapor Pressure of a Solution Containing Ionic Solute

Predict the vapor pressure of a solution prepared by mixing 35.0 g solid Na2SO4
(molar mass = 142 g/mol) with 175 g water at 25C. The vapor pressure of pure water at 25C is
23.76 torr.

= 22.1 torr

We can determine the molecular mass of a solute by using the vapor pressure of a
solution if the mass of the solute is known.
P
solvent = oso ln
Psolvent

solvent =

nsolvent
nsolvent + nx

solve for nx and remember,

g
= MM
mol

Solutions in which both solute and solvent are liquid and the liquids are volatile do not
behave ideally. Both solute and solvent contribute to the vapor pressure. If the solute is
more volatile than the solvent, the vapor pressure of the solution is higher than the vapor
pressure of the solvent. In this case, the molecules have a higher tendency to escape than
expected. We call this a positive deviation from Raoults law. The enthalpy of solution
for this type of deviation is positive. (endothermic)

Properties of Solutions

10

Ptotal = PA + PB = A PA0 + B PB0 (same as Daltons Law)

Exercise 7

Calculating the VP of a Solution Containing Two Liquids

A solution is prepared by mixing 5.81 g acetone (C3H6O, molar mass = 58.1 g/mol) and 11.9 g
chloroform (HCCl3, molar mass = 119.4 g/mol). At 35C, this solution has a total vapor pressure of
260. torr. Is this an ideal solution? The vapor pressures of pure acetone and pure chloroform at
35C are 345 and 293 torr, respectively.

Not an ideal solution

Boiling-point Elevation Because vapor pressure is lowered by the addition of a


nonvolatile solute, more E must be added to the system to achieve a vapor pressure equal to
the atmospheric pressure (definition of normal BP), so the boiling point is increased.
Boiling Point Elevation: Tb = Kb m i

Kb = molal boiling-point elevation constant (for water = 0.51C kg/mol)


i = vant Hoff factor
m = concentration in molality
T = change in temperature

Freezing-point Depression Because vapor pressure is lowered by the addition of a


nonvolatile solute, less E must be added to the system to achieve a temperature at which the
vapor pressure of the solid and the liquid are equal (definition of FP or MP). If the vapor
pressure of the liquid is lowered, the freezing point decreases. This is why NaCl and CaCl2
are used on icy roads and sidewalks to keep them from freezing in really cold weather.

Properties of Solutions

11

WHY IS A SOLUTIONS FREEZING POINT DEPRESSED? Molecules cluster in order to freeze.


They must be attracted to one another and have a spot in which to cluster. Solute molecules
get in the way! The more ions in solution, the greater the effect on the freezing point and the
boiling point. A solution does not have a sharply defined freezing point, a solvent does.
Useful for separation purposes in fractional crystallization.

Freezing Point Depression: T = Kf m i

Kf = molal freezing-point depression constant (for water = 1.86 C kg/mol)


add 6 qts. of antifreeze to 12 qts. cooling system in order to lower the FP to 34F and
raise the BP to +226 F

Determining the molar mass (MM) of a solute using freezing-point depression or


boiling-point elevation
solute concentration must be low (0.10m)
disadvantagecompound must be nonvolatile and stable at the boiling point.
still used widely
remember that the units you seek are grams/mole!
EXAMPLE: Calculate the freezing point and boiling point of a solution of 100. g ethylene
glycol (C2H6O2) in 900. g of water.

Properties of Solutions

12

Exercise 8

Calculating the Molar Mass by Boiling-Point Elevation

A solution was prepared by dissolving 18.00 g glucose in 150.0 g water. The resulting solution was
found to have a boiling point of 100.34C. Calculate the molar mass of glucose. Glucose is a
molecular solid that is present as individual molecules in solution.

= 180 g/mol

Exercise 9

Freezing-point Depression

What mass of ethylene glycol (C2H6O2, molar mass = 62.1 g/mol), the main component of
antifreeze, must be added to 10.0 L water to produce a solution for use in a cars radiator that freezes
at 10.0F (23.3C)? Assume the density of water is exactly 1.00 g/mL.

= 7.76 103 g (or 7.76 kg)

Properties of Solutions

13

Exercise 10

Determining Molar Mass by Freezing-Point Depression

A chemist is trying to identify a human hormone, which controls metabolism, by determining its
molar mass. A sample weighing 0.546 g was dissolved in 15.0 g benzene, and the freezing-point
depression was determined to be 0.240C. Calculate the molar mass of the hormone.

= 776 g/mol

Osmotic Pressure: a special use of PV=nRT

Semipermeable or selectively permeable membrane


membrane which allows solvent but not solute molecules to
pass through (small molecules can pass but large ones cannot)

Osmosisa special case of diffusion; water travels along a


concentration gradient.
Osmosis occurs when water molecules move through a
semipermeable membrane from a region of lower solute
concentration to a region of higher solute concentration.
Is driven by the need nature has to establish an equilibrium.

Osmotic pressure() the pressure that must be


applied to a solution to prevent the net movement
of water from solvent to solution (osmosis).
The osmotic pressure of a solution is proportional
to the number of solute particles in a given volume
of solution, that is, to the molarity. The equation is
similar to the ideal gas law since both relate the
pressure of a system to its concentration and
temperature.

n
Osmotic Pressure: = MRTi or = RTi
V
= osmotic pressure in atm
M = molarity of the solution
R = 0.08206 L atm/molK
T= temperature in Kelvin
i = vant Hoff factor
Properties of Solutions

14

The use of osmotic pressure calculations for determining the molecular mass of an
unknown substance is more accurate than the use of freezing-point depression or
boiling point elevation data because a small concentration of solute produces a relatively
large osmotic pressure.
Ideal for measuring molar masses of large molecules of biological importance.

EXAMPLE: The concentration of hemoglobin in blood is roughly 15.0g/100.mL of solution.


Assume that a solution contains 15.0g of hemoglobin dissolved in water to make 100.mL of solution
and that the osmotic pressure of this solution is found to be 0.0500 atm at 25oC. What is the
molecular mass of hemoglobin? (The osmotic pressure of a 1 m solution at 25oC is 24.45 atm)

15

(0.08206)(298)
nRT
dRT
g
0.1

=
= 73, 400
or MM =
; so, MM =
V

0.050
mol
Exercise 11

Determining Molar Mass from Osmotic Pressure

To determine the molar mass of a certain protein, 1.00 103 g of it was dissolved in enough water
to make 1.00 mL of solution. The osmotic pressure of this solution was found to be 1.12 torr at
25.0C. Calculate the molar mass of the protein.

= 1.66 104 g/mol

Exercise 12

Isotonic Solutions

What concentration of sodium chloride in water is needed to produce an aqueous solution isotonic
with blood ( = 7.70 atm at 25C)?

= 0.158 M

Properties of Solutions

15

Exercise 13

Osmotic Pressure

The observed osmotic pressure for a 0.10 M solution of Fe(NH4)2(SO4)2 at 25C is 10.8 atm.
Compare the expected and experimental values for i.

expected = 5
experimental = 4.4

Applications of Osmosis:
Dialysis a phenomenon in which a semipermeable
membrane allows transfer of both solvent molecules and
small solute molecules and ions.

occurs in walls of most plant and animal cells


kidney dialysis is one of most important applications
waste molecules move into the wash solution and filter
the blood.

isotonic solution solutions that have the same osmotic pressure (Ex. IV fluids)
hypertonic solution has higher osmotic pressure (cells bathed in a hypertonic
solution would shrivelcrenation) Treating the surface of food with salt causes this
to happen to bacteria, thus protecting or preserving the food.
hypotonic solution has lower osmotic pressure (cells bathed in a hypotonic solution
would bursthemolysis)

reverse osmosis the process occurring when the high


external pressure on a solution causes a net flow of solvent
through a semipermeable membrane from the solution to the
solvent

used in desalination (the membrane here acts as a molecular


filter to remove solute particles) The need for this process will
probably increase as the need for drinkable water increases.

Properties of Solutions

16

Colloids (also called colloidal dispersions)


Thomas Graham, 1860albumin, starch, gelatin and glue diffuse only very slowly and
could not be crystallized. He called these substances colloids.
a suspension of tiny particles in some medium
The dispersed colloidal particles are larger than a simple molecule but small enough to
remain distributed and not settle out.
A colloidal particle has a diameter between 1 and 1000 nm and may contain many atoms,
ions, or molecules.
Because of their small particle size, colloids have an enormous total surface area.
The particles stay suspended because of electrostatic repulsion.
hydrophobic/hydrophilic ends
Coagulation, destruction of a colloid, occurs by heating
(particles collide so hard that they stick together) or by the
addition of an electrolyte (neutralizes ion layers). This process
is important in removal of soot from smoke so that air quality
has improved somewhat in industrialized cities.
Tyndall effect the scattering of light by particles
Used to distinguish between a suspension and a true
solution. A true solution has particles that are too small to
scatter light.
Brownian motion a characteristic movement in which the
particles change speed and direction erratically (solvent molecules collide with the
colloidal particles).
Suspensions are temporary solutions. They will settle eventuallycolloids will not
do this.
Solutions are permanent. Particles are really small. Colloids lie in between solutions
and suspensions!

Examples of Some Common Colloids:


Foam colloidal dispersion of a gas dispersed in a liquid or solid (ex. Whipped
cream and marshmallows)
Aerosol colloidal dispersion of a liquid or solid dispersed in a gas (ex. Fog and
smoke)
Emulsion colloidal dispersion of a liquid dispersed in a solid or liquid (ex. Butter
and milk)
Sol colloidal dispersion of a solid dispersed in a liquid or solid (ex. Paint or ruby)

Properties of Solutions

17

AP* Chemistry
Arrhenius Made Easy
(At Least As Easy As Its Ever Going To Get!)
Chemistry is defined as the study of matter and energy. Unfortunately, the study of matter consumes
most of our class time. Why? Its easier. Matter is tangible; the amount of matter present is easily
measured with a balance or other simple device. Students can directly observe matter in the case of
liquids and solids or at least observe its effects in the case of gases. Students can also easily observe
changes in matter as chemical reactions take place. The study of energy, on the other hand, is far more
challenging since only the effects of energy changes can be measured. Consequently, two sets of
measurements must be made, final and initial, and calculations are sure to follow.
How do we know that the study of matter dominates AP* Chemistry classrooms? Simple, at the
reading of the exams, year after year, students do a fine job of explaining changes in matter, but rarely
tie the changes in matter to the changes in energy. Valuable points are lost. Students dont realize that
the changes in matter are a direct result of the changes in energy and that it is a cause and effect
relationship. Students simply dwell on the effect and neglect the cause. This topic within the kinetics
unit focuses on the cause, the energy cause. Additionally, it provides the essential link between the
study of kinetics and the study of thermodynamics.

The Collision Model


What we know so far:
The rate of a chemical reaction depends on the concentration of the reactants.
The order of each reactant depends on the detailed reaction mechanism.
The temperature of the reaction affects the value of the rate constant.
The general rule of thumb is that a 10C increase in temperature doubles the reaction rate.
The molecules must collide in order to react, but thats not allthey must collide with
sufficient energy and the correct orientation (geometry) so that the collisions are effective.
What else do we need to know?
Why the relationship between an increase in temperature and an increase in rate is not a direct
relationship.
Why thermodynamically spontaneous reactions such as combustion reactions or
C(graphite) C(diamond) dont just happen spontaneously.
Why the activation energy is so very important to both kinetics and thermodynamics.

The Relationship Between Energy and Speed


In the 1880s, Svante Arrhenius (the acid guy) first proposed the existence of threshold energy, called
the activation energy, which must be overcome to produce a chemical reaction. The collision model
is simple, the kinetic energy of the molecules before collision is converted to potential energy as the
molecules are distorted during a collision to break bonds and rearrange the atoms into the product
molecules.

*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
2008 by Ren McCormick. All rights reserved.

Consider this reaction:


2 BrNO(g) 2 NO(g) + Br2(g)

We envision reaction progress as shown above.


Never be surprised if the words transition state are replaced with activated complex.
These two terms describe the highly unstable collection of atoms bound together at the top of
the energy hump.
The next collision occurring between the activated complex and any other molecule will
supply more energy to the unstable species and can break bonds. Which bonds are broken
determines whether it slides back to re-form reactants or slides forward to create products.
Likewise, reaction progress can be replaced with time.
The activation energy, Ea, is the threshold energy and must be overcome if the reaction is to
proceed. If you are asked to compare graphs of this shape, remember that the taller the
hump, the larger the Ea, the smaller the value of the rate constant, k, and the slower the
rate.
E is the net energy change and represents the enthalpy, H, of the reaction. Is the above
reaction exothermic or endothermic?
How does temperature affect Ea?

Temperature is defined as the average kinetic energy of the molecules.


The higher the temperature, the higher the average KE, the more energetic the molecules.
Think heat em up, speed em up.
The more energetic the molecules, the more energetic the collisions!

Examine this graph:


Which temperature is greater?
Which temperature has more molecules with
enough energy to overcome the activation energy?

Arrhenius Made Easy

Generally, when the temperature is doubled, the


fraction of molecules having high enough E to
overcome Ea , WAY MORE than doubles, which
explains WHY the relationship between reaction
rate and temperature is NOT linear. It is
exponential! Need proof?

If we graph the value of the rate constant, k, versus the Kelvin


temperature, we get the graph pictured right. See? Not linear, but
rather, exponential. That means that the natural log function is in your
immediate future [again].
Double the Kevlin temperature and you more than double the rate
constant. Since Calculus is not a pre-requisite for AP Chemistry, we
linearlize the data, just as we did for integrated rate law, so we can
deal with the mathematics more simply. Slope is your friend!

The Arrhenius Equation


Arrhenius derived the following equation, which is way too complicated:

Scary, huh? Relax; you dont have to memorize that one! Ill spare you the derivations that allow us
to arrive at the one you do need to know:

This version allows us to simplify the relationship between the rate constant and Kelvin temperature.
A replaces the constants p and Z in the original equationyoull be asked to solve for k, Ea, or T.

Arrhenius Made Easy

To summarize, if you plot ln k vs. the reciprocal of Kelvin


temperature, you get a straight line with a slope equal to
Ea
.
R
That means Ea =

R slope.

This is activation ENERGY, so use the ENERGY R which


8.31 J
is
. If you prefer Algebra methods over graphical
K mole
k E 1 1
methods, there is a two-point formula as well which is: ln 2 = a .
k1 R T1 T2

Graphing Calculator Tutorial (Not intended to insult your intelligence.)


First, you need to recognize when you have an Arrhenius equation problem on your hands! It is when
you are given k-time data OR are asked to calculate the activation energy, Ea.
ENTERING DATA INTO LISTS

Press y to clear all lists.


Press and arrow to the first cell in L1 if necessary.
Enter your temperature data in L1 and your k values in L2.

PERFORMING A BATCH TRANSFORM

To obtain reciprocal Kelvin temperatures:


Press | and/or } repeatedly until L1 is highlighted (Go to the tippy top of L1).
Press y to convert the Celsius temperatures to reciprocal Kelvin
temperatures. If Kelvin temperatures were given in the problem, then simply press
y to calculate the reciprocals of the Kelvin temperatures.
To obtain the natural log of the k values:
Press ~ and/or } repeatedly until L2 is highlighted (Go to the tippy top of L2).
Press y to convert the rate constant values to lnk.
RUNNING A LINEAR REGRESSION & GRAPHING THE DATA

To run the linear regression, view the statistics and paste the equation into Y= :
Press ~ (to get to CALC) yy~ (to YVARS) . The
statistics relating to the linear regression (line of best fit) will be displayed. Record the slope!
Remember Ea = R slope.
Press yo and make sure only one plot is ON. Set the plot to " L1 L2.
To view the graph, press ys. If additional equations are being graphed, press yo
to clear them out.
Arrhenius Made Easy

DETERMINING y WHEN GIVEN x

To calculate k when given the Kelvin temperature:


First realize that your graph is lnk vs. 1/T.
Press yr to get to CALCULATE and select VALUE.
Enter the Kelvin temperature given and press .
o If you get an error message, its because your window is not set properly. The
calculator can only calculate what is displayed on the graphing screen.
o Stop. Ask yourself if your x-value is within the data you graphed (if so, you are
interpolating) or outside the range (if so, you are extrapolating). If interpolating, try
againyou should not get an error!
o If extrapolating, you may need to quit the graph screen (yz) and calculate the
reciprocal Kelvin temperature. Once you have that value, press p to examine
your Xmin and Xmax. Use your arrow keys to adjust the values so that your desired
value is included within the values displayed on the graph.
o Once youve adjusted the window, press yr and enter the Kelvin temperature
given and press .
The y-value displayed is the natural log of k, NOT the value of k. Record the y-value.
Quit the graph screen by pressing yz and then press y and enter the number you
recorded followed by .
DETERMINING x WHEN GIVEN y

To calculate the Kelvin temperature when given k:

First realize that your graph is lnk vs. 1/T.


Press o and to Y2. Press and enter the k value given in the question.
Press s. If you see the intersection of the two lines, Press
yr to get to CALCULATE, select INTERSECTION and
calculate the ordered pair of the point of intersection. You are interested in the x-value, but
remember the x-value displayed is the reciprocal of the Kelvin temperature you seek. Record
the x-value displayed on the screen.
o If you do NOT see the point of intersection, then press p and adjust your
window until you do. This may require some trial and error. The calculator can only
calculate what is displayed on the graph, so the intersection must be displayed.
Quit the graph screen by pressing yz and calculate the inverse of the reciprocal Kelvin
temperature displayed by entering the x-value you recorded and pressing . Record the
Kelvin temperature. Convert back to Celsius if the problem requires.

Arrhenius Made Easy

Arrhenius #1 (Adapted from Zumdahl, 5th edition #53)


Experimental values for the temperature dependence of the rate constant for the gas-phase reaction
NO + O3 NO2 + O2
are as follows:
T (K)
195
230.
260.
298
369

k (L/mol s)
1.08 109
2.95 109
5.42 109
12.0 109
35.5 109

Show all work and pay particular attention to sig. figs. and units when reporting your answers.
(a.) Is this reaction fast or slow? Justify your answer.

(b.) What is the overall order of this reaction? Justify your answer.

(c.) What is the activation energy for this reaction?

(d.) What is the value of k when the temperature is 455 K?

(e.) What is the temperature when the rate constant has a value of 22.5 109 M1 s1?

Arrhenius Made Easy

Arrhenius #2 (Adapted from Brady, 4th edition #96)


The following data were collected for a reaction.
k (L mol1 s1)
2.88 10-4
4.87 10-4
7.96 10-4
1.26 10-3
1.94 10-3

T (C)
320
340
360
380
400

Show all work and pay particular attention to sig. figs. and units when reporting your answers.
(a.) Is this reaction fast or slow? Justify your answer.

(b.) What is the activation energy for this reaction?

(c.) What is the value of k when the temperature is 640 K?

(d.) What is the temperature when the rate constant has a value of 50.5 104 M1 s1?

Arrhenius Made Easy

Arrhenius #3 (Adapted from Chang, 6th edition #37)


Variation of the rate constant with temperature for the first-order reaction
2 N2O5(g) + Cl2(g) 2 N2O4(g) + O2(g)
is given in the following table.
k ( s1)
1.74 10-5
6.61 10-5
2.51 10-4
7.59 10-4
2.40 10-3

T (C)
25
35
45
55
65

Show all work and pay particular attention to sig. figs. and units when reporting your answers.
(a.) Is this reaction fast or slow? Justify your answer.

(b.) What is the activation energy for this reaction?

(c.) What is the value of k when the temperature is 100C?

(d.) What is the temperature when the rate constant has a value of 9.65 104 s1?

Arrhenius Made Easy

Arrhenius #4 (Adapted from Chang, 6th edition #39)


Given the same reactant concentrations, the reaction
CO(g) + Cl2(g) COCl2(g)
at 250C is 1.50 103 times as fast as the same reaction at 150 C.
(a.) Calculate the activation energy for this reaction.

(b.) What is the value of k when the temperature is 100C?

Arrhenius #5 (Adapted from Whitten, Davis, Peck 5th edition #51)


Biological reactions nearly always occur in the presence of enzymes as catalysts. The enzyme
catalase, which acts on the decomposition of hydrogen peroxide, reduces the Ea for the reaction from
72 kJ/mol (uncatalyzed) to 28 kJ/mol (catalyzed) at 25C. The total E for the reaction is
204 kJ/mol.
(a.) Write the balanced chemical equation for the decomposition of hydrogen peroxide.

(b.) Draw and label a reaction coordinate (potential energy) diagram for this reaction at 25C.

(c.) What is the activation energy of the uncatalyzed reverse reaction?


(d.) What is the activation energy for the catalyzed reverse reaction?

Arrhenius Made Easy

#6 (adapted from the 2004 AP Chemistry Exam)


The following data was collected during the decomposition reaction of a colored chemical
species, X, into colorless products monitored with a spectrophotometer by measuring changes
in absorbance over time. The reaction was carried out at 25C and 1atm pressure. Species X
has a molar absorptivity constant of 2.75 103 cm1M1 and the path length of the cuvette
containing the reaction mixture is 1.00 cm. The data for the experiment are given in the table
below.
[X]
(M)
?
6.25 105
5.00 105
3.50 105

Absorbance

0.330
0.172
0.138
0.096

Time
(min)
0.0
10.0
15.0
?

(a.) Calculate the initial concentration of the colored species.

(b.) Use the data given for concentration and time to determine the order of the reaction.
Justify your answer.

(c.) What is the value of the rate constant? Specify its units.

(d.) Calculate the number of minutes it takes for the absorbance to drop from 0.330 to 0.096.

(e.) Calculate the half-life of the reaction. Include units with your answer.

Arrhenius Made Easy

10

An additional experiment was performed to determine the value of the rate constant for this reaction.
It was determined that the reaction had a rate constant of 1.15 104 at 35C.
(f.) What is the activation energy for this reaction?

(g.) What is the value of k when the temperature is 45C?

Arrhenius Made Easy

11

Kinetics Concept Map

graph lnk vs. 1/[T]

graph [A] vs. time

graph
ln[A] vs. time

graph
1/[A] vs. time

Arrhenius Made Easy

12

Arrhenius #1 (Adapted from Zumdahl, 5th edition #53)


Ill hold your hand through the first one! Remember, pages 4 & 5 in the student handout serve as your cheat
sheet AND the kids have no fear. They do this kind of stuff a lot in math class. If YOU get stuck, they can
probably bail you out!
Experimental values for the temperature dependence of the rate constant for the gas-phase reaction
NO + O3 NO2 + O2
are as follows: (3 SF)

Calculator screen:

Do not be alarmed that it rounded the values!

Before batch transform:


T (K)
195
230.
260.
298
369

k (L/mol s)
1.08 109
2.95 109
5.42 109
12.0 109
35.5 109

Show all work and pay particular attention to sig. figs. and units when reporting your answers.
(a.) Is this reaction fast or slow? Justify your answer.
Fast. The k values are enormous at these relatively low Kelvin temperatures, indicating a very fast
reaction. Students should link the magnitude of k to the magnitude of the temperatures given to receive
full credit for this question.
(b.) What is the overall order for this reaction? Justify your answer.
Second order. Examine the units given on k. Never, ever forget that rate = M/time. For that to be the
case, the units given for k would have to be multiplied by M2
k L
k
M
M 2 = k
[ A][ A] =
rate =
M s
mols
s

(c.) What is the activation energy for this reaction?


First, note that the temperature data is already Kelvin. Batch
transform the data so that we have 1/T in L1 and lnk in L2. The data
screen is shown above. Next, calculate a linear regression (paste the
equation into Y1) to determine the slope:
The slope is equal to 1435.7 using more than three sig. figs.

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

The Ea = R slope
So, Ea = (8.31 J/molK) (1435.7 K)
= 11,930 J/mol
= 11,900 J/mol (3SF) = 11.9 kJ/mol
1

Note, we ignore the units on lnk after taking the natural logthe units become one.
Therefore, the units on the slope are (1/(1/K)) which is plain old units of K which thus cancel,
so that Ea is reported in J/mol.
Point out to students that this Ea value makes sense. There is relatively low activation energy required
for a reaction occurring at very low temperatures with enormous k-values.

(d.) What is the value of k when the temperature is 455 K?


QUICK TIP: Press q to fit your graph to a standard window. (Notice that the regression
line disappears and the graph looks blank, but thats OK.) We have to do this since the
calculation we are asked to make is outside the window range that q set for us and the
calculator can only calculate a value if it is displayed in the
graph window.
Realize that temperatures are x-values, and more importantly,
we need to take the reciprocal of 455 K.
Press yr and X= appears on your screen. Next,
enter 455 then press to calculate the reciprocal of 455 K.
Finally press to get the y-value on the final screen
displayed at right.

Realize that the y-value you just found is NOT k! Its the natural log of k.
Press yz to quit the graph screen followed by y 24.92 (I rounded) and press .
Record k to 3SF and put the proper units (see the table heading from the original data).
Our k value is equal to 6.65 1010 L/mol sec.

(e.) What is the temperature when the rate constant has a value of 22.5 109 M1s1?

Now we are looking for x when we know y. Remember our


x-values are 1/T, not T.
Press o and until your cursor arrives at Y2=. Press and
enter the k value given in the problem, 22.5 109.
Press s. If you see the intersection there is no need to adjust
the window.
If you do NOT see the intersection (because you pressed q
earlier), press q. If you still do NOT see an intersection,
press p and adjust the X & Y MIN and MAX until the
intersection is displayed.
Press yr to calculate the x-value.
Record it since it is not the temperature, but rather the reciprocal.

Press yz to quit the graph screen.


Enter the x-value you recorded and press .
Our calculated temperature is 339.07 = 339 K (3SF).

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

Arrhenius #2 (Adapted from Brady, 4th edition #96)


The following data were collected for a reaction. (3* SFTs are 2SF, but become 3 when converted to
Kelvins)
k (L mol1 s1)
2.88 104
4.87 104
7.96 104
1.26 103
1.94 103

T (C)
320
340
360
380
400

Show all work and pay particular attention to sig. figs. and units when reporting your answers.
(a.) Is this reaction fast or slow? Justify your answer.
Slow. The value for the rate constant, k is very small at these VERY high Celsius temperatures.
Students should link the magnitude of k to the magnitude of the temperatures given to receive full
credit for this question.
(b.) What is the activation energy for this reaction?
Be careful entering this into the calculator. The columns are reversed! Also note the given
temperatures are Celsius.

So, Ea = R (slope) = 79,075 J/mol = 79.1 kJ/mol (2 SF). This makes sense since it is an
enormous activation energy at VERY high temperatures with small k values.

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

(c.) What is the value of k when the temperature is 640C?

640 C is way outside our range. Its KELVIN reciprocal is 0.001095. You must change
the window.

Y = 2.527, but thats lnk


k = 0.07989 = 0.0799 L mol1 s1 which is much faster since we doubled the initial starting
temperature!

(d.) What is the temperature when the rate constant has a value of 50.5 104 M1 s1?

Youll have to adjust the window to display this intersection. ln(50.5 104) = -5.3, so adjust the
window to display that y-value.
QUICK TIP: If you have trouble adjusting the window, or are simply in a hurry, press
q. This gives you the standard 4 quadrant graph and allows you to see your intersections
(at least most of the time) so you can skip setting your window entirely!
The x-value is 0.001386 which is 1/T.
T = 721.5 K = 722 K or better yet, 449C since the original temperatures were recorded in
degrees Celsius.

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

Arrhenius #3 (Adapted from Chang, 6th edition #37)


Variation of the rate constant with temperature for the first-order reaction
2N2O5(g) 2N2O4(g) + O2(g)
is given in the following table.
k ( s1)
1.74 10-5
6.61 10-5
2.51 10-4
7.59 10-4
2.40 10-3

T (C)
25
35
45
55
65

Show all work and pay particular attention to sig. figs. and units when reporting your answers.
(a.) Is this reaction fast or slow? Justify your answer.
Slow. The value for the rate constant, k is very small at these relatively low Celsius temperatures.
Students should link the magnitude of k to the magnitude of the temperatures given to receive full
credit for this question.
(b.) What is the activation energy for this reaction?
Be careful entering this into the calculator. The columns are reversed! Also note the given
temperatures are Celsius.

So, Ea = R (slope) = 102,980 J/mol = 103 kJ/mol (3 SF, since Kelvin temperatures were
used for the graph). This activation energy is reasonable since it is a large value at relatively
low Celsius temperatures for a reaction with small k values.

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

(c.) What is the value of k when the temperature is 100C?

The Kelvin reciprocal of 100 degrees Celsius is equal to


0.00268
Using zoom 6, y = lnk = 2.594287 so, k = 0.0747 s-1

(d.) What is the temperature when the rate constant has a value of 9.65 104 s1?

The y-value is lnk, so enter that value into Y2=


Find the intersection and realize that the x-value is the
reciprocal Kelvin temperature.
x = 0.00303191 = 1/K ; K = 329.825 = 56.8C (3 SF).

Arrhenius #4 (Adapted from Chang, 6th edition #39)


Given the same reactant concentrations, the reaction
CO(g) + Cl2(g) COCl2(g)
at 250C is 1.50 103 times as fast as the same reaction at 150 C.
(a.) Calculate the activation energy for this reaction.

Students may have a difficult time getting started. Since the problem states times as fast
as students should assign a value of 1 as the k-value for the slow reaction and 1,500 as a
k-value for the fast reaction.
The Celsius temperatures are given but must be converted to Kelvin and also converted to
reciprocals. Notice the perfect r. No surprise since we only have two points to plot!

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

The slope = 16,179, so Ea= R(slope)


= 134,447 J/mol = 134 kJ/mol.

(b.) What is the value of k when the temperature is 100C?


The reciprocal of 100 degrees Celsius = 0.00268. Reset the window or just use zoom 6.

y = 5.127 = ln k, so k = 5.93 103.

Arrhenius #5 (Adapted from Whitten, Davis, Peck 5th edition #51)


Biological reactions nearly always occur in the presence of enzymes as catalysts. The enzyme catalase, which
acts on the decomposition of hydrogen peroxide, reduces the Ea for the reaction from 72 kJ/mol (uncatalyzed)
to 28 kJ/mol (catalyzed) at 25C. The total E for the reaction is 204 kJ/mol.
(a.) Write the balanced chemical equation for the decomposition of hydrogen peroxide.
H2O2 ( A ) O2(g) + H2O( A )
(b.) Draw and label a reaction coordinate (potential energy) diagram for this reaction at 25C.

(c.) What is the activation energy of the uncatalyzed reverse reaction?


The amount of energy required for the reverse reaction is the sum of the energy released plus the
activation energy for the uncatalyzed reaction, therefore, 276 kJ/mol
(d.) What is the activation energy for the catalyzed reverse reaction?
The amount of energy required for the reverse reaction is the sum of the energy released plus the
activation energy for the catalyzed reaction, therefore, 232 kJ/mol

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

#6 (adapted from the 2004 AP Chemistry Exam)


The following data was collected during the decomposition reaction of a colored chemical species, X,
into colorless products monitored with a spectrophotometer by measuring changes in absorbance over
time. The reaction was carried out at 25C and 1atm pressure. Species X has a molar absorptivity
constant of 2.75 103 cm1M1 and the path length of the cuvette containing the reaction mixture is 1.00
cm. The data for the experiment are given in the table below.
[X]
(M)
?
6.25 105
5.00 105
3.50 105

Absorbance

0.330
0.172
0.138
0.0960

Time
(min)
0.0
10.0
15.0
?

(a.) Calculate the initial concentration of the colored species.


A = Ac = abc

= 2.75 103
c=

A
0.330
= 1.20 104 M
=
1
1
3
A
2.75 10 cm M (1.00 cm )

(b.) Use the data given for concentration and time to determine the order of the reaction. Justify your
answer.

Using concentration-time data: Perform three linear regressionsL1,L2; L1,L3; L1,L4.


L1, L4 yields the best r value the reaction is second order since the graph of 1/concentration vs.
time is linear.

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

(c.) What is the value of the rate constant? Specify its units.
The value of k = slope= 776.19 = 776 M1 min1

(d.) Calculate the number of minutes it takes for the absorbance to drop from 0.330 to 0.096.

Be sure you have only one stat plot on and that it is set L1, L4 for the x,y values.
An absorbance of 0.096 corresponds to a concentration of 3.50 105 M.
Our last time entered is 15 minutes, obviously the reaction proceeds further to reach an absorbance
as low as 0.0960.
The window must be adjusted for the increase in time. This is trial and error. I used 40 minutes as a
starting point.
Write an equation in y2= to the reciprocal of 3.50 105 or 28,571.
Calculate the intersection of the two lines. The time required is 26.1 minutes.

(e.) Calculate the half-life of the reaction. Include units with your answer.

The -life is the time it takes for a given concentration to be halved.


of the original concentration is 0.60 104, so reset Y2= to the reciprocal of that value.
Calculate the intersection. The -life is equal to 10.8 minutes

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

An additional experiment was performed to determine the value of the rate constant for this reaction. It was
determined that the reaction had a rate constant of 1.15 104 at 35C.
(f.) What is the activation energy for this reaction?

Be sure and re-set your stat plot to L1,L2.


Use the k from part c and this one to construct a graph of lnk vs. 1/Kelvin temperature.
The slope of the line is equal to 24,744 as shown below.
Ea = R (slope) = 205,623 J/mol = 206 kJ/mol

(g.) What is the value of k when the temperature is 45C?

The Kelvin reciprocal of 45 degrees Celsius is 0.0031, so the window must be adjusted.
lnk = 11.876 k = 143,774 = 1.44 105 M1 min1

Arrhenius Made Easy SOLUTIONS


Ren McCormick, AP, Strategies, Inc.

10

AP* Chemistry
CHEMICAL EQUILIBRIA: GENERAL CONCEPTS
THE NATURE OF THE EQUILIBRIUM STATE: Equilibrium is the state where the rate of the forward
reaction is equal to the rate of the reverse reaction. At these conditions, concentrations of all reactants and
products remain constant with time once equilibrium has been established at constant temperature.
In stoichiometry, we assumed chemical systems went to completion. A chemist would be quick to point out
that the vast majority of chemical reactions do not go to completion; they just have very large K values! Never,
ever forget that equilibrium is TEMPERATURE DEPENDENT.
Reactions are reversible. This is indicated by double arrows.

Dynamic equilibrium-- indicates that the reaction is proceeding in the forward and in the reverse
direction simultaneously and once equilibrium is established, the rate of each direction is equal. This
also keeps the concentration of reactants and products constant (which is not to be confused with
equal).
The nature and properties of the equilibrium state are the same, no matter what the direction of
approach.
Examples: Look at the following plot of the reaction between steam and carbon monoxide in a closed
vessel at a high temperature where the reaction takes place rapidly.

THE EQUILIBRIUM POSITION


Whether the reaction lies far to the right (favors products) or
to the left (favors reactants) depends on three main factors:

Initial concentrations (more collisions--faster


reaction)
Relative energies of reactants and products (nature
goes to minimum energy)
Degree of organization of reactants and products
(nature goes to maximum disorder)

The significance of K:
K > 1 means that the reaction favors the products at equilibrium
K < 1 means that the reaction favors the reactants at equilibrium
THE EQUILIBRIUM EXPRESSION: A general description of the equilibrium condition proposed by
Gudberg and Waage in 1864 is known as the Law of Mass Action. Equilibrium is temperature dependent,
however, it does not change with concentration or pressure.

equilibrium constant expression--for the general reaction


aA + bB cC + dD
Equilibrium constant: K = [C]c[D]d
[A]a[B]b

* Note* K, Kc, Keq may all be used here!

*AP is a registered trademark of the College Board, which was not involved in the production of this product. 2013 by Ren McCormick. All rights
reserved.

The product concentrations appear in the numerator and the reactant concentrations in the denominator.
Each concentration is raised to the power of its stoichiometric coefficient in the balanced equation.
- [ ] indicates concentration in Molarity (mol/L)
- Kc--is for concentration (aqueous)
- Kp--is for partial pressure (gases)
- K values are often written without units

USING EQUILIBRIUM CONSTANT EXPRESSIONS


Pure solids--do not appear in expressionyoull see this in Ksp problems soon!
Pure liquids--do not appear in expressionH2O(l) is pure, so leave it out of the calculation
Water--as a pure liquid or reactant, does not appear in the expression. (55.5 M will not change
significantly)
o Weak acid and weak base equations are heterogeneous [multi-states of matter; pure liquid and
aqueous components] equilibria.
o Solubility of salts also fits into this category. The initial solid component has a constant
concentration and is therefore left out of the equilibrium expression.

Exercise 1

Writing Equilibrium Expressions

Write the equilibrium expression for the following reaction:


4 NH3(g) + 7 O2(g) 4 NO2(g) + 6 H2O(g)

K = [NO2]4[H2O]6
[NH3]4[O2]7
Exercise 2

Equilibrium Expressions for Heterogeneous Equilibria

Write the expressions for K and Kp for the following processes:


a. The decomposition of solid phosphorus pentachloride to liquid phosphorus trichloride and chlorine gas.
b. Deep blue solid copper(II) sulfate pentahydrate is heated to drive off water vapor to form white solid copper(II) sulfate.

A: K = [Cl2]
Kp = PCl2
B: K = [H2O]5
Kp = PH2O5

Chemical Equilibria: General Concepts

CHANGING STOICHIOMETRIC COEFFICIENTS


when the stoichiometric coefficients of a balanced equation are multiplied by some factor, the K is
raised to the power of the multiplication factor (Kn). Thus, 2x is K squared; 3x is K cubed; etc.
REVERSING EQUATIONS
take the reciprocal of K ( 1/K)
ADDING EQUATIONS
multiply respective Ks (K1 K2 K3 )

Exercise 3

Calculating the Values of K

The following equilibrium concentrations were observed for the Haber process at 127C:
[NH3] = 3.1 102 mol/L
[N2] = 8.5 101 mol/L
[H 2] = 3.1 103 mol/L
a. Calculate the value of K at 127C for this reaction.

b. Calculate the value of the equilibrium constant at 127C for the reaction:
2 NH3(g) N2(g) + 3 H2(g)

c. Calculate the value of the equilibrium constant at 127C for the reaction given by the equation:
1
N2(g) + 3 H2(g) NH3(g)
2

A: K = 3.8 104
B: K = 2.6 10-5
C: K = 1.9 102

Chemical Equilibria: General Concepts

Exercise 4

Equilibrium Positions

The following results were collected for two experiments involving the reaction at 600C between gaseous sulfur dioxide and oxygen
to form gaseous sulfur trioxide:

Show that the equilibrium constant is the same in both cases.

K1 = 4.36
K2 = 4.32

Kc & Kp--NOT INTERCHANGEABLE!


Kp = Kc(RT)
where n is the change in the number of moles of gas going from reactants to products:

n = total moles gas produced total moles gas reacting


o R = universal gas law constant 0.0821 L atm/ mol K
o T = temperature in Kelvin

Kc = Kp if the number of moles of gaseous product = number of moles of gaseous


n
0
reactant since (RT) = (RT) = 1

Kp = Kc(RT)n is often referred to as the politically correct (pc) equation to help you remember the
order of the Ks in the equation!

Chemical Equilibria: General Concepts

Exercise 5

Calculating Values of Kp

The reaction for the formation of nitrosyl chloride


2 NO(g) + Cl2(g) 2 NOCl(g)
was studied at 25C. The pressures at equilibrium were found to be
PNOCl = 1.2 atm
PNO = 5.0 10-2 atm
PCl2 = 3.010-1 atm
Calculate the value of Kp for this reaction at 25C.

= 1.9 103

Exercise 6

Calculating K from Kp

Using the value of Kp obtained in Sample Exercise 13.4, calculate the value of K at 25 C for the reaction:
2 NO(g) + Cl2(g) 2 NOCl(g)

= 4.6 104

Chemical Equilibria: General Concepts

MAGNITUDE OF K--what does it mean anyway? When greater than one, formation of products is
favored. When less than one, formation of reactants is favored.
Can you...
1. write an equilibrium constant expression?
2. tell how K is changed if the stoichiometric coefficients are changed on an equation?
3. tell how to find K for a summary equation?
4. tell how K depends on the way equilibrium concentrations are expressed and how to
convert K in terms of Kc vs. Kp?
5. explain what K is telling you about a reaction?

THE REACTION QUOTIENT


For use when the system is NOT at equilibrium.
For the general reaction
aA + bB cC + dD
Reaction quotient = Qc = [C]c[D]d
[A]a[B]b
Qc has the appearance of K but the concentrations are not necessarily at equilibrium.
1. If Q < K, the system is not at equilibrium: Reactants products to make Q = K at equil.
2. If Q = K, the system is at equilibrium.
3. If Q > K, the system is not at equilibrium: Reactants products to make Q = K at equil.
Quite useful for predicting what will happen under special conditions.
Exercise 7

Using the Reaction Quotient

For the synthesis of ammonia at 500C, the equilibrium constant is 6.0 10-2. Predict the direction in which the system
will shift to reach equilibrium in each of the following cases:
a. [NH3]0 = 1.0 10-3 M;

[N2]0 = 1.0 10-5 M;

[H2]0 = 2.0 10-3 M

b. [NH3]0 = 2.00 10-4 M; [N2]0 = 1.50 10-5 M; [H2]0 = 3.54 10-1 M

c. [NH3]0 = 1.0 10-4 M;

[N2]0 = 5.0 M;

[H2]0 = 1.0 10-2 M


A: shift left
B: no shift
C: shift right

Chemical Equilibria: General Concepts

SOME CALCULATIONS WITH THE EQUILIBRIUM CONSTANT


General steps for solving equilibrium problems.
1. Set up RICE TABLEwrite a balanced reaction, place initial concentrations into the
table, determine the change in initial concentrations in terms of x, calculate the
equilibrium concentration expressions (0.25 M x).
R
I
C
E

=
=
=
=

write a balanced reaction for the predominant reacting species


fill in the initial concentrations
determine the change that is taking in place in terms of x
express the equilibrium concentrations in terms of x

2. Set up the equilibrium expression and set it equal to its value, if given.
3. Celebrate if you are given equilibrium concentrations! Just skip down to the E line and
fill them in. You may be asked to work backwards to determine the change in
equilibrium.
4. If you are given a K value, then use it to solve for x and use x to calculate the equilibrium
concentrations.
Hints:
Look for very small K values (where K < 105), "x" may be negligible.
If "x" is large enough to impact the equilibrium values, then you must subtract it
from the initial concentration. Your math will be simplified if the problem is a
perfect square. If not, you must use the quadratic formula. You are allowed to use
your calculator with a solver or program for solving the quadratic.
If none of the initial concentrations are zero, then Q must be calculated first to
determine the direction of the shift before following the above general steps.
Exercise 8

Calculating Equilibrium Pressures I

Dinitrogen tetroxide in its liquid state was used as one of the fuels on the lunar lander for the NASA Apollo missions.
In the gas phase it decomposes to gaseous nitrogen dioxide:
N2O4(g) 2 NO2(g)
Consider an experiment in which gaseous N2O4 was placed in a flask and allowed to reach equilibrium at a temperature
where Kp = 0.133. At equilibrium, the pressure of N2O4 was found to be 2.71 atm. Calculate the equilibrium pressure of
NO2(g).

= 0.600 atm

Chemical Equilibria: General Concepts

Exercise 9

Calculating Equilibrium Pressures II

At a certain temperature a 1.00-L flask initially contained 0.298 mol PCl3(g) and 8.70 10-3 mol PCl5(g). After the
system had reached equilibrium, 2.00 10-3 mol Cl2(g) was found in the flask. Gaseous PCl5 decomposes according to
the reaction
PCl5(g) PCl3(g) + Cl2(g)
Calculate the equilibrium concentrations of all species and the value of K.

[Cl2] = 2.00 10-3 M


[PCl3] = 0.300 M
[PCl5] = 6.70 10-3 M
K = 8.96 10-2

Exercise 10

Calculating Equilibrium Concentrations I

Carbon monoxide reacts with steam to produce carbon dioxide and hydrogen. At 700 K the equilibrium constant is 5.10.
Calculate the equilibrium concentrations of all species if 1.000 mol of each component is mixed in a 1.000-L flask.

[CO] = [H2O] = 0.613 M


[CO2] = [H2] = 1.387 M

Chemical Equilibria: General Concepts

Exercise 11

Calculating Equilibrium Concentrations II

Assume that the reaction for the formation of gaseous hydrogen fluoride from hydrogen and fluorine has an equilibrium
constant of 1.15 102 at a certain temperature. In a particular experiment, 3.000 mol of each component was added to
a 1.500-L flask. Calculate the equilibrium concentrations of all species.

[H2] = [F2] = 0.472 M


[HF] = 5.056 M
Exercise 12

Calculating Equilibrium Pressures

Assume that gaseous hydrogen iodide is synthesized from hydrogen gas and iodine vapor at a temperature where the
equilibrium constant is 1.00 102. Suppose HI at 5.000 10-1 atm, H2 at 1.00010-2 atm, and I2 at 5.000 10-3 atm are
mixed in a 5.000-L flask. Calculate the equilibrium pressures of all species.

PHI = 4.29 10-1 atm


PH2 = 4.55 10-2 atm
PI2 = 4.05 10-2 atm

Chemical Equilibria: General Concepts

EXTERNAL FACTORS AFFECTING EQUILIBRIA

Le Chateliers Principle: If a stress is applied to a system at equilibrium, the position of the


equilibrium will shift in the direction which reduces the stress.
products
Shifts occur to reestablish equilibrium positions. Think about K! Generally,
reactants

Adding or removing a reagent causes the equilibrium to shift to reestablish K.


As long as you milk a mamma cow, she keeps making more milk!

Increasing pressure causes the equilibrium to shift to the side containing the fewest number of
moles of gas. The converse is also true.

Adding a catalyst to a reaction has causes no shift and has NO EFFECT on K. It just causes
equilibrium to be established faster!

Changing the temperature is a lot like adding or removing a reactant or product. Well, as
long as you think of heat energy as a reactant or product.

Think of it this way:


ENDOTHERMIC: A + B C + D

+H value (heat is added into the system \ heat is a reactant)

Rewrite: A + B + heat C + D
EXOTHERMIC: A + B C + D

H value (heat is lost from the system \ heat is a product)

Rewrite: A + B C + D + heat
Exercise 13

Using Le Chateliers Principle I

Arsenic can be extracted from its ores by first reacting the ore with oxygen (called roasting) to form solid As4O6, which is
then reduced using carbon:
As4O6(s) + 6 C(s) As4(g) + 6 CO(g)
Predict the direction of the shift of the equilibrium position in response to each of the following changes in conditions.
a. Addition of carbon monoxide
b. Addition or removal of carbon or tetraarsenic hexoxide (As4O6)
c. Removal of gaseous arsenic (As4)

A: shift left
B: no shift
C: shift right
Chemical Equilibria: General Concepts

10

Exercise 14

Using Le Chateliers Principle II

Predict the shift in equilibrium position that will occur for each of the following processes when the volume is reduced.
a. The preparation of liquid phosphorus trichloride by the reaction:
P4(s) + 6 Cl2(g) 4 PCl3(l)
b. The preparation of gaseous phosphorus pentachloride according to the equation:
PCl3(g) + Cl2(g) PCl5(g)
c. The reaction of phosphorus trichloride with ammonia:
PCl3(g) + 3 NH3(g) P(NH2)3(g) + 3 HCl(g)

A: shift right
B: shift right
C: no shift

Exercise 15

Using Le Chateliers Principle III

For each of the following reactions, predict how the value of K changes as the temperature is increased.
a. N2(g) + O2(g) 2 NO(g)

H = 181 kJ

b. 2 SO2(g) + O2(g) 2 SO3(g)

H = 198 kJ

A: increases
B: decreases

Chemical Equilibria: General Concepts

11

AP* Chemistry

Solubility Equilibrium
SOLUBILITY EQUILIBRIA (The Solubility-Product Constant, Ksp)
Weve got good news and weve got bad news

Which do you want first?

The good news: Solubility equilibrium is really simple.


The bad news: You know all those solubility rules that state a substance is insoluble? They are actually a little
bit soluble after all. Only the future attorneys among you read the fine print. Soluble is often defined as
greater than 3 grams dissolving in 100 mL of water. So, there is a lot of wiggle room for solubility up to 3
grams! This type of equilibria deals with that wiggle room. Apologies for lying to you.
If you can actually see that a salt is insoluble, usually evidenced by solid stuff sitting on the bottom of the
container, then the solution is actually saturated. Saturated solutions of salts present due to a chemical reaction
taking place present yet another type of chemical equilibria.
Slightly soluble salts establish a dynamic equilibrium with the hydrated
cations and anions in solution. Examine the formation of AgCl (s) as a
solution of AgNO3(aq) is squirted into a solution of NaCl(aq).

When the solid is first added to water, no ions are initially present.

As dissolution proceeds, the concentration of ions increases until


equilibrium is established. This occurs when the solution is
saturated.

The equilibrium constant, the Ksp, is no more than the product of the
ions in solution. (Remember, solids do not appear in equilibrium
expressions.)

For a saturated solution of AgCl, the equation would be:


AgCl(s) Ag+(aq) + Cl(aq)

The solubility product expression for the AgCl(s) precipitate would be:
Ksp = [Ag+][Cl]

The AgCl(s) does not appear in the equilibrium expression since solids are left out. Why?
Because, the concentration of the solid remains relatively constant.

A table of Ksp values follows on the next page.

*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product. 2008 by Ren
McCormick. All rights reserved

Write the Ksp expression for each of the following reactions and find its value in the table above.
CaF2(s) Ca+2 + 2 F

Ksp =

Ag2CrO4(s) 2 Ag+ + CrO42

Ksp =

CaC2O4(s) Ca+2 + C2O42

Ksp =

DETERMINING Ksp FROM EXPERIMENTAL MEASUREMENTS


In practice, Ksp values are determined by careful laboratory measurements using various spectroscopic
methods.
Remember STOICHIOMETRY? Surely, youve made peace with the concept by now

Solubility Equilibria

Example: Lead(II) chloride dissolves to a slight extent in water according to the equation below.
PbCl2(s) Pb+2 + 2Cl
Calculate the Ksp if the lead ion concentration has been found to be 1.62 102M.
If leads concentration is x, then chlorides concentration is 2x. So. . . .
Ksp = (1.62 102)(3.24 102)2 = 1.70 105
Exercise 1

Calculating Ksp from Solubility I

Copper(I) bromide has a measured solubility of 2.0 104 mol/L at 25C. Calculate its
Ksp value.

Ksp = 4.0 108

Exercise 2

Calculating Ksp from Solubility II

Calculate the Ksp value for bismuth sulfide (Bi2S3), which has a solubility of
1.0 1015 mol/L at 25C.

Ksp = 1.1 1073


Solubility Equilibria

ESTIMATING SALT SOLUBILITY FROM Ksp


Relative solubilities can be deduced by comparing values of Ksp BUT, BE CAREFUL!
These comparisons can only be made for salts having the same ION:ION ratio.
Please dont forget solubility changes with temperature! Some substances become less soluble in cold water
while other increase in solubility! Aragonite is an example.
Example: The Ksp for CaCO3 is 3.8 109 @ 25C. Calculate the solubility of calcium carbonate in pure
water in (a) moles per liter & (b) grams per liter:

Exercise 3

Calculating Solubility from Ksp

The Ksp value for copper(II) iodate, Cu(IO3)2, is 1.4 107 at 25C. Calculate its solubility at 25C.

= 3.3 103 mol/L

Exercise 4

Solubility and Common Ions

Calculate the solubility of solid CaF2 (Ksp = 4.0 1011) in a 0.025 M NaF solution.

= 6.4 10-8 mol/L

Solubility Equilibria

Ksp AND THE REACTION QUOTIENT, Q


With some knowledge of the reaction quotient, we can decide
whether a precipitate (ppt) will form AND
what concentrations of ions are required to begin the precipitation of an insoluble salt.
1. Q < Ksp, the system is not at equil. (unsaturated)
2. Q = Ksp, the system is at equil. (saturated)
3. Q > Ksp, the system is not at equil. (supersaturated)
Precipitates form when the solution is supersaturated!!!
Precipitation of insoluble salts

Metal-bearing ores often contain the metal in the form of an insoluble salt, and, to complicate
matters, the ores often contain several such metal salts.
Dissolve the metal salts to obtain the metal ion, concentrate in some manner, and ppt. selectively
only one type of metal ion as an insoluble salt.

Exercise 5

Determining Precipitation Conditions

A solution is prepared by adding 750.0 mL of 4.00 103 M Ce(NO3)3 to 300.0 mL of 2.00 102 M KIO3.
Will Ce(IO3)3 (Ksp = 1.9 1010) precipitate from this solution?

yes

Solubility Equilibria

Exercise 6

Precipitation

A solution is prepared by mixing 150.0 mL of 1.00 10-2 M Mg(NO3)2 and


250.0 mL of 1.00 101 M NaF. Calculate the concentrations of Mg2+ and F
at equilibrium with solid MgF2 (Ksp = 6.4 109).

[Mg2+] = 2.1 10-6 M


[F-] = 5.50 10-2 M

SOLUBILITY AND THE COMMON ION EFFECT


Experiments show that the solubility of any salt is always less in the
presence of a common ion.
Why? LeChteliers Principle, thats why! Be reasonable and use
approximations when you can.
The pH can also affect solubility. Evaluate the equation to see which
species reacts with the addition of acid or base.
Would magnesium hydroxide be more soluble in an acid or a base? Why?
Mg(OH)2(s) Mg2+(aq)

Solubility Equilibria

+ 2 OH(aq)

(milk of magnesia)

SOLUBILITY, ION SEPARATIONS, AND QUALITATIVE ANALYSIS


This section will introduce you to the basic chemistry of various ions.
It also illustrates how principles of chemical equilibria can be applied in the laboratory.
Objective: Separate the following metal ions from an aqueous sample containing ions of silver, lead(II),
cadmium(II) and nickel(II).

From your knowledge of solubility rules, you know that chlorides of lead and silver will form
precipitates while those of nickel and cadmium will not. Adding dilute HCl to sample will ppt. the lead
and silver ions while the nickel and cadmium will stay in solution.
Separate the lead and silver precipitates from the solution by filtration. Heating the solution causes
some of the lead chloride to dissolve. Filtering the HOT sample will separate the lead (in the filtrate)
from the silver (solid remaining in funnel with filter paper).
Separating cadmium and nickel ions require precipitation with sulfur. Use the Ksp values to determine
which ion will precipitate first as an aqueous solution of sulfide ion is added to the portion of the sample
that still contains these ions. Which precipitates first?

Solubility Equilibria

Exercise 7

Selective Precipitation

A solution contains 1.0 104 M Cu+ and 2.0 103 M Pb2+. If a source of I- is added gradually to this
solution, will PbI2 (Ksp = 1.4 108) or CuI (Ksp = 5.3 1012) precipitate first?
Specify the concentration of I necessary to begin precipitation of each salt.

CuI will precipitate first


Concentration in excess of 5.3 10-8 M required
SOLUBILITY AND COMPLEX IONS
The formation of complex ions can often dissolve otherwise
insoluble salts.
Often as the complex ion forms, the solubility equilibrium
shifts to the right (away from the solid) and causes the
insoluble salt to become more soluble.
Example: If sufficient aqueous ammonia is added to silver chloride, the
latter can be dissolved as [Ag(NH3)2]+ forms, which is soluble.
That is a significant improvement with regard to the solubility of AgCl(s).
The equilibrium constant for dissolving silver chloride in ammonia is not large, but, if the concentration of
ammonia is sufficiently high, the complex ion and chloride ion must also be high, and silver chloride will
dissolve. Of course, this process is quite smelly!

Solubility Equilibria

AP* General Equilibrium Free Response Questions

page 1

General Equilibrium Problems


1983
Sulfuryl chloride, SO2Cl2, is a highly reactive gaseous compound. When heated, it decomposes as follows:
SO2Cl2(g) p SO2(g)+ Cl2(g)
This decomposition is endothermic. A sample of 3.509 grams of SO2Cl2 is placed in an evacuated 1.00 liter
bulb and the temperature is raised to 375 K.
(a) What would be the pressure in atmospheres in the bulb if no dissociation of the SO2Cl2(g) occurred?
(b) When the system has come to equilibrium at 375 K, the total pressure in the bulb is found to be
1.43 atmospheres. Calculate the partial pressures of SO2, Cl2, and SO2Cl2 at equilibrium at 375 K.
(c) Give the expression for the equilibrium constant (either Kp or Kc) for the decomposition of SO2Cl2(g)
at 375 K. Calculate the value of the equilibrium constant you have given, and specify its units.
(d) If the temperature were raised to 500 K, what effect would this have on the equilibrium constant?
Explain briefly.
1988
At elevated temperatures, SbCl5 gas decomposes into SbCl3 gas and Cl2 gas as shown by the following
equation:
SbCl5(g) p SbCl3(g) + Cl2(g)

(a) An 89.7 gram sample of SbCl5 (molecular weight 299.0) is placed in an evacuated 15.0 liter
container at 182C.
1. What is the concentration in moles per liter of SbCl5 in the container before any
decomposition occurs?
2. What is the pressure in atmospheres of SbCl5 in the container before any decomposition occurs?
(b) If the SbCl5 is 29.2 percent decomposed when equilibrium is established at 182C, calculate the value
for either equilibrium constant Kp or Kc, for this decomposition reaction. Indicated whether you are
calculating Kp or Kc.
(c) In order to produce some SbCl5, a 1.00 mole sample of SbCl3 is first placed in an empty 2.00 liter
container maintained at a temperature different from 182C. At this temperature, Kc, equals 0.117.
How many moles of Cl2 must be added to this container to reduce the number of moles of SbCl3 to
0.700 mole at equilibrium?

(1) AP is a registered trademark of the College Board. The College Board was not involved in the production of and does not endorse this product. (2) Test
Questions are Copyright 1984-2008 by College Entrance Examination Board, Princeton, NJ. All rights reserved. For face-to-face teaching purposes,
classroom teachers are permitted to reproduce the questions. Web or Mass distribution prohibited.

AP* General Equilibrium Free Response Questions

page 2

1992
2 NaHCO3(s) p Na2CO3(s) + H2O(g) + CO2(g)
Solid sodium hydrogen carbonate, NaHCO3, decomposes on heating according to the equation above.
(a) A sample of 100. grams of solid NaHCO3 was placed in a previously evacuated rigid 5.00-liter container
and heated to 160C. Some of the original solid remained and the total pressure in the container was 7.76
atmospheres when equilibrium was reached. Calculate the number of moles of H2O(g) present at
equilibrium.
(b) How many grams of the original solid remain in the container under the conditions described in (a)?
(c) Write the equilibrium expression for the equilibrium constant, Kp, and calculate its value for the reaction
under the conditions in (a).
(d) If 110. grams of solid NaHCO3 had been placed in the 5.00-liter container and heated to 160C, what
would the total pressure have been at equilibrium? Explain.
1995
CO2(g) + H2(g) p H2O(g) + CO(g)
When H2(g) is mixed with CO2(g) at 2,000 K, equilibrium is achieved according to the equation above. In one
experiment, the following equilibrium concentrations were measured.
[H2] = 0.20 mol/L
[CO2] = 0.30 mol/L
[H2O] = [CO] = 0.55 mol/L
(a) What is the mole fraction of CO(g) in the equilibrium mixture?
(b) Using the equilibrium concentrations given above, calculate the value of Kc, the equilibrium constant for
the reaction.
(c) Determine Kp in terms of Kc for this system.
(d) When the system is cooled from 2,000 K to a lower temperature, 30.0 percent of the CO(g) is converted
back to CO2(g). Calculate the value of Kc at this lower temperature.
(e) In a different experiment, 0.50 mole of H2(g) is mixed with 0.50 mole of CO2(g) in a 3.0-liter reaction
vessel at 2,000 K. Calculate the equilibrium concentration, in moles per liter, of CO(g) at this
temperature.

AP* General Equilibrium Free Response Questions

page 3

2003B
2 HI(g) p H2(g) + I2(g)
After a 1.0 mole sample of HI(g) is placed into an evacuated 1.0 L container at 700. K, the reaction
represented above occurs. The concentration of HI(g) as a function of time is shown below.
(a) Write the expression for the equilibrium constant, Kc , for the reaction.

(b) What is [HI] at equilibrium?


(c) Determine the equilibrium concentrations of H2(g) and I2(g).
(d)

On the graph above, make a sketch that shows how the concentration of H2(g) changes as a
function of time.

(e) Calculate the value of the following equilibrium constants at 700. K.


(i) Kc
(ii) Kp
(f) At 1,000 K, the value of Kc for the reaction is 2.6 102. In an experiment, 0.75 mole of HI(g),
0.10 mole of H2(g), and 0.50 mole of I2(g) are placed in a 1.0 L container and allowed to reach
equilibrium at 1,000 K. Determine whether the equilibrium concentration of HI(g) will be greater
than, equal to, or less than the initial concentration of HI(g). Justify your answer.

AP* General Equilibrium Free Response Questions

page 4

2008B
Answer the following questions regarding the decomposition of arsenic pentafluoride, AsF5(g).
(a) A 55.8 g sample of AsF5(g) is introduced into an evacuated 10.5 L container at 105C.
(i) What is the initial molar concentration of AsF5(g) in the container?
(ii) What is the initial pressure, in atmospheres, of the AsF5(g) in the container?
At 105C, AsF5(g) decomposes into AsF3(g) and F2(g) according to the following chemical equation.

AsF3(g) + F2(g)
AsF5(g)

(b) In terms of molar concentrations, write the equilibrium-constant expression for the decomposition
of AsF5(g).
(c) When equilibrium is established, 27.7 percent of the original number of moles of AsF5(g) has
decomposed.
(i) Calculate the molar concentration of AsF5(g) at equilibrium.
(ii) Using molar concentrations, calculate the value of the equilibrium constant, Keq, at 105C.
(d) Calculate the mole fraction of F2(g) in the container at equilibrium.

AP* General Equilibrium Free Response Questions

page 5

2010B
The compound butane, C4H10, occurs in two isomeric forms, n-butane and isobutane (2-methyl propane).
Both compounds exist as gases at 25C and 1.0 atm.
(a) Draw the structural formula of each of the isomers (include all atoms). Clearly label each structure.
(b) On the basis of molecular structure, identify the isomer that has the higher boiling point. Justify your
answer.
The two isomers exist in equilibrium as represented by the equation below.

isobutane(g)
n-butane(g)

Kc = 2.5 at 25C

Suppose that a 0.010 mol sample of pure n-butane is placed in an evacuated 1.0 L rigid container at 25C.
(c) Write the expression for the equilibrium constant, Kc, for the reaction.
(d) Calculate the initial pressure in the container when the n-butane is first introduced (before the
reaction starts).
(e) The n-butane reacts until equilibrium has been established at 25C.
(i) Calculate the total pressure in the container at equilibrium. Justify your answer.
(ii) Calculate the molar concentration of each species at equilibrium.
(iii) If the volume of the system is reduced to half of its original volume, what will be the new
concentration of n-butane after equilibrium has been reestablished at 25C? Justify your answer.
Suppose that in another experiment a 0.010 mol sample of pure isobutane is placed in an evacuated
1.0 L rigid container and allowed to come to equilibrium at 25C.
(f) Calculate the molar concentration of each species after equilibrium has been established.

AP* General Equilibrium Free Response Questions

page 6

General Equilibrium Essay Questions


1988
NH4HS(s) p NH3(g) + H2S(g)

H = +93 kilojoules

The equilibrium above is established by placing solid NH4HS in an evacuated container at 25C.
At equilibrium, some solid NH4HS remains in the container. Predict and explain each of the following.
(a) The effect on the equilibrium partial pressure of NH3 gas when additional solid NH4HS is introduced
into the container.
(b) The effect on the equilibrium partial pressure of NH3 gas when additional H2S gas is introduced into
the container.
(c) The effect on the mass of solid NH4HS present when the volume of the container is decreased.
(d) The effect on the mass of solid NH4HS present when the temperature is increased.

1997
For the gaseous equilibrium represented below, it is observed that greater amounts of PCl3 and Cl2 are
produced as the temperature is increased.
PCl5(g) p PCl3(g) + Cl2(g)
(a) What is the sign of S for the reaction? Explain.
(b) What change, if any, will occur in G for the reaction as the temperature is increased. Explain your
reasoning in terms of thermodynamic principles.
(c) If He gas is added to the original reaction mixture at constant volume and temperature, what will
happen to the partial pressure of Cl2? Explain.
(d) If the volume of the original reaction is decreased at constant temperature to half the original volume,
what will happen to the number of moles of Cl2 in the reaction vessel? Explain.

AP* General Equilibrium Free Response Questions

page 7

1998
C(s) + H2O(g) p CO(g) + H2(g)

H = +131 kJ

A rigid container holds a mixture of graphite pellets (C(s)), H2O(g), CO(g), and H2(g) at equilibrium.
State whether the number of moles of CO(g) in the container will increase, decrease, or remain the same
after each of the following disturbances is applied to the original mixture. For each case, assume that all
other variables remain constant except for the given disturbance. Explain each answer with a short
statement.
(a) Additional H2(g) is added to the equilibrium mixture at constant volume.
(b) The temperature of the equilibrium mixture is increased at constant volume.
(c) The volume of the container is decreased at constant temperature.
(d) The graphite pellets are pulverized.

AP* Solubility Equilibrium Free Response Questions

page 1

1985
At 25C the solubility product constant, Ksp, for strontium sulfate, SrSO4, is 7.6 107. The solubility product
constant for strontium fluoride, SrF2, is 7.9 1010.
(a) What is the molar solubility of SrSO4 in pure water at 25C?
(b) What is the molar solubility of SrF2 in pure water at 25C?
(c) An aqueous solution of Sr(NO3)2 is added slowly to 1.0 liter of a well-stirred solution containing
0.020 mole F and 0.10 mole SO42 at 25C. (You may assume that the added Sr(NO3)2 solution does not
materially affect the total volume of the system.)
1. Which salt precipitates first?
2. What is the concentration of strontium ion, Sr2+, in the solution when the first precipitate begins
to form?
(d) As more Sr(NO3)2 is added to the mixture in (c) a second precipitate begins to form. At that stage, what
percent of the anion of the first precipitate remains in solution?

1990
The solubility of iron(II) hydroxide, Fe(OH)2, is 1.43 103 gram per liter at 25 C.
(a) Write a balanced equation for the solubility equilibrium.
(b) Write the expression for the solubility product constant, Ksp, and calculate its value.
(c) Calculate the pH of the saturated solution of Fe(OH)2 at 25 C.
(d) A 50.0-milliliter sample of 3.00 103 molar FeSO4 solution is added to 50.0 milliliters of 4.00 106
molar NaOH solution. Does a precipitate of Fe(OH)2 form? Explain and show calculations to support
your answer.

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AP* Solubility Equilibrium Free Response Questions

page 2

1994
MgF2(s) p Mg2+(aq) + 2 F(aq)
In a saturated solution of MgF2 at 18C, the concentration of Mg2+ is 1.21 103 molar. The equilibrium
is represented by the equation above.
(a) Write the expression for the solubility-product constant, Ksp, and calculate its value at 18 C.
(b) Calculate the equilibrium concentration of Mg2+ in 1.000 liter of saturated MgF2 solution at 18C to
which 0.100 mole of solid KF has been added. The KF dissolves completely. Assume the volume
change is negligible.
(c) Predict whether a precipitate of MgF2 will form when 100.0 milliliters of a 3.00 103 molar
Mg(NO3)2 solution is mixed with 200.0 milliliters of a 2.00 103 molar NaF solution at 18C.
Calculations to support your prediction must be shown.
(d) At 27C the concentration of Mg2+ in a saturated solution of MgF2 is 1.17 103 molar. Is the
dissolving of MgF2 in water an endothermic or an exothermic process? Give an explanation to support
your conclusion.

1998
Solve the following problem related to the solubility equilibria of some metal hydroxides in aqueous
solution.
(a) The solubility of Cu(OH)2 is 1.72 106 gram per 100. milliliters of solution at 25C.
(i) Write the balanced chemical equation for the dissociation of Cu(OH)2(s) in aqueous
solution.
(ii) Calculate the solubility (in moles per liter) of Cu(OH)2 at 25 C.
(iii) Calculate the value of the solubility-product constant, Ksp, for Cu(OH)2 at 25C.
(b) The value of the solubility-product constant, Ksp, for Zn(OH)2 is 7.7 1017 at 25C.
(i) Calculate the solubility (in moles per liter) of Zn(OH)2 at 25C in a solution with a
pH of 9.35.
(ii) At 25C, 50.0 milliliters of 0.100-molar Zn(NO3)2 is mixed with 50.0 milliliters of
0.300-molar NaOH. Calculate the molar concentration of Zn2+(aq) in the resulting
solution once equilibrium has been established. Assume that volumes are additive.

AP* Solubility Equilibrium Free Response Questions

page 3

2004
1. Answer the following questions relating to the solubilities of two silver compounds, Ag2CrO4 and
Ag3PO4.
Silver chromate dissociates in water according to the equation shown below.
Ag2CrO4(s) p 2 Ag+(aq) + CrO42(aq)

Ksp = 2.6 1012 at 25C

(a) Write the equilibrium-constant expression for the dissolving of Ag2CrO4(s).


1
(b) Calculate the concentration, in mol L , of Ag+(aq) in a saturated solution of Ag2CrO4 at 25C.
(c) Calculate the maximum mass, in grams, of Ag2CrO4 that can dissolve in 100. mL of water

at 25C.
(d) A 0.100 mol sample of solid AgNO3 is added to a 1.00 L saturated solution of Ag2CrO4 .

Assuming no volume change, does [CrO42] increase, decrease, or remain the same? Justify
your answer.

In a saturated solution of Ag3PO4 at 25C, the concentration of Ag+(aq) is 5.3 105 M. The equilibrium
constant expression for the dissolving of Ag3PO4 (s) in water is shown below.
Ksp = [Ag+]3[PO43]
(e) Write the balanced equation for the dissolving of Ag3PO4 in water.
(f) Calculate the value of Ksp for Ag3PO4 at 25C.
(g) A 1.00 L sample of saturated Ag3PO4 solution is allowed to evaporate at 25C to a final volume of

500. mL. What is [Ag+] in the solution? Justify your answer.