Photodegradation Rate Constants for Anthracene and Pyrene Are Similar in/on Ice and in Aqueous Solution

2018 ◽  
Vol 52 (21) ◽  
pp. 12225-12234 ◽  
Author(s):  
Ted Hullar ◽  
Danielle Magadia ◽  
Cort Anastasio
Keyword(s):  
Aqueous Solution ◽  
Rate Constants ◽  
Photodegradation Rate

scholarly journals Photodecay of guaiacol is faster in ice, and even more rapid on ice, than in aqueous solution

2020 ◽  
Vol 22 (8) ◽  
pp. 1666-1677
Author(s):  
Ted Hullar ◽  
Fernanda C. Bononi ◽  
Zekun Chen ◽  
Danielle Magadia ◽  
Oliver Palmer ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Rate Constants ◽  
Photodegradation Rate ◽  
Frozen Solutions

Guaiacol photodegradation rate constants in solution, liquid-like regions in ice (frozen solutions), and at the air–ice interface (vapor-deposited to snow).

scholarly journals Enhanced photodegradation of dimethoxybenzene isomers in/on ice compared to in aqueous solution

2021 ◽  
Author(s):  
Ted Hullar ◽  
Theo Tran ◽  
Zekun Chen ◽  
Fernanda Bononi ◽  
Oliver Palmer ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Rate Constants ◽  
Light Absorption ◽  
Inorganic Compounds ◽  
Photochemical Reactions ◽  
Quantum Yields ◽  
Experimental Conditions ◽  
Substantial Impact ◽  
Photodegradation Rate ◽  
The Impact

Abstract. Photochemical reactions of contaminants in snow and ice can be important sources and sinks for various organic and inorganic compounds. Snow contaminants can be found in the bulk ice matrix, in internal liquid-like regions (LLRs), or in quasi-liquid layers (QLLs) at the air-ice interface, where they can readily exchange with the firn air. Some studies have reported that direct photochemical reactions occur faster in LLRs and QLLs than in aqueous solution, while others have found similar rates. Here, we measure the photodegradation rate constants of the three dimethoxybenzene isomers under varying experimental conditions, including in aqueous solution, in LLRs, and at the air-ice interface of nature-identical snow. Relative to aqueous solution, we find modest photodegradation enhancements (3- and 6-fold) in LLRs for two of the isomers, and larger enhancements (15- to 30-fold) at the air-ice interface for all three isomers. We use computational modeling to assess the impact of light absorbance changes on photodegradation rate enhancements at the interface. We find small (2–5 nm) bathochromic (red) absorbance shifts at the interface relative to in solution, which increases light absorption, but this factor only accounts for less than 50 % of the measured rate constant enhancements. The major factor responsible for photodegradation rate enhancements at the air-ice interface appears to be more efficient photodecay: estimated dimethoxybenzene quantum yields are 6- to 24-fold larger at the interface compared to in aqueous solution and account for the majority (51–96 %) of the observed enhancements. Using a hypothetical model compound with an assumed Gaussian-shaped absorbance peak, we find that a shift in the peak to higher or lower wavelengths can have a minor to substantial impact on photodecay rate constants, depending on the original location of the peak and the magnitude of the shift. Changes in other peak properties at the air-ice interface, such as peak width and height (i.e., molar absorptivity) can also impact rates of light absorption and direct photodecay.

Ferricyanide Oxidation of Butanol Homogeneously Catalysed by Chlororuthenium Complexes

1979 ◽  
Vol 32 (9) ◽  
pp. 1905 ◽  
Author(s):  
AF Godfrey ◽  
JK Beattie
Keyword(s):  
Aqueous Solution ◽  
Complex Formation ◽  
Linear Dependence ◽  
Rate Constants ◽  
Homogeneous Catalyst ◽  
Basic Solution ◽  
Rate Law ◽  
Kinetics Of ◽  
Solution Estimates ◽  
Butanol Concentration

The oxidation of butan-1-ol by ferricyanide ion in alkaline aqueous solution is catalysed by solutions of ruthenium trichloride hydrate. The kinetics of the reaction has been reinvestigated and the data are consistent with the rate law -d[FeIII]/dt = [Ru](2k1k2 [BuOH] [FeIII])/(2k1 [BuOH]+k2 [FeIII]) This rate law is interpreted by a mechanism involving oxidation of butanol by the catalyst (k1) followed by reoxidation of the catalyst by ferricyanide (k2). The non-linear dependence of the rate on the butanol concentration is ascribed to the rate-determining, butanol-independent reoxidation of the catalyst, rather than to the saturation of complex formation between butanol and the catalyst as previously claimed. Absolute values of the rate constants could not be determined, because some of the ruthenium precipitates from basic solution. With K3RuCl6 as the source of a homogeneous catalyst solution, estimates were obtained at 30�0�C of k1 = 191. mol-1 s-1 and k2 = 1�4 × 103 l. mol-1 s-1.

Photodegradation of New Methylene Blue N in Aqueous Solution Using Zinc Oxide and Titanium Dioxide as Catalyst

2012 ◽  
Author(s):  
Rusmidah Ali ◽  
Boon Siew Ooi
Keyword(s):  
Aqueous Solution ◽  
Methylene Blue ◽  
Zinc Oxide ◽  
Titanium Dioxide ◽  
Optimum Condition ◽  
Metal Ion ◽  
Optimum Ratio ◽  
Photodegradation Rate ◽  
Uv Visible ◽  
Uv Lamp

Dalam kajian ini, ZnO dan TiO2 digunakan sebagai fotomangkin dalam pendegradasian pewarna New Methylene Blue N (NMBN). Kadar fotodegradasi diukur menggunakan alat spektrofotometer UV-Vis. Dalam kajian ini, New Methylene Blue N menunjukkan nilai serapan pada λ = 590 nm dan λ = 286 nm. Lampu UV (λ = 354 nm) digunakan dalam proses fotodegradasi. Dalam proses degradasi menggunakan ZnO menunjukkan 81.42% NMBN terdegradasi pada λ = 590 nm dan 77.75% pada λ = 286 nm. Sebaliknya, degradasi menggunakan TiO2 adalah 25.68% pada λ = 590 nm dan 26.37% pada λ = 286 nm. Peratus degradasi New Methylene Blue N ialah 88.89% dan 68.94% pada masing-masing λ = 590 nm dan λ = 286 nm apabila ditambahkan dengan H2O2. Campuran ZnO dan TiO2 dalam nisbah 85: 15 (0.085 g; 0.015 g) merupakan campuran fotomangkin yang paling optimum iaitu dengan peratus degradasi NMBN sebanyak 96.97% dan 93.61% pada λ = 590 nm dan λ = 286 nm. Penambahan ion logam Cu2+ memberikan peratus degradasi tertinggi berbanding ion logam lain iaitu 83.83% pada λ = 590 nm. Penambahan ion logam Pb2+ memberikan peratus degradasi tertinggi pada λ = 286 nm iaitu 81.25% pewarna terdegradasi. Keadaan optimum dicapai pada pH 5.90, dengan peratus degradasi tertinggi iaitu 92.84% dan 89.30% pada masing-masing λ = 590 nm dan λ = 286 nm. Kata kunci: New Methylene Blue N; fotodegradasi; larutan; ZnO; TiO2 In this study, ZnO and TiO2 are used as photocatalyst to degrade the dye, New Methylene Blue N (NMBN). The photodegradation rate was measured using UV-Visible spectrophotometer. In this study, New Methylene Blue N showed absorption values at λ = 590 nm and λ = 286 nm. UV lamp (λ = 354 nm) is used in the photodegradation process. Results showed that ZnO is a better photocatalyst compared to TiO2. The degradation by ZnO showed that 81% of NMBN was degraded at λ = 590 nm and 77.75% at λ = 286 nm. In contratst, the degradation using TiO2 was 25.68% at λ = 590 nm and 26.37% at λ = 286 nm. The percent degradation of New Methylene Blue N is 88.89% and 68.94% at λ = 590 nm and λ = 286 nm respectively when H2O2 was added. A mixture of ZnO and TiO2 in the ratio of 85: 15 (0.085 g: 0.015 g) is the most optimum ratio for the mixed photocatalyst where the degradation percentage of NMBN are 96.97% and 93.61% at λ = 590 nm and λ = 286 nm. The addition of Cu2+ metal ion gave the highest percentage of degradation (83.83% at λ = 590 nm) compared to other metal ions. The addition of Pb2+ gave the highest percentage of degradation at λ = 286 nm with 81.25% degradation of the dye. The optimum condition was achieved at pH 5.90, which gave the highest percentage degradation, 92.84% and 89.30% at λ = 590 nm and λ = 286 nm respectively. Key words: New Methylene Blue N; photodegradation; aqueous; ZnO; TiO2

scholarly journals Kinetic and Thermodynamic Studies of Chromium (VI) Sorption by Pure and Carbonized Fluted Pumpkin waste biomass (Telfairia occidentalis Hook F.)

2012 ◽  
Vol 27 ◽  
pp. 11-18
Author(s):  
Timi Tarawou ◽  
Michael Horsfall
Keyword(s):  
Aqueous Solution ◽  
Rate Constants ◽  
Industrial Effluents ◽  
Second Order ◽  
Order Kinetic ◽  
Waste Biomass ◽  
Fluted Pumpkin ◽  
Chromium Vi ◽  
Telfairia Occidentalis ◽  
Pseudo Second Order

The adsorption of chromium (VI) ions from aqueous solution was studied using pure and carbonized fluted pumpkin waste biomass (FPWB). The kinetic data shows a pseudo-first-order mechanism with rate constants of 1.26 × 10-2 and 1.933 × 10-2 mg g-1 min-1 for the pure and carbonized FPWB, respectively. While the pseudo-second-order mechanism has rate constants of 0.93 × 10-1 and 1.33 × 10-1 mg g-1 min-1 for the pure and carbonized waste biomass respectively. The pseudo-second order kinetic model was found to be more suitable for describing the experimental data based on the correlation coefficient values (R2) of 0.9975 and 0.9994 obtained for pure waste biomass (PWB) and carbonized waste biomass (CWB), respectively. The results obtained from this study show that PWB and CWB have very high removal capacity for chromium (VI) from aqueous solution over a range of reaction conditions. Thus, fluted pumpkin waste biomass (Telfairia occidentalis Hook F) is a potential sorbent for the treatment of industrial effluents containing chromium (VI) contaminant.DOI: http://dx.doi.org/10.3126/jncs.v27i1.6436 J. Nepal Chem. Soc., Vol. 27, 2011 11-18Uploaded date: 16 July, 2012

An efficient and eco-friendly method for the thiol-Michael addition in aqueous solutions using amino acid ionic liquids (AAILs) as organocatalysts

2020 ◽  
Vol 92 (1) ◽  
pp. 97-106
Author(s):  
Roberto Figueroa Guíñez ◽  
José G. Santos ◽  
Ricardo A. Tapia ◽  
Jackson J. Alcazar ◽  
Margarita E. Aliaga ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Ionic Liquids ◽  
Amino Acid ◽  
Efficient Method ◽  
Michael Addition ◽  
Rate Constants ◽  
Michael Reaction ◽  
High Rate ◽  
Reusable Catalyst ◽  
Reaction Conditions

AbstractA series of amino-acid based ionic liquids (Bmim[AA]s) have been synthesized and evaluated as catalysts, in aqueous solution. The results of a kinetic study of the thiol-Michael reaction of L-Cysteine with trans-β-nitrostyrene demonstrated the advantages of using (Bmim[AA]s) as organocatalysts. The benefits include high rate constants; mild reaction conditions; and, a reusable catalyst, which leads to a simple and efficient method for these important kinds of reactions.

Studies of radiation-induced reactions of ethylene in aqueous solution II. Reactions in the presence of oxygen as studied by pulse radiolysis and γ -irradiation techniques

1967 ◽  
Vol 300 (1463) ◽  
pp. 443-454 ◽  
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Rate Constants ◽  
Pulse Radiolysis ◽  
Major Product ◽  
Peroxy Radicals ◽  
Ferrous Ions ◽  
Constant Composition ◽  
Γ Irradiation ◽  
Radiation Induced

The radiolysis of dilute aqueous solutions containing ethylene and oxygen has been investigated. Pulse radiolysis was used to measure the rate constants for the addition of hydroxyl radicals to ethylene, the binary decomposition of the resulting hydroxyethyl radicals and their addition to ethylene and reaction with oxygen to yield peroxy radicals. The rate constants have also been determined for the mutual interaction of the peroxy radicals and their reaction with ferrous ions. The principal products of γ -irradiation were aldehydes and organic hydroperoxides. Hydrogen peroxide was found in yields close to the molecular yield from water. The polymer produced in the absence of oxygen was not formed, and glycollaldehyde, reported as a major product by previous workers, could not be detected. At constant composition of the gas mixtures, product yields were unaffected by total pressure in the range up to 40 atm, but were strongly dependent on the proportion of oxygen. Aldehyde yields were markedly greater at pH 1.2 than in neutral solution. The influence of ferrous ions an d of added hydrogen peroxide has been determined. The pulse radiolysis and γ -irradiation experiments complement one another and show that the radiation-induced oxidation of ethylene in aqueous solution involves the same primary reactions as occur in the absence of oxygen, followed by the formation and further reactions of peroxy radicals.

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