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1984[X]
121Author    GiorgioG W Greening, KonradG. WeilRequires cookie*
 Title      
 Abstract    The electrolytic conductivity of pure molten silver chloride and of molten silver chloride doped with up to 2mole% of CaCl2, CdCl2, CsCl, LiCl has been measured in the temperature range 460°C to 620°C. The changes in the conductivity of silver chloride when doped with ionic salts are found to be analogous to the conductivity changes found in binary alkali halide mixtures. E le c tro ly tic C o n d u c tiv ity o f P u r e a n d D o p e d M o lte n S ilv e r C h lo r id e 
  Reference    Z. Naturforsch. 39a, 764—767 (1984); received June 7 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0764.pdf 
 Identifier    ZNA-1984-39a-0764 
 Volume    39 
122Author    Ko Young, Shin Und, Hanns-Peter BoehmRequires cookie*
 Title     
 Abstract    e o b a c h tu n g e n v o n S ta p e lf e h lo r d n u n g e n b e i d e r O x y d a tio n d e r zw eiten z u r e r s te n S tu f e d e s G ra p h ith y d ro g e n s u lfa ts Observation of stacking disorder during the oxidation of second stage to first stage graphite hydrogensulfate Graphite has been oxidized to graphite hydrogensulfate with (NH4)2S2Og in concentrated H2S04. The stage 2 compound formed very rapidly, but further oxidation to stage 1 could be fol­ lowed conveniently. X-ray diffraction of the intermediate phases showed nonintegral (00/)-reflec-tions indicative of partial interstratification disorder. The interlayer spacing of the stage 1 compound increased with continued oxidation. The degree of oxidation as function of oxidation time has been determined from the position of the minima in the reflectance spectra. The density of the compounds and the ratio of acid molecules to anions in the intercalated layers has been estimated using these data and those of buoyancy measurements. There is a minimum in packing density early in the formation of the first stage. The kinetics of intercalation seems to be first order with respect to the free interlayer spaces. 
  Reference    Z. Naturforsch. 39a, 768—777 (1984); eingegangen am 24. Mai 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0768.pdf 
 Identifier    ZNA-1984-39a-0768 
 Volume    39 
123Author    G. Amoretti, G. Calestani, D. C. GioriRequires cookie*
 Title     
 Abstract    h e R efin ed S t r u c t u r e o f TI1S2 a n d th e I m p l ic a ti o n s o n th e S u p e rp o s itio n M o d e l A n a ly s is o f TI1S2: G d 3+ S p in H a m ilto n ia n P a r a m e te r s The crystal structure of ThS2 has been refined starting from single crystal diffractometry data. The accurate determination of the positional parameters allows us to reexamine the SPM analysis of the second degree crystal field parameters for Gd3+ in ThS2 matrix. The fitting of the EPR data is still possible by means of a suitable two exponents power law for the intrinsic parameter only if the substitutional Gd3+ ion displaces in the mirror (bc) plane with respect to the undistorted Th4+ site. The resulting increase of the mean metal-ligand distances agrees with the expected expansion of the ligand cage around the trivalent Gd ion. The applicability of the proposed method to examine the impurity induced distortions in an host crystal is discussed too. 
  Reference    Z. Naturforsch. 39a, 778—782 (1984); received May 21. 1984 
  Published    1984 
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 Identifier    ZNA-1984-39a-0778 
 Volume    39 
124Author    H. Haeuseler, G. SchneiderRequires cookie*
 Title      
 Abstract    Lattice Dynamics of Compounds with Matlockite-Tvpe Structure On the basis of the rigid ion model and polarizable ion model, lattice dynamical calculations have been carried out for the fluorohalides BaFCl and BaFBr and for the oxyhalides LaOCl, LaOBr, YOC1, SmOCl and GdOCl which crystallize with the tetragonal Matlockite-type structure (PbFCl-type). The results of these calculations: short range force constants, effective dynamical charges and polarizabilities are communicated and discussed. Bonding in the fluorohalides is much more ionic than in the oxyhalides. G itte rd y n a m ik v o n V e rb in d u n g e n m it M a t l o c k i t -S t r u k t u r 
  Reference    Z. Naturforsch. 39a, 783—788 (1984); eingegangen am 15. Juni 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0783.pdf 
 Identifier    ZNA-1984-39a-0783 
 Volume    39 
125Author    Klaus Scheffler, B. Hartmut, Ch Stegmann, P. Ulrich, SchulerRequires cookie*
 Title     
 Abstract    u r T ie f te m p e r a tu r k o n f o r m a tio n v o n P h e n o x y ls y s te m e n Studies of the Low Temperature Conformation of Phenoxyls by ESR, ENDOR and TRIPLE-Resonance In a series of ortho-and para-substituted phenoxyls the coupling of the /?-nuclei (H and P) is caused by hyperconjugation and 7r-cr-mechanisms, leaving open the signs of the combined HFS constants. By examining the ENDOR and TRIPLE spectra these couplings turned out to be nega­ tive. Thus the sign of the well known temperature gradient of these parameters, due to hindered rotation of the substituted group, is positive, leading to a planar conformation of the radicals at low temperature. E S R -, E N D O R -u n d T R I P L E -U n te r s u c h u n g e n 
  Reference    Z. Naturforsch. 39a, 789—793 (1984); eingegangen am 14. Juni 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0789.pdf 
 Identifier    ZNA-1984-39a-0789 
 Volume    39 
126Author    Ivan GutmanRequires cookie*
 Title      
 Abstract    Three recursion relations for the algebraic structure count are deduced, which are closely analogous to the well-known recursion relation for the number of Kekule structures. An efficient graphical method for the calculation of algebraic structure count is proposed. 
  Reference    Z. Naturforsch. 39a, 794—796 (1984); received March 21 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0794.pdf 
 Identifier    ZNA-1984-39a-0794 
 Volume    39 
127Author    Ivan Gutman, Ahmed ShalabiRequires cookie*
 Title     
 Abstract    o p o lo g ic a l P r o p e r tie s o f B e n z e n o id S y s te m s X X IX . O n H o s o y a 's T o p o lo g ic a l In d e x Some properties of Hosoya's topological index Z and the modjfied topological index Z of benzenoid hydrocarbons are examined. A simple relation between Z and Z has been established, namely Z= Z1+a, where a = 0.02. 
  Reference    Z. Naturforsch. 39a, 797—799 (1984); received April 19 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0797.pdf 
 Identifier    ZNA-1984-39a-0797 
 Volume    39 
128Author    M. Woznyj, F. X. Prielmeier, H.-D LüdemannRequires cookie*
 Title     
 Abstract    r e s s u r e D e p e n d e n c e o f th e M e ltin g a n d S e l f D if f u s io n in 2 ,2 -d im e th y lp ro p a n e , 2 ,2 -d im e th y lp r o p io n itr ile , a n d 2 -m e th y lp ro p a n o l-2 The melting pressure curves of 2,2-dimethylpropane, 2,2-dimethylpropionitrile and 2-methyl-propanol-2 and the pressure dependence of the hex <=> fee transition of 2,2-dimethylpropane have been determined in the pressure range between 0.1 and 200 MPa. The self diffusion coeffi­ cients D in the liquid state of the three compounds have been determined as function of pressure (Fmax — '20 MPa) from the melting pressure curve up to ca. 450 K. At high temperatures and high pressures the self diffusion coefficients of the three compounds become rather similar. The influence of the hydroxylgroup upon the diffusivity of (CH3)3COD is most clearly seen at the lowest temperatures. The isobars of C(CH3)4 and (CH3)3CCN are straight lines with identical slopes. For (CH3)3COD all isobars show a curvature. From the data in the Arrhenius representa­ tion activation volumes and activation energies are derived. For C (CH3)4 the density dependence of D can be described with the rough hard sphere model. 
  Reference    Z. Naturforsch. 39a, 800—806 (1984); received June 15 1984 
  Published    1984 
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 Identifier    ZNA-1984-39a-0800 
 Volume    39 
129Author    MichaelC. BöhmRequires cookie*
 Title      
 Abstract    The band structure of the metal-ligand-metal (M-L-M) bridged quasi one-dimensional (ID) cyclopentadienylmanganese polymer, MnCp 1, has been studied in the unoxidized state and in a partly oxidized modification with one electron removed from each second MnCp fragment. The tight-binding approach is based on a semiempirical self-consistent-field (SCF) Hartree-Fock (HF) crystal orbital (CO) model of the INDO-type (intermediate neglect of differential overlap) combined with a statistical averaging procedure which has its origin in the grand canonical ensemble. The latter approximation allows for an efficient investigation of violations of the trans­ lation symmetries in the oxidized ID material. The oxidation process in 1 is both ligand-and metal-centered (Mn 3d.2 states). The mean-field minimum corresponds to a charge density wave (CDW) solution with inequivalent Mn sites within the employed repeat-units. The symmetry adapted solution with electronically identical 3d centers is a maximum in the variational space. The coupling of this electronic instability to geometrical deformations is also analyzed. The ligand amplitudes encountered in the hole-state wave function prevent extremely large charge separations between the 3d centers which are found in ID systems without bridging moieties (e.g. Ni(CN)g~ chain). The symmetry reduction in oxidized 1 is compared with violations of spatial symmetries in finite transition metal derivatives and simple solids. The stabilization of the valence bond-type (VB) solution is physically rationalized (i.e. left-right correlations between the 3d centers). The computational results derived for 1 are generalized to oxidized transition metal chains with band occupancies that are simple fractions of the number of stacking units and to ID systems that deviate from this relation. The entropy-influence for temperatures 7* + 0 is shortly discussed (stabilization of domain or cluster structures). S y m m e try V io la tio n s in P a r t i a l l y O x id iz e d O n e -D im e n s io n a l (I D) T r a n s itio n M e ta l P o ly m e r s . M e ta l-L ig a n d -M e ta l (M -L -M) B rid g e d S y s te m s 
  Reference    Z. Naturforsch. 39a, 807—829 (1984); received June 22 1984 
  Published    1984 
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 Identifier    ZNA-1984-39a-0807 
 Volume    39 
130Author    SalatRequires cookie*
 Title     
 Abstract    The integrability of Hamiltonians of the type H(PX , P2, 0], Q2) = X Pi ' <7,(0,, Q2), G, 2 n-1=1,2 periodic in 0,, is investigated numerically and analytically. With G, = co, (01, £>2) and = X 03 i the unperturbed frequencies co, = 6//0/9F, are independent of the momenta, and 1=1,2 KAM theory cannot be applied. Surface of section plots and Fourier analysis of orbits reveal that "most" Hamiltonians are integrable. Possibly non-integrable Hamiltonians do not show "island plus ergodic region" structure but sequences which tend towards infinity. No theory is available to distinguish completely the classes of integrable and non-integrable functions Gj(Qi,Q2). In such a theory the problem of "small denominators" would play an essential role just as in KAM theory. In te g ra b ility o f N o n -K A M H a m ilto n ia n s 
  Reference    Z. Naturforsch. 39a, 830—841 (1984); received June 30 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0830.pdf 
 Identifier    ZNA-1984-39a-0830 
 Volume    39 
131Author    L. J. Gallego, J. M. López, J. A. AlonsoRequires cookie*
 Title      
 Abstract    The Conformal Solution and Flory's expressions for the free energy of mixing AGM of a binary liquid alloy have been modified by using a form for the enthalpy of mixing AHM which incor­ porates the concentration dependence given by Miedema's semiempirical model. This model emphasizes the importance of the atomic cell-surface area concentration in evaluating AHM. The modified forms of AGM have been used to construct the liquidus curves of NaCs and NaK. L iq u id u s C u rv e s o f E u te c tic N a K a n d N a C s S y s te m s 
  Reference    Z. Naturforsch. 39a, 842—845 (1984); received May 24 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0842.pdf 
 Identifier    ZNA-1984-39a-0842 
 Volume    39 
132Author    W. Möller, H. Gg, WagnerRequires cookie*
 Title      
 Abstract    Measurements of the Rate Constant of the Reaction NH2 + CH4 -* NH3 + CH} behind Incident Shock Waxes The rate constant of the reaction NH2 + CH4-> • NH3 + CH3 was measured at temperatures of about 1800 K by time-resolved UV-spectroscopy of the products behind incident shock waves. NH: was produced by the presence and thermal decomposition of hydrazine. The data were evaluated by fitting simulated concentration-time-profiles to the measured ones. A mean rate constant k = (4 ± 2) 10" cm3 mol"1 s-1 1730 < T/K < 1950 was obtained. The temperature dependence of the reaction is discussed. M e s s u n g d e r G e s c h w in d ig k e its k o n s ta n te n d e r R e a k t io n N H 2+ C H 4 N H 3 + C H 3 h i n te r e in f a lle n d e n S t o ß w e lle n 
  Reference    Z. Naturforsch. 39a, 846—852 (1984); eingegangen am 3. Mai 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0846.pdf 
 Identifier    ZNA-1984-39a-0846 
 Volume    39 
133Author    Antonio Guarnieri, Gerhard TolkmitRequires cookie*
 Title      
 Abstract    The millimeterwave spectrum of fluoroacetonitrile (CH:FCN) in the ground state has been investigated in the region between 50 and 150 GHz. The transitions have been fitted to a Hamil­ tonian using three rotational constants, five quartic and seven sextic centrifugal distortion constants in the symmetric top reduction by van Eijck and Typke and in the s-reduction of Watson. Further Watson's "determinable constants" have been calculated. M illim e te rw a v e S p e c tr u m a n d C e n tr if u g a l D i s t o r t i o n A n a ly s is o f F lu o ro a c e to n itr ile in th e G r o u n d S t a t e 
  Reference    Z. Naturforsch. 39a, 853—857 (1984); received June 4 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0853.pdf 
 Identifier    ZNA-1984-39a-0853 
 Volume    39 
134Author    W. Stahl, E. Fliege, H. DreizlerRequires cookie*
 Title      
 Abstract    We performed a pulse sequence experiment utilizing a technique, which is comparable with two-dimensional NMR-spectroscopy. Some theoretical considerations based on the three-level Bloch equations are given. This double resonance technique may be useful for the assignment of complicated spectra. T w o -D im e n sio n a l M ic ro w a v e F o u r ie r T r a n s f o r m S p e c tr o s c o p y 
  Reference    Z. Naturforsch. 39a, 858—864 (1984); received June 27 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0858.pdf 
 Identifier    ZNA-1984-39a-0858 
 Volume    39 
135Author    Dines Christen, Kjaus-J RammeRequires cookie*
 Title      
 Abstract    The rotational spectra of vibrationally excited CF3NC states (v4, v6, v7, v8, 2v8 and 3vg) have been recorded and analyzed for the transitions J: 1 — ► 2, 2 — * • 3 and 3 4 using (for the degenerate states) a simplified frequency expression based on perturbation theory. The following vibration/rotation interaction parameters were derived (in MHz): a4: 0.145, a6: — 5.585, q%\ 4.241, x7: 2.350, <?7: 1.438, a8: -10.610, and <?8: 5.101. The Coriolis constant £88 was determined to be 0.672 in good agreement with the value calculated from the force field. 
  Reference    Z. Naturforsch. 39a, 865—870 (1984); received June 30 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0865.pdf 
 Identifier    ZNA-1984-39a-0865 
 Volume    39 
136Author    H. Bürger, R. Eujen, A. Rahner, P. Schulz, S. CradockRequires cookie*
 Title      
 Abstract    Fourier transform infrared spectra of the monoisotopic species H374Ge79Br and H374Ge81Br have been recorded in the v, /v4 region near 2100 cm-1 with a resolution of 0.015 cm-1 and in the v6 and 2 v6 regions near 580 and 1150 cm"1 with a resolution of 0.04 cm"1. Rotational analyses based on ~ 1500, — 1100 and ~ 300 data of v,/v4, v6 and 2 v6 respectively for each isotopomer have been performed, and ground state and excited state vibrational, rotational and rovibrational parameters have been determined, v,, 2115.815 0(2)/2115.813 4(2) cm"1, and v4, 2126.016 5(1)Z2126.016 7(1) cm"1 (H374Ge79Br/H374Ge81Br), are weakly coupled by Coriolis x, y reso­ nance. C) 4 ~ -0.021. v6, 577.601 2(4)/577.541 7(4) cm"1, and v4 are affected by / (±2. ±2) resonance. Furthermore, the hot bands (v, + v3) — v3, (v3 -(-v4) — v3, (v3 + v6) — v3, 2 vg12 — vj1 and 2 — vf1 have been detected and analyzed. V ib ra tio n a l S p e c tr a a n d F o r c e C o n s t a n t s o f S y m m e tr ic T o p s , X I H I |1] F o u r ie r T r a n s f o r m I n f r a r e d S p e c t r a o f M o n o i s o t o p i c H 3G e B r S p e c ie s in th e vi /V4 a n d ve R e g io n 
  Reference    Z. Naturforsch. 39a, 871—879 (1984); received June 2 1984 
  Published    1984 
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 Identifier    ZNA-1984-39a-0871 
 Volume    39 
137Author    Isao OkadaRequires cookie*
 Title      
 Abstract    The experimental findings by Klemm et al. that in molten LiCl the isotope effect on the lithium mobilities increases with temperature and that the isotope effect between the two iso­ topically pure melts, i.e. 6LiCl and 7LiCl is greater than that in natural LiCl are reflected by the self-exchange velocities of the Li-isotopes near the Cl~-ions obtained by MD. M D -S im u la tio n o f M o lte n L iC l; S e lf -E x c h a n g e V e lo c itie s o f L i-Is o to p e s n e a r C l~ -Io n s 
  Reference    Z. Naturforsch. 39a, 880—887 (1984); received June 22 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0880.pdf 
 Identifier    ZNA-1984-39a-0880 
 Volume    39 
138Author    W.A P Luck, H. Y. ZhengRequires cookie*
 Title     
 Abstract    ffe c t o f S o lv e n ts a n d T e m p e r a tu r e o n O —H s t r e tc h i n g B a n d o f M e th a n o l: M e a s u r e o f v a n d e r W a a l s I n t e r a c t i o n s Prof. Dr. G. Kortüm zum 80. Geburtstag gew idmet The frequency shift of methanolic OH stretching bands by different nonpolar solvents at different temperatures can be described quantitatively by an equation proposed recently relating it to the temperature dependence of van der Waals interactions. The method shows that methanolic OH groups are surrounded by about 40% more solvent molecules than t-butanol OH groups. Frequency shifts of CH3OH by binary solvent mixtures demonstrate an averaged potential with small preference of the solvent with higher interaction. 
  Reference    Z. Naturforsch. 39a, 888—892 (1984); received June 19 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0888.pdf 
 Identifier    ZNA-1984-39a-0888 
 Volume    39 
139Author    Y. Riad, AdelN. Asaad, G.-AS. Gohar, A. A. AbdallahRequires cookie*
 Title    K in e tic s a n  
 Abstract    d M e c h a n is m le a d in g to D im e r ic R e d o x P r o d u c t s o f 4 -N itro s o b e n z a ld e h y d e in A lk a lin e D i o x a n e -W a t e r M e d ia Dedicated to Prof. Dr. Y. Iskander on the occasion of his 70th birthday A Cannizzaro disproportionation reaction of 4-nitrosobenzaldehyde (I) and sodium hydroxide in dioxane-water media is kinetically studies by UV-Vis. absorption spectroscopy. The reaction did not give the expected products, namely 4-nitrosobenzyl alcohol and 4-nitrosobenzoic acid, but gave equimolecular quantities of 4,4'-diformylazoxybenzene (II) and 4,4'-dicarboxyazoxy-benzene (III) and was found to exhibit third-order kinetics, second-order in aldehyde and first-order in base. The rate constants as well as the activation thermodynamic parameters were calcu­ lated for different temperatures and different dioxane-water compositions, and discussed on the bases of dielectric constant, viscosity and heat of mixing of the medium components. The rate determining step is a hydride ion transfer from the adduct (formed from the attack of one hydroxide ion on molecule of I) to another molecule of I. A mechanism is given to explain the formation of the end reaction products. 
  Reference    Z. Naturforsch. 39a, 893—898 (1984); received June 1 1984 
  Published    1984 
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 Identifier    ZNA-1984-39a-0893 
 Volume    39 
140Author    P. J. Nandapurkar, V. Hlavacek, J. Degreve, R. Janssen, P. Van RompayRequires cookie*
 Title     
 Abstract    e ta ile d S ta b ility A n a ly s is — P a tte r n o f G ro w th a n d E f fe c t o f I n h o m o g e n ity A detailed stability analysis of the one dimensional steady state solutions for the Brusselator model under the conditions of diffusion of initial (non-autocatalytic) components has been performed both for zero flux as well as fixed boundary conditions. In addition to subcritical as well as supercritical bifurcations, situations have been observed where all solution branches at a bifurcation point are unstable. A case of degenerate steady state bifurcation (2 solutions emanating from the same bifurcation point) has also been noticed. A transient simulation of the system in growth reveals the importance of growth rate on the pattern selection process and suggests that the selection of branches at a bifurcation point may be influenced by perturbations/ fluctuations. It also indicates that a stability analysis of the bifurcation diagram alone cannot decide the state of the system in a transient process, and under certain situations complex behavior may be observed at limit points. Numerical calculations on coupled cells indicate that a heterogenity in the system can introduce multiple (two) time scales in the system. As the ratio of time scales increases, aperiodic or irregular oscillations are observed for the 'fast' variable. A combination of cells with one cell in a steady-state mode and the other in a periodic motion results in a combined motion of the entire system. For a distributed parameter system, a heterogenity can cause development of sharp local concentration gradients, alter the stability properties of steady state as well as periodic solu­ tions and can cause partitioning of the system. R e a c tio n -D iffu s io n D is s ip a tiv e S y s te m s — 
  Reference    Z. Naturforsch. 39a, 899—916 (1984); received May 4 1984 
  Published    1984 
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 TEI-XML for    default:Reihe_A/39/ZNA-1984-39a-0899.pdf 
 Identifier    ZNA-1984-39a-0899 
 Volume    39 
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