A BRIEF HISTORY OF CHEMICAL KINETICS (AND OF CRE)

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A BRIEF HISTORY OF CHEMICAL KINETICS (AND OF CRE)




~440 BC:
Democritus
proposes the concept an of
atom
to describe the indivisible and
indestructible particles that were thought to compose the substance of all things.



~250 BC:
Archimedes

deduces the law of

the
levers
and could evaluate the relative
density of bodies by observing their
buoyancy force

when immersed in water.



1635:
John Winthrop
, Jr., opens
America's first chemical plant

in Boston. They
produce saltpeter (used in
gunpowder
) and alum (used in
t
anning
).



1644:
Evangelista Torricelli

devises the
barometer
.



1647
Blaise Pascal

determines the
pressure of air
. He also invents a machine to
perform
addition and subtraction;

the Pascalina, a remote precursor of calculating
machines.



1662:

Robert Boyle

f
ound that the volume occupied by the same sample of any gas at
constant temperature is inversely proportional to the pressure. This statement is known
as
Boyle's law
.



1749: England begins a
Lead
-
Chamber Method

to produce
sulfuric acid
.



1766:
Henry Cavend
ish
discoveres "inflammable air" (
hydrogen
), which he
concluded to be a combination of water and phlogiston (oxygen), since its combustion
yielded water.



1772:
Daniel Rutherford

describes "residual air", the first published description of
nitrogen
.



1775:

Antoine Lavoisier

showes that
fire

is due to the
exothermic reaction

between
combustable substances and oxygen. He named

a gas discovered by Cavendish, that
burned to produce water, hydrogen (Greek, water producer). Also demonstrated that
CO
2
, nitric acid
, and sulfuric acid contained oxygen.



1780:
Antoine Lavoisier

and
Pierre Laplace

publish their Memoire on Heat, in
which they reach the conclusion that
respiration is a form of combustion
.



1787:
Jacques Alexandre César Charles

studies the
volume changes

o
f gases with
changes in temperature.



1789:
Nicholas Le Blanc

develops his process for converting
common salt into soda
ash
.



1802:
Louis Joseph Gay
-
Lussac

announces the
ideal gas law
.



1802: The
E. I. du Pont de Nemours and Company

(Du Pont) is founded an
d builds
a
gunpowder factory

along the banks of the Brandywine River near Wilmington,
Delaware.



1804:
Nicholas Theodore de Saussure

publishes experiments on
photosynthesis
, and
described the
balanced equation

of the process.



1809:
Nicolas François Appert
, inventor and bacteriologist, demonstrates a
procedure for preservation of foods by
canning
.



1810:
Joseph Louis Gay
-
Lussac

deduces the equations of
alcoholic fermentation
.



1811:
Amadeo Avogadro

demonstrates that equal volumes of all gases under the
same

temperature and pressure contain the same number of molecules, and that a fixed
number of molecules of any gas will weigh proportional to its molecular weight.
Presently the accepted value for the
Avogadro number is 6.023 x 10^23 molecules
per gram
-
mol
.



1824:
Sadi Carnot

publishes his Reflexions sur la Puissance Motrice du Feu, setting
various outstanding principles that constitute the basis of actual
Thermodynamics
.



1828:
Friederich Wöhler

synthesizes the first
organic compound from inorganic
compounds
,

preparing Urea by reacting lead cyanate with ammonia.



1828:
Robert Brown

first describes
Brownian motion
.



1835:
Jöns Jacob Berzelius

demonstrates that the
hydrolysis of starch

is catalyzed
more efficiently by malt diastase than by sulphuric acid. He pub
lished the first general
theory of
chemical catalysis
.



1842:
Julius Robert Mayer

enunciates the
Law of Conservation of Energy

(1st Law
of Thermodynamics), after establishing the work equivalent of Heat.



1845:
Herman von Helmoltz

and
Julius Robert Mayer

f
ormulate the
Laws of
Thermodynamics
.



1845:
Alfred Kolbe

synthesizes
acetic acid
.



1846:
Joule

demonstrates the
equivalence for various forms of energy

(heat
-

electrical
-

mechanical).




1850
: Wilhelmy (Germany) studied the rate of inversion of sucrose (hy
drolysis
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.



1850's
: The first
petroleum refinery

consisting of a
one
-
barrel still

is built in
Pittsburgh by

Samuel Kier.

1853:
Kerosene

is extracted
from petroleum
.

1854: The
Pennsylvania Rock Oil Company

becomes the
first oil company

in the
U.S.

1955:
Benjamin Silliman
, of New Haven, Connecticut, obtains valuable products by
distilling petroleum
. They includ
e;
tar
,
naphthalene
,
gasoline
, and
various
solvents
.

1856: Seeking to make a substitute for quinine, the first artificial aniline
coal tar dye

is developed by
William H. Perkin
.

1858:
Friederich August Kekulé von Stradonitz

proposes that
carbon atoms can

form chains
.

1859: The
first
commercially successful U.S.
oil well

is drilled by
E. L. Drake

near
Titusville, Pennsylvania. This 70 foot well
launches the petroleum industry
.



1863:

Ernest Solvay

perfects his method for producing
sodium bicarbonate
.



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 coeffic
ients 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 H
2
O
2

and HI
and between KMn
O
4

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 T
C
.




1865: The first U.S
.
petroleum pipeline

is built from an oil field near Titusville,
Pennsylvania to a nearby railroad. 1866:
Dynamite

is developed by
Alfred Nobel
.



1866:
Celluloid

is invented by a British entrepreneur named
Alexander Parkes

("The
Father of Plastics").



1869:
Dmitri Mendelejeff

published a chemical elements arrangement table. This is
the basis of the well known
periodic table
.



1869:
Celluloid

was produced by
John Hyatt

in Albany, New York. The
breakthrough came about because of a search for an
ivory substitute
that could be
used to make billiard balls
. Celluloid was the
first synthetic plastic

to receive
wide
commercial use
.



1870:
Justus von Liebeg
proposed that all ferments were
chemical reactions rather
than vital impulses
.



1872:
Carl Friederich Wilhem Ludwig

and
Eduard Pfünger

studied the gas
exchange process in the blood and showed that
oxidation occurs in the tissues rather
than in the blood
.



1874: German graduate student
Othmar Zeider

discovers the chemical formula for
DDT
.



1876: The
American Chemical Socie
ty

(ACS) is formed.



1878:
Josiah Willard Gibbs

developed the theory of
Chemical Thermodynamics

introducing fundamental equations and relations to calculate multiphase equilibrium,
the phase rule, and the free enrgy concept. His work remained unknown until

1883,
when
Wilhelm Ostwald

discovered his work and translated it to German.



1879:
Saccharin
is discovered by Constantin Fahlberg, a chemist at Johns Hopkins
University. The
calorie free sweetener

is 300 times stronger than sucrose and has
been sold comme
rcially since about 1900.



1880:
George Davis

proposes a "
Society of Chemical Engineers
" in England.



1883:
Osborne Reynolds

published his paper on the
Reynolds' Number
, a
dimensionless quantity which characterizes
laminar and turbulent

flow by relating
kine
tic
(or inertial)
forces

to
viscous forces

within a fluid.



1884
: van't Hoff (The Netherlands) published his "Studies of Chemical
Dynamics" (
É
tudes de dynamique chimique), in which he generalized and
further developed the work of Wilhelmy, Harcourt and Esso
n. 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.

1884: The
Solvay
process

is trans
ferred to the
United States

and the Solvay Process Co. begins making
soda ash in Syracuse.



1884:
Svante Arrhenius

and
Friederich Ostwald

independently
defined acids

as
substances which release hydrogen ions when dissolved in water.



1884:
Viscose Rayon

is
invented by the French chemist Hilaire Chardonnet.



1885: The
gasoline automobile

is developed by
Karl Benz
. Before this, gasoline was
an unwanted fraction of petroleum which caused many house fires because of its
tendency to explode when placed in Kerosen
e lamps.



1886: The
first

modern
Oil Tanker
, the
Gluckauf
, was built for Germany by England.



1887:
Emil Fischer

elaborated the structural patterns of
proteins
.



1887
: Ostwald (Germany; Latvia) introduces the terms "reaction order" and
"half
-
life" in his "Leh
rbuch der allgemeinen Chemie."




1888:
George Davis

provides the blueprint for a new profession as he presents a series
of
12 lectures on Chemical Engineering

at the Manchester, England.



1888: The
Massachusetts Institute of Technology

begins "
Course X
" (ten
), the first
four year Chemical Engineering program in the United States.



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 "Arrhe
nius 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 parameter
s 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:



1892:
Die
sel

develops his
internal combustion engine
.



1892:
Pennsylvania

begins its
Chemical Engineering curriculum
.



1893:
Sorel
published "La rectification de l'alcool" were he developed and applied the
mathematical theory of the
rectifying column for binary mixt
ures
.
William
Ostwald

proved that
enzymes are catalysts
.



1894:
Tulane

begins its
Chemical Engineering curriculum
.



1895:
Linde

develops his process for
liquefying air
.



1897: Badishe produces
synthetic Indigo

on a commercial scale in Germany. 1900:
John Herr
eshoff
, of the Nichols Chemical Co., develops the first
contact method



1901:
George Davis

publishes a "
Handbook of Chemical Engineering
."



1901:
Oil Drilling

begins in
Persia
.



1903:
Arthur Noyes
, a prominent MIT professor, established a
Research Laboratory

of Physical Chemistry
.



1908: The
American Institute of Chemical Engineers

(AIChE) is founded.



1908:
Cellophane

is discovered by a Swiss chemist named Jacques Brandenberger.



1908:
Svante Arrhenius

argues that the
greenhouse effect

from coal and petroleum
u
se is warming the globe.



1908:
Dr. Leo Baekeland

("The Father of the Plastics Industry") discovers
Bakelite

in his laboratory in Yonkers, N.Y.



1910:
Bakelite production begins

at the General Bakelite Company. The plastic finds
widespread use in; electric
insulation
, electric
plugs and sockets
,
clock bases
,
iron
handles
, and
jewelry
.



1910:
Synthetic Ammonia

is first produced by the
Haber Process

in Ludwigshafen,
Germany.



1910: A U.S.
Rayon plant

is constructed by the American Viscose Co.



1913: The Standar
d Oil Co. (Indiana) begins the
thermal cracking of petroleum

in
"
Burton Stills
".



1913
: Chapman (UK) introduced and Bodenstein (Germany) developed the
steady
-
state approximation in chain reactions, according to which the rate of
change of intermediate produ
cts is negligible.

1915: The
unit operations

concept
is articulated by
Arthur Little
.



1915: The
Corning Glass Works

begins marketing
Pyrex glass
.



1917
: Trautz (Germany) and Lewis (UK) independently proposed that the rate
of reaction is determined by the f
requency 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 deve
loped 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 r
esponsible 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 PEDAGOGI
CAL) 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, ba
sic 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 Eng
ineers' 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
P
rinciples: 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, Perr
y, 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 Re
sidence 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. Br
ö
tz (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
Engin
eers.
"



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
Rea
ctors.
"

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' Handbo
ok,
" 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.



1
976
: 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 delightfu
l,
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. B
utt (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,
"
entitle
d "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) p
ublish 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," wri
tten 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 bala
nce 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 i
ncreasingly
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
"pe
troleum 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 Chemi
cal 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 perh
aps 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 "
Introduct
ion 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.


Ref.: "The World of Physical C
hemistry," by K. J. Laidler, Oxford Univ. Press, 1993

http://www1.cems.umn.edu/orgs/aiche/archive/history/h_time.html



http://www.ems.psu.
edu/~radovic/KineticsHistory.html