CL 101 – Practice Problem Set (Answers are in parenthesis after the problem)

Chemical Reaction Kinetics

1. Consider the following reaction: 2 NO( g ) + O2 ( g ) 2 NO2 ( g ) . At a particular instance
when the O2 concentration is decreasing at the rate of 0.2mol/litre.s, at what rate does the
concentration of NO2 change? [0.4mol/litre.s]
2. What is the order with respect to each of the reactant and overall order of the following
reactions?
a) 5Br − + BrO3− + 6H + → 3Br2 + 3H 2O (a liquid-phase reaction)
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The experimental rate law is: k  Br −   BrO3−   H + 
b) CH 3CHO → CH 4 + CO2 (a gas-phase reaction)
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The experimental rate law is: k CH 3CHO2 [a) 1 + 1 + 2 = 4; b) 1.5]
3. The rate law for a reaction involving A, B and C has been found to be:
rate = k[ A]2 [ B][C ]1.5 . How would the rate of reaction change when (i) Concentration of
[C] is quadrupled [4 times]; (ii) Concentration of both [A] and [B] are doubled [8 times]
4. The rate of the reaction X + 2Y → Z is 4 10−3 mol.litre−1.s −1 if
 X  = Y  = 0.2M (= mol / litre) and the rate constant is 2 10−2 s−1 . What is the overall
order of the reaction? [1.0]
5. A first order reaction takes 8 hours for 90% completion. Calculate the time required for
80% completion. [5.6hrs]
6. The rate constant for a first order reaction is 1.54 ×10 -3 s-1. Calculate its half life time.
[450s]
7. The half-life of a first order reaction X → Y + Z is 6.932 104 s . What percentage of X
would be decomposed on heating at 5000K for 100min? [5.6%]
8. Show that in case of first order reaction, the time required for 99.9% completion is nearly
ten times the time required for half completion of the reaction.
9. The rate constant of a reaction at 400 and 200K are 0.04 and 0.02s-1 respectively.
Calculate the value of activation energy. [2305 J.mol-1]
10. The rate constant ‘k’ of a reaction varies with temperature T according to the following
Arrhenius equation. When a graph is plotted for log k vs. 1/T a straight line with a slope
of – 4000K is obtained. Calculate the activation energy. [76.6 kJ mol-1]
11. The rate of formation of a dimer A2 from the monomer A in a second order reaction
2A → ( A)2 is 7.5 × 10-3 mol. litre-1.s-1 at 0.05 mol. litre-1 monomer concentration.
Calculate the rate constant. [3.0 mol.litre.s-1]
12. The decomposition of Cl2O7 at 500K in the gas phase to Cl2 and O2 is a first order
reaction. After 1 minute at 500K, the pressure of Cl2O7 falls from 0.08 to 0.04 atm.
Calculate the rate constant in s-1. 1.153×10-2 s -1 
13. A gas phase reaction has energy of activation 200 kJ.mol-1. If the frequency factor (k0) of
the reaction is 1.6 × 1013s-1. Calculate the rate constant at 600 K. 6.21×10-5 s -1 
14. For the reaction 2X + Y → Z , find the rate law and the rate constant from the following
data:
 X  (mol.litre-1) Y  (mol.litre-1) Reaction Rate(mol.s-1)
0.2 0.02 0.15

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 0.4 0.02 0.30
0.4 0.08 1.20
 Rate = k  X Y  ; k = 37.5mol -1 .litre.s -1 
15. The half-life of the homogeneous gaseous reaction SO2Cl2 → SO2 +Cl2 which obeys first
order kinetics is 8.0 minutes. How long will it take for the concentration of SO2Cl2 to be
reduced to 1% of the initial value?  52.93min 
16. The time for half change in a first order decomposition of a substance A is 60 seconds.
Calculate the rate constant. How much of A will be left after 180 seconds?
0.01155s -1 ; 12.5% 
17. A zero-order reaction is 20% complete in 20 minutes. Calculate the value of the rate
constant. In what time will the reaction be 80% complete? 1.0mol.s -1 ; 80min 
18. Benzene diazonium chloride in aqueous solution decomposes according to the equation
C6 H 5 N 2Cl → C6 H 5Cl + N 2 . Starting with an initial concentration of 10 g.litre -1, the
volume of N 2 gas obtained at 50°C at different intervals of time was found to be as under:
t (min) 6 12 18 24 30 
Gas volume (ml) 19.3 32.6 41.3 46.5 50.4 58.3
Show that the above reaction follows the first order kinetics. What is the value of the rate
constant?  0.0676 min -1 
19. From the following data, show that the decomposition of hydrogen peroxide is a reaction
of the first order:
t (min) 0 10 20
Volume (ml) 46.1 29.8 19.3

Where t is the time in minutes and V is the volume of standard KMnO4 solution required
for titrating the same volume of the reaction mixture.  k = 0.0435 min -1 
20. Consider a first order reaction in which the reactant concentration decays by 40% in
50min. How much time is needed for the concentration to decay by 80%. 157.6 min 

Thermodynamics
21. 5000J of heat are added to 2 moles of an ideal monoatomic gas initially at a temperature
of 5000K, while the gas performs 7500 J of work. What is the final temperature of the
gas? The specific heat CV = 1.5R, where R = the universal gas constant = 8.314 J / mole
0
K. [4000K]
22. Compute the internal energy change and temperature change for the two processes
involving 1.0mole of an ideal monoatomic gas (CV = 1.5R): (a) 1500J of heat are added
and gas does no work; (b) 1500J of work are done by the gas and no heat is added [(a)
1500J, 1200K, (b) 1500J, 1200K]
23. 2.5 kJ of work must be delivered isobarically on a rod from a piston/cylinder containing
air at 500 kPa. What is value of diameter cylinder is needed to restrict the rod motion to
maximum 0.5 m? [0.113 m]
24. A gas initially at 1 MPa, 500°C is contained in a piston-cylinder arrangement of initial
volume of 0.1 m3. The gas expanded isothermally to a final pressure of 100 kPa.
Determine the work. [230.3 kJ]

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25. A cylinder has 0.1kg of air with a 5 kg piston on top. A valve at the bottom of cylinder is
opened to let out the air out and the piston (diameter = 2.5cm) drops by 0.25m. What is
the work involved in the process? [– 0.0245kJ]
26. A chiller cools liquid water (Sp. Ht = 4.2 J/gmK) for air-conditioning purposes. Assume
2.5 kg/s water at 20oC and 100 kPa is cooled to 5oC in a chiller. How much heat transfer
(kW) is needed? [156.75 kW]
27. A piston/cylinder contains 0.001 m3 air at 300 K, 150 kPa. The air is now compressed in a
process in which PV12.5 = Constant, to a final pressure of 600 kPa. Find the work
performed by the air and the heat transfer. [W = -0.192 kJ, Q = -0.072 kJ]
28. Assuming the validity of Raoult’s law for vapour liquid equilibrium, i.e.,
yi P = xi Pi sat , ( i = 1,.....N ) , do the following calculations for a benzene (1) / toluene (2)
vapour-liquid system:
a) Given x1 = 0.33 and T = 100oC, find y1 and P [P= 109.12kPa, y1 = 0.545 ]
b) Given y1 = 0.33 and T = 100oC, find x1 and P [P = 92.04kPa, x1 = 0.169 ]
c) Given T = 105oC and P = 120kPa, find x1 and y1[x1 = 0.33, y1 = 0.485]
d) For part (c) if the mole fraction of benzene averaged across the vapour and liquid
phases is 0.3685, what molar fraction of the system is vapour? Assume that between
the vapour and liquid phases there is a total of 1.0moles. [0.231]
The Antoine equations for the two liquids are:
2726.81 3056.96
ln P1sat (kPa) = 13.7819 − 0 ; ln P2sat (kPa) = 13.9320 − 0
t ( C ) + 217.572 t ( C ) + 217.625

Dimensional Analysis
29. A fluid is flowing past a solid body. The force ‘F’ exerted on the body by the fluid is a
function of the fluid velocity u, the fluid density ρ, the fluid viscosity µ, and the diameter
of the body d. By dimensional analysis obtained the dimensionless groups formed from
the variables given. Use the π-theorem and the M, L, T system of units, and select u, ρ
and d as the fundamental variables.
 F / d2 du  
 1 =  u 2 ;  2 =  
 
30. A drop of liquid spreads over a horizontal surface. We want to obtain the dimensionless
groups of the variables which will influence the rate at which the liquid spreads. The rate
at which a drop spreads, say u R m/s, will be influenced by:
• viscosity of the liquid (µ-dimensions) = ML-1T-1
• volume of the drop (V-dimensions) = L3
• density of the liquid (ϼ-dimensions) = ML-3
• acceleration due to gravity, g-dimensions = LT-2
• and surface tension of the liquid, σ-dimensions = MT-2.
Noting the dimensions of u R as LT-1, there are six variables and hence, (6-3) = 3
dimensionless groups. Taking V, ϼ and g as the recurring set show that the following relation
uR2  µ2 n1     
n2

obtains for function of uR: 0.33 =   2    

(V g )  g  V    g V 0.67  
Hint: Since V, ϼ and g are the recurrent variables the fundamentals M, L and T need to be
expressed as function of these three recurrent variables. Following that the remaining
variables apart from the recurrent ones may be expressed in terms of the recurrent ones.
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