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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.
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.
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.
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!
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
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
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
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)
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
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
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
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
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.
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.
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)
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
10
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:
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.
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
11
Exercise 3
The reaction between bromate ions and bromide ions in acidic aqueous solution is given by the equation
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
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.
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]
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.
13
Exercise 4
The decomposition of N2O5 in the gas phase was studied at constant temperature.
Time (s)
0
50
100
200
300
400
(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
(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
15
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
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
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
A 0
ln
kt
A
By definition, when t t 1 ,
A 0
ln
A 0
A 0
2
A0
ln
A
0
2
kt 1 ; clean it up a bit
2
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.
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
19
Exercise 7
A certain first-order reaction has a half-life of 20.0 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?
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]
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
ln[A] = kt + ln[A]0
1
1
kt
A
A0
Slope = k
Slope = k
Slope = k
[A] versus t
ln[A] versus t
1
versus t
A
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.
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
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:
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]
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
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)
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
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
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)
H
C=C
H
ethene (ethylene)
+ H2(g)
H
H
ethane
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.
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!
25
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
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.
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)
(slow)
(fast)
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)
(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.
page 5
Problems
1981
(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)
(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)
page 6
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
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)
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.
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.
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.
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.
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.
*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
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
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.
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
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.
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.
Exercise 3
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
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)
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
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.
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.
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:
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
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
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
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
Exercise 7
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.
Properties of Solutions
11
Properties of Solutions
12
Exercise 8
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.
Properties of Solutions
13
Exercise 10
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
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.
15
(0.08206)(298)
nRT
dRT
g
0.1
=
= 73, 400
or MM =
; so, MM =
V
0.050
mol
Exercise 11
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.
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.
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)
Properties of Solutions
16
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.
*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.
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.
R slope.
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
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.
(e.) What is the temperature when the rate constant has a value of 22.5 109 M1 s1?
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.
(d.) What is the temperature when the rate constant has a value of 50.5 104 M1 s1?
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.
(d.) What is the temperature when the rate constant has a value of 9.65 104 s1?
(b.) Draw and label a reaction coordinate (potential energy) diagram for this reaction at 25C.
Absorbance
0.330
0.172
0.138
0.096
Time
(min)
0.0
10.0
15.0
?
(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.
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?
11
graph
ln[A] vs. time
graph
1/[A] vs. time
12
Calculator screen:
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
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.
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?
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.
640 C is way outside our range. Its KELVIN reciprocal is 0.001095. You must change
the window.
(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.
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.
(d.) What is the temperature when the rate constant has a value of 9.65 104 s1?
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!
Absorbance
0.330
0.172
0.138
0.0960
Time
(min)
0.0
10.0
15.0
?
= 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.
(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.
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?
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
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 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.
*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
Exercise 1
K = [NO2]4[H2O]6
[NH3]4[O2]7
Exercise 2
A: K = [Cl2]
Kp = PCl2
B: K = [H2O]5
Kp = PH2O5
Exercise 3
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
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:
K1 = 4.36
K2 = 4.32
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!
Exercise 5
Calculating Values of Kp
= 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
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?
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 = 5.0 M;
=
=
=
=
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
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
Exercise 9
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.
Exercise 10
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.
Exercise 11
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.
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.
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.
Rewrite: A + B + heat C + D
EXOTHERMIC: A + B C + D
Rewrite: A + B C + D + heat
Exercise 13
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
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
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
H = 198 kJ
A: increases
B: decreases
11
AP* Chemistry
Solubility Equilibrium
SOLUBILITY EQUILIBRIA (The Solubility-Product Constant, Ksp)
Weve got good news and weve got bad news
When the solid is first added to water, no ions are initially present.
The equilibrium constant, the Ksp, is no more than the product of the
ions in solution. (Remember, solids do not appear in equilibrium
expressions.)
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.
*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 =
Ksp =
Ksp =
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
Copper(I) bromide has a measured solubility of 2.0 104 mol/L at 25C. Calculate its
Ksp value.
Exercise 2
Calculate the Ksp value for bismuth sulfide (Bi2S3), which has a solubility of
1.0 1015 mol/L at 25C.
Exercise 3
The Ksp value for copper(II) iodate, Cu(IO3)2, is 1.4 107 at 25C. Calculate its solubility at 25C.
Exercise 4
Calculate the solubility of solid CaF2 (Ksp = 4.0 1011) in a 0.025 M NaF solution.
Solubility Equilibria
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
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
Solubility Equilibria
+ 2 OH(aq)
(milk of magnesia)
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.
Solubility Equilibria
page 1
(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.
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.
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.
On the graph above, make a sketch that shows how the concentration of H2(g) changes as a
function of time.
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.
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.
page 6
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.
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.
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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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.
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)
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