Infrared and Raman studies of nitrate impurity in nitrite complexes

Brooker, M. H.; Irish, D. E.

doi:10.1021/ic50072a007

Cited by 19 publications

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“…Infrared and Raman methods of analyses for small amounts of NO3-in NO2-were advanced. Evidence for NO3 -impurity in nitrite complexes has also been reported (24). Vibrational bands due to NO,-are thus assigned with full knowledge of NO3-impurity.…”

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Infrared and Raman Spectroscopic Studies of Solid Alkali Metal Nitrites

Brooker¹,

Irish²

1971

Can. J. Chem.

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Infrared and Raman spectra of solid LiNO,.H,O, LiNO,, NaNO,, KNO,, and CsNO, are presented and discussed. Pronounced changes in the spectra of LiNO,.H,O during dehydration to anhydrous LiN0, are interpreted as evidence for an ordered distribution of NO2-ions over two non-equivalent sites (akin to linkage isomerism) in anhydrous LiN0,. The frequencies of the internal modes of the nitrite ion shift to lower values with increasing cation size. Vibrational bands due to nitrate ion present as an impurity are assigned.Les spectres infrarouge et Raman des LiNO,.H,O, LiNO,, NaNO,, KNO, et CsNO, sont presentks et discutks. Les changements prononcks qui se produisent dans les spectres pendant la dkshydratatlon du sel LiN02.HZ0 B LiNOz sont interprktks comme preuve d'une distribution ordonnde des ions NOzsur deux sites non tquivalents (vkritable isomkrisme de liaison) dans le sel anhydre LiN0,. Les frkquences des modes internes de l'ion nitrite sont abaisskes lorsque la dimension du cation augmente. Les bandes vibrationnelles dues a l'ion nitrate present comrne impuretk sont assignkes.Canadian Journal of Chemistry, 49, 1289 (1971) Introductionreported to decompose at 200 "C before melting An interest in the vibrational spectra of con-at 225 "C (19). The solid potassium and caesium centrated electrolyte solutions and in N+ nitrites take the form of unmanageable plastics vibrations of ions similar to nitrate (1) has recently with of water; however, caused us to focus attention on metal nitrites, definite hydrates of these are many of which are extremely water soluble. (19,20). Sodium nitrite, on the other hand, forms When interpreting data for concentrated solu-well defined single crystals. The discovery by tions and melts, knowledge about the probe ion Strijk and MacGillavr~ (21) of the ferroelectric in static, cationic environments is an asset. Al-phase transition in NaNO, prompted considerthough NaNO, has been extensively studied and able infrared (12-15) and Raman (l 6, 7, KNO, to a lesser extent (2-17), no systematic studies, most of which have been performed on comparison including other alkali metal nitrites single and concerned with various has been reported. this study Raman spectra phenomena associated with order-disorder ferroand multiple internal reflectance (m.i.r.) infrared spectra of powders have been obtained. The An consideration prior the m.i.r. technique is particularly useful for dis-measurement of the physical properties of nitrites closing features of intense absorption bands, the be sample purity. The assay positions of which are not distorted by con-reagent grade KN02 varies 89 97% tfibutions from longitudinal optical modes "itrite ; even NaNO2 seldom exceeds 98% minior Christiansen filter effects (18). An interesting mum nitrite assay.are H20, consequence of this study has been the observa-OH-, C1-, C032-, and NO3-; of these the tion of spectral changes on dehydration of the NO3-is most serious. Potassium nitrite is known lithium nitrite monohydrate which can be to form a solid solution with NO3-...

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confidence: 70%

Infrared and Raman Spectroscopic Studies of Solid Alkali Metal Nitrites

Brooker¹,

Irish²

1971

Can. J. Chem.

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“…The Cs 2 NaLn(NO 2 ) 6 (Ln = Y, Tb, Eu) complexes were analogously synthesized. Brooker and Irish have pointed out the presence of nitrate impurities in nitrite complexes, and this was carefully checked.…”

Section: Methodsmentioning

confidence: 99%

Experimental and Theoretical Studies of the Vibrational and Electronic Spectra of a Lanthanide Ion at a Site of T_h Symmetry: Pr³⁺ in Cs₂NaPr(NO₂)₆

Ning

Faucher³

et al. 2011

Inorg. Chem.

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The Pr(3+) ion in Cs(2)NaPr(NO(2))(6) is situated at a site of T(h) symmetry with 12-coordination to O atoms of bidentate nitrito groups. First-principles calculations of the vibrational modes of the complex were carried out using the density functional theory with the generalized gradient approximation Perdew-Burke-Ernzerhof exchange-correlation functional. The calculations that treated the Pr(3+) 4f electrons as valence electrons showed better agreement with the experimental vibrational assignments compared with those treating the 4f electrons a part of the inner core. The (1)D(2) → (3)H(4) emission spectra of Cs(2)NaPr(NO(2))(6) at 7 K enabled assignments to be made for the crystal-field (CF) levels of the ground-state multiplet. The emission of the dilute system Cs(2)NaY(NO(2))(6):Pr(3+) was dominated by NO(2)(-) triplet emission, which was quenched at elevated temperatures by energy transfer to trace Eu(3+) impurity. From magnetic dipole calculations and the vibronic fingerprint, detailed assignments are given for the complex 10 K electronic absorption spectrum of Cs(2)NaPr(NO(2))(6) between 3940 and 18800 cm(-1), and the derived Pr(3+) 4f(2) energy-level data set has been fitted by calculation. By comparison with Cs(2)NaPrCl(6), the fourth-order CF parameter in Cs(2)NaPr(NO(2))(6) is relatively small so that interaction with a 4fnp configuration is not important. From the NO(2)(-) absorption bands above 20,000 cm(-1), the N-O bond length change upon excitation is small, whereas the angle O-N-O opens by more than 10° in the triplet state. By contrast to the NO(2)(-) internal vibration frequencies, which except for the wagging mode show only minor changes with the environment, the triplet-state energy shows a linear decrease with an increase of the lanthanide (Ln(3+)) ionic radius in Cs(2)NaLn(NO(2))(6). Using the eigenvectors from the energy-level fit, the variation of the inverse magnetic susceptibility with temperature has been calculated between 1 and 100 K and the values are somewhat lower than those from experiment.

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“…Crystal data: Ground-state structure for [Ni(dppe)(h 1 -NO 2 )Cl], T = 100 K, C 26 H 24 ClNNiO 2 P 2 , M r = 538.56, monoclinic, space group Cc (No. 9), Z = 4, a = 13.4279 (18), b = 11.4341 (16), c = 17.039(2) , b = 110.546(2)8, V = 2449.7(6) 3 , Station 9.8, Daresbury Laboratory, l = 0.6940 , m = 1.056 mm À1 , T min /T max = 0.765, 2q max = 61.368, 13 952 reflections collected, 7372 unique [R int = 0.064], wR 2 = 0.129, R 1 = 0.0525 (I > 2s(I)), Flack parameter = 0.035 (11). 70 % converted structure of [Ni(dppe)(NO 2 )Cl], T = 100 K, C 26 H 24 ClNNiO 2 P 2 , M r = 538.56, monoclinic, space group Cc (No.…”

Section: Methodsmentioning

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“…The d(NO 2 ) band shifts 14 cm À1 to 829 cm À1 and the n(N-O) band shifts 71 cm À1 to 1404 cm À1 . These shifts to higher energy are characteristic of the formation of the nitrito-(h 1 -ONO) isomer [16] and show almost complete conversion (Figure 1 a; inset).…”

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“…The ground state nitro-(h 1 -NO 2 ) isomer has characteristic Raman bands, particularly the d(NO 2 ) deformation (815 cm À1 ) and one of the n(N-O) stretches (1333 cm À1 ), with the other n(N-O) band being weak and for these studies less informative. [16] The sample was irradiated at 115 K for 10 min using the visible light from the illuminator on the confocal Raman microscope, resulting in the crystal changing color from red towards yellow. The Raman spectrum was then re-recorded after photolysis.…”

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Reversible 100 % Linkage Isomerization in a Single‐Crystal to Single‐Crystal Transformation: Photocrystallographic Identification of the Metastable [Ni(dppe)(η¹‐ONO)Cl] Isomer

et al. 2009

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Infrared and Raman studies of nitrate impurity in nitrite complexes

Cited by 19 publications

References 2 publications

Infrared and Raman Spectroscopic Studies of Solid Alkali Metal Nitrites

Infrared and Raman Spectroscopic Studies of Solid Alkali Metal Nitrites

Experimental and Theoretical Studies of the Vibrational and Electronic Spectra of a Lanthanide Ion at a Site of T_h Symmetry: Pr³⁺ in Cs₂NaPr(NO₂)₆

Reversible 100 % Linkage Isomerization in a Single‐Crystal to Single‐Crystal Transformation: Photocrystallographic Identification of the Metastable [Ni(dppe)(η¹‐ONO)Cl] Isomer

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Infrared and Raman studies of nitrate impurity in nitrite complexes

Cited by 19 publications

References 2 publications

Infrared and Raman Spectroscopic Studies of Solid Alkali Metal Nitrites

Infrared and Raman Spectroscopic Studies of Solid Alkali Metal Nitrites

Experimental and Theoretical Studies of the Vibrational and Electronic Spectra of a Lanthanide Ion at a Site of Th Symmetry: Pr3+ in Cs2NaPr(NO2)6

Reversible 100 % Linkage Isomerization in a Single‐Crystal to Single‐Crystal Transformation: Photocrystallographic Identification of the Metastable [Ni(dppe)(η1‐ONO)Cl] Isomer

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Experimental and Theoretical Studies of the Vibrational and Electronic Spectra of a Lanthanide Ion at a Site of T_h Symmetry: Pr³⁺ in Cs₂NaPr(NO₂)₆

Reversible 100 % Linkage Isomerization in a Single‐Crystal to Single‐Crystal Transformation: Photocrystallographic Identification of the Metastable [Ni(dppe)(η¹‐ONO)Cl] Isomer