Infrared intensities of liquids XXV: Dielectric constants, molar polarizabilities and integrated intensities of liquid toluene at 25°C between 4800 and 400cm−1

2005 ◽  
Vol 750 (1-3) ◽  
pp. 78-93 ◽  
Author(s):  
John E. Bertie ◽  
Yoram Apelblat ◽  
C. Dale Keefe
1996 ◽  
Vol 50 (8) ◽  
pp. 1047-1057 ◽  
Author(s):  
John E. Bertie ◽  
Zhida Lan

The previously reported nonreproducibility of the intensity of the OH stretching band of liquid water has been explored. It was found that it can be eliminated in measurements with the Circle® multiple ATR cell by ensuring that the ATR rod is coaxial with the glass liquid holder. It was also found that normal laboratory temperature variations of a few degrees change the intensity by ⩽∼1% of the peak height. A new imaginary refractive index spectrum of water has been determined between 4000 and 700 cm1 as the average of spectra calculated from ATR spectra recorded by four workers in our laboratory over the past seven years. It was obtained under experimental and computational conditions superior to those used previously, but is only marginally different from the spectra reported in 1989. In particular, the integrated intensities of the fundamentals are not changed significantly from those reported in 1989. The available imaginary refractive index, k, values between 15,000 and 1 cm−1 have been compared. The values that are judged to be the most reliable have been combined into a recommended k spectrum of H2O(l) at 25 °C between 15,000 and 1 cm−1, from which the real refractive index spectrum has been calculated by Kramers–Kronig transformation. The recommended values of the real and imaginary refractive indices and molar absorption coefficients of liquid water at 25 ± 1 °C are presented in graphs and tables. The real and imaginary dielectric constants and the real and imaginary molar polarizabilities in this wavenumber range can be calculated from the tables. Conservatively estimated probable errors of the recommended k values are given. The precision with which the values can be measured in one laboratory and the relative errors between regions are, of course, far smaller than these probable errors. The recommended k values should be of considerable value as interim standard intensities of liquid water, which will facilitate the transfer of intensities between laboratories.


1979 ◽  
Vol 33 (4) ◽  
pp. 346-348 ◽  
Author(s):  
Kerin Scanlon ◽  
Leo Laux ◽  
John Overend

In principle it is apparent that Fourier transform infrared spectroscopy offers a number of significant advantages in the determination of infrared intensities integrated over the rotational fine structure in vibration-rotation bands. One expects that there should be no problem with photometric accuracy; yet, before embarking on a systematic program of study, we believe it important to establish that the method will work in practice. As a test case we have chosen the V2 fundamental of CO2 at 673 cm−1 since this is, in our experience, as difficult a band as any when it comes to measuring integrated intensities. We have, using a Digilab FTS-20 spectrometer, determined a value of the integrated intensity, Γ2 = 7901 ± 105 cm2/mol which should be compared with the value previously determined on a dispersive instrument, Γ2 = 7882 ± 110 cm2/mol. We have also determined a value of Γ3 = 25,300 ± 570 cm2/mol for the integrated intensity of the antisymmetric stretching fundamental.


1978 ◽  
Vol 33 (5) ◽  
pp. 557-563 ◽  
Author(s):  
Ivan Juchnovski ◽  
Rositza Kuzmanova ◽  
Jordan Tsenov ◽  
José Kaneti ◽  
Ivan Binev

AbstractThe nitrile infrared intensities of a series of a,β-diaryl cyanoethylenes were juxtaposed to the associated substituent constants, HMO and SCF-MO indices and fair to excellent correlations were established. The competitive resonance of the nitrile group with alpha-and beta-aryl substituents is discussed. HMO calculations were used to estimate the steric hindrance to conjugation caused by polycyclic substituents and SCF-MO calculations were made to obtain uniform predictions of nitrile intensities and frequencies for hetero-cyclic derivatives of acrylonitrile.


1985 ◽  
Vol 39 (3) ◽  
pp. 392-401 ◽  
Author(s):  
John E. Bertie ◽  
Hans H. Eysel

The CIRCLE ATR accessory has been used to measure the optical and dielectric constants of organic liquids and water. The method, based on Fresnel's equations, is described in detail, and the agreement between the results obtained and literature values is shown to be adequate for chemical use. The utility of optical and dielectric constants for the calculation of traditional infrared intensities in liquids and of dipole moment derivatives is outlined.


1995 ◽  
Vol 49 (6) ◽  
pp. 840-851 ◽  
Author(s):  
John E. Bertie ◽  
Zhida Lan ◽  
R. Norman Jones ◽  
Yoram Apelblat

This is the last of four papers that present the detailed measnrements and results that led to the acceptance by the International Union of Pure and Applied Chemistry of Secondary Infrared Absorption Intensity Standards for liquids. In this paper accurate infrared absorption intensities of liquid dichloromethane at 25°C are presented. The accuracy was estimated from the ±1.5% average agreement of integrated intensities over specific wavenumber ranges between spectra measured by five spectroscopists in four laboratories. The use of data from different instruments in different laboratories has significantly included the effect of systematic instrumental errors. The spectra from the different spectroscopists have been averaged, unweighted, to give intensity spectra of dichloromethane that are presented as the best available. The results obtained agree with the only measurements that have been made against a primary standard, the estimated accuracy of which is about 5.5%. The spectra of the molar absorption coefficient and or the real and imaginary refractive indices are reported as tables and graphs between 6500 and 800 cm−1. Also reported are the peak heights and the areas under band groups in the molar absorption coefficient and imaginary refractive index spectra. The imaginary refractive index, k(ν˜), and molar absorption coefficient, Em(ν˜), values are believed to be accurate to an average ±2.3% over the 36 measured bands. The baseline k(ν˜) values are believed to be accurate to ∼8% below 6000 cm−1, ∼1% below 4500 cm−1, and ∼25% above 6000 cm−1, where the absorption is extremely weak. The areas under band groups in the k(ν˜) and Em(ν˜) spectra are believed to be accurate to 1.5% averaged over the 15 measured band groups and to 1.0% over the 10 band groups below 3600 cm−1. The real refractive index, n(ν˜), values are believed to be accurate to 0.2%.


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