The near ultraviolet absorption spectra ofortho- andmeta-thiocresols

The absorption spectra ofortho- andmeta-thiocresols have been studied in the present investigation. The ortho-thiocresol spectrum consists of about forty-five bands of rather a diffuse nature and in general low intensity in the region from 2873 Å to 2600 Å. The maximum number of bands is obtained by using a path length of 330 cm. for absorption, the temperature of the bulb being maintained at 14°C. Several of these bands are assigned as due tov-v-transitions. The (0, 0) band is chosen at 35386 cm.^?1 which is the strongest band on the longer wavelength side. Vibrational frequencies in the excited state have values 729, 957 and 1159 and combinations and overtones of these are present. Themeta-thiocresol spectrum consists of about forty bands of rather a diffuse nature and very weak intensities in the region from 2900 Å to 2590 Å. The maximum number of bands is obtained by using a path length 200 cm. for absorption and by keeping the temperature of the bulb at 20° C. The (0, 0) band is chosen to be that at 34793 cm.^?1 which is the strongest band on the longer wavelength side. Vibrational frequencies in the excited state have values 492, 611, 720, 845, 965, 1016 and 1155 cm.^?1 and combinations and overtones of these are present.     

Infrared spectrum of ferroelectric lithium hydrazinium sulphate [Li (N2H5) SO4]

Dielectric observations on lithium hydrazinium sulphate have shown earlier that it is ferroelectric over a range of temperatures from below ?15° C. to above 80° C. and a new type of hydrogen bond rearrangement which would allow the protons to migrate along the chain has also been suggested by others. The infrared spectrum of LiH _z S in the form of mull and as single crystal sections parallel and perpendicular to the ‘C’ axis exhibit about 21 well-defined absorption maxima. The position and the width of the maxima agree with the known structure of the crystal according to which the hydrazine group exists in the form of the hydrazinium ion, NH₂·NH ₃ ⁺ and the observed N⁺-H frequencies agree better with the new correlation curve given by R. S. Krishnan and K. Krishnan (1964). However it has been pointed out that from a comparative study of the new infrared spectra of hydrazonium sulphate and lithium ammonium sulphate that the absorption band at 969 cm.^?1 is due to N-N stretching vibration and that the fairly intense band between 2050–2170 cm.^?1 is due to the bending vibrations of the NH ₃ ⁺ group.     

Emission spectrum of chlorine excited in the presence of argon

The weak band system in the region 2365-2239 Å is discussed in this paper. The wavelengths and the wavenumbers of the bands photographed with the first order of a 21-ft. grating spectrograph are recorded. The vibrational analysis of the bands and their corresponding intensity distribution are also given. The analysis shows that the lower state of the system is the same as that of the 2600-2390 Å system discussed in the earlier paper and is the 3π (O_u ⁺) state established by Elliott at 17658 cm.^?1 The constants of the upper state arew ₀′ = 261·5 cm.^?1,w ₀′x ₀′ = 0·812 cm.^?1, T₀=61290 cm.^?1.     

Lacunary subsets of orthonormal sets

В РАБОтЕ РАссМАтРИВА УтсьS _Р-пОДсИстЕМы О. Н.с. В ЧАстНОстИ, ДОкАжыВА Етсь слЕДУУЩАь тЕОРЕ МА, кОтОРАь НЕУсИльЕМА. тЕОРЕМА.пУсть Р>2 —ЧЕ тНОЕ ЧИслО, δ — пРОИжВО льНОЕ ЧИслО, 0<δ≦p?2,Φ= {Φ _n(x)} _n=1 ^N —O.H.C.,x?[0,1],пРИЧЕМ ∥ Φ _n∥_p≦M, n=1,2,...,N, гДЕР=Р+δ, 0М<∞. тОгДА Иж сИстЕМы Ф МОж НО ВыБРАть пОДсИстЕМ У \(\Phi ' = \left\{ {\varphi _{n_k } } \right\}_{k = 1}^{N'} ,N' \geqq N^{\alpha (\delta )} ,\alpha (\delta ) = \frac{{2\delta }}{{p(p - 2 + \delta )}}\) , тАкУУ, ЧтО Дль лУБОгО п ОлИНОМА \(P(x) = \sum\limits_{k = 1}^{N'} {a_k \varphi _{n_k } (x)} \) ИМЕЕ т МЕстО ОцЕНкА $$(\mathop \sum \limits_{k = 1}^{{\rm N}'} a_k^2 )^{1/2} \leqq \left\| P \right\|_p \leqq c_{p,M,\delta } (\mathop \sum \limits_{k = 1}^{{\rm N}'} a_k^2 )^{1/2} $$ (c _p, m, δ — пОстОьННАь, жАВИ сьЩАь тОлькО Отp, M, δ, НО НЕ От N ИлИ кОЁФФИцИЕНтОВ пО лИ-НОМА). пРИВОДьтсь И ДРУгИЕ РЕжУльтАты А НАлОгИЧНОгО хАРАктЕ РА.     

Raman spectrum of dimethyl sulfoxide (DMSO) and the influence of solvents

The Raman spectrum of DMSO is recorded with a Hilger two-prism spectrograph andλ 4358 Å excitation. In addition to all the Raman lines reported earlier, six new lines at 898, 925, 1223, 1309, 2811 and 2871 cm.^?1 are observed and tentative assignments are given. The influence of solvents (CCl₄, CHCl₃, CH₃COOH) on the S=O bond is also studied. A shift from the liquid phase value,i.e., 1043 cm.^?1 to 1054, 1052 and 1009 cm.^?1 in the respective solvents is observed. The possibilities of association effects and hydrogen bonding are discussed.     

Emission spectrum of chlorine excited in the presence of argon

The spectrum of chlorine excited in the presence of argon has been photographed with a 21-ft. grating spectrograph in the first order. Two band systems in the region 2600–2390 Å and 2365–2239 Å are observed which appear to be respectively analogous to the 2950–2670 Å and 2660–2590 Å systems of bromine reported earlier by Venkateswarlu and Verma. The wavelengths and the wavenumbers of all the bands in the system 2600–2390 Å are given. The vibrational scheme along with the corresponding Franck-Condon parabola is also given. The analysis suggests that the lower state of the system is the 3π(O _u ⁺_ state established by Elliott at 17658 cm.^?1 and that the upper state is at 67773 cm.^?1 The vibrational constants obtained arew ₀′ = 246·6 cm.^?1,w ₀′x ₀′ = 0·615 cm.^?1,w ₀″ = 255·2 cm.^?1,w ₀″x ₀″ = 5·5 cm.^?1,w ₀″y ₀″ = ?0·0155 cm.^?1 andw ₀″z ₀″ = 0·00115 cm.^?1     

The near ultraviolet absorption spectrum of tetrahydro-naphthalene

The near ultraviolet absorption spectrum of tetrahydronaphthalene commonly known as tetralin consists of sharp bands in the region from 2800 to 2500 Å. The spectrum consists of about sixty bands. The maximum number of bands is obtained by using a path length of 200 cm. at room temperature which was nearly 30° C. Several of these very sharp bands have to be assigned tov-v transitions. The 0, 0 band is chosen to be at 36790 cm^?1. Vibrational frequencies in the excited state have values 1185, 951 and 682 and combinations and overtones of these are present. Assignments of the different frequencies are discussed.     

Emission spectrum of bromine excited in the presence of argon

The wavelengths and wavenumbers of the band heads of the system 3150–2970 Å as obtained from the plates taken on the first order 21′ grating spectrograph are given along with the vibrational analysis. This system is shown to be due to a transition from an upper electronic state at T_e = 48516 cm.^-1 with ω′ _e = 162·0 cm.^?1 and ω′ _e χ′ _e = 0·29 cm.^?1 to the well-known³ Π _u (O _u ⁺) state at T_e = 15918 cm.^-1 This lower state is common with that of the system 2950–2670 Å.     

Vinyl polymerization

Polymerization of Acrylamide initiated by cobaltic ions in aqueous solution at 15° C. and 20° C. in HClO₄ and H₂SO₄ media have been studied. Kinetics have been followed by determining the rate of cobaltic ion disappearance as well as monomer disappearance with variations in cobaltic, monomer and hydrogen ion concentrations, temperature, ionic strength, etc. Besides polymer reaction it has been observed that side reactions like water oxidation and monomer oxidation also contribute to rate of cobaltic ion disappearance. Certain anomalous results in H₂SO₄ medium have been observed. A reaction scheme involving CoOH²⁺ and Co³⁺ as initiators in HClO₄ and H₂SO₄ media respectively and mixed termination—mutual and linear—has been suggested. Certain rate parameters involving rate constants for initiation, propagation, termination and the corresponding activation energies have been evaluated.     

Paramagnetic resonance of Gd3+ in SmCl3·6H2O single crystals

The Paramagnetic Resonance of Gd³⁺ in SmCl₃·6H₂O single crystals, grown from solution, is studied at room temperature. A six line spectrum for H//Z and a seven line spectrum for H//X corresponding to ΔM=± 1 transitions are observed. Their angular variation in ZX plane from?=0° to?=90°, is studied and the spin-Hamiltonian analysis is presented. The probable amount of admixture of the next higher electronic state⁶P_7/2 with the ground state⁸S_7/2 is also estimated.     

Mixed complexes of iron (III)—thiocyanate with some nitrogen and oxygen donors and their analytical applications

Methods for the determination of iron (III) as thiocyanate complex in the presence of neutral donors like isoquinoline and antipyrine have been developed. The two methods are of equal sensitivity (ε=18,000±100 lit. mole^?1 cm^?1) but operate at widely different hydrogen ion concentrations ranging from 10^?5 N(pH 5·0) to 7N. The interference of various foreign substances has been studied in the two methods. The application of these methods in the analysis of alloys and commercial HCl for iron has been explored and the composition of the extracting species established.     

Quasikonvexe Multiplikatoren starker Konvergenz

пУсть {f _k; f _k ^* ?X×X^* — пОлНАь БИОРтОгОНАльНАь сИс тЕМА В БАНАхОВОМ пРОстРАН стВЕ X (X^* — сОпРьжЕННОЕ пРОст РАНстВО). пУсть (?→+0) $$\begin{gathered} S_n f = \sum\limits_{k = 0}^n {f_k^* (f)f_k ,} K(f,t) = \mathop {\inf }\limits_{g \in Z} (\left\| {f - g} \right\|_x + t\left| g \right|_z ), \hfill \\ X_0 = \{ f \in X:\mathop {\lim }\limits_{n \to \infty } \left\| {S_n f - f} \right\|_x = 0\} ,X_\omega = \{ f \in X:K(f,t) = 0(\omega (t))\} , \hfill \\ \end{gathered} $$ гДЕZ?X — НЕкОтОРОЕ пОД пРОстРАНстВО с пОлУН ОРМОИ ¦·¦ И Ω — МОДУль НЕпРЕРыВНО стИ УДОВлЕтВОРьУЩИИ Усл ОВИУ sup Ω(t)/t=∞. пОслЕДОВАтЕ льНОстьΤ={Τ _k} кОМплЕксНых ЧИ сЕл НАжыВАЕтсь МНОжИтЕл ЕМ сИльНОИ схОДИМОст И ДльX _Τ, жАпИсьΤ?М[X _Τ,X _Τ], ЕслИ Д ль кАжДОгО ЁлЕМЕНтАf?X _Τ сУЩЕстВ УЕт тАкОИ ЁлЕМЕНтf ^τ?х₀, ЧтОf _k ^* (f ^τ)=Τ_kf _k ^* (f) Дль ВсЕхk. ДОкА жАНО сРЕДИ ДРУгИх слЕДУУЩ ЕЕ УтВЕРжДЕНИЕ. тЕОРЕМА. пУсmь {f_k; f _k ^* } —Н ЕкОтОРыИ (с, 1)-БАжИс тАк ОИ, ЧтО ВыпОлНьУтсь НЕРАВЕН стВА тИпА НЕРАВЕНстВА ДжЕ ксОНА с пОРьДкОМ O(?_n) u тИ пА НЕРАВЕНстВА БЕРНшmЕИ НА с пОРьДкОМ O(1/?_n). ЕслИ пОслЕДОВАтЕл ьНОсть Τ кВАжИВыпУкл А И ОгРАНИЧЕНА, тО $$\tau \in M[X_{\omega ,} X_0 ] \Leftrightarrow \omega (\varphi _n )\tau _n \left\| {S_n } \right\|_{[X,X]} = o(1).$$ ЁтОт ОБЩИИ пОДхОД НЕМ ЕДлЕННО ДАЕт клАссИЧ ЕскИЕ РЕжУльтАты, ОтНОсьЩИ Есь к ОДНОМЕРНыМ тРИгОНОМЕтРИЧЕскИМ РьДАМ. НО тЕпЕРь ВОжМО жНы ДАльНЕИшИЕ пРИлОжЕН Иь, НАпРИМЕР, к РАжлОжЕНИьМ пО пОлИ НОМАМ лЕжАНДРА, лАгЕР РА ИлИ ЁРМИтА.     

Isotope shift studies of the ultra-violet and visible bands of P16O and P18O

The spectra of P¹⁶O and P¹⁸O were excited in sealed discharge tubes containing neon (2–3 mm. pressure), oxygen gas enriched to 65 per cent. of¹⁸O and trace amounts of phosphorus vapour and photographed on a 3 m. grating spectrograph at a dispersion of 2·5 Å/mm. Isotope shift studies in theβ-bands confirmed the earlier vibrational scheme of Curryet al. and showed conclusively that the red as well as the violet degraded bands belonged to the sameβ-system. The present studies of isotope shifts also confirmed the vibrational assignments of the extensive ultraviolet bands involving the² Σ ^??X² Π transition and theγ-bands (A² Σ ⁺?X² Π). In the case of the visible bands, they provided evidence for the first time that the bands at 5585 Å, 5962 Å and 6385 Å belonged to one system and involved 0–0, 0–1 and 0–2 transitions respectively.     

Rotational analysis of the 0-0 band of the A3 ∏ inv-X3 ∑ − system of ND

The 0-0 band of the A³ ∏ _inv?X³ ∑ ^? system of ND was excited in an electrodeless microwave oscillator (2450 Mc./s.) discharge and photographed on a 6·6 meter concave grating spectrograph in the second order at a dispersion of 0·56 A/mm. Twenty-five out of the predicted twenty-seven branches have been identified in the rotational structure of the 0-0 band. From a rotational analysis, the following rotational constants have been determined: (i)X ³ ∑ ^? state—

     

Vibrational spectra and normal vibrations of acetanilide and N-deuterated acetanilide

The Raman and infra-red spectra of acetanilide and N-methylacetamide and of their N-deuterated compounds have been recorded. The vibrational frequencies of acetanilide have been assigned and the nature of the Amide I, II and III bands in acetanilide and N-methylacetamide has been investigated by the study of the changes in the frequencies of these bands in the spectra of their deuterated compounds. Acetanilide and deuterated acetanilide molecules have been subjected to normal co-ordinate treatment and the mixing up of the skeletal frequencies arising out of the in-plane vibrations has been determined. These results indicate that as in secondary amides, the amide II and amide III bands in acetanilide are due to the combined contribution ofδ (NH) andν (C-N) vibrations, but the contribution ofν (C-N) to the amide II band is less in acetanilide and deuterated acetanilide than in cases of N-methylacetamide and deuterated N-methylacetamide.     

Emission spectrum of bromine excited in the presence of argon

The wavelengths and wavenumbers of the band heads of the system 2660-2590 Å as obtained from the plates taken on the first order 21-feet grating spectrograph are given along with its vibrational analysis. This system is shown as the transition from an upper state at T _e =56776 cm.^?1 withω _e = 108·0 cm.^?1 to the³ Π _u (O _u ⁺) state at T _e =15918 cm.^?1 The lower state is the same as that of the two systems in the regions 2950-2670 Å and 3150-2970 Å reported earlier.     

Isotope shifts in the second negative bands of O 2 +

The second negative bands of O ₂ ⁺ , lying in the region 5000–1850 Å, have been photographed using oxygen enriched in¹⁸O. A study of the isotope shifts in the band heads revealed that thev″ numbering is to be increased by one unit whereas thev′ numbering remains unaltered. This change in vibrational numbering leads to a revision of the molecular constants of O ₂ ⁺ , especially of those in its ground state. These are discussed and the extension of the band system in the vacuum ultra-violet region reported. The possibility of developing a simple spectrographic method for the isotopic assay of oxygen using the isotope shifts in this band system is pointed out. The revised rotational and vibrational constants in theX ² II _g ground state of O ₂ ⁺ molecule are as follows :

$$\begin{gathered} \omega _e = 1903 \cdot 85 cm.^{ - 1} , \hfill \\ \omega _e x_e = 16 \cdot 18 cm.^{ - 1} , \hfill \\ B_e = 1 \cdot 6920 cm.^{ - 1} \hfill \\ and \hfill \\ r_e = 1 \cdot 1161 {\AA}. \hfill \\ \end{gathered} $$     

Electrodeposition of copper on copper single crystal (100) face in presence of chloride ions

Observations of copper electrodeposits on to the (100) plane of copper was made from highly purified solutions of copper sulphate containing known concentration of hydrochloric acid from 10^?10 to 10^?1 m/L. In pure solutions at current densities of 5 and 10 mA/cm.² layers and pyramids were noticed. In the presence of hydrochloric acid of concentration 10^?9 to 10^?5 m/L there is a gradual decrease of distance between successive steps. At 10^?4 m/L of HCl there was the breaking of layers giving rise to ridge type of growth. With the increase of concentration to 3·5×10^?3 m/L pyramids appear again. On increasing the concentration of HCl to 10^?2 m/L there was the formation of triangular pyramids of cuprous chloride and on still increasing the concentration, polycrystalline type of deposit was noticed. The transition from layer to ridge, ridge to pyramids and to polycrystalline deposit occurs at all c.d. studied but the critical concentration of HCl needed for the transition depends upon the current density.     

Emission spectrum of bromine excited in the presence of argon—part I

Bromine was excited by an uncondensed transformer discharge in the presence of argon. The spectrum obtained was found to be different from what one gets without the presence of a foreign gas and consists of (1) a short discrete band system in the region 3150–2970 Å, (2) an extensive discrete band system in the region 2950–2670 Å, (3) a short and weak discrete system in the region 2660–2590 Å and a set of diffuse bands in the region 3340–3190 Å. The wavelengths and wave numbers of the band heads of the system 2950–2670 Å, as obtained from the measurements of the plates taken on the first order 21-ft. grating spectrograph, are given along with the vibrational analysis. This system is shown to be due to a transition from an upper electronic state at 51802 cm.^-1 with ω′_e = 150·5 cm.^-1 and ω′_e X′_e = 1·15 cm.^-1 to the well known³ II _α (O₂ ⁺) state at 15918 cm.^-1     

A new2 Π-X2 Π band system of NS

Vibrational and rotational analysis of some bands forming a new band system of NS is given. It is also shown that the system involves the ground X² Π _reg. state of the molecule, and is due to the transition² Π _reg.→X² Π _reg. The bands form a singlev″=0 progression withv′=7, 8, 9 and 10. The assignment of these quantum numbersv′, v″ is supported by (1) Δ₂F″ (J) values which are identical with those for thev″=0 bands of theβ andγ systems and (2) the isotopic shift data from¹⁵NS bands, respectively. The derived vibrational and rotational constants for the new² Π _reg. state are as follows (cm.^?1 units):

	T e	ω e	ω e x e	B e	D e
2 Π 3/2..	30364·8	803·3	3·82	0·6030	2·0×10?6
2 Π ½..	30292·3	797·0	3·63	0·5898	2·0×10?6