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Surface Chemistry
of Carbon Capture
Surface Chemistry
of Carbon Capture
Climate Change Aspects

K. S. Birdi
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-­­2742
© 2020 by Taylor & Francis Group, LLC
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Contents

Author, ix

Chapter 1   ■   Introduction to Surface Chemistry of Carbon

Capture1
1.1 INTRODUCTION TO SURFACE CHEMISTRY
OF CARBON CAPTURE 1
1.1.1 Temperature of the Earth
(Sun—Atmosphere—Earth)13
1.2 CARBON CAPTURE AND STORAGE (CCS)
(SURFACE CHEMISTRY ASPECTS) 14
1.2.1 Mechanisms of Adsorption at the Gas—
Solid Interface 19
1.2.2 Nature of Solid Surfaces (Used for Gas
Adsorption)20
1.2.3 Gas—Solid Adsorption Isotherms 24
1.2.4 Gas Absorption in Fluids Technology 25
1.2.5 Carbon Dioxide Captured by Different
Processes26
1.3 APPLICATION OF CCS ON CONTROL OF
CARBON DIOXIDE CONCENTRATION IN AIR 28
1.3.1 Flue Gases and Pollution Control 29

v
vi   ■    Contents

Chapter 2   ■   Adsorption (on Solids) and Absorption

(in Fluids) of Gases (CCS Procedures)
(Surface Chemistry Aspects) 31
2.1 INTRODUCTION 31
2.2 ADSORPTION OF GAS ON SOLIDS 33
2.2.1 Theory of Adsorption of Gas on Solid Surfaces
(Basic Remarks) 39
2.2.2 Solids with Special Characteristics of Gas
Adsorption54
2.2.3 Gas Adsorption Isotherms 56
2.2.4 Solid Surface Structures 62
2.2.5 Thermodynamics of Gas Adsorption on Solid 65
2.2.6 Determination of Heat (Enthalpy) of Gas
Adsorption on Solids (From Indirect Non-­
Calorimetric Methods) 66
2.2.7 Entropy of Gas—Solid Adsorption 67
2.2.8 Advanced Experimental Procedures of Gas
Adsorption on Solids: STM (Scanning Tunneling
Microscope)68
2.3 GAS ABSORPTION IN FLUIDS 69
2.3.1 Absorption of CO2 in Aqueous Solutions 71

Chapter 3   ■   Surface Chemistry of Solids 73

3.1 INTRODUCTION 73
3.2 SOLID SURFACE CHEMISTRY (WETTING
PROPERTIES OF SOLID SURFACES) 77
3.3 SURFACE TENSION OF SOLIDS (SURFACE FORCES) 81
3.3.1 Definition of Solid Surface Tension (γsolid)82
3.3.2 Contact Angle (θ) of Liquids on Solid Surfaces 83
3.4 MEASUREMENT OF CONTACT ANGLES AT
LIQUID—SOLID INTERFACE 84
3.5 ADSORPTION OF GAS ON SOLID SURFACE
(SPECIFIC ROLE OF SOLID SURFACE TENSION) 87
3.5.1 Gas Adsorption Measurement Methods 89
 Contents   ■    vii

Chapter 4   ■   Carbon Capture and Sequestration (CCS)

Technology (Basic Remarks) 95
4.1 INTRODUCTION 95
4.2 CCS TECHNOLOGY AND DIFFERENT
METHODS OF CAPTURE 102
4.2.1 Carbon Capture Methods 104
4.2.2 Storage in Geological Rock Formations 110
4.2.3 Economical Aspects of CCS Technology
Application110

Chapter 5   ■   A Short Review of Different Carbon Dioxide

(CO2) Capture Processes (Adsorption on
Solids and Absorption in Fluids) 113
5.1 ADSORPTION OF CO2 (GAS) ON SOLIDS 114
5.2 ABSORPTION OF GASES (GAS ABSORPTION
REVIEW)130

APPENDIX A: SURFACE CHEMISTRY ESSENTIALS, 143

APPENDIX B, 175

APPENDIX C, 191

BIBLIOGRAPHY, 201

INDEX, 217
Author

K. S. Birdi joined Standard Oil of California, Richmond (1957–1958),

after graduating from the University of California, Berkeley, 1957. He
joined (chief-chemist) UniLever Copenhagen, Copenhagen, Denmark
(1959–1966). Later, he was appointed associate professor (1966–1985) and
research professor in 1985 (Technical University, Copenhagen; Nordic
Science Foundation), and was then appointed, in 1990 (retired in 1999), to
the School of Pharmacy, University of Copenhagen, as professor in physical
chemistry. Professor Birdi has published various books related to surface
and colloid chemistry: (Handbook of Surface and Colloid Chemistry, 1st
Ed. (1997), 2nd Ed. (2003), 3rd Ed. (2009), and 4th Ed. (2016), CRC Press,
Boca Raton, FL, USA; Surface Chemistry and Geochemistry of Hydraulic
Fracturing, CRC Press, Boca Raton, FL, 2017). Professor Birdi has
participated in various national and international research projects related
to North Sea oil explorations and European Union joint projects.

ix
 Chapter 1

Introduction to
Surface Chemistry of
Carbon Capture

1.1 INTRODUCTION TO SURFACE CHEMISTRY

OF CARBON CAPTURE
The Earth is surrounded by atmosphere (air), and water is found in great
oceans (covering almost 75% of the surface of the Earth):
ATMOSPHERE
...............................
...............................
...............................
EARTH—OCEANS
Furthermore, the Earth—atmosphere—sun system
SUN—ATMOSPHERE—EARTH
composes a configuration that mankind has admired and studied for many
centuries. Ancient religions and civilizations have worshipped certain spe-
cific natural elements for thousands of years, and some religions still wor-
ship them. These elements were

Air (atmosphere, wind)

Water (rivers, oceans)
1
2   ■    Surface Chemistry of Carbon Capture

Sun (light, heat, radiation)

Fire (flame, combustion)

COMPOSITION OF AIR (ATMOSPHERE)

The composition of air (or the atmosphere), as known today, is a mixture
of different gases (near the surface of Earth):

nitrogen (N2: 28 gm/mol) (78%);

oxygen (O2: 32 gm/mol) (21%);
argon (Ar: 40 gm/mol) (0.9%);
carbon dioxide (CO2: 44 gm/mol) (0.04%);
water (H2O: 18 gm/mol) (vapor) (traces);
other gases (hydrogen, etc.) (traces).

The global average temperature of the Earth is primarily regulated by the

heat received from the Sun (Appendix C). Furthermore, the energy (heat,
radiation) reaching the Earth from the Sun has to pass through the atmo-
sphere surrounding the Earth. This means that the sun’s energy (radiation)
has to interact with

gas molecules (and dust particles) in the air (atmosphere)

reflection by air/clouds
reflection from Earth, trees, and ocean surface

The heat from the Sun (the surface temperature of the Sun is 5500°C) is trans-
mitted by the infrared wave length of the radiation. The infrared is absorbed
by some gases found in the atmosphere (e.g., carbon dioxide, methane, etc.).
These gases are called greenhouse gases (GHGs). The absorbed infrared
energy is reflected in all directions, which increases the temperature of the
planet Earth. In the present text, there is only interest in carbon dioxide and
its interactions with the temperature balance of the Earth.
The concentration of carbon dioxide (CO2) in air is reported to be
increasing over the past century (ca. 2 ppm/year) (IPCC, 1995, 2005a, b,
2007, 2019; IEA (International Energy Agency) 2011, 2012, 2013, 2014a, b, c,
 Introduction to Surface Chemistry of Carbon Capture   ■    3

2015a, b, c, d, 2016e; EPA Handbook, 2011; Dubey et al., 2002; Sanz-­Pérez,

2016; Rackley, 2010; Dennis, 2014; CSIRO, 2013; Albo et al., 2010; Oh,
2010; Hinkov et al., 2016). This has been attributed to fossil fuel burning
(combustion) (anthropogenic CO2) (Leung et al., 2014; McDonald et al.,
2015). Furthermore, the increase in population and increased energy
demand leads to increase in anthropogenic CO2.
This book relates to the carbon (i.e., CO2) capture and surface chemistry
properties of carbon dioxide (CO2), especially its connections to the change in
temperature (average temperature) of Earth. However, it is useful to describe
some general remarks about the atmosphere (air) and its characteristics.
The composition (and temperature and pressure) of air varies with
height over Earth. In other words, when one considers the composition of
air, the height has to be considered. The gradient of composition of air (i.e.,
variation of composition with height) might be dependent on time scale
(and space). Similarly, water (e.g., oceans, rivers, lakes, drinking water)
contains different salts (sodium, calcium, chlorides, sulfates, etc.) that
are known to interact with some components of air (for example, carbon
dioxide, oxygen). Mankind has been aware of the essential role played by
these elements for the existence of life on Earth. Even though millions of
miles away, the Sun provides heat to the Earth. Besides heat, the Sun also
emits other kinds of energy to Earth, for example, radiation, ultraviolet
light, and so on. The atmosphere surrounding the Earth has four distinct
layers (Saha, 2008; Lang, 2006):

0 to 10 miles (0 to 16 km: temperature range, ca. 20°C to −50°C)

TROPOSPHERE: This is the region of human activities.
10 to 30 miles (16 to 50 km: temperature range, ca. −50°C to 0°C)
STRATOSPHERE: The ozone gas (O3) layer, which absorbs the
ultraviolet (UV) radiation from the sun, is found in this region. The
temperature is higher at higher altitude, owing to the absorbance of
ultraviolet radiation from the Sun.
31 to 53 miles (50 to 80 km: temperature range from ca. 0°C to 90°C)
MESOSPHERE: In the mesosphere, the temperature decreases as
altitude increases.
53 to 75 miles (80 to 200 km: temperature from ca. >90°C) THERMO‑
SPHERE: In this region temperature increases with altitude, owing
to absorption of highly energetic solar radiation.
4   ■    Surface Chemistry of Carbon Capture

This clearly shows the complex sun—atmosphere system and the interac-
tions relating to temperature on the Earth.
Further, mankind has used fire (with respect to food, combustion pro-
cesses, energy (electricity, mechanical), transportation) in many differ-
ent applications and technologies (both directly and indirectly) for many
hundreds of years. It is also recognized that all these elements are essential
for the existence of life on Earth. Fire or combustion of fossil fuels in the
modern age is described as

COMBUSTION: FOSSIL FUELS + OXYGEN (FROM AIR) = FIRE

(heat, electricity, mechanical energy, etc.) (CO2 produced)

This process (i.e., the production of carbon oxide) is anthropogenic and is

currently related to the world population (e.g., food and energy demands).
It is thus seen that the above process of combustion adds CO2 to the air. At
the same time, it must be stressed that carbon dioxide in air is essential for
the existence of life on Earth.

PHOTOSYNTHESIS AND CARBON DIOXIDE CYCLE

The most significant process with regard to life and all kinds of living spe-
cies on the Earth is the supply/production of food. The latter is singularly
provided by the complex system that is dependent on the photosynthesis
process (Paoletti et al., 2002; Raschi et al., 2000):

CARBON DIOXIDE (CO2) + SUN SHINE + WATER < PHOTOSYN-

THESIS > ALL KINDS OF PLANTS/FOODS/CARBOHYDRATES

Each gas component in air is known to have a specific role in the life cycle
on Earth. For example, even though the concentration of carbon dioxide
(CO2) in air is at present only 400 ppm (0.04%), it provides all carbo‑
naceous food to life. Food is obviously the most necessary product for
the existence of life on Earth. Actually, the photosynthesis process is the
opposite of fossil fuel combustion, and CO2 is captured in plants and so
on. It is important to mention that all the carbon atoms in plants on Earth
are supplied by the CO2 in air (via photosynthesis). Furthermore, the
food is digested by all living species on Earth by the metabolism process
(Appendix C):
 Introduction to Surface Chemistry of Carbon Capture   ■    5

The CO2—food—metabolism cycle:

CO2 in air (photosynthesis) >>>> Food >>>> Metabolism
(exhale CO2)

This shows that in the life cycle on Earth all the carbonaceous components
are solely provided by CO2 in the air (EPA Handbook, 2011). Actually, it
is clear now that all these natural elements are interrelated and are basic
necessities for life on Earth. The characteristics of the different gases in air
(atmosphere) for example:

Oxygen (O2: 21% in air) is essential for all living species (as a source
of metabolic and other reactions, for example, oxidation). Further-
more, oxygen is an essential component of all combustion reac-
tions. In all combustion processes, when fossil fuels, wood, etc.,
are burned in air (containing 21% oxygen, O2) the reaction is as
follows:

Fuel (consisting of carbon and hydrogen molecules): (Cx Hy) + O2 (gas) = CO2
(gas) + H2O

CO2 (even though present at a very low concentration, ca. 400 ppm)
supplies all the food (photosynthesis process) for all living species
(as well as all the organic molecules, which mainly consist of carbon
atoms). Most significantly, it is important to mention that the con-
centration of CO2 in air must be sufficient to support the need for
plant growth on the Earth. Therefore, one will expect that there must
be a minimum concentration of CO2 (in air) in order to sustain life
on Earth (Appendix C).
Nitrogen (N2: 78%) Even though nitrogen does not interfere directly
in the life cycle, it is converted to ammonia (NH3) after interaction
with hydrogen and is used as fertilizer for growing plants (food). This
means that the increasing demands for abundant food production
globally (related to an increase in world population) need fertilizer to
assist in this demand.

The different gases in air exhibit different physicochemical properties (as

regards to solubility in water, absorption of infrared light, etc.). As regards
the solubility in water, it is found that the solubility of oxygen and nitrogen
6   ■    Surface Chemistry of Carbon Capture

is very low. However, CO2 is soluble in water (i.e., in oceans/lakes/rivers)

(IPCC, 2007; Rackley, 2010). Hence, one finds that there is a very large
amount of CO2 in oceans, which is in equilibrium with air.

CARBON DIOXIDE IN AIR === (EQUILIBRIUM) ===

CARBON DIOXIDE IN OCEANS

This means that any changes in the concentration of CO2 in either phase
(e.g., air or water) will lead to a corresponding change in the other phase
(Chapter 1.3; Appendix C).
CARBON CAPTURE AND STORAGE (CCS)
The purpose of this book is to address the present technologies available to
control the CO2 increase (due to anthropogenic CO2 emissions). The CO2
(as gas) can be captured/sequestered by different processes (Chapter 5)
called carbon capture and storage or CCS processes (Chapter 4) (figure 1.1).
CCS (carbon capture and storage):

Carbon dioxide (CO2) <> Capture process <> Storage of captured CO2

One finds in literature that carbon (i.e., CO2) can be captured (from flue
gases) by various methods (Suzuki, 1990; Vargas et al., 2012; Krishna & van
Baten, 2012; Yu et al., 2012; Bolis et al., 1999; Hinkov et al., 2016; Rackley, 2010):

gas/adsorption on solid
gas/absorption in fluid
other different technologies to capture carbon (CO2)

(CO2

CO2

CO2
FIGURE 1.1 Carbon capture and (DEPLETED OIL/GAS RESERVOIRS,
storage (CCS) schematics. COAL MINES, SALINE AQUIFERS)
 Introduction to Surface Chemistry of Carbon Capture   ■    7

These studies are described in Chapter 2.

It is also important to mention (briefly) other related phenomena before
describing carbon capture and its surface chemistry aspects. Mankind
is increasingly interested in understanding and controlling the various
phenomena surrounding the Earth (such as pure drinking water, clean
air, average temperature of the Earth). The average global temperature
(this term is very complex, as one might expect) on Earth is related to dif-
ferent energy sources/sinks and equilibrium between the latter.

SOURCES OF HEAT AND SINKS IN EARTH

In general, the Earth’s heat balance with its surroundings (energy sources
or energy sinks) that need to be considered are as follows (Appendix C):

SOURCES OF HEAT

Sun (major)
Mankind combustion technologies (oil + natural gas + coal)
Diverse sources of energy (plants, forests, storms, etc.)
Earth core (temperature is very high)

SOURCES OF HEAT SINK

Evaporation of water (from oceans, lakes, rivers, etc.) to make clouds/

trees (which reflect the Sun’s heat)

DYNAMICS OF TEMPERATURE OF EARTH

It must be mentioned that there is no parameter (e.g., temperature, pressure,
wind velocity, etc.) that is static at any point of observation on the surface
of Earth. All parameters are varying with time and space on the Earth. For
example, on the average, on a typical day, the temperatures (near the sur-
face) at any place on Earth are higher during the daytime than in the night:

Temperatures at different parts of the Earth

CITY DAY/NIGHT TEMPERATURE (°C)
DATES MAY 2018 JANUARY 2019
COPENHAGEN −1/−1 3/−2
8   ■    Surface Chemistry of Carbon Capture

LONDON 11/4 6/−1

FRANKFURT 10/−3 3/−2
LIVIGNO 1/−6 −5/−13
MOSCOW −7/−20 −7/−7
CALGARY −6/−17 −2/−13
DELHI 28/14 19/6
NICE 12/7 14/2
BUENOS AIRES 28/16 32/26
MALAGA 18/10 17/11
NEW YORK 7/0 2/−2
MANILA 28/21

In addition, the temperature of oceans also changes with day/night/sum-

mer/winter parameters. The day/night temperature data merely show the
heat (dynamics) the Sun adds to the Earth at different places (and times)
on the Earth. These observations indicate that the temperature fluctuations
existing at every moment around the clock and the huge magnitude of the
Sun’s energy (which fluctuates between day and night) reaching the Earth.
It is obvious from these data that any analyses of average temperature of
the Earth would be rather complex. Especially considering the fact that
mankind has no control over what process are prevalent on the Sun and
the changes that may have a profound effect on the climate on the Earth.
In the same context, the heat reaching the Earth from the Sun is also
different with time and space. The rotation of the Earth also contributes
to the dynamics of temperature at any given time or place. Further, the
dynamics of temperature is known to create weather turbulence, that is,
weather changes (as regards temperature, winds, waves, storms, etc.) due
to differences in heat at night/day but also other related phenomena over
weeks/months/years.

ATMOSPHERE AND THE SUN

The atmosphere surrounding the Earth is a very important element as
regards life on Earth. The composition of atmosphere (air) and its tem-
perature (and pressure) are found to vary with distance from the surface
 Introduction to Surface Chemistry of Carbon Capture   ■    9

of Earth. The Sun’s energy gives rise to heat on Earth (see day/night tem-
perature). The atmosphere (and clouds) controls the amount of heat reach-
ing the Earth in some complicated paths (e.g., absorption, reflection, etc.).
The Sun is ca. 92 million miles (160 million kms) away from the
Earth. The Sun’s energy (as heat) is found to be enormous as compared to
anthropogenic processes (Appendix C). The degree of sunshine reflected by
the atmosphere is also a very important element. The degree of reflection
by the atmosphere is also dependent on height (from the surface of Earth).
This book relates to surface chemistry (a special theme in general chem-
istry) (Chapter 3; Appendix A) and its relation to control/storage of CO2 in
the atmosphere (current concentration = 0.04% = 400 ppm). Over the past
few decades (especially after the industrial revolution) the concentration
of CO2 has been found to be increasing (Figure 1.2) (IPCC, 2019):

TYPICAL CO2 (PPM) DATA (YEAR/PPM):

1960/310 ppm
1975/330 ppm
1980/340 ppm
1995/360 ppm
2010/390 ppm
2017/410 ppm

CO2

FIGURE 1.2 Change of CO2 concentration in air (near the surface of Earth).
10   ■    Surface Chemistry of Carbon Capture

This observation is attributed to the increasing use of fossil fuels (pro-

portional to increasing population). Currently, global consumption of dif-
ferent fossil fuels is ca. 33% each (equivalent to 100 million barrels/day oil)
oil, coal, and natural gas.
At the energy/power plants where fossil fuels are used, the flue gas con-
tains ca. 10% CO2 as compared to 0.04% (400 ppm) in air. Carbon capture
(by application of CCS) can be used in order to mitigate the increasing
CO2 concentration. In fact, it has been recognized that CCS is the only
viable technology to mitigate increases in CO2 and control climate change
(Chapter 4). This book describes the technology and surface chemistry
of carbon capture and storage (CCS). The main approach is to present a
review of CCS technology as found in the current literature.

GREENHOUSE GASES (GHGs) IN THE AIR

Climate change (temperature increase over the past decades) on Earth is
related to greenhouse gas (GHG) emission (Dennis, 2014; Yu et al., 2012;
OECD/IEA, 2016; Rackley, 2010).
The main GHGs are

Methane (CH4)
Carbon dioxide (CO2)
Nitrogen oxides (NOx).
Fluorocarbons (Fx (H)y)

Methane and CO2 are found in nature as free gases. CO2 is also produced
by all fossil fuel combustion processes. However, NOx and FxHy are anthro-
pogenic pollutants and are present in all flue gases.
It is important to mention the significant role played by the Sun in
regard to the heat (temperature) balance of Earth. The mass of the Sun
is almost 95% of the total solar system. The Sun is mainly composed of
hydrogen gas (92%), plus about 8% helium and other elements (Manuel,
2009).
The heat reaching the Earth from the Sun is very dynamic. The daily
cycle (i.e., sunrise/sunset) imparts dynamic heat transfer. Further, Sun
surface is found to show flare activity, which is variable over time. The
latter is also found to be variable. Further, the clouds in the Earth’s atmo-
sphere reflect the heat from sun. Since there are different kinds of clouds,
 Introduction to Surface Chemistry of Carbon Capture   ■    11

the degree of reflection of the Sun’s rays is dependent on this latter param-
eter. All in all, one thus finds that heat transfer from the Sun to the Earth
is highly variable from day to day (as well as in time and space). In addi-
tion, one must mention that the difference in temperature on Earth from
day to night can be as high as 20°C. Further, the solar energy reaching the
Earth consists of different wavelengths (as seen from diffraction through
a prism). The range of light from Sun is from 380 nm (violet) to 750 nm
(red):

VIOLET, INDIGO, BLUE, GREEN, YELLOW, ORANGE, RED

(WAVELENGTH: nm = 10–9 m)

The mechanism of climate change on Earth would thus be expected to be

rather a complex phenomenon, reflected in average global temperature
change. For many decades, it was suggested that the heat (infrared) from
the Sun is absorbed by GHGs, and this is expected to induce an increase
in the temperature of the Earth. GHGs (such as CO2, CH4) are molecules
in air that absorb infrared light. This leads to heat absorption from the
reflected Sun’s energy falling on the Earth (Li et al., 2011). It is estimated
that the average power density of solar radiation at the outside of the atmo-
sphere of Earth is approximately 1366 W/m2, which is called the solar con-
stant. Further, it is found from this figure and the surface area of the Earth
that the annual solar energy reaching the Earth is ca. 5,460,000 EJ/year.
It is important to compare this with the annual energy consumption by
man, which is about 500 EJ. This means that mankind consumes/emits
only 0.01% of solar energy.

CHANGE OF CONCENTRATION OF CO2 IN AIR

(AND CO2 IN OCEANS)
It is also important to mention the possible reason/source for the CO2
increase in air in the recent century. With the rapid increase of the global
population and the industrialization of more and more countries, the
demand for energy is growing almost proportional to the world popula-
tion. Currently over 85% of global energy demand is supplied by the burn-
ing (combustion) of fossil fuels (e.g., natural gas + oil + coal). It is also
expected that fossil fuels will continue to be the main source of energy
in the foreseeable future. The burning (combustion) of these fossil fuels
releases CO2 into the atmosphere; this disturbs the carbon (CO2) balance
12   ■    Surface Chemistry of Carbon Capture

of the planet, which has been steady over hundreds of millions of years.
Although anthropogenic CO2 emissions are relatively small as compared
to natural carbon fluxes, such as photosynthetic fluxes, the increased
release has had obvious influences on the global climate in a very short
period of time (Robinson et al., 2007; IPCC, 2007, 2019).
The estimates of CO2 as found in different states (either emissions or as
stored) are estimated as follows (as Gt of carbon, C):

Anthropogenic CO2 from fossil fuel combustion (variable): 8 Gt C/year

CO2 as present in biosphere and oceans: 40,000 Gt C
CO2 in atmosphere: 780 Gt C

It is obvious from these data that oceans are an important factor as regards
CO2 (material balance) emission/capture technology. CO2 found in the
oceans is considered as being a buffer, which can absorb/release any amount
of CO2 in air as needed (Appendix C). Analyses show that since the begin-
ning of the industrial age in ca. 1750, the CO2 concentration (average) in
the atmosphere has increased from 280 to 410 ppm in 2017 (Figure 1.2)
(IPCC, 2007, 2019).
The increase of the CO2 concentration in atmosphere influences the
balance of incoming and outgoing energy (i.e., heat) in the atmosphere
system (owing to its GHG properties), leading to the rise of the average
surface temperature of Earth. Thus, CO2 has often been cited as the pri-
mary anthropogenic GHG, while other GHGs are also expected to con-
tribute to this phenomenon.
In different industries where fossil fuels are burned (through the pro-
cess of combustion), the flue gases are known to contain some other pol-
lutant gases (such as CO, NOx, SO2, etc.) besides CO2. In all cases, flue
gases from coal/oil-­fired plants have been purged of these different pollut-
ants for many decades. However, CO2 from these flue gases has not been
captured to the same extent.
The timescale of the data for CO2 (Figure 1.2) is obviously short as com-
pared to geological timescales. However, there are studies in the literature
that do give (indirect) estimates of Earth data for much longer timescales
(Appendix C).
It is also found that the seasonal variation of CO2 is approximately
±5 ppm (i.e., summer/winter). The concentration of CO2 drops in summer
owing to the uptake through photosynthesis in plants. This thus indicates
 Introduction to Surface Chemistry of Carbon Capture   ■    13

that approximately 5 ppm of CO2 is captured by plants/forests, a varia-

tion of ca. ±10% during the summer months. CO2 is found to be soluble
in water (Appendix C). The solubility increases (ca. three-­fold) at 0°C as
compared to at 30°C. In other words, in oceans (where one finds a very
large amount of CO2), the concentration of CO2 would vary with tempera-
ture (i.e., from summer to winter) (IPCC, 2007).
Geological studies have shown that prior to the modern industrial human
technology, the surface and atmosphere of the Earth maintained a steady
state with a relatively constant amount of CO2, about 280 ppm, for several
millennia before the invention of fire (and steam engines, etc.) (Appendix C).
This may also indicate that the minimum concentration of CO2 in air would
be approximately 280 ppm. Furthermore, equilibrium between the two
states (i.e., CO2 in air and CO2 in oceans) (equation 1.1) must be maintained
to sustain the necessary growth of food/plants and to support life. Over
hundreds of millennia, the atmospheric CO2 concentration (and Earth’s
temperature) has varied naturally, owing to variations in the Earth’s tilt and
its orbit around the sun. The natural state of the climate for the past million
years or more has been cold (glacial ice ages) with periodic warm (inter-
glacial) periods. It is also reported that the average global temperature has
increased by about 1°C since the Industrial Revolution (Appendix C).

1.1.1 Temperature of the Earth (Sun—Atmosphere—Earth)

The average temperature of the Earth is primarily controlled by the Sun’s
radiation. The temperature of the Earth that is discussed in the literature
is measured at some fixed points on the Earth (Appendix C).

SUN—ATMOSPHERE—EARTH
This subject is beyond the scope of this book, but a short mention is useful
for the general discussion of climate change. It is obvious that the amount
of heat the Earth receives from the Sun is a rather complex phenomenon.
The Earth is also known to both receive and lose heat through different
processes. It is thus useful to consider briefly the comparative quantity of
sources of heat involved in the Earth’s climate.
All the planets in the solar system are entirely controlled by the Sun
(for example, as regards different properties of the solar planets such as
temperature, path, etc.).
Measurements show that the average power density of solar radiation
just outside the atmosphere of the Earth is 1366 W/m2 (solar constant)
(Chen, 2011). It is however found that the temperature of the Sun (surface
14   ■    Surface Chemistry of Carbon Capture

temperature of the sun: 5500°C) is increasing owing to chemical reactions.

Further, the energy reaching the Earth is fluctuating (both as a function of
time and place). The solar activity (flares and other eruptions) vary daily
and yearly.
From this data one has estimated the energy falling on Earth from Sun
in the following process (Manuel, 2009; Chen, 2011; Sheer, 2013):

Total energy of solar radiation reaching

Earth per year = 5.46 × 1024 J = 5,460,000 EJ/year.

It is found that this quantity is very large as compared to some anthropo-

genic energy sources. The annual global energy consumption (between the
years 2005 and 2010) has been reported to be about 500 EJ. This amounts
to ca. 0.01% (500/546,000 × 100) of the annual solar energy reaching Earth.
In these calculations, the average solar power on the Earth was assumed to
be 1366 W/m2. However, not all solar radiation that falls on Earth’s atmo-
sphere reaches the ground. About 30% of solar radiation is reflected into
space. About 20% of solar radiation is absorbed by clouds and gas mol-
ecules in the air. About three-­quarters of the surface of the Earth is covered
by water (oceans). The oceans therefore absorb a large part of the heat from
sunshine. This phenomenon is further complicated by the fact that water
shows some abnormal behavior as regards density and temperatures. How-
ever, theoretically, even if only 10% of total solar radiation is utilizable,
0.1% of it can power the entire world.

1.2 CARBON CAPTURE AND STORAGE (CCS)

(SURFACE CHEMISTRY ASPECTS)
After the capture of CO2 by the CCS technology, the carbon (CO2) needs
to be stored or used in some useful application (Chapter 4). This step in
CCS has been investigated, and many studies have been reported. The eco-
nomic aspects of CCS have been also investigated (Rackley, 2010).
The purpose of this book is to describe the surface chemistry aspects of
carbon capture (i.e., CO2) (Dennis, 2014). The storage step may consist of
different processes, depending on the nature of the application. The CCS
technology thus in simple terms means (Figure 1.4):

STEP I: Anthropogenic CO2: fossil fuel combustion (burning)

STEP II: Anthropogenic CO2 ==== CO2 capture and storage (CCS)
STEP III: Storage methods for captured CO2
 Introduction to Surface Chemistry of Carbon Capture   ■    15

It is important to specify the major sources of CO2 (where CO2 is present

in free state):

a. atmospheric CO2;
b. anthropogenic CO2 (from fossil fuel burning);
c. CO2 dissolved in oceans/lakes.

This means that free CO2 is in equilibrium in the I and III states (Appen-
dix C). In other words, if its concentration changes in one state, it will
change in the other states correspondingly (e.g., increase or decrease).
State II is variable. The CCS technology can thus be applied to these two
(I and II) major states where CO2 is present in the free state. Further,
since CO2 is soluble in water (1.45 gm/liter), large quantities are thus
present in oceans/lakes/rivers (Appendix C).
Furthermore, since CO2 in the atmosphere is essential for the growth of
plants on Earth, there must be a minimum of its concentration in order to
maintain life on Earth.

CO2 Equilibrium:
Minimum Concentration of CO2 in Air === CO2 in Oceans

One may estimate this minimum CO2 concentration (without any anthro-
pogenic CO2 emissions) to be equal to approximately 280 ppm. This figure
is related to the average CO2 concentration before the beginning of the
Industrial Revolution. CCS technology thus has to address the following
parameters (Ionel et al., 2008; Metz et al., 2005; IEA, 2014b; Beising, 2007;
Scheer, 2007; IPCC, 2007; Hinkov et al., 2016; Leung et al., 2014; Rackley,
2010):

control/capture of anthropogenic contributions of CO2 to air;

reduce/control the CO2 in atmosphere.

The main CCS approach relates to:

Anthropogenic CO2 production (combustion of fossil fuels)

Increase in CO2 concentration in air
Capture of CO2 (at the source: flue gas, directly from air)
16   ■    Surface Chemistry of Carbon Capture

CCS thus relates to control and monitoring of CO2 concentration in air.

After this capture process, there is a need for storage or similar technol-
ogy. A short specific survey of CO2 capture techniques will be given to
the reader to help in future research trends and analyses (Chapter 5;
Appendix B). Most of the carbon capture processes currently are mainly
related to surface chemical principles (adsorption, absorption, mem-
brane separation, cryogenic process, CO2 hydrate formation, etc.) (Sec-
tion 1.2.1). Currently, the main research on CCS is based on two main
surface chemical processes: adsorption and absorption. This is the main
theme of this book. The surface chemistry aspects will be delineated with
the help of classical thermodynamics of adsorption theory (as described
by Gibbs adsorption theory) (Chattoraj & Birdi, 1984; Adamson & Gast,
1997; Bolis, 2013; Yang, 2003; Myers & Monson, 2002; Keller et al., 1992;
Yu et al., 2012; Birdi, 1997, 1999, 2003, 2009, 2010, 2014, 2016, 2017; Rack-
ley, 2010). However, some additional carbon capture techniques will also
be briefly mentioned.
The concentration of CO2 as found in different (major) sources (natural
and anthropogenic) varies as follows:

in atmosphere (ca. 400 ppm = 0.04%)

flue gas from a coal/oil-­fired plants (ca. 10%)
flue gas from a natural gas (>95% CH4) fired plant (ca. 2%)

This variation means that the CCS technology needed for these sources
will be different (as related to the concentration of CO2). Further consider-
ations as regards the parameters of CO2 variables:

CO2 concentration in air has increased from 280 ppm to 400 ppm over a
few centuries;
CO2 is soluble in water (e.g., oceans, lakes, rivers) (CO2 concentration has
also increased in oceans).

This shows that anthropogenic CO2 leads to an increase in its concentra-

tion both in air and in oceans/lakes/rivers (due to CO2 solubility in water).
It is estimated that the anthropogenic CO2 from fossil fuel combus-
tion is about 25 million tons/year (increased by about 15% over the past
50 years). The cost of application of CCS technology has been evaluated
 Introduction to Surface Chemistry of Carbon Capture   ■    17

(Appendix C). This subject is out of the scope of this book and will be
discussed only briefly.
It is thus seen that to define the average concentration of CO2 in the
atmosphere is not quite simple. The general process of capture of CO2
(CCS) is (Figure 1.1; Appendix C):

CO2 (as gas) ==== CO2 (capture process: absorbed/adsorbed/etc.)

The most plausible process generally suggested is to capture CO2 at its pro-
duction site (i.e., flue gas from coal-­, oil-­, or gas-­fired plants). Currently
there are various procedures that are suggested to capture CO2 from the
flue gas of industrial plants. At present, there are two well-­established pro-
cedures of capturing gases from flue gases (Figure. 1.3):

absorption (Section 2.2)

(gas is captured by interaction with a suitable fluid)

adsorption (Section 2.1)

(gas is captured by interaction with a solid)

FIGURE 1.3 Gas adsorption and absorption processes.

18   ■    Surface Chemistry of Carbon Capture

Other procedures for carbon capture (Rackley, 2010) (Chapter 5;

Appendix C).
Binding of CO2 to minerals (oxides, hydroxides) to form
carbonates
Polymer membrane gas separators (size exclusion)

In the case of gas absorption in fluids, the gas molecules have to

1. pass (as bubbles) through the surface of the fluid;

2. diffuse into the fluid (under stirring).

This means that the overall process will include various steps (Chap-
ters 2 and 5). CO2 may dissolve in the fluid, or it may interact with some
component(s) in the solution.

AMOUNTS OF CO2 IN DIFFERENT STATES

It is important to consider the quantities of CO2 involved for CCS tech-
nology. The global CO2 emissions from different fossil fuel combustion
processes are reported to be as follows (approximate data in gigatons
(Pg = Gt) CO2/year):

GAS (5 Pg) + OIL (10 Pg) + COAL (9 Pg) = TOTAL CO2 EMISSIONS
= 24 Pg

As reference, it is interesting to mention that the current consumption

of oil globally is 100 million barrels per day. The various sources of CO2
(wherever fossil fuels are used) emissions are

CHEMICAL INDUSTRY 1
CEMENT INDUSTRY 1
STEEL INDUSTRY 2
TRANSPORTATION 5
ELECTRIC POWER GENERATION 10
OTHER INDUSTRIES (ETC.) 5

(1 Pg = 1015 g = 1 gigaton (Gt) = 109 metric tonnes = 1012 kg)

Another random document with
no related content on Scribd:
 C’est une des caractéristiques du génie de Henri Poincaré qu’il
réunit un prodigieux esprit d’invention à un esprit critique
extrêmement aiguisé. Sa critique semble même aller parfois
jusqu’au scepticisme; il contemplait sans tristesse les ruines des
théories. Alors que d’autres constatent avec regret que certaines
idées ne s’accommodent plus aux faits, et commencent par penser
que ceux-ci ont été mal vus ou mal interprétés, Poincaré a plutôt une
tendance contraire, bien qu’elle se soit peut-être atténuée dans les
dernières années. Ainsi un jeune physicien ayant cru jadis pouvoir
s’inscrire contre la célèbre expérience de Rowland, d’après laquelle
une charge électrique en mouvement produit un champ magnétique
conformément à la théorie de Maxwell, cette annonce ne parut pas
étonner Poincaré. Nul n’eut moins que lui la notion statique d’une
science se reposant sur quelques conquêtes définitives, et c’est ce
qui explique que plusieurs se soient crus autorisés à tirer de certains
de ses écrits, où il poussait sa tendance critique presque jusqu’au
paradoxe, des conclusions sur la vanité de la Science contre
lesquelles il dut protester.
Quelques Préfaces des Leçons de Poincaré ont vivement attiré
l’attention. Dans l’Introduction du Livre Électricité et Optique, il
discute ce qu’on doit entendre par «interprétation mécanique d’un
phénomène». Cette interprétation est ramenée d’après lui à la
possibilité de la formation d’un système d’équations de Lagrange
avec un certain nombre de paramètres que
l’expérience atteint directement et permet de mesurer. Dans ces
équations figurent l’énergie cinétique et une fonction des forces
. Cette possibilité étant supposée, on pourra toujours déterminer
masses (masses visibles ou cachées) et leurs coordonnées (
) fonctions des (en prenant assez grand), de manière
que la force vive de ce système de masses soit égale à l’énergie
cinétique figurant dans les équations de Lagrange.
L’indétermination est ici très grande, et c’est précisément là qu’en
veut venir Poincaré, dont la conclusion est que, s’il y a une
explication mécanique, il y en a une infinité. Il faut avouer, dirons-
nous, que cette indétermination est même trop grande, car on perd
complètement de vue les corps en présence. Ainsi, suivant les
formes qu’auront l’ensemble des masses partiellement
indéterminées , on n’aura pas nécessairement dans la suite les
mêmes mouvements; il pourra, par exemple, y avoir ou non des
chocs. Que devient aussi la répartition des forces réelles dans les
systèmes en partie fictifs auxquels on est ainsi conduit?
Dans la Préface de sa Thermodynamique, Poincaré, voulant
descendre en quelque sorte jusqu’au fond du principe de la
conservation de l’énergie, conclut que «la loi de Meyer est une forme
assez souple pour qu’on puisse y faire rentrer presque tout ce qu’on
veut». Il semble à la vérité un peu effrayé de sa conclusion, car il
ajoute plus loin qu’il ne faut pas «pousser jusqu’à l’absolu». Nous
retrouverons cet esprit hypercritique, si j’ose le dire, clans certains
écrits philosophiques de Poincaré.
Poincaré, sans cesse curieux de nouvelles théories et de
nouveaux problèmes, ne pouvait manquer d’être attiré par
l’Électromagnétisme qui tient une si grande place dans la Science de
notre époque. On ne saurait trop admirer avec quelle sûreté et
quelle maîtrise il repense les diverses théories, les faisant ainsi
siennes. Il leur donne parfois une forme saisissante, comme quand,
dans l’exposition de la théorie de Lorentz, il distingue entre les
observateurs ayant les sens subtils et les observateurs ayant les
sens grossiers. La considération, bien personnelle à Poincaré, de ce
qu’il appelle «la quantité de mouvement électromagnétique», la
localisation de celle-ci dans l’éther et sa propagation avec une
perturbation électromagnétique sont venues rétablir d’importantes
analogies. Le Mémoire sur la dynamique de l’électron, écrit en 1905,
restera dans l’histoire du principe de la relativité; le groupe des
transformations de Lorentz, qui n’altèrent pas les équations d'un
milieu électromagnétique, y apparaît comme la clef de voûte dans la
discussion des conditions auxquelles doivent satisfaire les forces
dans la nouvelle dynamique. La nécessité de l’introduction dans
l’électron de forces supplémentaires, en dehors des forces de liaison
est établie, ces forces supplémentaires pouvant être assimilées à
une pression qui régnerait à l’extérieur de l’électron. Poincaré
montre encore quelles hypothèses on peut faire sur la gravitation
pour que le champ grafivique soit affecté par une transformation de
Lorentz de la même manière que le champ électromagnétique.
 On sait l’importance qu’a prise aujourd’hui le principe de la
relativité, dont le point de départ est l’impossibilité, proclamée sur la
foi de quelques expériences négatives, de mettre en évidence le
mouvement de translation uniforme d’un système au moyen
d’expériences d’optique ou d’électricité faites à l’intérieur de ce
système. En admettant, d’autre part, que les idées de Lorentz et ses
équations électromagnétiques sont inattaquables, on a été conduit à
regarder comme nécessaire le changement de nos idées sur
l’espace et sur le temps; espace et temps ( ) n’ont plus
leurs transformations séparées et entrent simultanément dans le
groupe de Lorentz. La simultanéité de deux phénomènes devient
une notion toute relative; un phénomène peut être antérieur à un
autre pour un premier observateur, tandis qu’il lui est postérieur pour
un second. Les mathématiciens, intéressés par un groupe de
transformations qui transforment en elle-même la forme quadratique
( = vitesse de la lumière) se sont livrés à
d’élégantes dissertations sur ce sujet et ont sans doute contribué à
la popularité du principe de relativité. A d’autres époques, on eût
peut-être, avant de rejeter les idées traditionnelles de l’humanité sur
l’espace et le temps, passé au crible d’une critique extrêmement
sévère les conceptions sur l’éther et la formation des équations de
l’électromagnétisme; mais le désir du nouveau ne connaît pas de
bornes aujourd’hui. Les objections ne manquent pas cependant, et
d’illustres physiciens, comme Lord Kelvin et Ritz, sans parler des
vivants, ont émis des doutes très motivés. La Science assurément
ne connaît point de dogmes, et il se peut que des expériences
positives précises nous forcent un jour à modifier certaines idées
devenues notions de sens commun; mais le moment en est-il déjà
venu?
Poincaré voyait le danger de ces engouements, et, dans une
conférence sur la dynamique nouvelle, il adjurait les professeurs de
ne pas jeter le discrédit sur la vieille Mécanique qui a fait ses
preuves. Et puis, il a vécu assez pourvoir les principaux
protagonistes des idées nouvelles ruiner partiellement au moins leur
œuvre. Dans tout ce relativisme, il reste un absolu, à savoir la
vitesse de la lumière dans le vide, indépendante de l’état de repos
ou de mouvement de la source lumineuse. Cet absolu va
probablement disparaître, les équations de Lorentz ne représentant
plus qu’une première approximation. Les plus grandes difficultés
viennent de la gravitation, au point que certains théoriciens de la
Physique croient ne pouvoir les lever qu’en attribuant de l’inertie et
un poids à l’énergie, d’où en particulier la pesanteur de la lumière. Si
Poincaré avait vécu, il eût sans doute été conduit à rapprocher des
vues actuelles son essai de 1905 sur la gravitation. Au milieu des
incertitudes qui se présentent aujourd’hui en électro-optique, son
esprit lumineux va nous manquer singulièrement. Il faut avouer que
dans tout cela les bases expérimentales sont fragiles, et peut-être
Poincaré eût-il suggéré des expériences apportant un peu de
lumière dans cette obscurité.
Un des derniers travaux de Poincaré a été une discussion
approfondie de la théorie des quanta, édifiée par Planck, d’après
laquelle l’énergie des radiateurs lumineux varierait d’une manière
discontinue. De ce point de vue «les phénomènes physiques, dit
Poincaré, cesseraient d’obéir à des lois exprimables par des
équations différentielles, et ce serait là sans aucun doute la plus
grande révolution et la plus profonde que la philosophie naturelle ait
subie depuis Newton». Quelque grande, en effet, que doive être
cette révolution, il est permis toutefois de remarquer que des
circonstances plus ou moins analogues se sont déjà présentées.
Ainsi, dans un gaz à la pression ordinaire, ou peut parler de pression
et l’on peut appliquer les équations différentielles de la dynamique
des fluides; il n’en est plus de même dans un gaz raréfié, où il n’est
plus possible de parler de pression. Il faudra peut-être nous résigner
à faire usage, suivant les limites entre lesquelles nous étudions une
catégorie de phénomènes, de représentations analytiques
différentes, si pénible que puisse être cette sorte de pluralisme pour
ceux qui rêvent d’unité. Mais c’est là encore le secret de l’avenir, et il
serait imprudent d’affirmer qu’on ne trouvera pas quelque biais
permettant de rétablir dans nos calculs la continuité.
 V.
Les nombreux écrits de Poincaré, sur ce qu’on appelle la
philosophie des sciences, ont fait connaître son nom à un public très
étendu. Nous entrons ici dans un autre domaine que celui des
recherches proprement scientifiques, et je n’ai pas l’intention
d’étudier à fond cette partie de son œuvre. Il y est tout d’abord
singulièrement difficile de se rendre compte de l’originalité de telle
ou telle étude; ainsi, dans ses écrits sur l’hypothèse dans la Science,
Poincaré s’est rencontré plus d’une fois avec divers auteurs, mais
l’illustration de son nom, consacrée par tant de découvertes
mathématiques, donnait à ses opinions une autorité particulière. La
forme en ces questions est aussi de grande importance. La phrase
concise de Poincaré, allant droit au but, parfois avec une légère
pointe de paradoxe, produit une singulière impression; on est un
moment subjugué, même quand on sent qu’on n’est pas d’accord
avec l’auteur. Mainte page de Poincaré a produit sur plus d’un
lecteur un vif sentiment d’admiration en même temps qu’une sorte
d’effroi et d’agacement devant tant de critique.
On a parlé quelquefois de la philosophie de Poincaré. En fait,
penseur indépendant, étranger à toute école, Poincaré ne chercha
jamais à édifier un système philosophique, comme un Renouvier, un
Bergson ou même un William James. Il a écrit des livres de
«Pensées», où savants et philosophes trouvent ample matière à
réflexions. Il n’est esclave d’aucune opinion, pas même de celle qu’il
a émise antérieurement, et il sera un jour intéressant de suivre
certaines variations de la sa pensée, où l’on voit quelque peu
s’atténuer ce qu’on a appelé son nominalisme. Il fut ainsi conduit à
expliquer certaines affirmations qui, prises trop à la lettre, avaient été
mal comprises et utilisées dans un dessein dont il n’avait aucun
souci.
 Si l’on voulait toutefois caractériser d’un mot les idées de
Poincaré, on pourrait dire que sa philosophie est la philosophie de la
commodité. Dans quelques unes de ses pages, le mot commode
revient constamment et constitue le terme de son explication.
D’aucuns pensent qu’il faudrait donner les raisons de cette
commodité, et, parmi eux, les plus pressants sont les biologistes
toujours guidés par l’idée d’évolution. La commodité résultera pour
eux d’une longue adaptation, et, ainsi approfondie, deviendra un
témoignage de réalité et de vérité. A l’opposé des évolutionnistes,
d’autres ne voient que l’esprit humain tout formé et sa fonction la
pensée. A certaines heures au moins, Poincaré fut de ces derniers,
et cet idéalisme lui a inspiré des pages d’une admirable poésie qui
resteront dans la littérature française; telle cette dernière page de
son Livre sur la valeur de la Science, qui débute par ces mots «Tout
ce qui n’est pas pensée est le pur néant». Entre des doctrines si
différentes toute communication est impossible, et l’on arrive à se
demander si l’on peut discuter de l’origine des plus simples notions
scientifiques, sans avoir à l’avance une foi philosophique à la
formation de laquelle auront d’ailleurs concouru d’autres éléments
que des éléments proprement scientifiques.
Pour ne pas rester uniquement dans les généralités, arrêtons-
nous un moment sur les principes de la Géométrie. Poincaré part
d’un esprit humain, dans lequel l’idée de groupe préexiste et
s’impose comme forme de notre entendement. L’esprit, après un
travail d’abstraction aboutissant aux premiers concepts de la
Géométrie (point, droite, etc.), cherche à exprimer les rapports de
position des corps; il le fait au moyen de l’idée de groupe, prenant le
groupe le plus commode et le plus simple qui est le groupe de la
géométrie dite euclidienne. Les propriétés géométriques ne
correspondent, pour Poincaré, à aucune réalité; elles forment un
ensemble de conventions que l’expérience a pu suggérer à l’esprit,
mais qu’elle ne lui a pas imposées. L’évolutionniste dont je parlais
plus haut voit là de grandes difficultés, non pas seulement pour la
raison banale que la dualité ainsi posée entre l’esprit et le milieu
extérieur est contraire à sa doctrine, mais parce que, cherchant à
retracer la genèse des origines de la Géométrie dans l’espèce
humaine, il lui paraît impossible de séparer l’acquisition des notions
géométriques et celles des notions physiques les plus simples, la
Géométrie ayant dans des temps très anciens fait partie de la
Physique. Sans changer l’ensemble de ces notions, on ne peut,
semble-t-il, remplacer le groupe euclidien par un autre, et les
exemples cités de transport d’un homme dans un autre milieu (où
cet homme commencerait par mourir) sont plus pittoresques que
probants. On retombe ainsi, sous un autre point de vue, sur les
idées de Gauss qui considérait comme un fait expérimental que la
courbure de notre espace est nulle, et regardait, contrairement à
Poincaré, que la géométrie euclidienne est plus vraie que les
géométries non euclidiennes. Il y a sans doute bien des hypothèses,
ne disons pas des conventions, en Géométrie. C’en est une par
exemple, oubliée quelquefois, que notre espace est simplement
connexe. Peu importe quelle est la connexité de l’espace, quand on
se borne à envisager une partie assez petite, celle-ci s’étendît-elle
jusqu’aux lointaines nébuleuses, mais il pourrait en être autrement
quand on considère l’espace dans son ensemble.
Tous les esprits élevés trouveront, dans l’œuvre philosophique et
littéraire de Poincaré, matière à longues réflexions, soit qu’ils se
laissent convaincre par sa dialectique, soit qu’ils cherchent des
arguments contraires. Certaines pages sont d’une austère grandeur,
comme celle où la pensée est qualifiée d’«éclair au milieu d’une
longue nuit». Non moins suggestive est la parenthèse ouverte un
peu avant «étrange contradiction pour ceux qui croient au temps»,
où l’on est presque tenté de voir un demi-aveu. Les inquiétudes
qu’on peut concevoir au sujet de la notion même de loi furent-elles
jamais exprimées avec plus de profondeur que dans l’étude sur
l’évolution des lois? J’ai déjà fait allusion au prétendu scepticisme de
Poincaré. Non, Poincaré ne fut pas un sceptique; à certaines heures,
il fut pris, comme d’autres, d’angoisse métaphysique, et il sut
éloquemment l’exprimer. Mais tournons le feuillet, et le savant,
confiant dans l’effort de l’esprit humain pour atteindre le vrai, nous
apparaît dans des pages admirables sur le rôle et la grandeur de la
Science. Les plus belles peut-être forment cet hymne à l’Astronomie
qu’il faudrait faire lire aux jeunes gens à une époque où tend à
dominer le souci exclusif de l’utile. Aucune des préoccupations de
notre temps ne fut d’ailleurs étrangère au noble esprit de Poincaré;
c’est ce dont témoigne une de ses dernières études sur la morale et
la science, où l’argumentation est irréprochable, si par morale on
entend la morale impérative de Kant.
On ne ferme pas sans tristesse ces volumes d’un contenu si riche
et dont quelques parties auraient été l’objet de nouveaux
développements, si la plume n’était tombée des mains de leur
auteur. Tous ceux qui ont le culte de la Science pure et
désintéressée ont été douloureusement émus par sa mort
prématurée, mais ce sont surtout les sciences mathématiques qui
sont cruellement frappées par cette disparition. Poincaré fut, avant
tout, un profond mathématicien, qui, pour la puissance d’invention,
est l’égal des plus grands. L’heure n’est pas venue de porter un
jugement définitif sur son œuvre que le temps grandira encore, ni de
le comparer aux plus célèbres géomètres du siècle dernier: peut-être
Henri Poincaré fût-il encore supérieur à son œuvre?
[1] On sait qu’un savant Finlandais M. Sundmann vient de donner
une solution complète du problème des trois corps. Il serait injuste
de ne pas reconnaître que les travaux antérieurs de Poincaré ont
eu une grande influence sur les recherches de l’astronome
d’Helsingfors. J’ai fait une étude des Mémoires de M. Sundmann
dans un article récent de la Revue générale des Sciences (15
octobre 1913) et dans le Bulletin des Sciences Mathématiques
(octobre 1913).
[2] C’est en approfondissant cette idée, et en ne craignant pas de
comprendre dans son analyse le cas des chocs que M.
Sundmann est arrivé à une solution du problème de trois corps
(voir la note ci-dessus).

53717 Paris,—Imprimerie Gauthier-Villars, 55, quai des Grands-

Augustins.

AU LECTEUR
L’orthographe d’origine a été conservée et n’a pas été harmonisée, mais les
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corrigées.
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 *** END OF THE PROJECT GUTENBERG EBOOK L'ŒUVRE DE
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