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Chemisches Zentralblatt 2 0 7 7 Chemisches Zentralblatt. 1936 Band II. Nr. 12. IG. September. A. Allgemeine und physikalische Chemie. Clarence Smith, Moderne chemische Nomenklatur. Vorlesung vor der engl. ehem. Gesellschaft über die Nomenklatur in der anorgan. u. organ. Chemie. (J. ehem. Soe. London 1936. 1067— 78. Juli.) B e h r l e . Malcolm Dole, Das relative Atomgewicht des Sauerstoffes im Wasser und in der Luft. Eine Disktission über die Verteilung der Sauerstoffisotope in der Atmosphäre und über die chemische Atomgewichtsgrundlage. Der in einer früheren Arbeit (C. 1 9 3 6 .1. 2028) mitgeteilte Wert für den D.-Untcrsehied des Sauerstoffs der Luft gegenüber dem des W. von 4,6 y wird erneut bestimmt u. nun zu 6 y gefunden. Dieser Unterschied kann erklärt werden unter der Annahme, daß sich ein isotopes Austauschgleichgewicht — von U ßE Y u. G k e iff (C. 1935. II. 2919) angegeben — bei — 50° in den tieferen Regionen der Stratosphäre emsteilt. Die Verteilung der Sauerstoffisotope in der Atmosphäre ist mit Hilfe der hyposometr. Höhenformel berechnet, doch ist die durch die Schwere hervor­ gerufene Trennung nicht genügend, um das größere At.-Gew. des Luftsauerstoffs quanti­ tativ zu erklären. — Die ehem. u. physikal. At.-Gew.-Grundlagen werden einer Dis­ kussion unterworfen, u. es wird vorgeschlagen, eine einheitliche Grundlage zu schaffen, die auf der M. eines reinen Isotops, z. B. dom leichten Wasserstoff, begründet ist. (J. ehem. Physies 4. 268— 75. April 1936. Northwestern, Univ., Departm. of Che­ mistry.) Sa l z e r . Charles H. Greene und Roger J. Voskuyl, Eine Erklärung fü r die relativ hohe 01B-Konzentration der Atmosphäre. D o l e (vorst. Ref.) fand, daß der Luftsauerstoff eine um 6 y größere D . aufweist als der Sauerstoff des W. Weiter fanden WEBSTER, W a h l u . U r e y (C. 1935. I. 2937), daß W., das aus dem Sauerstoff des Kohlendioxyds liergestellt ist, eine um 10,2 y größere D . aufweist als W ., das denselben Wasserstoff enthält, dessen Sauerstoff aber im Gleichgewicht mit dem Kohlendioxyd steht. Das Kohlendioxyd der Atmosphäre steht im Gleichgewicht mit dem W. der Erde. Pflanzen, die 2 Sauerstoffatome aus dem C02 u. 1 Sauerstoffatom aus dem Sauerstoff des W. auf­ nehmen, geben an die Atmosphäre 1 Molekül Sauerstoff ab, u. bauen das restliche Sauerstoffatom in die Pflanze ein. Wenn bei diesem Prozeß keine Bevorzugung eines Sauerstoffisotops auftritt, so ist zu erwarten, daß der durch Pflanzen produzierte Luft­ sauerstoff ungefähr eine um 6,8 y größere D . aufweist als der des W . Dieser Wert ist nur wenig größer als der von DOLE experimentell gefundene. Der geringe Unterschied kann entweder durch andere Prozesse, die sich gegen die Einstellung eines wahren Gleichgewichts auswirken, oder durch eine bevorzugte Aufnahme von O18 bei dem Aufbau der pflanzlichen Substanz verursacht sein. — Vff. kommen hieraus zu dem Schluß, daß W ., das aus dem Sauerstoff von Kohlenhydraten hergestellt wird, dieselbe oder eino etwas größere D . haben wird, wie das aus atmosphär. Sauerstoff hergestellte W. (J. Amer. ehem. Soc. 58. 693— 94. 6/4. 1936. Cambridge, Massachusetts, Radcliffe College, Byerly Lab.) SALZER. R. K. Asundi und R. Samuel, Elektronenkonfiguration und Bindungsenergie. Es wird versucht, eine Beziehung zwischen den Bindungsenergien, wie sie aus den Banden­ spektren bekannt sind, u. sowohl den Plätzen der Molekülpartner im period. System als auch der Elektronenkonfiguration des gesamten Moleküls herzuleiten. Als Grund­ lage zu der Arbeit dienen die Oxyde der 3. Gruppe des period. Systems u. die Halogenide der 4. Gruppe. Es wird die Beziehung der Dissoziationsenergie zu der Elcktronen- konfiguration diskutiert. (Proc. Indian Acad. Sei. Sect. A. 3. 466— 81. Mai 1936.) F a h l . H. C. Corben, Bemerkung über die Beziehung zwischen Eernabstand und Oruppen- nummer zweiatomiger Hydride. Vf. gibt eine empir. Formel für den Zusammenhang zwischen Kemabstand im Gleichgewicht u. Gruppennummer (Zahl der Elektronen in Schwerer Wasserstoff vgl. S. 2081, 2092, 2144. XVIII. 2. 136 2078 A . A l l g e m e in e u n d physikalische C h e m i e . 1936. II. nicht abgeschlossenen Schalen) an, die an den bekannten Beobaehtungsdaten geprüft wird u. bisher nicht gemessene Werte des Abstands vorherzusagen gestattet. (Philos. Mag. J. Sei. [7] 22. 144— 45. Juli 1936. Melbourne [Victoria], Univ., Queens College.) H e n n e b e r g . F. M. Schemjakin und A. A. Witt, Zur Theorie physikalisch-chemischer peri­ odischer Prozesse. Es werden zwei theoret. mögliche Fälle von period. Rkk. diskutiert u. es wird gezeigt, daß es unter gewissen Bedingungen des Rk.-Verlaufes möglich ist, die Periodizität der Rk. durch das Massenwirkungsgesetz u. das FlCK Sche Diffusionsgesetz zu erklären. (Acta physicochim. U. R. S. S. 2 . 171— 76; J. physik. Chem. [russ.: Shumal fisitscheskoi Chimii] 6 . 612— 15. 1935. Moskau, Univ., Chem. Fakultät u. Physikal. Inst.) K l e v e e . I. I. Sasslawski, Allgemeine Charakteristik der Volumänderungen bei Reaktionen in Lösungen. (J. physik. Chem. [russ.: Shurnal fisitscheskoi Chimii] 5. 1440— 44. Iwanowo. — C. 1 9 3 4 . II. 2376.) K l e v e r . W . Feitknecht und G. Fischer, Zur Chemie und Morphologie der basischen Salze zweiwertiger Metalle. IV. Über basische Kobaltbromide. 12. Mitt. über basische Salze. (11. vgl. C. 1 9 3 6 . I. 961.) Es existieren mindestens vier bas. Kobaltbromide. Ihre Bldg. ist zum Teil stark gehemmt, sind sie aber einmal hergestellt, ist ihre Beständig­ keit groß u. sio bleiben über große Konz.-Intervalle metastabil. Bei gewöhnlicher Temp. u. Konzz. kleiner als 1,5-mol. entsteht grünes bas. Bromid. Es kann nur bei ca. 50° u. langsamer Hydrolyse in mikrokrystalliner Form erhalten werden. — Dio untere Beständigkeitsgrenze liegt bei ca. 3,5- 10_2-mol. Bei noch kleinerer Konz, wandelt es sich in Hydroxyd um. Dies Bromid ist wahrscheinlich bei allen Konzz. nur metastabil u. bleibt nur bestehen, weil die Bldg. der anderen bas. Bromide bei diesen Tempp. u. Konzz. zu stark gehemmt ist. — Die Idealformel ist CoBr2- 9 Co(OH),, doch schwankt der Hydroxydgeh. um ca. ± 2 Molo. Das Löslichkeitsprod. beträgt beim Hydroxyd 3,3-10-16, wie sich aus der Co-Konz. beim Gleichgewicht Hydroxyd/bas. Salz u. dem pH der Lsg. berechnen läßt. — Die Hydrolyse bei ca. 100° u. Konzz. von mehr als 0,5-mol (bei 180° von 0,18-mol. an), führt zu rotviolettem bas. Bromid der Formel CoBr2-3 Co(OH)2, häufig mit einem ganz geringen Uberschuß an Hydroxyd. Es kann leicht grobkrystallin erhalten werden. Die Ausbildungsform der Iirystalle ändert sich mit der Temp. Boi Erwärmung des grünen bas. Bromids in Bromidlsg. von Konzz. zwischen 3,5-10~2 u. ca. 0,1-mol. entsteht in kleinen Mengen dunkelblau­ violettes bas. Bromid unbekannter Zus. — Ein viertes bas. Bromid entsteht bei Er­ hitzen von grünem Bromid unter verd. Bromidlsg. auf Tempp. über 150°. — Aus konz. Kobaltbromidlsgg., die kleine Mengen Chlorid enthalten, scheidet sich neben rotviolettem Bromid ein bas. Mischchloridbromid aus, das isomorph mit bas. rosa­ farbigem Kobaltchlorid ist, bei dem ca. % der Cl-Ionen durch Br-Ionen ersetzt ist. Es handelt sich wahrscheinlich um das Endglied einer Mischkrystallreilie, die vom Chlorid ausgeht. (Helv. chim. Acta 19. 448— 66. 2/5. 1936. Bern, Chem. Inst. d. Univ.) _ BÜSSEM. W . Feitknecht, Über die Konstitution der festen basischen Salze zweiwertiger Metalle. I. Basische Kobalthalogenide mit „Einfachschichtengitter“ . 13. Mitt. über basische Salze. (12. vgl. vorst. Ref.) Es wird eine Methode angegeben, das Struktur­ prinzip bas. Kobalthalogenide mit Einfachsehichtengittem zu klären. Die Krystalle mit Einfachschichtengittem sind dadurch gekennzeichnet, daß sich zweidimensionale Makromolekeln übereinanderlagem, aber so, daß in den Hydroxydschichten ein Teil der Hydroxylionen durch andere Anionen ersetzt ist. Es konnte dieser Typ bei den Verbb. CoC12-3 Co(OH)2, CoBr2-3 Co(OH)2 u. dem Mischkrystall zwischen diesen beiden Verbb., der bis zu einem Geh. von 33u/o Br an Stelle von CI stabil ist, festgestellt werden. (Helv. chim. Acta 1 9 . 467— 74. 2/5. 1936. Bern, Chem. Inst. d. Univ.) BÜSSEM. W . Feitknecht und A. Collet, Über die Konstitution der festen basischen Salze zweiwertiger Metalle. II. Basische Nickelhalogenide mit „Einfachschichtengitter“ . (I. vgl. vorst. Ref.) Aus Nickelchloridlsgg. mittlerer Konz, erhält man durch Fällung mit Natronlauge u. Erhitzen des Fällungsprod. auf 100° u. darüber bas. Chlorid, welches einen großen Homogenitätsbereich besitzt. Das Verhältnis Nickelchlorid: Nickel­ hydroxyd schwankt in den Grenzen 1: 1,9 bis 1: 4,3. Nach der mittleren Zus. geben Vff. ihm die Formel NiCl2-3 Ni(OH),. Aus konz. Lsg. entsteht die Verb. NiCl2-Ni(OH)2 bzw. NiCl(OH). Aus Nickelbromidlsg. entsteht durch Umsetzung mit Natronlauge bei 200° ein bas. Nickelbromid der Idealformel NiBr2-3 Ni(OH)2. Hier ist der Homo­ genitätsbereich enger, das Verhältdis NiBr2: Ni(OH), schwankt zwischen 1: 2,8 u. 1936. I I. A . A l l g e m e in e u n d p Hy s i k a Hîs c h e C h e m i e . 20 79 1: 3,3. Das hydroxydroiehere bas. Chlorid u. das bas. Bromid sind isomorph u. krystalli- sieren im CdJ2-Typ. CI- u. (OH)-Ionen sind statist. über dio ihnen zukommenden Gitterplätze vorteilt. Gegenüber dom im gleichen Typ krystallisierenden Ni(OH)2 ist das Achsenverhiiltnis c/a nach größeren Worten verschoben. Daraus erklärt sieh, daß keine kontinuierliche Mischbarkeit zwischen den bas. Halogeniden u. dem Hydroxyd besteht. Die bas. Salze müssen deshalb als selbständige Verbb. aufgefaßt werden. — Das NiCI(OH) besitzt eine rhomboedr. Zelle wie das NiCl2. Es wird keine Entscheidung getroffen, ob die Cl-Ionen auf der einen, die (OH)-Ionen auf der anderen Seite dor Ni-Ionenschicht angeordnet sind oder die Anionen statist. über die ihnen zukommenden Gitterplätze verteilt sind. Die beschriebenen Salze gehören der Klasse der bas. Salze mit „Einfachschichtengitter“ an. (Helv. chim. Acta 19. 831— 41. 1/7. 1936. Bern, Chem. Inst. d.
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