CHEMICAL ENGINEERING Page 1 of 9

REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)

Lecture 1
TOPIC: Collection and analysis of data

Reactor Technology
Fundamentals

ENCH3RT

COLLECTION AND ANALYSIS OF DATA

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REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)
Lecture 1
TOPIC: Collection and analysis of data
Collection and analysis of rate data
The present section primarily deals with the identification of kinetic models for homogeneous reactions, although some of the
techniques developed can also be used for the analysis of heterogeneously catalysed processes.
Power-law expressions for the reaction rate are composed of a temperature dependent term (the rate constant) and
composition dependent terms (concentrations of species together with reaction orders), e.g.

𝐴𝐴 + 𝐵𝐵 ⟶ 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝

𝛽𝛽
−rA = kCA𝛼𝛼 CB

In this section, the main task is to determine the specific values for k, α and β. This information can then be incorporated into
the material balance for the reactor of interest.
Kinetic data for homogeneous reactions are most conveniently obtained using batch reactors. Often, but not always, the
experiment is carried out without change in the total working volume of the system (i.e. constant volume batch reactor).
Different variables can be monitored as the reaction proceeds, e.g. concentration, pressure and volume at different times. As a
rule, always try to express the material balance in terms of the monitored variable.
Four basic methods of analysing batch reactor rate data will be presented:

1. Differential
2. Integral
3. Initial rate
4. Half-life 2
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REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)
Lecture 1
TOPIC: Collection and analysis of data
Differential method of rate analysis
Such an analysis is recommended when the reaction is irreversible and the rate is expected to be a function of the
concentration of one reactant, e.g.,
−rA = kCA𝑛𝑛
However, 2nd order reactions can also be studied as well, provided they are carried out in the pseudo-first order regime (excess
of one reactant).

Suppose that an experiment was conducted in a constant volume batch reactor and that the concentration of the reactant was
recorded as a function of time. The material balance is:

d𝐶𝐶A
= rA
dt
Suppose that the assumed rate law is −rA = kCA𝑛𝑛 . Substitution into the material balance yields:

d𝐶𝐶A
= −kCA𝑛𝑛
dt
Or
dCA
ln − = lnk + nlnCA
dt
dC
The reaction order is the gradient of a plot of ln − A versus ln CA. The intercept yields the rate constant at the
dt
specific temperature. Of course we have CA versus time data, so we have to differentiate either graphically or
numerically to determine the rate at specific points in time.
For equally spaced data points Δt, 3
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REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)
Lecture 1
TOPIC: Collection and analysis of data

Time t0 t1 t2

Concentration CA0 CA1 CA2

dCA
the following three-point differentiation formulas can be used to calculate :
dt
dCA −3CA0 +4CA1 −CA2
= (1)
dt 𝑡𝑡0 2∆t

dCA 1
= CA2 − CA0 (2)
dt 𝑡𝑡1 2∆t

dCA 1
= CA0 − 4CA1 + 3CA2 (3)
dt 𝑡𝑡2 2∆t

Equation 1 and 3 are used for the first and last data points, respectively, whilst Equation 2 is used for all intermediate points.

Equal area graphical differentiation is described in Appendix A of Fogler. You can also attempt to draw tangents to
the CA vs t curve at points of interest and use the slope as an estimation of the rate. Finally, one may also fit the
concentration time data to a polynomial and then differentiate analytically to obtain a functional dependence of rate
on time e.g.,
rA = 𝑎𝑎𝑎𝑎 + 𝑏𝑏t 2 +ct 3 4
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REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)
Lecture 1
TOPIC: Collection and analysis of data
Suppose that for a non-equimolar gas phase reaction carried out in a sealed batch vessel we have chosen to monitor the
change in the total pressure of the system, rather than the concentration of species (the former is generally easier and less
intrusive).
−d𝐶𝐶A
= −rA = kCA𝑛𝑛
dt

CA = CA0 1 − X A
Also,
P0 𝑇𝑇
𝑉𝑉 = 𝑉𝑉0 (1 + δyA,0 X A )
𝑃𝑃 𝑇𝑇0
The last equation can be used to show that

1
XA = 𝑃𝑃 − 𝑃𝑃0
𝛿𝛿𝑃𝑃𝐴𝐴0
where 𝑃𝑃A0 = 𝑦𝑦𝐴𝐴0 𝑃𝑃0 . Thus the concentration of species A at a given time can be written in terms of total pressure:

𝑃𝑃𝐴𝐴𝐴 − 𝑃𝑃 − 𝑃𝑃0 /𝛿𝛿

𝐶𝐶𝐴𝐴 =
𝑅𝑅𝑅𝑅
Substitution into the material balance gives:
𝑛𝑛
1 𝑑𝑑𝑑𝑑 𝑃𝑃𝐴𝐴𝐴 − 𝑃𝑃 − 𝑃𝑃0 /𝛿𝛿
= 𝑘𝑘
𝛿𝛿𝛿𝛿𝛿𝛿 𝑑𝑑𝑑𝑑 𝑅𝑅𝑅𝑅
It is then possible to carry out differential analysis of rate data directly using pressure vs time data.

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REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)
Lecture 1
TOPIC: Collection and analysis of data
NOTE

𝛽𝛽
For reactions of the type A + B → products and the postulated rate law −rA = kCA𝛼𝛼 CB , the differential method of rate analysis
can also be used. Suppose that the experiments are carried out with a large excess of B such that the concentration of B does
not change appreciably during the experiment, we can then write

−rA = k , CA𝛼𝛼
𝛽𝛽
where k , = kCB , and proceed as before to determine the order with respect to A. Another experiment with an excess of A can
be conducted to determine the order with respect to B and so on.
This is usually the first type of rate analysis considered, since most of the required information is already available in
the literature and it does not involve time consuming numerical or graphical differentiation.
The procedure is:
- Guess the reaction order
- Integrate the material balance
- Plot the data in such a system of co-ordinates in which a straight line can be obtained
- In a nonlinear relation results, make another guess for the reaction order and proceed as before

We usually consider zero, first or second order expressions when carrying out the analysis.
For example, consider the reaction A → products.

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REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)
Lecture 1
TOPIC: Collection and analysis of data

1) Assume zero order

d𝐶𝐶A
= −𝑘𝑘
dt

The integrated form:

CA = CA0 − 𝑘𝑘𝑘𝑘
2) Assume first order
d𝐶𝐶A
= −𝑘𝑘CA
dt

The integrated form:

𝐶𝐶A0
ln = 𝑘𝑘𝑘𝑘
CA

3) Assume second order

d𝐶𝐶A
= −𝑘𝑘CA2
dt
The integrated form:
1 1
− = 𝑘𝑘𝑘𝑘
𝐶𝐶A 𝐶𝐶A0

Each of these integrated expressions can be tested for linearity by plotting the respective data. Sometimes it would
be difficult to determine which order gives the best straight line. Differential analysis would yield better results in
this case.

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REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)
Lecture 1
TOPIC: Collection and analysis of data
Method of initial rates
Application of the first two methods to systems exhibiting reaction reversibility is more difficult and often less accurate. The
method of initial rates is applied if there is a significant reverse reaction effect during the late stage of the reaction. The method
assumes that at the initial moment (when the amount of products is still negligible or even zero), the rate of the reverse
reaction is insignificant and can be ignored when analysing the data.
The procedure is:
- Perform a series of runs at different initial concentrations of the reactant.
- For each run determine the initial reaction rate using:

dCA
= rA0
dt 𝑡𝑡0

This can be accomplished for example by extrapolation of the C vs t data to t0.

- Correlate the initial reaction rates against the initial concentration using

0 𝑛𝑛
−𝑟𝑟𝐴𝐴0 = 𝑘𝑘 𝐶𝐶𝐴𝐴
Or

𝑙𝑙𝑙𝑙 −𝑟𝑟𝐴𝐴0 = 𝑙𝑙𝑙𝑙𝑙𝑙 + 𝑙𝑙𝑙𝑙 𝐶𝐶𝐴𝐴0

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REACTOR TECHNOLOGY FUNDAMENTALS (ENCH3RT)
Lecture 1
TOPIC: Collection and analysis of data
Method of half-lives
We have already defined the parameter 𝑡𝑡1/2 as the time it takes for the concentration of the reactant to fall to half of its initial
value.
For an n-th order reaction carried out in a constant-volume batch reactor:

d𝐶𝐶A
− = −𝑟𝑟A = 𝑘𝑘𝐶𝐶𝐴𝐴0
dt
Integration yields

𝑛𝑛−1
1 𝐶𝐶𝐴𝐴0
𝑡𝑡 = 𝑛𝑛−1 −1
𝑘𝑘𝐶𝐶𝐴𝐴) 𝐶𝐶𝐴𝐴

provided that the rate constant is known at a few experimental temperatures. An equivalent form of the Arrhenius
equation is:

−Ea 1 1
k = k 0 exp −
R T T0

where T0 is any chosen reference temperature and k0 is the rate constant at the reference temperature.