Essays on Chemical Kinetics

A BRIEF HISTORY OF TIME IN CHEMISTRY Gregory S. Yablonsky Parks College of Engineering, Aviation and Technology,

Saint Louis University, St. Louis, Missouri, USA •

• “The history of science is the only history which can illustrate the progress of mankind” • (George Sarton)

• “The only reason for time is so that everything doesn’t happen at once”

• Albert Einstein A. INITIAL STORY

• The first step. • There were 500 bricks inside the airplane. One brick was dropped. How many bricks are remained inside the airplane? • Correct! 499! • The second step. How to put an elephant into the refrigerator? Three-stage procedure: (1) To open the refrigerator; (2) To put the elephant into the refrigerator (3) To close the refrigerator • The third step. How to put an reindeer into the refrigerator? Four-stage procedure: (1) To open the refrigerator; (2) To take the elephant out of the refrigerator; (3) To put a reindeer to the refrigerator ; (4) To close the refrigerator lio

• The fourth step

A lion, the king of animals, has the birthday party. All animals came to this party except one. Who is this one? • Certainly, the reindeer! • The fifth step An old lady crossed the African river with crocodiles. However she survived. Why? • Correct! • All crocodiles attended the lion’s party! • The sixth step, the final one. Unfortunately this old lady died at the same day. Why? • She was hit by the brick which was dropped from the airplane. • The level of complexity of this example is very correspondent to the complexity of chemical reaction. It is the multi-stage process It is the temporal process. It is the cyclic process. There are three conservation laws: • (1) Conservation of the number of all animals • (2) Conservation of the number of bricks • (3) conservation of the space of refrigerator • Also there is a catalyst, the brick. EXAMPLE: 2H2 + O2 = 2H2O B. Time and chemical complexity Pre-history • Many activities of human beings are complex chemical reactions which are occurred in time (1) Combustion as a source of energy since Neanderthal times…(“500, 000 years of combustion technology”); (2) Preparation of food and beverages (bier, wine); (3) Preparation of materials: Bronze from Cu and Sn containing ore (“Bronze age”); Iron using the ferrous metallurgy( “Iron Age”) Etc…Etc… Time and Complexity

• What is a meaning of chemical time? • Is it just a scale for presenting the complex reaction, i.e. complex sequence of chemical events(transformation)? • Or it is an exhibition (function) of complex chemical transformations? Three Meanings of Time

1. “Clock” time t (or astronomic, or external time): Change of chemical composition during ∆t 2. “Internal”, or “intrinsic” time: Time scale at which a reaction occurs 3. Residence time: “Transport time” as a measuring stick of the chemical reaction(s) G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 19 Reactions. Decoding Complexity C. Time in Chemistry: Starting Point

Discovery of Catalysis Catalysis is the fundamental chemical phenomenon that underlies

Life

90% of new chemical processes "Virtually every CO 2 conversion to roses chemical reaction that occurs in living Nontoxic auto-exhaust organisms is Petroleum fuels catalyzed by a specific enzyme." Most important The Living Cell - C. deDuve environmental Ammonia fertilizer technology G. Ertl's 2007 Nobel Chateau Lafite Rothschild (1887) prize involved study Nylon of this catalytic system Sulfuric acid L-dopa Hefty trash bags

Anti-freeze Chiral Rh complex Fuel cells creates a chiral product Plastic drain pipe W. Knowles shared Aspartame 2001 Nobel prize for work on this system Makes diet coke Roundup possible and on and on …… Natural Catalytic Phenomena

Catalyst Catalyst (enzyme) (enzyme) Regeneration Product Product Reactant Tissue, etc. Reactant (CO 2) (O 2, Carbohydrates) (CO 2) Animal Plant

Transformation

Reactant Reactant Energy out Energy in work, heat (UV-Vis Light) Story I : Catalysis (Germany: Johann – Wolfgang Doebereiner)

Catalysis discovery is more interesting than any Hollywood movie. Main characters of this historical movie are: 1. The chemist Johann-Wolfgang Doebereiner (1780-1856). 2. The great German poet Johann-Wolfgang Goethe (1749-1832), prime-minister of the small Weimar dukedom. 3. August, Duke of the Weimar dukedom 4. Russian Tsar’s sister and Duke’s daughter –in- law, Maria Pavlovna Johann Wolfgang Goethe (1749- 1832) Faust • "Stop time, • thou art so beautiful!“ • (“Faust”, Goethe) Goethe, “Faust”

• “Werd ich zum Augenblicke sagen: Verweile doch: du bist zu schoen • Dann magst du mich in Fesseln schlagen, • Dann will ich gern zugrude gehn”. Johann-Wolfgang Dobereiner (1780-1849) CATALYSIS Doebereiner never graduated from any university. Despite that Goethe hired him as a court apothecary. Doebereiner enthusiastically studied the reaction of hydrogen oxidation and found an amazing jump of the reaction rate (“an explosion”) in the presence of platinum Unfortunately, he had no platinum enough because of wars in South America. Grand Duchess Maria Pavlovna (1786-1859) Introducing the concept time

• Catalysis = dramatic change in time • A special ‘ catalytic force’, Berzelius (Sweden) • Discovery of catalysis promoted introducing the concept of time into chemistry. • However catalysis as a phenomenon was remaining mysterious until 1880s D. INTRODUCING TIME (1851)

Time is introduced into chemistry • Chemical kinetics was born • 1851, Williamson and Wilhelmi

• 1851, Williamson (USA), ‘’Some considerations on chemistry dynamics exemplified by the etherification theory” • Williamson seems to have been the first to use the term ‘dynamics’ regarding the non-steady state chemical processes. • “There are many evidences that chemical processes need time, but this commonly accepted fact is not taken into account in treating various phenomena” (Williamson) 1851, Williamson and Wilhelmi

• 1851, Wilhelmi (Germany): the first kinetic quantitative relationship in studies of acids on the cane sugar • -(dZ/dT) = MZS, • where Z and S are the amounts of sugar and acid catalyst, respectively; T is the reaction time, and M is the mean amount of sugar which has undergone conversion during an infinitesimal period of time under the effect of unit concentration of the catalyzing agent (Wilhelm )Ostwald about Wilhelmi

• “We must consider Wilhelmi as an inventor of the concept of the chemical reaction rate”… • “Wilhelmi’s study had remained absolutely ignored though it has been published in a rather widespread Annals of Physics by Poggendorf… It remained unknown for the later researchers working on similar problems…Only after this field of science had already been so developed that some people began to think about its history, the basic Wilhelmi’s study came to light”… Wilhelm Ostwald (1853-1932) Ostwald’s conceptual breakthrough (1880s-1890s)

• Ostwald gave the first essential interpretation of catalysis. • What is catalysis as a phenomenon? • Ostwald’s answer: “CATALYSIS IS JUST KINETICS”

Ostwald (1895): “A catalyst accelerates a chemical reaction without affecting the position of the equilibrium.” E. The main law of chemical kinetics The Mass-Action-Law (1860s – 1880s)

• The Guldberg-Waage-van’t Hoff’s case story

• Guldberg-Waage (Norway)

van’t Hoff (Netherlands) Cato Maximilian Guldberg (1836-1902) Peter Waage (1833-1900) Jacobus Henricus van 't Hoff (1852-1911) The Hidden History of Chemical Kinetics, I

Gul’dberg and Waage , Norway, 1862-1867 Mass-Action-Law( M.A.L.) Equilibrium formulation “ In chemistry like in mechanics the most natural methods will be to determine forces in the equilibrium states”.

Kpq = Kp 'q', where p, q, p' q' are the " action masses" Initially, Guldberg and Waage used an expression Kp αqβ = K(p')α (q')β

The Hidden History of Chemical Kinetics, II

Gul’dberg and Waage, 1879 Dynamic Formulation of the Mass-Action-Law (M.A.L.) R = K pαααqβββrγγγ The Hidden History of Chemical Kinetics, III

Van’t Hoff, Netherlands, the first winner of the Nobel award (1901) on chemistry 1884, “Essays on chemical kinetics” Idea of normal transformation “The process of chemical transformations is characterized solely by the number of molecules whose interaction provides this transformation” (A ⇔B; 2A ⇔ B; A+B ⇔ C; 2A+B ⇔ C) Strong discussion with Gul’dberg and Waage: “As a theoretical foundation I have accepted not the concept of mass action ( I had to leave this concept in the course of my experiment)”. Van’t Hoff tried to eliminate mechanics from chemistry. The Hidden History of Chemical Kinetics, IV

Van’t Hoff believed that he found the chemical (not mechanical) LAW OF CHEMICAL KINETICS

However, his normal transformation dependences did not fit many real experimental data, e.g. hydrogen oxidation data Van ‘t Hoff’s Revolution Contradictions Van ‘t Hoff introduced the “natural” classification, but at the same time was of the opinion that “normal transformations” occur very rarely He considered the effect of the reaction medium, “disturbing factors”, to be the reason for this Semenov about Van ‘t Hoff’s “Essays”: “…when one is reading this book, one feels as if the author was very interested in the reasons for the abnormal course of reactions and the disturbing factors rather than in further extending his knowledge on normal processes, as he treated them as virtually evident… Van ‘t Hoff’s considerations on the abnormal behavior of reactions is three times as much.” G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 46 Reactions. Decoding Complexity The new idea: “chemical mechanism” (Ostwald? Shoenbein? Christiansen?)

It has an obvious “mechanical origin” Maxwell’s metaphor: BELL and MANY ROPES

In 1879, a vivid interpretation of complex systems as mechanical systems was given by Maxwell. “In an ordinary chime every bell has a rope that is drawn through a hole in the floor into the bell-ringer room. But let us imagine that every rope instead of putting into motion one bell participates in the motion of many parts of the mechanism and that the motion of every bell is determined not only by the motions of its own rope but the motions of several ropes; then let us assume that all this mechanism is hidden and absolutely unknown for the people standing near the ropes and capable of seeing only the holes ceiling above them”. The Hidden History of Chemical Kinetics, V

Chemical kinetics of the XX century is a ‘ centaurus’ which parts are different. 1. The ‘law’ related to the ‘natural classification’ belongs to van’t Hoff. 2. The name ‘mass-action-law’ is coined by Guldberg and Waage. 3. The idea of ‘mechanism’ belongs to ‘unknown parents’ (Ostwald? Schoenbein? Chrisitiansen?)

Christiansen compared the problem of elucidating the complex reaction mechanism with solving the crossword puzzles . • F. Three types of Chemical Kinetics Three Types of Chemical Kinetics

1. Applied kinetics 2. Detailed kinetics 3. Mathematical kinetics

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 50 Reactions. Decoding Complexity Applied Kinetics

r = f( T, p, c)

• Used for obtaining kinetic dependences for reactor and process design(synthesis of ammonia, • oxidation of ammonia, oxidation of SO2 etc) • Kinetic model → model of catalyst pellet → model of catalyst bed → model of reactor • Combinatorial catalysis

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 51 Reactions. Decoding Complexity Detailed Kinetics

• Aimed at reconstructing the detailed mechanism • Based kinetic and non-kinetic data

Detailed mechanism: Set of elementary steps Each elementary step consists of a forward and a reverse elementary reaction Kinetic dependence is governed by the mass- action law

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 52 Reactions. Decoding Complexity 1890-1920ies

• Introducing the idea of “mechanism” of chemical reaction (“detailed mechanism” of the complex reaction) Cyclic mechanisms via intermediates • A. Cyclic mechanism of the catalytic reaction via different intermediates (surface or liquid phase intermediates) • B. Cyclic mechanism of the gas or liquid chain reaction via radicals • C. Cyclic mechanism of the enzyme reaction (Michaelis-Menten mechanism) Nikolay Semyonov (1896-1986) Cyril Hinshelwood (1897 – 1967) Irving Langmuir (1881 – 1957) Mathematical Kinetics

• Deals with the analysis of mathematical models • Deterministic models are a set of algebraic, ordinary differential or partially differential equations • Stochastic models are based on Monte-Carlo methods • Direct and inverse kinetic problems

Kinetic parameters Estimation of kinetic are known parameters G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 57 Reactions. Decoding Complexity temporal change of transport change due to = + amount of component change reaction

Non-Steady-State Models

dc = f ()c, k dt describes the temporal evolution of a chemical reaction mixture from an initial state to a final state • closed system: equilibrium • open system: steady state

Three methods for studying non-steady-state behavior: • change in time t: change in dynamic space ( c,t) • change of parameters k: change in parametric space ( c,k) • change of a concentration with respect to others: change in phase space

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical Reactions. Decoding 59 Complexity Rutherford Aris (1929 – 2005) • G. Experimental Devices of Chemical Kinetics Typical Requirements to Kinetic Experiments: • Isothermicity • Intensive heat exchange with surroundings • Dilution of reactive medium • Rapid recirculation • Uniformity of the chemical composition • Intensive mixing Reactors for Kinetic Experiments

Batch reactor CSTR Continuous-flow reactor with recirculation

feed product feed product

recycle

PFR Differential PFR feed product feed product

catalyst zone

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical Reactions. Decoding 63 Complexity Reactors for Kinetic Experiments

Convectional pulse reactor

Diffusional pulse reactor / TAP reactor

Thin-zone TAP inert reactor zone

catalyst zone G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical Reactions. Decoding 64 Complexity Types of Temporal Evolution − Relaxation Simple exponential relaxation Relaxation with induction period

c c

t t Relaxation of different components at different time scales

c fast

intermediate slow

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 65 t Reactions. Decoding Complexity Types of Temporal Evolution − Relaxation

Relaxation with “overshoots” (1) & (3) and start in “wrong” direction (2)

3 c 1

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 66 Reactions. Decoding Complexity Types of Temporal Evolution − Relaxation Relaxation with different steady states

t Damped oscillations

G.B. Marin & G.S. Yablonsky t (2011). Kinetics of Chemical 67 Reactions. Decoding Complexity Belousov-Zhabotinsky reaction Types of Temporal Evolution − Relaxation

Regular oscillations around a Chaotic oscillations steady state

c c

t t

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 69 Reactions. Decoding Complexity Anatoly Zhabotinsky (1938 – 2008) Gerhard Ertl (1936 - ) Progress in time resolution for 150 years

• From second to femptoseconds (10 -15 sec) Time and Complexity

(1) EVERYTHING IS CHANGING. HOWEVER THE FINAL POINT IS KNOWN. IT IS AN EQUILIBRIUM (2) EVERYTHING IS CHANGING. HOWEVER SOMETHING IS CONSTANT. SOME CHANGES ARE VERY DETERMINED. What is that? • Closed chemical system • (1) Conservation of the total mass of every chemical element • (2) Conservation of the energy –in accordance with the first law of thermodynamics • (3) The entropy has to be increased in time (or the free Gibbs energy has to be decreased in time ) – in accordance with the second law of thermodynamics Equilibrium as the final point. Principle of detailed equilibrium. Under equilibrium conditions, the principle of detailed equilibrium (Onsager, 1931; Nobel prize of 1968) is valid. This principle determines relationships between parameters. They are valid at any moment of time, not only under equilibrium conditions. Equilibrium as the final point

• The equilibrium dependence of the complex chemical composition is known in advance based on the thermodynamics. It is very different from the kinetic dependence . The last one is unknown in advance . • An equilibrium thermodynamics is our ‘solid foundation’. • Reduction of complex model: relationships between concentrations; partial eliminating of time

• Different assumptions on temporal behavior: • -limiting character of some step (some steps are the slowest ones) • Partial equilibrium of some steps (some steps are the fastest ones) • Pseudo-steady-state approximation = ‘eliminating time’ for some substances ‘Eliminating time’ for some substances • Pseudo-Steady-State hypothesis (PSSH) • Two-stage ‘scientific trick’ • (1) Introduce ‘fast’ intermediates • (2) Eliminate time for these intermediates The Hidden History of Chemical Kinetics, VI

“Reaction is not a single act drama” (Schoenbein) There are many intermediates (X) According to the Pseudo-Steady-State Hypothesis (P.S.S.H.), Rate of intermediate generation = Rate of intermediate consumption

Ri.gen (X, C) = Ri.cons (X, C) Then, X = F(C) and Reaction Rate R(X, C)=R (C, F(C))=R(C) P.S.S.H, or Bodenstein’s Principle A paradox of PSSH. Reflecting complexity, we are introducing new unobserved substances (intermediates). At the same time, we are eliminating intermediates searching for simplicity. “The first who applied this theory was S. Chapman and half the year later Bodenstein referred to it in the paper devoted to the hydrogen reaction with clorine. His efforts to confirm his view point were so energetic that this theory is quite naturally associated with his name ” (Christiansen) Max Bodenstein (1871 – 1942) P.S.S.H. has been applied in many areas of chemical kinetics: Reactions in gaseous phase Heterogeneous catalytic reactions Enzyme reactions Etc. New type of eliminating time: Invariances in dual experiments • Comparing the temporal trajectories which are started from the very different initial conditions (mostly from the symmetrical ones), there was found a simple thermodynamic relationship between them at any moment of time, not only at the final point. Reversible reactions

Batch reactor,

• , from (1,0) • , from 0,1 () Remarkably, = = is constant! () ℒ = ℒ = + + + + Yablonsky, G.S., Constales, D., Marin, G.B. Equilibrium relationships for non- equilibrium chemical dependencies. Chem. Eng. Sci. 66 (1) 111-114 (2011). I. STOP TIME ! Founders of infinitesimal calculus: Newton and Leibnitz Calculus’ foundation: Cavalieri is a precursor of infinitesimal calculus

In Europe, the foundational work was a treatise due to Bonaventura Cavalieri, who argued that volumes and areas should be computed as the sums of the volumes and areas of infinitesimal thin cross-sections Isaac Newton (1642-1727) Gottfried Wilhelm Leibnitz (1646-1716) ‘Drop-by-drop’: titration, determination of the equivalent point The origins of volumetric analysis are in late- 18th-century French chemistry. Francois Antoine Henri Descroizilles developed the first burette (which looked more like a graduated cylinder) in 1791. Joseph Louis Gay-Lussac developed an improved version of the burette that included a side arm, and coined the terms "pipette" and "burette" in an 1824 paper on the standardization of indigo solutions Manfred Eigen (1927): Chemical relaxation, but not calculus Experimental calculus in chemistry: John T. Gleaves • Temporal Analysis of Products (TAP) , a vacuum transient response experiment performed by injecting a small number of gas molecules into an evacuated reactor containing a solid sample, which provides precise kinetic characterization of gas- solid interactions with submillisecond time resolution (developed by J.T. Gleaves in 1988) Non-Steady-State Kinetic Screening

TAP: Temporal Analysis of Products • Series of pulses of very small intensity • Change of catalyst composition in controlled manner • Sequence of infinitesimal steps produces a finite change → “chemical calculus”

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 96 Reactions. Decoding Complexity TAP Reactor System-Overview ) Continuous flow valve valvePulse A Inert Exit flow Exitflow (F

0.0 time (s) 0.5

Reactant mixtureReactant Microreactor Catalyst

Product

Vacuum (10 -8 torr) spectrometerMass Thin-zone and Single Particle Reactor Configurations

Thin-zone

Single-particle TAP Multipulse Experiment Combines State-Defining & State-Altering Experiment

Inert Reactant Product

State-defining Experiment State-altering Experiment

Insignificant change

0.0 Small number of pulses 0.0 Large number of pulses Principles of the TAP-experiment

• 3 principles : • (1) Insignificant change of catalyst composition during the single pulse • (2) Controlled change of catalyst composition during the series of pulses • (3) Uniformity of the active zone regarding the composition ======And… Transport is well-defined : Knudsen diffusion • Interrogative kinetics, a systematic approach combining small stepwise changes in catalyst surface composition with precise kinetic characterization after each change to elucidate the evolution of catalyst properties and provide information on the relationship between surface composition and kinetic properties. (developed by J.T. Gleaves and G. Yablonsky in 1997) Interrogative Kinetics (IK) Approach

Was firstly introduced in the paper: Gleaves, J.T., Yablonskii, G.S., Phanawadee, Ph., Schuurman, Y. “TAP-2: An Interrogative Kinetics Approach” Appl. Catal ., A: General, 160 (1997) 55.

The main idea is to combine two types of experiments:

A state-defining experiment in which the catalyst composition and structure change insignificantly during a kinetic test

A state-altering experiment in which the catalyst composition is changed in a controlled manner Legend: Step 2: Decision tree in determining mechanisms for oxygen pre-covered surface ER - Eley-Rideal LH - Langmuir-Hinshelwood OAP -Oxygen Additional Process Buffer - spectator CO

Testing rates

Testing parameters

ER+OAP TAP-results

• About 20 machines working in the world • About 10 research groups US -St. Louis, Houston Europe – Belgium, Ghent; Netherlands, Delft ; N. Ireland, UK, Belfast; Germany – Ulm, Rostock, Bohum; France –Lyon; Spain; Switzerland –Zuerich; Asia- Japan – Tokyo, Toyota City; Thailand – Bangkok. Many catalytic reactions : oxidation of simple molecules, many reactions of complete and selective oxidation of hydrocarbons Non-Steady-State Catalytic Processes

• Automotive catalytic processes • Reverse-flow processes • Oxidation-reduction processes for selective hydrocarbon oxidation • Circulating fluidized-bed reactors • Chemical looping combustion (CLC) (total oxidation of hydrocarbons by metal oxides)

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 105 Reactions. Decoding Complexity Difference from the Faust’s strategy

In chemical time studies, we would like to stop any moment of time, not just the beautiful one. • J. Temporal Patterns of Complex Mechanisms Parallel versus Consecutive Reactions

k1 B

k1 k2 A A B C C k2

cA cA cB c B,max cB concentrations concentrations cC

time t tmax time t

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical Reactions. Decoding 108 Complexity • Non-linear phenomena: • Ignition, Extinction, Oscillations, Chaos Relaxation Characteristics

Critical slowing down causes a dramatic increase in the time to achieve steady state:

τ ss (s)

pB (Pa)

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 110 Reactions. Decoding Complexity Other Catalytic Oscillators

Mechanism for CO oxidation by Vishnevskii and Savchenko

bursts

A B

t (h)

states of metal surface

A B C

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 111 Reactions. Decoding Complexity • In catalysis, all these phenomena are explained using mechanism of competition • between different species, in particular different species adsorbed over the catalyst K. Time of Events. Events and Coincidences in Chemical Kinetics What are events in history and social life ?

• The Berlin Wall comes down • Abdication of the Spanish King • Annexation of Crimea by Russia • Prince William marries Kate Middleton What are events in chemical kinetics?

• Concentration peak • Rate peak • Intersection of concentration dependences • Ignition or extinction • Oscillations • Etc…Etc… Coincidences: two or more events at the same time (D.Constales, G. Yablonsky, G. Marin, 2010-2013)

• Surprising properties of the simple kinetic models; in particular, A->B->C. Coincidences (cont’d)

• Solutions Coincidences (cont’d)

• Acme, k2=k 1/2 Coincidences (cont’d)

• Triple Intersection: Lambert point,

k2=1.1739… k 1 Coincidences (cont’d)

• Inspecting the peculiarities of the experimental data, we may immediately infer the domain of the parameters. • Intersections, extrema and their ordering are an important source of as yet unexploited information. Concidences and Events for two-step consective reaction (Constales, Yablonsky, Marin, Chem. Eng. Sci., 2012) Felix de Boeck, Abstract Composition (1919) • M. History of Chemical Time History of Chemical Kinetics

1810s – Catalysis discovered Döbereiner 1820s Davy

1830s Catalysis distinguished as a special Berzelius phenomenon

1860s Mass-action law Guldberg & Waage

1880s – Natural classification of reactions Van ‘t Hoff 1890s Catalysis is purely kinetic Ostwald phenomenon Principle of independence of reactions Ostwald Concept of reaction mechanism Schönbein G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 124 Reactions. Decoding Complexity History of Chemical Kinetics

1900s – “Wegscheider’s paradox” Wegscheider 1910s Discovery of chain reactions Bodenstein Catalytic cycle Christiansen Quasi-steady-state hypothesis Chapman Bodenstein Catalysis occurs on surface Langmuir

1920s – Discovery of branching chain reactions Semenov Hinshelwood Concept of active catalyst sites 1930s Taylor Discoveries in enzyme adaptation and bacterial Monod genetics Theory of absolute reaction rates Eyring, Evans, Polyani

Onsager reciprocal relationships Onsager G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 125 Reactions. Decoding Complexity Trends in Chemical Kinetics (> 1940s)

• Precise characterization of catalyst activity through kinetic experiments • Development of theory that allows decoding the chemical complexity – Heterogeneous catalysis: Horiuti, Boreskov, Temkin – Enzyme catalysis: King & Altman, Volkenstein & Goldstein

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 126 Reactions. Decoding Complexity History of Chemical Kinetics

1950s – Analysis of multi-step catalytic Christiansen 1960s reactions Discovery of oscillating reactions Belousov Zhabatinsky 1970s – Concept of turnover frequency Boudart 1980s Models for thermodynamics of Prigogine irreversible processes 1980s – Novel observation techniques in Ertl 1990s kinetic studies Density functional theory Kohn

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 127 Reactions. Decoding Complexity “Kinetic Nobel Prize Winners”

NOBEL AWARDS IN KINETICS Van ‘t Hoff (1901), Chemistry

Arrhenius (1903), Chemistry

Ostwald (1909), Chemistry

Langmuir (1932), Chemistry

Hinshelwood & Semenov (1956)

Monod (1965), Physiology or Medicine

Eigen (1967), Chemistry G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 128 Reactions. Decoding Complexity “Kinetic Nobel Prize Winners”

Onsager (1968), Chemistry

Prigogine (1977), Chemistry

Herschbach, Lee & Polanyi (1986), Chemistry

Ertl (2007), Chemistry

Karplus, Lewitt & Warshel (2013), Chemistry

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 129 Reactions. Decoding Complexity L. Revisited list of different meanings of chemical time 1. “Clock” time t , or astronomic time, or ‘external’ time. 2. “Transport time” as a measuring stick of the chemical process 3. “Internal”, or “intrinsic” chemical time (s). A. Intrinsic times of separate reactions. B. ‘Cyclic’ time of the catalytic cycle. 4. Times of Events (Moments of Events) New Trends

RATE–REACTIVITY MODEL HOW TO PRECISELY CHARACTERIZE ACTIVITY OF SOLID MATERIAL ? • Using the Rate-Reactivity Model one can characterize an ability of the solid material to transform one substance into another substance Insignificant chemical perturbation of the solid material

• Reaction Rate determines the ‘Future State’ • Instantaneous Gas Concentration determines the ‘Present State’ • ‘Integral Gas Change’ (Uptake-Release) estimates a Composition of Solid Material which is determined by the ‘Past’ (History of material) Chemical time

• Rate = function ( Instantaneous concentration, Integral chemical change) • Future = function (Present, Past) N. Interdisciplinary influence of ‘chemical time’ studies • Radioactive decay • From chemical chain reactions to chemical nuclear chain reactions • Understanding bioprocesses based on models of chemical kinetics • Ecological models, in particular Lotka-Volterra model • Psychology • Sex behavior Oscillators

Lotka-Volterra or predator-prey equations dx =x() α−β y x is number of some prey (rabbits), y is dt number of some predator (foxes), α, β, γ dy δ =y() γ−δ x and are parameters dt

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical 136 Reactions. Decoding Complexity Curious example

• Otto Weininger “Sex and Character, Principal Investigation” (6 th edition, 1914): • “The law of sexual affinity has many similarities with one known law of theoretical chemistry…It is close to the phenomena associated with the law of mass action”…His final conclusion is: “It is quite evident what I mean: sexual attraction of two individuals being together for a long time or saying it better, locked together, can evolve even when they first had an aversion to one another, which is similar to a chemical process that needs much time until it becomes observable”.” Interesting questions from psychology

• Why fear and isolation can affect our perception of the speed of time? • Why time speeds up as you get older? • Etc… Etc.. Prof. Hudson Hoagland, his wife and his student. I

• Hudson Hoagland (1899-1982) was a Professor of General Physiology and Chairman of the Biology Department of Clark University, 1931-1944. • “In 1932… my wife fell ill with influenza and developed a temperature one afternoon of nearly 104 F (40.0 C) She had asked me to an errand something at the drugstore, and, although I was gone only twenty minutes, she insisted that I must have been away much longer. Since she is a patient lady, this immediately set me to thinking along the lines just indicated and then hurrying to find a stop watch. I then, without telling her why, asked my wife to count to sixty at a speed she believed to be one per second. As a trained musician, she had a good sense of short intervals”. Prof. Hudson Hoagland, his wife and his student. II

• “She repeated this count 25 times in the course of her illness, her speed of counting was measured with a stop watch, and her temperature was recorded each time. She unknowingly counted faster at higher at lower temperatures” (“Voices of Time”, 1981) • Prof. Hoagland found the corresponding temperature dependence (so called Arrhenius dependence) and determined – in style of chemical kinetics- • Energy of activation = 24, 000 cal/mol • His explanation: it was caused by some group of cells in the brain (‘chemical clock’). • Hoagland’s speculation: chemical pacemaker involves oxidative metabolism Prof. Hudson Hoagland, his wife and his student. III

“In the next experiment Hoagland convinced his student to submit diathermy – that is for his body to be wrapped tightly and then artificially raised to 38.8 C using an electric current. Bearing in mind that a body temperature of 40 C degrees would be considered potentially life-threatening emergency, the student was surprisingly rather anxious, which Hoagland remarked rendered his initial time estimations somewhat erratic. Once the student had managed to relax, his perception of time were altered in the same way they were for Hoagland’s wife ” – in accordance with “Time Warped” by Claudia Hammond, 1982 Prof. Hudson Hoagland, his wife and his student. IV Prof. Hoagland tested just two people , and the result was the same: Energy of activation was bigger than 20, 000 cal/mol Keith Leidler said: “I f the energy barrier for a process is greater than about 5 kcal/mole it is almost certain that chemical processes, involving the breaking of primary chemical bonds, are involved. ..It is therefore extremely likely that all of the processes mentioned above (creeping of ants, flashing offireflies, chirping of tree crickets including the psychological ones), are essentially chemical ones”. • O. General Scientific, Philosophical and Religious Aspects Time and Relativity

• Newton and Einstein.

• Newton needed absolute time and absolute space in order to express his laws. Einshtein’s Time in Relativity

• “Before one can begin to understand the effect of relativity theory on our notions of time, it is necessary to realize that the theory is concerned solely with the relation between the times assigned to events at different places and with the variation of those times with a state of motion which the observer ascribes to himself and his measuring instruments. This disposes of number of mistaken ideas which have served, not only to make the theory appear unnecessary mysterious, but also to give it an entirely false aspect” (Herbert Dingle, president of the Royal Astronomic Society) ‘Time is gone’

• Nevertheless, some philosophers after Einstein tried to completely eliminate time from the scientific picture of the World. • “We have learned that we live in four- dimensional and not a three-dimensional world, and that space and time –or, better, space-like separations and time-like separations – are just two aspects of a single four-dimensional continuum…Indeed, I don’t believe that there are any longer any philosophical problems about Time” (Henry Putnam, 1969) Time is Regained

• See “Time is Reborn: From the Crisis in Physics to the Future of the Universe” by the Lee Smolin, Houghton Mifflin Harcourt, 2013 Chemical Time

• Specific features of traditional Chemical Time:

• (1) It is the LOCAL TIME • (2) It is always a combination of the • ‘PAST’, ‘PRESENT’ and ‘FUTURE’ Ecclesiastes.4 MEANINGS OF TIME (1) CYCLIC TIME “The sun rises and the sun sets, and hurries back to where it rises. The wind blows to the south and turns to the north… Whatever is has already been, and what will be has been before”

ECCLISIASTES. 4 MEANINGS OF TIME. (2) LINEAR TIME

• «All go to the same place» • “…the day of death better than the day of birth” ECCLISUASTES. 4 MEANINGS OF TIME. (3) MOMENT

• 7 Go, eat your food with gladness, and drink your wine with a joyful heart, for God has already approved what you do. 8 Always be clothed in white, and always anoint your head with oil. 9 Enjoy life with your wife, whom you love, all the days of this meaningless life that God has given you under the sun—all your meaningless days . ECCLISIASTES. 4 MEANINGS OF TIME (4) TIME OF EVENTS • 3 meanings of time • There is a time for everything, and a season for every activity under the heavens: • 2 a time to be born and a time to die, a time to plant and a time to uproot, 3 a time to kill and a time to heal, a time to tear down and a time to build, 4 a time to weep and a time to laugh, a time to mourn and a time to dance, 5 a time to scatter stones and a time to gather them, a time to embrace and a time to refrain from embracing, 6 a time to search and a time to give up, a time to keep and a time to throw away, 7 a time to tear and a time to mend, a time to be silent and a time to speak, 8 a time to love and a time to hate, a time for war and a time for peace. • “The main mystery of the world is that it can be comprehended” Albert Einstein • This comprehension gives us an ability to know: • THE WORLD IS STILL A MYSTERY Gregory S. Yablonsky “It has seen further it is by standing on the shoulders of giants” (Isaac Newton, Letter to Robert Hook, February 1676) Acknowledgements

John Gleaves Denis Constales Guy Marin Prof. John T. Gleaves Prof. Guy B. Marin Prof. Denis Constales THANK YOU FOR YOUR ATTENTIVE PATIENCE ! References

(1) G. B. Marin, G. Yablonsky, “ Kinetics of Chemical Reactions. Decoding Complexity”. Wiley-VCH, 2011 (2) G. Yablonskii, V. Bykov, A. Gorban, V. Elokhin, “Kinetic Models of Catalytic Reactions”, Elsevier, 1991 (3) “Voices of Time, A Cooperative Survey of Man’s View of Time as Expressed by the Sciences and by the Humanities”, the second edition, editor J.T. Fraser, 1981 (4) C. Hammond, “Time Warped. Unlocking Mysteries of Time Perception”, 2012