Kinetics of the interactions between dyes and micelles

1986 ◽  
Vol 64 (5) ◽  
pp. 955-959 ◽  
Author(s):  
Vincent C. Reinsborough ◽  
Josef F. Holzwarth
Keyword(s):  
Hydrophobic Interactions ◽  
Sodium Dodecylsulfate ◽  
Bulk Solution ◽  
Sds Micelles ◽  
Ph Jump ◽  
Wide Ph Range ◽  
Ph Range ◽  
Rate Limiting ◽  
Kinetics Of ◽  
Continuous Flow Method

The rates of association of three azo dyes, methyl red (MR), methyl orange (MO), and pyridine-2-azo-p-dimethylaniline (PADA), with sodium dodecylsulfate (SDS) and cetyltrimethylammonium bromide (CTAB) micelles in water were measured at 25 °C over a wide pH range by the continuous flow method of integrating observation (CFMIO). The association was considered in 3 steps: bulk solution encounter, pH jump, and electrostatic and hydrophobic interactions. Either the first or third step is rate limiting depending on the charge of the dye. The rate constant of association of neutral PADA, MR, and MO with SDS micelles is approximately 2 × 106 dm3mol−1s−1 while charging the dyes positively increases k to 109 dm3mol−1 s−1. Increasing the hydrophobicity of dye or micelle increases k for the interaction with the neutral dye species. Changes in k with pH for the dye–CTAB association were less pronounced.

scholarly journals Single entity electrochemistry and the electron transfer kinetics of hydrazine oxidation

Nano Research ◽  
2021 ◽  
Author(s):  
Ruiyang Miao ◽  
Lidong Shao ◽  
Richard G. Compton
Keyword(s):  
Electron Transfer ◽  
Bulk Solution ◽  
Relative Contribution ◽  
Rate Determining Step ◽  
Multistep Process ◽  
Ph Range ◽  
Electro Catalytic Oxidation ◽  
Single Particle Impact ◽  
The Impact ◽  
Kinetics Of

AbstractThe mechanism and kinetics of the electro-catalytic oxidation of hydrazine by graphene oxide platelets randomly decorated with palladium nanoparticles are deduced using single particle impact electrochemical measurements in buffered aqueous solutions across the pH range 2–11. Both hydrazine, N2H4, and protonated hydrazine N2H5+ are shown to be electroactive following Butler-Volmer kinetics, of which the relative contribution is strongly pH-dependent. The negligible interconversion between N2H4 and N2H5+ due to the sufficiently short timescale of the impact voltammetry, allows the analysis of the two electron transfer rates from impact signals thus reflecting the composition of the bulk solution at the pH in question. In this way the rate determining step in the oxidation of each specie is deduced to be a one electron step in which no protons are released and so likely corresponds to the initial formation of a very short-lived radical cation either in solution or adsorbed on the platelet. Overall the work establishes a generic method for the elucidation of the rate determining electron transfer in a multistep process free from any complexity imposed by preceding or following chemical reactions which occur on the timescale of conventional voltammetry.

scholarly journals A study of the oxidation of butan-1-ol and propan-2-ol by nicotinamide-adenine dinucleotide catalysed by yeast alcohol dehydrogenase.

1975 ◽  
Vol 147 (3) ◽  
pp. 541-547 ◽  
Author(s):  
C J Dickenson ◽  
F M Dickinson
Keyword(s):  
Alcohol Dehydrogenase ◽  
Ternary Complexes ◽  
Kinetics Of Oxidation ◽  
Yeast Alcohol Dehydrogenase ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Ph Range ◽  
Rate Limiting ◽  
Kinetics Of ◽  
Flow Experiments

1. The kinetics of oxidation of butan-1-ol and propan-2-ol by NAD+, catalysed by yeast alcohol dehydrogenase, were studied at 25 degrees C from pH 5.5 to 10, and at pH 7.05 from 14 degrees to 44 degrees C, 2. Under all conditions studied the results are consistent with a mechanism whereby some dissociation of coenzyme from the active enzyme-NAD+-alcohol ternary complexes occurs, and the mechanism is therefore not strictly compulsory order. 3. A primary 2H isotopic effect on the maximum rates of oxidation of [1-2H2]butan-1-ol and [2H7]propan-2-ol was found at 25 degrees C over the pH range 5.5-10. Further, in stopped-flow experiments at pH 7.05 and 25 degrees C, there was no transient formation of NADH in the oxidation of butan-1-ol and propan-2-ol. The principal rate-limiting step in the oxidation of dependence on pH of the maximum rates of oxidation of butan-1-ol and propan-2-ol is consisten with the possibility that histidine and cysteine residues may affect or control catalysis.

scholarly journals Voltammetric studies of the reactions of iron–sulphur clusters ([3Fe-4S] or [M3Fe-4S]) formed in Pyrococcus furiosus ferredoxin

1998 ◽  
Vol 335 (2) ◽  
pp. 357-368 ◽  
Author(s):  
Sarah E. J. FAWCETT ◽  
David DAVIS ◽  
Jacques L. BRETON ◽  
Andrew J. THOMSON ◽  
Fraser A. ARMSTRONG
Keyword(s):  
Pyrococcus Furiosus ◽  
Ph Dependence ◽  
Distinct Species ◽  
Bulk Solution ◽  
Protein Film ◽  
Protein Film Voltammetry ◽  
Significant Difference ◽  
The Status ◽  
Wide Ph Range ◽  
Ph Range

Reactions of the [3Fe-4S] cluster and various metallated [M3Fe-4S] adducts co-ordinated in the ferredoxin from the hyperthermophile Pyrococcus furiosus have been studied by protein-film voltammetry, bulk-solution voltammetry, solution kinetics and magnetic CD (MCD). The [3Fe-4S] cluster exhibits two couples, [3Fe-4S]+/0 and [3Fe-4S]0/2-. Film voltammetry is possible over a wide pH range (2–8), revealing that the [3Fe-4S]+/0 couple shows a complex pH dependence with pKred1 = 2.8, pKox = 4.9 and pKred2 = 6.7. From MCD, pKred1 corresponds with protonation of [3Fe-4S]0 to give a spectroscopically distinct species, as reported for ferredoxins from Azotobacterand Sulfolobus. The status of the disulphide/disulphydryl entity makes no significant difference to the data (given for the -S-S- form). Formation of the hyper-reduced [3Fe-4S]2- state is observed, requiring 3H+ for the overall 3e- reduction of [3Fe-4S]+, the change therefore being electroneutral. By comparison with the ferredoxin from Desulfovibrio africanus, uptake of Fe(II) and other M(II) by [3Fe-4S]0 to give [M3Fe-4S] clusters is slow (t1/2 > 10 min at room temperature, slower still if the protein is adsorbed on the electrode), whereas reaction with Tl(I) to produce [Tl3Fe-4S] is very rapid (t1/2 ≪ 1 s), suggesting that co-ordination of Tl does not require reorganization of the protein structure. Rates of formation of [3Fe-4S] from [M3Fe-4S] adducts increase sharply at high potentials, showing that metal release involves a labile ‘super-oxidized ’ [M3Fe-4S]3+ state.

Kinetics of the Cu(II) – Nitrilotriacetic Acid Reaction

1974 ◽  
Vol 52 (24) ◽  
pp. 4106-4108 ◽  
Author(s):  
James Maguire
Keyword(s):  
Complex Formation ◽  
Nitrilotriacetic Acid ◽  
Stopped Flow ◽  
Kinetic Behavior ◽  
First Order ◽  
Acid Reaction ◽  
Decreasing Ph ◽  
Ph Range ◽  
Rate Limiting ◽  
Kinetics Of

The kinetics of the reaction between Cu(II) and nitrilotriacetic acid (NTA) to form the 1:1 complex have been studied by the stopped-flow technique over the pH range 2–6. The reaction is kinetically first order in both [Cu(II)] and [NTA]total; the rate constant has a minimum value of 1.1 × 105 l mol−1 s−1 in the pH range 3.5–5 and increases with either increasing or decreasing pH. An explanation for the observed kinetic behavior may be that in the case of the monoprotonated species HNTA2− there is a rate-limiting transfer of a proton from nitrogen before complex formation takes place, and that this transfer is facilitated with increasing acidity.

Kinetics of Base-Catalysed Hydrolysis and Cyclisation of Substituted Acetamide and Benzamide O-(Phenoxycarbonyl)oximes

1999 ◽  
Vol 64 (10) ◽  
pp. 1641-1653 ◽  
Author(s):  
Jaromír Mindl ◽  
Jaromír Kaválek ◽  
Helena Straková ◽  
Vojeslav Štěrba
Keyword(s):  
Reaction Mechanism ◽  
Ph Dependence ◽  
Bond Formation ◽  
Reaction Step ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Substituted Benzamide ◽  
Ph Range ◽  
Rate Limiting ◽  
Kinetics Of

The reaction kinetics of acetamide O-(4-nitrophenoxycarbonyl)oxime have been studied in aqueous buffers at pH 2-11. At pH > 9, the pH dependence of kobs is linear with slope 1, the cyclisation to 3-methyl-1,2,4-oxadiazol-5(4H)-one and 4-nitrophenol being the only reaction. At pH < 7.5, the only reaction is the hydrolysis giving 4-nitrophenol and acetamidoxime. The dependence of kobs on pH has been used to determine the rate equation and to propose the reaction mechanism. The cyclisation kinetics of substituted benzamide O-(phenoxycarbonyl)oximes have been studied in the pH range from 9.25 to 11. The reaction mechanism has been proposed based on the ρ constants found. In the first reaction step, the proton is split off from the NH2 group; the subsequent, rate-limiting step involves simultaneous N-C bond formation and C-O bond splitting.

Kinetic of oxidation of methyl orange by vanadium(V) under conditions VO2+ and decavanadates coexist: Catalysis by Triton X-100 micellar medium

2019 ◽  
Author(s):  
Chem Int
Keyword(s):  
Methyl Orange ◽  
Solution Ph ◽  
Vanadium Concentration ◽  
Limiting Behavior ◽  
First Order ◽  
First Order Kinetics ◽  
Ph Range ◽  
Kinetic Pattern ◽  
Triton X ◽  
Kinetics Of

The kinetics of oxidation of methyl orange by vanadium(V) {V(V)} has been investigated in the pH range 2.3-3.79. In this pH range V(V) exists both in the form of decavanadates and VO2+. The kinetic results are distinctly different from the results obtained for the same reaction in highly acidic solution (pH &lt; 1) where V(V) exists only in the form of VO2+. The reaction obeys first order kinetics with respect to methyl orange but the rate has very little dependence on total vanadium concentration. The reaction is accelerated by H+ ion but the dependence of rate on [H+] is less than that corresponding to first order dependence. The equilibrium between decavanadates and VO2+ explains the different kinetic pattern observed in this pH range. The reaction is markedly accelerated by Triton X-100 micelles. The rate-[surfactant] profile shows a limiting behavior indicative of a unimolecular pathway in the micellar pseudophase.

Kinetics of cyclization of S-ethoxycarbonylmethylisothiouronium chloride to 2-imino-4-thiazolidone

1979 ◽  
Vol 44 (3) ◽  
pp. 912-917 ◽  
Author(s):  
Vladimír Macháček ◽  
Said A. El-bahai ◽  
Vojeslav Štěrba
Keyword(s):  
Hydrochloric Acid ◽  
Dilute Hydrochloric Acid ◽  
Base Catalysis ◽  
General Base ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Kinetics Of Formation ◽  
Acid Catalyzed ◽  
Rate Limiting ◽  
Kinetics Of

Kinetics of formation of 2-imino-4-thiazolidone from S-ethoxycarbonylmethylisothiouronium chloride has been studied in aqueous buffers and dilute hydrochloric acid. The reaction is subject to general base catalysis, the β value being 0.65. Its rate limiting step consists in acid-catalyzed splitting off of ethoxide ion from dipolar tetrahedral intermediate. At pH < 2 formation of this intermediate becomes rate-limiting; rate constant of its formation is 2 . 104 s-1.

Polarographic and spectrophotometric behaviour of some N-p-phenyl substituted benzamidines

1991 ◽  
Vol 56 (12) ◽  
pp. 2791-2799 ◽  
Author(s):  
Juan A. Squella ◽  
Luis J. Nuñez-Vergara ◽  
Hernan Rodríguez ◽  
Amelia Márquez ◽  
Jose M. Rodríguez-Mellado ◽  
...  
Keyword(s):  
Spectrophotometric Study ◽  
Absorption Bands ◽  
Electrochemical Parameters ◽  
Wide Ph Range ◽  
Group A ◽  
Substituent Constants ◽  
Ph Range ◽  
The Waves

Five N-p-phenyl substituted benzamidines were studied by DC and DP polarography in a wide pH range. Coulometric results show that the overall processes are four-electron reductions. Logarithmic analysis of the waves indicate that the process are irreversible. The influence of the pH on the polarographic parameters was also studied. A UV spectrophotometric study was performed in the pH range 2-13. In basic media some variations in the absorption bands were observed due to the dissociation of the amidine group. A determination of the pK values was made by deconvolution of the spectra. Correlations of both the electrochemical parameters and spectrophotometric pK values with the Hammett substituent constants were obtained.

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