A Low Temperature Infrared Study of Self-association in Thiols

1972 ◽  
Vol 50 (22) ◽  
pp. 3594-3600 ◽  
Author(s):  
R. Bicca de Alencastro ◽  
C. Sandorfy
Keyword(s):  
Hydrogen Bonding ◽  
Low Temperature ◽  
Infrared Spectra ◽  
Low Temperatures ◽  
Infrared Study ◽  
Text Type ◽  
Stretching Vibration ◽  
Aliphatic Thiols ◽  
Self Association ◽  
Associated Species

The infrared spectra of several aliphatic thiols and of benzenethiol were measured between 2400 and 2700 cm−1, and 4800 and 5300 cm−1 in a 1:1 mixture of CCl3F and C2F4Br2, at temperatures ranging from 20 to −190 °C. Dimerization takes place at low temperatures and more highly associated species also appear. Free S—H groups are present in the solutions as well as in the pure liquids, even at the lowest temperatures. The association is of the [Formula: see text] type in aliphatic thiols; both [Formula: see text] and [Formula: see text] bonds are found in the case of benzenethiol and α-toluenethiol. Hydrogen bonding has little effect on the anharmonicity of the S—H stretching vibration.

A Low-temperature Infrared Study of Self-association in Thiolic Acids

1973 ◽  
Vol 51 (9) ◽  
pp. 1443-1447 ◽  
Author(s):  
R. Bicca de Alencastro ◽  
C. Sandorfy
Keyword(s):  
Low Temperature ◽  
Low Temperatures ◽  
Carbonyl Groups ◽  
Infrared Study ◽  
Text Type ◽  
Stretching Vibration ◽  
Self Association ◽  
High Concentrations ◽  
Associated Species ◽  
Anharmonicity Constants

The i.r. spectra of thioloacetic and thiolobenzoic acids were measured in both the fundamental and first overtone regions of the S—H stretching vibration, in a mixture of CCl3F and C2F4Br2, at temperatures ranging from 20 to −190 °C. [Formula: see text] type bonds are formed at low temperatures or at high concentrations of solute. Two different species can be detected. The first is probably an open dimer and the second a cyclic dimer. The S—H anharmonicity constants are of the order of 50–60 cm−1, for both free and associated species, and have about the same value as in aliphatic or aromatic mercaptans. Carbonyl groups have lower anharmonicities. Their value is about 10 cm−1, for both free and associated species.

Low Temperature Infrared Study of Hydrogen Bonding in Dissolved Pyrrole and Indole

1973 ◽  
Vol 51 (7) ◽  
pp. 1075-1082 ◽  
Author(s):  
Marie-Claude Bernard-Houplain ◽  
C. Sandorfy
Keyword(s):  
Hydrogen Bonding ◽  
Low Temperature ◽  
Spectroscopic Methods ◽  
Infrared Study ◽  
Stretching Vibration ◽  
Self Association ◽  
Associated Species

Self-association by hydrogen bonding in the case ot pyrrole was studied by i.r. spectroscopic methods. The fundamental first and second overtones of the NH stretching vibration were measured at different concentrations and at temperatures ranging from 22 to −190 °C. The existence of at least two associated species in solution has been ascertained. 2,5-Dimethylpyrrole and indole were also studied and gave similar results.

A Low Temperature Infrared Study on the Association of Thiols with Pyridine and Triethylamine

1973 ◽  
Vol 51 (7) ◽  
pp. 985-990 ◽  
Author(s):  
R. Bicca De Alencastro ◽  
C. Sandorfy
Keyword(s):  
Low Temperatures ◽  
Bond Formation ◽  
Infrared Study ◽  
Hydrogen Bond Formation ◽  
Text Type ◽  
Predominant Species ◽  
Type Complex ◽  
Proton Donors ◽  
Stretching Vibration ◽  
Associated Species

The infrared spectra of solutions containing propane-1-thiol or benzenethiol as proton donors, and pyridine or triethylamine as proton acceptors were measured down to about −100 °C. The dependence of hydrogen bond formation on concentration and temperature was studied at the fundamental and overtone region of the S—H stretching vibration. The predominant species is found to be a 1:1 [Formula: see text] type complex. In addition, evidence was found for the existence of more highly associated species at low temperatures. Thiol–thiol [Formula: see text] type hydrogen bonds are also present in the case of benzenethiol–pyridine mixtures.

A Low Temperature Infrared Study of Hydrogen Bonding in N-Alkylacetamides

1973 ◽  
Vol 51 (21) ◽  
pp. 3640-3646 ◽  
Author(s):  
Marie-Claude Bernard-Houplain ◽  
C. Sandorfy
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Low Temperature ◽  
Infrared Spectra ◽  
Bond Formation ◽  
Coupling Constant ◽  
Infrared Study ◽  
Hydrogen Bond Formation ◽  
Stretching Vibration ◽  
Secondary Amides

The infrared spectra of N-methylacetamide and two other secondary amides were measured in solution at temperatures ranging from 22 to −190 °C in both the fundamental and the overtone regions. At least two hydrogen bonded species are found as association increases with decreasing temperature. The effect of hydrogen bond formation on the anharmonicity of the NH stretching vibration and on the NH stretching – NH bending coupling constant is examined.

scholarly journals Low-temperature infrared study of ammonium carbamate formation

1984 ◽  
Vol 62 (5) ◽  
pp. 945-948 ◽  
Author(s):  
C. Hisatsune
Keyword(s):  
Solid State ◽  
Low Temperature ◽  
Infrared Spectra ◽  
Low Temperatures ◽  
Hydrogen Ion ◽  
Ion Transfer ◽  
Infrared Study ◽  
Ammonium Carbamate

Two types of infrared spectra observed during the formation of ammonium carbamate [Formula: see text] from the reaction of NH3 and CO2 in the solid state at low temperatures have been re-examined. These spectra had been assigned previously to amorphous and crystalline ammonium carbamate but the present data suggest their origins to be [Formula: see text] and its unstable precursor (NH3)2CO2 in which CO2 is bent. Spectra of amorphous and crystalline ammonium carbamate have been distinguished by comparing the systems NH3/CO2 and NH3/CO2/H2O. Hydrogen ion transfer in the diammoniates occurred at about −80 °C for NH3/CO2 and about −40 °C for ND3/CO2.

A Low Temperature Infrared Study on the Association of Thiols with Organic Oxygen Bases

1974 ◽  
Vol 52 (5) ◽  
pp. 738-743 ◽  
Author(s):  
R. Bicca De Alencastro
Keyword(s):  
Low Temperature ◽  
Infrared Spectra ◽  
Infrared Study ◽  
Text Type ◽  
Organic Bases

The infrared spectra of mixtures of propane-1-thiol and several oxygen-containing weak organic bases have been measured between 2500 and 2650 cm−1, in a 1:1 mixture of CCl3F and C2F4Br2 at temperatures ranging from 20 to –190 °C. Association of the [Formula: see text] type was observed between propane-1-thiol and 2-methyl-tetrahydrofuran, or cyclopentanone. This association is less important between the thiol and hexachloropropanone. In the case of a thiol–furan mixture association of the [Formula: see text] type is strongly indicated.

Hydrogen bonding in the gas phase: the thermodynamic properties of hydrogen fluoride-ether complexes and their far infrared spectra

1971 ◽  
Vol 322 (1548) ◽  
pp. 137-146 ◽  
Keyword(s):  
Hydrogen Bonding ◽  
Gas Phase ◽  
Infrared Spectra ◽  
Equilibrium Constants ◽  
Far Infrared ◽  
Methyl Ethyl ◽  
Rotational Contour ◽  
Stretching Vibration ◽  
Conformational Rearrangements ◽  
Far Infrared Spectra

The equilibrium constants of gas-phase complexes of HF with dimethyl, methyl ethyl and diethyl ether have been measured at several temperatures using the Benesi-Hildebrand approximation on the absorption band of the HF stretching vibration in the complex. From these, values of Δ H of — 43, — 38 and — 30 kJ mol -1 respectively, have been determined. They are interpreted in terms of conformational rearrangements of the ethers when they form hydrogen bonds. The far infrared spectra of the complexes with both HF and DF have also been recorded and in each case a band observed at around 180 cm -1 which is assigned to the intermolecular stretching mode of vibration. For the complex between HF and dimethyl ether a rotational contour has been observed at about 10 cm -1 .

Low-temperature infrared studies of some acid–base reactions

1983 ◽  
Vol 61 (9) ◽  
pp. 2077-2088 ◽  
Author(s):  
Theresa Huston ◽  
I. C. Hisatsune ◽  
Julian Heicklen
Keyword(s):  
Hydrogen Bonding ◽  
Infrared Spectroscopy ◽  
Low Temperature ◽  
Infrared Spectra ◽  
Acid Base ◽  
Reaction Systems ◽  
Solid States ◽  
Infrared Studies

Low-temperature infrared spectroscopy has been used to examine the systems NH3 + H2O, NH3 + HCl, H2O + HCl, NH3 + HNO3, and NH2OH + HNO3. Hydrogen-bonding in the solid states greatly reduces the reactivities in these systems. Temperatures where reactions initiated in the systems NH3(s) + HCl(g), HNO3(s) + NH3(g), H2O(s) + HCl(g), and NH2OH(s) + HNO3(s) were, respectively, −145, −130, −127, and −125 °C. Infrared spectra of 2NH3•H2O, NH3•H2O, NH4Cl•3NH3, NH4NO3•3NH3, NH4NO3•2HNO3, NH2OH2+NO3−, NH3OH+NO3−, H3O+Cl−, H5O2+Cl−, and H5O2+Cl−•H2O have been identified in these reaction systems.

Hydrogen sulphide – halogen complexes studied by matrix isolation vibrational spectroscopy

1985 ◽  
Vol 63 (7) ◽  
pp. 1705-1707 ◽  
Author(s):  
U. P. Agarwal ◽  
A. J. Barnes ◽  
W. J. Orville-Thomas
Keyword(s):  
Low Temperature ◽  
Vibrational Spectroscopy ◽  
Infrared Spectra ◽  
Hydrogen Sulphide ◽  
Matrix Isolation ◽  
Reaction Products ◽  
Hydrogen Halides ◽  
Stretching Vibration

Infrared spectra are reported of mixtures of hydrogen sulphide with chlorine or bromine in low-temperature argon or nitrogen matrices. The H2S … Cl2 and H2S … Br2 complexes were identified from the perturbed halogen stretching vibration. Absorptions due to the corresponding hydrogen halides provided evidence that reaction was occurring between the hydrogen sulphide and halogen (despite the use of a twin-jet deposition), and other reaction products were tentatively identified from the observed absorptions.

scholarly journals Infrared spectroscopy of neutral water clusters at finite temperature: Evidence for a noncyclic pentamer

2020 ◽  
Vol 117 (27) ◽  
pp. 15423-15428 ◽  
Author(s):  
Bingbing Zhang ◽  
Yong Yu ◽  
Yang-Yang Zhang ◽  
Shukang Jiang ◽  
Qinming Li ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Infrared Spectra ◽  
Liquid Water ◽  
Vacuum Ultraviolet ◽  
Water Clusters ◽  
Bulk Water ◽  
Infrared Spectroscopic Study ◽  
Stretching Vibration ◽  
Hydrogen Bonding Networks ◽  
Neutral Water

Infrared spectroscopic study of neutral water clusters is crucial to understanding of the hydrogen-bonding networks in liquid water and ice. Here we report infrared spectra of size-selected neutral water clusters, (H2O)n(n= 3−6), in the OH stretching vibration region, based on threshold photoionization using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals observed in the 3,500−3,600-cm−1region of (H2O)5provide unique spectral signatures for the formation of a noncyclic pentamer, which coexists with the global-minimum cyclic structure previously identified in the gas phase. The main features of infrared spectra of the pentamer and hexamer, (H2O)n(n= 5 and 6), span the entire OH stretching band of liquid water, suggesting that they start to exhibit the richness and diversity of hydrogen-bonding networks in bulk water.

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