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Studies of the Solid and Liquid Phases of HF, HCl and HBr by Slow-Neutron Inelastic Scattering; Etude des Phases Solide et Liquide de HF, HCl Et HBr par la Diffusion Inelastique des Neutrons Lents; 0418 0417 0423 0427 0415 041d 0418 0415 0422 0412 0415 0420 0414 042b 0425 0418 0416 0418 0414 041a 0418 0425 0424 0410 0417 HF, HCl I HBr 0421 041f 041e 041c 041e 0429 042c 042e 041d 0415 0423 041f 0420 0423 0413 041e 0413 041e 0420 0410 0421 0421 0415 042f 041d 0418 042f 041c 0415 0414 041b 0415 041d 041d 042b 0425 041d 0415 0419 0422 0420 041e 041d 041e 0412 ; Estudio de las Fases Solida y Liquida del HF, HCl Y HBr por Dispersion Inelastica de Neutrones Lentos

Conference:

Abstract

The liquid and solid phases of HF, HCl and HBr were studied between 30 and 1200 cm{sup -1} using the inelastic scattering of cold neutrons (0.005 eV). These measurements were made in order to examine systematically the influence of an increasing degree of electronegativity and anion size on the low frequency molecular motions in both the solid and liquid phases. HF was first studied because it was known from X-ray diffraction data to form long zigzag hydrogen bonded chains in the solid state. The spectra of neutrons inelastically scattered from the liquid and solid phases of HF emphasize the high degree of association that exists through the liquid phase due to hydrogen bonding. The data for HF were compared for purposes of interpretation with similar scattering data for HF{sub 2}{sup -} and H{sub 2}F{sub 3}{sup -} ions which have structures similar to those units which comprise the zigzag hydrogen bonded chains in HF, The data were also compared with Raman and infrared measurements on HFj ions. These comparisons allowed frequencies characteristic of a single unit to be differentiated from those characteristics of the entire chain and from the low frequency lattice modes. A line observed at 0.067 eV has been  More>>
Authors:
Boutin, H.; [1]  Brookhaven National Laboratory, Upton, NY (United States)]; Safford, G. J. [2] 
  1. Picatinny Arsenal, Dover, NJ (United States)
  2. Brookhaven National Laboratory, Upton, NY (United States)
Publication Date:
Jun 15, 1965
Product Type:
Conference
Report Number:
IAEA-SM-58/43
Resource Relation:
Conference: Symposium on Inelastic Scattering of Neutrons, Bombay (India), 15-19 Dec 1964; Other Information: 18 refs., 2 tabs., 3 figs.; Related Information: In: Inelastic Scattering of Neutrons. Vol. II. Proceedings of the Symposium on Inelastic Scattering of Neutrons| 590 p.
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANIONS; BONDING; COLD NEUTRONS; DEFORMATION; DIPOLE MOMENTS; DIPOLES; ELECTRIC FIELDS; ELECTRONEGATIVITY; HYDROBROMIC ACID; HYDROCHLORIC ACID; HYDROFLUORIC ACID; INELASTIC SCATTERING; INTERACTION RANGE; NEUTRON SPECTRA; PHASE TRANSFORMATIONS; SLOW NEUTRONS; SOLIDS; X-RAY DIFFRACTION
OSTI ID:
22184066
Research Organizations:
International Atomic Energy Agency, Vienna (Austria)
Country of Origin:
IAEA
Language:
English
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA13M3410008601
Submitting Site:
INIS
Size:
page(s) 393-406
Announcement Date:
Jan 30, 2014

Conference:

Citation Formats

Boutin, H., Brookhaven National Laboratory, Upton, NY (United States)], and Safford, G. J. Studies of the Solid and Liquid Phases of HF, HCl and HBr by Slow-Neutron Inelastic Scattering; Etude des Phases Solide et Liquide de HF, HCl Et HBr par la Diffusion Inelastique des Neutrons Lents; 0418 0417 0423 0427 0415 041d 0418 0415 0422 0412 0415 0420 0414 042b 0425 0418 0416 0418 0414 041a 0418 0425 0424 0410 0417 HF, HCl I HBr 0421 041f 041e 041c 041e 0429 042c 042e 041d 0415 0423 041f 0420 0423 0413 041e 0413 041e 0420 0410 0421 0421 0415 042f 041d 0418 042f 041c 0415 0414 041b 0415 041d 041d 042b 0425 041d 0415 0419 0422 0420 041e 041d 041e 0412 ; Estudio de las Fases Solida y Liquida del HF, HCl Y HBr por Dispersion Inelastica de Neutrones Lentos. IAEA: N. p., 1965. Web.
Boutin, H., Brookhaven National Laboratory, Upton, NY (United States)], & Safford, G. J. Studies of the Solid and Liquid Phases of HF, HCl and HBr by Slow-Neutron Inelastic Scattering; Etude des Phases Solide et Liquide de HF, HCl Et HBr par la Diffusion Inelastique des Neutrons Lents; 0418 0417 0423 0427 0415 041d 0418 0415 0422 0412 0415 0420 0414 042b 0425 0418 0416 0418 0414 041a 0418 0425 0424 0410 0417 HF, HCl I HBr 0421 041f 041e 041c 041e 0429 042c 042e 041d 0415 0423 041f 0420 0423 0413 041e 0413 041e 0420 0410 0421 0421 0415 042f 041d 0418 042f 041c 0415 0414 041b 0415 041d 041d 042b 0425 041d 0415 0419 0422 0420 041e 041d 041e 0412 ; Estudio de las Fases Solida y Liquida del HF, HCl Y HBr por Dispersion Inelastica de Neutrones Lentos. IAEA.
Boutin, H., Brookhaven National Laboratory, Upton, NY (United States)], and Safford, G. J. 1965. "Studies of the Solid and Liquid Phases of HF, HCl and HBr by Slow-Neutron Inelastic Scattering; Etude des Phases Solide et Liquide de HF, HCl Et HBr par la Diffusion Inelastique des Neutrons Lents; 0418 0417 0423 0427 0415 041d 0418 0415 0422 0412 0415 0420 0414 042b 0425 0418 0416 0418 0414 041a 0418 0425 0424 0410 0417 HF, HCl I HBr 0421 041f 041e 041c 041e 0429 042c 042e 041d 0415 0423 041f 0420 0423 0413 041e 0413 041e 0420 0410 0421 0421 0415 042f 041d 0418 042f 041c 0415 0414 041b 0415 041d 041d 042b 0425 041d 0415 0419 0422 0420 041e 041d 041e 0412 ; Estudio de las Fases Solida y Liquida del HF, HCl Y HBr por Dispersion Inelastica de Neutrones Lentos." IAEA.
@misc{etde_22184066,
title = {Studies of the Solid and Liquid Phases of HF, HCl and HBr by Slow-Neutron Inelastic Scattering; Etude des Phases Solide et Liquide de HF, HCl Et HBr par la Diffusion Inelastique des Neutrons Lents; 0418 0417 0423 0427 0415 041d 0418 0415 0422 0412 0415 0420 0414 042b 0425 0418 0416 0418 0414 041a 0418 0425 0424 0410 0417 HF, HCl I HBr 0421 041f 041e 041c 041e 0429 042c 042e 041d 0415 0423 041f 0420 0423 0413 041e 0413 041e 0420 0410 0421 0421 0415 042f 041d 0418 042f 041c 0415 0414 041b 0415 041d 041d 042b 0425 041d 0415 0419 0422 0420 041e 041d 041e 0412 ; Estudio de las Fases Solida y Liquida del HF, HCl Y HBr por Dispersion Inelastica de Neutrones Lentos}
author = {Boutin, H., Brookhaven National Laboratory, Upton, NY (United States)], and Safford, G. J.}
abstractNote = {The liquid and solid phases of HF, HCl and HBr were studied between 30 and 1200 cm{sup -1} using the inelastic scattering of cold neutrons (0.005 eV). These measurements were made in order to examine systematically the influence of an increasing degree of electronegativity and anion size on the low frequency molecular motions in both the solid and liquid phases. HF was first studied because it was known from X-ray diffraction data to form long zigzag hydrogen bonded chains in the solid state. The spectra of neutrons inelastically scattered from the liquid and solid phases of HF emphasize the high degree of association that exists through the liquid phase due to hydrogen bonding. The data for HF were compared for purposes of interpretation with similar scattering data for HF{sub 2}{sup -} and H{sub 2}F{sub 3}{sup -} ions which have structures similar to those units which comprise the zigzag hydrogen bonded chains in HF, The data were also compared with Raman and infrared measurements on HFj ions. These comparisons allowed frequencies characteristic of a single unit to be differentiated from those characteristics of the entire chain and from the low frequency lattice modes. A line observed at 0.067 eV has been associated with the deformation frequency v{sub 2} of the F-H...F group in solid HF and has been correlated with similar frequencies in H{sub 2}F{sub 3}{sup -} and HF{sub 2}{sup -} ions as a function of the F-F distance. In addition, a broad peak observed at 0.007 eV has been attributed to a rotational motion of the F-H...F unit around the F-F bond. The spectrum of liquid HF is also discussed with respect to these motions. The spectra of liquid HCl (180 Degree-Sign K), solid HCl Phases I and III (143 and 85 Degree-Sign K, respectively), liquid HBr (193 Degree-Sign K) and solid HBr Phases I and II (153 and 103 Degree-Sign K, respectively) have been compared with the above data for HF. Those spectra show an increasing complexity compared to that of HF. This can be attributed to a weaker degree of association, which is expected from the decreasing electronegativity of the anion. The systematic study of these spectra in the various phases and at variais temperatures allows a distinction to be made between the low frequency motions characteristic of the lattice or of an hydrogen-bonded chain and those low frequency motions which involve nearest-neighbour interactions or short-range forces. The results of these measurements are in agreement with previous infrared data and indicate that hydrogen bonding is an influential factor in explaining the spectra of the solid phases of both HCl and HBr. These data are not in agreement, however, with theories that account for the solid phases of these compounds only in terms of simple dipole arrays or in terms of long-range interactions involving the dipole moment of one single unit interacting with an average electric field. (author) [French] Les auteurs ont etudie les phases liquide et solide de HF, HCl et HBr entre les raies d'absorption 30 et 1200 cm{sup -1} employant la methode de la diffusion inelastique des neutrons froids (0, 005 eV). Ils ont procede a ces mesures pour examiner systematiquement l'influence qu'un accroissement du degre d'electronegativite et la dimension des anions exercent sur les mouvements moleculaires de basse frequence dans la phase solide et la phase liquide. L'etude a d'abord porte sur HF du fait que les donnees obtenues par diffraction des rayons X avaient montre que dans ce compose a l'etat solide apparaissaient de longues chaines en zigzag liees par l'hydrogene. Les spectres des neutrons inelastiquement diffuses par les phases liquide et solide de HF font ressortir le haut degre d'association qui existe dans toute la phase liquide en raison de la liaison hydrogenee. Aux fins d'interpretation, les auteurs comparent les donnees relatives a HF a des donnees analogues relatives aux ions HF{sub 2}{sup -} et H{sub 2}F{sub 3}{sup -} dont les structures sont semblables a celle des elements de reseau qui comportent des chaines en zigzag liees par l'hydrogene. Ils les comparent egalement aux resultats des mesures faites sur les ions HF{sub 2}{sup -} par la methode de Raman et au moyen de l'infrarouge. Grace a ces etudes comparatives, ils ont pu differencier les frequences caracteristiques d'un seul element de celles qui caracterisent la chaine entiere et des modes de reseaux de basse frequence. La raie observee a 0,067 eV a ete associee a la frequence de deformation v{sub 2} du groupe F-H... F dans HF solide et rapportee aux frequences semblables dans les ions HH{sub 2}F{sub 3}{sup -} et HF{sub 2}{sup -} sous la forme d'une fonction de la distance F-F. En outre, l'origine d'un large pic, observe a 0,007 eV, a ete attribuee a un mouvement de rotation de l'element F-H' ' * F autour de la liaison F-F, Le spectre de HF a l'etat liquide fait egalement l'objet d'une discussion du point de vue de ces mouvements. Les spectres de HCl liquide (180 Degree-Sign K), des phases I et III de HCl solide (143 et 85 Degree-Sign K respectivement), de HBr liquide (193 Degree-Sign K) et des phases I et II de HBr solide (153 et 103 Degree-Sign K respectivement) font l'objet d'une comparaison avec les donnees susmentionnees relatives a HF. Ces spectres accusent une complexite croissante par rapport a celui de HF. Cette particularite peut etre due au moins haut degre d'association auquel on peut s'attendre etant donne la diminution de l'electronegativite de l'anion. L'etude systematique de ces spectres dans diverses phases et a diverses temperatures permet de faire une distinction entre les mouvements de basse frequence qui caracterisent le reseau ou une chaine liee par l'hydrogene et les mouvements de basse frequence qui font intervenir des interactions entre les voisins les plus proches ou des forces de faible portee. Les resultats de ces mesures concordent avec les donnees obtenues auparavant avec l'absorption infrarouge et indiquent que la liaison par l'hydrogene facilite dans une grande mesure l'explication des spectres correspondant aux phases solides de HCl et de HBr. Cependant, ces donnees ne concordent pas avec les theories qui rendent compte des phases solides de ces composes uniquement en fonction d'arrangements dipolaires simples ou d'interactions a grande distance faisant intervenir le moment dipolaire d'un seul element de reseau en interaction avec un champ electrique moyen. (author) [Spanish] Los autores han estudiado las fases liquida y solida del HF, HCI y HBr, entre 30 y 1200 cm{sup 1}, recurriendo a la dispersion inelastica de neutrones frios (0,005 eV). Estas mediciones se realizaron a fin de examinar sistematicamente la influencia que ejerce el aumento del grado de electronegatividad y del tamano de los aniones sobre los movimientos moleculares de baja frecuencia, tanto en fase solida como liquida. Se estudio en primer lugar el HF por saberse -segun datos obtenidos en experimentos de difraccion realizados con rayos X- que en el estado solido forma largas cadenas enlazadas en zigzag por el hidrogeno. El espectro de los neutrones inelasticamente dispersos en las fases liquida y solida del HF pone de relieve el alto grado de asociacion que existe en el estado solido como consecuencia del enlace hidrogeno. Los autores han comparado, con fines de interpretacion, los datos correspondientes al HF con datos analogos sobre la dispersion en el caso de los iones HF{sub 2}{sup -} y H{sub 2}F{sub 3}{sup -}, que presentan estructuras semejantes a las de las unidades que comprenden, en el HF, las cadenas enlazadas en zigzag por el hidrogeno. Tambien compararon esos datos con los resultados de las mediciones Raman y del espectro infrarrojo en los iones HFJ. Estas comparaciones permitieron distinguir entre las caracteristicas de frecuencia de una sola unidad, y de las caracteristicas de la cadena entera y de los modos reticulares de baja frecuencia. La raya observada a 0, 067 eV ha podido asociarse a la frecuencia de deformacion v{sub 2} del grupo F-H* * F en el HF solido, y se ha correlacionado con frecuencias analogas en los iones H{sub 2}F{sub 3}{sup -} y HFJ como una funcion de la distancia F-F. Ademas, el maximo ensanchado que se observa a 0,007 eV se ha atribuido a un movimiento rotatorio del grupo F-H' F alrededor del enlace F-F. Los autores tratan tambien del espectro del HF liquido en lo que respecta a esos movimientos. Han comparado los datos ya mencionados, relativos al HF, con los espectros del HCI liquido (180 Degree-Sign K), de las fases solidas I y III del HCI (143 y 85 Degree-Sign K, respectivamente), del HBr liquido (193 Degree-Sign K) y de las fases solidas I y II del HBr (153 y 103 Degree-Sign K, respectivamente). La mayor complejidad que esos espectros ofrecen en comparacion con el del HF puede atribuirse a un menor grado de asociacion, lo que es de esperar dada la decreciente electronegatividad del anion. El estudio sistematico de estos espectros en las diversas fases y a distintas temperaturas permite distinguir entre los movimientos de baja frecuencia, caracteristicos de la red o de una cadena de enlaces hidrogeno, y aquellos movimientos de baja frecuencia en los que intervienen interacciones de los atomos mas proximos o fuerzas de corto alcance. Los resultados de estas mediciones concuerdan con los datos acerca del espectro infrarrojo obtenidos previamente, e indican que el enlace hidrogeno constituye un importante factor para explicar los espectros del HCI y del HBr en fase solida. No obstante, esos datos no responden a las teorias que explican las fases solidas de esos compuestos unicamente en funcion de disposiciones dipolares simples o de interacciones de largo alcance en las que interviene el momento dipolar de una sola unidad en interaccion con un campos electrico de intensidad media. (author) [Russian] Zhidkie i tverdye fazy HF, HCl i NVg izuchalis' mezhdu 30 i 1200 sm{sup -1} pri pomoshhi neuprugogo rassejanija holodnyh nejtronov (0,005 jev). Jeti izmerenija proizvodilis' s cel'ju sistematicheskogo izuchenija vlijanija uvelichenija otricatel'nogo jelektricheskogo zarjada i razmerov anionov na nizkochastotnye molekuljarnye dvizhenija kak v tverdoj, tak i v zhidkoj fazah. HF issledovalsja pervym, t.k. dannye difrakcii rentgenovskih luchej pokazyvali, chto v tverdom sostojanii on obrazuet dlinnye zigzagoobraznye cepi s vodorodnoj svjaz'ju. Spektry nejaronov, neuprugo rassejannyh ot zhidkoj i tverdoj faz HF, jasno pokazali vysokuju stepen' associacii, sushhestvujushhuju vo vsej zhidkoj faze blagodarja vodorodnoj svjazi. S cel'ju interpretacii dannye po HF byli sopostavleny s dannymi analogichnogo rassejanija ionov HF i H{sub 2}F{sub 3}{sup -}, kotorye imejut struktury, analogichnye tem sostavnym chastjam v HF, kotorye vkljuchajut zigzagoobraznye cepi s vodorodnoj svjaz'ju. Jeti dannye byli takzhe sopostavleny s rezul'tatami izmerenij s pomoshh'ju infrakrasnyh luchej i izmerenij po metodu Ramana na ionah HF Pound-Sign . Jeti sopostavlenija pozvolili otlichit' chastotnuju harakteristiku otdel'noj sostavnoj chasti ot chastotnoj harakteristiki vsej cepi i ot nizkochastotnyh kolebanij reshetki. Linija, nabljudavshajasja pri 0,067 jev, byla associirovana s chastotoj deformacii v{sub 2} gruppy F-N...F v tverdom HF, i byla ustanovlena ee svjaz' s analogichnymi chastotami v ionah H{sub 2}F{sub 3}{sup -} i HF{sub 2}{sup -} kak frakcii rasstojanija F-F. Krome togo, shirokij pik, otmechennyj pri 0,007 jev, byl pripisan vrashhatel'nomu dvizheniju sostavnoj chasti F -F vokrug svjazi F -F. Spektr zhidkogo HF takzhe budet rassmatrivat'sja s tochki zrenija jetih dvizhenij. Spektry zhidkogo NS1 (180 Degree-Sign K), faz I i III tverdogo NS1 (143 i 85 Degree-Sign K sootvetstvenno), zhidkogo NVg (193 Degree-Sign K) i faz I i II tverdogo NVg (153 i 103 Degree-Sign K sootvetstvenno) byli sopostavleny s vysheukazannymi dannymi dlja HF. Jeti spektry pokazyvajut eshhe bol'shuju slozhnost', chem u HF. Jeto mozhet byt' ob{sup j}asneno bolee slaboj stepen'ju associacii, kotoruju mozhno ozhidat' v svjazi s umen'sheniem otricatel'nogo zarjada aniona. Sistematicheskoe izuchenie jetih spektrov v razlichnyh fazah i pri razlichnyh temperaturah pozvoljaet provesti razlichie mezhdu harakteristikami nizkokachestvennyh dvizhenij reshetki ili cepi s vodorodnoj svjaz'ju i harakteristikami teh nizkochastotnyh dvizhenij, kotorye zatragivajut vzaimodejstvija blizhajshego soseda ili blizkodejstvujushhie sily. Rezul'taty jetih izmerenij soglasujutsja s imejushhimisja dannymi, poluchennymi s pomoshh'ju infrakrasnyh luchej, i pokazyvajut, chto vodorodnaja svjaz' javljaetsja sushhestvennym faktorom ob{sup j}asnenija spektrov tverdyh faz kak HCl, tak i NVg. Odnako jeti dannye ne soglasujutsja s teoriej, kotoraja ob{sup j}asnjaet tverdye fazy jetih soedinenij tol'ko s tochki zrenija prostyh dipol'nyh sistem ili s tochki zrenija dal'nih vzaimodejstvij, zatragivajushhih dipol'nyj moment odnoj otdel'noj sostavnoj chasti, vzaimodejstvujushhej so srednim jelektricheskim polem. (author)}
place = {IAEA}
year = {1965}
month = {Jun}
}