Reaction of Thiourea with Hydrogen Peroxide: 13C NMR Studies of an Oxidative/Reductive Bleaching Process

1992 ◽  
Vol 62 (2) ◽  
pp. 94-100 ◽  
Author(s):  
Mustafa Arifoglu ◽  
William N. Marmer ◽  
Robert L. Dudley
Keyword(s):  
Hydrogen Peroxide ◽  
Redox Potential ◽  
Rapid Change ◽  
Molar Ratio ◽  
Initial Reaction ◽  
Neutral Medium ◽  
Sufficient Data ◽  
Nmr Studies ◽  
Ph Values ◽  
Thiourea Dioxide

Thiourea's reaction with hydrogen peroxide in solution under bleaching conditions at three different pH values has been investigated using 13C NMR spectroscopy. Since this reaction is fast and exothermic, it is essential that short total acquisition times be used to accumulate sufficient data to detect different species formed during the reaction. As the abundance of 13C in the reactants in the concentration range studied is very low, 13C-labeled thiourea was used as the starting material. Sufficient data were accumulated in short acquisition times (2–4 minutes) to identify different species formed during the reaction. The results showed that different intermediate products are formed during the reactions, depending on the pH of the medium and the molar ratio of the reactants. The reaction goes through a thiourea dioxide intermediate; this then hydrolyzes under heat and neutral or alkaline conditions to yield sulfonate anion and urea if the initial reaction of thiourea with hydrogen peroxide is allowed to take place in acidic/neutral medium (pH = 4.0–7.0). Because thiourea dioxide hydrolyzes in solution, there is a rapid change in redox potential from a positive value to a high negative value. The species causing the negative redox potential, and hence the species responsible for reductive bleaching, is believed to be the sulfinate anion. The reaction of thiourea with hydrogen peroxide in hydrochloric acid at pH < 1 results in the formation of formamidine disulfide dihydrochloride, which decomposes at pH values greater than 1.

scholarly journals MODIFICATION OF CHITOSAN BY THIOUREA DIOXIDE

2020 ◽  
Vol 64 (1) ◽  
pp. 73-78
Author(s):  
Ekaterina V. Naidenko ◽  
Sergei V. Makarov ◽  
Elizaveta A. Pokrovskaya ◽  
Anton M. Nikulin
Keyword(s):  
Hydrogen Peroxide ◽  
Ir Spectroscopy ◽  
Aqueous Solutions ◽  
Protonated Form ◽  
Oxidative Modification ◽  
Molar Ratio ◽  
Partial Substitution ◽  
Thiourea Dioxide ◽  
Substitution Degree ◽  
Carboxylic Groups

Thiourea dioxide (TDO, aminoiminomethanesulfinic acid, formamidinesulfinic acid) was used for the chemical modification of chitosan. The interaction of TDO with chitosan in the presence of alkali results in the guanidinylated chitosan, the substitution degree is 0.25-0.27 and does not depend largely on molar ratio of thiourea dioxide to chitosan. The structure of modified chitosan has been proved using UV and IR spectroscopy as well as elemental analysis. It is shown that modification of chitosan proceeds under mild conditions. Contrary to chitosan, its guanidinylated derivative has biocidal properties against Gram-positive and Gram-negative bacteria in the aqueous solutions close to neutral (pH 6.2). It can be explained by the partial substitution of amino groups by guanidine groups existing predominantly in the protonated form in the neutral aqueous solutions. The system thiourea dioxide-hydrogen peroxide was used for the oxidative modification of chitosan. It is shown that thiourea dioxide and hydrogen peroxide separately do not oxidize chitosan but in the presence of their mixture the formation of carboxylic groups in chitosan has been observed. The quantity of carboxylic groups in the modified and native chitosan has been determined by the titration with sodium hydroxide. The presence of carboxylic groups has been proved also using IR spectroscopy. It is shown that the quantity of carboxylic groups increases with the increase of the ratio [TDO]/[chitosan].

Photocatalytic Clearing of Disperse Dyed Polyester

2019 ◽  
Vol 6 (5) ◽  
pp. 10-15 ◽  
Author(s):  
Semiha Eren
Keyword(s):  
Hydrogen Peroxide ◽  
Uv Irradiation ◽  
Room Temperature ◽  
Color Difference ◽  
Polyester Fabric ◽  
Disperse Dyes ◽  
Wash Fastness ◽  
Ph Values ◽  
Thiourea Dioxide ◽  
Color Differences

Trials were conducted to examine the efficiency of photocatalytic afterclearing on disperse dyed polyester. The photocatalytic afterclearing was performed by ultraviolet (UV) irradiation and hydrogen peroxide (H2O2). Polyester fabric samples were dyed with three disperse dyes at 4% depth of shade, individually. The control afterclearing treatment was a conventional reductive clearing by thiourea dioxide and caustic soda. The H2O2 impregnated samples, using various concentrations of H2O2 at various pH values, were treated under 254 nm UV irradiation (5, 10, 20, and 30 min) at room temperature. Color, color difference, wash fastness, and tensile strength values of the samples were compared. Photocatalytic clearing of disperse dyed polyester was successful in giving comparable wash fastness results as compared to conventional reduction clearing without significant color differences.

scholarly journals Promising Immobilization of Industrial-Class Phospholipase A1 to Attain High-Yield Phospholipids Hydrolysis and Repeated Use with Optimal Water Content in Water-in-Oil Microemulsion Phase

2021 ◽  
Vol 11 (4) ◽  
pp. 1456
Author(s):  
Yusuke Hayakawa ◽  
Ryoichi Nakayama ◽  
Norikazu Namiki ◽  
Masanao Imai
Keyword(s):  
Water Content ◽  
Reaction Rate ◽  
Enzyme Reaction ◽  
Initial Reaction Rate ◽  
Industrial Applications ◽  
Molar Ratio ◽  
High Yield ◽  
Initial Reaction ◽  
Phospholipase A1 ◽  
Repeated Use

In this study, we maximized the reactivity of phospholipids hydrolysis with immobilized industrial-class phospholipase A1 (PLA1) at the desired water content in the water-in-oil (W/O) microemulsion phase. The optimal hydrophobic-hydrophilic condition of the reaction media in a hydrophobic enzyme reaction is critical to realize the maximum yields of enzyme activity of phospholipase A1. It was attributed to enzymes disliking hydrophobic surroundings as a special molecular structure for reactivity. Immobilization of PLA1 was successfully achieved with the aid of a hydrophobic carrier (Accurel MP100) combination with the treatment using glutaraldehyde. The immobilized yield was over 90% based on simple adsorption. The hydrolysis reaction was kinetically investigated through the effect of glutaraldehyde treatment of carrier and water content in the W/O microemulsion phase. The initial reaction rate increased linearly with an increasing glutaraldehyde concentration and then leveled off over a 6% glutaraldehyde concentration. The initial reaction rate, which was predominantly driven by the water content in the organic phase, changed according to a typical bell-shaped curve with respect to the molar ratio of water to phospholipid. It behaved in a similar way with different glutaraldehyde concentrations. After 10 cycles of repeated use, the reactivity was well sustained at 40% of the initial reaction rate and the creation of the final product. Accumulated yield after 10 times repetition was sufficient for industrial applications. Immobilized PLA1 has demonstrated potential as a biocatalyst for the production of phospholipid biochemicals.

scholarly journals Photocatalytic Treatment of Wastewater Containing Simultaneous Organic and Inorganic Pollution: Competition and Operating Parameters Effects

Catalysts ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 855
Author(s):  
Ahmed Amine Azzaz ◽  
Salah Jellali ◽  
Nasser Ben Harharah Hamed ◽  
Atef El Jery ◽  
Lotfi Khezami ◽  
...  
Keyword(s):  
Ultra Violet ◽  
Degradation Process ◽  
Molar Ratio ◽  
Experimental Conditions ◽  
Retention Capacity ◽  
Isotherm Study ◽  
Related Data ◽  
Ph Values ◽  
Pseudo Second Order ◽  
Maximum Retention

In the present study, methylene blue (MB) removal from aqueous solutions via the photocatalytic process using TiO2 as a catalyst in the presence of external ultra-violet light (UV) was investigated. The results of adsorption in the absence of UV radiation showed that adsorption reached an equilibrium state at 60 min. The experimental kinetic data were found to be well fitted by the pseudo-second-order model. Furthermore, the isotherm study suggested that dye uptake by TiO2 is a chemisorption process with a maximum retention capacity of 34.0 mg/g. The photodegradation of MB was then assessed under various experimental conditions. The related data showed that dye mineralization decreased when dye concentrations were increased and was favored at high pH values and low salt concentrations. The simultaneous presence of organic and inorganic pollution (Zinc) was also evaluated. The effect of the molar ratio Zn2+/MB+ in the solution at different pH values and NaCl concentrations was also monitored. The corresponding experimental results showed that at low values of Zn2+ in the solution (30 mg/L), the kinetic of the MB removal became faster until reaching an optimum at Zn2+/MB+ concentrations of 60/60 mg/L; it then slowed down for higher concentrations. The solutions’ carbon contents were measured during the degradation process and showed total mineralization after about 5 h for the optimal Zn2+/MB+ condition.

scholarly journals The utilization of the mesoporous Ti-SBA-15 catalyst in the epoxidation of allyl alcohol to glycidol and diglycidyl ether in the water medium

2015 ◽  
Vol 17 (4) ◽  
pp. 23-31 ◽  
Author(s):  
Agnieszka Wróblewska ◽  
Edyta Makuch ◽  
Małgorzata Dzięcioł ◽  
Roman Jędrzejewski ◽  
Paweł Kochmański ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Reaction Time ◽  
Allyl Alcohol ◽  
Water Solution ◽  
Reaction Medium ◽  
Diglycidyl Ether ◽  
Molar Ratio ◽  
Water Medium ◽  
Catalyst Content ◽  
Allyl Alcohol Epoxidation

Abstract This work presents the studies on the optimization the process of allyl alcohol epoxidation over the Ti-SBA-15 catalyst. The optimization was carried out in an aqueous medium, wherein water was introduced into the reaction medium with an oxidizing agent (30 wt% aqueous solution of hydrogen peroxide) and it was formed in the reaction medium during the processes. The main investigated technological parameters were: the temperature, the molar ratio of allyl alcohol/hydrogen peroxide, the catalyst content and the reaction time. The main functions the process were: the selectivity of transformation to glycidol in relation to allyl alcohol consumed, the selectivity of transformation to diglycidyl ether in relation to allyl alcohol consumed, the conversion of allyl alcohol and the selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The analysis of the layer drawings showed that in water solution it is best to conduct allyl alcohol epoxidation in direction of glycidol (selectivity of glycidol 54 mol%) at: the temperature of 10–17°C, the molar ratio of reactants 0.5–1.9, the catalyst content 2.9–4.0 wt%, the reaction time 2.7–3.0 h and in direction of diglycidyl ether (selectivity of diglycidyl ether 16 mol%) at: the temperature of 18–33°C, the molar ratio of reactants 0.9–1.65, the catalyst content 2.0–3.4 wt%, the reaction time 1.7–2.6 h. The presented method allows to obtain two very valuable intermediates for the organic industry.

scholarly journals Aferição do pH de diferentes agentes clareadores indicados para o clareamento intracoronário

2018 ◽  
Author(s):  
João Felipe Besegato ◽  
Gabriela Dos Santos Ribeiro Rocha ◽  
Marlene De Sousa Amorim ◽  
Fabio Martins Salomão ◽  
Daniel Poletto ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Statistical Analysis ◽  
Multiple Comparisons ◽  
The Other ◽  
Sodium Perborate ◽  
Distilled Water ◽  
Friedman Test ◽  
Time Intervals ◽  
Ph Values ◽  
Evaluation Time

Objective: to measure pH values of bleaching agents that are indicated to intracoronal bleaching technique in different time intervals. Methods: Each group (G) received five samples (n=5): G1 – distilled water (AD); G2 – hydrogen peroxide (H2O2) 30%; G3 – sodium perborate (PbS) + AD; G4 – PbS + H2O2 30%; G5 – sodium percarbonate (PcS) + AD; and G6 – PcS + H2O2 30%. pH values were stated using a digital pHmeter, in different time intervals: immediately after handling (T0), 24 hours (T1) and 168 hours after handling (T2). The results were submitted to statistical analysis through Kruskal-Wallis and Mann Whitney tests, in this order, allowing multiple comparisons among the groups. To verify the effect of time in each group, Friedman test was applied. Results: In the evaluation of the effect of time in each group, it was observed that G2 presented acid behavior, while the other groups exhibited values close to neutrality or alkaline. Conclusions: H2O2 30% was the only agent that showed acidic behavior in every evaluation time. Meanwhile, PcS + H2O had the highest pH values.

scholarly journals A facile and effective method for preparation of 2.5-furandicarboxylic acid via hydrogen peroxide direct oxidation of 5-hydroxymethylfurfural

2017 ◽  
Vol 19 (1) ◽  
pp. 11-16 ◽  
Author(s):  
Shuang Zhang ◽  
Long Zhang
Keyword(s):  
Hydrogen Peroxide ◽  
Reaction Time ◽  
Oxidation Mechanism ◽  
Molar Ratio ◽  
Alkaline Condition ◽  
Optimal Parameters ◽  
Direct Oxidation ◽  
Reaction Parameters ◽  
Alkaline Conditions ◽  
Furandicarboxylic Acid

Abstract In this paper, 2,5-furandicarboxylic acid (FDCA) was efficiently prepared by the direct oxidation of 5-hydroxymethylfurfural (5-HMF) using hydrogen peroxide (H2O2) in alkaline conditions without any catalysts. The effects of reaction parameters on the process were systematically investigated and the optimal parameters were obtained as follows: molar ratio of 5-HMF:KOH:H2O2 was 1:4:8, reaction temperature and reaction time were determined as 70°C and 15 minutes, respectively. Under these conditions, the yield of FDCA was 55.6% and the purity of FDCA could reach 99%. Moreover, we have speculated the detailed oxidation mechanism of 5-HMF assisted by hydrogen peroxide in alkaline condition to synthesize FDCA.

scholarly journals The effect of dissolved organic carbon on pelagial and near-sediment water traits in lakes

2011 ◽  
Vol 74 (2) ◽  
pp. 133-139 ◽  
Author(s):  
Krzysztof Banaś
Keyword(s):  
Organic Carbon ◽  
Dissolved Organic Carbon ◽  
Redox Potential ◽  
Environmental Conditions ◽  
Calcium Concentration ◽  
Total Hardness ◽  
Sediment Layer ◽  
Ph Values ◽  
Doc Concentration ◽  
Good Transparency

The effect of dissolved organic carbon (DOC) on the environmental conditions of macrophytes has been studied in 35 lakes divided into soft- and hardwater: oligohumic (&lt;4.0 mg C dm<sup>-3</sup>), α-mesohumic (4.0-8.0 mg C dm<sup>-3</sup>), β-mesohumic (8.1-16.0 mg C dm<sup>-3</sup>) and polihumic (&gt;16.0 mg C dm<sup>-3</sup>). The optimum environmental conditions for macrophytes have been found in oligohumic lakes, characterised by low water colour and its good transparency. In soft- and hardwater lakes increasing concentration of DOC is accompanied with an increase in the colour (r=0.95), while the visibility decreases. With increasing DOC in the near-sediment layer the pH values decrease while the concentration of nitrogen increases and the concentration of phosphorus slightly increases. In hardwater lakes with increasing DOC concentration, the redox potential, conductivity, total hardness and calcium concentration in the near-sediment water decrease, whereas the content of CO<sup>2</sup> remains at a very low level.

scholarly journals Bactericidal effect of hydrogen peroxide is prevented by the lactoperoxidase-thiocyanate system under anaerobic conditions

1980 ◽  
Vol 29 (3) ◽  
pp. 1190-1192
Author(s):  
J Carlsson
Keyword(s):  
Hydrogen Peroxide ◽  
Bactericidal Effect ◽  
Molar Ratio ◽  
Anaerobic Conditions ◽  
Streptococcus Sanguis

Streptococcus sanguis and Peptostreptococcus anaerobius were exposed to various combinations of the components of the lactoperoxidase-thiocyanate-hydrogen peroxide system. The bactericidal effect of hydrogen peroxide was prevented under anaerobic conditions by lactoperoxidase together with thiocyanate, but not by lactoperoxidase or thiocyanate alone. Thiocyanate was effective already at a molar ratio to hydrogen peroxide of 1:100.

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