Spectrophotometric measurement of solvent polarity with phenol blue as the probe

Kolling, Orland W.

doi:10.1021/ac00224a015

Cited by 36 publications

(35 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For example, the "dielectric" or "non-specific" solute-solvent interactions are the sum of dipole-dipole, solute polarizability-solvent dipole, solute dipole-solvent polarizability and polarizability-polarizability interactions. I), followed by reference number): 1 [20]; 2 to 4 (present work); 5 [21]; 6 [22]; 7 [23]; 8 [24]; 9 [25]; 10 [26]; 11 [27]; 12 [16b]; 13 to 16 [28]; 17 [29]; 18 [30]; 19 [31]; 20 [32] and 21 to 26 [33]. ") iv) -A corollary to (iii) is as follows: for a group of probes, each tested in a series of solvents, it should be possible, in principle, to correlate the multiple regression coefficients of Eq.…”

Section: Resultsmentioning

confidence: 99%

Solvatochromism in Pure Solvents: Effects of the Molecular Structure of the Probe

Novaki

Seoud

1996

Ber Bunsenges Phys Chem

View full text Add to dashboard Cite

The following solvatochromic probes were synthesized: 1-methyl-8-oxyquinolinium betaine (QB), sodium 1 -meth-yWoxyquinolinium betaine-5-sulphonate (QBS), and 1-methyl-3-oxypyridinium betaine (PB). Their solvatochromic behavior in 28 protic and aprotic solvents was investigated, and the data compared to those of 2,6-diphenyl-4-(2,4,6-triphenyl-l-pyridinio)-l-phenolate, (RB). Solvent polarity scales based on QB, QBS, and PB correlate linearly with the ET(30) scale of RB. The Taft-Kamlet-Abboud equation satisfactorily applies to the solvatochromic data of RB, QB, QBS and PB. The multiparameter regression coefficients (a) and (s) of the above mentioned equation show that the sensitivity of the probe to solvent dipolarity/polarizability, and hydrogen bond donation is clearly dependent on its molecular structure. This dependence was tested for a total of 26 probes of widely different structures. It is shown that this is a general behavior, i.e., log Iu I and 1s I are linearly dependent on the pK, and the dipole moment of the probe, respectively.

show abstract

Section: Resultsmentioning

confidence: 99%

Solvatochromism in Pure Solvents: Effects of the Molecular Structure of the Probe

Novaki

Seoud

1996

Ber Bunsenges Phys Chem

View full text Add to dashboard Cite

show abstract

“…π-π* transition of 4-nitroanisole 0.974 166 40% [28] π-π* transition of PDJ b 0.968 63 32% [29] π-π* transition of Nile Red 0.950 36 40% [30] π-π* transition of Phenol Blue 0.943 27 30% [31] π-π* transition of 5-dimethylamino-5′-nitro-2,2′-bithiophene 0.983 20 27% [32] Carbonyl stretching frequency of acetophenone 0.968 153 40% [28] OH stretching frequency of the methanol-diethyl ether HBed complex 0.948 17 29% [33] 13 C 3 chemical shift of (trifluoromethyl)benzene 0.954 15 19% [34] Log k 2 for the S N 2 reaction of tri-n-propylamine and iodomethane 0.954 44 28% [35] Log k 2 for the pyridine-catalyzed thermal decomposition of tert-butyl peroxyformate 0.979 17 31% [36] a Calculated from the standardized regression coefficients di′ and e′ as 100*di′/(di′+ e′). b 9-(α-perfluoroheptyl-β,β-dicyanovinyl)julolidine.…”

Section: Significance Of the E T (30) Parameter Of Non-hbd Solventsmentioning

confidence: 99%

Solvent polarity scales: determination of new E_T(30) values for 84 organic solvents

Cerón‐Carrasco

Jacquemin

Laurence

et al. 2014

J of Physical Organic Chem

189

167

View full text Add to dashboard Cite

The solvent polarity parameter E T (30) is newly measured from the solvatochromism of the betaine dye 30 for 84 solvents and re-measured for 186 additional ones. The results are organized in a database. It is shown that the validity of linear solvation energy relationships used for the determination of secondary E T (30) values is limited to non-hydrogen-bond donor solvents. Relationships with the chain length n are given for the determination of tertiary E T (30) values of the homologous H(CH 2 ) n Y solvent series. The parameter E T (30) is orthogonal to the function of the refractive index (n 2 À 1) / (2n 2 + 1). For non hydrogen-bond donor solvents, this allows to enter E T (30) as an almost pure electrostatic parameter in a new linear solvation energy relationship.

show abstract

“…26 Comparing independent data for six protic solvents (water, MeOH, EtOH, n-PrOH, i-PrOH, and n-BuOH), average absolute deviations are: p Ã (0.02), a (0.06), and b (0.09). 23,26 Relatively large uncertainties (10-20%) in absolute values of KAT parameters have been quoted, 27 and sources of the uncertainties are discussed elsewhere. 28…”

Section: Estimates Of Errorsmentioning

confidence: 99%

Correlations and predictions of solvent effects on reactivity: some limitations of multi‐parameter equations and comparisons with similarity models based on one solvent parameter

Bentley

Garley

2006

J of Physical Organic Chem

View full text Add to dashboard Cite

Three recent publications on multi-parameter correlations of solvent effects on solvolytic reactivity are re-examined, by considering 'similarity' and/or 'analogy'. Systematic errors due to compensation effects and to comparisons between dissimilar processes are found. Models for solvent nucleophilicity involving dissimilar spectroscopic processes (e.g. b or B parameters) give insensitive measures of low nucleophilicity. From qualitative considerations based on structural similarities, it is predicted that the sensitivities to changes to solvent polarity for solvolyses of chloroalkanes should be in the order: 1-adamantyl (3) > 2-methyl-2-adamantyl (1) > t-butyl (2). The predictions are confirmed quantitatively by simple linear free-energy relationships and similarity models, involving correlations with Y Cl (based on solvolyses of 1-chloroadamantane) or E T (30) (based on solvatochromism). Multiparameter correlations, indicating that solvolyses of 1 show a low sensitivity to both solvent polarity and electrophilicity, and also a negative sensitivity to solvent nucleophilicity, are shown to be unreliable. Large errors are also evident in recent KOMPH2 calculations. Conclusions are supported by comparing several multi-parameter treatments of solvolyses of 4-methoxyneophyl tosylate, for which there is a reliable set of kinetic data and a generally accepted mechanism.

show abstract

Spectrophotometric measurement of solvent polarity with phenol blue as the probe

Cited by 36 publications

References 10 publications

Solvatochromism in Pure Solvents: Effects of the Molecular Structure of the Probe

Solvatochromism in Pure Solvents: Effects of the Molecular Structure of the Probe

Solvent polarity scales: determination of new E_T(30) values for 84 organic solvents

Correlations and predictions of solvent effects on reactivity: some limitations of multi‐parameter equations and comparisons with similarity models based on one solvent parameter

Contact Info

Product

Resources

About

Spectrophotometric measurement of solvent polarity with phenol blue as the probe

Cited by 36 publications

References 10 publications

Solvatochromism in Pure Solvents: Effects of the Molecular Structure of the Probe

Solvatochromism in Pure Solvents: Effects of the Molecular Structure of the Probe

Solvent polarity scales: determination of new ET(30) values for 84 organic solvents

Correlations and predictions of solvent effects on reactivity: some limitations of multi‐parameter equations and comparisons with similarity models based on one solvent parameter

Contact Info

Product

Resources

About

Solvent polarity scales: determination of new E_T(30) values for 84 organic solvents