γ Radiolysis of Gaseous Carbon Dioxide at High Densities

Effect of water on the radiolysis of carbon dioxide

Carbon dioxide has been irradiated with electron pulses at a dose rate of 2 × 1027 eV g−1 s−1. The measured carbon monoxide yield is G(CO) = 7.8 ± 0.3. Addition of SF6, an electron scavenger, reduces this yield to G(CO) = 4.8 which is the same, within the experimental error, as the low dose rate yield G(CO) = 4.5 ± 0.5. The effect of SF6 and the difference between the high and low dose rate yields is explained by suppression of dissociative neutralization of the C2O4+ ion.

The propagation and termination reaction in the γ‐radiation‐induced ethylene polymerization in liquid carbon dioxide were investigated by a two‐stage irradiation. After irradiation at high dose rate, the polymerization occured at a considerable rate under the extremely low dose rate without initiation. The absolute propagation rate was determined in the second stage to be proportional to the square of ethylene fugacity and depended slightly on dose rate. The apparent activation energy for the propagation reaction is −9 kcal./mole. From these observations which are the same as those in bulk polymerization, it is concluded that carbon dioxide acts as a diluent of ethylene monomer in the propagation reaction. Also, carbon dioxide was shown to be inactive to the growing radicals without irradiation, but oxygen which is produced by the radiolysis of carbon dioxide at high dose terminates the growing radicals with formation of carbonyl in the polymer.

A drift tube and mass filter have been used to measure the rates of some O– negative ion molecule reactions, thought to be important in the radiolysis of carbon dioxide. Measurements of the clustering reaction O–+ CO2+ M → CO–3+ M in carbon dioxide give a third-order rate constant which falls with increasing pressure. This suggests an intermediate CO–3 ion with a lifetime of approximately 10–8 s. The limiting, low-pressure, rate constant is (1.1 ± 0.1)× 10–27 cm6 molecule–2 s–1 and, in the high-pressure limit, it is (2.7 ± 0.3)× 10–10 cm3 molecule–1 s–1. The rate also falls slowly with increasing reduced field. In O2 the rate constant is a factor of 3.5 lower, but it is difficult to measure the pressure dependence as accurately because CO–3 is also produced by the reaction: O–3+ CO2→ CO–3+ O2k=(5.5 ± 0.5)× 10–10 cm3 molecule–1 s–1. The rate constant measured in O2 for the associative detachment reaction O–+ CO → CO2+ e is (7.3 ± 0.7)× 10–10 cm3 molecule–1 s–1. Similar experiments in carbon dioxide are complicated by changes in the electron energy distribution as CO is added, but an upper limit of significantly less than 10–13 cm3 molecule–1 s–1 is suggested for the competing reaction: CO–3+ CO → 2CO2+ e. The reaction of O–3 with CO is very slow.

Ions in carbon dioxide at an atmospheric pressure—II. Effect of CO and O 2 addition

A pure carbon dioxide torch is generated by making use of 2.45 GHz microwave. Carbon dioxide gas becomes the working gas and produces a stable carbon dioxide torch. The torch volume is almost linearly proportional to the microwave power. Temperature of the torch flame is measured by making use of optical spectroscopy and thermocouple. Two distinctive regions are exhibited, a bright, whitish region of high-temperature zone and a bluish, dimmer region of relatively low-temperature zone. Study of carbon dioxide disintegration and gas temperature effects on the molecular fraction characteristics in the carbon dioxide plasma of a microwave plasma torch under atmospheric pressure is carried out. An analytical investigation of carbon dioxide disintegration indicates that substantial fraction of carbon dioxide molecules disintegrate and form other compounds in the torch. For example, the normalized particle densities at center of plasma are given by nCO2/nN = 6.12 × 10−3, nCO/nN = 0.13, nC/nN = 0.24, nO/nN = 0.61, nC2/nN = 8.32 × 10−7, nO2/nN = 5.39 × 10−5, where nCO2, nCO, nC, nO, nC2, and nO2 are carbon dioxide, carbon monoxide, carbon and oxygen atom, carbon and oxygen molecule densities, respectively. nN is the neutral particle density. Emission profiles of the oxygen and carbon atom radicals and the carbon monoxide molecules confirm the theoretical predictions of carbon dioxide disintegration in the torch.

We investigate the reaction pathways of nine important CO2-related reactions using the revDSD-PBEP86-D3(BJ)/jun-cc-pV(T+d)Z level and simultaneously employ an accurate composite method (jun-Cheap) based on coupled-cluster (CC) theory. Subsequently, the Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) is solved to calculate the temperature- and pressure-dependent rate constants. This work investigates reactions involving transition states that have been overlooked in previous literature, including the dissociation of singlet-state C3O2, the triple channel formation of C2O + CO to form C3O2, and the formation of O3 + CO. The results show that CO3 is highly prone to dissociation at high temperatures. Finally, the kinetic data show that over a wide temperature range, our calculations are consistent with previous experimental measurements. The majority of the reaction rate constants studied exhibit significant pressure dependence, while the O3 + CO reaction is pressure-independent at low temperatures. These results are instrumental in the development of detailed kinetic models for the CO2 radiolysis reaction network.

Radiolysis of carbon dioxide in the adsorbed state

Methane hydrate exists in huge amounts in certain locations, in sea sediments and the geological structures below them, at low temperature and high pressure. Production methods are in development to produce the methane to a floating platform. There it can be reformed to produce hydrogen and carbon dioxide, in an endothermic process. Some of the methane can be burned to provide heat energy to develop all needed power on the platform and to support the reforming process. After separation, the hydrogen is the valuable and transportable product. All carbon dioxide produced on the platform can be separated from other gases and then sequestered in the sea as carbon dioxide hydrate. In this way, hydrogen is made available without the release of carbon dioxide to the atmosphere, and the hydrogen could be an enabling step toward a world hydrogen economy.

Laparoscopic insufflation, proposed to reduce hepatic perfusion, may enhance hepatic tumor spread. It is unknown whether intraabdominal pressure or the gas itself influences hepatic tumor growth. In contrast to carbon dioxide, the alternative gas helium is believed to reduce malignant cell growth. For this study, 36 WAG/Rij rats were randomized in two experimental groups. The animals were laparoscopically insufflated with carbon dioxide ( n = 19) or helium gas ( n = 17). Liver metastases were induced by laparoscopic injection of 50,000 CC531 cells into the portal vein. Macroscopic and microscopic analyses of CC531 tumor cell growth, macrophages, and CD44v5, v6 were performed. Data were analyzed by Kruskal-Wallis, Dunn, and Holm tests. No significant differences in macroscopic and microscopic analyses were found between carbon dioxide and helium gas insufflations ( p > 0.05). Recent studies have shown that insufflation with carbon dioxide may result in increased hepatic tumor growth. The current study comparing carbon dioxide and helium insufflations could show for the first time either oncologic nor immunologic differences in relation to the liver between two different gases. In conclusion, elevated intraabdominal pressure during gas insufflation is responsible for hepatic disadvantages during pneumoperitoneum, not carbon dioxide gas itself.

The effect of various insufflation gases on tumor implantation in an animal model

Currently, air conditions on earth are getting worse over time due to the impact of air pollution. One example of air pollution is motor vehicle exhaust emissions. Exhaust gas emissions are the result of combustion residue in motor vehicle engines that use fuel. Motor vehicle exhaust emissions contain carbon monoxide (CO), hydrocarbons (HC), carbon dioxide gas (CO2) which have a negative impact on the environment and living creatures. This research will create a motor vehicle exhaust emission detection device. In this design, an Arduino microcontroller was used and the manufacture of this tool used an MQ-7 gas sensor to detect carbon monoxide (CO) gas, an MQ-2 sensor to detect hydrocarbon gas (HC), and an MQ-135 to detect carbon dioxide (CO2) gas. The emission test results will be sent to the application, this data includes plate number, vehicle type, vehicle brand, vehicle year and emission test results. The results of the carbon monoxide (CO) gas sensor calibration test taken from 5 data showed an error of 5.51%. The results of the hydrocarbon (HC) gas sensor calibration test taken from 5 data showed an error of 4.23%. The results of the carbon dioxide (CO2) gas sensor calibration test taken from 5 data showed an error of 1.06%. In the implementation of the tool and application, the test results were obtained for 15 vehicles. Where the highest hydrocarbon (HC) gas content value was 412 ppm, the highest carbon monoxide (CO) gas content value was 1.48%, and the highest carbon dioxide (CO2) gas content value was 21.4%.

Temperature and pressure dependence of the optical Kerr effect in liquid and gaseous carbon dioxide

Low oil recovery which is very predominant in shale oil reservoirs has stimulated petroleum engineers to investigate the applications of enhanced oil recovery methods in these formations. One such application is the injection of gases into the formation to stimulate increased oil recovery. In many gas flooding projects performed in the field, the miscibility of the gas injected is usually the most desired displacement mechanism, and carbon dioxide (CO2) gas has been recognized to be the best performing gas for injection due to its ability to be miscible with oil in the reservoir at low pressures compared to other gases such as nitrogen. This minimum miscibility pressure (MMP) is of very crucial importance because it is the primary limiting factor in the feasibility of a miscible gas flooding project. However, there are other limiting factors such as cost and availability and, in these instances, nitrogen (N2) and lean gas are the more preferred candidate as opposed to carbon dioxide gas. Mixing carbon dioxide gas with lean gas or with nitrogen in a required ratio can allow us to design an injection gas that will be suitable enough to satisfy both the availability and cost constraints and at the same time allow us to achieve a reachable and reasonable miscibility pressure. The objective of this paper is to investigate the effect of mixing nitrogen gas and carbon dioxide gas in a 50:50 ratio on oil recovery in tight oil formations. The experiment was performed with controlled constraints such as the same core sample, same crude oil and same core cleaning and saturation process which was repeated for each trial. The oil used was live oil from Eagle ford formation, and the gases used were nitrogen (99.9% purity), carbon dioxide and a mixture of nitrogen and carbon dioxide in a 50:50 ratio. The injection pressure ranged from 1000 to 5000 psi with pressure increments of 1000 psi, and the same flooding time was 6 h. The potential of the N2, CO2 and N2–CO2 mixture for improving oil recovery was assessed along with the breakthrough time. The results showed that CO2 gas had the highest recovery followed by the N2–CO2 mixture and N2 gas had the lowest recovery. The gas breakthrough time results showed that the N2–CO2 mixture had the longest breakthrough time, N2 had the shortest breakthrough time, and CO2 had a significantly longer breakthrough time than pure N2 gas. The RF increased with increasing pressure, but the gas breakthrough time decreased with increasing pressure. However, the incremental RF decreased in all three cases when the injection pressure was above 3000 psi.

<p style="text-align: justify;"><strong>Aims</strong>: During wine making, oxygen and carbon dioxide are often simultaneously present in the liquid phase. We propose a simple rational approach, based on usual chemical engineering and thermodynamic principles, to provide understanding and practical rules for controlling the effects of these two dissolved gases, and especially their inter-relationship. Furthermore, this study proposes an explanation for the “protective” effect against oxidation, which is reported when high concentrations of carbon dioxide are present in musts and wines.</p><p style="text-align: justify;"><strong>Methods and results</strong>: The theoretical quantitative relation, termed “binary gas equilibrium line”, between the maximum possible concentration of dissolved oxygen in respect to dissolved carbon dioxide was derived and, in our experiments, corresponded to C<sub>O2max</sub> ≅ -0,005 C<sub>CO2</sub> + 7,9 mg.L<sup>-1</sup>. Specific saturation experiments using simultaneous injection of air and gaseous carbon dioxide were performed and the experimental results allowed us to validate this theory in the case of gas bubbling in a liquid.</p><p style="text-align: justify;"><strong>Conclusion</strong>: It is shown that complete protection is only obtained when carbon dioxide is generated by the fermentation in the liquid. An interesting parallel conclusion is that micro-oxygenation is totally inefficient in such periods. In the case where there is no production of CO<sub>2</sub> but where a high initial dissolved carbon dioxide concentration is present, the “protective” effect acts only by reducing the rate of oxygen transfer.</p><p style="text-align: justify;"><strong>Significance and impact of the study</strong>: The physical understanding of this phenomenon can be found in the fact that as soon as a gaseous air or pure oxygen phase is in contact with a carbon dioxide saturated liquid, the dissolved carbon dioxide, which is not at equilibrium with the gaseous phase, tends to escape into this gaseous phase. This study points out the complexity of the gas-liquid equilibrium when two dissolved gases are simultaneously present in a liquid and its implication in the winemaking process.</p>