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# Course: Physical Chemistry II

Semestre 2018-1
Exercises Guide. Unit 4

Unit 4. Chemical Kinetics

1. Because it has a nonpolluting combustion product (water vapor), hydrogen gas is used for fuel aboard the
space shuttles and in earthbound cars with prototype engines:
a. Express the rate in terms of changes in [H2], [O2], and [H2O] with time.
b. When [O2] is decreasing at 0.23 mol/dm3 s, at what rate is [H2O] increasing?

2. At a particular temperature, two gases, A (red) and B (blue), react to form products. The following molecular
scenes represent four experiments run at the same volume, labeled 1 through 4 with their initial rates (in
mol/dm3.s):

a. What is the reaction order with respect to A? With respect to B? The overall order?
b. Write the rate law for the reaction.
c. Predict the initial rate of experiment 4.

3. The following data is recorded for the reaction: NOBr (g) → NO2 (g) + ½ Br2 (g)
Demonstrate that this reaction corresponds to a second-order reaction in the concentration of NOBr. Find
the values for rate constant and the half-life.
t (s) 0 6.2 10.8 14.7 20.0 24.6
[NOBr] (mol/dm3) 0.0250 0.0191 0.0162 0.0144 0.0125 0.0112

4. The rate law for the reaction described by N2O2 (g) → 2 NO (g)
is first order in the concentration of N2O2 (g). Derive an expression for the time dependent behavior of [NO],
the product concentration.

5. At 325ºC NO2 (g) reacts with CO (g), according the reaction: NO2 (g) + CO (g) → NO (g) + CO2 (g)
For determine the expression of the rate of law some experiments are developed. In the first one the initial
concentration of CO is varied, keeping the concentration of NO2 constant. In that case is found that the rate
of generation of products is independent of the changes. In another experiment, NO2 is made to absorb light
of a certain frequency, which allows the experimentalist to calculate the NO2 concentration from intensities
of absorption. The results obtained are the following:
t (s) 0 10 20 30 40 50
[NO2] (mol/dm3) 0.200 0.134 0.100 0.080 0.066 0.058
Find the expression of rate law and calculate the rate constant.

8.2 3.79 0. At 1000ºC.s) I 0. 8.6 1. If the initial C4H8 concentration is 2.25 0. For the reaction: 2 NOCl (g) → 2 NO (g) + Cl2 (g) were measured the following initial rates for different initial concentration of NOCl at 27ºC Run [NOCl] (mol/dm3) vo (mol/dm3.44 x10-8 III 0.674x10 4. What fraction of C4H8 has decomposed in this time? 7.3 3.2 3.s) I 0. a.76 1. what is the concentration after 0. The reaction between carbon disulfide and ozone: CS2 (g) + 2 O3 (g) → CO2 (g) + 2 SO2 (g) was studied using a large excess of CS2.458x10 9.52 0.00 M. with the very high rate constant of 87 s-1.37 0.50 0. The acid-catalyzed hydrolysis of an organic compound A at 30ºC has a half-life of 100 min when carried out in a buffer solution of pH=5 and 10 min when it occurs at pH=4.24 x10-8 Determine the order of reaction and the rate constant. Both half-life times are independent of the initial concentration of A. If the expression of rate law is : 𝑣 = 𝑘 𝐴 ! 𝐵 ! calculate the values for α.24 x10-8 6.60x10-9 II 0.Course: Physical Chemistry II Semestre 2018-1 Exercises Guide. β and k.50 0. The following data were obtained for the reaction N2O (g) → N2 (g) + ½ O2 (g) -3 -3 [N2O] 1.60x10-9 II 0.04 0. for the reaction 2 NO (g) + H2 (g) → N2 (g) + H2O (g) at a given temperature were measured the following initial rates for different initial concentrations of NO and H2 Run [NO] [H2] vo (mol/dm3) (mol/dm3) (mol/dm3.300x10-3 1.9 3.010 s? b. The pressure of ozone as a function of time is given in the following table.155x10-2 (mol/dm3) t1/2 (s) 1200 470 230 190 Assume the rate law for this reaction is: . to two molecules of ethylene (C2H4).44 x10-8 III 0. Unit 4 6. Is the reaction first order or second order with respect to ozone? t (s) 0 30 60 120 180 240 PO3 (torr) 1.29 7. Now.1 1. cyclobutane (C4H8) decomposes in a first-order reaction.

Starting with a sample of the pure cis isomer with [cis]o = 0. 9. At 25ºC. the equilibrium constant is 0. Calculate the rate for this decomposition reaction. The reaction cis-2-butene to trans-2-butene is first order in both directions.Course: Physical Chemistry II Semestre 2018-1 Exercises Guide.406 and the forward rate constant is 4. how long would it take for half the equilibrium amount of the trans isomer to form? . Unit 4 𝑑[𝑁! 𝑂] − = 𝑘 𝑁! 𝑂 ! 𝑑𝑡 and determine the reaction order of N2O (by plotting ln(t1/2) against ln([A]o).21 x 10-4 s-1.115 mol·dm-3.