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Chemistry 122

Mines, Spring, 2012


PS1-1

Answer Key, Problem Set 1Full Version

1. 13.26; 2. 13.32; 3. 13.34 (add part (e): Estimate / calculate the initial rate of the reaction); 4. NT1;
5. NT2; 6. 13.37; 7. 13.39; 8. 13.41; 9. NT3; 10. 13.44; 11. NT4
------------------------------
1. 13.26. Consider the reaction (represented by):
2 N
2
O(g) 2 N
2
(g) + O
2
(g)
(a) Express the rate of the reaction in terms of the change in concentration of each of the reactants and products.
(b) In the first 15.0 s of the reaction, 0.015 mol of O
2
is produced in a reaction vessel with a volume of 0.500 L. What is the
average rate of the reaction over this time interval?
(c) Predict the rate of change in the concentration of N
2
O

over this time interval. In other words, what is
t
O] [N
2
?
Answers: (a)
t t t A
A
=
A
A
=
A
A
=
] [O ] [N O] [N
reaction of Rate
2 2 2
2
1
2
1

(b) 0.0020 Ms
-1
(over the 1
st
15 s)
(c) -0.0040 Ms
-1

Explanation/Reasoning:
(a) Since the rates of loss and formation of the reactants and products are proportional to the coefficients in
the balanced equation (i.e., these rates are not all equal), a single rate of reaction will be obtained if
each rate of loss or formation is divided by the species coefficient in the balanced equation. That is why
rate of reaction is defined as
t x A
A

X] [ 1
if X is a reactant, and
t x A
A X] [ 1
if X is a product (with coefficient x).
(b) Average rate of reaction (expressed in terms of O
2
) =
t A
A ] [O
2

M 0.030
L 0.500
O mol 0.015
] [O
2
2
) (over = = A s st 15 1 O
2
[b/c M = moles / L]
Thus,
1 - 2
s M 0.0020
s 15.0
M 0.030 ] [O
= =
A
A
t

(c)
1 - 1 - 2 2 2 2
s M 0.0040 - ) s M (0.0020
] [O O] [N

] [O O] [N
2 = =
A
A
=
A
A

A
A
=
A
A

t t t t
2
2
1

I.e., the rate of change of N
2
O is twice the rate of formation of O
2
, which can be seen from the 2:1 ratio of N
2
O
lost : O
2
formed in the balanced equation. The negative sign is needed here because rate of change of N
2
O
was asked for rather than rate of loss (and rates of loss are always the opposite of rates of formation).
2. 13.32. Consider the reaction (represented by): NO
2
(g) NO(g) +
2
1
O
2
(g)
The following data were collected for the concentration of NO
2
as a function of time:
Time (s) 0 10 20 30 40 50 60 70 80 90 100
[NO
2
] (M) 1.000 0.951 0.904 0.860 0.818 0.778 0.740 0.704 0.670 0.637 0.606
(a) What is the average rate of the reaction between 10 and 20 s? Between 50 and 60 s?
(b) What is the rate of formation of O
2
between 50 and 60 s?

Answers: (a) 0.0047 Ms
-1
and 0.0038 Ms
-1
; (b) 0.0019 Ms
-1


Reasoning:
Answer Key, Problem Set 1
PS1-2
(a)
t
Rate . Avg
A
A
=
] [NO

2
here because the coefficient of NO
2
is 1. Thus,
From 10 s to 20 s,
1 - 2 2
s M 0.0047
s 10.
M 0.047
s 10 s 20
M 0.951 M 0.904 ] [NO ] [NO
= =

=
i f
i f
t t
Rate . Avg
From 50 s to 60 s,
1 - 2 2
s M 0.0038
s 10.
M 0.038
s 50 s 60
M 0.778 M 0.740 ] [NO ] [NO
= =

=
i f
i f
t t
Rate . Avg
(b) R(form, of O
2
) = R(loss of NO
2
) because of the coefficients in the equation (1 : for NO
2
: O
2
). Thus, the
(average) rate of formation of O
2
between 50 s and 60 s = x 0.0038 Ms
-1
(from (a))

= 0.0019 Ms
-1


3. 13.34. Consider the reaction (represented by):
2 H
2
O
2
(aq) 2 H
2
O (l) + O
2
(g)
The graph below (to the right in this key) shows the
concentration of H
2
O
2
as a function of time.

Use the graph to calculate each quantity:
(a) The average rate of the reaction between 10 and 20 s.
(b) The instantaneous rate of the reaction at 30 s.
(c) The instantaneous rate of formation of O
2
at 50 s
(d) If the initial volume of the H
2
O
2
is 1.5 L, what total amount of O
2

(in moles) is formed in the first 50 s of reaction?
(e) [added] Estimate / calculate the initial rate of the reaction.

Answers: (my results): (a) 0.0095 Ms
-1
; (b) 0.0063 Ms
-1
; (c)

0.0034 Ms
-1
; (d) 0.59 mol O
2
; (e) 0.014 Ms
-1


Strategy/Explanation:
(a) Avg. rate of reaction here =
t A
A

] O [H
2 2
2
1
because the coefficient of H
2
O
2
is a 2. So,
1) Find the values of [H
2
O
2
] at t = 10 and 20 s.
2) Calculate
t A
A

] O [H
2 2
2
1

(b) Instantaneous rate means the rate at a single point in time, rather than over a time interval. It can be
estimated by finding the (absolute value of the) slope of the tangent to a curve at a point in time. So in
this problem one must:
1) Draw a tangent to the curve at the point representing t = 30 s; and
2) Find the (absolute value of the) slope of the tangent line by picking any two points on the line and
using the definition of slope
x
y
A
A
= (which here represents
t A
A ] O [H
2 2
).
3) Multiply the result in (2) by - to get rate of reaction (see (a)).

(c) This is similar to (b) except that the rate of formation of O
2
is asked for (not rate of reaction).
However, since the coefficient of O
2
is 1, the rate of formation of O
2
equals the rate of reaction in this
problem! Thus, you can actually do exactly the same thing you did in (b) except do it at the point
corresponding to t = 50 s.
(d) Once you step back and really analyze this problem, hopefully you will recognize that it is actually just a
stoichiometry problem involving concentration and volume! You are asked for moles of O
2
formed in
the first 50 s, and you are effectively given the concentration of H
2
O
2
lost during this same time
interval (because you can get this from the graph by determining [H
2
O
2
]
50 s
[H
2
O
2
]
0 s
). So, the strategy
here is to go from
molarity of H
2
O
2
(A[H
2
O
2
]) moles of H
2
O
2
moles of O
2

Answer Key, Problem Set 1
PS1-3
The first step involves multiplying M by V (in L) to get moles. The second step involves multiplying by a
mole ratio from the balanced equation
|
|
.
|

\
|
2 2
2
O H mol 2
O mol 1
.
(e) Initial rate means the instantaneous rate at t = 0. Thus, do the same thing as in (b) except at t = 0 s.

Execution of Strategy:





















- I scanned the plot from the text and enlarged it in this key for better precision.
- I adjusted a line to make it go through the point on the curve at t = 30 s, and which appeared to
have the slope of the curve at that point (see dotted line on plot). I did the same for a line through
the points at t = 50 s (dashed line) and at t = 0 s (dot-dash line).
(a) At 10. s, [H
2
O
2
] = 0.75 M; at 20. s, [H
2
O
2
] = 0.56 M. Thus,
1 -
s M 0. 0095 = |
.
|

\
|
= |
.
|

\
|
=
A
A
=
s 10.
M 0.19 -
s 10. - 20.
M 0.75 - 0.56 ] O [H
2 2
2
1
2
1
2
1
t
Rate
(b) Looking at the dotted line and picking as my two points, the intercepts (just for convenienceyou could use
any two points), I get the points (0 s, 0.78 M) and (62 s, 0 M). Thus:
1 -
s M 0. 0063 = = |
.
|

\
|
= |
.
|

\
|
=
A
A
=
1 - 2 2
s M 9 2 0.006
s 62.
M 0.78 -
s 0. - 62.
M 0.78 - 0. ] O [H
2
1
2
1
2
1
t
Rate
(c) Looking at the dashed line, the y-intercept is (0 s, 0.55 M), and another point is (70. s, 0.08 M) [I didnt
pick the x-intercept here because it was slightly off my scale]. Thus:
1 -
s M 0. 0034 = = |
.
|

\
|
= |
.
|

\
|
=
A
A
=
1 - 2 2
s M 57... 3 0.003
s 70.
M 0.47 -
s 0. - 70.
M 0.55 - 0.08 ] O [H
2
1
2
1
2
1
t
Rate
(d) [H
2
O
2
]
50 s
= 0.22 M; [H
2
O
2
]
0 s
= 1.00 M. Thus, A[H
2
O
2
] = -0.78 M 0.78 M H
2
O
2
was lost (in 1
st
50 s)
2
O mol 0.59 5 8 0.5
lost O H mol 2
formed O mol 1
x L 5 1. x
L
O H mol 8 0.7
2 2
2 2 2
= = (formed in 1
st
50 s)
(e) Looking at the dot-dash line, the y-intercept is (0 s, 1.00 M), and the x-intercept is (36. s, 0. M) Thus:
1 -
s M 0. 014 = = |
.
|

\
|
= |
.
|

\
|
=
A
A
=
1 - 2 2
s M 8... 3 0.01
s 36.
M 1.00 -
s 0. - 36.
M 1.00 - 0. ] O [H
2
1
2
1
2
1
t
Rate
Uncertainty probably
about 0.0003 Ms
-1

due to slope estimation
Uncertainty proba-
bly about 0.0004
Ms
-1
due to slope
estimation
Uncertainty probably
about 0.001 Ms
-1

due to slope
estimation
Answer Key, Problem Set 1
PS1-4
4. NT1. Consider a reaction represented by the equation aA + bB cC and the following average rate data over some time period At:
1 -
s M 0.0080
A
=
A
A

t

1 -
s M 0.0120
B
=
A
A

t

1 -
s M 0.0160
C
=
A
A
t

Determine the coefficients (a, b, and c) in the standard balanced chemical equation (i.e., lowest whole #s)
Answer: 2 A + 3 B 4 C (i.e., a = 2; b = 3; c = 4)
Explanation: The ratio of coefficients in a balanced chemical equation must be equal to the ratio of changes
in mole values (in absolute value) of reactants and/or products during a chemical reaction. This is
essentially the meaning of the coefficients in a balanced equation. Assuming a fixed volume and a fixed
time interval (At), the rate of change of a species is directly proportional to concentration and thus moles:
Rate of change of X (M/s) [X] (M) moles of X (mol)
This means that the ratio of coefficients also equals the ratio of rates of change. For this problem, then,
since 0.0080 : 0.0120 : 0.0160 equals 8 : 12 : 16 (divide all values by 0.0100) which equals 2 : 3 : 4, the set
of lowest whole number coefficients would be 2, 3, and 4.

5. NT2; The reaction represented by the following equation was found to have the rate law shown.
2 N
2
O
5
(g) 4 NO
2
(g) + O
2
(g); Rate Law: Rate = k[N
2
O
5
(g)]
(a) What is the order of the reaction with respect to N
2
O
5
?
Answer: First order (because the exponent of [N
2
O
5
(g)] in the rate law is 1).
(b) How does the rate of formation of O
2
compare with the rate of loss of N
2
O
5
? (State the correct answer from among the
statements below and then explain your answer).
(i) O
2
forms half as fast as N
2
O
5
is lost. |
.
|

\
|
A
A
=
A
A
t t
] O [N ] [O
i.e.,
5 2 2
2
1

(ii) O
2
forms twice as fast as N
2
O
5
is lost.
(iii) O
2
forms four times as fast as N
2
O
5
is lost.
(iv) It depends on how much N
2
O
5
you start with.

Explanation: Since the amount of moles of O
2
produced is always half the amount of moles N
2
O
5

used up (based on the 2 : 1 ratio of N
2
O
5
: O
2
in the balanced equation), the rate of
formation of O
2
must be half the value of the rate of loss of N
2
O
5
.
(c) A specific trial of the above reaction is carried out, and the concentration vs. time plot of one of the species involved is plotted
below. Identify which species is depicted in the plot below, and then draw curves representing the other two species involved
in the reaction (copy the plot onto your paper, and be careful to be reasonably quantitatively accurate!) Give brief reasoning







(one possible) Answer
Explanation:
The balanced chemical equation is: 2 N
2
O
5
(g) 4 NO
2
(g) + O
2
(g)
What does this mean? It means that for every two moles of N
2
O
5
(g) that undergo reaction, four moles
(i.e., twice as many) of NO
2
and one mole (i.e., half as many) of O
2
will be formed. Thus, the limiting
value for the amount of NO
2
produced (i.e., the value when essentially all of the N
2
O
5
has reacted) is
twice the initial value of N
2
O
5
, whereas the limiting value for the amount of O
2
produced is half the initial
Time
Concentration
Time
Concentration
NO
2

O
2

N
2
O
5

Answer Key, Problem Set 1
PS1-5
value of N
2
O
5
. Note that the products concentrations should INCREASE with time since they are being
produced; the reactants concentration should DECREASE with time since it is being used up. If you
assume that you started with no products at t = 0, the plots for NO
2
and O
2
would start at the origin, and
the graph would look something like what is shown in the answer box (see above, right).

Note that the slope at any point in time (on a plot of concentration vs. time) represents the rate of
change of that species concentration at that time. So this is yet another way to see that at any point in
time during this reaction, the rate of increase of NO
2
is 4 times the value of the rate of increase of O
2
,
and the rate of formation of O
2
is half the value of the rate of loss of N
2
O
5
(see part (b) above).

NOTE #2: There is really no need to assume that you start without any products present (although that is what is often done, for
convenience, when we begin the discussion of kinetics). In the next chapter we will see many problems in which some products
are present at the start of some reaction. So IF you were to assume that you started with [NO
2
]
0
= [N
2
O
5
]
0
and [O
2
]
0
= 1.5 x
[N
2
O
5
]
0
, the plot would look as shown below (all curves have the same exact shape and size as above, but those for NO
2
and O
2

are just moved up relative to where they were in the prior plot):
















6. 13.37. What are the units of k for each type of reaction?
(a) first-order reaction s
-1

(b) second-order reaction M
-1
s
-1
Answers
(c) zero-order reaction Ms
-1

Reasoning / Proof
Write an example rate law for each case and then solve for k with units only (no numbers):
1
st
order: R = k[A]
1
1

= = s
M
s M R
k
units of terms in
[A]

2
nd
order: R = k[A]
2

1 1
1
2
1


= =

= = s M
M
s
M
s M R
k
units of terms in
2
[A]

0
th
order: R = k[A]
0
= k
1
= = s M R k
units of terms in


7. 13.39. A reaction in which A, B, and C react to form products is first order in A, second order in B, and zero order in C.
(a) Write a rate law for the reaction.
(b) What is the overall order of the reaction?
(c) By what factor does the reaction rate change if [A] is doubled (and the other reactant concentrations are held constant)?
(d) By what factor does the reaction rate change if [B] is doubled (and the other reactant concentrations are held constant)?
(e) By what factor does the reaction rate change if [C] is doubled (and the other reactant concentrations are held constant)?
(f) By what factor does the reaction rate change if the concentrations of all three reactants are doubled?

Time
Concentration
NO
2

O
2

N
2
O
5

Obviously, you could have started
with any initial concentrations of
NO
2
or O
2
, so I cant write all of the
possible correct answers here!
Another possible correct answer
Answer Key, Problem Set 1
PS1-6
Answers: (a) R = k[A][B]
2
[C]
0
(or just R = k[A][B]
2
)
(b) 3
(c) factor of 2
(d) factor of 4
(e) factor of 1 (no change)
(f) factor of 8
Explanations:
(a) An order is an exponent of a concentration term. If the reaction is first order in A, that means that
the exponent of [A] in the rate law is a 1. If it is second order in B, that means that the exponent of
[B] in the rate law is a 2. If it is zero order in C, that means that the exponent of [C] is zero (but since
anything to the zero power is one, that term can be left off entirely).
(b) Overall order = sum of individual orders = 1 + 2 + 0 = 3
(c) Whatever factor of change there is in the concentration, that value raised to the order is the factor of
change in the rate. When the order is 1, the factor of changes are equal, so if concentration doubles,
rate doubles.
Proof: R = k[A]
1
. Let the first [A] be [A](1); then after the concentration is doubled, [A](2) = 2 x [A](1)
R(1) = k[A](1), and after doubling the concentration, R(2) = k (2 x [A](1))
1
= 2 x k[A](1) = 2 x R(1).
The last mathematical equation means Rate after doubling [A] = 2 times the original Rate
(d) Whatever factor of change there is in the concentration, that value raised to the order is the factor of
change in the rate. When the order is 2, the factor of change of the rate equals the square of the
factor of change of the concentration, so if concentration doubles, rate quadruples.
Proof: R = k[B]
2
. Let the first [B] be [B](1); then after the concentration is doubled, [B](2) = 2 x [B](1)
R(1) = k[B](1)
2
, and after doubling the concentration, R(2) = k (2 x [B](1))
2
= 2
2
x k[B](1)
2
= 2
2
x R(1).
The last mathematical equation means Rate after doubling [B] = 4 times the original Rate
(e) If a reaction is zeroth order in C, that means that the rate is independent of [C]. I.e., if you double [C],
the rate remains the same.
(f) If more than one change in concentration occurs, the factor change in the rate is the product of the
factors of changes that would have occurred if each change had occurred on its own.
Proof: R = k[A][B]
2
. Let the first [A] be [A](1); then after the concentration is doubled, [A](2) = 2 x
[A](1). Let the first [B] be [B](1); then after the concentration is doubled, [B](2) = 2 x [B](1)
R(1) = k[A](1) [B](1)
2
, and after doubling both concentrations,
R(2) = k(2 x [A](1)) (2 x [B](1))
2
= 2 2
2
x k[A](1)[B](1)
2
= 22
2
x R(1) = 8 x R(1)
The last mathematical equation means Rate after doubling [A] and [B] = 8 times the original Rate
(Note: I left off [C] here for simplicity. We know that the rate is unaffected by a change in [C]
because it is zero order in C.)
8. 13.41. Consider the data below showing the initial rate of a reaction (A products) at several different concentrations of A.
(a) What is the order of the reaction? (b) Write a rate law for the reaction including the value of the rate constant, k.
Experiment (trial) [A]
0
(M) Initial Rate (M/s)
1 0.100 0.053
2 0.200 0.210
3 0.300 0.473

Answers: order is 2; R = k[A]
2
, where k = 5.3 M
-1
s
-1
or 5.25 M
-1
s
-1

Answer Key, Problem Set 1
PS1-7
Reasoning:
To find the order:
Verbal: Going from Trial 1 to Trial 2, the (initial) [A] doubles (0.100 M to 0.200 M, and the (initial) rate
quadruples (0.053 to 0.210 M/s; 0.210 / 0.053 = 3.96 ~ 4). That means the order of A must be 2 (2
m
=
4 m = 2). This can be checked / confirmed by noting that in going from Trial 1 to Trial 3, the [A]
triples, and the rate goes up by 0.473 / 0.053 = 8.92 ~ 9 times, which equals 3
2
. Thus (again), the order
is 2.
Brute Force Approach:
Set up the rate law: R = k[A]
m
(1)
Substitute values from Trials 1 and 2 into the rate law (1) above:
Trial 1: 0.053 M/s = k(0.100 M)
m

Trial 2: 0.210 M/s = k(0.200 M)
m

Now look at the ratio of rates and then substitute into the equation using the right-hand side
expressions for the rates (from above):
(Note: Although not necessary, I prefer to divide the equation having the larger rate in it by the one with the smaller rate
since I find it easier to work with values greater than one rather than fractions.)

So, dividing Trial 2s equation by Trial 1s, you get:
m
m
m
0.100
0.200
0.053
0.210

M) (0.100
M) (0.200
M/s 0.053
M/s 0.210
(1)
(2)
|
.
|

\
|
= = =
k
k
R
R

( ) 2 m 2.00 4 6 9 3.
m
= = ~
To find k:
Use any trial and just substitute in the values for initial rate and [A]. Now that the order (m, here) is
known, k will be the only unknown!
Trial 1: 0.053 M/s = k(0.100 M)
2

1 1
1
2
1


= =

= = s M
M
s
M
s M
k 5.3
5.3
0.0100
0.053
M) (0.100
M/s 0.053
2

As a check:
Trial 2: : 0.210 M/s = k(0.200 M)
2

1 1
1
2
1


= =

= = s M
M
s
M
s M
k 5.25
5.25
0.0400
0.210
M) (0.200
M/s 0.210
2

(NOTE: These two values are consistent with one another. The best thing to do in principle [e.g., if this were an actual set
of experiments] would be to calculate all three ks and then average them [this is what you will do for Experiments 20 and
21 in lab], but I will not do that here. On an exam, for a similar problem, you may choose any ONE trial and leave it at that.)

9. NT3. The following data were determined for the reaction represented by the equation:
2 ClO
2
(aq) + 2 OH
-
(aq) ClO
3
-
(aq) + ClO
2
-
(aq) + H
2
O(l)
The temperature was the same in all trials.
Trial [ClO
2
]
0
(M) [OH
-
]
0
(M) Initial Rate (M/s)
1 0.0500 0.100 2.88 x 10
-2
2 0.100 0.100 1.15 x 10
-1
3 0.100 0.0500 5.75 x 10
-2

(a) Determine the rate law (using k to represent the rate constant)
(b) Determine the (value and units of the) rate constant (at the temperature at which these data were collected).
(c) What would be the initial rate for a trial with [ClO
2
]
0
= 0.175 M and [OH
-
]
0
= 0.0844 M (at the same T)?

(note the cancellation of the ks, and units in the
numerator and denominator of both sides)
Answer Key, Problem Set 1
PS1-8

Answers: (a) R = k[ClO
2
]
2
[OH
-
]; (b) k = 115 M
-2
s
-1
; (c) 0.298 M/s
Reasoning:
The rate law will be of the form:
Rate = k[ClO
2
]
m
[OH
-
]
n
(1)
To find the orders (m and n):
Verbal: Going from Trial 1 to Trial 2, the (initial) [ClO
2
] doubles (0.05 M to 0.10 M) while the (initial) [OH
-
] is kept the same, and the (initial) rate goes up by (1.15 x 10
-1
M/s)/(2.88 x 10
-2
M/s) = 3.993 ~ 4 times.
That means the order of ClO
2
must be 2. In going from Trial 3 to Trial 2, the [OH
-
] doubles while the
[ClO
2
] is kept the same, and the rate also doubles (1.15 x 10
-1
M/s divided by 5.75 x 10
-2
= 2.00). That
means the order of OH
-
must be 1.
Brute Force Approach:
( )
m
k
k
R
R
2.00 4 ~
0.100
0.100
0.0500
0.100
3 9 3.9
M) (0.100 M) (0.0500
M) (0.100 M) (0.100
M/s 10 x 2.88
M/s 10 x 1.15
(1)
(2)
n m
n m
n m
2 -
-1
= |
.
|

\
|
|
.
|

\
|
= = =
2 = m
( )
n
k
k
R
R
2.00 2.00
0.0500
0.100
0.100
0.100
2.00
M) (0.0500 M) (0.100
M) (0.100 M) (0.100
M/s 10 x 5.75
M/s 10 x 1.15
(3)
(2)
n m
n m
n m
2 -
-1
= |
.
|

\
|
|
.
|

\
|
= = =
1 = n

Substituting into (1) with the two (now known) orders yields: (a) R = k[ClO
2
]
2
[OH
-
]

(b) To get the value of the rate constant, k, pick a trial and substitute in the values of R and
concentrations (along with the values of the orders). Here, Ill use Trial 1:
2.88 x 10
-2
Ms
-1
= k(0.0500 M)
2
(0.100 M)
1
M) (0.100 M) (0.0500
s M 10 x 2.88

2
-1 -2

= k
1 2 -
2
-1
115
) ( ) (
.2 5 11

=

= s M
M M
s M

(c) To get the initial rate for an experiment with [ClO
2
]
0
= 0.175 M and [OH
-
]
0
= 0.0844 M, just substitute into
the rate law (with k now known):
R = (115.2 M
-2
s
-1
)[ClO
2
]
2
[OH
-
] = (115.2 M
-2
s
-1
) (0.175 M)
2
(0.0844 M)
= 0.2977.. = 0.298 M/s

10. 13.44. The data below were collectted for a reaction represented by this equation:
CH
3
Cl(g) + 3 Cl
2
(g) CCl
4
(g) + 3 HCl(g)
Trial [CH
3
Cl]
0
(M) [Cl
2
]
0
(M) Initial Rate (M/s)
1 0.050 0.050 0.014
2 0.100 0.050 0.029
3 0.100 0.100
0.041
4 0.200 0.200 0.115

(a) Write an expression for the reaction rate law and calculate the value of the rate constant, k.
(b) What is the overall order of the reaction?
Answers:
(a) R = k[CH
3
Cl][Cl
2
]
1/2
;
k = 1.29 M
-1/2
s
-1

(b) 1.5
Answer Key, Problem Set 1
PS1-9
The rate law will be of the form:
Rate = k[CH
3
Cl]
m
[Cl
2
]
n
(1)
(a) To find the orders (m and n):
Verbal: Going from Trial 1 to Trial 2, the (initial) [CH
3
Cl] doubles (0.050 M to 0.100 M) while the (initial)
[Cl
2
] is kept the same, and the (initial) rate goes up by (0.029 M/s)/(0.014 M/s) = 2.07 ~ 2 times. That
means the order of CH
3
Cl must be 1. In going from Trial 2 to Trial 3, the [Cl
2
] doubles while the
[CH
3
Cl] is kept the same, and the rate goes up by (0.041 M/s divided by 0.029 =) 1.41 times. If one
notices that 1.41 is very close to
2
1
2 2 = it is clear that the order of Cl
2
must be .
Brute Force Approach:
( )
m
k
k
R
R
2.00 2 ~
0.050
0.050
0.0500
0.100
7 0 2.
M) (0.050 M) (0.0500
M) (0.050 M) (0.100
M/s 0.014
M/s 0.029
(1)
(2)
n m
n m
n m
= |
.
|

\
|
|
.
|

\
|
= = =
1 = m
( )
n
k
k
R
R
2.00 1.41
0.0500
0.100
0.100
0.100
1.41
M) (0.0500 M) (0.100
M) (0.100 M) (0.100
M/s 0.029
M/s 0.041
(2)
(3)
n m
n m
n m
= |
.
|

\
|
|
.
|

\
|
= = =
2
1
n 2.00
n
2
1
= = 2 (see below*)
*As will be shown in lab, one can also solve for n as follows:
( ) 0.5 46.. 9 0.4
31... 9 0.6
358... 4 0.3
ln(2.00)
ln(1.41)
ln(2.00) x ln(1.41) ln(2.00) ln(1.41) 2.00 1.41
n
~ = = = = = = n n
n

Substituting into (1) with the two (now known) orders yields: (a) R = k[CH
3
Cl][Cl
2
]
1/2


To get the value of the rate constant, k, pick a trial and substitute in the values of R and concentrations
(along with the values of the orders). Here, Ill use Trial 4 (just to get 3 SFs):
0.115 Ms
-1
= k(0.200 M)(0.200 M)
1/2
1/2
-1
M) M)(0.200 (0.200
s M 0.115

= k
1 1/2 -
1/2
-1
1.29
) )( (
57.. 8 1.2

=

= s M
M M
s M

(b) The overall order is 1 + = 1.5

11. NT4. State whether the statement is true or false AND IF FALSE, CHANGE A FEW WORDS TO MAKE IT CORRECT.
Note: I will ask a few questions like this on each of my exams! YOU MUST CORRECT ANY FALSE STATEMENT CORRECTLY
TO RECEIVE CREDIT ON AN EXAM FOR THESE!

(a) It is possible to change the rate constant for a reaction by changing the temperature.

TRUE (more discussion about this during Week 2).

(b) The reaction rate remains constant as a first-order reaction proceeds at a constant temperature.

FALSE. The reaction rate will continuously decrease as a reaction proceeds because the
concentrations of reactants will continuously decrease. It is the rate constant that remains constant
during any chemical reaction as long as the T is kept constant. Thus, two good ways to correct this
statement are:



Answer Key, Problem Set 1
PS1-10




OR



(c) The rate constant for a reaction is independent of reactant concentrations.

TRUE. Notice that most of these questions are forcing you to distinguish between rate and rate
constant. It is also important for you to distinguish both of these from rate law. The rate of reaction
varies with concentrations, but the rate constant does not vary with concentrations!






The reaction rate remains constant as a first-order reaction proceeds at a constant temperature.
The reaction rate remains constant as a first-order reaction proceeds at a constant temperature.
decreases
constant
OR heres yet a third way:
change first to zero !