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1.
Samuel González-Mancebo Javier Lacadena Yolanda García-Alonso Jesús Hernández-Benito Emilio Calle Julio Casado 《Monatshefte für Chemie / Chemical Monthly》2002,17(5):157-166
Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO+/NO2H2 + followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant. 相似文献
2.
M. Paz Fernndez-Liencres Emilio Calle Samuel Gonzlez-Mancebo Julio Casado Bartolom Quintero 《国际化学动力学杂志》1997,29(2):119-125
The kinetics of the reactions between sodium nitrite and phenol or m-, o-, or p-cresol in potassium hydrogen phthalate buffers of pH 2.5–5.7 were determined by integration of the monitored absorbance of the C-nitroso reaction products. At pH > 3, the dominant reaction was C-nitrosation through a mechanism that appears to consist of a diffusion-controlled attack on the nitrosatable substrate by NO+/NO2H2+ ions followed by a slow proton transfer step; the latter step is supported by the observation of basic catalysis by the buffer which does not form alternative nitrosating agents as nitrosyl compounds. The catalytic coefficients of both anionic forms of the buffer have been determined. The observed order of substrate reactivities (o-cresol ≈ m-cresol > phenol ≫ p-cresol) is explained by the hyperconjugative effect of the methyl group in o- and m-cresol, and by its blocking the para position in p-cresol. Analysis of a plot of ΔH# against ΔS# shows that the reaction with p-cresol differs from those with o- and m-cresol as regards the formation and decomposition of the transition state. The genotoxicity of nitrosatable phenols is compared with their reactivity with NO+/NO2H2+. © 1997 John Wiley & Sons, Inc. 相似文献
3.
Wincel H 《Journal of the American Society for Mass Spectrometry》2011,22(9):1570-1576
The thermochemical properties ΔH
o
n
, ΔS
o
n
, and ΔG
o
n
for the hydration of sodiated and potassiated monosaccharides (Ara = arabinose, Xyl = xylose, Rib = ribose, Glc = glucose,
and Gal = galactose) have been experimentally studied in the gas phase at 10 mbar by equilibria measurements using an electrospray
high-pressure mass spectrometer equipped with a pulsed ion beam reaction chamber. The hydration enthalpies for sodiated complexes
were found to be between −46.4 and −57.7 kJ/mol for the first, and −42.7 and −52.3 kJ/mol for the second water molecule. For
potassiated complexes, the water binding enthalpies were similar for all studied systems and varied between −48.5 and −52.7
kJ/mol. The thermochemical values for each system correspond to a mixture of the α and β anomeric forms of monosaccharide
structures involved in their cationized complexes. 相似文献
4.
Vesna Kuntić Dusěan Malesěev Zorica Radović Vladana Vukojević 《Monatshefte für Chemie / Chemical Monthly》2000,131(7):769-777
Summary. In the present work, rutin (3,3′ ,4′ ,5,7-pentahydrohyflavone-3-rhamnoglucoside) was determinated via a complexing reaction with a titanyloxalate anion. K2[TiO(C2O4)2] and rutin react in 50% ethanol forming a 1:2 complex in a pH range from 4.00 to 11.50, in which the TiO(C2O4)2
2− ion is linked to rutin through the 4-carbonyl and 5-hydroxyl group. The thermodynamic stability constant log β2
0 of the complex is determined to 10.80 at pH = 6.50. The change of the standard Gibbs free energy Δ G0 amounts to −61 kJċ mol−1, indicating that the process of complex formation is spontaneous. The optimal conditions for the spectrophotometric determination
of microconcentrations of rutin are at pH=6.40 and λ= 430 nm, where the complex shows an absorption maximum with a molar absorption coefficient a
430=(60±2)ċ103 dm3ċ mol−1ċ cm−1. The method is applied rutin determination from tablets.
Received January 4, 2000. Accepted (revised) February 17, 2000 相似文献
5.
Summary. Rhodococcus AJ270 is adsorbed by Dowex 1 at 15.4 mg dry weight per g resin with maximum amidase specific activity observed at lower
loadings. Bacteria form a monolayer on the resin surface, and adsorption is complete within 2 min. AJ270 can be entrapped
in agar and agarose gels (optimum loading: 20 mg dry weight bacteria per cm3 gel). Adsorption and entrapment improve amidase thermal stability 3–4 fold, and entrapment shifts the pH optimum from 8 to 7. Adsorbed and free bacteria show similar values for K
m and V
max, but entrapped bacteria have higher K
m values. Compared with bacteria adsorbed to Dowex, the activity per cm3 of matrix of agar-entrapped AJ270 is eight-fold higher. In stirred-tank reactors, exposure to acrylic acid reduces the amidase
activity of the biocatalyst in the hydrolysis of acrylamide. In column reactors, entrapped AJ270 suffers little reduction
in amidase activity against 0.25 M acrylamide over 22 h continuous operation.
Received November 18, 1999. Accepted December 14, 1999 相似文献
6.
Predrag Djurdjević Ratomir Jelić Ljubinka Joksović Mirjana Cvijović 《Monatshefte für Chemie / Chemical Monthly》2006,137(6):717-735
Summary. Solution equilibria between aluminium(III) ion and L-aspartic acid were studied by potentiometric, 27Al, 13C, and 1H NMR measurements. Glass electrode equilibrium potentiometric studies were performed on solutions with ligand to metal concentration
ratios 1:1, 3:1, and 5:1 with the total metal concentration ranging from 0.5 to 5.0 mmol/dm3 in 0.1 mol/dm3 LiCl ionic medium, at 298 K. The pH of the solutions was varied from ca. 2.0 to 5.0. The non-linear least squares treatment of the data performed with the aid of the Hyperquad program, indicated
the formation of the following complexes with the respective stability constants log βp,q,r given in parenthesis (p, q, r are stoichiometric indices for metal, ligand, and proton, respectively): Al(HAsp)2+ (log β1,1,1 = 11.90 ± 0.02); Al(Asp)+ (log β1,1,0 = 7.90 ± 0.03); Al(OH)Asp0 (log β1,1,−1 = 3.32 ± 0.04); Al(OH)2Asp− (log β1,1−2 = −1.74 ± 0.08), and Al2(OH) Asp3+ (log β2,1,−1 = 6.30 ± 0.04). 27Al NMR spectra of Al3+ + aspartic acid solutions (pH 3.85) indicate that sharp symmetric resonance at δ∼10 ppm can be assigned to (1, 1, 0) complex. This resonance increases
in intensity and slightly broadens upon further increasing the pH. In Al(Asp)+ complex the aspartate is bound tridentately to aluminum. The 1H and 13C NMR spectra of aluminium + aspartic acid solutions at pH 2.5 and 3.0 indicate that β-methylene group undergoes the most pronounced changes upon coordination of aluminum as well as
α-carboxylate group in 13C NMR spectrum. Thus, in Al(HAsp)2+ which is the main complex in this pH interval the aspartic acid acts as a bidentate ligand with –COO− and –NH2 donors closing a five-membered ring. 相似文献
7.
Andrei Blasko Alana Leahy-Dios William O. Nelson Steven A. Austin Robert B. Killion Gary C. Visor Ian J. Massey 《Monatshefte für Chemie / Chemical Monthly》2001,132(7):789-798
Summary. The kinetic and thermodynamic solubilities of Roche (Ro) pharmaceutical compounds were determined by HPLC, titrimetry, and UV/Vis spectroscopy in aqueous buffers and in non-buffered
systems. For kinetic solubility, a turbidimetric method that allows the rapid determination of solubilities using small amounts
of compounds (5–50 mg) was used. Two types of precipitation were observed during the kinetic solubility determinations: i) a disperse precipitation where the solution became foggy with very small particles uniformly distributed in the solution,
and ii) discrete precipitation characterized by formation of crystals that rapidly sediment. The thermodynamic solubility was determined
by shake flask and titrimetrically using a pH-STAT. The pH-STAT titrimetric method for the pH-thermodynamic solubility profile determination eliminates the buffer species and represents a new way to approach the solubility
characterization of pharmaceutical compounds. The strengths of the turbidimetric method for determining the kinetic solubility
are its rapidity, minimal compound requirements, and suitability for high throughput screening. The limitations are that the
maximum solubility is limited to less than 100 mg · cm−3, and the precipitation of trace impurities cannot be distinguished from precipitation of the analyte. The pH-STAT titrimetric approach for the thermodynamic solubility has a lower throughput and is suitable for the characterization
of the lead candidate. It is not limited in its solubility range and provides a common basis for the comparison of the solubility
values at different pH values in contrast to traditional buffered systems.
Received August 21, 2000. Accepted (revised) February 5, 2001 相似文献
8.
Günter Grampp Stephan Landgraf Tomasz Wesierski Beata Jankowska Ewa Kalisz Dana-Maria Sabou Boryana Mladenova 《Monatshefte für Chemie / Chemical Monthly》2002,133(10):1363-1372
Summary. The kinetics of the CrO(O2)2 formation by H2O2 and Cr2O7
2− in aqueous acidic media was measured at 293 ± 2 K in a pH range between 2.5 and 3.3. Using the stopped-flow method with rapid scan UV-VIS detection, the rate law of the formation
of CrO(O2)2 was determined. For the media HClO4, HNO3 and CH3COOH, the reaction order in the Cr2O7
2− concentration was found to be 0.5. For [H2O2] as well as for [H+], the reaction was first order in all acids used. In HCl and H2SO4 media the reaction was first order in Cr2O7
2−. At T = 293 ± 2 K the rate constant for the formation of Cr(O)(O2)2 was found to be (7.3 ± 1.9) · 102 M−3/2 s−1 in HClO4.
Corresponding author. E-mail: grampp@ptc.tu-graz.ac.at
Received January 30, 2002; accepted (revised) June 5, 2002 相似文献
9.
Zhenhai Liang Yanfa Sun Caimei Fan Xiaogang Hao Yanping Sun 《Journal of solution chemistry》2009,38(9):1119-1127
A Ti/SnO2 + RuO2 + MnO2 electrode was prepared by thermal decomposition of their salts. Results from SEM and XPS analyses, respectively, indicate
that the coating layer exhibits a compact structure and the oxidation state of Mn in the coating layer is +IV. The experimental
activation energy for the oxygen evolution reaction, which increased linearly with increasing overpotential, is about 8 kJ⋅mol−1 at the equilibrium potential (η=0). The electrocatalytic characteristics of the anode are discussed in terms of ligand substitution reaction mechanisms (Sn1
and Sn2). It was found that the transition state for oxygen evolution at the anode in acidic solution follows a dissociative
mechanism (Sn1 reaction). The Ti/SnO2 + RuO2 + MnO2 anode in conjunction with UV illumination was used to degrade phenol solutions, where the concentration of phenol remaining
was determined by high-performance liquid chromatography (HPLC). The results indicate that the degradation efficiency of phenol
on the anode can reach 96.3% after photoelectrocatalytic oxidation for 3 h. 相似文献
10.
The hydrolytic behavior of antimonic acid, Sb(OH)5o, was experimentally investigated, at fixed temperatures within the range 10–40 °C, by both titration of dilute Na-antimonate
solutions with HClO4 and single-point pH measurements of diluted Sb(OH)5o solutions. The thermodynamic constants, K
a, for the reaction:
were derived at different controlled temperatures, based on pH measurements, applying suitable mass and electrical balances
and correcting the concentrations of ionic species for medium effects. From the resulting log 10
K
a values, those of the corresponding isocoulombic equilibrium reaction:
were computed and used to derive its thermodynamic properties. These were finally combined with the corresponding thermodynamic
properties of the water association reaction, to obtain robust estimations of ΔG
ro, ΔS
ro and ΔH
ro for the ionogenic reaction. These are the first thermodynamic data at temperatures different from 25 °C for the ionization
reaction of Sb(OH)5o. The results of the present work confirm that Sb(OH)5o is a moderately weak and monoprotic acid with a pK
a of 2.848 at 25 °C. 相似文献
11.
A new adsorbent is proposed for the solid-phase extraction of phenol and 1-naphthol from polluted water. The adsorbent (TX-SiO2) is an organosilica composite made from a bifunctional immobilized layer comprising a major fraction (91%) of hydrophilic
diol groups and minor fraction (9%) of the amphiphilic long-chain nonionic surfactant Triton X-100 (polyoxyethylated isooctylphenol)
(TX). Under static conditions phenol was quantitatively extracted onto TX-SiO2 in the form of a 4-nitrophenylazophenolate ion associate with cetyltrimethylammonium bromide. The capacity of TX-SiO2 for phenol is 2.4 mg g−1 with distribution coefficients up to 3.4 × 104 mL g−1; corresponding data for 1-naphthol are 1.5 mg g−1 and 3 × 103 mL g−1. The distribution coefficient does not change significantly for solution volumes of 0.025–0.5 L and adsorbent mass less than
0.03 g; 1–90 μg analyte can be easily eluted by 1–3 mL acetonitrile with an overall recovery of 98.2% and 78.3% for phenol
and 1-naphthol, respectively. Linear correlation between acetonitrile solution absorbance (A
540) and phenol concentration (C) in water was found according to the equation A
540 = (6 ± 1) × 10−2 + (0.9 ± 0.1)C (μmol L−1) with a detection range from 1 × 10−8 mol L−1 (0.9 μL g−1) to 2 × 10−7 mol L−1 (19 μL g−1), a limit of quantification of 1 μL g−1 (preconcentration factor 125), correlation coefficient of 0.936, and relative standard deviation of 2.5%. A solid-phase colorimetric
method was developed for quantitative determination of 1-naphthol on adsorbent phase using scanner technology and RGB numerical
analysis. The detection limit of 1-naphthol with this method is 6 μL g−1 while the quantification limit is 20 μL g−1. A test system was developed for naked eye monitoring of 1-naphthol impurities in water. The proposed test kit allows one
to observe changes in the adsorbent color when 1-naphthol concentration in water is 0.08–3.2 mL g−1. 相似文献
12.
DTA and DSC were used to study the thermal behaviour of Ca(NO3)2·4H2O, Cd(NO3)2·4H2O, Mg(NO3)2·6H2O and their deuterated analogues. Evidence was found concerning the process of melting of the initial hydrates and deuterates,
followed by a one-stage dehydration of the melt to vield the respective anhydrous salt.
T
m, ΔH
m
o
, ΔS
m
o
and ΔH
deh
o
were determined and the ΔH
f
o
values for the investigated hydrates were calculated from the ΔH
deh
o
data.
Zusammenfassung DTA und DSC wurden zur Untersuchung des thermischen Verhaltens von Ca(NO3)2·4H2O, Cd(NO3)2·4H2O, Mg(NO3)2·6H2O und ihrer deuterierten Analoge eingesetzt. Man fand Aussagen bezüglich des Schmelzvorganges der Ausgangshydrate und Deuterate, gefolgt von einer Einschritt-Dehydratation der Schmelze unter Bildung der entsprechenden wasserfreien Salze. T m, ΔH m o , ΔS m o und ΔH deh o wurden ermittelt und die ΔH f o Werte für die untersuchten Hydrate wurden anhand der ΔH deh o berechnet.相似文献
13.
Vesna Kunti? Dusěan Malesěev Zorica Radovi? Vladana Vukojevi? 《Monatshefte für Chemie / Chemical Monthly》2000,18(5):769-777
In the present work, rutin (3,3′ ,4′ ,5,7-pentahydrohyflavone-3-rhamnoglucoside) was determinated via a complexing reaction with a titanyloxalate anion. K2[TiO(C2O4)2] and rutin react in 50% ethanol forming a 1:2 complex in a pH range from 4.00 to 11.50, in which the TiO(C2O4)2 2− ion is linked to rutin through the 4-carbonyl and 5-hydroxyl group. The thermodynamic stability constant log β2 0 of the complex is determined to 10.80 at pH = 6.50. The change of the standard Gibbs free energy Δ G0 amounts to −61 kJċ mol−1, indicating that the process of complex formation is spontaneous. The optimal conditions for the spectrophotometric determination of microconcentrations of rutin are at pH=6.40 and λ= 430 nm, where the complex shows an absorption maximum with a molar absorption coefficient a 430=(60±2)ċ103 dm3ċ mol−1ċ cm−1. The method is applied rutin determination from tablets. 相似文献
14.
Hong-Lin Zhang Zhe Kong Yong-Mei Yan Gan-Zuo Li Li Yu Fei Geng 《Journal of solution chemistry》2008,37(12):1631-1644
The power-time curves for the micelle formation process were determined for two anionic surfactants, sodium laurate (SLA)
and sodium dodecyl sulfate (SDS), in mixed alcohol + N,N-dimethylacetamide (DMA) solvent using titration microcalorimetry.
From the data of the lowest point and the area of the power-time curves, their critical micelle concentration (CMC) and ΔH
mo were obtained. The other thermodynamic functions of the micellization process (ΔG
mo and ΔS
mo) were also calculated with thermodynamic equations. For both surfactants, the effects of the carbon number (chain length)
of the alcohol, the concentration of alcohol, and the temperature on the CMC and thermodynamic functions are discussed. For
systems containing identical concentrations of a different alcohol, values of the CMC, ΔH
mo and ΔS
mo increased whereas ΔG
mo decreased with increasing temperature. For systems containing an identical alcohol concentration at the same temperature,
values of the CMC, ΔH
mo,ΔG
mo and ΔS
mo decrease with increasing carbon number of alcohol. For systems containing the same alcohol at the same temperature, the CMC
and ΔG
mo values increase whereas ΔH
mo and ΔS
mo decrease with increasing alcohol concentration. 相似文献
15.
A simple, sensitive and selective kinetic spectrofluorimetric determination of NO2 sampled by the droplet method in the atmosphere was proposed on the basis of the reaction of safranin O with nitrite. By
this reaction, a diazonium salt is formed, which causes a fluorescent reddish-orange dye color of the solution to change into
a non fluorescent blue color. The reaction was monitored fluorimetrically by measuring the decrease in fluorescence intensity
of safranin O at (λex/λem = 536 nm/579 nm) by a fixed-time method. The experimental conditions were optimized. Under the optimum conditions in the
concentration range of 7.5–400 ng/ml, a linear calibration curve (r2 = 0.9978) was obtained with a detection limit of 7.5 ng/ml. The method was applied successful ly to the determination of
nitrite in spiked water and NO2 in the atmosphere, as sampled by a liquid droplet method.
Received August 23, 1999. Revision February 29, 2000. 相似文献
16.
C. Fenn-Barrabaß A. Pohlmeier W. Knoche H. D. Narres M. J. Schwuger 《Colloid and polymer science》1998,276(7):627-637
Kinetics and equilibrium of the complexation of Al3+ with a polycarboxylic acid (PCA, random copolymer of maleic and acrylic acid with a mean molecular weight of 92 kDa) are
investigated by the stopped flow technique and potentiometric titration. The complexation proceeds according to the Eigen–Tamm
mechanism, i.e. in first diffusion-controlled step an outer sphere complex is formed. The second rate determining step is
the formation of the inner sphere complex, controlled by the exchange rate of hydration water. For this second step the rate
constant is k
1=3 s-1. It is in the order of magnitude of the water exchange at the Al3+ ion as expected for the Eigen–Tamm mechanism. The activation parameters are also determined. Parallel to this direct reaction
path a base catalyzed path is found, typical for complexation reactions of hydrolyzable metal ions.
Stable complexes are formed for which the overall association constant K
ass=Q
o(1+K
i) is determined by two parts: a chemical (intrinsic) part, described by the inner sphere association constant K
i=3 and an electrostatically controlled part described by the outer-sphere association quotient Q
o. The evaluation of the kinetic experiments allows to determine the value of log(Q
o) as a function of pH: 3.3<log Q
o<4.6. From these data the potential is calculated in the range −67 to ∝93 mV at pH values between 2 and 4.
For comparison, analogous experiments with the monomeric subunits of the polyacid, glutarate (GA), and tricarballylate (TCA),
are performed. The complexation with the monomeric subunits glutaric- and tricarballylic acid can be explained within the
classical view of a discrete outer sphere association constant Q
o.
Received: 13 November 1997 Accepted: 24 March 1998 相似文献
17.
Günter Grampp Stephan Landgraf Tomasz Wesierski Beata Jankowska Ewa Kalisz Dana-Maria Sabou Boryana Mladenova 《Monatshefte für Chemie / Chemical Monthly》2002,212(4):1363-1372
The kinetics of the CrO(O2)2 formation by H2O2 and Cr2O7
2− in aqueous acidic media was measured at 293 ± 2 K in a pH range between 2.5 and 3.3. Using the stopped-flow method with rapid scan UV-VIS detection, the rate law of the formation
of CrO(O2)2 was determined. For the media HClO4, HNO3 and CH3COOH, the reaction order in the Cr2O7
2− concentration was found to be 0.5. For [H2O2] as well as for [H+], the reaction was first order in all acids used. In HCl and H2SO4 media the reaction was first order in Cr2O7
2−. At T = 293 ± 2 K the rate constant for the formation of Cr(O)(O2)2 was found to be (7.3 ± 1.9) · 102 M−3/2 s−1 in HClO4. 相似文献
18.
Summary. Rh(III) polypyridine complexes ([Cp
*Rh(ppy)(H2O)]2+; ppy = 2,2′-bipyridine, 2,2′-bipyridine-4,4′-dicarboxylate, o-phenanthroline, tetrahydro-4,4′-dialkyl-bis-oxazole) oxidize in organic or aqueous alkaline solution primary and secondary alcohols to aldehydes or ketones and are thereby
reduced to the Rh(I) complexes Cp
*Rh(ppy). The Rh(III) form can be regenerated byoxidants like pyruvate or oxygen, making the reaction quasi-catalytic. The reaction follows anautocatalytic pathway; hydrogen transfer from the α-CH2 group of an alcoholate complex [Cp
*Rh(ppy)(OR)]+ to Cp
*Rh(I)(ppy) is suggested to yield the Rh(II) intermediate Cp
*Rh(ppy)H as the key and rate determining step. The knowledge of Rh(III)/Rh(I) redox potentials allows to estimate the thermodynamic
driving force of the reaction which is not more than about 300 mV. 相似文献
19.
P. Elumalai H. N. Vasan N. Munichandraiah 《Journal of Solid State Electrochemistry》1999,3(7-8):470-473
Charge-transfer resistance [R
ct = (dη/di)η = 0] and Tafel plots of current density (i) versus overpotential (η) data are generally known to yield values of the energy-transfer coefficient (α) and exchange current
density (i
o) of an electrochemical reaction. In the present investigation, the resistance (dη/di)η≠0 that could be calculated by differentiating a wide range of i−η curves was also shown to provide the values of α and i
o, by plotting ln(dη/di)η≠0 against η. Since α and i
o could also be evaluated directly from the experimental DC polarization data, the procedure was not of significant importance.
Nevertheless, it was considered important in evaluating α and i
o from AC impedance data, because the procedure was based on data analysis, which was much simpler than that reported in the
literature. A cobalt electrode prepared from fine metal powder was used in 1 M KOH electrolyte and the hydrogen evolution
reaction was studied by AC impedance at several potentials. The resistance values measured from the complex plane impedance
diagram were plotted against the potential, and the values of α and i
o were evaluated.
Received: 8 October 1998 / Accepted: 11 January 1999 相似文献
20.
Sancheeta Kolay Kallol K. Ghosh Amy MacDonald Jonathan Moulins Rama M. Palepu 《Journal of solution chemistry》2008,37(1):59-72
The thermodynamics of micellization and other micellar properties of alkyl- (C10-, C12-, C14- and C16-) triphenylphosphonium bromides in water + ethylene glycol (EG) (0 to 30% v/v) mixtures over a temperature range of 298 to
318 K and cetyltriphenylphosphonium bromide in water + diethylene glycol (DEG) mixtures (0 to 30% v/v) at 298 K have been
studied conductometrically. In all cases, an increase in the percentage of co-solvent results in an increase in the cmc values.
On the basis of these results, the thermodynamic parameters, the Gibbs energy (ΔG
mo), enthalpy (ΔH
mo) and entropy (ΔS
mo) of micellization have been evaluated. In addition to the conductivity measurements, kinetic experiments have also been done
to determine the dependence of observed rate constant for the nucleophilic substitution reaction of p-nitrophenyl acetate and benzohydroxamate ions in the presence of the surfactant cetyltriphenylphosphonium bromide with a
varying concentration of EG and DEG ranging from 0 to 50% v/v at pH=7.9 and 300 K. All of the reactions followed pseudo-first-order
kinetics. An increase in the surfactant concentration results in an increase in the reaction rate and for a given surfactant
concentration, the rate constant decreases as the concentration of co-solvent in the mixture increases. The kinetic micellar
effects have been explained by using the pseudophase model. The thermodynamic and structural changes originating from the
presence of solvents control the micellar kinetic effects. 相似文献