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1. What are the factors responsible for deviations from ideal plug flow in a tubular reactor?
The factors responsible for deviations from ideal plug flow in a tubular reactor are (i) Mixing in
longitudinal direction (formation of vortices and eddies, cause this effect) and (ii) Incomplete mixing in
radial direction (formation of parabolic velocity profile, may cause this effect).
2. What are the reasons for non-ideality in real reactors? (NOV/DEC 2013)
The reasons for non-ideality in real reactors are
Presence of stagnant regions (or dead zones), bypassing or short-circuiting – CSTR
Mixing in longitudinal direction, incomplete mixing in radial direction and Channeling - PFR
Note: Deviations from ideal performance divide into two classifications;
(i) The first is a flow arrangement in which elements do not mix, but follow separate paths through the
reactor (segregated flow). These elements are retained in the reactor for different times, that is, they have
different residence times.
(ii) The second is a flow arrangement whereby elements of fluid partially mix (micro mixing).
10. What is the requirement of tracer material used for the conduct of stimulus response experiment?
[Dec-2012]
The requirement of tracer material is;
It should be non-reactive or inert.
It should be soluble or miscible in the reacting fluid.
Properties (density) should be similar to reacting fluid.
It should be easily detectable.
It should not adhere on the walls of the reactor.
12. Sketch E (θ) for (i) ideal PFR (ii) ideal CSTR. (NOV/DEC 2014)
has been in reactor for less than time „t‟] = F(t) (Or) dF/dt = E(t) Note: These relationships only hold for
closed vessels.
14. What are mean residence time, standard deviation and skewness of a RTD function?
Mean residence time (tm): It is the mean time of passage, or when the curve passes by the exit or it is the
time corresponding to the peak value of either CPulse curve or ‘E’ curve. (First moment of probability
distribution of a real valued random variable)
1
s3 3
0
(t tm )3 E (t )dt
2
17. Define Peclet number. What are the values of Peclet number for (i) ideal CSTR (ii) ideal PFR?
The reactor Peclet number (NPe) is defined as the ratio of the rate of transport by convection to that of the
rate of transport by diffusion or dispersion. It is given by NPe = (U L)/D.
Where ‘D’ is the dispersion coefficient or coefficient of molecular diffusion (in m2/s), ‘U’ is the velocity of
fluid flow (in m/s) and ‘L’ is the length of the non-ideal tubular reactor (in ‘m’).
For ideal CSTR, NPe = 0 and for ideal PFR, NPe = ∞.
20. Differentiate between the segregated flow model and mixing models.
Complete segregation model or Segregated flow model
All molecules of same age group remain together as they travel through the reactor and are not mixed
till the exit point. This is called as complete segregation model.
Maximum mixed ness model or mixing model
Molecules of different age group are completely mixed at the molecular level as soon as they enter the
reactor. This is called as ‘complete micro mixing‘ or maximum mixed ness model.
Note: Both the models are said to be Zero parameter models.
3. A sample of tracer was injected as a pulse to a reactor and the effluent concentration (C) measured as a
function of time, resulting in the following data;
t, min 0 1 2 3 4 5 6 7 8 9 10 12 14
C, g/m3 0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
4. A first order reaction is carried out in a Non-ideal tubular reactor. Assuming that the axial dispersion model
is valid, derive an expression for conversion in the reactor. (NOV/DEC 2013)
5. The concentration reading in the table represents a continuous response to a pulse input;
t, min 0 5 10 15 20 25 30 35
C, gm/lit 0 3 5 5 4 2 1 0
This vessel is used as a reactor for a liquid decomposing with rate -rA = k CA & k = 0.307 min-1. Find the
conversion expected in the reactor and compare it with the PFR by
(i) Direct use of Tracer curve.
(ii) Using Dispersion model
6. A liquid macro fluid reacts according to A R as it flows through vessel. Find the conversion of ‘A’ for the
flow pattern shown below. [Dec-2012]
7. For a Non-ideal reactor described by N-Tank’s in series model, derive an expression for E().
8. Derive the equation to fine out the conversion from direct use of tracer data. (NOV/DEC 2013)
9. The tracer concentration in the effluent stream of a reactor as a function of time is tabulated as follows;
t (s) 0 100 200 300 460 500 670 735 840 960
C (g/m3) 0 2.9 8.7 12.4 10 6.5 3.0 1.5 0.5 0
Calculate the conversion as per the Tank’s-in-series model, if a first order irreversible liquid phase reaction
takes place in the reactor. The rate constant is k = 0.0056 s-1. (NOV/DEC 2014)
10. (i) Obtain the relationship between C, E and F functions. Derive expression for mean residence time.
(ii) Derive the equation to find out performance of reactor by the direct use of tracer curve. [Dec-2012]
11. From the pulse input in to vessel we obtain the following output signal
Time, min 0 1 3 5 7 9 11 13 15
Conc. 0 0 10 10 10 10 10 0 0
We want to represent the flow through the vessel with the tanks in series model. Determine the number of
tanks to use. . (May/June 2014)
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1. Define Catalysis.
“Catalysis” is a term refers to a process in which the rate of reaction is influenced by a substance (catalyst)
that remains chemically unaffected.
8. What is Chemisorption?
It is specific and involves forces much stronger than in physical adsorption.
The process is often irreversible.
The energy of activation is low for non-activated adsorption and high for activated adsorption.
11. Derive the Langmuir isotherm for the adsorption of a single species.
Since the adsorption is limited to complete coverage by a monomolecular layer, the surface may be divide
into two parts; the fraction ‘θ’ covered by the adsorbed molecule and the fraction (1 – θ), which is bare.
Since only those molecules striking the uncovered part of the surface can be adsorbed, the rate of adsorption
per unit of total surface will be proportional to (1 – θ); that is
rad = k p (1 – θ)
The rate of Desorption will be proportional to the fraction of covered surface. That is
rde = kI θ
At equilibrium, rad = rde or k p (1 – θ) = kI θ
Solving for ‘θ’, we get θ = k p/(kI + k p) = K p/(1 + K p) = v/vm
The above equation is called ‘Langmuir isotherm’. Where K = k/kI is the adsorption equilibrium constant,
expressed in units of (pressure)-1.
13. A non-porous catalyst particle is of size 2 microns and density is 2 g/cm3. Calculate the external
surface area per gram of the particle.
The external surface area per gram of the particle, Sg
= 6 / [(Size of the particle, dp) (Density of the particle, ρp)]
= 6 / {[2 x 10-4 (cm)] [2 (g/cm3)]}
Or Sg = 1.5 x 104 cm2/g
14. Explain the principle of mercury-penetration method for the determination of pore-size distribution
in a catalyst particle.
The mercury-penetration method for the determination of pore size distribution in a catalyst particle
depends on the fact that mercury has a significant surface tension and does not wet most catalytic surfaces.
This means that the pressure required to force mercury into the pores depends on the pore radius.
15. List the advantages of the Langmuir-Hinshelwood method in developing rate equations.
The advantages of the Langmuir-Hinshelwood method are;
The resultant rate equation may be extrapolated more accurately to concentrations beyond the range
of experimental measurements used.
The method does take into account adsorption and surface reactions (which must occur) in a
consistent manner.
2. Explain the various theories of adsorption and derive the related equation.
3. Explain the various methods of finding pore size distribution of catalyst. (NOV/DEC 2013)
4. Consider a solid catalyzed reaction A R + S. Assuming Langmuir-Hinshelwood model, derive the kinetic
Rate equation. Assume Surface reaction to be rate controlling.
5. Discuss the determination of Pore volume and Pore-volume distribution. [Dec 2102] (May / June 2014)
6. Tertiary butyl alcohol (TBA) is produced by the liquid phase hydration (W) of isobutene (I) over an
amberlyst-15 catalyst. The liquid is normally a multi-phase mixture of Isobutene, water and the solid
catalyst. The reaction can be represented as I + W TBA. If all the species set adsorbed on to the catalyst
surface and if the adsorption of Isobutene is rate limiting, derive the Rate equation for the reaction.
7. An isomerization reaction has the simple form of A R. Assuming that the reaction is isothermal and
reversible and that the external and internal diffusion steps have negligible concentration gradients, propose
the intrinsic rate equations for the following cases;
(i) The adsorption of ‘A’ on the catalyst is controlling.
(ii) The surface reaction between adsorbed ‘A’ and an adjacent vacant center is controlling.
8. Describe in detail the Nitrogen adsorption method for the determination of Surface area of a catalyst.
10. Explain in detail how the pore volume distribution of a solid catalyst is determined by the mercury
penetration method. (NOV/DEC 2014)
11. An 8.06g sample of Glaucosil is studied with N2 adsorption at -195.8oC. The following data are obtained. [Dec
2012]
Pressure (mm Hg) 6 25 140 230 285 320 430 505
Volume adsorbed (cm at 3
61 167 170 197 215 230 277 335
0oC and 1 atm)
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12. What is the effect of catalyst pellet size on the effectiveness factor?
In the regime of strong diffusion resistance, the rate (thus the effectiveness factor) varies inversely
proportional to the catalyst pellet size. So, Increase in pellet size will decrease the value of effectiveness
factor and vice-versa.
14. ‘In a catalyst pellet, if the rate of diffusion through the pores is much higher than the rate of reaction,
then the value of Thiele modulus will approach unity’. Justify this statement.
By the definition, we know that the Thiele modulus is the ratio of the intrinsic chemical reaction rate in the
absence of mass transfer limitation to the rate of diffusion through the particle.
If the rate of diffusion through the pores (denominator term) is much higher than the rate of reaction
(numerator term), then the value of Thiele modulus will approach unity.
17. When is it said that a reaction follows ideal mechanism in gas-solid catalytic reactions
19. Compare fixed and fluidized - bed reactors for gas-solid catalytic operation.
It is not possible to use fine size catalyst particles in fixed bed reactor. This results in plugging and
high pressure drop. High pressure increases the operating cost.
It is possible to use fine size catalyst particles in fluidized bed reactor. Fine size particles provide
large interfacial / contact area.
Catalyst regeneration can be a problem in fixed bed reactor. If the regeneration needs to be
frequently done, this problem will be bottleneck in operation.
Catalyst particle regeneration is quite easy in fluidized bed reactors. If the regeneration needs to be
done frequently, the catalyst particles can be entrained with the product stream, separated in
cyclone separator and then sent to the regenerator.
20. List some of the problems that would be encountered in the operation of a fluidized catalytic reactor.
In operation of a fluidized catalytic reactor, some difficulties can occur. They are;
Slugging: When the gas passes up through the catalyst bed in the form of large gas bubbles, it is
called as Slugging of fluidized bed.
Channeling: When the gas is not evenly distributed in the catalyst bed cross section and is
concentrated in channels through the catalyst bed, the phenomena is called as Channeling of
fluidized bed.
2. Show that the Effectiveness factor (η) for a first order reaction in an isothermal spherical catalyst pellet is
given by (NOV/DEC 2013)
3. A first order irreversible reaction takes place in a solid catalyst. Considering a single straight pore
(cylindrical or slab shaped) in the catalyst particle, develop an expression for concentration profile of the
reactant in the pore and derive the expression for effectiveness factor for the same. State all assumptions
made.
4. Explain briefly;
(i) Effectiveness factor under Non-isothermal conditions.
(ii) Effective Thermal conductivity and the effect of Pore volume on it.
5. A first order heterogeneous irreversible reaction A R is taking place within a spherical catalyst pellet
which is plated throughout the pellet. The reactant concentration midway between the external surface and
the center of the pellet is equal to 1/10 of the concentration at the external surface. The concentration of the
reactant at the external surface is 0.001 gmol/lit. The pellet diameter is 2 x 10 -3 cm and the diffusion
coefficient is 0.1 cm2/s.
(i) What is the concentration of the reactant at a distance of 3 x 10-4 cm from the external pellet surface?
(ii) To what diameter should the pellet be reduced, if the effectiveness factor is to be 0.8?
6. (i) Derive a mathematical equation for the design of a fixed bed (packed bed) catalytic reactor in which a
first order gas phase reaction A R is carried out
(ii) Compare the packed bed reactor and fluidized bed reactor for a catalytic chemical reaction.
Calculate the weight of the catalyst for 40% conversion in a packed bed reactor, if the molal feed rate is
increased to 125 kmol/hr. (NOV/DEC 2014)
8. Discuss the effect of heat and mass transfer on the performance of industrial catalytic reactors. (NOV/DEC
2013)
9. Obtain an expression for finding out the Effectiveness factor for spherical catalyst particle.
[Dec 2012] (May/June 2014)
10. Explain the operation of (i) Fluidized bed catalytic reactor (ii) Packed bed catalytic reactor
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2. Give two examples of an fluid-solid reaction in which the particles do not change their size on
reaction.
Iron is prepared form crushed and sized magnetic ore in continuous-countercurrent, three stage,
fluidized bed reactors according to the reaction
Fe3O4 (s) + 4 H2 (g) → 3 Fe (s) + 4 H2O (g)
With steam, water gas is obtained by the reactions
C (s) + H2O (g) → CO (g) + H2 (g)
C (s) + 2 H2O (g) → CO2 (g) +2 H2 (g)
4. Briefly explain the Progressive Conversion Model for the gas-solid non-catalytic reactions.
Solid reactant is converted continuously and progressively throughout the particle.
The reaction rates are different at different locations within the particle.
This model does not match with the real situations.
6. In the ‘Shrinking Core Model’ for gas-solid non-catalytic reactions, explain the term ‘Shrinking
Core’.
Shrinking Core means, at any time, there exists an unreacted core of material which shrinks in size during
reaction.
8. What are the limitations of Shrinking Core Model? (NOV/DEC 2014) (May June 2014)
It is the best simple representation for the majority of reacting gas-solid systems. However, there are two
broad exceptions to this statement;
First, Slow reaction of a gas with a very porous solid will not fit to the reality.
Second, when solid is converted by the action of heat and without needing contact with gas – Such
as baking bread, roasting chickens are mouth watering examples of such reactions.
10. Bring out the differences between ‘Progressive Conversion Model’ and ‘Shrinking Core Model’ used
in gas-solid non-catalytic reactions.
Progressive-conversion model:
Solid reactant is converted continuously and progressively throughout the particle.
The reaction rates are different at different locations within the particle.
This model does not match with the real situations.
Shrinking-core model:
At any time there exists an unreacted core of material which shrinks in size during reaction.
The reaction rate depends on the movement of unreacted core and the resistances involved in it.
Most of the practical situations (burning of coal, wood, briquettes, etc.) show that this model
approximately matches with reality.
12. What are the three rate controlling steps assumed in the Shrinking Core Model for gas-solid non-
catalytic reactions?
The three rate controlling steps assumed in the Shrinking Core Model for gas-solid non-catalytic reactions
are;
Diffusion of gaseous reactant A through the film surrounding the particle to the surface of the solid.
Penetration and diffusion of A through the blanket of ash to the surface of the unreacted core.
Reaction of gaseous A with solid at this reaction surface.
13. State all the assumptions made in the Shrinking Core Model used for gas-solid non-catalytic
reactions.
The assumptions made in the Shrinking Core Model used for gas-solid non-catalytic reactions are;
The pellet retains its shape during reaction.
There is no gaseous region between the pellet and the product layer.
The temperature is uniform throughout the heterogeneous region.
The densities of the porous product and the reactant (solid) are the same, so that the total radius of
the pellet does not change with time.
14. Explain the resistances that would encountered during the burning of coal.
The resistance that would be encountered during the burning of coal are;
Diffusion resistance offered by the gas film surrounding the surface of the solid (coal) particle.
Diffusion resistance offered by the blanket of ash surrounding the unreacted core of the (coal)
particle.
Reaction resistance on the surface of the unreacted core (coal).
15. Explain how the rate determining step is calculated in gas-solid non-catalytic reactions.
The kinetic runs with different sizes of particles can distinguish between reactions in the chemical and
physical steps control (for gas-solid non-catalytic reactions) as,
t R1.5 to 2.0 for film diffusion controlling
t R2 for ash layer diffusion controlling
tR for chemical reaction controlling.
16. Sketch the concentration profile for the gas-solid non-catalytic reaction in which the resistance
through the ash layer is rate controlling.
18. Find the rate controlling mechanism, form the following data
dP, cm XB t, hr
1 0.3 2
1 0.75 5
Solution: Since ‘dp’ is same for the two given data’s, we try to find the rate controlling mechanism by
considering the time‘t’ and conversion ‘XB’.
By assuming G-film surrounding the particles is rate controlling, we have
t/T = XB Where ‘T’ is the time for complete conversion.
Sub. the given first data into the above, we get T1 = 2/0.3 = 6.6667 hr
Sub. the given second data into the above, we get T2 = 5/0.75 = 6.6667 hr
Since T1 = T2, our assumption is correct.
That is, G-film surrounding the particles controls this reaction.
19. A gas-solid non-catalytic reaction taking place in a constant environment. It was found that the time
for complete conversion of 2mm particle is four times the time for complete conversion of 1mm
particle. What resistance is rate controlling?
Solution: Given D1 = 1mm, D2 = 2 mm and T2 = 4 T1.
From the given data, it was observed that
(T2 / T1) = (D2 / D1)2 or (R2 / R1)2
Or T α R2.
Thus, Diffusion through ash layer controls this reaction.
20. State how to reduce the gas film resistance for non-catalytic chemical reaction.
By increasing the mass transfer coefficient (kg), the gas film resistance (1/kg) can be reduced for non-
catalytic chemical reaction.
1. (i) Discuss the models used for studying the kinetics of non-catalytic reactions.
(ii) Derive the conversion vs. time relationship when gas film controls the reaction for spherical particles of
unchanging size according to unreacted core model. (NOV/DEC 2014)
2. Derive the relationship between Time and Conversion when Diffusion through Ash layer controls a Fluid-
Solid reaction as per the Shrinking core model. Also, show that the time ‘τ’ required for complete burning
of the solid particle is proportional to the square of the radius ‘R’
3. Obtain an expression for the global rate of reaction and Conversion vs. Time for the reaction A (g) + b B
(s) E (g) + F (s) considering a spherical pellet and Shrinking core model, when Chemical reaction
controlling this Gas-Solid non-catalytic reaction. (NOV/DEC 2013)
4. (i) Explain in detail the determination of rate controlling step for non-catalytic reaction.
(ii) A batch of solids of uniform size is treated by gas in a uniform environment. Solid is converted to give a
non-flaking product according to the shrinking core model. Conversion is about 7/8 for a reaction time of 1
hour and conversion is complete in two hours. What mechanism is rate controlling?
5. Spherical particles of zinc blende of size R = 1 mm are roasted in an 8% oxygen stream at 900°C and 1 atm.
The stoichiometry of the reaction is 2ZnS + 3O2 2ZnO + 2SO2 Assuming that reaction proceeds by the
shrinking-core model calculate the time needed for complete conversion of a particle and the relative
resistance of ash layer diffusion during this operation.
Data:
Density of solid, ρ = 0.0425 mol/cm3 , Reaction rate constant, k|| = 2 cm/sec , For gases in the ZnO layer, De
= 0.08 cm2/sec
Note that film resistance can safely be neglected as long as growing ash layer is present. [Dec 2012]
6. Two small samples of solids are introduced into a constant environment oven and kept there for one hour.
Under these conditions, 4mm particles are 58% converted and 2mm particles are 87.5% converted.
(i) Find the rate controlling mechanism for the conversion of solids.
(ii) Find the time needed for complete conversion of 1mm particles.
8. A feed consisting of 30% of 50µm, 40% of 100µm, and 30% of 200µm particles is to be fed continuously in
a thin layer onto a moving grate cross-current to a flow of reactant gas. For the planned operating conditions
the time required for complete conversion is 5, 10, and 20 minutes for the three sizes of particles. Find the
conversion of solids for a mean residence time of 8 minutes in the reactor.
9. A fluidized bed reactor is operating at steady state with a solid feed of varying size distribution as
mentioned below; 50µm – 20%, 80µm – 20%, 100µm – 25%, 150µm – 15% and 200µm – 20%.
The fluidizing gas phase reactant has uniform composition. The time for complete conversion is 4, 8, 12, 16
and 19 minutes respectively of the above mentioned particles. The feed rate is 1.3 kg/min and the reactor
contains 15 kg of solids. Assuming the solids are hard and remain unchanged in size & weight and also that
chemical reaction is rate controlling, calculate the average fractional conversion of the solid particles. .
(NOV/DEC 2014)
10. (i) Discuss the models used for studying the kinetics of non-catalytic reactions.
(ii) Discuss different reactors available for carrying out non-catalytic chemical reaction. [Dec 2012]
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4. ‘Enhancement factor is always greater than or equal to one’. Justify this statement.
7. Does the enhancement factor decrease or increase with Hatta number? Explain.
Yes, Enhancement factor (E) decrease or increases with Hatta number (M H). Because the evaluation of ‘E’
depends on two quantities;
The enhancement factor for an infinitely fast reaction (Ei)
Maximum possible conversion in the film compared with maximum transport through the film
(MH2).
10. Give examples for absorption with chemical reaction. (NOV/DEC 2013) (NOV/DEC 2014)
12. In a gas-liquid reaction, it was observed that the reaction occurs on a plane with in the liquid film. Is
the reaction slow, fast or instantaneous? Explain.
The reaction is either instantaneous of fast, with low concentration of liquid.
For instantaneous reaction, the reaction plane exists where the two reactants interact in the liquid
film.
For fast reactions, the reaction zone exists where the two reactants completely reacted in the liquid
film
This approach tries to apply the mathematics of the penetration theory to be more plausible physical picture.
The liquid is pictured as two regions, a large well mixed bulk and an interfacial region that is renewed so
fast that it behaves as a thick film. The surface renewal theory is caused by liquid flow.
15. What are the various resistances involved in developing rate equations for gas-liquid reactions?
The various resistances involved in developing rate equations for gas-liquid reactions are;
Mass transfer resistances, to bring the reactants together.
The resistance of the chemical reaction step.
16. Sketch the concentration profile for an instantaneous gas-liquid non-catalytic reaction.
Refer: “Chemical Reaction Engineering” by O. Levenspiel, Chapter no: 23, Page no: 531.
The penetration theory for mass transfer. Here the interfacial region is imagined to be very thick
continuously generated by flow. Mass transfer now involves diffusion in to this film. In this and other
theories the interfacial concentration in the liquid is assumed to be in equilibrium with that in the gas
18. What are the advantages of slurry reactors over fixed beds?
The advantages of slurry reactors over fixed beds are
a. It usually has a higher rate
b. It holds good for fast reactions on porous catalyst
Note: Slurry reactors can use very fine particles, and this lead to problems of separating catalyst from
liquid. (Only disadvantage of slurry reactor)
20. List the types of flow regime that are possible in trickle bed reactors.
In trickle bed reactor, four types of flow regimes are possible;
Trickle flow regime: In this regime, gas flow is continuous.
Dispersed bubble regime: In this regime, liquid phase is continuous and the gas moves into the
bubbles.
Spray regime: In this regime, gas flow rate is high while liquid rate is low. Liquid falls in droplets
through the gas phase.
Pulsed flow regime: In this regime, flow rates of both gas and liquid are high
1. Consider the Gas-Liquid Non-catalytic reaction A (g) + b B (l) Products. Derive the global rate equation
assuming the reaction to be instantaneous and for the reaction taking place on
(i) Gas-Liquid interface. (ii) A plane located in the Liquid film. (May/ June 2014) (NOV/DEC 2014)
3. Discuss the various design equation available for the absorber, for various type reaction with various
contacting pattern.
4. Derive the rate equation for fluid-fluid reaction for the following cases;
(i) Intermediate reaction in the film and in the main body of the liquid.
(ii) Slow reaction in the main body of liquid with film resistance. (NOV/DEC 2014)
6. Discuss in detail the Design procedure (PBR) for the reaction A (g) + b B (l) Products with Moderately
to Infinitely fast rate in which the phases are being Counter-current Plug flow.
7. Discuss the various design equation available for the absorber, for various type reaction with various
contacting pattern.
8. Elaborate briefly about the design principle of tower reactor. (NOV/DEC 2013)
9. (i) What are the various equipments used in Fluid-Fluid contacting with reaction?
(ii) Discuss in detail about Slurry reaction kinetics. (NOV/DEC 2014)
10. The concentration of an undesirable impurity ‘A’ in air is to be reduced from 0.10% to 0.02% by absorption
in pure water. Find the height of tower required for counter current operations. Data: For consistency, units
are given in moles, meters, and hours;
For the packing used,
kA(g) a = 32,000 mol/hr-m3-atm
kA(l) a = 0.1 hr-1
The solubility of A in water, HA = 125 x 10-6 atm-m3/mol
Liquid mass flow rate, L = 7 X 1015 mol/hr-m2
Gas flow rate, G = 1 X 1015 mol/hr-m2 at = 1 atm
Molar density of liquid, CT = 56,000 mol/m3