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Peter Styring - Carbon Dioxide Utilisation: Closing the Carbon Cycle

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Peter Styring Carbon Dioxide Utilisation: Closing the Carbon Cycle

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Carbon Dioxide Utilisation: Closing the Carbon Cycle explores areas of application such as conversion to fuels, mineralization, conversion to polymers, and artificial photosynthesis as well as assesses the potential industrial suitability of the various processes. After an introduction to the thermodynamics, basic reactions, and physical chemistry of carbon dioxide, the book proceeds to examine current commercial and industrial processes, and the potential for carbon dioxide as a green and sustainable resource.

While carbon dioxide is generally portrayed as a bad gas, a waste product, and a major contributor to global warming, a new branch of science is developing to convert this bad gas into useful products. This book explores the science behind converting CO2 into fuels for our cars and planes, and for use in plastics and foams for our homes and cars, pharmaceuticals, building materials, and many more useful products.

Carbon dioxide utilization is a rapidly expanding area of research that holds a potential key to sustainable, petrochemical-free chemical production and energy integration.

  • Accessible and balanced between chemistry, engineering, and industrial applications
  • Informed by blue-sky thinking and realistic possibilities for future technology and applications
  • Encompasses supply chain sustainability and economics, processes, and energy integration

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Peter Styring - Carbon Dioxide Utilisation: Closing the Carbon Cycle
Carbon Dioxide Utilisation: Closing the Carbon Cycle
Peter Styring
Carbon Dioxide Utilisation: Closing the Carbon Cycle

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Chapter 1
What is CO2? Thermodynamics, Basic Reactions and Physical Chemistry
Michael North Green Chemistry Centre of Excellence, Department of Chemistry, The University of York, Heslington, York, UK
Abstract

This introductory chapter introduces the structural, physical and spectroscopic properties of carbon dioxide and shows how these are linked to its role in global warming. The phase behaviour of carbon dioxide is introduced including the accessibility of a supercritical phase. The kinetics and thermodynamics of reactions involving carbon dioxide are introduced to provide a theoretical basis for understanding the reactions of carbon dioxide and the limitations as to what catalysis can achieve. Finally, the commercially important chemical reactions of carbon dioxide are surveyed within this kinetic and thermodynamic framework.

Keywords
kinetics; thermodynamics; reactivity; phase-behaviour; structure

Chapter Outline

1.1. Introduction
Carbon dioxide (CO2) is a triatomic
The carbon dioxide molecule has a linear structure in which each carbonoxygen bond has a length of 116.3 pm and is composed of a - and shows various representations of carbon dioxide.
FIGURE 11 Representations of carbon dioxide The chemical reactivity of - photo 1
FIGURE 1.1 Representations of carbon dioxide.
The chemical reactivity of carbon dioxide is determined by the polarisation of the carbon oxygen bonds, and the chemistry is dominated by the reaction of carbon dioxide with nucleophiles which react at the central carbon atom ( its chemical reactivity.
This is the basis of many metal-induced and metal-catalysed reactions of carbon dioxide. The area is however complicated by the numerous ways in which carbon dioxide can coordinate to one or more metals due to its ability to coordinate through either carbon or oxygen and to bridge between metal atoms. As shown in If just the monometallic complexes are considered, an electron deficient metal will coordinate to one of the oxygen atoms (O1) Picture 2 and this does not change the geometry of the carbon dioxide, but will withdraw electron density from it, thus making the carbon atom more susceptible to attack by nucleophiles. In contrast, metals with loosely held electrons may coordinate to the carbon atom of carbon dioxide (C1) Picture 3 which both makes the carbon atom less electron deficient and hence less susceptible to attack by nucleophiles: this also changes the overall geometry of the CO2 unit from linear to bent.
SCHEME 11 Reaction of carbon dioxide with nucleophiles FIGURE 12 - photo 4
SCHEME 1.1 Reaction of carbon dioxide with nucleophiles.
FIGURE 12 Carbon dioxide metal complex geometries 12 Spectroscopy and its - photo 5
FIGURE 1.2 Carbon dioxide metal complex geometries.
1.2. Spectroscopy and its role in climate change
The carbon dioxide molecule has three vibrational modes: two stretches (symmetric and anti-symmetric) and a bend (
The infrared active vibrations of carbon dioxide are directly responsible for its role as a greenhouse gas. The Earth's atmosphere is transparent to visible light coming cycle, so that the concentration of carbon dioxide in the atmosphere builds up. Each 188 million tonnes of carbon dioxide emitted due to fossil fuel burning raises the atmospheric carbon dioxide concentration by 1 ppm by volume.
FIGURE 13 Carbon dioxide vibrations 13 Phase behaviour and solvent - photo 6
FIGURE 1.3 Carbon dioxide vibrations.
1.3. Phase behaviour and solvent properties
The p-T phase diagram a gas), but which has a density (like a liquid). Above this point there is no way to distinguish between the gas and liquid.
Compared to other common chemicals, the supercritical region of carbon dioxide occurs at relatively accessible temperatures and pressures. As a result, liquid or supercritical carbon dioxide has attracted considerable interest as a green solvent for chemical reactions, eventually be vented to atmosphere, but from not having to produce and eventually incinerate the conventional solvent.
FIGURE 14 Carbon dioxide phase diagram The polarity of supercritical carbon - photo 7
FIGURE 1.4 Carbon dioxide phase diagram.
The polarity of supercritical carbon dioxide can be varied from that of pentane to that of pyridine simply by varying its density. though carbon dioxide can be reduced to formic acid, formaldehyde, methanol or methane by hydrogen in the presence of a suitable catalyst.
Another way in which carbon dioxide can be advantageously used as a solvent is as a modifier to the properties of a second solvent. If carbon dioxide is dissolved in a conventional solvent under pressure,.
Alternatively, the carbonic acid can act as an acid catalyst during a reaction which then automatically neutralises itself when the pressure is released at the end of the reaction.
The pH of a water/supercritical carbon dioxide mixture can be as low as 2.8
SCHEME 12 Formation of carbonic acids from carbon dioxide and water or - photo 8
SCHEME 1.2 Formation of carbonic acids from carbon dioxide and water or alcohols.
SCHEME 13 Formation of carbamic acids and ammonium carbamates from carbon - photo 9
SCHEME 1.3 Formation of carbamic acids and ammonium carbamates from carbon dioxide and amines.
1.4. Kinetics and thermodynamics
Carbon dioxide is a thermodynamically very stable molecule with a standard heat of formation (fHo) of 394 kJ/mol. Hence there is a commonly held view that carbon dioxide chemistry is always going to be difficult as reactions will be thermodynamically uphill. However, shows a general reaction of carbon dioxide. The heat of reaction is determined by the difference between the heat of formation of all the products and that of all the reactants.
Thus, it is entirely possible for reactions involving carbon dioxide to be exothermic. An industrially important example is the reaction between carbon dioxide and ethylene oxide
SCHEME 14 General reaction of carbon dioxide and its enthalpy of reaction - photo 10
SCHEME 1.4 General reaction of carbon dioxide and its enthalpy of reaction.
SCHEME 15 Synthesis of ethylene carbonate from carbon dioxide and ethylene - photo 11
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