Microwave spectrum, conformational equilibrium, 14 N quadrupole coupling constants, dipole moment, vibrational frequencies and quantum chemical calculations for acrylamide

Marstokk, K.-M.; Møllendal, Harald; Samdal, Svein

doi:10.1016/s0022-2860(99)00362-2

Cited by 33 publications

(66 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The dipole moment of the s‐ trans conformer of methyl acrylate is known to be approximately 1 D larger than the one of the s‐ cis conformer, which may be the case with acrylamides as well. Whereas the dipole moment of the s‐ cis conformer of AAm is approximately the same as of its saturated analogue, the dipole moment of the M‐MAAm monomer might be larger than the apparent dipole moment of the saturated monomer segment in the polymer. This situation may result in stronger intermolecular interactions and thus in a shorter monomer–solvent distance, which would reduce the difference in partial molar volume of educts and transition‐state structure and may explain the observed lower absolute Δ ‡ V °( k p ) for M‐MAAm.…”

Section: Resultsmentioning

confidence: 94%

“…Both types of intermolecular interactions operate in the case of acrylamide polymerizations in water. Dipole moments of acrylamides are fairly high, for example, 3.44 D for AAm (s‐ cis conformer), 3.55 D for propanamide, the saturated analogue of AAm, and 3.8 D for DM‐AAm (s‐ cis conformer) . They are thus well above 1.85 D, which is the dipole moment of a water molecule .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Propagation Kinetics of the Radical Polymerization of Methylated Acrylamides in Aqueous Solution

Schrooten

Lacı́k

Stach

et al. 2013

Macro Chemistry & Physics

View full text Add to dashboard Cite

Propagation rate coeffi cients, k p , of the radical polymerization of N , N -dimethylacrylamide ( N , N -dimethylprop-2-enamide), N -methylmethacrylamide ( N ,2-dimethylprop-2-enamide), and methacrylamide (2-methylprop-2-enamide) in aqueous solution are measured via pulsed-laser polymerization in conjunction with size-exclusion chromatography within wide ranges of monomer concentration, temperature, and pressure. As observed for aqueous solutions of other monomers, k p decreases signifi cantly towards higher monomer concentration. For methacrylamide, a higher activation energy and a larger volume of activation are found as compared with N , N -dimethylacrylamide. These two activation parameters are almost identical for N -methylmethacrylamide and for N , N -dimethylacrylamide. radical polymerization processes. Among them, the propagation rate coeffi cient, k p , is of particular relevance. For k p measurement, pulsed-laser polymerization (PLP) in conjunction with polymer analysis by size-exclusion chromatography (SEC) is the well-established method recommended by the IUPAC Subcommittee on "Modeling of Polymerization Kinetics and Processes". [ 5 ] By PLP-SEC, k p is determined via Equation 1 :where X b is the degree of polymerization at the point of infl ection (POI) of the molar-mass distribution (MMD), which may be found from maxima in the fi rst-derivative curve of the logarithmic MMD. [ 6 ] X 1 is obtained from the position of the fi rst such maximum on the low-molar-mass side of the MMD and is identifi ed with the number of propagation steps occurring in the preselected time interval t 0 between two successively applied laser pulses. Monomer concentration, c M , is determined as the arithmetic mean of monomer concentrations before and after application of the sequence of laser pulses required for generating the PLP sample for SEC analysis. The degree of monomer conversion should not exceed a few percent to avoid signifi cant changes in monomer concentration, which would

show abstract

Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Propagation Kinetics of the Radical Polymerization of Methylated Acrylamides in Aqueous Solution

Schrooten

Lacı́k

Stach

et al. 2013

Macro Chemistry & Physics

View full text Add to dashboard Cite

show abstract

“…The calculated infrared spectra at the MP2/aug‐cc‐pVDZ level of theory for the syn monomer and the E1 dimer, together with the di‐imidic acid structure, are compared with the experimental spectrum of Duarte et al ., as shown in Figure . A detailed spectral analysis by comparing the calculated monomer spectra with the experimental spectra had been performed in previous studies by different research groups . In particular, Singh et al .…”

Section: Resultsmentioning

confidence: 99%

“…In addition, acrylamide in its own right is an interesting chemical species for theoretical studies because of several reasons. First, concerning one of its possible tautomer forms, an imidic acid, previous infrared and Raman spectra showed no sign of the existence of such a tautomeric form. However, in condensed‐phase samples, the imidic acid form can be reached through a double proton transfer reaction, which could possibly compete with the monomer tautomerization.…”

Section: Introductionmentioning

confidence: 95%

Hydrogen‐bonding Structures and Energetics of Acrylamide Isomers, Tautomers, and Dimers: An ab initio Study and Spectral Analysis

Wang

Lin

Chao

2016

J Chinese Chemical Soc

View full text Add to dashboard Cite

Hydrogen‐bonding patterns and energetic profiles of acrylamide isomers (syn‐ and skew‐), tautomers (amide and imidic acid forms) and 13 stable dimers have been studied using the second‐order Møller–Plesset perturbation theory with basis sets up to aug‐cc‐pVTZ. Syn‐acrylamide is the most stable monomer with a reaction barrier of 4.15 kcal/mol for the syn–skew isomerization reaction. The direct amide–imidic acid tautomerization reaction is separated by too high a barrier to surpass. The most stable dimer corresponds to the planar double‐hydrogen‐bonded configuration, indicating its crucial role in determining the stability of the formed complex. Moreover, hydrogen bonds have significant effects on the infrared spectral features, which can be consistently explained solely based on the acrylamide dimeric structures and energetics without monomeric and dimeric tautomer forms. The results are useful for studying the stability of the acrylamide clusters in condensed‐phase samples such as those in food chemistry studies.

show abstract

“…However, such comparisons are difficult because for most of the amides corresponding to the nitriles observed in the ISM, one of the most powerful tools for such detections, the millimeter wave spectrum, has never been recorded. Only microwave spectra can be found for propionamide (Marstokk et al 1996), acrylamide (Marstokk et al 2000), or propiolamide (Little & Gerry 1978). The particular case of glycinamide (NH 2 CH 2 C(O)NH 2 ) has to be detailed.…”

Section: Introductionmentioning

confidence: 99%

Rotational spectroscopic study and astronomical search for propiolamide in Sgr B2(N)

Alonso

Kolesníková

Беллоче

et al. 2021

A&A

View full text Add to dashboard Cite

Context. For all the amides detected in the interstellar medium (ISM), the corresponding nitriles or isonitriles have also been detected in the ISM, some of which have relatively high abundances. Among the abundant nitriles for which the corresponding amide has not yet been detected is cyanoacetylene (HCCCN), whose amide counterpart is propiolamide (HCCC(O)NH2). Aims. With the aim of supporting searches for this amide in the ISM, we provide a complete rotational study of propiolamide from 6 to 440 GHz. Methods. Time-domain Fourier transform microwave spectroscopy under supersonic expansion conditions between 6 and 18 GHz was used to accurately measure and analyze ground-state rotational transitions with resolved hyperfine structure arising from nuclear quadrupole coupling interactions of the 14N nucleus. We combined this technique with the frequency-domain room-temperature millimeter wave and submillimeter wave spectroscopies from 75 to 440 GHz in order to record and assign the rotational spectra in the ground state and in the low-lying excited vibrational states. We used the ReMoCA spectral line survey performed with the Atacama Large Millimeter/submillimeter Array toward the star-forming region Sgr B2(N) to search for propiolamide. Results. We identified and measured more than 5500 distinct frequency lines of propiolamide in the laboratory. These lines were fitted using an effective semi-rigid rotor Hamiltonian with nuclear quadrupole coupling interactions taken into consideration. We obtained accurate sets of spectroscopic parameters for the ground state and the three low-lying excited vibrational states. We report the nondetection of propiolamide toward the hot cores Sgr B2(N1S) and Sgr B2(N2). We find that propiolamide is at least 50 and 13 times less abundant than acetamide in Sgr B2(N1S) and Sgr B2(N2), respectively, indicating that the abundance difference between both amides is more pronounced by at least a factor of 8 and 2, respectively, than for their corresponding nitriles. Conclusions. Although propiolamide has yet to be included in astrochemical modeling networks, the observed upper limit to the ratio of propiolamide to acetamide seems consistent with the ratios of related species as determined from past simulations. The comprehensive spectroscopic data presented in this paper will aid future astronomical searches.

show abstract

Microwave spectrum, conformational equilibrium, 14 N quadrupole coupling constants, dipole moment, vibrational frequencies and quantum chemical calculations for acrylamide

Cited by 33 publications

References 39 publications

Propagation Kinetics of the Radical Polymerization of Methylated Acrylamides in Aqueous Solution

Propagation Kinetics of the Radical Polymerization of Methylated Acrylamides in Aqueous Solution

Hydrogen‐bonding Structures and Energetics of Acrylamide Isomers, Tautomers, and Dimers: An ab initio Study and Spectral Analysis

Rotational spectroscopic study and astronomical search for propiolamide in Sgr B2(N)

Contact Info

Product

Resources

About