Assignment III

Effect of Temperature on Rate of Reaction

1. What factors determine whether a collision between two molecules will lead to a
chemical reaction?
2. According to collision theory, why does temperature affect the value of rate constant?
3. Find the activation energy (in kJ/mol) of the reaction if the rate constant at 600K is
3.4 M-1s-1 and 31.0 at 750K.
4. Find the rate constant if the temperature is 289K, Activation Energy is 200kJ/mol and
pre-exponential factor is 9 M-1s-1.
5. Find the new rate constant at 310K if the rate constant is 7 M -1s-1 at 370K, Activation
Energy is 900kJ/mol.
6. Calculate the activation energy if the pre-exponential factor is 15 M-1s-1, rate constant
is 12M-1s-1 and it is at 22K.
7. Find the new temperature if the rate constant at that temperature is 15M -1s-1 while at
temperature 389K the rate constant is 7M -1s1, the Activation Energy is 600kJ/mol.
8. The activation energy for the isomerzation of cyclopropane to propane is 274kJ/mol.
By what factor does the rate of reaction increases as the temperature rise from 500C
to 550C?
9. The activation energy for the isomerisation of methyl isonitrile is 160kJ/mol.
Calculate the fraction of methyl isonitrile molecules that have an energy of 160kJ or
greater at 500K and 510K. Compare the results by calculating the ratio at these two
temperatures.
10. The gas phase reaction between methane and diatomic sulphur was studied at 550C.
The relevant data are shown in the following table:
T, C k, M-1s-1
550 1.1
625 6.4
What is the value of rate constant at 600C?
11. The rate constant for gas phase decomposition of dinitrogen pentoxide has the
following temperature dependence:
T,(K) 338 318 298
-1
k,sec 0.0049 0.0005 0.000035
Using graphical method, determine the activation energy for the reaction. Show
enough work so I know that you know what you are doing.
12. A second order reaction 2HI  H2 + I2 (gas phase reaction) is studied over a range of
temperatures. The results obtained are given below:
Temp, K 633 666 697 715 781
Rate 1.78x10-5 1.07x10-4 5.01x10-4 1.05x10-3 1.51x10-2
constant (k)
conc.-1 sec-1
(a) use the data given to determine the activation energy for the reaction. (b)
determine by what factor the rate increases when the temperature rises from 300K to
310K. (c) calculate the kinetic energies of fixed mass of a gas at 310K and 300K
13. For the reaction H2 + Cl2 2HCl + Heat, which way would the equilibrium shift if
heat is added from the outside source? What does this do to the Keq?
14. The rate of the reaction CH3COOC2H5 + OH-  C2H5OH + CH3COO- was
measured at several temperatures and the following data were obtained:
T,C 15 25 35 45
-1 -1
k, M s 0.0521 0.101 0.184 0.332
 Using these data, determine the value of activation energy. Compare your result with
the activation energy obtained from two data point method.
15. For the reaction N2O4 + heat  2NO2, which way would equilibrium shift if heat is
added from the outside source? What does this do to Keq?
16. The temperature dependence on the rate constant for a reaction is tabulated as
follows:
T,C 600 650 700 750 800
-1 -1
k, M s 0.028 0.22 1.3 6.0 23
Calculate activation energy and frequency factor by graphical method.
17. For questions 13 and 15, what will happen when heat is removed from the each of the
reactors?
18. The decomposition of NO2 follows a second order rate equation. Data at different
temperature are as follows:
T(K) 592 603 627 651.5 656
k(cc/mol.sec) 522 755 1700 4020 5030
Compute the activation energy and frequency factor.
19. The rate constants of a reaction are 1.6x10-3 and 1.625x10-2 sec-1 at 10C and 30C
respectively. Calculate the activation energy.
20. Calculate G# for a dimerization reaction at 326C having k = 1.42x10-2 lit.mol-1 sec-1.
21. The reaction C2H5Cl  C2H4 + HCl is studied over a range of temperatures. A series
of typical results is given below:
Temp,C 410 420 430 440 450 460 470 480
4 -1
10 xk, s 0.264 0.483 0.868 1.54 2.685 4.61 7.80 13.0
Calculate the value of activation energy and frequency factor.
22. Calculate the rate of reaction and rate constant at 700K and 1atm pressure for the
decomposition of HI assuming its collision diameter is 350pm.
23. The frequency of decomposition of ethyl vinyl ether is 2.7x1011 sec-1. Calculate the
entropy of activation at 530C.
24. The activation energy and frequency factor for a reaction A2 + B2  2AB are 15.5
mol-1 and 10.9x1010 dm3 mol-1sec-1, respectively. Calculate the value of H# and S#
at 1000K.
25. The value of S# for a reaction has been obtained as -80.5 Jk-1 mol-1 at 400K. Find the
value of A for the reaction.
26. The pre exponential terms for a bimolecular gas reaction occurring at 350C are
8.0x1010 dm3 mol-1 sec-1. Calculate the entropy of the activation.
27. The plot of log k vs 1/T i.e. Arrhenius plot was liner with a negative slope 4.5x10 3
and the intercept equal to 11.90 for a reaction. Calculate the value of activation
energy, frequency factor and S#.
28. What is the activation energy of a process which is observed to increase by a factor of
three (3) when the temperature is increased from room temperature (20°C) to 40°C?
29. A first order chemical reaction is found to have an activation energy (EA) of 250
kJ/mole and a pre-exponential (A) of 1.7 x 1014 s–1.
(a) Determine the rate constant at T = 750°C.
(b) What fraction of the reaction will be completed at 600°C in a period of 10
minutes?
(c)At what temperature will the reaction be three times as fast as at 750°C?
30. The “diffusion constant” (D) in diffusion processes corresponds to a rate constant (k).
At what temperature (in °C) will a diffusion constant (D) be 5 x 10 –11 (cm2/s)? (Given
are EA = 315 kJ/mole and Do, the pre-exponential, equals 1.70 cm2s–1.)
31. A French publication gives the following experimental data for the catalytic
decomposition of urea:

T°C: 147.5 131.5 160.5 139.5

–1 –3 –3 –3
k1 (min ): 2.44x10 5.00x10 10.57x10 31.5x10–3
What is the activation energy (EA) for this reaction?
32. In rate studies it is convenient for data analysis to use graphic presentations of the
variables (for example, c and t or k and T). In each of the following expressions, x and
y are variables and other terms are constants. What function of x and what function of
y would you plot in each case to achieve a straight line presentation?
(1) ax = by +c
(2) x = Ae–y/RT
(3) xy = ax + by
33. What activation energy (EA) is required to cause a reaction rate to increase by a factor
of 3 for a 10°C temperature rise at: (a) 300K? (b) 1000K?
34. Consider the decomposition of NO2. 2NO2(g) 2NO(g)+O2(g) at 650K, the rate
constant is 1.66sec-1 and at 750K is 7.39sec-1. Calculate activation energy.
35. A reaction rate doubles when the temperature increases from 25C to 40C. Calculate
activation energy.
36. Determine the activation energy for a reaction from experimental data given below for
first order rate constant of a particular organic compound with water with
temperature:
T,K 300 320 340 355
-1 -11 -9 -8
k,sec 3.2x10 1x10 3.0x10 2.4x10-7
Calculate activation energy and frequency factor. What is the value of rate constant
for this reaction at 400K?
37. A substance (X) decomposes into A and B in parallel paths with rate constants given
by:
kA = 1015 e–(125,000/RT)
kB = 1013 e–(83,600/RT)
At what temperature will the two products be formed at the same rate?
38. A chemical first order reaction is found to be half-completed after 100 s at 300°C and
after 20 s at 500°C. What is the activation energy (E A) for the reaction (in J/mole)?
39. For a chemical reaction the following k values were obtained at the indicated
temperatures:
T°C: 0 25 35 45
k (s–1): 1.06x10–5 3.19x10–4 9.86x10–4 2.92x10–3
What is the pre-exponential factor (A) of the Arrhenius equation?
40. It is frequently stated that, for chemical reactions proceeding at room temperature, the
rate increases by a factor of two (2) upon temperature rise of 10°C. Assuming this
statement to be reasonable, what would be the activation energy (EA) of such
chemical reactions?
41. Consider a series of reaction having the following energy profiles: Assuming that all
three reactions have nearly same frequency factor, rank the reaction from slowest to
fastest.
 42. A chemical reaction has a rate constant (k) of 9.3 x 10 –6 per second at 350K and of 6.9
x 10–4 per second at 400K.
(a) Determine the activation energy (E A) for this reaction.
(b) Determine the rate constant for 450K.
43. A first order chemical reaction is found to have an activation energy (E A) of 250
kJ/mole and a pre-exponential (A) of 1.7 x 1014 s–1.
(a) Determine the rate constant at T = 750°C.
(b) What fraction of the reaction will be completed at 600°C in a period of 10
minutes?
(c) At what temperature will the reaction be three times as fast as at 750°C?
44. If a first order reaction has activation energy of 104 kJ/mole and a pre-exponential A
of 5 x 1013 s–1, at what temperature will the reaction have a half-life of:
(a) one (1) minute? (b) one month of 30 days?
45. A first order reaction has an activation energy (E A) of 120 kJ/mole and a pre-
exponential factor (A) of 6 x 1012 s–1. At what temperature will the reaction have a
half-life (t1/2) of 30 days?
46. The following data is provided for the rate constant for the hydrogenation of ethylene
on a copper based catalyst. The rate expression is rate=kPH2. The units of the rate
constant are mol/s/atm/cm3. The activation energy is known to be 12837cal/mol and
the pre exponential is 2561 mol/s/atm/cm3, based on another experimental study.
Perform the analysis to determine if the data is consistent with these values.

Fill In the blanks

1. The rate of most chemical reactions ___ as the temperature rises.
2. How is this experimentally observed temperature effect reflected in the rate
expression? The _____ rate at ______ temperature is due to an _________ in the rate
constant with increasing temperature.
3. The rate constant, and hence the rate of reaction, increases rapidly with temperature,
approximately_____________ for each 10 degree rise.
4. The central idea of the collision model is that molecules must_________ to react. The
____________ the number of collisions occurring per second, the ___________ the
reaction rate.
5. As the ____________ of reactant molecules increases, the number of collisions
increases, leading to an ___________ in reaction rate.
6. Increasing temperature increases molecular__________. As molecules move faster,
they collide more___________ and more __________ increasing the reaction rate.
7. For most reactions, only a tiny fraction of the ______________ lead to reactions.
8. In most reactions, molecules must be ___________ in a certain way during collision
in order for reaction to occur.
9. Indeed, a great many collision do not lead to reaction, merely because the molecules
are not_____________.
10. The minimum amount of energy required to initiate a chemical reaction is
called _____________.
11. Define: activated complex or transition state.
12. The fraction of molecules that has an energy equal to or greater than the
activation energy is given by__________
13. Arrhenius noted that for most reactions the increase in rate with increasing
temperature is ______________ (Liner/non linear).
14. Arrhenius found that most reaction rate data obeyed an equation based on
three facts:___ , ____ and ____.