Factor analysis as a complement to band resolution. V. Complexing of pentachlorophenol and acetone in carbon tetrachloride solution

1978 ◽  
Vol 56 (23) ◽  
pp. 2959-2965 ◽  
Author(s):  
J. Korppi-Tommola ◽  
H. F. Shurvell
Keyword(s):  
Factor Analysis ◽  
Carbon Tetrachloride ◽  
Complex Formation ◽  
Infrared Spectrum ◽  
Equilibrium Constants ◽  
Complex Model ◽  
Carbon Tetrachloride Solution ◽  
Linear Relationships

Complex formation between pentachlorophenol and acetone and acetone-d6 in carbon tetrachloride solution has been studied in both the hydroxyl and carbonyl stretching regions of the infrared spectrum. Factor analysis of the digitized spectra indicates three absorbing components for each set of solutions in the hydroxyl stretching region. Concentration studies revealed roughly linear relationships between the areas of the 'free' ν(OH) band and both of the resolved complex bands, suggesting that two different 1:1 complexes occur in CCl4 solution. In the ν(CO) region only one band due to complex formation was detected. Equilibrium constants for the isotopically different complexes at about 30 °C are reported. In the hydroxyl stretching region, band resolution was also carried out using four components which gave a better fit to the observed spectrum. A set of equilibrium constants were then obtained. However, considerable difficulties were met in the calculations and in the interpretation of these results, so that the three band, two complex model is preferred.

scholarly journals Proton transfer equilibria, temperature and substituent effects on hydrogen bonded complexes between chloranilic acid and anilines

2000 ◽  
Vol 14 (3) ◽  
pp. 99-107 ◽  
Author(s):  
Gamal A. Gohar ◽  
Moustafa M. Habeeb
Keyword(s):  
Hydrogen Bond ◽  
Complex Formation ◽  
Proton Transfer ◽  
Equilibrium Constants ◽  
Bond Formation ◽  
Substituent Effects ◽  
Substituted Anilines ◽  
Chloranilic Acid ◽  
Hydrogen Bond Formation ◽  
Linear Relationships

The proton transfer equilibrium constants (KPT) for 1 : 1 complex formation between Chloranilic Acid (CA) and a series ofp- andm‒substituted anilines have been measured in 1,4-dioxane spectrophotometrically. The results supported the concept of amine-solvent hydrogen bond formation (short range solvation effect). Beside, this effect, theKPTvalues were apparently affected by the electron donation power of the aniline ring substituent, which was transmitted to the interaction center via resonance and inductive effects. Linear relationships betweenKPTand σ-Hammett substituent constants, or pKvalues formandpanilines,were obtained verifying the above conclusions. The solute-solvent hydrogen bond formation might increase the reactivity of the aniline nitrogen than would the inductive effect of the alkyl group, in case of CA-N-alkyl aniline complexes. The thermodynamic parameters for the proton transfer complex formation were estimated and it was indicated that the solvent–aniline hydrogen bond formation was preferred in the case ofp-substituted aniline complexes more than in the case of the correspondingm‒isomer. It has been found that the proton transfer process was enthalpy and entropy controlled.

Factor analysis as a complement to band resolution techniques. VI. Complex formation between pentachlorophenol-OD and acetone

1979 ◽  
Vol 57 (20) ◽  
pp. 2707-2713 ◽  
Author(s):  
J. Korppi-Tommola ◽  
H. F. Shurvell
Keyword(s):  
Principal Component Analysis ◽  
Factor Analysis ◽  
Complex Formation ◽  
Equilibrium Constant ◽  
Isotope Effect ◽  
Infrared Spectra ◽  
Equilibrium Constants ◽  
Principal Component ◽  
Proton Donor ◽  
Good Agreement

Complex formation between pentachlorophenol-OD (PCP-OD) and acetone and acetone-d6 in CCl4 solution has been studied. Digitized infrared spectra in the O—D stretching region ν(OD) of PCP-OD and the C—O stretching region ν(CO) of acetone have been recorded from solutions of various concentrations. The present results are compared with previous work on complex formation between PCP and the same acceptor molecules. In the ν(OD) region, factor analysis (principal component analysis) and a concentration study of the areas of the resolved band components suggest that two (1:1) complexes occur in solution. The equilibrium constant obtained for one of the complexes shows an isotope effect due to deuteration of the proton donor. In the ν(CO) region, only one band due to complexed species was resolved. Equilibrium constants calculated using the results from the ν(OD) and ν(CO) regions are in good agreement with each other.

SPECTROSCOPIC STUDIES OF ALCOHOLS: II. THE CONFORMATION OF 2-HALOETHANOLS IN CARBON TETRACHLORIDE SOLUTION

1964 ◽  
Vol 42 (2) ◽  
pp. 326-339 ◽  
Author(s):  
P. J. Krueger ◽  
H. D. Mettee
Keyword(s):  
Carbon Tetrachloride ◽  
Equilibrium Constants ◽  
Spectroscopic Studies ◽  
Kcal Mole ◽  
Band Shift ◽  
Carbon Tetrachloride Solution ◽  
Hydrogen Bond Interactions ◽  
Conformational Equilibria ◽  
Intramolecular Hydrogen ◽  
Conformational Free Energy

Of the five conformers predicted for 2-haloethanols, only two (halogen and OH trans and gauche) can be positively identified by high resolution infrared spectroscopy. From the temperature dependence of the relative intensities of the fundamental OH stretching bands of the trans and gauche forms of the compounds XCH2CH2OH2 where X = F, Cl, Br, and I, the gauche conformers are shown to be energetically favored in dilute carbon tetrachloride solution, with enthalpy differences between the two conformers of 2.07 ± 0.53, 1.20 ± 0.09, 1.25 ± 0.08, and 0.81 ± 0.09 kcal/mole respectively. Equilibrium constants and the conformational free energy and entropy differences are reported. Inter- and intra-molecular OH … X hydrogen-bond interactions are found to be similar in that the enthalpy increases in the order X = I < Br < Cl < F, and is linearly related to a decrease in the fundamental OH band shift, in contrast to the Badger–Bauer relationship. The molecular and thermodynamic factors governing conformational equilibria involving intramolecular hydrogen bonds are discussed.

Factor analysis as a complement to infrared band resolution. VII. The temperature dependence of the self association of phenol in carbon tetrachloride solution

1980 ◽  
Vol 58 (4) ◽  
pp. 353-360 ◽  
Author(s):  
B. U. Petelenz ◽  
H. F. Shurvell
Keyword(s):  
Factor Analysis ◽  
Carbon Tetrachloride ◽  
The Self ◽  
Infrared Band ◽  
Absorption Bands ◽  
Carbon Tetrachloride Solution ◽  
A Value ◽  
Polymeric Species ◽  
Self Association ◽  
Infrared Absorption Bands

Infrared absorption bands in the OH stretching region of phenol in carbon tetrachloride solution have been recorded for various concentrations and at several temperatures between 25 and 60 °C. Factor analysis of the digitized spectra was carried out and the presence of three absorbing components in the OH stretching band was indicated at all temperatures in the range of 25–60 °C. The three components are assigned to monomer, linear dimer, and a polymeric species. It is suggested that the polymeric species is a cyclic trimer.Band contour resolution was carried out to obtain areas of the component bands. The variation of the monomer and dimer band areas with temperature was used to obtain a value for the enthalpy of dimerization of −15.8 ± 0.6 kJ mol−1.

scholarly journals N-H···O hydrogen bonding: An FT-IR, NIR study of N-methylformamide-ether systems

2010 ◽  
Vol 75 (2) ◽  
pp. 157-163 ◽  
Author(s):  
Branislav Jovic ◽  
Aleksandar Nikolic ◽  
Erna Davidovic ◽  
Slobodan Petrovic
Keyword(s):  
Hydrogen Bonding ◽  
Carbon Tetrachloride ◽  
Complex Formation ◽  
Diethyl Ether ◽  
Equilibrium Constants ◽  
Electron Donors ◽  
Butyl Ether ◽  
Dibutyl Ether ◽  
Spectroscopic Characteristics ◽  
Ft Ir

This paper reports the results of an FT-IR and NIR study of N-methylformamide in carbon tetrachloride solution in presence of ethers as the O-electron donors, i.e., diethyl ether (DEE), diisopropyl ether (DiPE), methyl t- -butyl ether (MtBE), dibutyl ether (DBE), dipentyl ether (DPE), tetrahydrofuran (THF) and tetrahydropyran (THP). The spectroscopic characteristics of the N-H???O hydrogen bonded complexes are given. In addition, the equilibrium constants for 1:1 complex formation were determined at 25?C using Mid-IR and NIR measurements.

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