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Hydrothermal Reduction
of Carbon Dioxide
to Low-Carbon Fuels
ELECTROCHEMICAL ENERGY STORAGE AND CONVERSION
Series Editor: Jiujun Zhang
National Research Council Institute for Fuel Cell Innovation
Vancouver, British Columbia, Canada
Published Titles
Hydrothermal Reduction of Carbon Dioxide to Low-Carbon Fuels
Fangming Jin
Carbon Nanomaterials for Electrochemical Energy Technologies: Fundamentals and Applications
Shuhui Sun, Xueliang Sun, Zhongwei Chen, Jinli Qiao, David P. Wilkinson, and Jiujun Zhang
Redox Flow Batteries: Fundamentals and Applications
Huamin Zhang, Xianfeng Li, and Jiujun Zhang
Electrochemical Energy: Advanced Materials and Technologies
Pei Kang Shen, Chao-Yang Wang, San Ping Jiang, Xueliang Sun, and Jiujun Zhang
Electrochemical Polymer Electrolyte Membranes
Jianhua Fang, Jinli Qiao, David P. Wilkinson, and Jiujun Zhang
Electrochemical Supercapacitors for Energy Storage and Delivery: Fundamentals and Applications
Aiping Yu, Victor Chabot, and Jiujun Zhang
Photochemical Water Splitting: Materials and Applications
Neelu Chouhan, Ru-Shi Liu, and Jiujun Zhang
Metal–Air and Metal–Sulfur Batteries: Fundamentals and Applications
Vladimir Neburchilov and Jiujun Zhang
Electrochemical Reduction of Carbon Dioxide: Fundamentals and Technologies
Jinli Qiao, Yuyu Liu, and Jiujun Zhang
Electrolytes for Electrochemical Supercapacitors
Cheng Zhong, Yida Deng, Wenbin Hu, Daoming Sun, Xiaopeng Han, Jinli Qiao, and Jiujun Zhang
Solar Energy Conversion and Storage: Photochemical Modes
Suresh C. Ameta and Rakshit Ameta
Lead-Acid Battery Technologies: Fundamentals, Materials, and Applications
Joey Jung, Lei Zhang, and Jiujun Zhang
Lithium-Ion Batteries: Fundamentals and Applications
Yuping Wu
Graphene: Energy Storage and Conversion Applications
Zhaoping Liu and Xufeng Zhou
Proton Exchange Membrane Fuel Cells
Zhigang Qi
Hydrothermal Reduction
of Carbon Dioxide
to Low-Carbon Fuels
Edited by
Fangming Jin
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2018 by Taylor & Francis Group, LLC

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Printed on acid-free paper
International Standard Book Number-13: 978-1-4987-3183-6 (Hardback)

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This book contains information obtained from authentic and highly regarded sources. Reasonable efforts
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Contents
Editor........................................................................................................................vii
Contributors...............................................................................................................ix
Chapter 1 Water under High-Temperature and High-Pressure Conditions

and Some Special Reactions under Hydrothermal Conditions............. 1
Zheng Shen, Wei Zhang, Xu Zeng, Fangming Jin,
Guodong Yao, and Yuanqing Wang
Chapter 2 Catalytic Hydrothermal Reactions for Small Molecules Activation....... 23

Yuanqing Wang and Fangming Jin
Chapter 3 Hydrothermal Water Splitting for Hydrogen Production

with Other Metals................................................................................ 37
Xu Zeng, Heng Zhong, Guodong Yao, and Fangming Jin
Chapter 4 Hydrothermal Water Splitting for Hydrogen Production with Iron.... 47

Xu Zeng, Heng Zhong, Guodong Yao, and Fangming Jin
Chapter 5 Hydrothermal CO2 Reduction with Iron to Produce Formic Acid...... 61

Jia Duo, Guodong Yao, Fangming Jin, and Heng Zhong
Chapter 6 Hydrothermal Reduction of CO2 to Low-Carbon Compounds........... 79

Ge Tian, Chao He, Ziwei Liu, and Shouhua Feng
Chapter 7 Hydrothermal CO2 Reduction with Zinc to Produce Formic Acid..... 91

Yang Yang, Guodong Yao, Binbin Jin, Runtian He,
Fangming Jin, and Heng Zhong
Chapter 8 Autocatalytic Hydrothermal CO2 Reduction with Manganese

to Produce Formic Acid.................................................................... 109
Lingyun Lyu, Fangming Jin, and Guodong Yao
v
vi Contents
Chapter 9 Autocatalytic Hydrothermal CO2 Reduction with Aluminum

to Produce Formic Acid.................................................................... 127
Binbin Jin, Guodong Yao, Fangming Jin, and Heng Zhong
Chapter 10 Cu-Catalyzed Hydrothermal CO2 Reduction with Zinc

to Produce Methanol......................................................................... 141
Zhibao Huo, Dezhang Ren, Guodong Yao, Fangming Jin,
and Mingbo Hu
Chapter 11 Hydrothermal Reduction of CO2 with Glycerine.............................. 153

Zheng Shen, Minyan Gu, Meng Xia, Wei Zhang, Yalei Zhang,
and Fangming Jin
Chapter 12 Hydrothermal Reduction of CO2 with Compounds Containing

Nitrogen............................................................................................. 185
Guodong Yao, Feiyan Chen, Jia Duo, Fangming Jin,
and Heng Zhong
Chapter 13 Perspectives and Challenges of CO2 Hydrothermal Reduction........ 199

Ligang Luo, Fangming Jin, and Heng Zhong
Index.......................................................................................................................205
Editor
Fangming Jin, PhD, is a distinguished professor in the School of Environmental
Science and Engineering at Shanghai Jiao Tong University, China. She earned her
PhD from Tohoku University, Japan. From 2007 to 2010, she was promoted to pro-
fessor at Tongji University, China and also to chair professor sponsored by the Chang
Jiang Scholar Program (administered by the Ministry of Education of the People’s
Republic of China). In 2010, she moved to Tohoku University as a professor, and then
in July 2011, she moved to Shanghai Jiao Tong University and received an honor of
“Recruitment Program of Global Experts” Talents in Shanghai. Her research focuses
on the application of hydrothermal reactions for the conversion of CO2 and biomass
into fuels and chemicals, which aims to explore a potentially useful technology for
the improvement of the carbon cycle by mimicking nature. She has authored more
than 200 scientific publications, including peer-reviewed papers, patents, and book
chapters, and gave about 30 plenary/keynote/invited presentations. Prof. Jin is also
a visiting professor at Tohoku University and a Fellow of the Graduate School of
Environmental Studies at Tohoku University.
vii
http://taylorandfrancis.com
Contributors
Feiyan Chen Mingbo Hu
School of Environmental Science and State Key Laboratory of Pollution
Engineering Control and Resources Reuse
State Key Laboratory of Metal Matrix College of Environmental Science and
Composites Engineering
Shanghai Jiao Tong University Tongji University
Shanghai, China Shanghai, China
Jia Duo Zhibao Huo

School of Environmental Science and School of Environmental Science and
Engineering Engineering
State Key Laboratory of Metal Matrix Shanghai Jiao Tong University
Composites Shanghai, China
Shanghai Jiao Tong University
Shanghai, China Binbin Jin
School of Environmental Science and
Shouhua Feng Engineering
State Key Laboratory of Inorganic State Key Laboratory of Metal Matrix
Synthesis and Preparative Chemistry Composites
College of Chemistry, Jilin University Shanghai Jiao Tong University
Changchun, China Shanghai, China
Minyan Gu Fangming Jin

State Key Laboratory of Pollution School of Environmental Science and
Control and Resource Reuse Engineering
Tongji University State Key Laboratory of Metal Matrix
Shanghai, China Composites
Chao He Shanghai, China
Department of Earth and Planetary
Sciences and
Johns Hopkins University
Baltimore, Maryland Graduate School of Environmental
Studies
Runtian He Tohoku University
School of Environmental Science and Sendai, Japan
Engineering
State Key Laboratory of Metal Matrix Ziwei Liu
Composites MRC Laboratory of Molecular Biology
Shanghai Jiao Tong University Cambridge Biomedical Campus
Shanghai, China Cambridge, United Kingdom
ix
x Contributors
Ligang Luo Yuanqing Wang

School of Environmental Science and RIKEN Research Cluster for Innovation
Engineering Nakamura Laboratory
State Key Laboratory of Metal Matrix Wako
Composites Saitama, Japan
Shanghai, China and
Lingyun Lyu Tongji University

School of Environmental Science and Shanghai, China
Engineering
State Key Laboratory of Metal Matrix and
Composites
Shanghai Jiao Tong University Fritz Haber Institute of the Max Planck
Shanghai, China Society
Berlin, Germany
Dezhang Ren
School of Environmental Science and Meng Xia
Engineering State Key Laboratory of Pollution
Shanghai Jiao Tong University Control and Resource Reuse
Shanghai, China Tongji University
Shanghai, China
Zheng Shen
National Engineering Research Center Yang Yang
for Facilities Agriculture School of Environmental Science and
Institute of Modern Agricultural Engineering
Science and Engineering State Key Laboratory of Metal Matrix
Tongji University Composites
Shanghai, China Shanghai Jiao Tong University
Shanghai, China
Ge Tian
State Key Laboratory of Inorganic Guodong Yao
Synthesis and Preparative Chemistry School of Environmental Science and
College of Chemistry, Jilin University Engineering
Changchun, China State Key Laboratory of Metal Matrix
Composites
Shanghai, China
Contributors xi
Xu Zeng Yalei Zhang

National Engineering Research Center State Key Laboratory of Pollution
for Facilities Agriculture Control and Resource Reuse
Institute of Modern Agricultural Tongji University
Science and Engineering Shanghai, China
Tongji University
Shanghai, China Heng Zhong
Research Institute for Chemical Process
Wei Zhang Technology
National Engineering Research Center National Institute of Advanced
for Facilities Agriculture Industrial Science and Technology
Institute of Modern Agricultural Sendai, Japan
Science and Engineering
Tongji University
Shanghai, China
http://taylorandfrancis.com
1 Water under High-
Temperature and High-
Pressure Conditions and
Some Special Reactions
under Hydrothermal
Conditions
Zheng Shen, Wei Zhang, Xu Zeng, Fangming Jin,
Guodong Yao, and Yuanqing Wang
CONTENTS
1.1 Introduction.......................................................................................................1
1.2 Ion Product......................................................................................................... 2
1.3 Water Density....................................................................................................2
1.4 Dielectric Constant............................................................................................3
1.4.1 Dielectric Constant of HTW..................................................................5
1.5 Hydrogen Bonding.............................................................................................6
1.6 Hydrolysis........................................................................................................ 11
1.7 Isomerization................................................................................................... 12
1.8 Dehydration..................................................................................................... 13
1.9 Retro Aldol Reaction....................................................................................... 14
1.10 Decarboxylation and Decarbonylation............................................................ 15
References................................................................................................................. 16
1.1 INTRODUCTION
For water under high-temperature and high-pressure conditions, there are diverse
terminologies that have been used in the literature. For example, high-temperature
water (HTW) is defined as liquid water above 200°C [1]. Hot compressed water can
also be used to denote water above 200°C and at sufficiently high pressure [2]. Water
can be divided into subcritical water (below its critical point) and supercritical water
(above its critical point) based on its critical point (Tc = 373°C, Pc = 22.1 MPa). The
lower limit of temperature of subcritical water can be 100°C in the liquid state [3].
The terminology “near-critical water” is also often employed [4]. Aqueous phase
1
2 Hydrothermal Reduction of Carbon Dioxide to Low-Carbon Fuels
processing is employed in the liquid water at temperatures of 200–260°C and at

pressures of 10–50 bar to produce H2, CO, and light alkanes from sugar-derived
feedstocks [5]. The terminology “hydrothermal,” which is originally from geol-
ogy, has been more broadly and popularly used in literatures to refer to the reaction
medium of high-temperature and high-pressure water. According to the different
main products, it can be divided into hydrothermal carbonization (usually conducted
at 100–200°C) [6], hydrothermal liquefaction (often at 200–350°C) [7], and hydro-
thermal gasification (often at 350–750°C) [8]. Therefore, in this chapter, the termi-
nology “hydrothermal” will be mostly adopted to denote water above 100°C and
0.1 MPa, including subcritical and supercritical water.
The products distribution from hydrothermal biomass conversion, including
gas, liquid, and solid, mainly depends on the properties of water at different states.
Two competing reaction mechanisms are present: an ionic or polar reaction mecha-
nism typical of liquid-phase chemistry at low temperature and a free radical reac-
tion mechanism typical of gas-phase reactions at high temperature [9,10]. The latter
radical reactions are preferred, leading to gas formation [11]. In addition, molecular
reaction, which is different from ionic and radical reactions, is molecular rearrange-
ment enhanced by coordination with water and proceeds around the critical region
of water [12].
Herein, in the following sections, the representative properties of water under
high-temperature and high-pressure conditions will be introduced, such as ion prod-
uct, density, dielectric constant, and hydrogen bonding, and some special reactions
under hydrothermal conditions will be discussed.
1.2 ION PRODUCT
The product of the concentrations of H+ and OH− in the water is denoted as the ion
product (Kw), which is also called self-ionization constant (the unit of which is mol2/
kg2). As the temperature increases, the ion product of water increases from Kw = 10 −14
mol2/kg–2 at room temperature to approximately 10 −11 mol2/kg–2 at around 300°C
at constant pressure (250 bar) [2]. Above the critical temperature, the ion product
decreases sharply with increasing temperature [2]. In the ranges when water has
a bigger Kw value, water may show enhanced acidic or basic catalytic activity for
reactions owing to the high concentration of H+ and OH− ions [7]. Furthermore, it
is expected to get a higher yield of target chemicals by adding minimal amounts of
either acid or base catalysts. Antal et al. proposed that the ionic reactions are favored
at Kw > 10 −14 and that free radical reactions are favored at Kw < 10 −14 [13]. In this sec-
tion, five classes of reactions that often take place in the conversion of biomass are
discussed, with one typical example to show the influence of ion product of water in
the acid- or base-catalyzed reaction.
1.3 WATER DENSITY
Water density is another important property that can be varied greatly with tempera-
ture and pressure under hydrothermal conditions. Water density decreases with the
increase in temperature at constant pressure. For example, water density decreases
WHTP and Some Special Reactions under Hydrothermal Conditions 3
from about 800 kg/m3 (like liquid phase) to about 150 kg/m3 (like gas phase) with-
out phase change as the temperature increases from 300°C to 450°C. Meanwhile,
water density controlled by temperature and pressure can be related to ion product by
Equation 1.1 using a fitting method proposed by Marshall and Franck [14].
B C D  F G
log K w = A + + 2 + 3 +  E + + 2  log ρ, (1.1)
T T T  T T 
where T is temperature in Kelvin, ρ is density in g/cm3, and A to G are fitting

parameters. This result indicates that the chemistry of biomass conversion can also
be controlled by water density. However, it is not to say that water density affects
the reaction mechanism only by changing the ion product of water. Water density
changes can reflect the changes of water at the molecular level, such as solvation
effect, hydrogen bonding, polarity, dielectric strength, molecular diffusivity, and
viscosity, which will influence the chemistry inside [15]. In supercritical water, the
reaction mechanism varies from a reaction atmosphere that favors radical reaction
to one that favors ionic reactions dictated by the water density [16]. Experimental
data showed that reactions seemed to proceed via ionic pathways in the high-density
water while radical reactions seemed to be the main reaction pathways in the less
dense supercritical water [9]. Westacott et al. [17,18] investigated tert-butyl chloride
dissociation in supercritical water by computational methods and found that water
density affected the competition between ionic and radical reaction mechanisms.
The ionic heterolytic dissociation was preferred over the radical homolytic dissocia-
tion when water density was larger than 0.03 g/cm3 [17,18]. In this section, different
reaction mechanisms via ionic or radical pathways affected by water density were
introduced using different feedstocks.
1.4 DIELECTRIC CONSTANT
The ratio of the permittivity of a substance to the permittivity of free space is denoted
as the dielectric constant. The dielectric constant of water under ambient condition
is 78.5. Water under this condition could be used as good solvent for the polar mate-
rials. However, it cannot be used to dissolve hydrocarbon and gases. The dielec-
tric constant of water as a function of temperature can be seen in Figure 1.1 [19].
As shown in Figure 1.1, the dielectric constant of water decreases sharply with the
increase of water temperature. HTW under subcritical and supercritical conditions
behaves like many organic solvents that can dissolve organic compounds completely
forming a single fluid phase. The advantages of a single supercritical phase reaction
medium are that higher concentrations of reactants can often be attained and no
interphase mass transport processes hindering the reaction rates were indispensable.
As a consequence of the lack of data, attempts to estimate the properties of
aqueous species at high temperature and/or high pressure rely on the estimated or
extrapolated dielectric constant values [20]. The dielectric constant dependence on
the pressure, proposed by Bradley and Pitzer [21], can be seen in Figure 1.2. Bradley
used an equation suggested by Tait in 1880 for volumetric data. As shown in this
100
80
Dielectric constant (−)

60
40
20
0
0 100 200 300 400 500 600
Temperature (°C)
FIGURE 1.1 Dielectric constant of water as a function of temperature. Dashed line:

25 MPa; solid line: 50 MPa; dotted line: 100 MPa. Reprinted from Journal of Bioscience
and Bioengineering, 117, Akizuki M, Fujii T, Hayashi R, Oshima Y, Effects of water on reac-
tions for waste treatment, organic synthesis, and bio-refinery in sub- and supercritical water,
10–18, Copyright 2014, with permission from Elsevier.
140
130
120 T = 273 K
Dielectric constant
110 T = 298 K
100
T = 323 K
90
80 T = 348 K
70
60
0 400 800 1200 1600 2000
P (MPa)
FIGURE 1.2 Dielectric constant of water as a function of pressure at constant tempera-

tures (273 K, 298 K, 323 K, and 348 K) (fine lines: Bradley’s equation [21]; thick lines:
adjusted values extracted from the International Association for the Properties of Water and
Steam [22]). Reprinted with permission from Bradley DJ, Pitzer KS (1979) Thermodynamics
of electrolytes. 12. Dielectric properties of water and Debye-Hueckel parameters to 350°C
and 1 kbar. Journal of Physical Chemistry 83 (12):1599–1603. Copyright 2013 American
Chemical Society.
figure, at constant temperature, the dielectric constant values increased linearly with
the increase of pressure. It should be noted that the original Bradley equation does not
reproduce adequately the data available from the International Association for the
Properties of Water and Steam [22] used in Figure 1.2 for pressure above 400 MPa,
particularly at and above 323 K. However, the trends are similar, which can approxi-
mately represent the change of dielectric constant with different pressure.
1.4.1 Dielectric Constant of HTW

The dielectric constant of HTW attracted much attention. Islam et al. compared the
dielectric constant (ε) of superheated water at different temperature and pressure, as
shown in Table 1.1 [23]. The dielectric constant values of water decreased with the
increase of temperature from 44 at 150°C to 2 at 350°C. These values are between
those of organic solvent ethanol (ε = 24 at 25°C) and methanol (ε = 33 at 25°C), indi-
cating that superheated water can be used as an organic solvent. Moreover, super-
heated water is readily available, nontoxic, reusable, and very low in cost as well as
environmentally friendly. Therefore, superheated water can be used as an alternative
cleaning technology, instead of using organic solvents or toxic and strong aqueous
liquid media, for example, the extraction of dioxins [24], pesticides [25], polychlo-
rinated biphenyls [26], and polycyclic aromatic hydrocarbons (PAHs) [27]. Lagadec
et al. reported that the optimum subcritical water extraction was at 275°C in 35 min
for all low- and high-molecular-weight PAHs from contaminated manufactured gas
plant soil [25]. Moreover, it can also be used to determine a superior instant ana-
lytical technique (using gas chromatography oven as heater) by using organic sol-
vent [27]. However, a complete extraction technology with shorter extraction time
at a temperature range (from 100°C to 300°C) using subcritical water for industrial
application has not been determined; therefore, an additional study is necessary [23].
Notably, the dielectric constant of supercritical water is very special, because the
dielectric constant under this condition is much lower, and the number of hydrogen
bonds is much smaller and their strength is much weaker. Supercritical water above
374°C and 221 bar shows that water is greatly diminished—frequently less than
reduced local molecular ordering and less effective hydrogen bonding as character-
ized by its lower dielectric constant (about 1 to 3) [28]. As a result, supercritical water
TABLE 1.1
Dielectric Constant (ε) of Subcritical Water
and Common Organic Solvent
ε (at Subcritical Water °C) ε of Common Organic Solvent at 25°C
44 (150) 1.9 (n-hexane)
35 (200) 21 (acetone)
27 (250) 24 (ethanol)
20 (300) 33 (methanol)
2 (350) 39 (acetonitrile)
TABLE 1.2
Dielectric Constant and Density of Water at Some
Supercritical Conditions
Temperature (°C) Pressure (MPa) Density (g/cm3) Dielectric Constant
400 25 0.17 2.4
400 30 0.35 5.9
500 25 0.09 1.5
500 30 0.12 1.7
350 25 0.63 14.85
behaves like many organic solvents so that organic compounds have complete misci-
bility with supercritical water. Moreover, gases are also miscible in supercritical water;
thus, a supercritical water reaction environment provides an opportunity to conduct the
chemical reactions in a single fluid phase that would otherwise occur in a multiphase
system under conventional conditions [29]. Therefore, supercritical water exhibits con-
siderable characters of solvent, which can dissolve nonpolar materials and gas, and the
characters of easy diffusion and motion [30]. The dielectric constant of supercritical
water corresponds to the value of polar solvent under ambient conditions. The dielec-
tric constant of ambient water varies continuously over a much larger range in the
supercritical state. This variation offers the possibility of using pressure and tempera-
ture to influence the properties of the reaction medium. Therefore, it is possible for the
formation of a C–C bond with organometallic catalytic reactions, which always needs
organic solvent. Gomez-Briceno et al. compared the dielectric constant of water at differ-
ent supercritical conditions, 400°C and 500°C, and two pressures values, 25 and 30 MPa,
as shown in Table 1.2 [31]. The data showed that the dielectric constant decreased signifi-
cantly with the decrease of temperature. However, the influence was very small.
Water with a large dielectric constant will exhibit a strong effect with the micro-
structure of water and eventually influence the reaction [2]. The large dielectric con-
stant indicates that substances whose molecules contain ionic bonds tend to dissociate
in water, yielding solutions containing ions. This occurs because water as a solvent
opposes the electrostatic attraction between positive and negative ions that would pre-
vent ionic substances from dissolving. These separated ions become surrounded by
the oppositely charged ends of the water dipoles and become hydrated. This ordering
tends to be counteracted by the random thermal motions of the molecules. Water mol-
ecules are always associated with each other through as many as four hydrogen bonds,
and this ordering of the structure of water greatly resists the random thermal motions.
Indeed, it is this hydrogen bonding that is responsible for its large dielectric constant.
1.5 HYDROGEN BONDING
Because of hydrogen bonding, WHTP (water under high temperature and pressure
conditions) exhibits many unique properties that are quite different from those of
ambient liquid water.
The number of hydrogen bonds per water molecule at different temperature and den-
sity is shown in Figure 1.3. It can be concluded from Figure 1.3 that with increasing
temperature and decreasing density, hydrogen bonding in water becomes weaker and
less persistent [32]. For example, water at 673 K and ~0.5 g/cm3 retains 30–45% of the
hydrogen bonding that exists at ambient conditions, whereas water at 773 K and ~0.1 g/
cm3 retains 10–14% [33]. The hydrogen bonding network in ambient liquid water exists
in the form of infinite percolating large clusters of hydrogen-bonded water molecules, but
the hydrogen bonding network in WHTP exists in the form of small clusters of hydrogen-
bonded water molecules [32,34–36]. In general, the average cluster size of hydrogen-
bonded water molecules decreases with increasing temperature and decreasing density.
For instance, the size of most of the clusters at 773–1073 K and 0.12–0.66 g/cm3 consists
of five water molecules or less, although there exist a small number of clusters that are
as large as about 20 water molecules [32,35,36]. These results show that less hydrogen
bonding results in much less order in WHTP than ambient liquid water and that indi-
vidual water molecules can participate in elementary reaction steps as a hydrogen source
or catalyst during hydrothermal conversion of biomass into high-valued chemicals.
Many studies have reported on water molecules supplying hydrogen atoms that par-
ticipate in reactions such as the steam reforming of glucose [37,38] and biomass [39,40];
the pyrolysis of alkyldiammonium dinitrate [41]; the oxidation of methylene chloride
[42], lactic acid [43], and carbon monoxide [44–46]; the hydrogenation of dibenzothio-
phene [47] and heavy oils [48]; the co-liquefaction of coal and cellulose [49]; and the
alcohol-mediated reduction of CO2 and NaHCO3 into formate [50,51]. They produced
hydrogen in situ by partially oxidizing the organic compounds to generate carbon mon-
oxide, which then underwent the water–gas shift reaction (CO + H2O ↔ CO2 + H2). The
authors proposed that the reactive intermediate generated by the water–gas shift reaction
10
100
ηHB/n (Å3)
80
60
40
700 900 1100
T(K)
ηHB
257 kg/m3
659 kg/m3
0.1
0.8 1 1.2 1.4
1000/T (1/K)
FIGURE 1.3 Number of hydrogen bonds per water molecule. [From Mizan TI, Savage PE,
Ziff RM (1996) Temperature dependence of hydrogen bonding in supercritical water. Journal
of Physical Chemistry 100 (1):403–408.]
was the actual hydrogenation agent and not the hydrogen molecule itself. As shown in
Figure 1.4, our recent study found that CO2 or NaHCO3 could be transformed into for-
mate by alcohol-mediated reduction under hydrothermal alkaline conditions [50,51].
Hydrogen–deuterium exchange data also provide evidence for hydrogen supply
by water as deuterium was found to be incorporated into the products of hydrocarbon
pyrolyses in supercritical D2O [52,53]. More recently, in order to discover the reac-
tion mechanism for the production of hydrogen and lactic acid from glycerol under
alkaline hydrothermal conditions, we identified the different intermediates involved
during reactions by investigating the water solvent isotope effect with 1H-NMR,
2H-NMR, LC–MS, and Gas-MS analyses as shown in Figure 1.5 [53]. The results
from solvent isotope studies showed that (1) almost all of the H atoms on the β-C
Keto-enoltautomerization
(Step 1)
H H H
H C OH H C OH H C OH
− OH − OH −
H C OH + H C O3 C OH + C O +
H 2C O 3 H 2C O 3
H C OH H C H C H
H H H
Glycerin 2-hydroxypropenol Hydroxyacetone
Hydrogen-transfer reduction
(Step 2) H
H
H O H O H
H
H or H
O 2H 2O
H C OH O O C
O O
H2O + O
C O + H C H H C H C O
− C C
HC O 3
OH O C O
H C H C O C O H C H
O
H
H H C H H C H H
Pyruvaldehyde Formate
Hydroxyacetone
H Transition state H
(Step 3) Benzilic acid rearrangement

H O
C O C O
H 2O
C O + HC O −3 H C OH +
CO2
H C H H C H
H H
Pyruvaldehyde Lactate
FIGURE 1.4 The proposed pathway of the hydrogen-transfer reduction of NaHCO3 with
glycerine. [From Shen Z, Zhang YL, Jin FM (2012) The alcohol-mediated reduction of CO2
and NaHCO3 into formate: a hydrogen transfer reduction of NaHCO3 with glycerine under
alkaline hydrothermal conditions. Rsc Adv 2 (3):797–801.]
OH (C)
H2O (C)
H H
(a) 1H−NMR (in H2O) 30 min C HO OH
D H
H (B) H
(D) (D)
B CH3CH(OH)COO−
HCOO −
(b) 1H−NMR (in H2O) 60 min

CH3CH(OH)COO −
−
HCOO
CH3CH(OH)COO−
(c) 1H−NMR (in H2O) 90 min
CH3CH(OH)COO−
HCOO −
HOD
(d) 1H−NMR (in D2O) 30 min C
D
HCOO − CH3CH(OH)COO−
D 2O
(e) 2H−NMR (in D2O) 30 min
−
CD3CD(OD)COO
− CD3CD(OD)COO−
DCOO
ppm 9 8 7 6 5 4 3 2 1 0
FIGURE 1.5 1H-NMR spectra for the solution after the hydrothermal reaction of 0.33 M
glycerol at 300°C with 1.25 M NaOH in H2O for (a) 30 min, (b) 60 min, (c) 90 min, and
(d) 1H-NMR and (e) 2H-NMR spectra with 1.25 M NaOD in D2O for 30 min. [From Zhang
YL, Shen Z, Zhou XF, Zhang M, Jin FM (2012) Solvent isotope effect and mechanism for the
production of hydrogen and lactic acid from glycerol under hydrothermal alkaline conditions.
Green Chemistry 14 (12):3285–3288.]
of lactic acid were exchanged by D2O, suggesting that the hydroxyl (–OH) group
on the 2-C of glycerol was first transformed into a carbonyl (C=O) group and then
converted back into an –OH group to form lactic acid; (2) a large amount of D was
found in the produced hydrogen gas, which shows that the water molecules acted as
a reactant; and (3) the percentage of D in the produced hydrogen gas was far more
than 50%, which straightforwardly showed that acetol was formed in the first place
as the most probable intermediate by undergoing a dehydration reaction rather than
a dehydrogenation reaction.
The natural abundance of hydronium and hydroxide ions suggests that some
acid- and base-catalyzed reaction may proceed in HTW in the absence of an added
catalyst [54–67]. Alcohol dehydration is nominally catalyzed by either acid or base
in the presence of added catalysts. In WHTP, however, experimental data suggest
that the dominant mechanism is acid catalysis and the dehydration reactivity depends
on the structure of the alcohol [54–60].
Experimental data suggest that water molecules can also catalyze a reaction by
directly participating in the transition state and reducing its energy. This form of
catalysis is important for reactions involving some types of intramolecular hydrogen
transfer. For example, Klein, Brill, and coworkers proposed a type of water catalysis
for the intramolecular hydrogen-transfer step during the conversion of nitroaniline
to benzofurazan as shown in Figure 1.6 [64] and the decarboxylation of acetic acid
derivatives in WHTP [65].
Arita et al. reported that hydrogen can be generated by an ethanol oxidation reac-
tion catalyzed by water molecules and that half of the produced hydrogen could
come from the water in accordance with the proposed reaction mechanism in Figure
1.7 [61]. Moreover, Takahashi et al. suggested that water molecules played significant
catalytic roles in ethanol oxidation reactions based on ab initio density functional
theory calculations [66].
H
H
O O
H H
H H H H H H
N O N O N O O
N
N N N N
O O O −H2 O
H transfer
Benzofuroxan
FIGURE 1.6 Water catalysis for the intramolecular hydrogen transfer during the conversion
of nitroaniline to benzofurazan. [From Wang XG, Gron LU, Klein MT, Brill TB (1995) The
influence of high-temperature water on the reaction pathways of nitroanilines. J Supercrit
Fluids 8 (3):236–249.]
H
H H
H O H
H H H O H O
H H H
H3C CH O H
H H3C CH O H3C C
O H H O
O H O H H
FIGURE 1.7 Proposed transition state consisting of an ethanol molecule and two water
molecules in supercritical water without catalyst. [From Arita T, Nakahara K, Nagami K,
Kajimoto O (2003) Hydrogen generation from ethanol in supercritical water without catalyst.
Tetrahedron Letters 44 (5):1083–1086.]
1.6 HYDROLYSIS
As shown in Figure 1.8, hydrolysis is one of the major (and usually initial) reactions
that occur during conversion of biomass in which glycosidic bonds between sugar
units are cleaved to form simple sugars such as glucose and partially hydrolyzed
oligomers. Hydrolysis can happen both in acid- and base-catalyzed reactions, while
the former reaction condition (acidic) is more often adopted because base cataly-
sis leads to more side reactions [68,69]. The hydrolysis of cellulose to glucose is a
widely investigated reaction in biomass conversion because cellulose is the major
component of plant biomass and the product glucose is a very important intermedi-
ate [70]. Under hydrothermal conditions, cellulose reacts with water and is hydro-
lyzed into glucose or other monomers proceeding through C–O–C bond cleavage
and accompanied by further degradation. Three possible reaction paths of cellobiose
hydrolysis are demonstrated, including acid-, base-, and water-catalyzed ways [69].
Acid hydrolysis proceeds through the formation of a conjugated acid followed by the
glycosidic bond cleavage and leads to the two glucose units. In the base pathway,
the OH− attacks at the anomeric carbon atom, renders the cleavage of the O bridge,
and again yields the two glucose units. The water-catalyzed reaction is character-
ized by H2O adsorption. Then, water and the glycosidic bond split simultaneously
and form two glucoses again. Sasaki et al. [71,72] conducted cellulose decomposi-
tion experiments with a flow-type reactor from 290°C to 400°C at 25 MPa. Higher
hydrolysis product yields (around 75%) were obtained in supercritical water than
in subcritical water. The reason was attributed to the difference of reaction rate in
the formation and degradation of oligomer or glucose. At a low-temperature region,
CHO
OH H OH
OH
O Hydrolysis HO H
O HO
HO O H OH
OH O
H OH
OH n
CH2OH
Cellulose Glucose
FIGURE 1.8 Hydrolysis of cellulose.

the glucose or oligomer conversion rate was much faster than the hydrolysis rate of
cellulose. However, around the critical point, the hydrolysis rate jumped to more
than an order of magnitude higher level and became faster than the glucose or oligo-
mer decomposition rate. The direct observation by diamond anvil cell showed that
the cellulose disappeared with a more than two orders of magnitude faster rate at
300–320°C than that estimated [72]. This phenomenon indicated that the presence
of a homogeneous hydrolysis atmosphere caused by the dissolution of cellulose or
hydrolyzed oligomers around the critical temperature thus resulted in the high cel-
lulose hydrolysis rate. The additional acid catalysts including homogeneous and het-
erogeneous catalysts would also enhance the yield of glucose, which was around
50–80% [70]. The base catalyst might cause more side reactions [69] but could
inhibit the formation of char, which was very crucial in the continuous flow reactor
to prevent plug [73].
1.7 ISOMERIZATION
As shown in Figure 1.9, the isomerization between glucose and fructose is very com-
mon and has been considered as one key step in biomass conversion. The difference
in their reactivity and selectivity for target materials makes the tunable transforma-
tion to a specific one (usually from glucose to fructose) highly desirable [74]. This
reaction is typically catalyzed by the base catalyst, named Lobry de Bruyn–Alberda
van Ekenstein transformation. The mechanism proceeds by deprotonation of alpha
carbonyl carbon of glucose by base, resulting in the formation of a series of enolate
intermediates. The overall process involves hydrogen transfer from C-2 to C-1 and
from O-2 to O-1 of an alpha hydroxy aldehyde to form the corresponding ketone.
Kabyemela et al. [75] found that the isomerization from fructose to glucose is neg-
ligible compared with its reversion under hydrothermal conditions because glucose
and fructose have the same product distribution except for 1,6-anhydroglucose,
which is not observed in the decomposition of fructose. Recently, Wang et al. [76]
reported another Lewis acid-catalyzed pathway of isomerization via intramolecular
hydride transfer for glucose–fructose. In addition to glucose–fructose isomerization,
there is another important isomerization between glyceraldehydes and dihydroxy-
acetone under hydrothermal conditions [77].
CHO CH2OH
H OH O
HO H Isomerization HO H
H OH H OH
H OH H OH
CH2OH CH2OH
Glucose Fructose
FIGURE 1.9 Isomerization between glucose and fructose.

1.8 DEHYDRATION
Dehydration reactions of biomass comprise an important class of reactions in the
area of sugar chemistry. As shown in Figure 1.10, fructose can be dehydrated into
hydroxymethylfurfural (HMF) with loss of three water molecules by acid-catalyzed
reaction. Antal et al. [78] proposed that HMF is produced from fructose via cyclic
intermediates. Recent studies confirmed that the HMF formation was from the acid-
catalyzed dehydration of C6 sugars in the furanose form [79,80]. Hence, fructose,
which contains 21.5% of furanose tautomers in aqueous solution, can be converted
to HMF easier than glucose, which contains only 1% of furanose tautomers in aque-
ous solutions. The rehydration of HMF with two molecules of water would produce
levulinic acid and formic acid [81]. Levulinic acid can be further converted into
γ-valerolactone via hydrogenation with hydrogen [82], which can be converted into
liquid alkenes in the molecular weight range appropriate for transportation fuel [83].
Asghari and Yoshida obtained the best yield of HMF (65%) from fructose
achieved at a temperature of 513 K for a residence time of 120 s [84]. Since glucose
is more common than fructose in biomass conversion, researchers usually adopt a
two-step strategy to produce HMF from glucose: (1) isomerization of glucose into
fructose catalyzed by base and (2) dehydration of fructose into HMF by acid [85].
Since water under high temperatures and pressures can play the role of both acid
and base catalysts, a high yield of HMF can be obtained under hydrothermal condi-
tions in one step. Takeuchi et al. [86] reported that the total highest yields of HMF
and levulinic acid from glucose were about 50%, which occurred at 523 K for 5 min
with H3PO4 as a catalyst, and the highest yield of levulinic acid was about 55% at
523 K for 5 min with HCl as a catalyst. For the three mineral acids (HCl, H2SO4, and
H3PO4), it was found that both the pH and the nature of the acids had great influence
on the decomposition pathway [84]. The order for the production of HMF using the
three acids was as follows: H3PO4 > H2SO4 > HCl [86]. On the contrary, the order for
production of levulinic acid was as follows: HCl > H2SO4 > H3PO4 [86].
There are some drawbacks in the acid-catalyzed formation of HMF from fructose
or glucose. Kinetic studies [87–89] showed that humins formation from glucose
and HMF cannot be neglected. The activation energy of its formation from glucose
and HMF was estimated at 51 and 142 kJ/mol, respectively, while dehydration of
CH2OH
O
HO H Dehydration O
HO O
H OH
3H2O
H OH
CH2OH
Fructose HMF
FIGURE 1.10 Dehydration of fructose into HMF.

glucose to HMF and rehydration of HMF to levulinic acid were 160 and 95 kJ/mol,
respectively [89]. To minimize the formation of humins and enhance the selectivity
toward HMF, a biphasic solution with water and organic phase was adopted that
would continuously extract HMF as it is produced [90–93]. Yang et al. reported a
61% yield of HMF from glucose using a biphasic reactor of water/tetrahydrofuran
with AlCl3·6H2O catalyst at 160°C [91].
1.9 RETRO ALDOL REACTION

Many researchers [67,71,75,77,94] have examined intermediate products for the
hydrothermal degradation of glucose and cellulose at a reaction temperature of
near 300°C. As shown in Figure 1.11, through these studies, it was revealed that
some compounds containing three carbon atoms, such as glyceraldehyde, dihy-
droxyacetone, and pyruvaldehyde, were formed by the base catalytic role of HTW.
Furthermore, there was isomerization occurring between glyceraldehyde and dihy-
droxyacetone followed by their subsequent dehydration to pyruvaldehyde [77]. The
ketone (fructose) can undergo reverse aldol reaction by C3–C4 bond cleavage to
form glyceraldehydes. These C3 carbon compounds were considered as the precur-
sors of lactic acid from transformation of pyruvaldehyde [67]. On the other hand,
the intermediates glycoaldehyde and erythrose were transformed from glucose by
retro aldol reaction [71,75]. In organic chemistry, retro aldol reaction can usually be
catalyzed by either an acid or a base. Experimental data suggested, however, that
retro aldol reaction under hydrothermal conditions was base catalyzed [2]. Sasaki et
al. [95] reported that the retro aldol reaction selectively proceeded at higher tempera-
tures (above 673 K) and lower pressure (below 25 MPa). At a low temperature, the
retro aldol reaction was preferred in an alkali environment [96].
CH2OH
O
Retro aldol reaction OH
HO H
2
H OH O
HO
H OH
CH2OH
Fructose Glyceraldehyde
CHO
H OH O
Retro aldol reaction
HO H O + OH
H OH OH
HO
H OH
OH
CH2OH
Glucose Glycolaldehyde Erythrose
FIGURE 1.11 Retro aldol reaction of fructose and glucose.

These formed intermediates from C2-C3 or C3-C4 bond cleavage by reverse

aldol reaction from hexoses can then be fast transformed into mainly lactic acid
and other low molecular acid in which glyceraldehyde can produce a higher yield of
lactic acid [94]. Lactic acid is a key chemical and acts as a building block for biode-
gradable lactic acid polymers with limited environmental impact. Yan et al. [97,98]
showed that the addition of base catalyst [NaOH and Ca(OH)2] can increase the yield
of lactic acid. The highest yield of lactic acid from glucose was 27% with 2.5 M
NaOH and 20% with 0.32 M Ca(OH)2 at 300°C for 60 s [97]. A very recent study
by Sánchez et al. [99] also found that the highest-yield lactic acid of 45% from corn
cobs was obtained using 0.7 M Ca(OH)2 at 300°C for 30 min. The reason that the
base catalyst increased the yield of lactic acid can be attributed to the enhancement
of the reaction pathway for lactic acid production discussed above. Another pos-
sible reason is that the lactate formed actually by alkaline solution prevents it from
decomposition [100]. Compared with NaOH at lower alkaline concentration [95],
Ca(OH)2 more effectively promoted the production of lactic acid than NaOH at the
same OH− concentration. It is probably because Ca2+ was more capable than Na+ in
forming complexes with two oxygen atoms in the hexoses. When the concentration
of Ca(OH)2 increased from 0.32 to 0.4 M, it did not lead to an increase in lactic acid
yield, while the optimum OH− concentration for NaOH was 2.5 M. This difference
can be attributed to the fact that the saturated solubility of NaOH is higher than that
of Ca(OH)2.
1.10 DECARBOXYLATION AND DECARBONYLATION [100–104]

HCOOH → H 2 + CO 2 (decarboxylation) (1.2)
HCOOH → H 2O + CO (decarbonylation) (1.3)
The reactions of formic acid play a key role in the chemistry of hydrothermal reaction,
partly because it was the simplest acid and a product of many acid/base-catalyzed
or oxidation reactions, and partly because itself or formate is considered to be the
intermediate of water–gas shift reaction and reduction of carbon dioxide [105]. The
understanding of its reactivity especially coupled with the properties of water will
facilitate the researches on energy production and environment protection. As shown
in Equations 1.2 and 1.3, for the decomposition of formic acid, there existed two com-
petitive pathways: decarboxylation and decarbonylation. Early experimental results
showed that, in the gas phase, decarbonylation dominated, but in the liquid phase,
decarboxylation dominated [101,106]. Yu and Savage [101] conducted the formic acid
decomposition experiments from 320°C to 500°C, at pressures from 18.3 to 30.4 MPa,
and at 1.4- to 80-s reaction times. Conversion rates ranging from 38% to 100% were
obtained with the major products of CO2 and H2. In their experiments, the decarbon-
ylation product CO was also detected and the yields were always at least an order
of magnitude lower than the yields of decarboxylation. The reason why decarboxyl-
ation dominated in the liquid phase can be explained by the presence of water as a
homogeneous catalyst that can catalyze decarboxylation more than decarbonylation by

a theoretical calculation [102]. The kinetic data also supported the assumption of
a homogeneous reaction based on the consistency with the reaction rate law that
was first order in formic acid [101]. However, Wakai et al. [103] indicated that the
reactor wall might show a catalytic role in the formic acid decomposition, which
is a heterogeneous reaction according to an NMR investigation. Compared with its
acidic environment, Jin et al. [100] found that the addition of alkali could prevent
the formic acid decomposition even with the presence of oxidant H2O2 at 250°C
for 60 s.
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But there were with him the son of the thousand-man and his
equerry, and they pressed him and said: “Go, O Prince, back to
Russia, if the Lord will deliver you!” But the time was not propitious.
As we said before, the Pólovtses returned from Pereyáslavl, and
Ígor’s advisers said to him: “You harbour a proud thought and one
that is not pleasing to God; you do not intend to take the man and
run with him, but why do you not consider that the Pólovtses will
return from the war, and we have heard that they will slay all the
princes and all the Russians, and there will be no glory for you, and
you will lose your life.” Prince Ígor took their advice to heart, being
afraid of the return of the Pólovtses, and bethought himself of flight.
He was not able to run away either in daytime or at night, for the
guards watched him, but he found an opportune time at the setting of
the sun. And Ígor sent his equerry to Lavór, saying: “Cross on the
other side of the Tor with a led horse,” for he intended to fly to Russia
with Lavór. At that time the Pólovtses were drunk with kumys; and it
was towards evening when his equerry came back and told him that
Lavór was waiting for him. Ígor arose frightened and trembling, and
bowed before the image of the Lord and the honourable cross, and
said: “Lord, knower of hearts! If Thou, Master, wilt save me,
unworthy one,”—and he took the cross and the image, lifted the
tent’s side, and crawled out. His guards were gambling and feasting,
for they thought that the Prince was asleep. He arrived at the river,
waded across, and mounted the horse; thus they both rode by the
tents.
This deliverance the Lord granted on a Friday, in the evening. He
then walked eleven days to the town of Donéts, and thence he went
to his Nóvgorod, and they were much rejoiced. From Nóvgorod he
went to his brother Yarosláv in Chernígov, to ask for help in the
Posémie. Yarosláv was glad to see him, and promised him aid. Ígor
travelled thence to Kíev to Grand Prince Svyatosláv, and Svyatosláv
was glad to see him, as was also Rúrik.
FOOTNOTES:
[19] For notes consult the Word of Ígor’s Armament (p. 80 et
sqq.).
[20] A Finnish tribe.
[21] Town in the country of the Vyátiches.
[22] The country along the river Sem.
The Word of Ígor’s Armament. (End of XII.
century.)
No other production of Russian antiquity has roused so
much interest in Russia and abroad as this version of Ígor’s
expedition by an unknown poet of the end of the twelfth
century. Thirty-five translations into modern Russian,
numerous translations into Little-Russian, Polish, Bohemian,
Servian, Bulgarian, Hungarian, German, French, witness to
the enormous popularity this production has attained. The
historical background of the poem is found in the recital from
the Kíev Chronicle, which is given on pp. 71-80. The disasters
which befell Ígor and his army are probably told with better
effect in that prosaic version; but the superior value of the
Word lies in its being a precious relic of the popular poetry of
the end of the twelfth century, such as no other nation can
boast of. The Nibelungenlied and the Chanson de Roland are
chiefly productions of a literary character, while the Word
bears every evidence of representing the untutored labour of
a popular bard.
Who the author was, when he lived, for whom he sang, are
all unanswered questions, but from internal evidence we
glean that he sang for his contemporaries while Ígor was still
alive. From his apostrophe to Yarosláv Osmomýsl, who died
in 1187, we may infer that the poem was written before that
year, and it is not unlikely, from his vivid description of the
battle at the Kayála, that he was an eye-witness of the
expedition which took place in 1185. From the absence of
biblical references it is generally assumed that the author was
not a member of the clerical profession. Here, however,
various difficulties arise. It is quite incomprehensible why
there should be so many references to pagan divinities at a
time when Christianity had been deep-rooted in Russia for
fully two centuries; why, except for the evident imitation of
many passages in the Zadónshchina, there should be no
reference to the poem by any medieval writer, and why only
one copy of so remarkable a work should have been
preserved. If this poem came so very near being lost to
posterity, how many other remarkable productions of that
early period have disappeared? It is not at all impossible that
there existed an extensive popular poetry, of which only the
barest traces have come down to us. This suspicion is
strengthened by the emphatic mention by the author of the
Word of a poet Boyán who had lived before his days.
A copy of the poem was discovered by Count A. I. Músin-
Púshkin, Procurator-General of the Holy Synod, in 1795. He it
was who in rummaging St. Petersburg bookstalls had
discovered the manuscript of Néstor’s Chronicle. From a
monk he procured a collection of eight pieces, the fifth of
which was this poem. He published the Word, as this poem is
called in the manuscript, in 1800, with a modern Russian
translation. The manuscript itself was burnt in the Moscow
conflagration of 1812. The poem has since been edited a
countless number of times, and equally large is the mass of
critical essays to explain the many dark and corrupt places of
what now must pass for the original. When we consider that
there are not less than six versions of the Word in French, it
seems strange that it is now first rendered into English in its
entirety. There is an imperfect translation of a small part of it
in H. H. Munro’s The Rise of the Russian Empire, Boston and
London, 1900.
Were it not well for us, O brothers, to commence in the ancient

strain the sad story of the armament of Ígor,[23] Ígor son of
Svyatosláv? And let the song be told according to the accounts of
the time, and not according to the cunning of Boyán[24] the Wise, for
Boyán the Wise, when he wished to make a song, soared with his
thoughts in the tree, ran as a grey wolf over the earth, flew as a
steel-grey eagle below the clouds. When he recalled the strife of
former time, he let loose ten falcons o’er a flock of swans, and every
swan each touched sang first a song: to old Yarosláv,[25] to brave
Mstisláv[26] who slew Redédya before the Kasóg army, to fair
Román Svyatoslávich.[27] But Boyán, O brothers, did not let loose
ten falcons on a flock of swans, but laid his inspired fingers on the
living strings, and they themselves sounded the glory to the princes.
Let us begin, O brothers, this tale from Vladímir[28] of old to the
late Ígor who strengthened his soul by his valour, and sharpened it
by the courage of his heart, and having filled himself with a manly
spirit, led his valiant army for the land of Russia into the country of
the Pólovtses.[29]
II
Then Ígor looked up to the bright sun, and saw that he had
covered in darkness[30] all his warriors. And Ígor spoke to his
druzhína: “O brothers and druzhína! It is better to be cut to pieces
than to be made a captive! Let us, O brothers, mount our swift
horses that we may behold the beautiful Don!”
A strong desire filled the Prince’s soul to drink from the great Don,
and his eagerness blinded him to the evil omen.
“For I wish,” he said, “to break the spear on the border of the
Pólovts land together with you, sons of Russia! I want to lay down
my head, and drink with my helmet from the Don!”
O Boyán, nightingale of ancient time! It were for you to spell this
army, soaring like a nightingale over the tree of thought, flying like an
eagle below the clouds, stringing together words for the deeds of
that time, racing over Troyán’s[31] footsteps over fields to the
mountains. You ought to have sung a song to Ígor, his grandson:
“Not a storm has driven the falcons over the broad fields: flocks of
crows hasten to the great Don.”... Or you might have sung thus,
inspired Boyán, grandson of Velés[32]:
“The horses neigh beyond the Sulá[33]; glory resounds in Kíev;
trumpets blare in Nóvgorod[34]; the standards are at Putívl[35]; Ígor
waits for his beloved brother Vsévolod. And Vsévolod, the Grim
Aurochs, spoke to him: “My only brother, my only light, glorious Ígor,
we are both sons of Svyatosláv! Saddle, O brother, your swift steeds,
for mine are ready for you, having been saddled in advance at
Kursk! My Kurians are tried warriors, nurtured by the sound of
trumpets, rocked in helmets, fed at the point of the spear. The roads
are known to them; the ravines are familiar to them; their bows are
drawn; their quivers open, their swords—whetted. They race over
the fields like grey wolves, seeking honour for themselves, and glory
for their Prince.”
III
Then Prince Ígor stepped into the golden stirrup and galloped over
the clear field. The sun barred his way in darkness; night groaning
with the cries of birds awoke him; beasts howled, and Div[36] called
in the top of a tree, sending the news to the unknown land, to the
Vólga, the Sea border,[37] the Sulá country, Surózh[38] and Korsún,
[39] and to you, idol of Tmútorokan![40] But the Pólovtses hastened
by untrodden roads to the great Don; the carts creaked at midnight,
like swans let loose.
Ígor leads his soldiers to the Don: the birds in the thicket forbode
his misfortune; the wolves bristle up and howl a storm in the
mountain clefts; the eagles screech and call the beasts to a feast of
bones; the foxes bark for the crimson shields. O Russian land, you
are already beyond the mound![41] Night is long and murky; the
dawn withholds the light; mist covers the fields; the nightingale’s
song is silent; the cawing of the crows is heard. The Russians bar
the long fields with their crimson shields, seeking honour for
themselves and glory for the Prince.
IV
Early in the morning, on the Friday, they crushed the pagan
Pólovts host, and, spreading like arrows over the field, seized fair
Pólovts maidens, and with them gold and gold-worked stuffs and
costly velvet; with cloaks and coats and Pólovts lace they bridged
their way over bogs and muddy places. A red flag, white pennon, red
panache, silver cross-beam, for the brave son of Svyatosláv!...[42]
Olég’s valiant brood has flown afar and dreams in the field! They
thought not to offend the falcon, gerfalcon, nor you, black raven,
pagan Pólovts! But Gza ran like a grey wolf, with Konchák[43] in his
track, to the great Don.
Very early the next morning a bloody dawn announces the day.
Black clouds come from the sea and try to veil four suns,[44] while
blue lightnings quiver through them. There is to be a mighty thunder,
and the rain is to go down in arrows by the great Don! There spears
will be broken; there swords will be blunted against Pólovts helmets
on the Kayála,[45] by the great Don. O Russian land, you are already
beyond the mound!
Behold the winds, Stribóg’s[46] grandchildren, blow arrows from
the sea on Ígor’s valiant army. The earth groans, the rivers flow
turbid; dust covers the fields; the banners whisper. The Pólovtses
come from the Don, and from the sea, and from all sides: the
Russian army recedes. The devil’s children fill the field with their
cries, but the brave Russians line it with their crimson bucklers.
Grim Aurochs Vsévolod! You stand in the van; you pour arrows on
the warriors; you thunder with steel swords against their helmets.
Wherever you, Aurochs, lead, gleaming with your golden helmet,
there fall the heads of the pagan Pólovtses, their Avar[47] helmets
cloven by your tempered swords, Grim Aurochs Vsévolod! What
wound does he brook, O brothers, having forgotten his honours and
manner of life, and Chernígov town, his paternal golden throne, and
the caresses of his sweetheart, Glyeb’s fair daughter,[48] and the
habits and customs of his home?
VI
Troyán’s age is past, gone are the years of Yarosláv; past are the
expeditions of Olég,[49] the son of Svyatosláv. That Olég had
fostered discord with his sword, and had sowed arrows over the
land. In Tmútorokan city he stepped into the golden stirrup. Great
Yarosláv, that was, heard the tocsin,[50] and Vsévolod’s son Vladímir
closed his ears all the days at Chernígov.[51] But Glory brought
Borís,[52] the son of Vyachesláv, before the judgment seat and
bedded him, brave young prince, on the green feather grass of the
steppe, through Olég’s offence....
Then, in the days of Olég Gorislávich,[53] feuds were sown and
grew, and Dazhbóg’s[54] grandchildren perished, and the years of
men were shortened by the discord of the princes. In those days the
warriors rarely walked behind the plough in the Russian land, but the
ravens croaked as they divided the dead bodies, and crows
chattered, flying to the banquet. Such were the wars and expeditions
then, but the like of this war was never known.
VII
From early morning until evening, from evening until daylight fly
tempered arrows, thunder the swords against the helmets, resound
the steel spears in a strange field, within the country of the
Pólovtses. The black earth beneath the hoofs was sown with bones,
and watered with blood, and a harvest of sorrow went up in the
Russian land.
What noise is that, what din, so early in the morning before dawn?
Ígor leads his army; he is sorry for his beloved brother Vsévolod.
They fought a day, they fought another[55]; upon the third at noon fell
the standards of Ígor. The brothers separated on the bank of the
swift Kayála. Here there was not enough of bloody wine; here the
brave Russians ended the feast: they gave their host their fill to
drink, and themselves fell for the Russian land. The grass withered
from sorrow, and the trees in anguish bent down to the earth.[56]
VIII
There befell a hapless hour, O brothers! Already had the

wilderness covered Russia’s hosts, when Mischief arose in the hosts
of Dazhbóg’s grandchildren: she walked as a maiden in Troyán’s
land,[57] splashed her swan pinions in the blue sea,[58] and splashing
them in the Don, recalled heavy times.
Through the feuds of the princes ruin came from the pagans, for
brother spoke to brother: “This is mine and that is mine also,” and
the princes said of trifling matters, “They are important,” and created
discord among themselves; and the pagans came from all sides
victorious into the Russian land.
Oh, far has the falcon[59] flown, driving the birds by the sea, but
Ígor’s brave army will rise no more! Konchák called, and Gza raced
over the Russian land, hurling fire from a flaming horn.[60] Russian
women wept, saying: “No longer will our thoughts reach our dear
ones, nor shall we ever see them with our eyes, nor be adorned with
tinkling gold and silver!”
And Kíev groaned under its sorrow, and Chernígov on account of
its misfortunes. Sadness spread over the Russian land, and a heavy
gloom. The princes fostered discord among themselves, and the
pagans victoriously overran the country, receiving tribute, a
squirrel[61] from each house.
It is Ígor and Vsévolod, Svyatosláv’s brave sons, who through their
discord had wakened dishonour which their father, Svyatosláv[62] of
Kíev, the great, the mighty, had put to sleep: he had invaded the
Pólovts land and had carried terror to them, with his mighty armies
and tempered swords; had levelled their hills and ravines, ruffled
their rivers and lakes, dried up their streams and swamps; and, like a
whirlwind, had snatched pagan Kobyák[63] away from his mighty,
steel-clad Pólovts army by the Ázov Sea, until Kobyák fell in Kíev
city, in the council-room of Svyatosláv. Germans, Venetians, Greeks
and Moravians sing the glory of Svyatosláv, but blame Prince Ígor
who had merged his wealth in the Kayála, the Pólovts river, and had
filled it with Russian gold. Here Ígor was unseated from his golden
saddle and placed upon the saddle of a slave.
IX
The city walls were silent, and merriment was dead. Svyatosláv
saw a troubled dream: “In Kíev on the mount you enveloped me last
night,” he said, “in a black shroud on a bed of yew; they poured out
to me blue wine mixed with bitterness; from empty quivers they
showered large gems upon my lap, and tried to comfort me. Already
are there boards without a cross beam in my hall of gold, and all
night have the devilish crows been cawing.”[64] ...
The boyárs spoke to the Prince: “Prince, sorrow has enthralled
your mind. Two falcons flew from their paternal throne of gold to find
the city of Tmútorokan, and anxious to drink from the Don with their
helmets. The falcons’ wings have been clipped by the pagan swords,
and they have been enmeshed in iron fetters. On the third day it was
dark: two suns were dimmed,[65] two red torches went out, and with
them two young moons, Olég[66] and Svyatosláv, were shrouded in
darkness. On Kayála river darkness veiled the day: the Pólovtses
had invaded the Russian land, like a litter of lynxes.... Fair Gothic[67]
maidens sing upon the shore of the blue sea, tinkling with the
Russian gold: they sing the times of Bus, recall Sharokán’s[68]
revenge. But we, your druzhína, are anxious for the feast.”
Then great Svyatosláv uttered golden words, mingled with tears:
“Oh, my nephews, Ígor and Vsévolod! Too early did you begin to
strike the land of the Pólovtses with your swords, and to seek glory
for yourselves. You were vanquished ingloriously, for ingloriously
have you spilled the blood of the pagans! Your brave hearts are
forged with hard steel and tempered in daring exploits. See what you
have done with my silvery hair! I no longer see with me my mighty,
warlike brother Izyasláv with his Chernígov druzhína.... They
overwhelmed their enemies with dirks, not bearing bucklers, but
raising a warcry and resounding the glory of their forefathers. But
you spoke: ‘We alone will vanquish! Let us ourselves gain the future
glory, and share the glory of our fathers!’ Why should not an old man
feel young again? When the falcon is moulting, he drives the birds
far away, and allows not his nest to be hurt. But alas, the princes will
not aid me! My years have turned to nothing. At Rim[69] they cry
under the swords of the Pólovtses, and Vladímir[70] groans under his
wounds. Bitterness and sorrow has befallen the son of Glyeb!”
Grand Prince Vsévolod![71] Fly from afar not only in thought, but
come to protect your paternal throne: for you could dry up the
Vólga[72] with your oars, and empty the Don with your helmets. If you
were here, a Pólovts slave-girl would be worth a dime, and a man-
slave—half a rouble.[73] And you know, together with the brave sons
of Glyeb, how to hurl the Greek fire on land.
You, Grim Aurochs Rúrik and David![74] Did not your golden
helmets swim in blood? Did not your valiant druzhína bellow like
aurochses, when they were wounded by tempered swords in a
strange field? Put your feet, O lords, into your golden stirrups to
avenge the insult to the Russian land, the wounds of Ígor, the valiant
son of Svyatosláv!
Yarosláv Osmomýsl of Gálich![75] You sit high upon your throne
wrought of gold, propping with your iron-clad army the Carpathian
mountains, barring the king’s path, closing the gates of the Danube,
hurling missiles higher than the clouds, sitting in judgment as far as
the Danube. Your thunders pass over the land, and you hold the key
to the gates of Kíev; sitting on your paternal throne, you slay the
sultans in their lands. Slay, O lord, Konchák, the pagan villain, to
avenge the Russian land, the wounds of Ígor, the valiant son of
Svyatosláv!
And you, valiant Román[76] and Mstisláv! A brave thought carries
you into action.[77] You fly high in your onslaught, like a falcon
circling in the air, about to swoop down upon the birds. You wear iron
hauberks under Latin helmets, and the earth has trembled from you
in many a pagan land: the Lithuanians, Yatvyágans, Deremélans and
Pólovtses threw down their warclubs and bent their heads under
those tempered swords. But now, O Prince, Ígor’s sun is dimmed,—
the tree, alas, has shed its leaves. Along the Ros[78] and the Sulá
the Pólovtses have sacked the towns, but Ígor’s brave army will rise
no more. The Don calls you, O Prince, and the other princes to
victory!
Olég’s sons have hastened to the war. Íngvar and Vsévolod,[79]
and the three sons of Mstisláv,[80] a mighty winged brood! Not by the
lot of war have you acquired power. Of what good are your golden
helmets, and Polish warclubs and shields? Bar the enemy’s way with
your sharp arrows, to avenge the Russian land, the wounds of Ígor,
the valiant son of Svyatosláv!
XI
The Sulá no longer flows with a silvery stream by Pereyáslavl

town,[81] and the Dviná flows turbid by mighty Pólotsk, agitated by
the pagans. Izyasláv,[82] Vasílko’s son, alone made his sharp swords
ring against the Lithuanian helmets, outstripping the glory of his
grandfather Vsesláv, but himself was worsted by Lithuanian swords,
and fell under crimson shields, upon the bloodstained grass. Lying
on his death-bed, he spoke[83]: “O Prince, the birds have covered
your druzhína with their wings, and the beasts have lapped their
blood.” There was not present the brother Bryachisláv, nor the other,
Vsévolod; alone he lost the pearl soul out of his valiant body through
the golden necklace. The voices were subdued, merriment died
away. The trumpets blare at Goródno.
Yarosláv and all grandchildren of Vsesláv![84] Furl your standards,
sheath your blunted swords, for you have leaped away from your
grandfather’s glory! You have with your discords invited the pagan
hosts against the Russian land, against the life of Vsesláv, for
through your strife has come the enslavement by the Pólovts land.
In the seventh age of Troyán,[85] Vsesláv cast his lot for his
beloved maiden.[86] He bestrode his horse, and galloped to the city
of Kíev, and with the thrust of the spear possessed himself of
golden-throned Kíev. He galloped hence as a grim beast to the south
of Byélgorod,[87] and disappeared in the blue mist; next morning he
clanked with the battering-ram, and opened the gates of Nóvgorod;
he shattered the glory of Yarosláv,[88] and raced as a wolf to the
Nemíga from Dudútki.[89]
On the Nemíga, ricks are stacked with heads, and they flail with
tempered chains; the body is placed on the threshing-floor, and the
soul is winnowed from the body. Not with grain were sown the bloody
banks of the Nemíga, but with the bones of Russian sons.
Prince Vsesláv sat in judgment over his people, apportioned cities
to the princes, but himself raced a wolf[90] in the night, and by
cockcrow reached from Kíev to Tmútorokan, and as a wolf crossed
the path of great Khors.[91] When they rang the bell in the church of
St. Sophia for matins, early in the morning at Pólotsk, he heard the
ringing in Kíev. Though his cunning soul could pass into another
body, yet he often suffered woe. Thus wise Boyán of old has justly
said: “Neither the cunning, nor the agile, nor the swift bird can
escape the judgment of the Lord!”
Oh, the Russian land must groan as it recalls the former days and
the ancient princes! It was not possible to nail Vladímir to the hills of
Kíev[92]: now there are standards of Rúrik, and others of David....[93]
XII
Yaroslávna’s[94] voice is heard; like a cuckoo in a lonely spot she

calls plaintively in the morning: “I will fly,” she says, “like a cuckoo
along the Danube,[95] will wet my beaver sleeve in the river Kayála,
will wipe off the Prince’s bloody wounds on his manly body!”
Yaroslávna weeps in the morning at Putívl town on the wall,
saying: “O wind, mighty wind! Why, master, do you blow so strong?
Why do you on your light wings carry the Khan’s arrows against the
warriors of my beloved one? Is it not enough for you to blow on high
below the clouds, rocking the ships on the blue sea? Why, master,
have you dispersed my happiness over the grass of the steppe?”
saying: “O famous Dnieper, you have pierced the rocky mountains
across the country of the Pólovtses! You have rocked on your waves
the boats of Svyatosláv as far as the army of Kobák.[96] Fondly bring
to me, master, my sweetheart, that I may not in the morning send
tears after him out to sea.”
saying: “Bright, three times bright sun, you give warmth and joy to
all! Why, master, have you thrust your burning beams on the warriors
of my beloved one? Why have you in the waterless plain dried up
their bows, and sealed their quivers in sorrow?”
XIII
The sea is agitated at midnight: mists are borne in the darkness.

God shows to Ígor a way out of the land of the Pólovtses into the
country of Russia to his father’s golden throne. The evening twilight
has gone out. Ígor sleeps; Ígor is awake: Ígor in his thought
measures the plains from the great Don to the small Donéts. His
steed is ready at midnight. Ovlúr whistles beyond the river, gives a
sign to the Prince,—Prince Ígor will be no more!
The earth resounded, the grass rustled, the Pólovts’ tents
trembled. But Ígor raced like an ermine in the reeds, like a white
duck over the water; he jumped on a swift steed, dismounted as a
light-footed wolf, and hastened to the plain of the Donéts; and as a
falcon flew through the mist, killing geese and swans for his
breakfast and dinner and supper. When Ígor flew as a falcon, Ovlúr
raced as a wolf, shaking off the cold dew, for they had worn out their
swift steeds.
The Donéts spoke: “Prince Ígor, great is your honour, and the grief
to Konchák, and joy to the Russian land!”
Ígor spoke: “O Donéts, great is your honour, having rocked the
Prince on your wave, having spread out for him the green grass on
your silver banks, having cloaked him with warm mists under green
trees. You have guarded him as a duck on the water, as a gull on the
waves, as a mallard in the air. Not thus the river Stúgna[97]: though
having a scanty stream, it has swallowed other brooks, and has
spread the floods over the bushes. To the young Prince Rostisláv the
Dnieper has closed its dark banks. Rostisláv’s mother weeps for the
young Prince. The flowers faded in their sorrow, and the trees bent in
anguish to the ground.”
It is not magpies that are in a flutter: Gza and Konchák ride in
Ígor’s track. Then the raven did not croak, the jackdaws were silent,
the magpies did not chatter, only leaped from branch to branch. The
woodpeckers indicated the road to the river by their pecking; the
nightingales announced the day by their merry song.
Said Gza to Konchák: “Since the falcon is flying to his nest, let us
shoot the fledgling[98] with our golden darts.”
Said Konchák to Gza: “Since the falcon is flying to his nest, let us
enmesh the fledgling with a fair maiden!”
And Gza spoke to Konchák: “If we enmesh him with a fair maiden,
we shall have neither the young falcon, nor the fair maiden, and the
birds will attack us in the Pólovts plain.”
XIV
Boyán has said: “Hard it is for you, O head, to be without your

shoulders; ill it is for you, O body, to be without a head.” Even so is
the Russian land without Ígor.
The sun shines in the heaven,—Prince Ígor in the land of Russia!
Maidens sing at the Danube: their voices are carried over the sea to
Kíev. Ígor rides over the Boríchev,[99] to the church of the Holy Virgin
of Pirogóshch. The country is happy, the towns rejoice; they sing
songs to the elder princes, and then to the younger. Let us sing the
glory of Ígor Svyatoslávich, of Grim Aurochs Vsévolod, Vladímir
Ígorevich! Hail, princes and druzhína, who battle for the Christians
against the pagan host! Glory to the princes and the druzhína!
Amen!
FOOTNOTES:
[23] Ígor was the son of Svyatosláv Ólgovich of Nóvgorod

Syéverski, and grandson of Olég of Tmútorokan.
[24] From the references to the princes whose praise he sang,
it is evident that he lived at the end of the eleventh and the
beginning of the twelfth centuries. Nothing else is known of this
famous poet.
[25] Yarosláv, the son of Vladímir, lived from 1019-1054: he was
the author of the Russian Code (see p. 45).
[26] Mstisláv, Prince of Tmútorokan, was the brother of
Yarosláv ( † 1036). In 1022 he killed in duel the giant Redédya,
chief of the Kasógs who dwelt between the Black and Caspian
seas, and conquered their country.
[27] Román was a brother of Ígor’s grandfather Olég; he was
killed by the Pólovtses in 1079.
[28] Vladímir the Great, father of Yarosláv.
[29] A Turkish tribe, related to the Pechenyégs, who called
themselves Cumanians. They occupied the south of Russia as far
as Hungary.
[30] See account of the eclipse in the Chronicle (p. 72).
[31] Troyán is counted among the ancient Russian divinities in
The Holy Virgin’s Descent into Hell (p. 97); but evidently he is also
a reminiscence of the Roman Emperor Trajan, whose ramparts
and roads are still to be traced along the Danube.
[32] The god of the flocks, i. e., of wealth and abundance. It is
not quite clear why the poet is called his grandson.
[33] Tributary of the Dnieper.
[34] Nóvgorod Syéverski, Ígor’s capital, in the Government of
Chernígov.
[35] The appanage of Ígor’s son Vladímir, in the Government of
Kursk.
[36] A bird of ill-omen; according to some, divinity of darkness.
[37] The border of the Black Sea.
[38] The Ázov Sea.
[39] The ancient Tauric Chersonese, near the modern
Sebastopol.
[40] An ancient city of the Khazars, on the eastern shore of the
Ázov Sea, on the peninsula of Tamán. It became a Russian
possession in the tenth century.
[41] A frequently recurring sentence, the meaning of which
seems to be: You are lost beyond redemption!
[42] The trophies won by Ígor.
[43] Gza and Konchák, khans of the Pólovtses, were the
leaders of the expedition. See p. 77.
[44] The four suns are: Ígor, his brother Vsévolod, his son
Vladímir of Putívl, and his nephew Svyatosláv Ólgovich of Rylsk.
[45] Tributary of the Don.
[46] God of the winds.
[47] Descendants of the Avars still live between Georgia and
Circassia.
[48] Her name was Ólga.
[49] Olég is the grandfather of Ígor. The poet here recalls
former encounters with the Pólovtses. Not having been able to
agree with his uncles, Izyasláv who had occupied the throne in
Kíev, and Vsévolod who had his appanage of Chernígov, Olég
escaped to Román the Fair of Tmútorokan, and decided to get his
rights by means of arms. He led three times the Pólovtses into
Russia (in 1078, 1079 and 1094).
[50] That is, in the other world.
[51] Vladímir Monomákh hastened to his father’s aid. See his
Instruction, p. 55.
[52] Olég and his cousin, Borís, were at that time absent from
Chernígov. When they arrived and opposed themselves to the
superior force of Izyasláv, Olég advised Borís to surrender; but he
would not listen and made an attack upon his uncle’s army and
was killed.
[53] Olég is called the son of “Góre,” i. e., woe.
[54] The Russians are sons of Dazhbóg, the god of the sun,
while the enemy are the “devil’s children.”
[55] The first day the Russians defeated the Pólovtses; the
next, the Pólovtses defeated the Russians; on the third day, which
was a Sunday, the Kovúans ran away, and at noon Ígor was
made prisoner. See the Chronicle, p. 74.
[56] Nature sympathises with the Russians.
[57] That is, far away; see note 5, p. 82.
[58] The Sea of Ázov.
[59] That is, Ígor; the Pólovtses are the birds.
[60] The Chronicle says the Pólovtses hurled the Greek fire.
[61] A silver coin.
[62] This Svyatosláv, the son of Vsévolod Ólgovich, had been
the Prince of Chernígov. He was Grand Prince of Kíev from 1174-
1194. He had to give up his throne twice, but in 1181 ascended it
for the third time. He is called Ígor’s and Vsévolod’s father by
seniority, though he was only their uncle by relationship.
[63] The Russians obtained a famous victory over the
Pólovtses, of whom 7000 were taken prisoners, in 1184.
[64] A series of evil omens.
[65] Ígor and Vsévolod.
[66] Probably the son of Ígor; but he was only eleven years old
during the expedition.
[67] Descendants of the Goths who had settled along the Black
Sea had been found and described as late as the sixteenth and
even seventeenth centuries in the Crimea and in the Tamán
peninsula.
[68] These Gothic girls evidently sang the exploits of Pólovts
princes. Sharokán had made an incursion into Russia in 1107, but
he was defeated and had to flee. In 1111 Sharokán returned with
an immense army to avenge his defeat.
[69] Now Rómen, in the Government of Poltáva.
[70] Vladímir of Pereyáslavl. See the Chronicle, p. 78.
[71] Vsévolod Yúrevich, Prince of Súzdal, whose father, Yúri
Dolgorúki, had been Grand Prince at Kíev.
[72] In 1183 Vsévolod made an expedition against the
Bulgarians of the Vólga; he went down the Vólga as far as Kazán,
and then proceeded on foot.
[73] That is, if Vsévolod were there, he would be so victorious
against the Pólovtses as to lower the price of Pólovts slaves.
[74] The sons of Rostisláv Mstislávich, and great-grandchildren
of Vladímir Monomákh.
[75] Yarosláv Osmomýsl ( † 1187) was the Prince of Gálich,
which in his days extended as far as the Prut and the Danube and
included part of Moldavia. His daughter was Ígor’s wife.
[76] Román Mstislávich ( † 1205), Prince of Volhynia, twice
occupied the throne in Gálich. He fought successfully against the
Lithuanians and Yatvyágans, and when he was Prince of Gálich
he saved Constantinople from the impending danger of a Pólovts
and Pechenyég invasion. The Chronicle says of him: “He rushed
against the pagans like a lion, raged like a lynx, and destroyed
them like a crocodile, and crossed their lands like an eagle, for he
was as brave as an aurochs,” and “The Pólovtses used to frighten
their children with his name.”
[77] Mstisláv was probably the brother of Íngvar and Vsévolod,
mentioned below.
[78] Tributary of the Dnieper.
[79] The sons of Yarosláv Izyaslávich, Prince of Lutsk, who was
Grand Prince of Kíev in 1173.
[80] Román, Svyatosláv and Vsévolod, sons of Mstisláv, great-
grandchildren of Vladímir Monomákh.
[81] The Pólovtses divided among themselves the towns along
the Sulá. See the Chronicle, p. 77.
[82] Izyasláv’s appanage was Goródno, in the Government of
Minsk, hence farther down “The trumpets blare at Goródno.”
[83] Izyasláv addresses himself.
[84] These are opposed to the brave Izyasláv, who is also a
descendant of Vsesláv. Vsesláv Bryachislávich, Prince of Pólotsk,
was, in 1064, defeated by Izyasláv and his brothers on the
Nemíga; later he was enticed by Izyasláv to Kíev, where he was
imprisoned. In 1067 Izyasláv was driven out by the Kíevans, and
Vsesláv was made Grand Prince. Izyasláv attacked Vsesláv at
Byélgorod, but the latter fled to Pólotsk.
[85] The exact meaning of the “seventh age of Troyán” is not
known; some distant time is designated.
[86] That is, for Kíev.
[87] Ten versts from Kíev.
[88] Tributary of the Svísloch, in the Government of Minsk.
[89] Near Nóvgorod.
[90] The chronicles and popular tradition make Vsesláv a
werewolf and a sorcerer.
[91] Another name for Dazhbóg, the god of the sun.
[92] That is, for ever to retain Vladímir in Kíev.
[93] Now there is discord.
[94] Evfrosíniya (Euphrosyne), daughter of Yarosláv Osmomýsl
of Gálich, Ígor’s second wife.
[95] A standing formula for rivers in general, here the Kayála.
[96] Expedition of 1184.
[97] A swampy river in the Government of Kíev. Rostisláv
Vsévolodovich, the son of Vsévolod and Anna, the daughter of a
Pólovts Khan, and the brother of Vladímir Monomákh. After an
unsuccessful attack upon the Pólovtses, he escaped from
captivity by jumping into the Stúgna, but being in heavy armour
he was drowned.
[98] Vladímir, the son of Ígor, who was also taken captive. He
really married Konchák’s daughter and returned with her to Kíev
in 1187.

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Hydrothermal Reduction of Carbon

Dioxide to Low-Carbon Fuels 1st

Electrochemical Reduction of Carbon Dioxide Overcoming

An Economy Based on Carbon Dioxide and Water Potential

Forest Carbon Practices and Low Carbon Development in

Carbon Dioxide and Organometallics 1st Edition Xiao-

Energy Technology 2016 Carbon Dioxide Management and

Energy Technology 2018 : Carbon Dioxide Management and

Fundamentals and Applications of Supercritical Carbon

Integration of Low Carbon Technologies in Smart Grids

© 2018 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-4987-3183-6 (Hardback)

Visit the Taylor & Francis Web site at

and the CRC Press Web site at

Chapter 1 Water under High-Temperature and High-Pressure Conditions

Chapter 2 Catalytic Hydrothermal Reactions for Small Molecules Activation....... 23

Chapter 3 Hydrothermal Water Splitting for Hydrogen Production

Chapter 4 Hydrothermal Water Splitting for Hydrogen Production with Iron.... 47

Chapter 5 Hydrothermal CO2 Reduction with Iron to Produce Formic Acid...... 61

Chapter 6 Hydrothermal Reduction of CO2 to Low-Carbon Compounds........... 79

Chapter 7 Hydrothermal CO2 Reduction with Zinc to Produce Formic Acid..... 91

Chapter 8 Autocatalytic Hydrothermal CO2 Reduction with Manganese

Chapter 9 Autocatalytic Hydrothermal CO2 Reduction with Aluminum

Chapter 10 Cu-Catalyzed Hydrothermal CO2 Reduction with Zinc

Chapter 11 Hydrothermal Reduction of CO2 with Glycerine.............................. 153

Chapter 12 Hydrothermal Reduction of CO2 with Compounds Containing

Chapter 13 Perspectives and Challenges of CO2 Hydrothermal Reduction........ 199

Jia Duo Zhibao Huo

Minyan Gu Fangming Jin

Ligang Luo Yuanqing Wang

Lingyun Lyu Tongji University

Xu Zeng Yalei Zhang

processing is employed in the liquid water at temperatures of 200–260°C and at

where T is temperature in Kelvin, ρ is density in g/cm3, and A to G are fitting

Dielectric constant (−)

FIGURE 1.1 Dielectric constant of water as a function of temperature. Dashed line:

FIGURE 1.2 Dielectric constant of water as a function of pressure at constant tempera-

1.4.1 Dielectric Constant of HTW

(Step 3) Benzilic acid rearrangement

(b) 1H−NMR (in H2O) 60 min

FIGURE 1.8 Hydrolysis of cellulose.

FIGURE 1.9 Isomerization between glucose and fructose.

FIGURE 1.10 Dehydration of fructose into HMF.

1.9 RETRO ALDOL REACTION

Glucose Glycolaldehyde Erythrose

FIGURE 1.11 Retro aldol reaction of fructose and glucose.

These formed intermediates from C2-C3 or C3-C4 bond cleavage by reverse

1.10 DECARBOXYLATION AND DECARBONYLATION [100–104]

HCOOH → H 2O + CO (decarbonylation) (1.3)

homogeneous catalyst that can catalyze decarboxylation more than decarbonylation by

Were it not well for us, O brothers, to commence in the ancient

There befell a hapless hour, O brothers! Already had the

The Sulá no longer flows with a silvery stream by Pereyáslavl

Yaroslávna’s[94] voice is heard; like a cuckoo in a lonely spot she

The sea is agitated at midnight: mists are borne in the darkness.

Boyán has said: “Hard it is for you, O head, to be without your

[23] Ígor was the son of Svyatosláv Ólgovich of Nóvgorod

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1.4.1 Dielectric Constant of HTW

1.9 RETRO ALDOL REACTION

1.10 DECARBOXYLATION AND DECARBONYLATION [100–104]