The peroxides formed during hydrocarbon slow combustion and their role in the mechanism

The peroxides formed during the slow combustion of five hydrocarbons in a flow system have been identified and the approximate yields estimated. With propane at 327°C and 2, 2, 3-trimethylbutane at 365 to 385°C the products contained only traces of hydrogen peroxide, its addition compounds with aldehyde and (with C 3 H 8 ) peracetic acid. With n -butane between 310 and 345°C and cylohexane between 290 and 316°C appreciable yields of peroxide were obtained (~ 10 to 20% of the hydrocarbon oxidized). These consisted of the monohydroperoxides, hydrogen peroxide and their addition compounds with aldehydes. With n -C 4 H 10 the relative amount of H 2 O 2 free and combined ( ~ 50% of the total peroxide yield) was much higher than with C 6 H 12 and some perpropionic acid was also detected. With n -heptane between 240 and 310°C the yield of peroxide in the products was also con­ siderable ( ~ 20% of the hydrocarbon reacted), and consisted mainly of dihydroperoxyheptane and its addition compounds with aldehydes (mainly formaldehyde), with much smaller amounts of monohydroperoxide and hydrogen peroxide (free and combined with aldehyde), diheptylperoxide and possible trihydroperoxyheptane. Packing the vessel increased the relative amount of aldehyde-addition compounds but did not affect the yield of free aldehyde, which apparently depended only on the temperature, being zero at 240°C. All aldehydes up to C 5 H 11 CHO were formed at higher temperatures, but those from C 3 to C 6 only in small yield. A little β -dicarbonyl compound and carboxylic acids were also detected in the products. The modes of formation and decomposition of the peroxides is discussed. It is suggested the dihydroperoxyheptane resulted from the abstraction of a hydrogen atom internally in the C 7 H 15 O 2 radical from the CH 2 group β or γ to the point of original attack, that aldehydes were produced partly by heterogeneous hydroperoxide decomposition and partly by decomposition of RO 2 radicals, and that with n -heptane the aldehyde-hydroperoxide compounds were formed mainly on the walls of the reaction vessel. Chain branching in the oxidation of propane and 2, 2, 3-trimethylbutane was presumably due exclusively to the oxidation of aldehydes formed, whereas with the other three hydrocarbons branching due to homo­geneous peroxide decomposition was probably important up to about 350°C.

The oxidation of toluene and ethylbenzene has been studied in a static system using a spherical reaction vessel (700 ml.) over the temperature range 300 to 500°C, and at total pressures up to 600 mm. Cool flames were observed in the oxidation of both hydrocarbons, but only the reaction of ethylbenzene gave rise to a ‘blue’ flame at higher temperatures. With neither hydrocarbon did periodicity in light intensity, or pressure pulses, occur. The ignition diagrams for 4 to 1 fuel + oxygen mixtures have been mapped out. With ethyl­benzene, the cool flame was maintained in a flow system, its spectrum was photographed and shown to be similar to that of fluorescent formaldehyde. The products of the reaction con­tained acetophenone, benzaldehyde and benzoic acid, phenol, quinol, hydrogen peroxide and methoxyhydroperoxide. The results have been compared with corresponding data for the oxidation of paraffin hydrocarbons, and it is concluded that, with both aromatic compounds, the processes allowing the possibility of cool-flame formation are themselves secondary in nature.


TAPPI Journal ◽  
2012 ◽  
Vol 11 (7) ◽  
pp. 37-46 ◽  
Author(s):  
PEDRO E.G. LOUREIRO ◽  
SANDRINE DUARTE ◽  
DMITRY V. EVTUGUIN ◽  
M. GRAÇA V.S. CARVALHO

This study puts particular emphasis on the role of copper ions in the performance of hydrogen peroxide bleaching (P-stage). Owing to their variable levels across the bleaching line due to washing filtrates, bleaching reagents, and equipment corrosion, these ions can play a major role in hydrogen peroxide decomposition and be detrimental to polysaccharide integrity. In this study, a Cu-contaminated D0(EOP)D1 prebleached pulp was subjected to an acidic washing (A-stage) or chelation (Q-stage) before the alkaline P-stage. The objective was to understand the isolated and combined role of copper ions in peroxide bleaching performance. By applying an experimental design, it was possible to identify the main effects of the pretreatment variables on the extent of metals removal and performance of the P-stage. The acid treatment was unsuccessful in terms of complete copper removal, magnesium preservation, and control of hydrogen peroxide consumption in the following P-stage. Increasing reaction temperature and time of the acidic A-stage improved the brightness stability of the D0(EOP)D1AP bleached pulp. The optimum conditions for chelation pretreatment to maximize the brightness gains obtained in the subsequent P-stage with the lowest peroxide consumption were 0.4% diethylenetriaminepentaacetic acid (DTPA), 80ºC, and 4.5 pH.


TAPPI Journal ◽  
2018 ◽  
Vol 17 (11) ◽  
pp. 601-607
Author(s):  
Alan Rudie ◽  
Peter Hart

The use of 50% concentration and 10% concentration hydrogen peroxide were evaluated for chemical and mechanical pulp bleach plants at storage and at point of use. Several dangerous occurrences have been documented when the supply of 50% peroxide going into the pulping process was not stopped during a process failure. Startup conditions and leaking block valves during maintenance outages have also contributed to explosions. Although hazardous events have occurred, 50% peroxide can be stored safely with proper precautions and engineering controls. For point of use in a chemical bleach plant, it is recommended to dilute the peroxide to 10% prior to application, because risk does not outweigh the benefit. For point of use in a mechanical bleach plant, it is recommended to use 50% peroxide going into a bleach liquor mixing system that includes the other chemicals used to maintain the brightening reaction rate. When 50% peroxide is used, it is critical that proper engineering controls are used to mitigate any risks.


2020 ◽  
Vol 17 (2) ◽  
pp. 172
Author(s):  
HARMAN AGUSAPUTRA ◽  
MARIA SUGENG ◽  
AYLY SOEKAMTO ◽  
ATIK WULANDARI

<p><strong>Abstract</strong></p><p><strong>Background:</strong> Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) as antiseptic has been used frequently to clean woundsin in hospitals and clinics. Hydrogen peroxide has the effectof strong oxidative that can kill pathogens. It can clean up debris and necrotic tissuesin wounds. Hydrogen peroxidealso has hemostatic effect that can help to stop bleeding. Besides antiseptic effects, hydrogen peroxide i s suspected of having negative effect in wound healing. Hydrogen peroxide presumably could cause delayed wound healing by exudate formation and delayed epithelial growth.</p><p><strong>Method</strong>: This study was conducted in the laboratory using 48 white mice that were divided into 2 groups. All the mice were purposely wounded. Afterwards in one group the wounds were clean up using hydrogen peroxide, while in the other group without hydrogen peroxide as control. The wounds of both groups were observed on day 1, day 3 and day 7. On day 1 and day 3, both groups did not show significant difference.</p><p><strong>R</strong><strong>esult</strong> : on day 7 showed that the wound healing in hydrogen peroxide group were delayed. Fifty percent of them had the formation of exudate and 62.5% of them showed delayed epithelial growth.</p><p><strong>Conclusion </strong>: This study could show hydrogen peroxide as wound antiseptic has delayed wound healing effect.</p><p><strong>Keyword</strong>: hydrogen peroxide, wound healing</p>


2018 ◽  
Vol 69 (8) ◽  
pp. 2081-2088 ◽  
Author(s):  
Alin Alexandru Odor ◽  
Edwin Sever Bechir ◽  
Deborah Violant ◽  
Victoria Badea

Moderate and severe periodontitis represents a challenge in the non-surgical periodontal therapy. Due to the lack of evidence regarding the antimicrobial effectiveness of 940 nm diode laser in periodontal treatment, this study aimed to evaluate the antimicrobial effect of hydrogen peroxide (H2O2) photolysis performed with 940 nm diode laser in the treatment of moderate and severe periodontitis. Twenty-five patients with 100 teeth were selected for this pilot study. The test teeth were randomly assigned to one of the four treatment groups: Group 1: scaling and root planning (SRP) (control group); and the following experimental groups: Group 2: H2O2; Group 3: 940 nm diode laser therapy; Group 4: 940 nm diode laser therapy and H2O2. Clinical examinations, like probing depth (PD), clinical attachment level (CAL) and bleeding on probing (BOP) were performed before and after the treatment. The microbiological evaluation, effectuated before and after the treatment, included nine periodontal bacteria species and investigated by means of real-time PCR assay. The clinical and bacterial differences in the tested groups, was assessed between control group and the other three experimental groups, as well as between the experimental groups. The total bacteria load was reduced for all four studied groups. Group 4 (diode laser + H2O2) showed significant bacterial reduction of the major periodontal bacteria like Pg., Tf., Td., Pi., Pm., Fn (p[0.001) than the other 3 groups (p]0.001). Also the periodontal clinical parameters, like PD, CAL and BOP showed a significant reduction after the photolysis of H2O2 with the 940 nm diode laser (p[0.001). Differences between tested groups showed a significant beneficial results in regard to Group 4.It is suggested that the photoactivation of H2O2 with the 940 nm diode laser can be used successfully in adjunctive to the non-surgical periodontal treatment as a bactericidal tool.


1988 ◽  
Vol 53 (8) ◽  
pp. 1636-1646 ◽  
Author(s):  
Viliam Múčka ◽  
Kamil Lang

Some physical and catalytic properties of the two-component copper(II)oxide-chromium(III)oxide catalyst with different content of both components were studied using the decomposition of the aqueous solution of hydrogen peroxide as a testing reaction. It has been found that along to both basic components, the system under study contains also the spinel structure CuCr2O4, chromate washable by water and hexavalent ions of chromium unwashable by water. The soluble chromate is catalytically active. During the first period of the reaction the equilibrium is being established in both homogeneous and heterogeneous catalytic systems. The catalytic activity as well as the specific surface area of the washed solid is a non-monotonous function of its composition. It seems highly probable that the extreme values of both these quantities are not connected with the detected admixtures in the catalytic system. The system under study is very insensitive with regard to the applied doses of gamma radiation. Its catalytic properties are changed rather significantly after the thermal treatment and particularly after the partial reduction to low degree by hydrogen. The observed changes of the catalytic activity of the system under study are very probably in connection with the changes of the valence state of the catalytically active components of the catalyst.


1991 ◽  
Vol 56 (4) ◽  
pp. 923-932
Author(s):  
Jana Stejskalová ◽  
Pavel Stopka ◽  
Zdeněk Pavlíček

The ESR spectra of peroxidase systems of methaemoglobin-ascorbic acid-hydrogen peroxide and methaemoglobin-haptoglobin complex-ascorbic acid-hydrogen peroxide have been measured in the acetate buffer of pH 4.5. For the system with methaemoglobin an asymmetrical signal with g ~ 2 has been observed which is interpreted as the perpendicular region of anisotropic spectrum of superoxide radical. On the other hand, for the system with methaemoglobin-haptoglobin complex the observed signal with g ~ 2 is symmetrical and is interpreted as a signal of delocalized electron. After realization of three repeatedly induced peroxidase processes the ESR signal of the perpendicular part of anisotropic spectrum of superoxide radical is distinctly diminished, whereas the signal of delocalized electron remains practically unchanged. An amino acid analysis of methaemoglobin along with results of the ESR measurements make it possible to derive a hypothesis about the role of haptoglobin in increasing of the peroxidase activity of methaemoglobin.


1990 ◽  
Vol 55 (10) ◽  
pp. 2377-2380
Author(s):  
Hamza A. Hussain

Nitroxide free radicals prepared from diethylamine, piperidine and pyrrolidine by oxidation with hydrogen peroxide were studied by ESR spectroscopy. The changes in the 14N splitting constant (aN) caused by the addition of KBr or tetraethylammonium bromide were measured in dependence on the concentration of the ions. For diethylamine nitroxide and piperidine nitroxide, the results are discussed in terms of two equilibria: the one, involving the anion, is associated with a gain or loss of hydrogen bonds to the nitroxide oxygen atom, the other is associated with the formation of solvent shared units involving the cation, which results in changes in the hydrogen bonding strenght. The large increase in the aN value in the case of pyrrolidine nitroxide is explained in terms of an interaction from one side of the positively charged N atom; the increase in aN in the case of diethylamine and piperidine nitroxides is explained in terms of interactions with both sides of the positively charged N atom.


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