123 Phases in CeLa2Cu2MgO8 samples

A tetragonal 123 phase with the composition close to CeLa₂ { Cu ₂ ²⁺ } [Mg²⁺]O₈ (the braces indicate the Cu(2) positions; the brackets indicate the Cu(1) positions) with the parameters a = b = 0.3909(3) nm, c = 1.6591(8) nm was prepared at 860°C under an oxygen atmosphere with an elevated oxygen pressure. When the lanthanum-for-barium substitution was incomplete, the resulting 123 phase had the composition close to CeLa_1.7Ba_0.3{ Cu _1.7 ²⁺ } [Mg]O₈ with the unit cell parameters a = b = 0.3868(3) nm, c = 1.6578(8) nm that contains Cu³⁺ in the Cu(2) positions. The partial substitution of barium for lanthanum (the melting point of barium oxide is almost 500°C lower that of the lanthanum oxide) appreciably facilitated the synthesis: the 123 phase in this sample was more than 90%. The existence of Cu³⁺ in the Cu(2) positions enhanced the electrical conductivity of the sample.     

Preparation and Structure of Cerium Titanates Ce2TiO5, Ce2TiO7, and Ce4Ti9O24

Compounds Ce₂TiO₅, Ce₂Ti₂O₇, and Ce₄Ti₉O₂₄ were prepared by heating appropriate mixtures of solids containing Ce⁴⁺ and Ti³⁺ or Ti which were placed in a platinum-silica-ampoule combination at T = 1250°C (3d) under vacuum. The new compounds were characterized by powder patterns. We obtained Ce₂TiO₅ which is isotypic to La₂TiO₅ and crystallizes in the Y₂TiO₅-type (space group Pnma) with a = 10.877(6) Å, b = 3.893(1) Å, c = 11.389(8) Å, Z = 4. Ce₂Ti₂O₇ is isotypic to La₂Ti₂O₇ and crystallizes in the monoclinic Ca₂Nb₂O₇ type (space group P 2₁) with a = 7.776(6) Å, b = 5.515(4) Å, c = 12.999(6) Å, β = 98.36(5), Z = 4. The compound Ce₄Ti₉O₂₄ crystallizes orthorhombic with a = 14.082(4) Å, b = 35.419(8) Å, c = 14.516(4) Å, Z = 16. The new cerium titanate Ce₄Ti₉O₂₄ is isotypic to Nd₄Ti₉O₂₄ (space group Fddd (No. 70)) which represents a novel type of structure.     

空气中合成固溶体荧光粉Ba2(Zn, Mg)Si2O7:Ce3+,Eu2+,Eu3+及其发光特性

采用高温固相法在空气中合成了Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu,yCe³⁺系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba_1.97-yZn_1-xMg_xSi₂O₇:0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu²⁺离子的4f⁶5d¹-4f⁷跃迁,590~725 nm红光区窄带谱源于Eu³⁺的⁵D₀-⁷F_J (J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu³⁺在Ba_1.97-yZn_1-xMg_xSi₂O₇基质中被还原成了Eu²⁺;当x=0.1时,荧光粉Ba_1.97Zn_0.9Mg_0.1Si₂O₇:0.03Eu的绿色发光最强,表明Eu³⁺被还原成Eu²⁺离子的程度最大。当共掺入Ce³⁺离子后,形成Ba_1.97-yZn_0.9Mg_0.1Si₂O₇:0.03Eu,yCe³⁺荧光粉体系,其发光随着Ce³⁺离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba_1.96Zn_0.9Mg_0.1Si₂O₇:0.01Ce³⁺,0.03Eu的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba₂Zn_0.9Mg_0.1Si₂O₇基质中的能量传递与发光机理。     

Ba1.63La7.39Si11N23Cl0.42:Ce3+ – A Nitridosilicate Chloride with a Zeolite‐Like Structure

The nitridosilicate chloride Ba_1.63La_7.39Si₁₁N₂₃Cl_0.42:Ce³⁺ was synthesized by metathesis reaction starting from LaCl₃, BaH₂, CeF₃ and the product of the ammonolysis of Si₂Cl₆. The title compound is stable towards air and moisture. Diffraction data of a microcrystal were recorded using microfocused synchrotron radiation. X‐ray spectroscopy confirms the chemical composition of the crystal. IR spectra corroborate absence of N–H bonds. The compound is homeotypic to Ba₂Nd₇Si₁₁N₂₃ and crystallizes in space group Cmmm with a = 11.009(3), b = 23.243(8), c = 9.706(4) Å and Z = 4, R₁(all) = 0.0174. According to bond valence sum calculations, some crystallographic positions show complete occupancy by Ba or La whereas others contain significant amounts of both elements. In contrast to the structure prototype Ba₂Nd₇Si₁₁N₂₃, Ba_1.63La_7.39Si₁₁N₂₃Cl_0.42:Ce³⁺ contains chloride ions in channels of the SiN₄ tetrahedra network, hinting at various substitution possibilities of the complex zeolite‐like structure.     

Phase of the composition CaBaLaCu2FeO7.5: Synthesis, structure, M?sbauer spectra

The phase of the composition CaBaLaCu₂FeO_7.5 is synthesized from the previously obtained CaCuO₂, La₂Cu₂O₅, and BaFeO₂ double oxides enriched up to 14.7% in ⁵⁷Fe. The phase has the orthorhombic crystal system with the unit cell parameters as follows: a = 0.3882(3) nm, b = 0.3911(3) nm, c = 1.1823(8) nm. Based on the M?sbauer spectra analysis, the conclusion is drawn that iron atoms occupy only Cu(1) sites in the lattice, while more than 90% of them are in the Fe⁴⁺ valence state (80% of these atoms have the tetragonal pyramidal coordination).     

123 Phases of composition CaBa2Cu2WO8 with substitutions of sodium and potassium for calcium and barium

Tetragonal (123) phases of compositions Ca_0.7Na_0.3Ba₂Cu₂WO₈, CaBa_1.7Na_0.3Cu₂WO₈, and CaBa_1.7K_0.3Cu₂WO₈, where tungsten occurs in Cu(1) positions and Cu³⁺ is in Cu(2) positions, were prepared from CaWO₄, BaCuO₂, and sodium and potassium nitrates at 1073 K in an oxygen flow. These phases constitute at least 90% of the samples; their unit call parameters are as follows: a = b = 0.4177(3) nm, c = 1.2561(8) nm; a = b = 0.4182(3) nm, c = 1.2564(8) nm; and a = b = 0.4194(3) nm, c = 1.2603(8) nm, respectively. Their X-ray diffraction patterns feature peaks that indicate a superstructure with all three unit cell parameters being doubled. The samples have weak conductive properties (room-temperature electrical conductivity ranges between 10^?6 and 10^?7 Ohm^?1 cm^?1). Conductivity versus temperature curves are indicative of the semiconductor character of the samples. Superconducting transitions do not occur up to 65 K.     

Ce1－xNdxO2－δ固溶体的电子顺磁共振谱和阻抗谱的研究

利用溶胶-凝胶方法在800 ℃焙烧10 h后, 合成了固溶体Ce_1－xNd_xO_2－δ (x＝0.05～0.55), X射线衍射(XRD)测试表明固溶体已经形成立方萤石结构; 电子顺磁共振谱(EPR)研究表明在固溶体Ce_1－xNd_xO_2－δ中随着掺杂量x的增大, Ce^3＋离子含量减少, 说明掺杂Nd^3＋离子可以抑制Ce^4＋的还原; 交流阻抗谱的测量表明固溶体Ce_0.9Nd_0.1O_2－d 具有离子导电特性, 600和700 ℃时的电导率分别为4.25×10^－3和1.12×10^－2 S•cm^－1, 活化能为0.68 eV.     

Tt‐Tt (Tt = Si,Ge) Dumb‐Bell Structures at Different Valence Electron Concentrations: Ln2MgSi2 (Ln = La,Ce), Yb2Li0.5Ge2, and Yb1.75Mg0.75Si2

The isostructural compounds Yb₂MgSi₂, La_2.05Mg_0.95Si₂, and Ce_2.05Mg_0.95Si₂, as well as Yb₂Li_0.5Ge₂ and Yb_1.75Mg_0.75Si₂, respectively, were synthesized from stoichiometric mixtures of the corresponding elements in sealed Nb‐ ampoules under argon atmosphere. The structures were determined by single crystal X‐ray diffraction: Yb₂MgSi₂ (P4/mbm (No. 127), a = 7.056(1), c = 4.130(1) ų, Z = 2), La_2.05Mg_0.95Si₂ (P4/mbm, a = 7.544(1), c = 4.464(1) ų, Z = 2), and Ce_2.05Mg_0.95Si₂ (P4/mbm, a = 7.425(1), c = 4.370(1) ų, Z = 2), Yb₂Li_0.5Ge₂ (Pnma (No. 62), a = 7.0601(6), b = 14.628(1), c = 7.6160(7) Å, V = 786.5ų, Z = 4), Yb_1.75Mg_0.75Si₂ (Pnma, a = 6.9796(1), b = 14.4009(1), c = 7.5357(1) Å, V = 757.43(2) ų, Z = 4). All compounds contain exclusively Tt‐Tt dumb‐bells (Tt = Si, Ge). The Si‐Si Zintl anions exhibit only very small variations of bond lengths which seem to be more due to cation matrix effects than to effective bond orders.     

Rare‐Earth‐Rich Magnesium Compounds RE23Rh7Mg4 (RE = La,Ce, Pr,Nd, Sm,Gd) with Tetrahedral Mg4 Clusters

The rare earth‐rich compounds RE₂₃Rh₇Mg₄ (RE = La, Ce, Pr, Nd, Sm, Gd) were prepared by induction‐melting the elements in sealed tantalum tubes. The new compounds were characterized by X‐ray powder diffraction. They crystallize with the hexagonal Pr₂₃Ir₇Mg₄ type structure, space group P6₃mc. The structures of La₂₃Rh₇Mg₄ (a = 1019.1(1), c = 2303.7(4) pm, wR2 = 0.0827, 1979 F² values, 69 variables), Nd₂₃Rh₇Mg₄ (a = 995.4(2), c = 2242.3(5) pm, wR2 = 0.0592, 2555 F² values, 74 variables) and Gd₂₃Rh_6.86(5)Mg₄ (a = 980.5(2), c = 2205.9(5) pm, wR2 = 0.0390, 2083 F² values, 71 variables) were refined from single crystal X‐ray diffractometer data. The three crystallographically different rhodium atoms have trigonal prismatic rare earth coordination with short RE–Rh distances (283–300 pm in Nd₂₃Rh₇Mg₄). The prisms are condensed via common edges, leading to a rigid three‐dimensional network in which isolated Mg₄ tetrahedra (312–317 pm Mg–Mg in Nd₂₃Rh₇Mg₄) are embedded. Temperature dependent magnetic susceptibility data of Ce₂₃Rh₇Mg₄ indicate Curie‐Weiss behavior with an experimental magnetic moment of 2.52(1) μ_B/Ce atom, indicative for stable trivalent cerium. Antiferromagnetic ordering is evident at 2.9 K.     

Photometrische Scandiumbestimmung mit Glyoxal-bis-(2-hydroxyanil)

Zusammenfassung Bei der photometrischen Untersuchung der Reaktion von Sc³⁺ mit Glyoxal-bis(2-hydroxyanil) (GBHA) wurden die Bedingungen für die Bildung von Komplexen festgelegt und eine empfindliche Methode der photometrischen Sc-Bestimmung ausgearbeitet. Diese ist in Anwesenheit von Nd³⁺, Y³⁺, La³⁺ und Al³⁺ anwendbar, wird aber von UO₂ ²⁺, Cu²⁺, Ce³⁺, Ti⁴⁺, Ce⁴⁺+ und Tl³⁺ gestört.     

Physico-chemical studies on the chelation behaviour of biologically active 2-hydroxy-1-naphthaldehyde semicarbazone (HNAS) with some lanthanons

Summary The chelation behaviour of the complexes of La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Y³⁺, Tb³⁺, Dy³⁺, Ho³⁺ with biologically active 2-Hydroxy-1-naphthaldehyde semicarbazone (HNAS) has been studied potentiometrically in 75% (v/v) dioxane-water medium at various ionic strengths. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of n andpL. The formation constants of metal chelates and the values ofS _min have been calculated. The order of formation constants of chelates was found to be: La³⁺3+3+3+3+3+3+3+3+3+3+.

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Physikochemische Untersuchungen zur Komplexierung von biologisch aktivem 2-Hydroxy-1-naphthaldehyd-Semicarbazon (HNAS) mit Lanthanoiden

Zusammenfassung Das Chelierungsverhalten von La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Y³⁺, Tb³⁺, Dy³⁺ und Ho³⁺ mit 2-Hydroxy-1-naphthaldehydsemicarbazon (HNAS) wurde potentiometrisch in 75% (v/v) Dioxan-Wasser bei verschiedenen Ionenstärken untersucht. Die Werte für n undpL wurden nach der Methode von Bjerrum und Calvin in der Modifikation von Irving und Rossotti bestimmt. Die Komplexbildungskonstanten der Metallchelate und die WerteS _min wurden ermittelt. Die Reihung der Komplexbildungskonstanten war La³⁺3+3+3+3+3+3+3+3+33+.

     

空气中合成固溶体荧光粉Ba_2(Zn,Mg)Si_2O_7∶Eu~(2+),Eu~(3+),Ce~(3+)及其发光特性

采用高温固相法在空气中合成了Ba1.97-yZn1-xMgxSi2O7∶0.03Eu,y Ce3+系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba1.97-yZn1-xMgxSi2O7∶0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu2+离子的4f 65d1-4f 7跃迁,590~725 nm红光区窄带谱源于Eu3+的5D0-7FJ(J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu3+在Ba1.97-yZn1-xMgxSi2O7基质中被还原成了Eu2+;当x=0.1时,荧光粉Ba1.97Zn0.9Mg0.1Si2O7∶0.03Eu的绿色发光最强,表明Eu3+被还原成Eu2+离子的程度最大。当共掺入Ce3+离子后,形成Ba1.97-yZn0.9Mg0.1Si2O7∶0.03Eu,y Ce3+荧光粉体系,其发光随着Ce3+离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba1.96Zn0.9Mg0.1Si2O7∶0.03Eu,0.01Ce3+的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba2Zn0.9Mg0.1Si2O7基质中的能量传递与发光机理。     

Enhancing Photoactivity of TiO2(B)/Anatase Core–Shell Nanofibers by Selectively Doping Cerium Ions into the TiO2(B) Core

Cerium ions (Ce³⁺⁾ can be selectively doped into the TiO₂(B) core of TiO₂(B)/anatase core–shell nanofibers by means of a simple one‐pot hydrothermal treatment of a starting material of hydrogen trititanate (H₂Ti₃O₇) nanofibers. These Ce³⁺ ions (≈0.202 nm) are located on the (110) lattice planes of the TiO₂(B) core in tunnels (width≈0.297 nm). The introduction of Ce³⁺ ions reduces the defects of the TiO₂(B) core by inhibiting the faster growth of (110) lattice planes. More importantly, the redox potential of the Ce³⁺/Ce⁴⁺ couple (E°(Ce³⁺/Ce⁴⁺)=1.715 V versus the normal hydrogen electrode) is more negative than the valence band of TiO₂(B). Therefore, once the Ce³⁺‐doped nanofibers are irradiated by UV light, the doped Ce³⁺ ions—in close vicinity to the interface between the TiO₂(B) core and anatase nanoshell—can efficiently trap the photogenerated holes. This facilitates the migration of holes from the anatase shell and leaves more photogenerated electrons in the anatase nanoshell, which results in a highly efficient separation of photogenerated charges in the anatase nanoshell. Hence, this enhanced charge‐separation mechanism accelerates dye degradation and alcohol oxidation processes. The one‐pot treatment doping strategy is also used to selectively dope other metal ions with variable oxidation states such as Co^2+/3+ and Cu^+/2+ ions. The doping substantially improves the photocatalytic activity of the mixed‐phase nanofibers. In contrast, the doping of ions with an invariable oxidation state, such as Zn²⁺, Ca²⁺, or Mg²⁺, does not enhance the photoactivity of the mixed‐phase nanofibers as the ions could not trap the photogenerated holes.     

Nd5(AsO3)4Cl3: The First Oxo‐Arsenate(III)‐Chloride of the Lanthanides

Single crystals of Nd₅(AsO₃)₄Cl₃ (monoclinic, P2/n, Z = 2, a = 1026.0(1), b = 543.35(3), c = 1400.2(1) pm, β = 93.48(1)°) were obtained from the reaction of Nd₂O₃, As₂O₃ and NaCl in a sealed silica ampoule. In the crystal structure the Nd³⁺ ions are linked by AsO₃^3? groups into layers that alternate with layers of Cl^? ions. Two of the three crystallographically different Nd³⁺ ions are coordinated by eight oxygen atoms, the third one has four oxygen and four chlorine atoms as neighbours.     

Hydrothermal Synthesis and Structural Characterization of a Novel Organic—Inorganic Hybrid Compound {[Cu（2,2′—bpy）2]2—Mo8O26}

A novel organic-inorganic hybrid compound {[Cu(2,2′-bpy)2]2Mo8O26} has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group, Pna21,with a=2.4164(5),b=1.8281(4),c=1.1877(2)nm,V=5.247(2)nm^3,Z=4,and final R1=0.0331,wR2=0.0727.The structure consists of discrete {[Cu(2,2′-bpy)2]2Mo8O26} clusters,constructed from a β-octamolybdate subunit[Mo8O26]^4- covalently bonded to two [Cu(2,2′-bpy)2]^2 coordination complex cations via bridging oxo groups.In addition,the spectroscopic properties and thernal behavior of this compound have been investigated by spectroscopic techniques (UV-vis,IR,Raman and EPR spectra) and TG analysis.     

Crystal Structure and Characterization of Two Layered Copper(II) Coordination Polymers with Anions of 3‐Phosphonopropionic Acid and (RS)‐2‐Phosphonobutyric Acid

Blue single crystals of Cu[μ₃‐O₃P(CH₂)₂COOH] · 2H₂O ( 1 ) and Cu[(RS)‐μ₃‐O₃PCH(C₂H₅)COOH] · 3H₂O ( 2 ) were prepared in aqueous solutions (pH = 2.5–3.5). 1 crystallizes in space group Pbca (no. 61) with a = 812.5(2), b = 919.00(9), and c = 2102.3(2) pm. Cu²⁺ is fivefold coordinated by three oxygen atoms stemming from [O₃P(CH₂)₂COOH]^2– anions and two water molecules. The Cu–O bond lengths range from 194.0(3) to 231.8(4) pm. The connection between the [O₃P(CH₂)₂COOH]^2– anions and the Cu²⁺ cations yields a polymeric structure with layers parallel to (001). The layers are linked by hydrogen bonds. 2 crystallizes in space group Pbca (no. 61) with a = 1007.17(14), b = 961.2(3), c = 2180.9(4) pm. The copper cations are surrounded by five oxygen atoms in a square pyramidal fashion with Cu–O bonds between 193.6(4) and 236.9(4) pm. The coordination between [O₃PCH(C₂H₅)COOH]^2– and Cu²⁺ results in infinite puckered layers parallel to (001). The layers are not connected by any hydrogen bonds. Each layer contains both R and S isomers of the [O₃PCH(C₂H₅)COOH]^2– dianion. Water molecules not bound to Cu²⁺ are intercalated between the layers. UV/Vis spectra suggest three d–d transition bands at 743, 892, 1016 nm for 1 and four bands at 741, 838, 957, and 1151 nm for 2 , respectively. Magnetic measurements suggest a weak antiferromagnetic coupling between Cu²⁺ due to a super‐superexchange interaction. Thermoanalytical investigations in air show that the compounds are stable up to 95 °C ( 1 ) and 65 °C ( 2 ), respectively.     

Synthesis and Structure of the New Compound La2O(CN2)2 Possessing an Interchanged Anion Proportion Compared to the Parent La2O2(CN2). Synthese und Kristallstruktur der neuen Verbindung La2O(CN2)2 mit einem vertauschten Anionenverhältnis gegenüber der Bezugsverbindung La2O2(CN2)

La₂O(CN₂)₂ was synthesized from a 1:1:2 molar reaction mixture of LaCl₃, LaOCl, and Li₂(CN₂) at 650 °C. Well developed single crystals were grown from a LiCl‐KCl flux. The crystal structure was refined as monoclinic (space group C2/c, Z = 2, a = 13.530(2) Å, b = 6.250(1) Å, c = 6.1017(9) Å, β = 104.81(2)°) from single crystal X‐ray diffraction data. The La³⁺ and (CN₂)^2— ions in the crystal structure of La₂O(CN₂)₂ can be compared to Fe³⁺ and S₂^2— ions in the cubic pyrite structure, being arranged like in a distorted NaCl type structure with their centers of gravity. In addition, the O^2— ions in La₂O(CN₂)₂ are occupying 1/4 of the tetrahedral voids formed by the arrangement of metal ions.     

Crystal Structure Investigations and Thermal Behavior of the Five‐Leg Spin Ladder Compound La8Cu7O19

La₈Cu₇O₁₉ was synthesized by solid state reaction of the oxides La₂O₃ and CuO at 1288 K in air. The crystal structure was determined by a joint Rietveld refinement of X‐ray and neutron powder diffraction data. La₈Cu₇O₁₉ crystallizes in the monoclinic space group C2/c (No. 15) with the lattice parameters a = 13.8310(4)Å, b = 3.75827(9)Å, c = 34.5917(8)Å and β = 99.332(2)°. La₈Cu₇O₁₉ is the n = 3 member of the homologous series La_4+4nCu_8+2nO_14+8n. The Cu—O sub‐structure in La₈Cu₇O₁₉ contains infinite ribbons, which can be described as perovskite type layers with a width of n = 3 Jahn‐Teller‐elongated octahedra, and Cu—O planes of complex geometry. DSC/TG‐measurements in different gas atmospheres show peritectic decomposition of La₈Cu₇O₁₉. The anisotropic thermal expansion of the lattice parameters was investigated using synchrotron radiation. The Madelung part of lattice energy was calculated and compared with the corresponding values of other lanthanum cuprates.     

Strukturchemische und impedanzspektroskopische Untersuchungen an Mg2+-stabilisierten Na+/Pr3+-β″-Al2O3-Kristallen

Structural Chemistry and Impedance Spectroscopy of Mg²⁺ stabilized Na⁺/Pr³⁺-β″-Aluminas The structure with the ionic distribution in the conduction planes of a Pr³⁺-exchanged Mg²⁺ stabilized Na⁺-β″-alumina crystal, composition determined by electron microprobe analysis to Na_1.19Pr_0.13Mg_0.49Al_10.49O₁₇ (degree of exchange ξ = 25%, related to Na⁺ content), has been investigated by single crystal X-ray diffraction methods at room temperature (R3 m, Z = 3, a = 561.8(2) pm, c = 3 361.5(11) pm). Pr³⁺ is slightly shifted in the ab-plane from the centrosymmetric 9 d (mO) into a 18 h site. Na⁺ occupies 18 h as well as 6 c (BR) positions. Ionic conductivity data of Mg²⁺ stabilized Na⁺/Pr³⁺-β″-Al₂O₃ crystals with varying degree of exchange determined by impedance spectroscopy are given in an Arrhenius diagram. With growing Pr³⁺ content the conductivity σ decreases with increasing activation energy.