CHEMICAL KINETICS

Integrated Rate Equations for reactions of different orders :

 A 0 −  A 
Zero Order Reaction : k =
t
2.303 a
First Order Reaction : k = log
t (a − x )
EXERCISE

1. For the following reaction 2NO2=2NO+O2,write the expression of rate of reaction

Ans: – ½d(NO2)/dt=+1/2d(NO)/dt=+d(O2)/dt

2. What is the effect of temperature on activation energy?

Ans: There is no effect of temperature on activation energy.
3. For what type of reactions the rate constant shall have the same units as the rate of
reaction?
Ans: Zero order reaction.
4 Which will dissolve in water faster, powdered sugar or crystalline sugar and why?

Ans. Powdered sugar will dissolve in water faster as it has more surface area.

5. Which reaction takes place faster and why?

C(s) + ½O2 (g) → CO(g) at 500°C
C(s) + ½O2 (g)→CO(g)at1000°C
Ans: The second reaction is faster because increase in temperature increases the number
of effective collisions and hence increase in rate.

6. Identify the order of the reaction from the unit of rate constant:-Lmol1S-1
Ans. Unit of K=[1/conc]n-1S-1so,n=2, it is2ndorder.
7. Give the unit of rate constant of i) zero ii) 1storder iii) 2ndorder
reaction

Ans i) molL-1s-1 ii) s-1 iii)mol-1Ls-1

8. What will be the effect of temp on rate constant?

Ans. It is nearly doubled with 100 rise in temp. However exact dependence is given by
Arrhenius equation:-
K=Ae-Ea/RT

9. The rate law of the reaction 2NO+2H2=N2+2H2O is 1st order with respect to H2 and 2nd
order with respect to NO, write down the rate law for this reaction.

Ans. Rate=k[H2][NO]2

10. Name the factors influencing the rate of reaction.

Ans i) concentration of reactants ii) Temp of reactant iii) Nature of reactants

 iv) Exposure of radiation v) Catalyst

11. Give the difference between elementary and complex reaction.

Ans : If the molecularity of the reaction is sum of molecules of same or different reactant,
then it is called elementary reaction but if the reaction proceeds through more than
one step then it is called complex reaction.
12 What is a pseudo 1st order reaction? Give example.

Ans. Reaction whose actual order is different from that expected by using rate law
expression is called pseudo1st order reactions.
RCOOR/+H2O=RCOOH+R/OH follow 1st order kinetics. Rate=k[RCOOR/]

13 Give the difference between order and molecularity of the reaction.

Molecularity of the reaction Order of the reaction

1. theoretical concept 1.determined experimentally.
2.can have integral value 2. can have fractional value
3.cannot be zero 3.can be zero
4.does not tell about mechanism 4.slowest step in the mechanism is the clue of
of reaction mechanism

Ans.
14. What is the effect of positive and negative catalyst on the rate of the reaction.
Ans. Positive catalyst lowers the activation energy, thereby increase the rate of reaction
whereas negative catalyst increases the activation energy, and thereby decrease the
rate of reaction.
15. For a general reaction A ⎯→ B, plot of concentration of A vs time is given below
Answer the following question on the basis of this graph.
(i) What is the order of the reaction?
(ii) What is the slope of the curve?
(iii) What are the units of rate constant?

Ans: (i)Zero order (ii)Slope = − K (iii) mol L-1 s-1

16. Draw the plot of ln K vs 1/T for a chemical reaction. What does the intercept represent?
What is the relation between slope and Ea
Ans:-
17.. (i) From the expression
Rate = P ZAB e –Eq/RT explain the term P and ZAB
(ii) Define activation energy

Ans. (i) P →probability factor

ZAB →collision frequency (no. of particle colliding per sec per unit volume)
(ii) The minimum extra energy required by the reactant to cross the energy barrier.
18. Explain the following:-
(i)the reaction between H2(g) and O2(g) is highly feasible yet allowing the gases to
stand at room temperature in the same vessel does not lead to the formation of water.
(ii)rate of a reaction increase with rise in temperature.

Ans. (i) Activation energy for the reaction is very high at room temperature.
(ii)At higher temperatures, larger fraction of colliding particles can cross the energy
barrier (i.e. the threshold energy), which leads to faster rate.
19. Show that the time required for 99% completion is twice the time required for 90%
completion.

Ans. t = 2.303/k*log[A0]/[A]
t0.99/t0.90 = 2.303/klog102xk/2.3031/log10= 2
20. Time required to decompose SO2Cl2 to half of its initial amount is 60 min. If the
decomposition is a first order reaction, calculate the rate constant.

Ans:- t1/2 = 0.6931/k, k=0.6931/60x60 = 1.925x104 S-1

21. A gaseous hypothetical reaction 2A→ 4B+C is carried out in a closed vessel in 10 sec.
The concentration of B is found to increase by 5x10-3molL-1, calculate
i) rate of appearance of B ii)Rate of disappearance of A iii)Rate of reaction

Ans: i) Rate of appearance of B=5x10-3molL-1/10 = 5x10-4molL-1S-1

ii) Rate of disappearance of A=1/2x5x10-4 mol L-1S-1= 2.5x10-4 molL-1S-1
iii)Rate of reaction=¼ x rate of appearance of B = 1.25x10-4 mol L-1S-1
22. The amount of 6C14 isotope in a piece of wood was found to be 1/5th of that present in a
fresh piece of wood. Calculate the age of wood.t1/2=5577years.

Ans: t= [2.303t1/2]/0.693 x log[N0/N]

N=N0/5, t=12953years
23. The rate constant of a zero order reaction in A is 0.003 mol L-1sec-1 How long will it
take for the initial concentration of A to fall from 0.10M to 0.075 M ?
Ans:

24. The composition of a hydrocarbon follows the equation

K = (4.5 X1011 sec-1)e-28000K/T. Calculate the value of Ea

Ans:- 232.79 kJ/mol

25. The rate law for the reaction, 2Cl2O → 2Cl2 + O2 at 200OC is found to be :
rate = k[Cl2O]2
(i) How would the rate change if [Cl2O] is reduced to one-third of its original value?
(ii) How should the [Cl2O] be changed in order to double the rate?
(iii) How would the rate change if [Cl2O] is raised to threefold of its original value?
.
Ans (i) Rate equation for the reaction,
r = k[Cl2O]2
Let the new rate be r'; so
r' = k[(Cl2 O)/3]2 = 1/9 r
(ii) In order to have the rate = 2r, let the concentration of Cl2O be x.
So 2r = kx2 .... (i)
We know that r = k[Cl2O]2 .... (ii)
Dividing Eq. (i) by (ii),
2r/r = (kx2 )/(k[Cl2O]2 )
or 2 = x2/[Cl2O]2
or x2 = 2[Cl2O]2
or x = √2 [Cl2 O]
(iii) New rate = k[3Cl2O]2 = 9k[Cl2O]2 = 9r

26.

Hint:. Rate = K [A] [B]2 K = 6 L2 mol-2 S-1

27. For a reaction, the energy of activation is zero. What is the value of rate constant at 300
K if k = 1.6 106 s–1 at 280 K? (R = 8.31 J K–1 mol–1)

Ans

28. The following data were obtained during the first order thermal decomposition of
N2O5 (g) at constant volume. 2N2O5 (g) → . 2N2O4 (g) + O2
Calculate the rate constant.
Sl.No. Time(S) Pressure (atm)
1. 0 0.5
2. 100 0.512

Ans: Let the pressure of N2O5 (g) decrease by 2x atom . As two moles of N2O5 (g) and one
mole of
O2(g) the pressure of N2O4(g) increases by 2x atm and that of O2 increases by x atm.
2N2O5 (g) → . 2N2O4 (g) + O2
t=0 0.5 atm 0atm 0 atm
time (0.5 – 2x) atm 2x atm xatm
Pt = PN2O5 . + PN2O4 + PO2
= (0.5 – 2x) + 2x + x
= 0.5 + x
x = Pt – 0.5
 PN2O5 = 0.5 – 2x
= 0.5 – 2 (Pt – 0.5) = 1.5 – 2Pt
At , t = 100 s; pt = 0.512 atm.PN2O5 = 1.5 – 2 x 0.512 = 0.476atm.
Using: K = (2.303/t) log (Pt / PA)
K= 4.98x10-4s-1.

29. If the activation energy of a reaction is 80.9kJ/mol, calculate the fraction of molecules at
400 OC which have enough energy to react to form the products.

Ans :- Fraction of molecule which are active at a temperature is given as , =k/A= e-Ea/RT
log K/A =-Ea/2.303RT, K/A= 5.257x10-7

30. A first order reaction is 50% completes in 40 min at 300 K and in 20 minutes at
320 K. Calculate the activation energy of the reaction.

Ans.
K2 Eq  1 1 
log = −
K1 2.303R  T1 T2 
Eq  1 
 log(2) =
2.202 x 8.314  300 x 320 


0.693 / 20 Eq  1 1 
 log = −
0.693 / 40 2.202 x 8.314  300 320 
2.303 x 8.314 x 0.301 x 300 x 320
Eq =
20
= 27663 J / mol
= 27.6 KJ / mol