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 tanning). 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 found 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 Cavendish 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 CO2, 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 of 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 and 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 published 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 formulate 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 (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. 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 include; 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 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. 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 Society (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 commercially 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 kinetic (or inertial) forces to viscous forces within a fluid. 1884: van't Hoff (The Netherlands) published his "Studies of Chemical Dynamics" (Études 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. 1884: The Solvay process is transferred 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 Kerosene 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 "Lehrbuch 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 "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: 1892: Diesel 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 mixtures. 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 Herreshoff, 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 use 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 Standard 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 products 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 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. Brötz (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.
Ref.: "The World of Physical Chemistry," 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