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Kinetics Practice Problems

1. The document describes experiments determining the order of reactions based on plots of concentration vs time data. A plot of [NO2] vs time was not linear, showing the reaction was not zero order. A plot of ln[NO2] vs time was also not linear, showing the reaction was not first order. However, a plot of 1/[NO2] vs time was linear, indicating the reaction was second order in NO2. 2. Graphing integrated rate laws is an alternative to initial rate methods for determining reaction order from a single experiment by examining the characteristic shapes of concentration vs time plots. 3. Determining order from graphs is advantageous as it requires only data from one experiment rather than multiple initial rate

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Luke Meredith
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65 views

Kinetics Practice Problems

1. The document describes experiments determining the order of reactions based on plots of concentration vs time data. A plot of [NO2] vs time was not linear, showing the reaction was not zero order. A plot of ln[NO2] vs time was also not linear, showing the reaction was not first order. However, a plot of 1/[NO2] vs time was linear, indicating the reaction was second order in NO2. 2. Graphing integrated rate laws is an alternative to initial rate methods for determining reaction order from a single experiment by examining the characteristic shapes of concentration vs time plots. 3. Determining order from graphs is advantageous as it requires only data from one experiment rather than multiple initial rate

Uploaded by

Luke Meredith
Copyright
© © All Rights Reserved
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
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1. Consider the reaction AB, what is the order of the reaction and what is the rate expression?

[A] [B] Rate


Experiment
1M 1M 0.1
1
Experiment
1M 3M 0.1
2
Experiment
2M 1M 0.2
3

-1
Answer: Rate = 0.1 sec [A]. First-order.
Using Experiments 1 and 2, you should be able to figure out that the rate is independent of [B]
(B tripled, rate did not change). Using Experiments 1 and 5, you should see that the rate doubled
1 0
when [A] doubled. Thus the rate expression is Rate = k [A] [B] . To figure out k, plug this into
-1
experiment 1 to obtain: 0.1= k (1M), thus k = 0.1 sec .

2. For the reaction of NO and O2 at 660K,

2NO(g) + O2(g)2NO2(g)

[NO]
[O2] mol/L Rate disappearance of NO (mol/L*s)
mol/L
-5
0.010 0.010 2.5 x 10
-4
0.020 0.010 1.0 x 10
-5
0.010 0.020 5.0 x 10

a. Determine the order of reaction for each reactant. NO = second order, O2 = first order

2
2. Write the rate equation for the reaction. Rate = k[NO] [O2]
2 2
3. What is the rate constant? k = 25 L / mol *s
-4
4. What is the rate when [NO] = 0.025 M and [O2] = 0.05 M? rate = 7.8 x 10 mol/L*s
Nitryl fluoride is an explosive compound that is made by the oxidation of nitrogen dioxide with
fluorine. 2NO2(g) + F2(g)2NO2F(g)

[NO2] [F2] [NO2F]


mol/L mol/L mol/L
Rate disappearance of NO (mol/L*s)
-4
0.0010 0.0050 0.0020 2.0 x 10
-4
0.0020 0.0050 0.0020 4.0 x 10
-4
0.0020 0.0020 0.0020 1.6 x 10
-4
1.6 x 10
0.0020 0.0020 0.0010

1. What is the rate law for the reaction? Rate = k[NO2] [F2]
2. What is the order of the reaction with respect to each reactant and product? NO2 = 1, F2 =
1, NO2F = 0.
2 2
3. Calculate the rate constant k. k = 40 L / mol *s

-4
The reaction FClO2  FClO(g) + O(g) is first order with a rate constant of 6.76 x 10 /s at 322 C.

What is the half life of the reaction at 322 C?

3
a) 3.03 x 10 s.
-3
b) 1.03 x 10 s.
3
c) 1.03 x 10 s.

Answer/explanation:
-4 3
Half life (first order) = ln2/k = 0.693/6.76 x 10 /s = 1.03 x 10 s.

For the reaction in question 20: If the initial partial pressure of FClO2 (g) in a container at 322 C
is 0.040 atm, how long will it take to fall to 0.010 atm?
3
a) 2.06 x 10 s
6
b) 1.06 x 10 s

3
c) 103 x 10 s
Answer/Explanation: By noting that the final pressure is one-fourth the initial pressure, the
answer comes quickly. The pressure drops to half its original value in the first half life, and half
of that in the second half life.

3
Thus, the answer is two half lives, 2(t1/2) = 2.06 x 10 s.

You learned that the integrated rate law for each common type of reaction (zeroth, first, or
second order in a single reactant) can be plotted as a straight line. Using these plots offers an
alternative to the methods described for showing how reactant concentration changes with time
and determining reaction order. We will illustrate the use of these graphs by considering the
thermal decomposition of NO2 gas at elevated temperatures, which occurs according to the
following reaction:

2NO2(g)−→Δ2NO(g)+O2(g)(5.7.1)(5.7.1)2NO2(g)→Δ2NO(g)+O2(g)

Experimental data for this reaction at 330°C are listed in Table 5.7.15.7.1; they are provided as
[NO2], ln[NO2], and 1/[NO2] versus time to correspond to the integrated rate laws for zeroth-,
first-, and second-order reactions, respectively.

The actual concentrations of NO2 are plotted versus time in part (a) in Figure 5.7.15.7.1.
Because the plot of [NO2] versus t is not a straight line, we know the reaction is not zeroth order
in NO2. A plot of ln[NO2] versus t (part (b) in Figure 5.7.15.7.1) shows us that the reaction is
not first order in NO2 because a first-order reaction would give a straight line. Having eliminated
zeroth-order and first-order behavior, we construct a plot of 1/[NO 2] versus t (part (c)
in Figure 5.7.15.7.1). This plot is a straight line, indicating that the reaction is second order in
NO2.
Figure 5.7.15.7.1: The Decomposition of NO2. These plots show the decomposition of a sample
of NO2 at 330°C as (a) the concentration of NO2 versus t, (b) the natural logarithm of [NO2]
versus t, and (c) 1/[NO2] versus t.

We have just determined the reaction order using data from a single experiment by plotting the
concentration of the reactant as a function of time. Because of the characteristic shapes of the
lines shown in Figure 5.7.25.7.2, the graphs can be used to determine the reaction order of an
unknown reaction. In contrast, the method of initial rates required multiple experiments at
different NO2 concentrations as well as accurate initial rates of reaction, which can be difficult to
obtain for rapid reactions.

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