Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

Chemical Reactor Design:

Reaction orders
The manner in which the reaction rate varies with the concentrations of the reactants
and products can be shown by the orders of the reaction. These are the powers to which
the concentrations are raised and are expressed as:

(9.1)

where αth is the order with respect to component A, and βth is the order with respect to
component B. The overall order of the reaction n is:

n=α+β (9.2)

The exponents α and β may be integers or fractions and may be both positive and
negative values, as well as the value of zero. In some cases, the exponents are
independent of temperature. Where the experimental data fit the expressions in the form
of Equation 1, the exponents will vary slightly with temperature. In these cases, the
observed correlation should be applied only in a restricted temperature interval. Not all
reactions can be expressed to have a specific order. As mentioned before, The units of the
reaction rate constant k vary with the overall order of the reaction. These units are those
of a rate divided by the nth power of concentration as evident from Equations 9.1 and 9.2.

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

Consider a reaction involving a reactant such that A → products. The rate equations
corresponding to a zero, first, second, and third order reaction together with their
corresponding units are:

Determining the order of reactions

There are two methods that could be used to obtain the order of reaction then the rate
equation which are the integral method and the differential method. In case of Integral
method for irreversible and isothermal reaction of a constant volume system.

 Zero order reactions

The rate of a chemical reaction is of a zero order if it is independent of the
concentrations of the participating substances. The rate of reaction is determined by such
limiting factors as:

1. In radiation chemistry, the energy, intensity, and nature of radiation.

2. In photochemistry, the intensity and wave length of light.
3. In catalyzed processes, the rates of diffusion of reactants and availability of surface
sites.

If the rate of the reaction is independent of the concentration of the reacting substance
A, then the amount dCA by which the concentration of A decreases in any given unit of

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

time dt is constant throughout the course of the reaction. The rate equation for a constant
volume batch system (i.e., constant density) can be expressed as:

(9.3)

Assuming that at time t1 the concentration of A is CA0, and at time t2 the concentration
is CAf, integrating Equation 3 between these limits gives:

If t1 = 0 and t2=t, therefore

CA0 – CAF = kt (9.4)

Plotting the concentration (CA) versus time t gives a straight line, where CA0 is the
intercept and k is the slope. The velocity constant k may include arbitrary constants
resulting from various limiting factors such as diffusion constants (DAB) and a fixed
intensity of absorbed light (I). In terms of the fractional conversion XA

CA0 XA= kt for (9.5)

Examples of zero order reactions are the intensity of radiation within the vat for
photochemical reactions or the surface available in certain solid catalyzed gas reactions.
Figure 9.1 shows plots of the zero order rate equations.

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

Fig. 9.1. Zero order reaction

H.W. 9.1. Derive the rate equation for (n= 0.25) order of isothermal reaction →
proceeds in a constant volume batch system.

 First order reactions

Consider the reaction → . The rate of a first order reaction is proportional to the
first power of the concentration of only one component. Assuming that there is no change
in volume, temperature, or any other factor that may affect the reaction, the amount dCA
that undergoes a chemical change in the short time interval dt depends only on the
amount of component A present at that instant. The rate for a first order reaction for a
constant volume batch system (i.e., constant density) can be expressed as:

(9.6)

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

Rearranging and integrating Equation 9.6 between the limits gives

If t1 = 0 and t2=t, therefore

(9.7)

In terms of the fractional conversion XA

-ln (1- XAf ) = kt (9.8)

A plot of –ln(1 – XA) or –ln CAf/CAO versus t gives a straight line through the origin.
The slope of the line is the rate constant k, as represented by Figure 9.2. The unit of the
rate constant k is sec–1.

Fig. 9.2. First order reaction

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

Many reactions follow first order kinetics or pseudo-first order kinetics over certain
ranges of experimental conditions. Examples are the cracking of butane, many pyrolysis
reactions, the decomposition of nitrogen pentoxide (N2O5), and the radioactive
disintegration of unstable nuclei.

 Second order reactions

second order reaction occurs when two reactants A and B interact in such a way that
the rate of reaction is proportional to the first power of the product of their
concentrations. Another type of a second order reaction includes systems involving a
single reactant. The rate at any instant is proportional to the square of the concentration of
a single reacting species.

Case 1

Consider the reaction → . The rate of a The rate equation for a

constant volume batch system (i.e., constant density) is:

(9.9)

The amount of A and B that have reacted at any time t can be described by the
following mechanism and set of equations.

From stoichiometry:

CB = CB0 – (CA0 – CA) (9.10)

Substituting Equation 9.10 into Equation 9.9, rearranging and integrating between the
limits gives

(9.11)

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

Equation 9.11 is resolved into partial fractions as

(9.12)

(9.13)

Equating the coefficients of CA and the constant on both the right and left side of
Equation 9.13 gives

Substituting p and q into Equation 9.12 and integrating between the limits gives

(9.14)

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

Fig. 9.3. Test for the reaction A + B  products

If CB0 is much larger than CA0, then the concentration of B remains approximately
constant, and Equation 9.14 approaches Equations 9.7 or 9.8 for the first order reaction.
Therefore, the second order reaction becomes a pseudo-first order reaction.

Case 2
This Case involves a system with a single reactant. In this case, the rate at any instant
is proportional to the square of the concentration of A. The reaction mechanism is
→ . The rate expression for a constant volume batch system (i.e., constant
density) is

(9.15)

Rearranging Equation 9.15 and integrating between the limits yields

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

(9.16)

In terms of the fractional conversion, XA

(9.17)

H.W. 9.2. Derive Equation 9.17.

Fig. 9.4. Test for the reaction 2A  products

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

Consider the second order reaction → , which is first order with

respect to both A and B, and therefore second order overall. The rate equation is:

(9.18)

The amount of A and B that have reacted at any time t can be described by the
following mechanism and set of equations.

and from stoichiometry:

(CA0 – CA) = 2(CB0 –CB) (9.19)

Then

(9.20)
Substituting Equation 9.20 into Equation 9.18 gives

(9.21)

Taking the partial fractions of Equation 9.21 with α = [CB0 – (1/2) CA0] gives

(9.22)

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Al-Muthanna University/ College of Engineering/ Chemical Engineering Department

Chemical Reactor Design Lect.: 09 Dr. Forat Yasir AlJaberi

After simplifying Equation 9.22, the final equation is

(9.23)

Fig. 9.5. Test for the reaction 2A + B  products

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