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Kinetics Problems

May 2012
Problem 4
Consider the gas phase reaction:

A+B→C

which is catalyzed by a solid catalyst and follows dual-site (both A and B adsorb)
Langmuir-Hinshelwood kinetics.
1) Write a reaction mechanism that accounts for all elementary steps involved in the
dual site catalytic cycle.
2) Derive the expression of the reaction rate for A, the limiting reactant, assuming the
surface reaction is the rate-determining step. Your expression should be in terms of the
partial pressures of each species, equilibrium constants, and temperature-dependent
rate constants. You must explicitly and clearly define any equilibrium or rate
constants you use.

Problem 6
Equilibrium data has been obtained for the reaction:
A(g) + 2B(g) = 2C(g)
with a stoichiometric feed of A and B. At 200°C and 1 bar, 25 mol % of the species in
the reactor was product C. At 300°C and 1 bar, 53.9% C was produced.
A) One mole of A and 2 moles of B react at 250°C and 2 bar. Based on the data
above, estimate the concentrations at equilibrium. Clearly state any reasonable
assumptions that you need to make to solve the problem.
B) As a process engineer, you wish to maximize the production of C. As completely as
you can, discuss the implications of the following strategies:
i. Increase temperature
ii. Increase pressure
iii. Add an inert to the feed stream

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Kinetics Problems

Problem 8
The following data were reported for a gas-phase constant volume decomposition of
dimethyl ether at 504°C in a batch reactor. Initially, only (CH3)2O was present.
Time(s)
Total Pressure (mm Hg)

390
408

777
488

1195 3155 ∞
562 799 931

It is known that the reaction (CH3)2O → CH4 + H2 + CO is first-order and goes to
completion.
A) What is the pressure at the start of reaction?
B) From the data provided, determine the reaction rate constant.

January 2012
Problem 3
Consider the following constant-volume liquid-phase complex reactions:
A→B ; (rB) = 1

mol/liter/hr

A→C ; (rC) = 2CA

mol/liter/hr

A→D ; (rD) = CA2

mol/liter/hr

The reaction is taking place in an ideal isothermal PFR and the initial concentration of A is 1 M
(no other chemical species are present initially). B is the desired product.
(a) Find the size of the PFR for 90% conversion of A if the flow rate Q =10 L/hr.
(b) What is the minimum and maximum instantaneous selectivity for B? Identify
conditions that correspond to the minimum and maximum instantaneous selectivity.
(c) Your boss thinks that the maximum concentration for B is 0.67 M under the condition
given above. Prove or disprove him. Provide detailed calculations.

2

Kinetics Problems

Problem 4
A certain type of chemical sensing device consists of a thin film of a porous inorganic material
grown on an impermeable quartz support. When the top surface of the film (of thickness L) is
initially exposed to a concentration (Co) of an analyte chemical A, the molecules of A diffuse
(with diffusivity D) into the porous film and increase its total mass as a function of time. The
change in mass is measured by vibrating the quartz substrate at high frequencies to determine its
resonance frequency, which depends on the total mass of the film on top of it. The film is
initially empty (it does not contain any molecules of A). The sensor response is considered
reliable when the spatially-averaged concentration of molecule A in the film reaches 50% of its
maximum possible value (Co).
(1) Write down the differential equation for the concentration of A at any location in the sensor and
at any time. Your answer must be a dimensionless differential equation with the dimensionless
variables and parameters clearly defined.
(2) Write the initial and boundary conditions accompanying this differential equation.
(3) Two different sensors of this type are available. Sensor I has a film of thickness 10 microns (1
micron = 10-6 m) of a material in which the diffusivity of A is 2×10-11 m2/s, whereas Sensor II
has a film of thickness 20 microns and is made of a material in which the diffusivity of A is
1×10-10 m2/s. Determine which sensor has a faster response.
(4) From the solution of the partial differential equation, it can be shown that the spatially-averaged
concentration of A in the film is given by:

  D(2n  1) 2  2t 
C (t )
8
 1 
exp

 , (n  0, 1, 2 ,...)
2 2
2
Co
(2
n

1)

4
L
n 0

If a reliable response is required in 2 seconds for a particular application, will the faster sensor
identified in Part (3) above be suitable for use? Neglect all terms with n > 1.

3

Kinetics Problems

Problem 7
You are studying an irreversible reaction between two materials A and B that produces your
desired product P. In order to design a reactor for this system you need to determine the rate law
(i.e. evaluate the reaction orders for A and B) and rate constant for the reaction. Your assistant
goes into the lab and runs a series of batch reactions for this process, i.e. they mix eight solutions
containing varying amounts of A and B (see Table 1 below for the concentrations of A and B at
time zero), quench the reactions after allowing each mixture to reaction for 10 seconds, and
spectroscopically measures the amount of product P in the solution after the 10 second reaction
period.
Table 1: Reaction experiment data. All concentrations given in moles/liter units (i.e. [M]).

Run #

[A]0

[B]0

[P] after 10 seconds reaction

1

0.037

0.133

0.0007

2

0.037

0.200

0.0016

3

0.185

0.133

0.0034

4

0.185

0.266

0.0118

5

0.278

0.200

0.0100

6

0.278

0.300

0.0209

7

0.370

0.133

0.0061

8

0.370

0.266

0.0216

Determine an appropriate expression for the rate law (i.e. determine an expression to calculate
d[P]/dt for a given concentration of A and B) and determine the rate constant for this rate law.
Clearly explain how you arrive at your answers to receive full credit.

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k2’. qv is the fraction of unoccupied surface sites on the catalyst. and k3) and the gas phase concentration of R (i. 5 . and surface reactions as follows: [ ] where [R] is the gas phase concentration of R. qRs is the fraction of surface sites occupied by R.e. k1’. qPs is the fraction of surface sites occupied by P unoccupied surface sites on the catalyst. derive an expression for the rate of formation of product P in terms of only the various reaction rate constants (i. We will treat these as “elementary reactions” with the rate constants for the reactions given as shown above. desorption. k2. In a manner similar to Langmuir. [R]). One can represent such a process using the following “reaction” scheme description which includes both expressions for chemisorptions and desorption and the surface reaction. It is known that the product molecule once desorbed has very limited propensity to chemisorb back onto the surface. If you assume that the rate limiting step in this sequence is the desorption of the product P from the catalyst surface. ANSWER THE FOLLOWING QUESTION: 1.e. we can write expressions for the rates of chemisorption.Kinetics Problems May 2011 Problem 3 You are interested in studying a surface reaction in which a reactant molecule (R) in the gas phase chemisorbs onto a catalytic surface and then combines with another chemisorbed reactant molecule on the surface in a dimerization reaction to produce a product molecule (P) which can then desorb from the catalytic surface. → → (1) (2) → (3) → (4) → (5) Here s represents a surface site where a molecule can be chemisorbed on the surface. k1.

6 L/min c(t) kg S/L Tank 2 (a) Solve for an expression giving the total volume of solution in Tank 1 as a function of time t. shown below.2 kg S/L is fed to the tank at a constant rate of 10 L/min. will it overflow before the concentration in Tank 1 gets to 0. Assume that the contents of both tanks are well mixed and the volume of the sucrose is negligible (and therefore the density of sucrose solution is the same as pure water). Fresh sucrose solution with a concentration of 0. (b) Solve for an expression giving c(t). does not overflow 6 . initially contains 200 L of a sucrose/water solution with a sucrose (S) concentration of 0.25 kg S/L. Concentrated sucrose solution is drained into Tank 2 (which is initially empty) at a rate of 6 L/min. (c) If Tank 2 can hold 200 L of liquid.Kinetics Problems Problem 4 Tank 1.25 kg S/L Tank 1 Conc. Soln. the concentration of sucrose in Tank 1 as a function of time t. Water is evaporated from Tank 1 at a rate of 4 kg/min. V1(t). 4 kg/min water evaporated Fresh feed 10 L/min 0. V2 = _________ L ____ yes.3 kg/L? Must show V2 volume as > or < 200 L to get credit.2 kg S/L At t = 0: V1 = 200 L c = 0. overflows _____ no.

A+B==C+D The reaction r = 0. The reaction is operated at 1 atm.2 CA.K-1 (assume constant over relevant temperature range) Cp’I = 40 J.mol-1. (mol/L/min). An irreversible reaction proceeds as follows.04 mol L is added at 1 L/min. 7 . The initial temperature is 400 K.K-1 (assume constant over relevant temperature range) Cp’B = 50 J. Determine: 1.min-1 a) Which temperature will the exit stream have? b) Which reactor volume is required to reach the desired conversion? If you did not find an exit stream temperature in part a) use 525 K for this part. What is the concentration B when the reactor volume doubles to 800 L? Problem 8 The first order gas phase reaction A  B is performed in an adiabatically operated CSTR. How do you have to adjust the feed stream to achieve this? The pressure and volume flow are remaining constant. A conversion of 90% is desired.K-1 (assume constant over relevant temperature range) ΔHr = -80 kJ.mol-1. c) For safety reasons it is decided to limit the temperature in the reactor to 500K. and the gas stream consists of 10% A and 90% inerts (I).mol-1 (assume constant over relevant temperature range) v0 = 20 L. Assume ideal gas behavior.Kinetics Problems Problem 5 To a well-stirred tank (with initial volume of 400L) containing 40 mol of B a stream of a at 0. How long will it take to exhaust B? 2. The following information is known: Cp’A = 50 J.mol-1.

What space time is needed to achieve 80% conversion of B? Problem 7 Write the series of elementary reaction steps that is consistent with the following surface reaction limited. An aqueous mixture containing A & B (CAo= 0.003 min-1. How many surface sites are involved in the rate-limiting step? 8 .2 mol/l).Kinetics Problems January 2011 Problem 1 The liquid phase reaction A + B → C is observed to be first order in A and zero order in B. Note. Langmuir Hinshelwood kinetic rate equation. the rate constant is 0.5 mol/L. and containing no C is reacted in a tubular Reactor (PFR).  ra  1  K P a kPa 1/ 2 a 1/ 2 Pb  K b Pb  K c Pc  2 The overall stoichiometric reaction is: A2 + 2 B 2C and the surface reaction can be considered to be irreversible. all constants shown in the rate law may be lumped constants. CBo = 0.

Kinetics Problems May 2010 Problem 2 Problem 5 9 .

Kinetics Problems Problem 7 10 .

Kinetics Problems January 2010 Problem 2 11 .

Kinetics Problems Problem 6 Problem 8 12 .

Kinetics Problems May 2009 Problem 2 13 .

Kinetics Problems Problem 4 14 .

and hence the volume flow rate F remains fixed throughout the system.. 15 . C2/C0) in terms of the feed volume flow rate. (1) Determine an equation for the relative concentration of the reactant exiting the system (i.e. The answer should be only in terms of the feed volume flow rate.e. it is decided that the combined volume of the two reactors will be fixed at a value Vt. Since the reactors are adiabatic. and the total reactor volume Vt. and either V1 or V2). V1/ Vt) that would give rise to the optimum overall conversion of the reactant. The exit stream from the first reactor has a molar concentration C1 of the reactant and is fed to the second reactor. The individual volumes of the two reactors are V1 and V2 respectively. (2) Determine the fractional volume of the first reactor (i. The liquid-phase reaction produces negligible volume change. which produces a final exit stream of concentration C2 of the reactant. they have different temperatures. the two rate constants.Kinetics Problems Problem 8 You are going to run an exothermic liquid-phase catalytic reaction (A B) in two sequential. Hence. the rate constants in the two reactors are different (k2 > k1).. steady-state CSTRs. Since the amount of catalyst available is limited. The feed to the first reactor is at a volume flow rate F and has a molar concentration C0 (moles per unit volume) of the reactant A. adiabatic. and the reactor volumes (Vt. the two rate constants. The reaction is first-order and irreversible.

Kinetics Problems January 2009 Problem 3 16 .

Kinetics Problems Problem 6 17 .

Problem 7 Enzyme is retained in a continuous flow bioreactor (Figure) using an ultrafiltration membrane. To compensate for this. FIN [kg active enzyme/day] Ea [kg/m3] Ei [kg/m3] FOUT [kg/day] = 0 Semipermeable membrane 18 . Time (s) 390 777 1195 3155 Total Pressure 408 488 799 931 ∞ Assuming that the reaction (CH3)2)O → CH4 + H2 + CO is irreversible and goes to completion. active enzyme is continuously added at a rate FIN to the reactor in order to maintain a constant concentration [Ea] of active enzyme in the reactor. the desired flux J cannot be achieved if the total concentration of enzyme [Etot] (active + inactive) exceeds a maximum value given by [Emax] = [Es] exp(-J/ke) where [Es] is a saturation concentration of enzyme and ke is an enzyme mass transfer coefficient. adding resistance to solution flow. Determine the maximum reactor operating time tmax as a function of J. the pressure drop across the membrane is continuously adjusted to maintain a constant flux J of the reaction mixture through the membrane. Initially. However. a) Assuming that all the enzyme in the reactor is initially active. b) The reactor must be shut down and cleaned when [Etot] exceeds [Emax] and the flux falls below J.Kinetics Problems May 2008 Problem 4 The following data were reported for a gas-phase constant volume decomposition of dimethyl ether at 504 C in a batch reactor. In order to maintain uniform effluent product quality. a gel layer of enzyme accumulates on the membrane. However. determine the reaction order and the reaction rate constant (with units). determine the total enzyme concentration [Etot] in the reactor as a function of time. Active enzyme in the reactor deactivates following first-order kinetics with rate constant kd. only (CH3)2O was present.

0 atm. which rises to 3.0 atm after 10 minutes of reaction. A → r R. starting with an equimolar mixture of A and an inert gas I. The plot below gives the fractional decomposition of NO2 fed versus the ratio of reactor volume V (m3) to the NO2 feed rate.Kinetics Problems January 2008 Problem 4 An irreversible zero order homogeneous gas reaction. If the same reaction is run in a constant pressure reactor at the same temperature with the same feed composition and initial pressure. What can you deduce from these data about the reaction order. Three different concentrations of NO2 are tested at different temperatures. Tests are run in a small experimental reactor that operates essentially as a CSTR. what is the % change in reactor volume after 10 minutes? Problem 7 An automotive exhaust clean-up system is tested by feeding a stream containing dilute amounts of NO2 in an inert gas. Each data point in the figure below represents a steady state run. FNO2 (gmol/hr) at different feed concentrations of NO2 (in parts per million by volume). rate constant. The initial total pressure of the reactor is 2. and activation energy? 19 . proceeds at an elevated temperature in an isothermal constant volume reactor.

Problem 6 An irreversible second order liquid-phase reaction is being run in a plug flow reactor. final conversion of reactant is 90%. The feed rate is 20 L/min at a reactant concentration of 10 mols/L. CA0)]. The initial concentration of B. and if the fresh feed concentration and rate are unchanged. The reaction rate can be represented as ( . you are to derive [CA = Function of (t. what is the overall percent conversion of reactant in the product now leaving the system? Problem 7 The following reaction is carried out in an adiabatic plug flow reactor: A+B  C+D Calculate the maximum conversion that may be achieved if the feed enters at 300 K.) = 500. b. In other words..) Using the equation derived.01 L mol-1 s-1.Kinetics Problems May 2007 Problem 1 A liquid reaction. A + 2 B → C. k=0.000 at 50 C F A0 = F B0 = 10 moles/min = 100 J/mol-K CPA = CPB = CPC = CPD 20 . The following data are available: ΔHr = -120 kJ/mole K (Eqbm. If 2/3 of the product stream leaving the PFR is recycled to the reactor entrance. a. calculate the reaction time required to achieve 85% conversion of A for the following set of conditions: CA0=1 M. k.rA ) = k CA5/4 CB3/4. CB0 = 2CA0. t. Show all steps.) Derive an equation that shows how the concentration CA is dependent on reaction time. The feed stream contains A & B only. Const. is taking place in a batch reactor under isothermal and constant volume conditions.

Do not simply calculate volumes for all possible configurations. an 800 dm3 PFR operating at 300 K and a 200 dm3 CSTR operating at 350 K. Data: volumetric flow rate v= 10 liters/min: Desired fractional conversion fA = 0. At 200oC and 1 bar. The two feed streams to the reactor mix to form a single feed stream that is equimolar in A and B. (iii) RSTR then PFR. CA0B = CB0B = 2 mol/dm3. A + B + P → P + P (P is the product). the rate expression can be represented as (-rA) = k CA CB CP. One mole of A and 2 moles of B react at 250 oC and 2 bar. (iv) PFR then CSTR.000 J/mol-K. Discuss the implications of the following strategies on maximizing the production of C: i. (ii) a single PFR. b.5*v0 = 5 dm3/min. Design a flow reactor configuration that requires smallest reactor volume and find this minimal reactor volume. Add an inert to the feed stream Problem 4 The liquid-phase reaction A + B → C is conducted in a flow reactor. C P0 = 0 M. (Configuration: a single s (i) CSTR. Problem 8 For a liquid autocatalytic reaction. 54% C was produced. E = 85. k=0. 21 . with a total volumetric flowrate of 10 dm3/min. 25 mol % of the species in the reactor was product C. Based on the data above. Increase preesure iii. Think carefully about the possibilities. Two reactors are available. Clearly state any assumptions that you make.Kinetics Problems January 2007 Problem 1 Equilibrium data has been obtained for the reaction: A(g) + 2B(g) = 2C(g) with a stoichiometric feed of A and B. k = 0.8.04 L2Mol-2Min-1 . a. CA0 = CB0 = 1 M. estimate the concentrations at equilibrium. vA0 = vB0 = 0.07 dm3/mol-min. At 300 oC and 1 bar. Increase temperature ii. Which of the two reactors will give us the highest conversion? At 300 K.

The rate at which ethanol is broken down in the bloodstream is limited by the regeneration of a coenzyme. For example. the study of how drugs are ingested. let’s consider the area of pharmacokinetics. (b) Calculate how long a person would have to wait to drive after rapidly drinking 2 tall martinis? Ethanol volume in a tall martini = 40g Volume of body fluid = 40L 22 . this step can be modeled as a zero order reaction with a specific rate of 0. Consequently. The ingestion of ethanol into the bloodstream and the elimination of ethanol can be modeled as a series reaction. distributed. (a) Write the series of reactions (all irreversible) that must be evaluated and label each step with its appropriate rate constant. eliminated and reacted within the body.192 g/hL of body fluid. The rate of absorption into the bloodstream from the gastrointestinal tract is a first order reaction with a specific rate constant of 10 h-1. In this problem. not just petrochemical reactions in industrial reactors as traditionally studied. we will model how long one must wait to drive after drinking a tall martini. the legal level of intoxication corresponds to about 1 g ethanol per liter of body fluid.Kinetics Problems May 2006 Problem 4 You can apply the principles of reaction kinetics to any type of rate process. In most states.

the eigenvalues of A are found by setting the determinant of (Aqual to zero. Under what rates k1 and k2 would you expect to see exponential growth? January 2006 Problem 2 You are a member of a research team of industrial chemists discussing plans to operate an ammonia processing plant: N2 (g) + 3H2 (g) = 2NH3 (g) a). Derive the time-dependent balance equations for CA(t) and CB(t). The eigenvalues of this dynamic balance indicate the stability of CA and CB. At equilibrium.) E. the partial pressure of NH3 is 50 atm. Under what rates k1 and k2 would you expect to see oscillations in the concentrations? F. Assuming the same operating temperature and equilibrium partial pressure of ammonia (50 atm). b). This would lower the operating costs and increase profitability. B. where I is the identity matrix. and what are they? Can you solve for the steadystate concentrations uniquely? Why or why not? C. with dx/dt and x terms.00 x 10-4 atm-2. Real eigenvalues that are negative indicate unstable behavior and exponential growth. (For matrix A. D. What are the steady-state concentrations of CA and CB? How many independent equations do you have? How many unknowns are there.Kinetics Problems Problem 8 Consider the reversible reaction AB with forward rate k1 and backward rate k2. One of your team members suggests that the plant could produce the same amount of ammonia if the reactants were in a 1:6 ratio of N2:H2 and could do so at a lower total pressure. A. is the team member correct? 23 . where x is a column vector consisting CA and CB. and the initial concentration CA(0) and CB(0). The plant operates close to 700 K. Write the dynamic balance as a matrix differential equation. Suppose you are given the volume V. at which temperature Kp is 1. Calculate the partial pressure of each reactant and the total pressure under these conditions. Eigenvalues with imaginary parts indicate oscillatory behavior. and uses the stoichiometric ratio 1:3 of N2:H2. Compute the eigenvalues of the system.

Assuming constant density and a rate constant of 0. It is critical that the temperature of the catalyst and the product stream be controlled to maintain the desired product specifications. a total surface area of AC.1 min-1. how large should the PFR be to achieve 50 % overall conversion of the reactant mixture fed? Problem 8 You are in charge of the CSTR (cross sectional area AR and total internal volume VR) unit pictured below. Assume that the catalytic reaction can be described as k 2A  B catalyst 24 . Tin h Fout. Tout Given Assumptions: 1. you are assigned the task of building a computational model of the system.in (the density of the A solution is A and it has a heat capacity CPA) and at a volumetric flowrate of Fin and temperature Tin. followed in series by a plug flow reactor. and a heat capacity of CPC. The reactor is used to perform the first order catalyzed conversion of reactant A to product B. a density C. In order to design a proper control system for this reactor.Kinetics Problems Problem 6 A first order. Fin. irreversible liquid phase reaction is to be carried out in a 40 L CSTR. Reactant A is fed to the reactor as a liquid solution at a concentration CA. The reactor is filled with very small solid metal catalyst pellets (diameter=Dc) that have a total volume of VC. A feed solution containing 4 mol / L of reactant is to be fed to the CSTR at a rate of 2 L / min. A second feed solution containing 2 mol / L is to be combined at a rate of 3 L / min with the intermediate product from the first reactor and the mixture fed to the PFR.

The tank is a gravity draining tank and thus the flow rate of liquid from the tank can be calculated from the height of liquid in the tank (h) as: Fout  CV h 8. 7. Assume that the product B has approximately the same density and heat capacity as the reactant A. and the reaction occurs on the catalyst surface. You can briefly describe (no more than 3 to 4 sentences) your choice for plot shapes and locations if you like. The system is operating at steady state when suddenly the temperature of the feed stream decreases substantially as shown in the attached graph.Kinetics Problems 2. Be sure to place the starting temperature (i. 5. The rate constant k for the reaction can be described by an Arrhenius relationship which is a function of the catalyst temperature (TC). The pellets are prevented from flowing out of the reactor by a screen on the exit stream. It is not. using dimensional analysis to determine how to construct the important terms in each equation. Assume that any heat transfer involving the pellets can be described using an overall heat transfer coefficient UC. Assume that the reactor is well insulated. Just write mass and energy balances. Sketch on the same graph what you would expect the catalyst pellet temperature and outlet stream temperature to do as a function of time. Assume that the each of the catalyst pellets are small enough that there is no internal spatial temperature variation in each pellet.e. i. the catalyst temperature (TC) does not have spatial dependence in each pellet. The reaction is exothermic and the heat of reaction of the catalytic process on a molar basis is given as Hrxn. 4. 6. temperature (Tin). Write down (do not solve) the important dynamic mass balance equation(s) that can be used to solve for the concentrations of materials in the reactor and the mass of material in the system in terms of state variables and input variables to the system.e. before t=0) for the catalyst and outlet stream in the correct relative position to the inlet stream temperature in creating the plot.in) can all vary with time. 25 . The flow rate (Fin). that the energy released from the reaction is transferred only to the catalyst particles first and not to the liquid. 3. Also assume that since the catalyst particles are metal. 3. Answer the following questions: 1. and concentration (CA. 9. Write down (do not solve) the important dynamic energy balance equation(s) for this system that could be used to solve for the temperatures of the catalyst and fluid in the reactor as a function of time. 2. HINT: This looks complicated.

Kinetics Problems Tin t=0 Time May 2005 Problem 6 26 .

Kinetics Problems Problem 8 January 2005 Problem 3 27 .

Kinetics Problems Problem 7 Problem 8 28 .

Kinetics Problems May 2004 Problem 3 Problem 4 29 .

Kinetics Problems Problem 7 30 .

Kinetics Problems Problem 8 31 .

Kinetics Problems January 2004 Problem 3 Problem 4 32 .

Kinetics Problems May 2003 Problem 3 33 .

Kinetics Problems Problem 4 34 .

Kinetics Problems January 2003 Problem 2 Problem 5 35 .

Kinetics Problems Problem 7 May 2002 Problem 2 36 .

Kinetics Problems Problem 5 37 .

Kinetics Problems January 2002 Problem 7 38 .

Kinetics Problems Problem 8 39 .

Kinetics Problems May 2001 Problem 4 40 .

Kinetics Problems Problem 5 Problem 6 41 .

Kinetics Problems January 2001 Problem 1 42 .

Kinetics Problems Problem 2 January 2000 Problem 4 43 .

Kinetics Problems Problem 5 44 .