a brief history of time in chemistry gregory s. … prof. yablonsky.pdfa brief history of time in...

A BRIEF HISTORY OF TIME

IN CHEMISTRY

Gregory S. YablonskyParks 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

• 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?

lio

• 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 Sncontaining 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?

19

G.B. Marin & G.S. Yablonsky

(2011). Kinetics of Chemical

Reactions. Decoding

Complexity

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)

C. Time in Chemistry: Starting Point

Discovery of Catalysis

Catalysis is the fundamental chemical phenomenon that underlies

Life90% of new chemical processes

CO2 conversion to roses Nontoxic auto-exhaust

Petroleum fuels

Ammonia fertilizerChateau Lafite Rothschild (1887)

NylonSulfuric acid

L-dopaHefty trash bags

Anti-freezeFuel cells

Plastic drain pipeAspartameRoundup

and on and on ……

"Virtually every chemical reaction that

occurs in living organisms is

catalyzed by a specific enzyme."

The Living Cell - C. deDuve Most important environmental

technologyG. Ertl's 2007 Nobel prize involved study

of this catalyticsystem

Chiral Rh complex creates a chiral

productW. Knowles shared 2001 Nobel prize for work on this system

Makes diet coke possible

Natural Catalytic Phenomena

ProductReactant

(O2, Carbohydrates)

Reactant(CO2)

Catalyst (enzyme)

Plant

Energy in (UV-Vis Light)

Reactant

ProductTissue, etc.

(CO2)

Transformation

Regeneration

Animal

Energy out work, heat

Reactant

Catalyst (enzyme)

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)

• "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)

CATALYSISDoebereiner 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

Kpαqβ = 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 pααααqββββrγγγγ

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

46



Reactions. Decoding

Complexity

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.”

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’tHoff.

2. The name ‘mass-action-law’ is coined by Guldbergand 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

50



Reactions. Decoding

Complexity

Three Types of Chemical Kinetics

1. Applied kinetics

2. Detailed kinetics

3. Mathematical kinetics

51



Reactions. Decoding

Complexity

Applied Kinetics

• 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

r = f(T, p, c)

52



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

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)

57



Reactions. Decoding

Complexity

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

are known

Estimation of kinetic

parameters

temporal change of transport change due to

amount of component change reaction

= +

G.B. Marin & G.S. Yablonsky (2011).

Kinetics of Chemical Reactions. Decoding

Complexity

59

Non-Steady-State Models

( ),d

fdt

=cc k

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

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



Complexity

63

Reactors for Kinetic Experiments

feed product feed product

recycle

feed product feed product

catalyst zone

Batch reactor CSTR Continuous-flow reactor with

recirculation

PFR Differential PFR



Complexity

64

Reactors for Kinetic Experiments

catalyst zone

inert

zone

Convectional pulse

reactor

Diffusional pulse

reactor / TAP reactor

Thin-zone TAP

reactor

65



Reactions. Decoding

Complexity

Types of Temporal Evolution − Relaxation

c

t

c

t

c

t

slowintermediate

fast

Simple exponential relaxation Relaxation with induction period

Relaxation of different components at different time scales

66



Reactions. Decoding

Complexity


c

t

3

2

1

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

67



Reactions. Decoding

Complexity


c

t

I

II

c

t

Relaxation with different steady states

Damped oscillations

Belousov-Zhabotinsky reaction

69



Reactions. Decoding

Complexity


c

t

c

t

Regular oscillations around a

steady state

Chaotic oscillations

Anatoly Zhabotinsky (1938 – 2008)

Gerhard Ertl (1936 - )

Progress in time resolution

for 150 years

• From second to femptoseconds (10 -15 sec)

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?

• (H) ELIMINATING TIME.• CONSIDERING CONSTRAINTS.

Chemical evolution

Two main statements

(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)

96



Reactions. Decoding

Complexity

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”

TC

Pulse valve

Microreactor

Mass spectrometer

Catalyst

Vacuum (10-8 torr)

Reactantmixture

0.0 time (s) 0.5

Exi

t fl

ow

(F A

)

Inert

Reactant

Product

Continuous flow valve

TAP Reactor System-Overview

Thin-zone and Single Particle Reactor

Configurations

Thin-zone

Single-particle

Small number of pulses

Insignificant change

0.0

State-defining Experiment

State-Defining & State-Altering Experiment

Inert Reactant Product

Large number of pulses0.0

State-altering Experiment

TAP Multipulse Experiment Combines

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)

The main idea is to combine two types of experiments:

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.

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

Interrogative Kinetics (IK) Approach

ER+OAP

Step 2: Decision tree in determining mechanisms

for oxygen pre-covered surface

Testing rates

Legend:

ER - Eley-Rideal

LH - Langmuir-Hinshelwood

OAP -Oxygen Additional Process

Buffer - spectator CO

Testing parameters

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

105



Reactions. Decoding

Complexity

• 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)

Non-Steady-State Catalytic Processes

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



Complexity

108

Parallel versus Consecutive Reactions

time t

con

cen

tra

tio

ns

cA cB

cC

con

cen

tra

tio

ns

time t

cA

cB

cC

A B C

k1 k2A

B

C

k1

k2

cB,max

tmax

• Non-linear phenomena:

• Ignition, Extinction, Oscillations, Chaos

110



Reactions. Decoding

Complexity

Relaxation Characteristics

Critical slowing down causes a dramatic increase in the time to

achieve steady state:

pB (Pa)

τss (s)

111



Reactions. Decoding

Complexity

Other Catalytic Oscillators

Mechanism for CO oxidation by Vishnevskii and Savchenko

states of metal surface

A B C

A B

C

t (h)

bursts

• 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


• Acme, k2=k1/2


• Triple Intersection: Lambert point,

k2=1.1739… k1


• 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

124

G.B. Marin & G.S. Yablonsky (2011). Kinetics of Chemical

Reactions. Decoding Complexity

History of Chemical Kinetics

1810s –1820s

Catalysis discovered DöbereinerDavy

1830s Catalysis distinguished as a special phenomenon

Berzelius

1860s Mass-action law Guldberg & Waage

1880s –1890s

Natural classification of reactionsCatalysis is purely kinetic phenomenonPrinciple of independence of reactionsConcept of reaction mechanism

Van ‘t HoffOstwald

OstwaldSchönbein

125




1900s –1910s

“Wegscheider’s paradox”

Discovery of chain reactions

Catalytic cycle

Quasi-steady-state hypothesis

Catalysis occurs on surface

Wegscheider

Bodenstein

Christiansen

Chapman Bodenstein

Langmuir

1920s –1930s

Discovery of branching chain reactions

Concept of active catalyst sites

Discoveries in enzyme adaptation and bacterial genetics

Theory of absolute reaction rates

Onsager reciprocal relationships

Semenov Hinshelwood

Taylor

Monod

Eyring, Evans, Polyani

Onsager

126



• 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

Trends in Chemical Kinetics (> 1940s)

127




1950s –1960s

Analysis of multi-step catalytic reactionsDiscovery of oscillating reactions

Christiansen

Belousov Zhabatinsky

1970s –1980s

Concept of turnover frequencyModels for thermodynamics of irreversible processes

BoudartPrigogine

1980s –1990s

Novel observation techniques in kinetic studiesDensity functional theory

Ertl

Kohn

128



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

“Kinetic Nobel Prize Winners”

129



Onsager (1968), Chemistry

Prigogine (1977), Chemistry

Herschbach, Lee & Polanyi (1986), Chemistry

Ertl (2007), Chemistry

Karplus, Lewitt & Warshel (2013), Chemistry

“Kinetic Nobel Prize Winners”

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–REACTIVITYMODEL

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

136



Reactions. Decoding

Complexity

Oscillators

Lotka-Volterra or predator-prey equations

( )dxx y

dt= α − β

( )dyy x

dt= γ − δ

x is number of some prey (rabbits), y is

number of some predator (foxes), α, β, γand δ are parameters

Curious example

• Otto Weininger “Sex and Character, Principal Investigation” (6th 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/molKeith 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

a brief history of time in chemistry gregory s. … prof. yablonsky.pdfa brief history of time in...

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