FUNDAMENTALS

Calculations. The technique followed to this purpose is to assume a type of equation or

a mechanism for which the mathematical equation can be developed, then to test the
fit of the data to the equation. if the firtst attempt is unsuccessful, the procedure is
repeated with other equations until a fit is obtained. when only limited use of the test
data is to be made or if the system is very complex, various plottings and cross
plottings of the data may be adequate for design purposes.
As already emphasized, a process design is the final step. this is to be distinguished
from a mechanical design which is concerned with such features of a plant as vessel
thicknesses, piping details, insulation, strcture, and foundations. A process design
involves the preparation of a flowsheet that shows the principal equipment, operating
conditions, flow quantities, and major control instruments; a heat and material
balance; utilities requirements,sketches showing the sizes and internals of the cost of
the plant. Not all these aspects can be stressed en this book, but the engineer should
always keep the ultimate goal in mind.
Rather constant use of mathematical is made throughout this subject, though the
breadth of mathematical knowledge required of the reader of this book does not
extend much beyond the most elementary differential equations and some numerical
techniques. Some of the need material is summarized in Chap. 12 for review or study.
In all fields of engineering, approximations often must be considered "good enough".
Data may not always be complete or accurate, or the mathematical difficulties may be
too great for a truly rigorous solution in the time available. Consequenly, numerical
methods for obtaining aproximate solutions of mathematics of kinetics are often used.
Even when rigorous solutions are possible, it may be more convenient to use
aprroximation, since any amateur can apply such methods to a great variety of
problems have whereas the expert mathematician is often needed to make the
analytical solution. Though usually simple in concept; aproximation methods have the
disadvantage of being tedious in application. Fortunately, increasing use of electronic
computers is relieving this burden on the ingineer. Also, bye making the use of short
intervals feasible, computers can on obtain solution fully as accurate as any obtained
by analytical methods.
2. Classification of reactions
Reactions may be classified in several ways. On the basis of mechanism, they may be,
for example:
1. Irreversible
2. Reversible
3. Simultaneous
4. Consecutive
A further classification from the point of mechanism is with respect to the number of
molecules actually participating in the reaction, the so-colled molecularity:
5. Unimolecular
6. Bimolecular
Related to the preceding is the classification with respect to order. This is
fundamentally a mathematical concept. As brought out later, the rate of a simple
reaction is proportional to the products of certain power of the concentrations or
active masses, as in the equation rate =𝑘𝐶𝑎𝑝 𝐶𝑏𝑞 . the exponent to which the
concentration of any particular reactant is raised is called the order with respect to
that substance, p or q and the order is identical with molecularity, but there are many
reactions which appear on experimental grounds to have zero or fractional orders. To
continue the classification, there are reactions of:
7. Integral orders, such as first, second, etc.
8. Fractional or zero order
With respect to operating conditions, there are the principal types:
9. Isothermal at constant volume
10. Isothermal at constant pressure
11. Adiabatic
12. Nonadiabatic and nonisothermal (programmed or heat-regulated)
Reactions may be classified according to the phases involved:
13. Homogeneous, gaseous or liquid or solid
14. Heterogeneous
a) Controlled by diffusive mass transfer
b) Controlled by chemical resistance
Furthermore, it is important to distinguish between:
15. Unanalyzed
16. Catalyzed
Equipment type is also a basis for differentiation, namely:
17. Stirred tank or tank battery
18. single- or multiple-tubular reactor
19. Reactor filled with solid particles, inert or catalytic
a) Fixed bed
b) Moving bed
c) Fluidized bed, dense phase or dilute phase.

FUNDAMENTS:
Finally there are the broad types:
20. Batch
21. Flow
22. Semibatch or semiflow
Clearly, these grouping are not mutually exclusive. Thus a reaction may be
irreversible- second- order, taking place under adiabatic and aproximately
constant pressure conditions in a flow reactor loaded with a solid catalyst in
particle form.
From the engineers point of view, the principal distinetions are draw between
homogeneous and heteregeneous and between batch and flow reactions.
These most influence the choice of equipment and operating condictions as
well as the desing methods.

3. The rate of a chemical reaction

A chemical reaction produces a rearrangement of the atoms of which
molecules are composed. The rate at which this occurs depends on the natures
of the participants and the circumstances. The more important factors have
been mentioned in sec. 1.
Quantitatively, the reaction rate is expressed as the number of units of mass of
some participant that is formed or transformed per unit of time t per unit of
volume v of the system. When the system volume remains constant, the rate
become the change in concentration c per unit of time.
Mathematically, these definitions are

In general

At constant volume only

Where n is the number of moles of reactant present at t. In terms of amount of

reactant that has been transformed in this time, ......................
The rate is.

For some types of reactions, it is possible to segregate the effects of the

amounts .... From those of the other variables. In formal terms, accord-ingly,
the rate equation may be written.

Here the term k is variously called the specific reaction rate (SRR), or the rate
coefficient, or the rate constant. By definition it is independent of the masses of
the participants but is influenced by all the other variables which influence the
rate of reaction. However, when operating conditions