Chemical Reactions in Thermal Carbonization Processing of Citric Acid-Urea Mixtures

‘The burning issue: molecules and energy’ describes how energy can be transferred through molecular reactions. Metabolic processes are the foundation of cellular life. All chemical reactions increase entropy (or disorder), but living cells maintain their order by carefully controlling metabolic reactions. In living organisms glucose is broken down into pyruvate through glycolysis. Pyruvate then enters the citric acid cycle, which is a series of reactions that generate electrons which generate ATP — the cell's ‘fuel’. Many scientists, most notably Alfred Nobel, have sought to develop molecules which contain huge amounts of energy safely. These molecules can be used to build civilization — or destroy life.

Download Full-text

Photochemical degradation of iron(III) citrate/citric acid aerosol quantified with the combination of three complementary experimental techniques and a kinetic process model

Atmospheric Chemistry and Physics ◽

10.5194/acp-21-315-2021 ◽

2021 ◽

Vol 21 (1) ◽

pp. 315-338

Author(s):

Jing Dou ◽

Peter A. Alpert ◽

Pablo Corral Arroyo ◽

Beiping Luo ◽

Frederic Schneider ◽

...

Keyword(s):

Citric Acid ◽

Mass Loss ◽

Gas Phase ◽

Organic Compounds ◽

Chemical Reactions ◽

Loss Rate ◽

Mass Loss Rate ◽

Organic Aerosol ◽

Photochemical Degradation ◽

Aerosol Aging

Abstract. Iron(III) carboxylate photochemistry plays an important role in aerosol aging, especially in the lower troposphere. These complexes can absorb light over a broad wavelength range, inducing the reduction of iron(III) and the oxidation of carboxylate ligands. In the presence of O2, the ensuing radical chemistry leads to further decarboxylation, and the production of .OH, HO2., peroxides, and oxygenated volatile organic compounds, contributing to particle mass loss. The .OH, HO2., and peroxides in turn reoxidize iron(II) back to iron(III), closing a photocatalytic cycle. This cycle is repeated, resulting in continual mass loss due to the release of CO2 and other volatile compounds. In a cold and/or dry atmosphere, organic aerosol particles tend to attain highly viscous states. While the impact of reduced mobility of aerosol constituents on dark chemical reactions has received substantial attention, studies on the effect of high viscosity on photochemical processes are scarce. Here, we choose iron(III) citrate (FeIII(Cit)) as a model light-absorbing iron carboxylate complex that induces citric acid (CA) degradation to investigate how transport limitations influence photochemical processes. Three complementary experimental approaches were used to investigate kinetic transport limitations. The mass loss of single, levitated particles was measured with an electrodynamic balance, the oxidation state of deposited particles was measured with X-ray spectromicroscopy, and HO2. radical production and release into the gas phase was observed in coated-wall flow-tube experiments. We observed significant photochemical degradation with up to 80 % mass loss within 24 h of light exposure. Interestingly, we also observed that mass loss always accelerated during irradiation, resulting in an increase of the mass loss rate by about a factor of 10. When we increased relative humidity (RH), the observed particle mass loss rate also increased. This is consistent with strong kinetic transport limitations for highly viscous particles. To quantitatively compare these experiments and determine important physical and chemical parameters, a numerical multilayered photochemical reaction and diffusion (PRAD) model was developed that treats chemical reactions and the transport of various species. The PRAD model was tuned to simultaneously reproduce all experimental results as closely as possible and captured the essential chemistry and transport during irradiation. In particular, the photolysis rate of FeIII, the reoxidation rate of FeII, HO2. production, and the diffusivity of O2 in aqueous FeIII(Cit) ∕ CA system as function of RH and FeIII(Cit) ∕ CA molar ratio could be constrained. This led to satisfactory agreement within model uncertainty for most but not all experiments performed. Photochemical degradation under atmospheric conditions predicted by the PRAD model shows that release of CO2 and repartitioning of organic compounds to the gas phase may be very important when attempting to accurately predict organic aerosol aging processes.

Download Full-text

Surface reactions observed by photoemission electron microscopy (PEEM)

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100121831 ◽

1992 ◽

Vol 50 (1) ◽

pp. 286-287

Author(s):

H.H. Rotermund

Keyword(s):

Electron Microscopy ◽

Electron Microscope ◽

Work Function ◽

Chemical Reactions ◽

Reaction Diffusion ◽

Dynamic Processes ◽

Clean Surface ◽

Crystal Surfaces ◽

Single Crystal Surfaces ◽

Photoemission Electron

Chemical reactions at a surface will in most cases show a measurable influence on the work function of the clean surface. This change of the work function δφ can be used to image the local distributions of the investigated reaction,.if one of the reacting partners is adsorbed at the surface in form of islands of sufficient size (Δ>0.2μm). These can than be visualized via a photoemission electron microscope (PEEM). Changes of φ as low as 2 meV give already a change in the total intensity of a PEEM picture. To achieve reasonable contrast for an image several 10 meV of δφ are needed. Dynamic processes as surface diffusion of CO or O on single crystal surfaces as well as reaction / diffusion fronts have been observed in real time and space.

Download Full-text

Microwaves: Application in Electron Microscopy

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100158248 ◽

1990 ◽

Vol 48 (3) ◽

pp. 140-141

Author(s):

Anthony S-Y Leong ◽

David W Gove

Keyword(s):

Electron Microscopy ◽

Light Microscopy ◽

Chemical Reactions ◽

Electromagnetic Waves ◽

Tissue Fixation ◽

Primary Method ◽

Dipolar Molecules ◽

Wide Range ◽

Time Required ◽

Cryostat Sections

Microwaves (MW) are electromagnetic waves which are commonly generated at a frequency of 2.45 GHz. When dipolar molecules such as water, the polar side chains of proteins and other molecules with an uneven distribution of electrical charge are exposed to such non-ionizing radiation, they oscillate through 180° at a rate of 2,450 million cycles/s. This rapid kinetic movement results in accelerated chemical reactions and produces instantaneous heat. MWs have recently been applied to a wide range of procedures for light microscopy. MWs generated by domestic ovens have been used as a primary method of tissue fixation, it has been applied to the various stages of tissue processing as well as to a wide variety of staining procedures. This use of MWs has not only resulted in drastic reductions in the time required for tissue fixation, processing and staining, but have also produced better cytologic images in cryostat sections, and more importantly, have resulted in better preservation of cellular antigens.

Download Full-text

Fine structure and properties of defects in naturally occurring silicates and oxides

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100175430 ◽

1990 ◽

Vol 48 (4) ◽

pp. 460-461

Author(s):

David R. Veblen

Keyword(s):

Chemical Reactions ◽

High Resolution Electron Microscopy ◽

Extended Defects ◽

Single Chain ◽

Naturally Occurring ◽

Resolution Electron ◽

Fine Structures ◽

Image Simulations ◽

Similar Crystal Structure

Extended defects and interfaces control many processes in rock-forming minerals, from chemical reactions to rock deformation. In many cases, it is not the average structure of a defect or interface that is most important, but rather the structure of defect terminations or offsets in an interface. One of the major thrusts of high-resolution electron microscopy in the earth sciences has been to identify the role of defect fine structures in reactions and to determine the structures of such features. This paper will review studies using HREM and image simulations to determine the structures of defects in silicate and oxide minerals and present several examples of the role of defects in mineral chemical reactions. In some cases, the geological occurrence can be used to constrain the diffusional properties of defects.The simplest reactions in minerals involve exsolution (precipitation) of one mineral from another with a similar crystal structure, and pyroxenes (single-chain silicates) provide a good example. Although conventional TEM studies have led to a basic understanding of this sort of phase separation in pyroxenes via spinodal decomposition or nucleation and growth, HREM has provided a much more detailed appreciation of the processes involved.

Download Full-text