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Chemisches Zentralblatt 3881 Chemisches Zentralblatt 1940. I. Halbjahr Nr. 26 26. Juni A. Allgemeine und physikalische Chemie. Hugh S. Taylor, Neue Ausblicke bei der Isotopentrennung. Vf. gibt einen zu­ sammenfassenden Überblick über die Methoden der Isotopentrennung u. behandelt bes. das Verf. der kombinierten Thermodiffusion u. Konvektion von CLUSIUS u . D ic k e l (C. 1938. II. 3201), seine Wrkg.-Weise u. Anwendungsmöglichkeit. (Nature [London] 144. 8— 9. 1/7. 1939. Princeton, Univ.) B e r n s t o r f f . Lars Onsager, Isotopentrennung durch Thermodiffusion. Allg. Betrachtungen über das für die Leistungsfähigkeit des Verf. krit. Verhältnis von Konvektion zu Diffusion. (Physic. Rev. [2] 5 7 . 562. 15/3. 1940. Yale Univ.) F l ü g g e . W . H. Furry und R. Clark Jones, Theorie der Isotopentrennung durch Thermo­ diffusion: Der zylindrische Fall. (Vgl. C. 1940. I. 824.) Während die experimentelle Anordnung stets zylindr. ist, existierten bisher nur Rechnungen für Thermodiffusion zwischen zwei parallelen Platten. Vff. führen die Rechnung durch sowohl für den Fall eines dünnen Drahtes in der Zylinderachse als auch für zwei konzentr. Zylinder. Die neue Rechnung verbessert erheblich die Übereinstimmung von Theorie u. Experiment; die Anordnung mit dom Draht ist rund 1,43-mal so wirksam wie die mit zwei Zylindern. (Physic. Rev. [2] 57. 561— 62. 15/3. 1940. Harvard Univ.) FLÜGGE. William W . Watson, Thermische Isotopentrennung. Die Konstruktion einer zweigliedrigen Thermodiffusionsanlage zur Anreicherung von 13C wird beschrieben. Sie liefert 2,77% 13C. Eine sechsgliedrige Anlage, die 2 0 % 13C ergeben soll, liegt ebenfalls vor. (Physic. Rev. [2] 57. 562. 15/3. 1940. Yale Univ.) F l ü g g e . Hubert Krüger, Über die Anreicherung des lsN-Isotops und einige spektroskopische Untersuchungen am 16N. Ausführliche Wiedergabe der C. 1938. II. 3202 referierten Arbeit. (Z. Physik 111. 467— 74. 1939. Berlin-Charlottenburg.) K l e v e r . * Eugen Baroni, Der Gehalt an Deuterium in atmosphärischen Niederschlägen. Bestimmungen des D20-Geh. von atmosphär. Ndd. an Hand von D.-Messungen weisen auf verhältnismäßig große Unterschiede im Deuteriumgeh. hin, die als Folgen von natürlichen Fraktionierungsvorgängen gedeutet werden können. (Atti X Congr. int. Chim., Roma 2. 110. 15.— 21/5. 1938. Wien, Univ., I. Chem. Labor.) H. E r b e . J. Mattauch und H. Lichtblau, Ein bemerkenswertes Isotop des Cassiopeiums. Es wird massenspektrograph. festgestellt, daß das von GOLLNOW (C. 1937. I. 2097) aus der Hyperfeinstrukturaufspaltung erschlossene zweite Isotop des Cp entgegen allen Vermutungen die Massenzahl 176 besitzt. Ähnlich wie 40K bildet es als gerades Isotop eines ungeraden Elementes eine Ausnahme. Da es benachbarte Isobare besitzt, muß für die natürliche ß-Aktivität des Cp dasselbe verantwortlich gemacht werden. Die photometr. Messung ergab die relative Häufigkeit 1?5Cp: 1,eCp — 100: 2,58 ± 0,07. Daraus ergibt sich mit dem neuen DElIPSTERschen Wert des Packungsanteils für Cp ein chem. At.-Gew. von 174,995 ± 0,1 in ausgezeichneter Übereinstimmung mit dem kürzlich von HÖNIGSCHMID neu bestimmten Wert von 174,99 (Vgl. C. 1938. I. 1059). Als obere Grenze für die Häufigkeit eventueller anderer Isotope kann für die Massen­ zahl 174 0,45%> für andere Massenzahlen je 0,4% angegeben werden. (Z. Physik 111. 514— 21. 30/1. 1939. Wien, Univ., Physikal. Inst.) K l e v e r . H. Schüler und H. Gollnow, Anhang zur vorstehenden Mitteilung. (Vgl. M at- TAÜCH u. LICHTBLAU, vorst. Ref.) Es wird darauf hingewiesen, daß das schwache Isotop ein großes mechan. Moment besitzen muß. (Z. Physik 111. 521—22. 30/1. 1939. Berlin-Dahlem, Max Planck-Ihst.) K l e v e r . Arthur J. Dempster, Die Isotopenhmstituticm von Hafnium, Yttrium, Cassio- peium und Tantal. Hafnium: Außer den von A s t o n angegebenen Isotopen 180, 179, 178, 177 u. 176 wurde ein neues der Massenzahl 174 mit einer Gesamthäufigkeit von 0,3% gefunden. Yttrium: Ein Isotop der M. 91 ist, wenn überhaupt, zu weniger als 0,05% bezogen auf das häufige 89Y vorhanden. Cassiopeium: Eine Linie der M. 176 entsprechend ist wahrscheinlich der Verunreinigung an Yb zuzuschreiben. Eine Linie der M. 177 entsprechend wurde aber nicht gefunden, sicher wäre die Häufigkeit eines *) Schwerer Wasserstoff s. auch S. 3885, 3886, 3898, 3907, 3909. X X II. 1. 251 3882 A . A l l g e m e in e u n d physikalische C h e m ie . 1940. I. solchen Isotops kleiner als Viooo vom häufigen 175Cp. Auf den Befund von M a t t a u c h u. L ic h t b l a u , (vgl. vorst. Reff.), daß 176Cp existiert u. die Tatsache der dadurch stattfindenden Durchbrechung der Regel über die Isotopenstruktur ungeradzahliger Elemente wird hingewiesen. Auf Veranlassung von H öNIGSCHMIDT wurde Tantal untersucht, da sein At.-Gew. bei einem Packungsquotienten von 1,5-10“ 4 auf die Existenz leichter Isotopen schließen läßt. Hätte ein solches leichteres Isotop die M. 179, so müßte seine Häufigkeit etwa 5% von häufigen 181Ta betragen. In einem Funken zwischen Ta-Elektroden konnte ein solches Isotop aber nicht gefunden werden. Seine Häufigkeit wäre sicher kleiner als 0,1% von der des 181Ta. Eine schwache Linie (0,15%) wurde bei 182 gefunden, die aber einem Hydrid zuzuschreiben ist. (Physic. Rev. [2] 55. 794. 15/4. 1939. Illinois, Chicago Univ.) T h i l o . H. Lichtblau, Die Isotopenverteilung und das Atomgewicht von Europium. Nach der von M a t t a u c h u . L i c h t b l a u (vgl. vorst. Reff.) angegebenen Meth. wird die Isotopenverteilung von Eu untersucht. Es ergab sich, daß Europium aus den beiden Isotopen 151Eu u. 153Eu im Mengenverhältnis 96,3 ± 1 ,2 : 100 besteht. Andere Isotopen wurden in Übereinstimmung mit A s t o n nicht gefunden, ihre obere Häufigkeitsgrenze würde maximal 0 ,4 % betragen. Aus den — gegenüber ASTONs Angaben veränderten — Häufigkeiten ergibt sich mit D e m p s te r s Packungsanteil das ehem. At.-Gew. des Eu jetzt zu 151,95. Baxter u . T u e m le r (C. 1938. II. 993) fanden ehem. das At.-Gew. 151,963 ± 0,002, KAPFENBERGER (C. 1939. I. 3) den Wert 151,901 ± 0,004. (Natur- wiss. 27. 260. 21/4. 1939. Wien, Univ:, I. u. II. Physikal. Inst.) T h i lo . Raymond H. Ewell, Berechnung von chemischen Gleichgewichten bei hohen Drucken. (Vgl. C. 1940. I. 1309.) An Beispielen wird die Zweckmäßigkeit der Anwendung des dritten Hauptsatzes in Verb. mit den neueren thermodynam. Begriffen (Flüchtigkeit /, Aktivitätskoeff. y) zur Berechnung der Gleichgewichte von Gasrkk. gezeigt. Für die Berechnung von y wird auf Grund einer modifizierten BERTHELOT-Gleichung folgende Formel empfohlen: lg y = (9 p TJ128 pc T) (1— 6 21c2/2'2) (Index c = krit. Daten). Eine neue Form der v a n DER WAALSschen Zustandsgleichung wird gegeben: (p + a/V7/. T) (F — b) = RT, wobei a = 0,4340- R'U T^I./p^U, b = 0,080 35■ RT J pc. Auch diese Gleichung liefert eine Formel für lg y. Es wird gezeigt, daß das Kleiner­ werden von y u. des Gleichgewichtskoeff. der y- Werte K y mit höherem Druck zu einer über die Erwartung auf Grund der üblichen Berechnung hinausgehenden Ausbeute­ steigerung mit dem Druck bei der Meihanolsynth., der A.-Synth. aus C„H4 u. H20 u. der HCN-Synih. aus C2H2 u. N2 führt. Die A.-Synth. ist nach den Berechnungen bei 150° u. 100 at durchführbar. Bei der HCN-Synth. nimmt die Ausbeute mit steigender Temp. u. steigendem Druck zu; bei 300° u. 200 at ist eine Umwandlung in fl. HCN zu 6,4% möglich. (Ind. Engng. Chem., ind. Edit. 32. 147— 53. Febr. 1940. Lafayette, Ind., Purdue Univ.) R. K. M ü l l e r . R. Vogel, Schlußbemerkung zur Diskussion mit Herrn Jänecke. (Vgl. C. 1939. II. 987.) Abschluß der Diskussion über das heterogene Gleichgewicht in bin. Mischungen mit maximalen Dampfdrücken. (Z. physik. Chem., Abt. A 185. 152. Nov. 1939.) H. E r b e . W . Feitknecht, Topochemische Grundlagen der Korrosion. Vf. zeigt die Bedeutung der topochem. Betrachtungsweise für die Erfassung des gesamten Gebietes der Korrosion, wobei allo Einflüsse von Struktur u. Form der Ausgangsmaterialien u. der Endprodd. auf den Korrosionsverlauf berücksichtigt werden. Als Beispiele für die Umsetzung von Metallen mit Gasen werden der Angriff von 0 2 auf Cu u. von JüTCZ-haltiger Luft auf N i im Hinblick auf die Form der entstehenden Korrosionsprodd. eingehend behandelt. Die Umsetzungen in Fll. werden an der Umwandlung von CaSOi -1/„ 11,¿0 in CaSOi -2 H M sowie von kryst. CaO in Ca(011)2 untersucht. Solche Pseudomorphosen bilden die Grundlagen zahlreicher Korrosionserscheinungen. Als Typ der Umsetzung „kompakt- disperser“ Stoffe wird die Rk. von MgO mit itfgCU-Lsg. beschrieben u. bes. auf die Er­ scheinung der Rk.-Lenkung hingewiesen, die durch die Form des Ausgangsstoffes bedingt ist u. bei der Veränderung der Zwischenprodd. bei der Metallkorrosion eine Rolle spielen kann. (Schweiz. Arch. angew. Wiss. Techn. 6. 1— 10. Jan. 1940. Bern, Univ., Chem. Inst.) B e r n s t o r f f . Vasilesco Karpen, über den A ngriff von Metallen. Der Angriff eines Metalls ist bestimmt durch die Abwesenheit des stat. Gleichgewichtes zwischen Kationen u. Elektronen des Metalls u. denjenigen der Lösung. Unter der Voraussetzung des Vor­ handenseins eines monovalenten Metalls u. daß im Anfänge die Lsg. keine Kationen enthält, gelangt man zu der Formel x = — E'/2 + YE '% + ME-erU+rlR-T (0 u. r stellen die Arbeit dar, die notwendig ist, um das elektroehem. Äquivalent der Kationen u. Metallelektronen in die Lsg. überzuführen. M u. E sind die entsprechenden 1940. I. A t. A xjfbatj d e r M a t e r i e . 3883 Konzz. der Elemente, x gibt die Rk.-Intensität weder). Handelt es sich um eine Säure- Isg., so ergibt sieh aus dieser Formel: Für gleiches 0 + z (für ein gegebenes Metall) wird x um so größer, die Rk.
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