The heats of dissociation of chlorine monoxide and chlorine dioxide

1931 ◽  
Vol 27 ◽  
pp. 648 ◽  
Author(s):  
Janet I. Wallace ◽  
C. F. Goodeve
Keyword(s):  
Chlorine Dioxide ◽  
Chlorine Monoxide

The flash photolysis of chlorine monoxide

1957 ◽  
Vol 243 (1232) ◽  
pp. 24-32 ◽  
Keyword(s):  
Chlorine Dioxide ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Reaction Scheme ◽  
Inert Gas ◽  
Short Chain ◽  
Large Excess ◽  
Straight Chain ◽  
Chain Reaction ◽  
Chlorine Monoxide

The flash photolysis of chlorine monoxide in a large excess of inert gas yields chlorine and oxygen, the normal products of photolysis, accompanied by measurable quantities of the ClO radical as an intermediate. The normal and chlorine-sensitized decompositions of chlorine monoxide are studied and a reaction scheme is proposed for the system which has the character of a short-chain reaction with CIO and CI acting as chain carriers. By a study of the decay of the CIO radical and the formation of chlorine dioxide, rate constants are derived for the CIO decay, the production of chlorine dioxide and the straight-chain decomposition of chlorine monoxide by the CIO radical.

THE PHOTODECOMPOSITION OF CHLORINE DIOXIDE IN CARBON TETRACHLORIDE SOLUTION

1937 ◽  
Vol 15b (12) ◽  
pp. 499-524 ◽  
Author(s):  
J. W. T. Spinks ◽  
H. Taube
Keyword(s):  
Thermal Decomposition ◽  
Carbon Tetrachloride ◽  
Quantum Yield ◽  
Light Intensity ◽  
Quantum Efficiency ◽  
Chlorine Dioxide ◽  
Concentration Effects ◽  
Low Light ◽  
Carbon Tetrachloride Solution ◽  
Chlorine Monoxide

Insolation of carbon tetrachloride solutions of chlorine dioxide initiates a thermal decomposition, the magnitude of which may exceed that for the photoreaction with low light intensity. This thermal decomposition is inhibited by keeping the solutions at 3 °C. or by adding water.In contradiction to the findings of other investigators, it is found that chlorine and oxygen are not the only products of photodecomposition. As products of the photodecomposition of chlorine dioxide at the wave-lengths 3650 and 4360 Å, the oxides Cl2O, Cl2O6, and Cl2O7 as well as chlorine and oxygen appear. The quantum efficiency at λ 3650 Å is 2, and at 4360 Å, 1.In the unsensitized decomposition, concentration effects are observed which are greatly decreased when the solutions are stirred.In the bromine sensitized decomposition with 5460 Å, there is less chlorine monoxide but relatively as much Cl2O6 and Cl2O7 formed as in the unsensitized reaction.In the sensitized decomposition the quantum yield is independent of the concentration of chlorine dioxide, but depends on the light intensity. The observed quantum yield for the sensitized reaction is 0.2 to 0.3.Mechanisms for the photo-reactions have been proposed.

Photolysis of Chlorine Dioxide and Absolute Rates of Chlorine Monoxide Reactions

Nature ◽  
1954 ◽  
Vol 174 (4434) ◽  
pp. 785-786 ◽  
Author(s):  
F. J. LIPSCOMB ◽  
R. G. W. NORRISH ◽  
G. PORTER
Keyword(s):  
Chlorine Dioxide ◽  
Chlorine Monoxide

Reactions of halogen oxides studied by flash photolysis. I. The flash photolysis of chlorine dioxide

1971 ◽  
Vol 323 (1552) ◽  
pp. 29-68 ◽  
Keyword(s):  
Chlorine Dioxide ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Vibrationally Excited ◽  
Extinction Coefficients ◽  
Chlorine Monoxide ◽  
Vibrational Levels ◽  
Halogen Oxides ◽  
Excited Oxygen

The production and decay of the CIO radical and of vibrationally excited oxygen following the isothermal flash photolysis of chlorine dioxide has been studied. From their dependence on flash energy and from the effects of added chlorine, oxygen and chlorine monoxide on the system, the following mechanism and rate constants are proposed: CIO 2 + hv → CIO + O 2CIO → CI 2 + O 2 K 1 = 2.7 x 10 7 l mol -1 s -1 O + CIO 2 → CIO + O 2 * ( v " ≼ 15) k 3 = 3.0 x 10 10 l mol -1 s -1 O + CIO → CI + O 2 * ( v " ≼ 14) k 4 = 7.0 x 10 9 l mol -1 s -1 CIO (CIO 2 ) + O 2 * ( v " = n ) → CIO (CIO 2 ) + O 2 * ( v " < n ) k 10 ( v " = 12) = 2 x 10 8 l mol -1 s -1 CI + O 2 * ( v " = n ) → CI + O 2 * ( v " < n ) k 11 ( v " = 12) = 7 x 10 9 l mol -1 s -1 O + O 2 * ( v " = n ) → O + O 2 * ( v " < n ) k 12 ( v " = 12) = 2 x 10 10 l mol -1 s -1 O + Cl 2 O → 2CIO k 6 = 5.2 x 10 9 l mol -1 s -1 The rate constants k 10 , k 11 and k 12 for O 2 * (v" = 6) and the relative values of k 3 for various vibrational levels have also been measured. Studies of the flash photolysis of mixtures of chlo­rine monoxide and chlorine dioxide and of chlorine and oxygen have yielded values of k 1 in agreement with that given above. The extinction coefficients of the CIO radical at 257.7, 277.2 and 292 nm were found to be 1150, 1700 and 1050 l mol -1 cm -1 respectively.

THE BROMINE-SENSITIZED DECOMPOSITION OF CHLORINE MONOXIDE IN GREEN LIGHT

1937 ◽  
Vol 15b (3) ◽  
pp. 113-123 ◽  
Author(s):  
A. G. Brown ◽  
J. W. T. Spinks
Keyword(s):  
Quantum Yield ◽  
Chlorine Dioxide ◽  
Wave Length ◽  
Green Light ◽  
Dark Reaction ◽  
Chlorine Monoxide

Chlorine monoxide undergoes a bromine-sensitized decomposition in light of wave-length 5460 A. The reaction involves short chains and is accompanied by an appreciable dark reaction. The quantum yield is 4.3 at 19 °C. A decrease in pressure occurring near the end of the reaction has been shown to be a photochemical effect, and it is due probably to the bromine-sensitized decomposition of chlorine dioxide formed during the combined light and dark reactions.A mechanism similar to that described by Finkelnburg, Schumacher and Stieger for the unsensitized reaction appears to account for most of the observations.

Elemental chlorine-free bleaching of North American hardwood kraft pulps: Evaluation of oxidant-reinforced extraction variables on overall bleaching optimization

TAPPI Journal ◽  
2013 ◽  
Vol 12 (10) ◽  
pp. 33-41 ◽  
Author(s):  
BRIAN N. BROGDON
Keyword(s):  
Response Surface ◽  
Chlorine Dioxide ◽  
North American ◽  
Yield Loss ◽  
Alkaline Extraction ◽  
Kraft Pulps ◽  
Pulp Bleaching ◽  
Response Surface Models ◽  
Elemental Chlorine ◽  
Surface Models

This investigation evaluates how higher reaction temperatures or oxidant reinforcement of caustic extraction affects chlorine dioxide consumption during elemental chlorine-free bleaching of North American hardwood pulps. Bleaching data from the published literature were used to develop statistical response surface models for chlorine dioxide delignification and brightening sequences for a variety of hardwood pulps. The effects of higher (EO) temperature and of peroxide reinforcement were estimated from observations reported in the literature. The addition of peroxide to an (EO) stage roughly displaces 0.6 to 1.2 kg chlorine dioxide per kilogram peroxide used in elemental chlorine-free (ECF) bleach sequences. Increasing the (EO) temperature by Δ20°C (e.g., 70°C to 90°C) lowers the overall chlorine dioxide demand by 0.4 to 1.5 kg. Unlike what is observed for ECF softwood bleaching, the presented findings suggest that hot oxidant-reinforced extraction stages result in somewhat higher bleaching costs when compared to milder alkaline extraction stages for hardwoods. The substitution of an (EOP) in place of (EO) resulted in small changes to the overall bleaching cost. The models employed in this study did not take into account pulp bleaching shrinkage (yield loss), to simplify the calculations.

Application of pure, thermostable, alkali-tolerant xylanase in bleaching of oxygen-delignified pine kraft pulp

TAPPI Journal ◽  
2015 ◽  
Vol 14 (11) ◽  
pp. 689-694
Author(s):  
QINGZHI MA ◽  
QI WANG ◽  
CHU WANG ◽  
NIANJIE FENG ◽  
HUAMIN ZHAI
Keyword(s):  
Intrinsic Viscosity ◽  
Chlorine Dioxide ◽  
High Purity ◽  
Kraft Pulp ◽  
Alkaline Media ◽  
Industrial Scale ◽  
Elemental Chlorine ◽  
Effect Of Oxygen ◽  
Alkaline Tolerant ◽  
Ecf Bleaching

The effect of oxygen (O2)-delignified pine kraft pulp pretreatment by high-purity, thermostable, and alkaline-tolerant xylanases on elemental chlorine free (ECF) bleaching of O2-delignification kraft pulp was studied. The study found that xylanase pretreatment preserved the intrinsic viscosity and yield of O2-delignified pulp while causing about 7% of delignification with high delignification selectivity. The xylanases with high purity, higher thermostability (75°C~80°C) in highly alkaline media (pH 8.0~9.5) could be applied on an industrial scale. Pulp pretreatment by the high-purity, thermostable, and alkaline tolerant xylanases could improve pulp brightness or reduce the chlorine dioxide (ClO2) consumption. In a D0ED1D2 bleaching sequence using the same amount of ClO2, the xylanase-pretreated pulp obtained a higher brightness (88.2% vs. 89.7% ISO) at the enzyme dose of 2 U/g pulp; or for the same brightness as control (88.2% ISO), the ClO2 dosage in the D0 stage was reduced by 27%, which represents a 16% savings in total ClO2 used for bleaching.

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