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Lecture 15
Analyzing data from laboratory reactors

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Objectives of analyzing data

• Determining catalyst activity, selectivity and stability.
• Determining the effect of important process variables such as
temperature, pressure, reactant concentrations.
• Finding a rate equation

Elimina?on of mass transfer and pore diffusion limita?ons

• In a solid catalyzed reaction, the presence of mass transfer and pore
diffusional resistances affect the rate of the reaction.
• To ensure that no internal or external mass transfer resistances are
present under the operating conditions, preliminary experiments are
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Elimination of mass transfer limitations

• Conversion data is obtained by increasing the flow rate of the feed but
keeping the W/FAO constant.
• At low fluid velocity, conversion increases with increasing fluid velocity
and subsequently becomes constant at higher flow rates, implying that
external mass transfer does not affect the rate of reaction at this fluid
velocity.
• Due to external mass transfer
limitation, the concentration of
reactant near catalyst surface is
lower than the bulk phase
concentration.
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• The effect is maximum at lower fluid velocity when the resistance to

transport is considerable.
• With increase in fluid velocity, the turbulence effectively enhances the
mixing in fluid phase and the concentration of reactant near the
catalyst surface approaches the bulk phase concentration.
• Consequently reaction rate increases increasing the conversion.
• At high velocity due to high
turbulence the mass transfer
limita?on is totally removed and
the reactant concentra?on near the
catalyst surface becomes equal to
that of bulk phase concentra?on
and the conversion reaches the
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• Thereafter any change in fluid velocity does not affect the conversion
as shown in the figure. Kinetic study should always be carried out at
conditions where the effect of external mass transfer on conversion
is negligible.

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Elimina?on of pore diffusion limita?ons

𝒓𝑷 𝝆𝑷
• Weisz criterion 𝑹𝟐𝑺 = ≤ 𝟏can be used to determine the
𝑪𝑺 𝑫𝒆
significance of intraparticle diffusion.
• Here Rs=pellet radius; rp = pellet density, Cs = surface concentration;
De effective diffusivity.
• Reactions should be carried out at the conditions when Weisz criterion
is satisfied so that the intraparticle diffusion could be neglected for
these operating conditions.
• The effectiveness of porous catalyst can also be determined
experimentally by measuring conversion with successively smaller
catalyst pellets until no further change in conversion occurs.
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• The pore diffusion resistance decreases the concentration within

the pellets thereby decreasing the conversion.
• The pore diffusion resistance is considered to be negligible for the
catalyst size range for which the conversion does not change with
size.
• For study of intrinsic reaction kinetics, catalyst pellet size is chosen
where the intraparticle diffusion could be neglected.

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Elimination of homogeneous phase reaction and deactivation

• When reaction is carried out over a fixed bed of solid catalyst there may be
possibility of non-catalytic homogeneous reactions occurring in gas phase.

• If any non-cataly?c homogeneous reac?ons occur along with

heterogeneous cataly?c reac?ons, then data collected will give erroneous
kine?cs for the heterogeneous reac?on.
• Hence, reaction should be carried out in an empty reactor without
using any catalyst to determine the contribution of homogeneous
phase reactions, if any, at the desired operating conditions.

• Kinetic study should be carried out at operating conditions for which

contribution of homogeneous phase reactions is negligible.
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• In addition, deactivation studies should be carried out by operating

the reactor for long run lengths.
• If any significant deac?va?on occurs, than it should be taken into
account for further analysis.

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Integral analysis of rate data

• A series of run are made in a packed bed at a fixed initial concentrations
CA0 and a fixed temperature T while varying the catalyst mass W and/or
initial molar flow rate FA0 to generate a range of W/FA0 values at
different conversions XA.
• A rate equation is then tested using the design equation for packed bed
reactor.

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• First simpler rate equations such as zero order, first order, second
order irreversible are tried.
• Mechanistic reaction models can also be tested.

• The W/FA0 and the right hand integral in equation (1) are evaluated
numerically and plotted to test for linearity (Fig 1).

• Linearity of the plot is used for judging if the selected rate equation
is a useful model for the data. If not then another rate equation may
be tried.
• If not then another rate equation may be tried.
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Differential analysis of rate data

• The data are collected as in the previous case.
• A plot of conversions XA versus W/FA0 is made for each set of runs at a
fixed temperature (Fig 2) .
• A best fit of data is made.
• Tangent to the fitted curve are drawn at regular interval along the
curve corresponding to the best fit.

• The slopes of this tangent are evaluated which correspond to the

reaction rate

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• Tangents can be evaluated more accurately by differentiating

the equation for best fit of data and evaluating the derivative at
various intervals over the data set.
• Values of –rA versus CA are plotted to determine the reaction
orders.
• For an irreversible reactions data are fitted by a simple power
rate law –rA = kCAn ,

• a plot of ln(-rA) vs lnCA is linear with a slope of order n.

• The rate constant value can be determined from the intercept.

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• The If rate vs temperature data available then it is possible to

determine the apparent ac?va?on energy from Arrhenius equa?on k =
A exp(-E/RT).

• The slope of the plot of ln k vs 1/T gives the activation energy E

of the reaction.

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Linear and nonlinear regression of rate data

For a Langmuir –Hinshelwood type rate equation

• Parameters k, KA, KB cannot be analyzed as simply as in power law

kinetics.
• k, KA, KB can be determined by linear least square or nonlinear least
square method.
• In linear least square method, the rate equation can be linearized as:

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• The parameters can be estimated by multiple regression technique

using the following equation for N experimental runs.
• For the ith run:

• The best values of the parameters a0, a1 and a2 are found by solving
following three equations:

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• The LH rate equation can also be solved by non-linear regression analysis.

• Linearized analysis is used to obtain the initial estimates of the rate

parameters and used in non-linear regression.

• In non linear analysis the rate law parameters are first estimated to
calculate the rate of reaction ‘rc’.

• Then the values of rate law parameters that will minimize the sum of the
squares of difference of the measured reaction rate rm and the calculated
reaction rate rc , that is the sum of (rm-rc)2 for all data points, are searched.
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• If there are N experiments with K number of parameter values to be

determined then the func?on to be minimized is given by:

• rim and ric are the measured and calculated reaction rate for ‘i’th run.

• The parameter values giving the minimum of the sum of squares, 𝝈2 ,

can be searched by various optimization techniques using software
packages.

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Initial rate analysis

• Ini?al rate analysis for a reac?on may be done to understand the
mechanism of a reac?on.

• Initial rate is the rate at zero conversion.

• It is obtained by extrapolation of the rate vs conversion data to zero

conversion.

• For higher accuracy, the conversion data are collected at very low
conversion region
• In this method, the dependence of initial rate data on partial pressure or
total pressure of the reactant is studied.
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Consider the reaction

The rate expression derived from Langmuir Hinshelwood model when

surface reac?on is controlling is:

Now at zero conversion all the product concentration will tend to zero,
hence putting CC =0 & CD =0, the rate expression [2] simplifies to:

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Where ri is the initial rate. Now, if a equimolal initial concentration of

CA and CB is used then C =C . Then assuming ideal gas mixture, CA=
pA/RT where p is the partial pressure of A.

Similarly CB = PB/RT where pB is the partial pressure of B .

Now since it is an equimolal mixture, then at ini?al condi?on PA=PB =Pt/2

Then substituting CA and CB in equation [3] becomes:

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For this mechanism a typical plot of initial rate ri as a function of total

pressure pt is shown in Fig 4B.

When reaction data satisfy this plot then the reaction is said to be
adsorption A controlling.

In similar way other models can be tested for fitting.

It should be used as only as preliminary kinetic analysis method.

It should be used as only as preliminary kinetic analysis method.

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Book Reference
• J. M. Smith, Chemical Engineering Kine?cs, McGrawHill Book
Company, 1981.
• J.J. Carberry , Chemical and cataly?c reac?on Engineering, Dover
Publica?ons,2001.
• D.W.Green, R.H. Perry, Perry ś chemical engineer ś handbook, 8th
Edi?on, McGrawHill Company,2007.
• H. S. Fogler, Elements of Chemical reac?on engineering, Pren?ce
Hall of India, 1999
• R. J. Farrauto, C. H. Bartholomew, Fundamentals of Industrial
cataly?c Processes, Blackie Academic & Professional, 1997

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