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Topics in Current Chemistry Collections
Margherita Venturi
Mila D’Angelantonio Editors
Applications
of Radiation
Chemistry in the
Fields of Industry,
Biotechnology
and Environment
Journal Editors
Massimo Olivucci, Siena, Italy and Bowling Green, USA

Wai-Yeung Wong, Hong Kong
Series Editors
Hagan Bayley, Oxford, UK

Kendall N. Houk, Los Angeles, USA
Greg Hughes, Codexis Inc, USA
Christopher A. Hunter, Cambridge, UK
Seong-Ju Hwang, Seoul, South Korea
Kazuaki Ishihara, Nagoya, Japan
Barbara Kirchner, Bonn, Germany
Michael J. Krische, Austin, Texas
Delmar Larsen, Davis, USA
Jean-Marie Lehn, Strasbourg, France
Rafael Luque, Córdoba, Spain
Jay S. Siegel, Tianjin, China
Joachim Thiem, Hamburg, Germany
Margherita Venturi, Bologna, Italy
Chi-Huey Wong, Taipei, Taiwan
Henry N.C. Wong, Hong Kong
Vivian Wing-Wah Yam, Hong Kong
Chunhua Yan, Beijing, China
Shu-Li You, Shanghai, China
Aims and Scope
The series Topics in Current Chemistry Collections presents critical reviews from
the journal Topics in Current Chemistry organized in topical volumes. The scope
of coverage is all areas of chemical science including the interfaces with related
disciplines such as biology, medicine and materials science.
The goal of each thematic volume is to give the non-specialist reader, whether in
academia or industry, a comprehensive insight into an area where new research is
emerging which is of interest to a larger scientific audience.
Each review within the volume critically surveys one aspect of that topic and
places it within the context of the volume as a whole. The most significant
developments of the last 5 to 10 years are presented using selected examples to
illustrate the principles discussed. The coverage is not intended to be an
exhaustive summary of the field or include large quantities of data, but should
rather be conceptual, concentrating on the methodological thinking that will allow
the non-specialist reader to understand the information presented.
Contributions also offer an outlook on potential future developments in the field.
More information about this series at http://www.springer.com/series/14181

Margherita Venturi • Mila D’Angelantonio
Editors
Applications of Radiation
Chemistry in the Fields of
Industry, Biotechnology
and Environment
With contributions from

Krzysztof Bobrowski • Emilio Bucio • Ana Maria del Carmen Calvo
Luigi Campajola • Maria Helena Casimiro • Andrzej G. Chmielewski
Mila D’Angelantonio • Francesco Di Capua • C. Dispenza
Andrea Docters • Luís M. Ferreira • Susana R. Gomes
Bumsoo Han • M. Jonsson • Joana J. H. Lancastre
Jesús E. López-Barriguete • Felipe López-Saucedo
María Virginia Miranda • Suresh D. Pillai • Víctor H. Pino-Ramos
Alejandro Ramos-Ballesteros • Alexandra P. Rodrigues
Gabriela Rodrigues • Mario Carlos Nazareno Saparrat
Shima Shayanfar • Konrad Skotnicki • G. Spadaro • Tomasz Szreder
Erzsébet Takács • Gustavo H. C. Varca • Margherita Venturi
László Wojnárovits • Raissa F. Zaikina • Yuriy A. Zaikin
Editors
Margherita Venturi Mila D’Angelantonio
University of Bologna ISOF-CNR
Bologna, Italy Bologna, Italy
Originally published in Top Curr Chem (Z) Volume 374 (2016),

© Springer International Publishing Switzerland 2017
ISSN 2367-4067 ISSN 2367-4075 (electronic)

ISBN 978-3-319-54144-0 ISBN 978-3-319-54145-7 (eBook)
DOI 10.1007/978-3-319-54145-7
Library of Congress Control Number: 2017933484
© Springer International Publishing AG 2017

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
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The registered company is Springer International Publishing AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Contents
Editorial ................................................................................................................... vii

Margherita Venturi, Mila D’Angelantonio
Radiation Induced Degradation of Organic Pollutants
in Waters and Wastewaters ..................................................................................... 1
László Wojnárovits, Erzsébet Takács
Electron Beam Technology for Environmental Pollution Control .................... 37
Andrzej G. Chmielewski, Bumsoo Han
Radiation Grafting for the Functionalization and Development
of Smart Polymeric Materials................................................................................ 67
Víctor H. Pino-Ramos, Alejandro Ramos-Ballesteros, Felipe López-Saucedo,
Jesús E. López-Barriguete, Gustavo H. C. Varca, Emilio Bucio
Radiation Engineering of Multifunctional Nanogels ........................................... 95
C. Dispenza, G. Spadaro, M. Jonsson
Chitosan-Based Matrices Prepared by Gamma Irradiation for Tissue
Regeneration: Structural Properties vs. Preparation Method ......................... 121
Maria Helena Casimiro, Joana J. H. Lancastre, Alexandra P. Rodrigues,
Susana R. Gomes, Gabriela Rodrigues, Luís M. Ferreira
Application of Radiation Chemistry to Some Selected Technological
Issues Related to the Development of Nuclear Energy ..................................... 147
Krzysztof Bobrowski, Konrad Skotnicki, Tomasz Szreder
Upgrading and Refining of Crude Oils and Petroleum Products
by Ionizing Irradiation ......................................................................................... 195
Yuriy A. Zaikin, Raissa F. Zaikina
The Use of Gamma Radiation for the Treatment of Cultural Heritage
in the Argentine National Atomic Energy Commission: Past, Present,
and Future ............................................................................................................. 227
Ana Maria del Carmen Calvo, Andrea Docters, María Virginia Miranda,
Mario Carlos Nazareno Saparrat
v
Contents
Electron Beam Technology and Other Irradiation Technology

Applications in the Food Industry..................................................................... 249
Suresh D. Pillai, Shima Shayanfar
Applications of Accelerators and Radiation Sources in the Field
of Space Research and Industry ........................................................................ 269
Luigi Campajola, Francesco Di Capua
Erratum to: Radiation Engineering of Multifunctional Nanogels ................. E1
C. Dispenza, G. Spadaro, M. Jonsson
Erratum to: Application of Radiation Chemistry to Some Selected
Technological Issues Related to the Development of Nuclear Energy........... E3
Krzysztof Bobrowski, Konrad Skotnicki, Tomasz Szreder
vi
Top Curr Chem (Z) (2017) 375:11
DOI 10.1007/s41061-016-0094-3
EDITORIAL
Editorial
Margherita Venturi1 • Mila D’Angelantonio2
Springer International Publishing Switzerland 2017
The chemical effects of high-energy radiations, such as those emitted by radioactive

substances, generated by high-energy machines and nuclear reactors, concern a
branch of chemistry called radiation chemistry. This term was proposed by Milton
Burton in 1942 for the needs of the Manhattan Project, the secret atomic energy
research program carried out in the United States during the Second World War. It
is interesting to notice, however, that the first radiation-chemical change was
observed as early as 1895 by Röntgen when he established the existence of a
penetrating, invisible radiation—X-rays—able to fog a photographic plate. Indeed,
as Burton wrote (C&EN, 1969, Feb. 10, 86): In May 1942, the title radiation
chemistry did not exist … I sought an appropriate name for an area that we quickly
realized has existed for 47 years without any name at all. The name radiation
chemistry came out of the hopper; I didn’t like it; I asked Robert Mulliken advice.
He couldn’t think of anything better and, with that negative endorsement, the old
field received its present name.
Since that time, radiation chemistry has developed at an incredible rate. For at least
30 years the interest focused on basic research, exploiting steady-state and time-
resolved techniques, in the field not only of chemistry, but also physics and biology.
These studies, reported in a large number of papers and books, endeavored to
understand the mechanisms of a wide variety of radiolytically induced reactions, and
to collect kinetic data and absorption spectra of the unstable species formed by the
interaction of high-energy radiations with very different systems, as far as chemical
This article is part of the Topical Collection ‘‘Applications of Radiation Chemistry’’; edited by
Margherita Venturi, Mila D’Angelantonio.
& Margherita Venturi

margherita.venturi@unibo.it
1
University of Bologna, Bologna, Italy
2
ISOF-CNR, Bologna, Italy
vii
Top Curr Chem (Z) (2017) 375:11
composition and aggregation state are concerned. These radiations were soon found to
induce useful chemical changes in various substrates resulting in their use for diverse
applications. The first applications were in medicine for diagnostic and therapeutic
purposes, but a variety of interesting industrial applications rapidly emerged, such as
sterilization of different materials and polymer preparation, modification, and
degradation. The applicative aspect of radiation chemistry strongly expanded, taking
advantage of the great amount of results provided by basic studies, so that today high-
energy radiations are employed with various aims in several other fields like
environment, biotechnology, cultural heritage, and food treatment.
These spectacular advances are illustrated in the present topical collection of Topics
in Current Chemistry that showcases contributions from the most prominent expert
groups. It indeed reports the outstanding developments in the industrial, biotechno-
logical, and environmental fields including several recent and interesting topics. These
are (a) radiation-induced degradation of organic pollutants in waters and wastewaters,
(b) advantages of radiation technology for upgrading and refining high-viscous oils
and petroleum products, (c) use of gamma radiations for treating cultural heritage,
(d) application of radiation chemistry to solve some technological issues related to
nuclear energy, (e) radiation-induced grafting for the functionalization and develop-
ment of smart polymeric materials, (f) radiation engineering of multifunctional
nanogels, (g) chitosan-based matrices prepared by gamma irradiation for tissue
regeneration, (h) electron beam technology for environmental pollution control,
(i) radiation technology applications in the food industry, and (j) application of
radiation sources and accelerators in the field of space research and industry.
We believe that this topical collection represents a good opportunity not only to
highlight the research activities carried out by exploiting the peculiar features of the
high-energy radiation with non-experts, but also to stimulate the interest of a wide range
of readers for this relatively new field. Finally, we would like to express our gratitude to
the colleagues who committed to deliver high-quality contributions, and to the editorial
staff at Springer for their support throughout the development of this topical collection.
Margherita Venturi
viii
Top Curr Chem (Z) (2017) 375:11
Mila D’Angelantonio
ix
Top Curr Chem (Z) (2016) 374:50
DOI 10.1007/s41061-016-0050-2
REVIEW
Radiation Induced Degradation of Organic Pollutants

in Waters and Wastewaters
László Wojnárovits1 • Erzsébet Takács1
Received: 18 March 2016 / Accepted: 28 June 2016 / Published online: 25 July 2016
Springer International Publishing Switzerland 2016
Abstract In water treatment by ionizing radiation, and also in other advanced

oxidation processes, the main goal is to destroy, or at least to deactivate harmful
water contaminants: pharmaceutical compounds, pesticides, surfactants, health-care
products, etc. The chemical transformations are mainly initiated by hydroxyl radi-
cals, and the reactions of the formed carbon centered radicals with dissolved oxygen
basically determine the rate of oxidation. The concentration of the target compounds
is generally very low as compared to the concentration of such natural ‘impurities’
as chloride and carbonate/bicarbonate ions or the dissolved humic substances
(generally referred to as dissolved organic carbon), which consume the majority of
the hydroxyl radicals. The different constituents compete for reacting with radicals
initiating the degradation. This manuscript discusses the radiation chemistry of this
complex system. It includes the reactions of the primary water radiolysis interme-
diates (hydroxyl radical, hydrated electron/hydrogen atom), the reactions of radicals
that form in radical transfer reactions (dichloride-, carbonate- and sulfate radical
anions) and also the contribution to the degradation of organic compounds of such
additives as hydrogen peroxide, ozone or persulfate.
Keywords Water treatment Advanced oxidation processes Degradation

Radiolysis Radical
This article is part of the Topical Collection‘‘Applications of Radiation Chemistry’’; edited by

‘‘Margherita Venturi,Mila D’Angelantonio.
& Erzsébet Takács

erzsebet.takacs@energia.mta.hu
1
Institute for Energy Security and Environmental Safety, Centre for Energy Research, Hungarian
Academy of Sciences, Konkoly-Thege M. út. 29-33, H-1121 Budapest, Hungary
Reprinted from the journal 1 123

Top Curr Chem (Z) (2016) 374:50
1 Introduction
In water treatment by ionizing radiation, the reactive intermediates of water

radiolysis and the radicals that form in radical transfer reactions induce the
degradation of the target harmful organic pollutants, pharmaceuticals, pesticides,
health care products, etc. [1, 2]. In real wastewater, there is always a competition
between the reactions of different constituents of the aqueous solutions for the
reactive water intermediates. The relative rates of reactions are determined by the
product of the rate constant (kx) and the concentration of a given component (Sx) in
the water: kx[Sx]. This product is called scavenging capacity. The weight of a
reaction of a reactive intermediate with compound x (wx) may be calculated using
the relation:
kx ½Sx
wx ¼ P ð1Þ
kx ½Sx
P
where the summation should go on for all solutes. kx ½Sx represents the total
scavenging capacity of the system [3]. The water that undergoes treatment beside
dissolved O2 molecules (2.8 9 10-4 mol dm-3, at 20 C) practically always con-
tains chloride ions, carbonate and hydrogen carbonate (bicarbonate) ions, and a
large number of different organic molecules. The organic content of drinking water,
and the water of lakes and rivers, is referred to as dissolved organic carbon (DOC,
defined as the fraction of organic substances that passes through a 0.45 lm filter).
DOC has diverse origin and composition within aquatic systems. Occasionally, high
concentrations of organic carbon indicate anthropogenic influences, but DOC is
mostly of natural origin. Organic carbon compounds usually form in decomposition
processes of plants or organisms living in water. DOC in natural waters is composed
of a heterogeneous mixture of organic compounds with molecular masses ranging
from less than 100 to 300,000 Daltons. Humic substances (fulvic and humic acids)
are the dominant DOC fractions in freshwater and costal seawater [4]. Due to the
undefined composition of DOC, scientific investigations with reactions of dissolved
organic matter are often carried out with standard samples from the Suwannee
River, purchased from the International Humic Substances Society (e.g., [5]).
The primary radicals that form during water irradiation react with the target
harmful organic molecules and also with DOC, chloride and bicarbonate/carbonate
ions, etc., forming secondary radicals. The properties and reactions of these
secondary radicals and their participation in the degradation reactions are also
detailed here, together with the reactions of primary water radiolysis intermediates.
Some additives, like ozone, hydrogen peroxide or persulfate, are known to increase
the oxidation efficiency of organic pollutants by transforming reductive interme-
diates to oxidizing species during irradiation. These reactions are also discussed.
This paper concentrates on the radical reactions and mechanisms that are important
from the point of view of water treatment. Practical implementation of the technique
is discussed in another paper in this issue.
123 2 Reprinted from the journal

Top Curr Chem (Z) (2016) 374:50
2 Reactions of Primary Radicals of Water Radiolysis with Organic

Molecules
2.1 Radiolysis of Liquid Water
An important characteristic of ionizing radiation is that its energy is absorbed non-

selectively so that molecules are ionized or excited according to their relative
abundance in the medium of interest [6]. In dilute solutions, the energy is
overwhelmingly absorbed by the solvent and the chemical reactions of the solute
molecules occur through reactions of the reactive intermediates formed due to
energy deposition in the solvent molecules. In radiation chemistry, there is a high
probability that during the energy deposition and in the subsequent fast reactions,
two or more reactive species are created close enough to each other that they can
mutually influence each other’s further reaction possibilities. This isolated space is
called spur. There is a competition between the reaction of intermediates in the spur
and their diffusing out of the spur (spur expansion). The intermediates that escape
the spur in the bulk become homogeneously distributed with respect to solute
molecules.
In the radiolysis of liquid water, the intermediates mainly form as a consequence
of ionization of water molecules. Excited-state water molecules may play a much
less significant role in radiolysis [6–10]:
ð2Þ
ð3Þ
H2 Oþ þ H2 O ! H3 Oþ þ OH ð4Þ
e þ n H 2 O ! e
aq ð5Þ
H2 O ! OH þ H ð6Þ
The radical cation, H2O? formed in reaction (2) may migrate over a distance of a
few water molecules by resonance electron transfer, but since H2O? is a strong acid
within 10-14 s it gives a proton to one of the surrounding water molecules according
to (4), and the process gives a hydroxonium ion and hydroxyl radical (OH). The
electron released in reaction (2) (dry electron) loses its kinetic energy in collisions
with surrounding water molecules and in less than 10-12 s is localized in a potential
energy well as a result of molecular dipoles rotating under the influence of the
negative charge. Thus, in reaction (5), the smallest anion, e-aq, a solvated (hydrated)
electron forms. The hydrated electron is also called aqueous electron. The excited
water molecules, H2O*, formed in reaction (3), decompose to OH and H in
reaction (6).
The yields (the so called G-values) of OH, e-
aq and H after the spur processes are
-1
0.28, 0.28 and 0.06 lmol J , respectively. The intermediates with these yields

Top Curr Chem (Z) (2016) 374:50
react with solute molecules present at a concentration level B10-3 mol dm-3. It is
estimated that about 40 % of the initially produced intermediates are consumed by
spur processes [6]. In the spur processes, H2 (0.047 lmol J-1) and H2O2
(0.073 lmol J-1) form and there is also some reformation of water molecules
(OH ? H? H2O).
2.2 The Diffusion Controlled Rate Constant
The rate constants of reactions of several inorganic radicals (e.g., OH, Cl or SO-
4 )
with organic molecules (mainly aromatics) approach the theoretical maximum, the
so-called diffusion controlled value, kdiff. There are several equations in the
literature for the estimation of the diffusion controlled limit; however, in practice,
the Smoluchowski relation is the one that is most often used for this purpose
[11, 12]:
kdiff ¼ 4pðDP þ DR ÞðrP þ rR ÞN 103 ðmol1 dm3 s1 Þ ð7Þ
In the equation, DP and DR are the diffusion coefficients of the attacked molecule
and the attacking radical, respectively, in m2 s-1 units. rP and rR are the reaction
radii of the corresponding species in m. N is Avogadro’s number. When the dif-
fusion coefficients and the reaction radii are used in these units, kdiff is obtained in
mol-1 dm3 s-1. For a typical aromatic molecule, DP and rP are around 0.5 9 10-9
m2 s-1 and 3.2 9 10-10 m, respectively [13]. In a study [12] on the temperature
dependence of the OH ? aromatic molecule reactions, 2.2 9 10-10 m and
2.3 9 10-9 m2 s-1 were used for rOH and DOH, respectively (Table 1). For the
numerical values of DSO4- and rSO4-, Rickman and Mezyk [14] suggested
1.1 9 10-9 m2 s-1 and 2.2 9 10-10 m, respectively. For the diffusion coefficient
and the reaction radius of the hydrogen atom, rH = 1.9 9 10-10 m and
DH = 7 9 10-9 m2 s-1 were used in several papers (e.g., [15]). In the paper of the
latter authors, rCl
2
= 1.85 9 10-10 m and DCl 2
= 1.41 9 10-9 m2 s-1 were used
in the calculation of the diffusion controlled rate constant of Cl2-. We assumed the
same reaction radius and diffusion coefficient values for Cl- -
2 and CO3 . The values
-
for eaq were taken from the book of Swallow [7].
The diffusion controlled rate constants for a given radical should vary with size
and structure of the reacting organic molecule. However, these variations are
probably small and the expected values do not change more than 10–20 %. In the
following, when interpreting the rate constants, we use the same kdiff for a radical,
independent of the reaction partner organic molecule [13]. kdiff is the highest for e- aq
and H reactions, due to the fast diffusion of these species in the matrix. It is the
lowest for the heaviest, SO- 4 . The kdiff values in the table are in reasonably good
agreement, with the highest reliable rate constants measured for OH, H, Cl- 2 and
CO-3 reactions, respectively. The k diff values for e -
aq and SO -
4 reactions seem to be
slightly underestimated. The charges of the reactants and ionic strength effects also
influence the reaction rates.
When the two reactants, the attacking radical and the organic molecule, approach
each other by diffusion, the rate of the chemical step is basically determined by the

Reprinted from the journal
Table 1 Diffusion coefficients and reaction radii for several inorganic radicals, and the estimated diffusion limited rate constants for reactions with simple aromatic
molecules
Top Curr Chem (Z) (2016) 374:50

Radical OH e-
aq H Cl-
2 CO-
3 SO-
4
DR, m2 s-1 2.3 9 10-9,a 4 9 10-9,d 7 9 10-9,b 1.41 9 10-9,b 1.41 9 10-9,e 1.1 9 10-9,c
-10,a -10,d -10,b -10,b -10,e
rR, m 2.2 9 10 3 9 10 1.9 9 10 1.85 9 10 1.85 9 10 2.2 9 10-10,c
-1 3 -1 10 10 10 9 9
kdiff, mol dm s 1.1 9 10 2.5 9 10 2.9 9 10 7.3 9 10 7.3 9 10 6.5 9 109
5
a
[12]
b
[15]
c
[14]
d
[7]
e
We assumed the same values as for Cl-
2
123
Top Curr Chem (Z) (2016) 374:50
chemical properties of the organic molecule. The rate constant of the chemical
reaction (kchem) can be estimated by the Noyes relation [16]:
1= 1 1
kobsd ¼ =kdiff þ =kchem ð8Þ
In the equation, kobsd and kdiff stand for the observed and the diffusion controlled
rate constant. The rate constant of the chemically activated reaction, kchem, is the
rate constant that would be measured if diffusion of the species was not rate
influencing [11]. Due to the diffusion limitation, kchem often shows much wider
structural variation than kobsd. This is especially true for radicals that can react with
kobsd close to the diffusion limitation [16].
The rate constants of hydrated electrons, hydrogen atoms and hydroxyl radicals,
published until 1988, are collected in the work of Buxton et al. [17]; an updated
version is available on the internet. The data for inorganic radicals other than OH,

e-
aq and H have been compiled by Neta et al. [18].
2.3 Reactions of the Hydroxyl Radical
During water treatment by ionizing radiation, and in practically all of the other
Advanced Oxidation Processes (AOP), hydroxyl radical is suggested to be the main
reactive intermediate that induces the degradation of organic molecules. Due to its
central role in different AOPs, the kinetics and mechanism of OH reactions with a
large variety of organic pollutants have been detailed in a large number of
publications. Here we give only a short overview.
In laboratory experiments, the primary processes of OH reactions are mostly
studied in N2O purged solutions (in the absence of dissolved O2) in order to convert
the hydrated electron into hydroxyl radical in Reaction (9). H reacts slowly with
N2O [6].
e
aq þ N2 O þ H2 O ! OH þ OH þ N2 k9 ¼ 9:1 109 mol1 dm3 s1 ð9Þ
In biochemical type investigations, when the presence of dissolved O2 is needed, the

experiments are often carried out in N2O:O2 mixtures with 4:1 ratio. Under these
conditions, the hydrated electrons are converted to OH, but the aqueous solutions
have dissolved O2 concentrations, just like under normal aerated conditions.
In reaction with dissolved organic molecules, OH may react in three different
ways: direct electron transfer, abstraction of H-atoms from C–H bonds, and addition
to the double bonds. Although the standard reduction potential of OH is high
(E0(OH/OH-) = 1.9 V vs. NHE, Table 2), direct electron transfer is rarely observed,
and when it is observed, intermediate complexes are likely to be involved [21].
Electron transfer may take place in OH reaction with phenolates, although the
electron transfer is also in competition with radical addition to the ring. These
reactions are shown in the example of phenoxide in (10) and (11). The rate constant of
the C6H5O- ? OH reaction is (k10 ? k11) = 9.6 9 109 mol-1 dm3 s-1 [13].
C6 H5 O þ OH ! C6 H5 O þ OH ð10Þ

Top Curr Chem (Z) (2016) 374:50
Table 2 One-electron
Pair E, V
reduction potentials vs. normal
hydrogen electrode (NHE) of
aq/e-
aq -2.9
some radicals used in radiation

chemical studies [19, 20] H?
aq/H -2.42
(CH3)2CO, H?/(CH3)2COH -1.39
CH3CHO, H?/CH3CHOH -1.25
CH2O, H?/CH2OH -1.18
O2/O-
2 -0.33
HO2, H?/H2O2, pH 0 1.48
CO- ? -
3 ,H /HCO3 , pH 7 1.78

OH/OH- 1.9
Cl-
2 /2 Cl
-
2.1
SO-
4 /SO4
2-
2.43
Cl/Cl- 2.6
C6 H5 O þ OH ! C6 H5 OHO ð11Þ
The rate constants of H-atom abstraction reactions are generally in the 1 9 107–
1 9 109 mol-1 dm3 s-1 range. The reactions take place with a considerable
selectivity: the rates increase in the order primary \ secondary \ tertiary H-atom.
Here, we show the reactions with methanol, ethanol, isopropanol and tert-butanol
[22]. In methanol and tert-butanol, three or nine primary H-atoms, respectively, are
available for H-abstraction (bond dissociation energies 402 kJ mol-1 and
418 kJ mol-1 [23]), and in ethanol and isopropanol there are two secondary and one
tertiary C–H bonds (389 and 384 kJ mol-1), respectively, as preferred sites of H-
abstraction. H-abstraction from the alcoholic OH also takes place, albeit with low
weight [21].

OH þ CH3 OH ! H2 O þ CH2 OH k12 ¼ 9 108 mol1 dm3 s1 ð12Þ

OH þ CH3 CH2 OH ! H2 O þ CH3 CHOH k13 ¼ 2:2 109 mol1 dm3 s1
ð13Þ

OH þ ðCH3 Þ2 CHOH ! H2 O þ ðCH3 Þ2 C OH k14 ¼ 2 109 mol1 dm3 s1
ð14Þ

OH þ ðCH3 Þ3 COH ! H2 O þ CH2 CðCH3 Þ2 OH
ð15Þ
k15 ¼ 6:2 108 mol1 dm3 s1
The a-hydroxymethyl, a-hydroxyethyl and a-hydroxyisopropyl radicals that form in
H-abstraction from methanol, ethanol and isopropanol, respectively, [Reactions
(12–14)] exhibit reducing character (Table 2). The radical formed in reaction with
tert-butanol (15) is a non-reducing radical. In the presence of dissolved O2, the alkyl
radicals transform to peroxides and the degradation may take place by Russel/
Bennett mechanism [24].

Top Curr Chem (Z) (2016) 374:50
Table 3 Rate constants of selected OH reactions in mol-1 dm3 s-1 units
Compound Rate constant References
9
Benzene 7.8 9 10 Selected [13]
Phenol 8.4 9 109 Selected [13]
p-Cresol 9.2 9 109 Selected [13]
9
Aniline 8.6 9 10 Selected [13]
Chlorobenzene 5.6 9 109 [12]
Nitrobenzene 3.5 9 109 Average [13]
Benzoic acid 1.9 9 109 [12]
Benzoate ion 5.9 9 109 Recommended [17]
17b-estradiol 5.3 9 109 [25]
p-Nonylphenol 1.1 9 1010 [26]
Bisphenol 6.9 9 109 [27]
Dimethyl-phthalate 3.4 9 109 [28]
2,4-Dichlorophenol 6.0 9 109 Average [29]
2,4-Dichlorophenoxyacetic acid 5.5 9 109 Recommended [29]
Atrazine 2.4 9 109 Recommended [29]
Simazine 2.6 9 109 Average [29]
Prometon 2.8 9 109 Average [29]
Fenuron 8.3 9 109 Recommended [29]
Monuron 7.3 9 109 [29]
9
Diuron 6.0 9 10 Average [29]
Chloramphenicol 2.5 9 109 [30]
Sulfacetamide 5.3 9 109 [31]
Sulfamethoxazole 8.5 9 109 [32]
Sulfamethazine 8.3 9 109 [32]
Penicillin G 8.1 9 109 Average [33–35]
Amoxicillin 7 9 109 Average [14, 35, 36]
Ampicillin 7.5 9 109 Average [33, 36]
Cloxacillin 7.1 9 109 Average [33, 36]
Salicylic acid 1.07 9 1010 [37]
Paracetamol 5.6 9 109 [38]
Diclofenac 8.12 9 109 [39]
Ketoprofen 4.6 9 109 [39]
Ibuprofen 6.1 9 109 [39]
Acid Red 265 9.3 9 109 [40]
Acid Blue 62 1 9 1010 [41]
Due to its electrophilic nature, OH reacts readily with C=C and C=N double
bonds, but not with C=O double bonds, which are electron-deficient at the carbon
atom, where the hydroxyl radical prefer to add. The rate constants of reactions with
aromatics (Table 3) are in a narrow range, between 2 9 109 mol-1 dm3 s-1 and
1 9 1010 mol-1 dm3 s-1 [13]. These kOHs are close to the diffusion controlled limit
of kdiff, OH = 1.1 9 1010 mol-1 dm3 s-1 (Table 1). The kOHs show some regular

Top Curr Chem (Z) (2016) 374:50
11.0
log kchem = (10.19 ± 0.04) - (0.82 ± 0.10) σ p
10.8 1
2 3
10.6 4 11
log kchem, mol-1 dm3 s-1 10.4 5

6 10
10.2 9 15 23
8 20
10.0 12 16 25
7
14 26
9.8 17 21
27

13
9.6
18 24
9.4 22
19
9.2
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
σp
Fig. 1 Correlation between the log kOH, chem-values and the rp Hammett substituent constants for
monosubstituted benzenes {data from Table 3 [corrected for diffusion, (Eq. 8)] and Ref. [13]}: 1.
phenoxide, 2. aniline, 3. phenol, 4. toluene, 5. phenylacetate ion, 6. ethylbenzene, isopropylbenzene, 7.
acetanilide, 8. benzoic acid ion, 9. phenethylalcohol, 10. benzene, 11. benzyl alcohol, 12. fluorobenzene,
13. iodobenzene, 14. bromobenzene, 15. chlorobenzene, 16. benzenesulfonate ion, 17. benzamide, 18.
benzaldehyde, 19. benzoic acid, 20. a-methylbenzyl-ammonium ion, 21. acetophenone, 22.
benzenesulfonic acid, 23. benzylammonium ion, 24. benzenesulfonamide, 25. anilinium ion, 26.
benzonitrile, 27. nitrobenzene
trend with the Hammett substituent constants, but the logarithms of the rate
constants do not give straight lines as a function of the substituent constants,
because the kOHs are controlled by both the chemical reactivity and the diffusion.
The logarithms of rate constants corrected for diffusion (Eq. 8), however, show
linear correlation with rp for monosubstituted benzenes (Fig. 1) and para-
substituted phenols [13]. The negative slope in Fig. 1, q = -0.82, shows
electrophilic reaction. The absolute value of q is smaller than that found in Cl-
2
(-1.5 [42]) and Br-
2 (-1.1 [43]) reaction with aromatic molecules or in NH2 (-3.3
[44]) reaction with phenoxide ions. The smaller negative q is due to the low
selectivity and high reactivity of OH.
As the first step, the reaction between the hydroxyl radical and the aromatic
molecule (PhX) leads to the formation of a loosely bound p-complex in a reversible
reaction [12]. The complex may dissociate, or transform to a r-complex
(hydroxycyclohexadienyl radical).

OH þ PhX pPhXOH ! rPhXOH ð16Þ
In aromatic compounds, electron-donating substituent directs OH into the ortho-
and para-positions; in the case of the electron withdrawing substituents, meta-
addition is preferred [45, 46]. The regioselectivity of hydroxyl radical addition
reaction may occur in the transition from the p-complex to the r-complex [21].
Addition to the ipso-position, presumably due to steric reasons generally has low
weight [47]. In the case of phenol, ipso-, ortho-, meta- and para-additions take place
with probabilities of 0.08, 0.50, 0.08 and 0.34, respectively.

Top Curr Chem (Z) (2016) 374:50
Scheme 1 Perhydroxyl radical elimination from the peroxyl radical in phenol oxidation
In OH addition to the aromatic ring, a carbon centered hydroxycyclohexadienyl

type radical forms; the fate of this radical is determined by the substituents on the
ring, on the pH of the solution and also on the dissolved O2 concentration. In neutral
O2-free solutions, these radicals mainly terminate in slow radical–radical reactions.
When the starting molecule is a phenol type compound (Scheme 1), in acid/base
catalyzed reactions, water elimination and phenoxyl radical formation is the
preferred reaction, especially at low and high pH values [48–50]. Cyclohexadienyl
type radicals readily react with dissolved O2, and the rate constants are in the
1 9 108–1 9 109 mol-1 dm3 s-1 range [51]. The O2 addition is fast and the adduct
is relatively stable when there is an electron donating substituent on the ring; the
opposite is true for electron withdrawing substituent. It is generally assumed that the
ring-opening takes place from a peroxyl radical structure [52–54]. Scheme 1 shows
ortho-addition to phenol and the reaction of the carbon centered hydroxycyclo-
hexadienyl radical with dissolved O2. The HO2 elimination from the peroxyl radical
is in competition with the ring-opening degradation.
The dissolved organic carbon (DOC) uses up a large fraction of available OH in
AOP; therefore, several measurements are published for the OH ? DOC reaction.
Although the characteristics (average molecular mass, composition, etc.) of DOC of
different origin may differ considerably, the rate constants determined fall in a
narrow range: 1.1 9 104–3 9 104 mgC-1 dm3 s-1. Westerhoff et al. [5] determined
kOH, DOC of 1.3 9 104 mgC-1 dm3 s-1 for the standard fulvic acid from the
Suwannee River. Lutze [55] gives a kOH, DOC of 1.14 9 104 mgC-1 dm3 s-1. The
DOC intermediates in pulse radiolysis were formed on the microsecond timescale
and decayed on the millisecond timescale [5].

Top Curr Chem (Z) (2016) 374:50
2.4 Reactions of the Hydrated Electron and Hydrogen Atom
Hydrogen atom (H) and hydrated electron (e- aq) compose an acid/base pair with a
pKa of 9.1 [6]. Both the forward and the backward reactions (17) and (-17) are
relatively slow, and due to the short lifetime of e-aq, these reactions do not have
much importance in pulse radiolysis investigations [56]. In steady-state experi-
ments, however, the H?e- aq conversion may have some effect on the product yields
in alkaline solutions:
e
aq þ H2 O OH þ H k17 ¼ 1:9 101 mol1 dm3 s1 ð17Þ
k17 ¼ 2:5 107 mol1 dm3 s1 ð17Þ

e-
aq is characterized by a strong light absorption band centered at 720 nm and a
maximum molar absorption coefficient of *20,000 mol-1 dm3 cm-1. The majority
of the oscillator strength is derived from the optical transitions from the equilibrated
s state to a p-like excited state. This very strong transient absorption band is used for
the determination of e- aq reaction rate constants by pulse radiolysis [21].
e-aq reactions are generally investigated in the 3.5–9 pH range with an additive
that removes OH. For this purpose, mostly 0.1–1 mol dm-3 tert-butanol is applied:
in such solutions, in reaction (15) OH is converted to CH2C(CH3)2OH, and the
latter radical has low reactivity with most of the solutes [57]. This technique is often
very useful for pulse radiolysis experiments. It should be emphasized, however, that
the tert-butanol-derived radicals are not always unreactive with certain substrates on
the timescale of 60Co c-radiolysis experiments, where the lifetime of radicals is
several orders of magnitude longer than under pulse radiolysis [58]. Therefore, the
disadvantage of tert-butanol is that CH2C(CH3)2OH may react with the other
radical intermediates present.
In reactions with organic molecules, e- aq reacts as a nucleophile (standard one-
electron reduction potential E0(aq/e- aq ) = 2.9 V, Table 2). It reacts preferentially
with low-lying vacant molecular orbital structures, such as aromatic hydrocarbons,
conjugated olefins, carboxyl compounds, and halogenated hydrocarbons
[6–10, 57–59]. Its reactivity is greatly enhanced by an electron withdrawing
substituent adjacent to the double bonds or attached to the aromatic rings.
e-aq reacts with many compounds that are capable of releasing an anion by
dissociative electron capture; these reactions can occur only when single bonds are
involved in the process [21]. In a number of reactions that are written as dissociative
electron attachment, however, short-lived radical anions are the intermediates.
Typically, these reactions take place with halogenated compounds, where the
electron ‘scavenging’ at the halogen site is followed by the elimination of the halide
ion. The reaction with chlorobenzene is assumed to be a two-step process via an
intermediate radical anion [Reaction (18)]. The first step is electron addition to the
vacant orbital, bond breakage occurs rapidly and the overall reaction essentially
appears as a dissociative electron capture process with elimination of the halide ion
Cl- [6, 60]:

Top Curr Chem (Z) (2016) 374:50
Table 4 Rate constants of

hydrated electron reactions in
mol-1 dm3 s-1 units
Benzene 1 9 107 [17]
Phenol 2 9 107 [17]
Aniline 3 9 107 [59]
Chlorobenzene 5 9 108 [60]
Nitrobenzene 3.7 9 1010 [17]
Benzoate ion 3.2 9 109 [17]
Dimethyl-phthalate 1.6 9 1010 [28]
2,4-Dichlorophenol 5 9 108 [61]
2,4-Dichlorophenoxyacetic acid 2.5 9 109 [62]
Atrazine 4.8 9 109 [63]
Fenuron *1 9 109 [64]
Diuron 1 9 1010 [65]
Monuron 2.1 9 109 [66]
Chloramphenicol 2.3 9 1010 [30]
10
Sulfamethoxazole 1 9 10 [32]
Sulfamethazine 2.4 9 1010 [32]
Penicillin G 2.7 9 109 [67]
Amoxicillin 5.2 9 109 [68]
Ampicillin 5.7 9 109 [67]
Cloxacillin 7.5 9 109 [67]
Salicylic acid 9 9 109 [37]
Paracetamol 5 9 108 [38]
Diclofenac 1.7 9 109 [39]
Ketoprofen 2.6 9 1010 [39]
Ibuprofen 8.9 9 109 [39]
Acid Blue 62 3 9 1010 [41]
Isobutylnaphthalene sulfonate 2.5 9 1010 [69]
e
aq þ C6 H5 Cl ! ½C6 H5 Cl ! C6 H5 þ Cl

k18 ¼ 5 108 mol1 dm3 s1
ð18Þ
Compounds with high electron affinity (e.g., nitro- and cyano-derivatives) react with
e-
aq with diffusion-controlled rate constants of *2.5 9 10
10
mol-1 dm3 s-1
(Tables 1, 4) with formation of the corresponding radical anions. The rate constants
with aldehydes and ketones are *4 9 109 mol-1 dm3 s-1. The electron is
accommodated on the carbonyl carbon. The e- aq rate constants for the reactions with
carboxylic acids, esters, and amides are in the order of *107 mol-1 dm3 s-1 [17].
Simple olefins do not react with e- aq at appreciable rates, but compounds with
extended p-electron delocalization react rapidly with the hydrated electron. The
keaq- values of maleates and fumarates, which contain conjugated double bonds
(e.g., O=C(OH)–HC=CH–C(OH)=O), are in the range of diffusion controlled-limit

Top Curr Chem (Z) (2016) 374:50
[70, 71]. The radical anion formed protonates instantaneously (Grotthuss mecha-
nism). The protonation reaction results in a carbon-centered radical at the carbonyl.
In reactions with aromatic molecules, e- aq adds to the ring with formation of a
radical anion. The rate constant is small (*107 mol-1 dm3 s-1) in the case of
benzene and alkylbenzenes, and the process is reversible; e- aq addition may be
followed by a thermally activated dissociation [21]. This dissociation is in
competition with the anion protonation, in which cyclohexadienyl radical (C6H7) is
produced [Reaction (19)].
þHþ
e
aq þ C6 H6 C6 H
6 !þ C6 H7 k19 ¼ 1 107 mol1 dm3 s1 ð19Þ
H
keaq- is higher (108–1010 mol-1 dm3 s-1), when an electron withdrawing sub-
stituent, such as –COOH, –Cl, or –NO2 group, is attached to the ring (Table 4). The
rate constants of e-aq reaction with benzoic acid, chlorobenzene (electron addition
followed by Cl- elimination reaction), and nitrobenzene are 7.1 9 109, 5 9 108 and
3.7 9 1010 mol-1 dm3 s-1, respectively [15, 61].
The H-atom yield in neutral or alkaline solutions is low, G = 0.06 lmol J-1. In

acidic solutions due to the e-aq?H conversion in (20), the yield is high, G = 0.34
-1
lmol J .
e þ
aq þ H ! H

k20 ¼ 2:3 1010 mol1 dm3 s1 ð20Þ
Under radiolysis conditions, the reactions of hydrogen atoms are usually investi-

gated in acidic solutions, below pH 3, in order to convert e- aq to H in (20). The OH
reactions are eliminated by using tert-butanol [Reaction (15)] [57]. The reactivity of
H with tert-butanol is low (1 9 106 mol-1 dm3 s-1 [72]) and this reaction leaves H
largely untouched. When the rate constant with the compound of interest (S) is
higher than 1 9 108 mol-1 dm3 s-1, and its concentration is above 1 9 10-3
mol dm-3, the presence of tert-butanol practically does not influence the H ? S
reaction.
Alam et al. [73] in their pulse radiolysis experiments investigated the H reactions
with several alcohols in N2O saturated solutions. OH formed in such system with
0.56 lmol J-1 yield reacted with the alcohols with rate constants an order of
magnitude higher than H. This high difference in rate constants allowed
differentiating OH and H reactions. Using this technique in rate constant
determination, one is not restricted to work in the acidic pH range.
H and OH do not absorb the light in the usual wavelength range (200–800 nm)
of pulse radiolysis studies. In transient measurements, the products of H or OH
reaction or competitive techniques are used to determine the rate constants.
H is a slightly less powerful reducing agent than e- 0 ?
aq (E (Haq/H ) = 2.4 V and
0 -
E (aq/eaq) = 2.9 V). It reduces metal ions with lower reduction potentials, e.g.,
transforms Cu2? to Cu?. There are two main types of H reactions with most organic
molecules: H-atom abstraction (from saturated molecules) and H-atom addition (to
the double bonds of unsaturated molecules). If there is a competition between
addition and abstraction, addition is preferred [21]. For H reactions, very few rate
constants are published compared to OH reactions, and the values are less reliable.

Top Curr Chem (Z) (2016) 374:50
Table 5 Rate constants of

hydrogen atom reactions in
mol-1 dm3 s-1 units
Methanol 1.1 9 106 [73]
Ethanol 1.7 9 107 [73]
tert-Butanol 1 9 106 [72]
Benzene 9.1 9 108 [17]
Toluene 2.6 9 109 [17]
Phenol 1.7 9 109 [74]
Benzyl alcohol 1.1 9 109 [17]
Aniline 2.4 9 109 [17]
Acetanilide 1 9 109 [17]
Benzoate ion 1.1 9 109 [17]
Benzenesulfonate ion 7.3 9 108 [17]
2,4-dichlorophoxyaceteic acid 1.4 9 109 [62]
Chloramphenicol 1 9 109 [30]
9
Ibuprofen 4 9 10 [76]
kHs determined in different laboratories (and eventually by different techniques)

may differ by more than a factor of two [17, 74]. In Table 5, the tabulated kH-values
are mostly averages of several determinations.
The rate constants of H-atom abstraction reactions of H are generally one to
three orders of magnitude smaller than those of OH; these abstraction reactions
strongly depend on the bond strength in both cases. In the addition reactions, H
behaves similarly to OH, i.e., as electrophiles [21, 75]. The rate constants for H
addition reactions are also similar to OH reactions, although here OH is also more
reactive than H. For aromatics, the kHs vary in a narrow range, between 7 9 108
and 3 9 109 mol-1 dm3 s-1 [17, 74]. The rate constant of H reaction with benzene
is 9.1 9 108 mol-1 dm3 s-1. When electron-releasing –OH (in phenol), or –NH2 (in
aniline) group is attached to the benzene ring, kH increases to 1.7 9 109 and
2.4 9 109 mol-1 dm3 s-1, respectively. However, due to the small number of the
published values and the large uncertainty in the data, a clear log kH-Hammett
substituent constant relation cannot be established. This is in sharp contrast to the

OH reactions. In the absence of the necessary data, we do not know anything about
the directing effect of the substituent, so we cannot decide whether ortho-para (like
in electrophiles) or meta (nucleophiles) direction takes place in the H ? substituted
aromatic molecule reactions. In a study of H and OH addition reactions to a large
number of acrylate type olefins, a strong correlation was found between the H and

OH addition rate constants [75].
H reactions may contribute to pollutant degradation in the acidic pH range. Since
in the H ? organic molecule reactions and also after protonation in the e- aq ? -
organic molecule reactions [see e.g., Reaction (19)], mainly carbon centered
radicals form, which readily react with dissolved O2, these reductive radicals also

Top Curr Chem (Z) (2016) 374:50
contribute to the oxidation of the organic molecules through the formed organic
peroxides [77].
3 Reactions of Radicals Formed in Radical Transfer Reactions
Water radiolysis is originally a ‘hybrid’ process: in the primary processes, equal

amounts of oxidizing and reducing species form. Due to the ‘natural’ impurities
(O2, Cl-, HCO3-/CO32-, etc.), the balance between oxidizing and reducing
intermediates changes quickly, mostly in favor of the oxidizing species. In order
to enhance the oxidizing capacity, the effects of some additives, like ozone,
hydrogen peroxide or persulfate, were also tested in the laboratory or in pilot-
plant experiments.
3.1 Reactions in the Presence of Dissolved Oxygen
When irradiation is used for water treatment, H and e-

aq mostly disappear in reaction
with the dissolved O2, with rate constants of 1.2 9 1010 and 1.9 9 1010 mol-1 dm3
s-1, respectively [17]:
H þ O2 ! HO2 k21 ¼ 1:2 1010 mol1 dm3 s1 ð21Þ
e
aq þ O2 ! O2 k22 ¼ 1:9 1010 mol1 dm3 s1 ð22Þ
HO2 and O- 2 interconvert with a pKa of 4.8 [78]. Due to the high rate constants, the
H and e- aq scavenging capacities (k[S], where [S] represents O2 concentration,
2.8 9 10-4 mol dm-3 at 20 C), are high at 3.4 9 106 and 5.3 9 106 s-1,
respectively. Any solute can compete with the H ? O2 and e- aq ? O2 reactions if
the scavenging capacity calculated for the dissolved compound is in this range. With
a diffusion controlled rate constant of *1010 mol-1 dm3 s-1, it requires a solute
concentration of *10-4 mol dm-3. Since this is a high concentration for envi-
ronmental water samples, H and e- aq reactions rarely play a determining role in
micropollutant degradation. However, at relatively high solute concentrations, and
at very high dose rates (electron beam irradiation) when considerable O2 depletion
occurs, the H and e- aq reactions may not be negligible.
O-
2 is a weak reductant, while HO2 is a moderate oxidant (Table 2). Unlike OH,
-
O2 and HO2 may not directly contribute to the degradation of organic pollutants
[78]. In the absence of suitable reaction partners, O-
2 and HO2 disappear from the
solution in slow radical–radical reactions giving H2O2; in neutral solutions, the
cross-reaction (24) dominates:
2 HO2 ! H2 O2 þ O2 k23 ¼ 8:3 105 mol1 dm3 s1 ð23Þ
HO2 þ O
2 þ H2 O ! H2 O2 þ O2 þ OH

k24 ¼ 9:7 107 mol1 dm3 s1
ð24Þ

Top Curr Chem (Z) (2016) 374:50
3.2 Reactions in the Presence of Hydrogen Peroxide
In aerated solutions, hydrogen peroxide is produced in the reactions of O-

2 /HO2 pair
with relatively large yield. Under certain conditions, H2O2 can be involved in
reactions with the reactive intermediates generating species that can considerably
influence the degradation of chemical pollutants. However, its effect on the
degradation mechanism is usually neglected, and only a few publications mention
the possible role of H2O2 in the degradation [79, 80]. In gamma radiolysis
experiments conducted in the presence of dissolved O2 in purified water, H2O2
forms with a yield of 0.3 lmol J-1. At doses [ 1 kGy, the H2O2 concentration-dose
curve reaches a plateau due to the competition between formation and decompo-

sition. H2O2 in (25) transforms the reductive e-aq to the oxidizing OH.
e
aq þ H2 O2 ! OH þ OH

k25 ¼ 1:1 1010 mol1 dm3 s1 ð25Þ
In real water treatment scenarios, in the presence of traces of transition metal ions,
H2O2 is expected to disappear in Fenton-like reactions. In experiments when a few
times 10-3 mol dm-3 H2O2 was introduced into the solution to be irradiated,
considerable increases in the degradation rates were found [80].
3.3 Reactions in the Presence of Ozone
Ozonization is a commonly employed method for the treatment of waters and

wastewaters (e.g., to improve quality of drinking water or as a pre-treatment step to
biodegradation). O3 reacts with dissolved organic molecules with two basically
different reaction mechanisms: it may react directly with the solute molecules or
through its decomposition products. In direct reaction, addition to double bonds,
insertion into r bonds, oxygen atom transfer, charge transfer, or hydrogen atom
abstraction can take place. The latter reaction is characteristic to molecules in which
the electron withdrawing groups decrease the C-H bond strength (aldehydes, acids,
amines). The rate constants of the O3 ? organic molecule reactions vary between
many orders of magnitude (10-2–108 mol-1 dm3 s-1). In the case of aromatic
molecules, electron donating substituent increases, and electron withdrawing
substituent decreases the rate constant [81].
In the presence of ozone/oxygen, the primary water radiolysis intermediates, H
and e-aq, react quickly with O3 with rate constants in the 10
10
mol-1 dm3 s-1 range.

The rate constant of the OH ? O3 reaction is 1.1 9 10 mol-1 dm3 s-1 [17]. The
8
reactions involving dissolved O3 result in reactive intermediates, among which is

the highly oxidizing OH [82–84]. The injection of O3 before or during irradiation
converts the reducing species of water radiolysis into the key intermediate, i.e., the
ozonide radical anion (O-
3 ), responsible for enhancing the OH yield in this system.
Here a simplified reaction mechanism is shown [85, 86]:
H þ O3 ! HO3 k26 ¼ 2:2 1010 mol1 dm3 s1 ð26Þ
HO3 ! O
3 þ H
þ
ð27Þ

Top Curr Chem (Z) (2016) 374:50
þH2 O
O
3 O þ O2 ! OH þ OH þ O2 ð28Þ
e
aq þ O3 ! O3 k29 ¼ 3:6 1010 mol1 dm3 s1 ð29Þ

OH þ O3 ! HO2 þ O2 k30 ¼ 1:1 108 mol1 dm3 s1 ð30Þ
O
2 þ O3 ! O3 þ O2 k31 ¼ 1:5 109 mol1 dm3 s1 ð31Þ
As a consequence of these reactions, almost all of the radiation energy is now used
for OH generation, resulting in great enhancement of the degradation rate, as was
demonstrated in laboratory and pilot plant experiments [83, 87].
3.4 Reactions of the Chloride Atom and Dichloride Radical Anion

OH reacts in fast reaction with Cl- ions forming ClOH- complex (Reaction 32),
with an equilibrium constant of 0.70 ± 0.13 mol-1 dm3. In acidic media (below pH
5–6), ClOH- may transform to Cl [Reaction (34)]. Cl is a strong oxidant that can
react directly with dissolved organic material (E0(Cl/Cl-) = 2.6 V). However, in
rapid complexation (35) with Cl-, Cl may transform to the dichloride radical anion
(Cl- -
2 ). Cl2 is also a strong oxidant with standard one-electron reduction potential of
-
E (Cl2 /2 Cl-) = 2.1 V [42].
0
The reactions of Cl- 2 are often investigated in N2O-saturated solutions at high

Cl concentration relative to the compound of interest (S), where most of OH are
-
scavenged by Cl-, forming Cl- 2 . The pH of the solution is adjusted to the acidic
range (pH 2–4) to ensure the efficient formation of Cl-
2 . Manifold reactions proceed
in such a system [17, 88].

OH þ Cl ClOH k32 ¼ 4:3 109 mol1 dm3 s1 ð32Þ
k32 ¼ 6:1 109 s1 ð32Þ
ClOH þ Hþ ðHOClHÞ k33 ¼ 3 1010 mol1 dm3 s1 ð33Þ
k33 ¼ 1 108 s1 ð33Þ
ðHOClHÞ Cl þ H2 O k34 ¼ ð5 2Þ 104 s1 ð34Þ
k34 ¼ 2:5 105 s1 ð34Þ
Cl þ Cl Cl

2 k35 ¼ 8:5 0:6 109 mol1 dm3 s1 ð35Þ
k35 ¼ 6:0 0:5 104 s1 ð35Þ
K ¼ k35 =k35 ¼ 1:4 105 mol1 dm3 ð36Þ
Cl
2 þ H2 O ðHOClHÞ þ Cl k37 ¼ 1300 s1 ð37Þ

Top Curr Chem (Z) (2016) 374:50
k37 ¼ ð8 2Þ 109 mol1 dm3 s1 ð37Þ
Cl
2 þ S ! products k38 ð38Þ
Cl þ S ! products k39 ð39Þ

Cl-
2 has an absorption maximum at 340 nm with e340 = 9600 mol
-1
dm3 cm-1, the

absorbance of Cl is negligible at this wavelength (albeit e340 nm is relatively high,
3800 mol-1 dm3 cm-1, the Cl concentration in equilibrium is very low). When a
compound of interest is present in the system (S), the decay of the 340-nm band
obeys first-order kinetics. In laboratory experiments, at the usual Cl- concentration
(0.1–1 mol dm-3), equilibrium (35) is assumed to be attained. If so, kobs (the decay
rate constant of the 340-nm band) can be expressed as (40) when k35[Cl-] ? k-
-
35 (k38 ? k39)[S] ? k37 ? k-34 and K[Cl ] 1 (for obtaining the exact rate law
and derivation of (40), we refer to Buxton et al. [89]):
kobs ¼ k37 þ k34 =ðK ½Cl Þ þ fðk39 =ðK ½Cl ÞÞ þ k38 g½S ð40Þ
In the OH ? Cl- system, at sufficiently high Cl- concentration in the acidic pH
range the Cl-
2 species dominates, and in the neutral or alkaline pH range the OH

dominates [90, 91]. In laboratory radiolysis experiments, in the neural or alkaline

pH ranges, the Cl/Cl-
2 species can also be produced in reactions with sulfate radical
anions:
SO
4 þ Cl

SO2
4 þ Cl

k41 ¼ 3:2 108 mol1 dm3 s1 ð41Þ
k41 ¼ 2:5 108 mol1 dm3 s1 ð41Þ

When Cl- - - -
2 is produced in the SO4 ? Cl reaction, the absorbance of SO4 slightly
disturbs the observation of the Cl2 intermediate in pulse radiolysis, and SO-
-
4 has
also a wide absorption band with kmax = 450 nm and e450 nm = 1630 ± 180 mol-1
dm3 cm-1 [91].
Under the usual experimental conditions in aqueous solutions, it is rather
complicated to study the Cl reactions [90, 92] due to the rapid complexation
reaction (35). For this purpose, photolysis of Cl2 is recommended in Cl- free
systems.
Cl2 þ hv ! 2Cl ð42Þ
In purified water, in the absence of suitable reactants, Cl-

2 may disappear from
the solution in disproportionation reaction:
Cl
2 þ Cl2 ! Cl2 þ 2Cl

2k43 ¼ 1:47 109 mol1 dm3 s1
ð43Þ
ðzero ionic strength ½88Þ
The reaction of Cl with benzene takes place with a rate constant of *1 9 1010
mol-1 dm3 s-1 [92]. It is assumed in the first step to produce p-complex that may
transform to r-complex (chlorocyclohexadienyl radical). This reaction and the
transformation of the p-complex to the r-complex was investigated several times in

Top Curr Chem (Z) (2016) 374:50
Scheme 2 Cl reaction with benzene
Table 6 Rate constants of Cl-2

reactions with organic molecules
-1 3 -1
in mol dm s units
Methanol 3.5 9 103 [42]
Ethanol 4.5 9 104 [42]
2-Propanol 1.2 9 105 [42]
Acetic acid \104 [42]
Fumaric acid 1.2 9 105 [93]
Fumaric acid, monoanion 2.0 9 106 [93]
Fumaric acid, dianion 4.5 9 106 [93]
Maleic acid 1.7 9 106 [93]
Maleic acid, monoion 1.25 9 106 [93]
Maleic acid, dianion 3.4 9 106 [93]
Benzene \105 [92]
Benzenesulfonic acid \105 [23]
Benzonitrile \105 [42]
Benzoic acid 2 9 106 [42]
Phenol 2.8 9 108 [42]
Aniline 1.2 9 107 [42]
7
Acetanilide *2 9 10 [42]
Pinene 1.7 9 108 [94]
organic phases. In aqueous system, the transformation is too fast to observe the p-
complex directly by the usual experimental techniques (Scheme 2).
The rate constants of Cl- 2 reactions with organic molecules are much smaller
than the diffusion controlled limit of c.a. 7.3 9 109 mol-1 dm3 s-1 (Table 1). Cl-
2
can abstract an H-atom from aliphatic compounds (see methanol, ethanol, 2-
propanol in Table 6) with rate constants between 103 and 105 mol-1 dm3 s-1 [18].
Olefinic compounds react with Cl- 2 by three orders of magnitude more rapidly than
the saturated analogues [42]. The reaction with olefins occurs with Cl-addition and
the kCl2 0s are in the 105–108 mol-1 dm3 s-1 range. Addition to the aromatic ring
may also take place with kCl2- of B107 mol-1 dm3 s-1, but the direct oxidation of
the aromatic ring by electron transfer seems to be the predominant pathway, and
electron-donating functional groups such as –OH, –OCH3 or –NH2 on the aromatic
ring enhance the rate of oxidation.

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smoothbore, his mother a pair of the famous La Roche dueling
pistols and a prayer book. The family priest gave him a rosary and
cross and enjoined him to pray frequently. Traveling all summer, they
arrived at Lake Winnipeg in the autumn and wintered there. As soon
as the ice went out in the spring the journey was continued and one
afternoon in July, Monroe beheld Mountain Fort, a new post of the
company’s not far from the Rocky Mountains.
“Around about it were encamped thousands of Blackfeet waiting
to trade for the goods the flotilla had brought up and to obtain on
credit ammunition, fukes (trade guns), traps and tobacco. As yet the
company had no Blackfoot interpreter. The factor perceiving that
Monroe was a youth of more than ordinary intelligence at once
detailed him to live and travel with the Piegans (a Blackfoot tribe)
and learn their language, also to see that they returned to Mountain
Fort with their furs the succeeding summer. Word had been received
that, following the course of Lewis and Clarke, American traders
were yearly pushing farther and farther westward and had even
reached the mouth of the Yellowstone. The company feared their
competition. Monroe was to do his best to prevent it.
“‘At last,’ Monroe told me, ‘the day came for our departure, and I
set out with the chiefs and medicine men at the head of the long
procession. There were eight hundred lodges of the Piegans there,
about eight thousand souls. They owned thousands of horses. Oh,
but it was a grand sight to see that long column of riders and pack
animals, and loose horses trooping over the plains. We traveled on
southward all the long day, and about an hour or two before
sundown we came to the rim of a valley through which flowed a
cotton wood-bordered stream. We dismounted at the top of the hill,
and spread our robes intending to sit there until the procession
passed by into the bottom and put up the lodges. A medicine man
produced a large stone pipe, filled it and attempted to light it with flint
and steel and a bit of punk (rotten wood), but somehow he could get
no spark. I motioned him to hand it to me, and drawing my sunglass
from my pocket, I got the proper focus and set the tobacco afire,
drawing several mouthfuls of smoke through the long stem.
“‘As one man all those round about sprang to their feet and
rushed toward me, shouting and gesticulating as if they had gone
crazy. I also jumped up, terribly frightened, for I thought they were
going to do me harm, perhaps kill me. The pipe was wrenched out of
my grasp by the chief himself, who eagerly began to smoke and
pray. He had drawn but a whiff or two when another seized it, and
from him it was taken by still another. Others turned and harangued
the passing column; men and women sprang from their horses and
joined the group, mothers pressing close and rubbing their babes
against me, praying earnestly meanwhile. I recognized a word that I
had already learned—Natos—Sun—and suddenly the meaning of
the commotion became clear; they thought that I was Great
Medicine; that I had called upon the Sun himself to light the pipe,
and that he had done so. The mere act of holding up my hand above
the pipe was a supplication to their God. They had perhaps not
noticed the glass, or if they had, had thought it some secret charm or
amulet. At all events I had suddenly become a great personage, and
from then on the utmost consideration and kindness was accorded to
me.
“‘When I entered Lone Walker’s lodge that evening—he was the
chief, and my host—I was greeted by deep growls from either side of
the doorway, and was horrified to see two nearly grown grizzly bears
acting as if about to spring upon me. I stopped and stood quite still,
but I believe that my hair was rising; I know that my flesh felt to be
shrinking. I was not kept in suspense. Lone Walker spoke to his pets,
and they immediately lay down, noses between their paws, and I
passed on to the place pointed out to me, the first couch at the
chief’s left hand. It was some time before I became accustomed to
the bears, but we finally came to a sort of understanding with one
another. They ceased growling at me as I passed in and out of the
lodge, but would never allow me to touch them, bristling up and
preparing to fight if I attempted to do so. In the following spring they
disappeared one night and were never seen again.’
“Think how the youth, Rising Wolf, must have felt as he
journeyed southward over the vast plains, and under the shadow of
the giant mountains which lie between the Saskatchewan and the
Missouri, for he knew that he was the first of his race to behold
them.” We were born a little too late!
“Monroe often referred to that first trip with the Piegans as the
happiest time of his life.”
In the moon of falling leaves they came to Pile of Rocks River,
and after three months went on to winter on Yellow River. Next
summer they wandered down the Musselshell, crossed the Big River
and thence westward by way of the Little Rockies and the Bear Paw
Mountains to the Marias. Even paradise has its geography.
“Rifle and pistol were now useless as the last rounds of powder
and ball had been fired. But what mattered that? Had they not their
bows and great sheaves of arrows? In the spring they had planted
on the banks of the Judith a large patch of their own tobacco which
they would harvest in due time.
“One by one young Rising Wolf’s garments were worn out and
cast aside. The women of the lodge tanned deerskins and bighorn
(sheep) and from them Lone Walker himself cut and sewed shirts
and leggings, which he wore in their place. It was not permitted for
women to make men’s clothing. So ere long he was dressed in full
Indian costume, even to the belt and breech-clout, and his hair grew
so that it fell in rippling waves down over his shoulders.” A warrior
never cut his hair, so white men living with Indians followed their
fashion, else they were not admitted to rank as warriors. “He began
to think of braiding it. Ap-ah’-ki, the shy young daughter of the chief,
made his footwear—thin parfleche (arrow-proof)—soled moccasins
(skin-shoes) for summer, beautifully embroidered with colored
porcupine quills; thick, soft warm ones of buffalo robe for winter.
“‘I could not help but notice her,’ he said, ‘on the first night I
stayed in her father’s lodge.... I learned the language easily, quickly,
yet I never spoke to her nor she to me, for, as you know, the
Blackfeet think it unseemly for youths and maidens to do so.
“‘One evening a man came into the lodge and began to praise a
certain youth with whom I had often hunted; spoke of his bravery, his
kindness, his wealth, and ended by saying that the young fellow
presented to Lone Walker thirty horses, and wished, with Ap-ah’-ki,
to set up a lodge of his own. I glanced at the girl and caught her
looking at me; such a look! expressing at once fear, despair and
something else which I dared not believe I interpreted aright. The
chief spoke: “Tell your friend,” he said, “that all you have spoken of
him is true; I know that he is a real man, a good, kind, brave,
generous young man, yet for all that I can not give him my daughter.”
“‘Again I looked at Ap-ah’-ki and she at me. Now she was smiling
and there was happiness in her eyes. But if she smiled I could not. I
had heard him refuse thirty head of horses. What hope had I then,
who did not even own the horse I rode? I, who received for my
services only twenty pounds a year, from which must be deducted
the various articles I bought. Surely the girl was not for me. I
suffered.
“‘It was a little later, perhaps a couple of weeks, that I met her in
the trail, bringing home a bundle of fire-wood. We stopped and
looked at each other in silence for a moment, and then I spoke her
name. Crash went the fuel on the ground, and we embraced and
kissed regardless of those who might be looking.
“‘So, forgetting the bundle of wood, we went hand in hand and
stood before Lone Walker, where he sat smoking his long pipe, out
on the shady side of the lodge.
“‘The chief smiled. “Why, think you, did I refuse the thirty
horses?” he asked, and before I could answer: “Because I wanted
you for my son-in-law, wanted a white man because he is more
cunning, much wiser than the Indian, and I need a counselor. We
have not been blind, neither I nor my women. There is nothing more
to say except this: be good to her.”
“‘That very day they set up a small lodge for us, and stored it
with robes and parfleches of dried meat and berries, gave us one of
their two brass kettles, tanned skins, pack saddles, ropes, all that a
lodge should contain. And, not least, Lone Walker told me to choose
thirty horses from his large herd. In the evening we took possession
of our house and were happy.’
“Monroe remained in the service of the Hudson’s Bay Company
a number of years, raising a large family of boys and girls, most of
whom are alive to-day. The oldest, John, is about seventy-five years
of age, but still young enough to go to the Rockies near his home
every autumn, and kill a few bighorn and elk, and trap a few beavers.
The old man never revisited his home; never saw his parents after
they parted with him at the Montreal docks. He intended to return to
them for a brief visit some time, but kept deferring it, and then came
letters two years old to say that they were both dead. Came also a
letter from an attorney, saying that they had bequeathed him a
considerable property, that he must go to Montreal and sign certain
papers in order to take possession of it. At the time the factor of
Mountain Fort was going to England on leave; to him, in his simple
trustfulness Monroe gave a power of attorney in the matter. The
factor never returned, and by virtue of the papers he had signed the
frontiersman lost his inheritance. But that was a matter of little
moment to him then. Had he not a lodge and family, good horses
and a vast domain actually teeming with game wherein to wander?
What more could one possibly want?
“Leaving the Hudson’s Bay Company, Monroe sometimes
worked for the American Fur Company, but mostly as a free trapper,
wandered from the Saskatchewan to the Yellowstone and from the
Rockies to Lake Winnipeg. The headwaters of the South
Saskatchewan were one of his favorite hunting grounds. Thither in
the early fifties he guided the noted Jesuit Father, De Smet, and at
the foot of the beautiful lakes just south of Chief Mountain they
erected a huge wooden cross and named the two bodies of water
Saint Mary’s Lakes.” Here the Canada and United States boundary
climbs the Rocky Mountains.
“One winter after his sons John and François had married they
were camping there for the season, the three lodges of the family,
when one night a large war party of Assiniboins attacked them. The
daughters Lizzie, Amelia and Mary had been taught to shoot, and
together they made a brave resistance, driving the Indians away just
before daylight, with the loss of five of their number, Lizzie killing one
of them as he was about to let down the bars of the horse corral.
“Besides other furs, beaver, fisher, marten and wolverine, they
killed more than three hundred wolves that winter by a device so
unique, yet simple, that it is well worth recording. By the banks of the
outlet of the lakes they built a long pen twelve by sixteen feet at the
base, and sloping sharply inward and upward to a height of seven
feet. The top of the pyramid was an opening about two feet six
inches wide by eight feet in length. Whole deer, quarters of buffalo,
any kind of meat handy was thrown into the pen, and the wolves,
scenting the flesh and blood, seeing it plainly through the four to six
inch spaces between the logs would eventually climb to the top and
jump down through the opening. But they could not jump out, and
there morning would find them uneasily pacing around and around in
utter bewilderment.
“You will remember that the old man was a Catholic, yet I know
that he had much faith in the Blackfoot religion, and believed in the
efficiency of the medicine-man’s prayers and mysteries. He used
often to speak of the terrible power possessed by a man named Old
Sun. ‘There was one,’ he would say, ‘who surely talked with the
gods, and was given some of their mysterious power. Sometimes of
a dark night he would invite a few of us to his lodge, when all was
calm and still. After all were seated his wives would bank the fire with
ashes so that it was as dark within as without, and he would begin to
pray. First to the Sun-chief, then to the wind maker, the thunder and
the lightning. As he prayed, entreating them to come and do his will,
first the lodge ears would begin to quiver with the first breath of a
coming breeze, which gradually grew stronger and stronger till the
lodge bent to the blasts, and the lodge poles strained and creaked.
Then thunder began to boom, faint and far away, and lightning dimly
to blaze, and they came nearer and nearer until they seemed to be
just overhead; the crashes deafened us, the flashes blinded us, and
all were terror-stricken. Then this wonderful man would pray them to
go, and the wind would die down, and the thunder and lightning go
on rumbling and flashing into the far distance until we heard and saw
them no more.’”
LIII
A. D. 1819
SIMON BOLIVAR
ONCE at the stilted court of Spain young Ferdinand, Prince of the

Asturias, had the condescension to play at tennis with a mere
colonial; and the bounder won.
Long afterward, when Don Ferdinand was king, the colonial
challenged him to another ball game, one played with cannon-balls.
This time the stake was the Spanish American empire, but
Ferdinand played Bolivar, and again the bounder won.
“Now tell me,” a lady said once, “what animal reminds one most
of the Señor Bolivar?”
And Bolivar thought he heard some one say “monkey,” whereat
he flew into an awful passion, until the offender claimed that the
word was “sparrow.” He stood five feet six inches, with a bird-like
quickness, and a puckered face with an odd tang of monkey. Rich,
lavish, gaudy, talking mock heroics, vain as a peacock, always on
the strut unless he was on the run, there is no more pathetically
funny figure in history than tragical Bolivar; who heard liberty, as he
thought, knocking at the door of South America, and opened—to let
in chaos.
“I don’t know,” drawled a Spaniard of that time, “to what class of
beasts these South Americans belong.”
They were dogs, these Spanish colonials, treated as dogs,
behaving as dogs. When they wanted a university Spain said they
were only provided by Providence to labor in the mines. If they had
opinions the Inquisition cured them of their errors. They were not
allowed to hold any office or learn the arts of war and government.
Spain sent officials to ease them of their surplus cash, and keep
them out of mischief. Thanks to Spain they were no more fit for
public affairs than a lot of Bengali baboos.
They were loyal as beaten dogs until Napoleon stole the Spanish
crown for brother Joseph, and French armies promenaded all over
Spain closely pursued by the British. There was no Spain left to love,
but the colonials were not Napoleon’s dogs. Napoleon’s envoys to
Venezuela were nearly torn to pieces before they escaped to sea,
where a little British frigate came and gobbled them up. The sea
belonged to the British, and so the colonials sent ambassadors,
Bolivar and another gentleman, to King George. Please would he
help them to gain their liberty? George had just chased Napoleon out
of Spain, and said he would do his best with his allies, the
Spaniards.
In London Bolivar unearthed a countryman who loved liberty and
had fought for Napoleon, a real professional soldier. General
Miranda was able and willing to lead the armies of freedom, until he
actually saw the Venezuelan troops. Then he shied hard. He really
must draw the line somewhere. Yes, he would take command of the
rabble on one condition, that he got rid of Bolivar. To get away from
Bolivar he would go anywhere and do anything. So he led his rabble
and found them stout fighters, and drove the Spaniards out of the
central provinces.
The politicians were sitting down to draft the first of many comic-
opera constitutions when an awful sound, louder than any thunder,
swept out of the eastern Andes, the earth rolled like a sea in a storm,
and the five cities of the new republic crashed down in heaps of ruin.
The barracks buried the garrisons, the marching troops were totally
destroyed, the politicians were killed, and in all one hundred twenty
thousand people perished. The only thing left standing in one church
was a pillar bearing the arms of Spain; the only districts not wrecked
were those still loyal to the Spanish government. The clergy pointed
the moral, the ruined people repented their rebellion, and the
Spanish forces took heart and closed in from every side upon the
lost republic. Simon Bolivar generously surrendered General
Miranda in chains to the victorious Spaniards.
So far one sees only, as poor Miranda did, that this man was a
sickening cad. But he was something more. He stuck to the cause
for which he had given his life, joined the rebels in what is now
Colombia, was given a small garrison command and ordered to stay
in his fort. In defiance of orders, he swept the Spaniards out of the
Magdalena Valley, raised a large force, liberated the country, then
marched into Venezuela, defeated the Spanish forces in a score of
brilliant actions, and was proclaimed liberator with absolute power in
both Colombia and Venezuela. One begins to marvel at this heroic
leader until the cad looms out. “Spaniards and Canary islanders!” he
wrote, “reckon on death even if you are neutral, unless you will work
actively for the liberty of America. Americans! count on life even if
you are culpable.”
Bolivar’s pet hobbies were three in number: Resigning his job as
liberator; writing proclamations; committing massacres. “I order you,”
he wrote to the governor of La Guayra, “to shoot all the prisoners in
those dungeons, and in the hospital, without any exception
whatever.”
So the prisoners of war were set to work building a funeral pyre.
When this was ready eight hundred of them were brought up in
batches, butchered with axes, bayonets and knives, and their bodies
thrown on the flames. Meanwhile Bolivar, in his office, refreshed
himself by writing a proclamation to denounce the atrocities of the
Spaniards.
Southward of the Orinoco River there are vast level prairies
called Llanos, a cattle country, handled by wild horsemen known as
the Llaneros. In Bolivar’s time their leader called himself Boves, and
he had as second in command Morales. Boves said that Morales
was “atrocious.” Morales said that “Boves was a man of merit, but
too blood-thirsty.” The Spaniards called their command “The Infernal
Division.” At first they fought for the Revolution, afterward for Spain,
but they were really quite impartial and spared neither age nor sex.
This was the “Spanish” army which swept away the second
Venezuelan republic, slaughtering the whole population save some
few poor starving camps of fugitives. Then Boves reported to the
Spanish general, “I have recovered the arms, ammunition, and the
honor of the Spanish flag, which your excellency lost at Carabobo.”
From this time onward the situation was rather like a dog fight,
with the republican dog somewhere underneath in the middle. At
times Bolivar ran like a rabbit, at times he was granted a triumph, but
whenever he had time to come up and breathe he fired off volleys of
proclamations. In sixteen years a painstaking Colombian counted six
hundred ninety-six battles, which makes an average of one every
ninth day, not to mention massacres; but for all his puny body and
feeble health Bolivar was always to be found in the very thick of the
scrimmage.
Europe had entered on the peace of Waterloo, but the ghouls
who stripped the dead after Napoleon’s battles had uniforms to sell
which went to clothe the fantastic mobs, republican and royalist, who
drenched all Spanish America with blood. There were soldiers, too,
whose trade of war was at an end in Europe, who gladly listened to
Bolivar’s agents, who offered gorgeous uniforms and promised
splendid wages—never paid—and who came to join in the war for
“liberty.” Three hundred Germans and nearly six thousand British
veterans joined Bolivar’s colors to fight for the freedom of America,
and nearly all of them perished in battle or by disease. Bolivar was
never without British officers, preferred British troops to all others,
and in his later years really earned the loyal love they gave him,
while they taught the liberator how to behave like a white man.
It was in 1819 that Bolivar led a force of two thousand five
hundred men across a flooded prairie. For a week they were up to
their knees, at times to their necks in water under a tropic deluge of
rain, swimming a dozen rivers beset by alligators. The climate and
starvation bore very heavily upon the British troops. Beyond the flood
they climbed the eastern Andes and crossed the Paramo at a height
of thirteen thousand feet, swept by an icy wind in blinding fog—hard
going for Venezuelans.
An Irishman, Colonel Rook, commanded the British contingent.
“All,” he reported, “was quite well with his corps, which had had quite
a pleasant march” through the awful gorges and over the freezing
Paramo. A Venezuelan officer remarked here that one-fourth of the
men had perished.
“It was true,” said Rook, “but it really was a very good thing, for
the men who had dropped out were all the wastrels and weaklings of
the force.”
Great was the astonishment of the royalists when Bolivar
dropped on them out of the clouds, and in the battle of Boyacá they
were put to rout. Next day Colonel Rook had his arm cut off by the
surgeons, chaffing them about the beautiful limb he was losing. He
died of the operation, but the British legion went on from victory to
victory, melting away like snow until at the end negroes and Indians
filled its illustrious companies. Colombia, Venezuela and Equador,
Peru and Bolivia were freed from the Spanish yoke and, in the main,
released by Bolivar’s tireless, unfailing and undaunted courage. But
they could not stand his braggart proclamations, would not have him
or any man for master, began a series of squabbles and revolutions
that have lasted ever since, and proved themselves unfit for the
freedom Bolivar gave. He knew at the end that he had given his life
for a myth. On the eighth December, 1830, he dictated his final
proclamation and on the tenth received the last rites of the church,
being still his old braggart self. “Colombians! my last wishes are for
the welfare of the fatherland. If my death contributes to the cessation
of party strife, and to the consolidation of the Union, I shall descend
in peace to the grave.” On the seventeenth his troubled spirit
passed.
LIV
A. D. 1812
THE ALMIRANTE COCHRANE
WHEN Lieutenant Lord Thomas Cochrane commanded the brig of

war Speedy, he used to carry about a whole broadside of her
cannon-balls in his pocket. He had fifty-four men when he laid his toy
boat alongside a Spanish frigate with thirty-two heavy guns and
three hundred nineteen men, but the Spaniard could not fire down
into his decks, whereas he blasted her with his treble-shotted pop-
guns. Leaving only the doctor on board he boarded that Spaniard,
got more than he bargained for, and would have been wiped out, but
that a detachment of his sailors dressed to resemble black demons,
charged down from the forecastle head. The Spaniards were so
shocked that they surrendered.
For thirteen months the Speedy romped about, capturing in all
fifty ships, one hundred and twenty-two guns, five hundred prisoners.
Then she gave chase to three French battle-ships by mistake, and
met with a dreadful end.
In 1809, Cochrane, being a bit of a chemist, and a first-rate
mechanic, was allowed to make fireworks hulks loaded with
explosives—with which he attacked a French fleet in the anchorage
at Aix. The fleet got into a panic and destroyed itself.
And all his battles read like fairy tales, for this long-legged, red-
haired Scot, rivaled Lord Nelson himself in genius and daring. At war
he was the hero and idol of the fleet, but in peace a demon, restless,
fractious, fiendish in humor, deadly in rage, playing schoolboy jokes
on the admiralty and the parliament. He could not be happy without
making swarms of powerful enemies, and those enemies waited
their chance.
In February, 1814, a French officer landed at Dover with tidings
that the Emperor Napoleon had been slain by Cossacks. The
messenger’s progress became a triumphal procession, and amid
public rejoicings he entered London to deliver his papers at the
admiralty. Bells pealed, cannon thundered, the stock exchange went
mad with the rise of prices, while the messenger—a Mr. Berenger—
sneaked to the lodgings of an acquaintance, Lord Cochrane, and
borrowed civilian clothes.
His news was false, his despatch a forgery, he had been hired by
Cochrane’s uncle, a stock-exchange speculator, to contrive the
whole blackguardly hoax. Cochrane knew nothing of the plot, but for
the mere lending of that suit of clothes, he was sentenced to the
pillory, a year’s imprisonment, and a fine of a thousand pounds. He
was struck from the rolls of the navy, expelled from the house of
commons, his banner as a Knight of the Bath torn down and thrown
from the doors of Henry VII’s Chapel at Westminster. In the end he
was driven to disgraceful exile and hopeless ruin.
Four years later Cochrane, commanding the Chilian navy, sailed
from Valparaiso to fight the Spanish fleet. Running away from his
mother, a son of his—Tom Cochrane, junior—aged five, contrived to
sail with the admiral, and in his first engagement, was spattered with
the blood and brains of a marine.
“I’m not hurt, papa,” said the imp, “the shot didn’t touch me. Jack
says that the ball is not made that will hurt mama’s boy.” Jack proved
to be right, but it was in that engagement that Cochrane earned his
Spanish title, “The Devil.” Three times he attempted to take Callao
from the Spaniards, then in disgusted failure dispersed his useless
squadron, and went off with his flag ship to Valdivia. For lack of
officers, he kept the deck himself until he dropped. When he went
below for a nap, the lieutenant left a middy in command, but the
middy went to sleep and the ship was cast away.
Cochrane got her afloat; then, with all his gunpowder wet, went
off with his sinking wreck to attack Valdivia. The place was a Spanish
stronghold with fifteen forts and one hundred and fifteen guns.
Cochrane, preferring to depend on cold steel, left the muskets
behind, wrecked his boats in the surf, let his men swim, led them
straight at the Spaniards, stormed the batteries, and seized the city.
So he found some nice new ships, and an arsenal to equip them, for
his next attack on Callao.
He had a fancy for the frigate, Esmeralda, which lay in Callao—
thought she would suit him for a cruiser. She happened to be
protected by a Spanish fleet, and batteries mounting three hundred
guns, but Cochrane did not mind. El Diablo first eased the minds of
the Spaniards by sending away two out of his three small vessels,
but kept the bulk of their men, and all their boats, a detail not
observed by the weary enemy. His boarding party, two hundred and
forty strong, stole into the anchorage at midnight, and sorely
surprised the Esmeralda. Cochrane, first on board, was felled with
the butt end of a musket, and thrown back into his boat grievously
hurt, in addition to which he had a bullet through his thigh before he
took possession of the frigate. The fleet and batteries had opened
fire, but El Diablo noticed that two neutral ships protected
themselves with a display of lanterns arranged as a signal, “Please
don’t hit me.” “That’s good enough for me,” said Cochrane and
copied those lights which protected the neutrals. When the
bewildered Spaniards saw his lanterns also, they promptly attacked
the neutrals. So Cochrane stole away with his prize.
Although the great sailor delivered Chili and Peru from the
Spaniards, the patriots ungratefully despoiled him of all his pay and
rewards. Cochrane has been described as “a destroying angel with a
limited income and a turn for politics.” Anyway he was
misunderstood, and left Chili disgusted, to attend to the liberation of
Brazil from the Portuguese. But if the Chilians were thieves, the
Brazilians proved to be both thieves and cowards. Reporting to the
Brazilian government that all their cartridges, fuses, guns, powder,
spars and sails, were alike rotten, and all their men an encumbrance,
he dismantled a squadron to find equipment for a single ship, the
Pedro Primeiro. This he manned with British and Yankee
adventurers. He had two other small but fairly effective ships when
he commenced to threaten Bahia. There lay thirteen Portuguese
war-ships, mounting four hundred and eighteen guns, seventy
merchant ships, and a garrison of several thousand men. El Diablo’s
blockade reduced the whole to starvation, the threat of his fireworks
sent them into convulsions, and their leaders resolved on flight to
Portugal. So the troops were embarked, the rich people took ship
with their treasure, and the squadron escorted them to sea, where
Cochrane grinned in the offing. For fifteen days he hung in the rear
of that fleet, cutting off ships as they straggled. He had not a man to
spare for charge of his prizes, but when he caught a ship he staved
her water casks, disabled her rigging so that she could only run
before the wind back to Bahia, and threw every weapon overboard.
He captured seventy odd ships, half the troops, all the treasure,
fought and out-maneuvered the war fleet so that he could not be
caught, and only let thirteen wretched vessels escape to Lisbon.
Such a deed of war has never been matched in the world’s annals,
and Cochrane followed it by forcing the whole of Northern Brazil to
an abject surrender.
Like the patriots of Chili and Peru, the Brazilians gratefully
rewarded their liberator by cheating him out of his pay; so next he
turned to deliver Greece from the Turks. Very soon he found that
even the Brazilians were perfect gentlemen compared with the
Greek patriots, and the heart-sick man went home.
England was sorry for the way she had treated her hero, gave
back his naval rank and made him admiral with command-in-chief of
a British fleet at sea, restored his banner as a Knight of the Bath in
Henry VII’s chapel, granted a pension, and at the end, found him a
resting-place in the Abbey. On his father’s death, he succeeded to
the earldom of Dundonald, and down to 1860, when the old man
went to his rest, his life was devoted to untiring service. He was
among the first inventors to apply coal gas to light English streets
and homes; he designed the boilers long in use by the English navy;
made a bitumen concrete for paving; and offered plans for the
reduction of Sebastopol which would have averted all the horrors of
the siege. Yet even to his eightieth year he was apt to shock and
terrify all official persons, and when he was buried in the nave of the
Abbey, Lord Brougham pronounced his strange obituary. “What,” he
exclaimed at the grave side, “no cabinet minister, no officer of state
to grace this great man’s funeral!” Perhaps they were still scared of
the poor old hero.
LV
A.D. 1823
THE SOUTH SEA CANNIBALS
FAR back in the long ago time New Zealand was a crowded happy
land. Big Maori fortress villages crowned the hilltops, broad farms
covered the hillsides; the chiefs kept a good table, cooking was
excellent, and especially when prisoners were in season, the people
feasted between sleeps, or, should provisions fail, sacked the next
parish for a supply of meat. So many parishes were sacked and
eaten, that in the course of time the chiefs led their tribes to quite a
distance before they could find a nice fat edible village, but still the
individual citizen felt crowded after meals, and all was well.
Then came the Pakehas, the white men, trading, with muskets
for sale, and the tribe that failed to get a trader to deal with was very
soon wiped out. A musket cost a ton of flax, and to pile up enough to
buy one a whole tribe must leave its hill fortress to camp in
unwholesome flax swamps. The people worked themselves thin to
buy guns, powder and iron tools for farming, but they cherished their
Pakeha as a priceless treasure in special charge of the chief, and if a
white man was eaten, it was clear proof that he was entirely useless
alive, or a quite detestable character. The good Pakehas became
Maori warriors, a little particular as to their meat being really pig, but
otherwise well mannered and popular.
Now of these Pakeha Maoris, one has left a book. He omitted his
name from the book of Old New Zealand, and never mentioned
dates, but tradition says he was Mr. F. C. Maning, and that he lived
as a Maori and trader for forty years, from 1823 to 1863 when the
work was published.
In the days when Mr. Maning reached the North Island a trader
was valued at twenty times his weight in muskets, equivalent say, to
the sum total of the British National Debt. Runaway sailors however,
were quite cheap. “Two men of this description were hospitably
entertained one night by a chief, a very particular friend of mine,
who, to pay himself for his trouble and outlay, ate one of them next
morning.”
Maning came ashore on the back of a warrior by the name of
Melons, who capsized in an ebb tide running like a sluice, at which
the white man, displeased, held the native’s head under water by
way of punishment. When they got ashore Melons wanted to get
even, so challenged the Pakeha to a wrestling match. Both were in
the pink of condition, the Maori, twenty-five years of age, and a
heavy-weight, the other a boy full of animal spirits and tough as
leather. After the battle Melons sat up rather dazed, offered his hand,
and venting his entire stock of English, said “How do you do?”
But then came a powerful chief, by name Relation-eater. “Pretty
work this,” he began, “good work. I won’t stand this not at all! not at
all! not at all!” (The last sentence took three jumps, a step and a turn
round, to keep correct time.) “Who killed the Pakeha? It was Melons.
You are a nice man, killing my Pakeha ... we shall be called the
‘Pakeha killkillers’; I shall be sick with shame; the Pakeha will run
away; what if you had killed him dead, or broken his bones”.... (Here
poor Melones burst out crying like an infant). “Where is the hat?
Where the shoes? The Pakeha is robbed! he is murdered!” Here a
wild howl from Melons.
The local trader took Mr. Maning to live with him, but it was
known to the tribes that the newcomer really and truly belonged to
Relation-eater. Not long had he been settled when there occurred a
meeting between his tribe and another, a game of bluff, when the
warriors of both sides danced the splendid Haka, most blood-
curdling, hair-lifting of all ceremonials. Afterward old Relation-eater
singled out the horrible savage who had begun the war-dance, and
these two tender-hearted individuals for a full half-hour, seated on
the ground hanging on each other’s necks, gave vent to a chorus of
skilfully modulated howling. “So there was peace,” and during the
ceremonies Maning came upon a circle of what seemed to be Maori
chiefs, until drawing near he found that their nodding heads had
nobody underneath. Raw heads had been stuck on slender rods,
with cross sticks to carry the robes, “Looking at the ’eds, sir?” asked
an English sailor. “’Eds was werry scarce—they had to tattoo a slave
a bit ago, and the villain ran away, tattooin’ and all!”
“What!”
“Bolted before he was fit to kill,” said the sailor, mournful to think
how dishonest people could be.
Once the head chief, having need to punish a rebellious vassal,
sent Relation-eater, who plundered and burned the offending village.
The vassal decamped with his tribe.
“Well, about three months after this, about daylight I was
aroused by a great uproar.... Out I ran at once and perceived that M
—’s premises were being sacked by the rebellious vassal who ...
was taking this means of revenging himself for the rough handling he
had received from our chief. Men were rushing in mad haste through
the smashed windows and doors, loaded with everything they could
lay hands upon.... A large canoe was floating near to the house, and
was being rapidly filled with plunder. I saw a fat old Maori woman
who was washerwoman, being dragged along the ground by a huge
fellow who was trying to tear from her grasp one of my shirts, to
which she clung with perfect desperation. I perceived at a glance
that the faithful old creature would probably save a sleeve.
“An old man-of-war’s man defending his washing, called out, ‘Hit
out, sir! ... our mob will be here in five minutes!’
“The odds were terrible, but ... I at once floored a native who was
rushing by me.... I then perceived that he was one of our own people
... so to balance things I knocked down another! and then felt myself
seized round the waist from behind.
“The old sailor was down now but fighting three men at once,
while his striped shirt and canvas trousers still hung proudly on the
fence.
“Then came our mob to the rescue and the assailants fled.
“Some time after this a little incident worth noting happened at
my friend M—’s place. Our chief had for some time back a sort of
dispute with another magnate.... The question was at last brought to
a fair hearing at my friend’s house. The arguments on both sides
were very forcible; so much so that in the course of the arbitration
our chief and thirty of his principal witnesses were shot dead in a
heap before my friend’s door, and sixty others badly wounded, and
my friend’s house and store blown up and burnt to ashes.
“My friend was, however, consoled by hundreds of friends who
came in large parties to condole with him, and who, as was quite
correct in such cases, shot and ate all his stock, sheep, pigs, ducks,
geese, fowls, etc., all in high compliment to himself; he felt proud....
He did not, however, survive these honors long.”
Mr. Maning took this poor gentleman’s place as trader, and
earnestly studied native etiquette, on which his comments are
always deliciously funny. Two young Australians were his guests
when there arrived one day a Maori desperado who wanted
blankets; and “to explain his views more clearly knocked both my
friends down, threatened to kill them both with his tomahawk, then
rushed into the bedroom, dragged out all the bedclothes, and burnt
them on the kitchen fire.”
A few weeks later, Mr. Maning being alone, and reading a year-
old Sydney paper, the desperado called. “‘Friend,’ said I; ‘my advice
to you is to be off.’
“He made no answer but a scowl of defiance. ‘I am thinking,
friend, that this is my house,’ said I, and springing upon him I placed
my foot to his shoulder, and gave him a shove which would have
sent most people heels over head.... But quick as lightning ... he
bounded from the ground, flung his mat away over his head, and
struck a furious blow at my head with his tomahawk. I caught the
tomahawk in full descent; the edge grazed my hand; but my arm,
stiffened like a bar of iron, arrested the blow. He made one furious,
but ineffectual attempt to wrest the tomahawk from my grasp; and
then we seized one another round the middle, and struggled like
maniacs in the endeavor to dash each other against the boarded

Applications of Radiation Chemistry in The Fields of Industry Biotechnology and Environment 1st Edition Margherita Venturi

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Applications of Radiation Chemistry in

the Fields of Industry Biotechnology

The Science of Clays Applications in Industry

Applications in Electronics Pervading Industry

Applications in Electronics Pervading Industry

Applications of Biopolymers in Science, Biotechnology,

Handbook of industrial chemistry and biotechnology

Applications in Electronics Pervading Industry,

Composite Materials for Industry, Electronics, and the

Current Developments in Biotechnology and

Massimo Olivucci, Siena, Italy and Bowling Green, USA

Hagan Bayley, Oxford, UK

Contributions also offer an outlook on potential future developments in the field.

More information about this series at http://www.springer.com/series/14181

With contributions from

Originally published in Top Curr Chem (Z) Volume 374 (2016),

ISSN 2367-4067 ISSN 2367-4075 (electronic)

Library of Congress Control Number: 2017933484

© Springer International Publishing AG 2017

Printed on acid-free paper

This Springer imprint is published by Springer Nature

Editorial ................................................................................................................... vii

Electron Beam Technology and Other Irradiation Technology

Margherita Venturi1 • Mila D’Angelantonio2

Springer International Publishing Switzerland 2017

The chemical effects of high-energy radiations, such as those emitted by radioactive

& Margherita Venturi

Radiation Induced Degradation of Organic Pollutants

László Wojnárovits1 • Erzsébet Takács1

Abstract In water treatment by ionizing radiation, and also in other advanced

Keywords Water treatment Advanced oxidation processes Degradation

This article is part of the Topical Collection‘‘Applications of Radiation Chemistry’’; edited by

& Erzsébet Takács

Reprinted from the journal 1 123

In water treatment by ionizing radiation, the reactive intermediates of water

123 2 Reprinted from the journal

2 Reactions of Primary Radicals of Water Radiolysis with Organic

2.1 Radiolysis of Liquid Water

An important characteristic of ionizing radiation is that its energy is absorbed non-

Reprinted from the journal 3 123

2.2 The Diffusion Controlled Rate Constant

123 4 Reprinted from the journal

2.3 Reactions of the Hydroxyl Radical

In biochemical type investigations, when the presence of dissolved O2 is needed, the

123 6 Reprinted from the journal

Reprinted from the journal 7 123

123 8 Reprinted from the journal

log kchem, mol-1 dm3 s-1 10.4 5

Reprinted from the journal 9 123

In OH addition to the aromatic ring, a carbon centered hydroxycyclohexadienyl

123 10 Reprinted from the journal

2.4 Reactions of the Hydrated Electron and Hydrogen Atom

k17 ¼ 2:5  107 mol1 dm3 s1 ð17Þ

Reprinted from the journal 11 123

Table 4 Rate constants of

123 12 Reprinted from the journal

Reprinted from the journal 13 123

Table 5 Rate constants of

kHs determined in different laboratories (and eventually by different techniques)

123 14 Reprinted from the journal

3 Reactions of Radicals Formed in Radical Transfer Reactions

Water radiolysis is originally a ‘hybrid’ process: in the primary processes, equal

3.1 Reactions in the Presence of Dissolved Oxygen

k17 ¼ 2:5 107 mol1 dm3 s1 ð17Þ

k32 ¼ 6:1 109 s1 ð32Þ

ClOH þ Hþ ðHOClHÞ k33 ¼ 3 1010 mol1 dm3 s1 ð33Þ

k33 ¼ 1 108 s1 ð33Þ

ðHOClHÞ Cl þ H2 O k34 ¼ ð5 2Þ 104 s1 ð34Þ

k34 ¼ 2:5 105 s1 ð34Þ

k35 ¼ 6:0 0:5 104 s1 ð35Þ

K ¼ k35 =k35 ¼ 1:4 105 mol1 dm3 ð36Þ

k37 ¼ ð8 2Þ 109 mol1 dm3 s1 ð37Þ

k41 ¼ 2:5 108 mol1 dm3 s1 ð41Þ