A BRIEF HISTORY OF CHEMICAL KINETICS (AND
OF CRE)
(Ref.: "The World of Physical
Chemistry," by K. J. Laidler, Oxford Univ. Press, 1993)
1850: Wilhelmy (Germany) studied the rate of inversion
of sucrose (hydrolysis into D-(+)-glucose and D-(-)-fructose in the presence of
an acid) and found it to be proportional to the concentrations of both the
sugar and the acid.
1864: Guldberg and Waage (Norway)
formulated their "law of mass action," according to which the
reaction "forces" are proportional to the product of the
concentrations of the reactants:
K=[R]r [S]s/([A]a
[B]b)
where a, b, r and s are the
stoichiometric coefficients in the chemical equation A+B=R+S. So the rate of
the forward reaction is proportional to [A]a [B]b and
that of the reverse reaction is proportional to {R]r [S]s.
1865: Harcourt and Esson (UK)
analyzed the reactions between H2O2 and HI and between
KMnO4 and (COOH)2. They wrote the corresponding
differential equations, integrated them and determined the concentration vs.
time relationships. They also proposed an equation for the temperature
dependence of the reaction rate, k = A TC.
1884: van't Hoff (The
Netherlands) published his "Studies of Chemical Dynamics" (Ιtudes de
dynamique chimique), in which he generalized and further developed the work of
Wilhelmy, Harcourt and Esson. In particular, he introduced the differential
method of analysis. He also analyzed the temperature dependence of the
equilibrium constant (now called the "van't Hoff equation") and of
forward and reverse reaction rates.
1887: Ostwald (Germany; Latvia)
introduces the terms "reaction order" and "half-life" in
his "Lehrbuch der allgemeinen Chemie."
1889: Arrhenius (Sweden) further
analyzed the temperature dependence of reaction rate, k = A exp(-B/T), and gave
it an "energy barrier" interpretation; this is now called the
"Arrhenius equation."
In the 20th century there have been
significant developments in the theory of chemical kinetics (determination of
rate constants and reaction orders from "first principles"). It is
not yet possible, however, to predict the kinetic parameters for real-world
chemical processes, and in reactor design we must rely on carefully planned and
executed experiments. These theoretical (and experimental) developments are
beyond the scope of an introductory CRE course, except for the following:
1913: Chapman (UK) introduced and
Bodenstein (Germany) developed the steady-state approximation in chain
reactions, according to which the rate of change of intermediate products is
negligible.
1917: Trautz (Germany) and Lewis
(UK) independently proposed that the rate of reaction is determined by the
frequency of molecular collisions. This is now known as the "collision
theory" of chemical reaction kinetics.
1920s: Langmuir (USA) studied the
kinetics of surface reactions and introduced what is now known as the
"Langmuir isotherm," which was further developed by Hinshelwood (UK)
into the "Langmuir-Hinshelwood mechanism" of heterogeneous reactions.
1934: Rice and Herzfeld (USA) show
that chain reactions involving free radicals (whose concentrations are
determined using the steady-state approximation) are responsible for the often
observed variations in the order (n=0.5, n=1, n=1.5, etc.) of thermal decomposition
of organic compounds such as ethane and acetaldehyde.
1935: Eyring (USA) developed a
statistical treatment called the "theory of absolute reaction rates"
or "transition state theory," according to which the reaction occurs
in two steps: (a) equilibrated conversion of the reactant(s) into an
"activated complex;" (b) decomposition of the complex (which occurs
at a definite rate).
SOME (MOSTLY PEDAGOGICAL) LANDMARKS IN
THE HISTORY OF CHEMICAL REACTION ENGINEERING (CRE)
1908: Creation of the AIChE.
1923: Walker, Lewis, McAdams and
Gilliland (USA) publish "Principles of Chemical Engineering."
Interestingly, even the 3rd edition
(1937) does not contain a chapter on CRE. (The chapters are mostly
unit-operations oriented: elements of industrial stoichiometry, fluid films,
flow of heat, fuels and power, combustion, furnaces and kilns, gas producers,
crushing and grinding, mechanical separation, filtration, basic principles of
vaporization processes, evaporation, general principles of diffusional
processes, absorption and extraction, distillation, humidity and wet- and
dry-bulb thermometry, air conditioning , drying.)
1934: 1st edition of Perry's
"Chemical Engineers' Handbook" is published, but it contains nothing
on reaction kinetics or reactor design. The closest section, written by
Stillman, Taylor and Graves, is entitled "Indicators, Quantitative Analysis,
Catalysis, Organic Chemistry."
1941: 2nd edition of Perry's
"Chemical Engineers' Handbook" is published.
1944: Denbigh (UK) publishes his paper on
"Velocity and Yield in Continuous Reaction Systems" (Trans. Faraday
Soc. 40, 352-373, 1944).
1947: Hougen and Watson (USA)
publish Part 3 of "Chemical Process Principles: Kinetics and Catalysis.
(See p. 1012 for a plot of reciprocal rate vs. conversion.)
1950: 3rd edition of Perry's
"Chemical Engineers' Handbook" is published. Section 4, entitled
"Physical and Chemical Principles," written by Bryant, Elgin, Perry,
Rossini and Whitwell, has a chapter on "Chemical reaction kinetics,"
containing a discussion of homogeneous and heterogeneous reactions (but not
reactor design).
1953: Danckwerts (UK) publishes
his paper on "Continuous Flow Systems -- Distribution of Residence
Times" (Chem. Eng. Sci. 2, 1-13, 1953).
1956: J. M. Smith (USA) publishes
his "Chemical Engineering Kinetics."
(No discussion of RTD nor of 1/r vs. X
graphs.)
1957: First symposium on CRE, at
the 12th Meeting of the European Federation of Chemical Engineering.
1958: W. Brφtz (Germany)
publishes "Fundamentals of Chemical Reaction Engineering" (English
translation of "Grundriss der chemischen Reaktionstechnik," published
in 1965).
1959: S. M. Walas (USA) publishes
"Reaction Kinetics for Chemical Engineers."
1962: O. Levenspiel (USA)
publishes "Chemical Reaction Engineering."
1963: Kramers and Westerterp (The
Netherlands) publish "Elements of Chemical Reactor Design and
Operation."
1963: 4th edition of Perry's
"Chemical Engineers' Handbook" is published. Section 4, written by
Perry, Sliepcevich, Green, Kobayashi and Leland (with acknowledgments to J. M.
Smith), is entitled "Reaction Kinetics, Reactor Design, and Thermodynamics."
1965: R. Aris (USA) publishes
"Introduction to the Analysis of Chemical Reactors."
Intriguingly, Prof. Neal Amundson
considers this to be "the first book [on CRE] that treated the whole
subject in a rational way" (Chem. Eng. Sci. 41, 1947-1955, 1986).
1965: K. G. Denbigh (UK)
publishes "Chemical Reactor Theory: An Introduction."
1965: E. E. Petersen (USA)
publishes "Chemical Reaction Analysis."
1971: Cooper and Jeffreys (UK)
publish "Chemical Kinetics and Reactor Design."
1972: Second edition of
Levenspiel's "CRE".
1973: Section 4 of the 5th
edition of "Chemical Engineers' Handbook," entitled "Reaction
Kinetics, Reactor Design and Thermodynamics," written by Lin, Van Ness and
Abbott, contains chapters on Fundamentals, Experimental techniques,
Interpretation of laboratory and pilot-plant data, Scale-up methods and Reactor
design.
1976: J. J. Carberry (USA)
publishes "Chemical and Catalytic Reaction Engineering."
1977: C. G. Hill (USA) publishes
"An Introduction to Chemical Engineering Kinetics & Reactor
Design."
1979: Levenspiel publishes
"The Chemical Reactor Omnibook," a delightful, hand-written and
problem-saturated complement to his "CRE".
1979: Froment (Belgium) and
Bischoff (USA) publish "Chemical Reactor Analysis and Design."
1979: Holland and Anthony (USA)
publish "Fundamentals of Chemical Reaction Engineering."
1980: J. B. Butt (USA) publishes
"Reaction Kinetics and Reactor Design."
1981: Third edition of Smith's
"Chemical Engineering Kinetics." (Does discuss RTD now, but not 1/r
vs. X graphs.)
1984: Section 4 of the 6th
edition "Perry's Chemical Engineers' Handbook," entitled
"Reaction Kinetics, Reactor Design and Thermodynamics," written by
Lin, Van Ness and Abbott, contains chapters on Fundamentals of chemical
reaction systems, Experimental techniques for kinetic-data acquisition,
Analyses of reaction kinetic data, Scale-up methods, and Reactor design (basic
principles and data).
1984: Westerterp, van Swaaij and
Beenackers (The Netherlands) publish a new edition of "Chemical Reactor
Design and Operation."
1984: Denbigh and Turner (UK)
publish 3rd edition of "Chemical Reactor Theory."
1984: Trambouze, Landeghem, and
Wauquier (France) publish "Chemical Reactors: Design/Engineering/Operation"
(English translation of "Les reacteurs chimiques: Conception/calcul/mise
en oevre," published in 1988).
1986: H. S. Fogler (USA)
publishes "Elements of Chemical Reaction Engineering."
1987: E. B. Nauman (USA)
publishes "Chemical Reactor Design."
1989: Holland and Anthony (USA)
publish 2nd edition of "Fundamentals of Chemical Reaction
Engineering."
1990: Froment (Belgium) and
Bischoff (USA) publish 2nd edition of "Chemical Reactor Analysis and
Design."
1995: Walas publishes
"Chemical Reaction Engineering Handbook of Solved Problems."
1997: Section 7 in the 7th
edition of "Perry's Chemical Engineers' Handbook," entitled
"Reaction Kinetics," written by S. M. Walas, contains chapters on
Reaction kinetics, Rate equations, Ideal reactors, Large scale operations,
Acquisition of data, and Solved problems.
There is also a separate section on Chemical Reactors.
1998: L. D. Schmidt (USA)
publishes "The Engineering of Chemical Reactions."
This is the first substantive
departure from Levenspiel's approach (and that of his followers) to
introductory CRE teaching. Argues that with Levenspiel's notation "there
was no logical way to solve mass and energy balance equations
simultaneously" and this notation "also prohibits the correct
handling of multiple reaction systems." In addition to what he considers
to be the core of CRE ("multiple reactions, energy management and
catalytic processes"), he discusses the increasingly important topics of
"environmental, polymer, solids, biological, and combustion reactions and
reactors." Prof. Schmidt also makes the point that teaching of CRE needs
to reflect the facts that (a) the profession is not dominated any more by
"petroleum processing and commodity chemical industries," and (b)
"[p]olymers, bioprocesses, microelectronics, foods, films, and
environmental concerns are now the growth industries needing chemical engineers."
1999: 3rd edition of Fogler's
"Elements of Chemical Reaction Engineering."
This now appears to be the most
"popular" textbook (see Shalabi et al., "Current Trends in
Chemical Reaction Engineering Education" in Chem. Eng. Educ., 1996, pp.
146-149). A derivative of Levenspiel's classic textbook, and perhaps its
successor, it emphasizes the multimedia approach: it has a CD-ROM, a web site
and uses PolyMath quite a bit.
1999: Levenspiel publishes the
3rd edition of "Chemical Reaction Engineering."
1999: Missen, Mims and Saville
(Canada) publish "Introduction to Chemical Reaction Engineering and
Kinetics," which includes a CD-ROM with E-Z Solve software and has a web
site.
2000: J. B. Butt publishes
"Reaction Kinetics and Reactor Design," second edition, revised and
expanded.
LRR3@psu.edu (1/31/2001)