The Photokinetics of Electron Transfer Reaction of Methylene Blue with Titanium Trichloride in Aqueous–Alcoholic Solvents

Nadeem, Syed Muhammad Saqib; Saeed, Rehana

doi:10.1002/jccs.201700112

Cited by 2 publications

(7 citation statements)

References 17 publications

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“…The liberation of free H + ions occurs through the reaction of titanium trichloride with water

2 TiC {normall}_{3} + 4 {normalH}_{2} O \to 2 Ti {normalO}_{2} + 6 [H^{+} C l^{-}] + {normalH}_{2}

\begin{matrix} Ph {normalH}^{+} + h v \to PhH {normals}^{+} & (excitation; rate = {([], I)}_{normala}) \end{matrix}

\begin{matrix} true \\ right \begin{matrix} PhH s^{+} \overset{k_{bold-italic bold1}}{\to} Ph {normalH}_{normalT}^{+} & ((), transition to triplet state; rate = α {[normalI]}_{a}) \end{matrix} \end{matrix}

\begin{matrix} true \\ right \begin{matrix} Ph {H_{T}}^{+} + TiC l_{3} \overset{k_{2}}{\to} Ph {normalH}^{+} + TiC l_{3} (collisional deactivation) \end{matrix} \end{matrix}

\begin{matrix} true \\ right \begin{matrix} Ph {normalH}_{normalT}^{+} \overset{k_{bold-italic bold3}}{\to} Ph H^{+} & ((), thermal de - excitation; rate = α <...>) \end{matrix} \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

“…In water, the value of k 2 is of the order of 10 8 for methylene blue, whereas it is of the order of 10 7 for methylene green. The rate constant k 6 is affected by the solvent in which the reaction is carried out, indicating a strong relationship between the polarity of the solvent medium and the rate of reaction . The rate constant k 9 represents the conversion of excited transition state to ground state by radiation of thermal energy.…”

Section: Resultsmentioning

confidence: 99%

“…The response of galvanometer is recorded firstly without a cell in the light beam ( D 0 ), then with a cell containing only solvent ( D m ), later with the cell filled with the reaction mixture before the start of the reaction at time zero ( D ni ), and finally with the cell filled with the reaction mixture after addition of titanium trichloride during the course of the photoinduced electron transfer reaction at time t ( D nt ). The progress of the reaction with respect to time was monitored by an equation of straight line:

\frac{log (D_{normalm} - D_{nt})}{D_{nt}} = \frac{ε φ L I_{0} (1 - α) t}{V} + \frac{log (D_{normalm} - D_{ni})}{D_{ni}}

…”

Section: Methodsmentioning

confidence: 99%

“…The liberation of free H + ions occurs through the reaction of titanium trichloride with water. 1,19…”

Section: Proposed Mechanism For the Photoinduced Electron Transfer Rementioning

confidence: 99%

“…The phenothiazine dyes undergo electron transfer reactions in a photosensitized state with different organic and inorganic compounds, resulting in the conversion of colored (chromic) dye into its leuco (colorless) form. [1][2][3][4][5] The electron transfer reactions of dye and different organic compounds are often catalyzed by UV radiations and chemicals such as ZnO and H 2 O 2 . [6][7][8] The kinetics of photoinduced electron transfer reaction is dependent upon the nature of the solvent, dye, the reactivity of reductant or oxidant, the acidity of the reaction medium, and electrolytic composition of the reaction medium.…”

Section: Introductionmentioning

confidence: 99%

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The photokinetics of phenothiazine dyes with titanium trichloride in different solvents

Nadeem

Saeed

2019

Int J of Chemical Kinetics

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The kinetic parameters of photoinduced electron transfer reaction of two phenothiazine dyes, methylene blue and methylene green with titanium trichloride, were determined in water and different aqueous‐alcoholic solvents at different acidities by using a specially designed optical system. The rate of photoinduced electron transfer reaction was measured by determining the quantum yield of the reaction. The methylene green had a higher reactivity as compared to methylene blue with titanium trichloride. The graphical analysis showed that the reaction of dye with titanium trichloride follows pseudo–first‐order kinetics. A reaction mechanism was proposed by considering the different excited states of dye and their possible interaction with the solvent and titanium trichloride. The different steps in the reaction mechanism were taken into consideration for deriving rate equations, which were used to determine the different rate constants in the reaction mechanism in different solvents.

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“…The liberation of free H + ions occurs through the reaction of titanium trichloride with water

2 TiC {normall}_{3} + 4 {normalH}_{2} O \to 2 Ti {normalO}_{2} + 6 [H^{+} C l^{-}] + {normalH}_{2}

\begin{matrix} Ph {normalH}^{+} + h v \to PhH {normals}^{+} & (excitation; rate = {([], I)}_{normala}) \end{matrix}

\begin{matrix} true \\ right \begin{matrix} PhH s^{+} \overset{k_{bold-italic bold1}}{\to} Ph {normalH}_{normalT}^{+} & ((), transition to triplet state; rate = α {[normalI]}_{a}) \end{matrix} \end{matrix}

\begin{matrix} true \\ right \begin{matrix} Ph {H_{T}}^{+} + TiC l_{3} \overset{k_{2}}{\to} Ph {normalH}^{+} + TiC l_{3} (collisional deactivation) \end{matrix} \end{matrix}

\begin{matrix} true \\ right \begin{matrix} Ph {normalH}_{normalT}^{+} \overset{k_{bold-italic bold3}}{\to} Ph H^{+} & ((), thermal de - excitation; rate = α <...>) \end{matrix} \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

\frac{log (D_{normalm} - D_{nt})}{D_{nt}} = \frac{ε φ L I_{0} (1 - α) t}{V} + \frac{log (D_{normalm} - D_{ni})}{D_{ni}}

…”

Section: Methodsmentioning

confidence: 99%

“…The liberation of free H + ions occurs through the reaction of titanium trichloride with water. 1,19…”

Section: Proposed Mechanism For the Photoinduced Electron Transfer Rementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The photokinetics of phenothiazine dyes with titanium trichloride in different solvents

Nadeem

Saeed

2019

Int J of Chemical Kinetics

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The kinetics of photo‐induced chemical transformation reaction of methylene blue and titanium trichloride in different solvents

Nadeem

Saeed

2018

J Chinese Chemical Soc

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The kinetics of photo-induced chemical transformation reaction of methylene blue (MB) and titanium trichloride (TiCl 3 ) was investigated in water and aqueous ethyl acetate by determining the quantum yield of the reaction using optical spectrometry as the analytical technique. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at a fixed concentration of MB. The effect of the solvent on the quantum yield was studied in the acidic range from 4.0 to 7.0. The quantum yield was maximum at acidity (pH/H o ) 5.0, while it decreased on either increase or decrease in acidity (pH/H o ). The quantum yield of the reaction was high in water and decreased in 10% aqueous ethyl acetate. The absence of any reaction intermediate was confirmed by spectral analysis of the partially reacted mixture. A reaction mechanism has been suggested in accordance with the existence of different excited states of MB. The quantum yield increased with increase in temperature. The effect of temperature on the quantum yield of the reaction was used to determine the activation energy (E a ) using Arrhenius relation, and other thermodynamic parameters, such as enthalpy change (ΔH*), free energy change (ΔG*), and entropy change (ΔS*), were also evaluated. K E Y W O R D S ethyl acetate, kinetic, methylene blue, thermodynamic, titanium trichloride 1 | INTRODUCTIONMethylene blue (MB) (C 16 H 18 ClN 3 S) is a polyaromatic, heterocyclic, and cationic dye with a thiazine ring structure. It has good solubility in water and other polar solvents. The structure of MB is shown below.

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The Photokinetics of Electron Transfer Reaction of Methylene Blue with Titanium Trichloride in Aqueous–Alcoholic Solvents

Cited by 2 publications

References 17 publications

The photokinetics of phenothiazine dyes with titanium trichloride in different solvents

The photokinetics of phenothiazine dyes with titanium trichloride in different solvents

The kinetics of photo‐induced chemical transformation reaction of methylene blue and titanium trichloride in different solvents

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