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Chemisches Zentralblatt 249 Chemisches Zentralblatt. 1936 Band II. Nr. 2. 8. Juli. A. Allgemeine und physikalische Chemie. C. B. Allsop, S. Glasstone, E. B. Maxted, E. A. Moelwyn-Hughes und G. B. B. M. Sutherland, Allgemeine und physikalische Chemie. Fortschrittsbericht: I. Ein­ führung (G l a s s t o n e ). II. Isotope (G l a s s t o n e ). III. Spektroskopie (S u t h e r l a n d ). IV. Best. thermodynam. Konstanten aus spektroskop. Daten nach statist. Methoden (G l a s s t o n e ). V. Chem. Kinetik (M o e l w y n -H u g h e s ). VI. Chemie der Oberflächen (Adsorption u. Katalyse) (M a x t e d ). V II. Physikal. Grundlagen des opt. Drehungs­ vermögens (A l l s OPP). V III. Dipolmomente u. Valenzwinkel (G l a s s t o n e ). (Annu. Bep. Progr. Chem. 3 2 . 39— 137. 1936.) S k a l iic s . L. F. Bates, Physik. Fortschrittsbericht über die Eigg. von Rochellesalz- kr y stallen. (Sei. Progr. 30. 465— 71. Jan. 1936. London, Univ. College.) S k a l i k s . J. M. Bijvoet, Chemische Reaktion und Atomtheorie. Vortrag: Die Fragen der Bindung von Atomen, der Gleichgewichtslage u. der Bk.-Geschwindigkeit werden ausführlich vom Standpunkte der Atom- u. Mol.-Theorie vor B o h r , der Theorie von B o h r u. der wellenmeqhan. Theorie behandelt. (Chem. Weekbl. 3 3 . 222— 31. 270— 77. 2/5. 1936. Amsterdam, Univ., Lab. f. Krystallographie.) B . K . MÜLLER. G. G. Gelman (Helman) und A. A. Shuchowitzki, Die grundlegenden Fragen der chemischen Umsetzungen in der heutigen Quantentheorie. Zusammenfassende Be­ sprechung der Anwendung der Quantentheorie bei den Unterss. von chem. Bkk., auf den Valenzbegriff u. bei der chem. Dissoziation. Insbesondere wird die physikal. Natur der homöopolaren Bindung u. einiger ihrer Eigg. betrachtet. (Fortsehr. Chem. [russ.: Uspechi Chimii] 4. 1149— 93. 1935.) K le v e r . A. S. Liperowski, Die Verschiebung der Isotopenketten durch ß-Strahlung und die Isotopie der seltenen Erden. Es wird in Analogie mit J o h n s t o n (C. 1 9 3 1 . II. 2417) ein Schema der Isotopen unter Berücksichtigung der Kerrizus. aufgestellt, nach dem die Isotopen untereinander in Ketten verbunden sind, die sich voneinander um ein a-Teilchen über je 2 Ordnungszahlen unterscheiden u. von Zeit zu Zeit durch ^-Strahlung erniedrigt werden. Auf Grund der aufgestcllten Theorie wird auch für die seltenen Erden ein Isotopenschema aufgestellt. Bezüglich der Einzelheiten muß auf das Original verwiesen werden. (Chem. J. Ser. A. J. allg. Chem. [russ. : Chimitscheski Shurnal. Sser. A. Shurnal obschtschei Chimii] 4. (66). 1157— 67.) K l e v e r . * W . Brandt, Der schwere Wasserstoff. Seine Bedeutung bei der Untersuchung chemischer und biologischer Fragen. Bericht. I. Entdeckung, Darst. u. Vork.; physikal. u. chem. Eigg. II. Die Best. von D. III. Die Lsg. chem. Fragen mit Hilfe des schweren H . IV. Die Lsg. biol. Fragen. (Chemiker-Ztg. 60. 285— 88. 4/4. 1936. Bonn.) Z e i s e . Clément Courty, Einige Betrachtungen über die „schiceren Wässer“ . Bericht über physikal. u. biol. Eigg., Nachweis u. natürliches Vork. des schweren W. (Bull. Sei.pharma- col. 43 (38). 153— 66. März 1936. Paris, Faculté des Sciences, Lab. de Chim. biol.) Z e i s e . P. Goldfinger und Léon Scheepers, Uber die systematische Berechnung und Herstellungstechnik des schweren Wassers. Vff. leiten Formeln ab zur Berechnung der Ausbeuten bei der elektrolyt. Anreicherung von D 20 u. stellen die hiermit erhaltene theoret. Abhängigkeit der Ausbeute vom Trennungsfaktor sowie die Konz.-Zunahme des D 20 als Funktion der Vol.-Verminderung bei der Elektrolyse tabellar, bzw. grapli. dar. Aus den Tabellen kann man entnehmen, daß das wirtschaftliche Optimum bei dem Verf. der wiederholten Elektrolyse nach jeweiliger Verbrennung des entstandenen Knallgases dann erreicht ist, wenn das Anfangsvol. des als Ausgangsmaterial dienenden gewöhnlichen W . auf V20— Vso reduziert ist, wobei man 45— 50°/o des im Ausgangs­ material enthaltenen D20 bekommt, während man ohne Wiedergewinnung 90 % ver­ liert. Ferner wird gezeigt, daß die Konstanthaltung des W.-Standes während der Elek­ trolyse durch wiederholte Zugabe von frischem W . zwar die Arbeit erleichtert, aber *) Schwerer Wasserstoff vgl. S. 259, 306. X V III. 2. 17 250 A . A l l g e m e in e u n d physikalische C h e m i e . 1936. II. die Ausbeute vermindert. Unter den angegebenen Bedingungen ergibt sieh 1 g Lsg. mit 9 0 % D 20 durch elektrolyt. Zers, von 10— 15 1 gewöhnlichem W ., entsprechend einem Strombedarf von 30000— 45000 Amp.-Stdn. Vff. konstruieren Elektrolysatoren aus Fe mit Elektrodenabständen von 6 mm u. Stromstärken von 400 Amp. sowie Stromdichten von 0,1— 0,3 Am p./qcm ; die angelegte Spannung beträgt jeweils 2,5 bis 3,0 V, wobei als Elektrolyt eine Lsg. von 1— 8 % NaOH verwendet wird. Dies entspricht einem Verbrauch von 100— 150 kWh pro g eines 90%ig. schweren W . Weiter beschreiben die Vff. Apparate zur Verbrennung von 3— 60 1 Knallgas pro Stunde bei der Elektrolyse; die Verbrennung erfolgt unter einem Druck von 100— 150 mm Hg, so daß Verluste u. Explosionsgefahren vermieden werden. Die Anlago der Vff. arbeitet ungefähr mit dem Trennungsfaktor 6. (J. Chim. physique 3 1 . 628— 46. 1934. Univ. de Liege, Lab. de Chim. phys., Electroch. et Chim. industr.) Z e i s e . John E. Bates, J. O. Haiford und Leigh C. Anderson, Ein Vergleich einiger physikalischer Eigenschaften von Wasserstoff- und Deuteriumjodid. Reines H J wird durch Überleiten von H 2 u. J2 über einen erhitzten Pt-Katalysator u. mehrfache Dest., reines D J durch Erhitzen eines J2-Überschusses mit D 2-Gas in einem vorher gut ent­ gasten Glaskolben u. anschließende Dest. nach U r e y u . R it te n b e r g (C. 1 9 3 4 . II. 2543) dargestellt. Die Gase kommen nur mit Glas u. Quarz in Berührung u. werden vor Licht geschützt, ehe die quantitativen Absorptionsspektren mit einem Sektor­ photometer u. Quarzspektrographen aufgenommen werden (Lichtquelle: das kon­ tinuierliche Spektrum eines Unterwasserfunkens zwischen W-Elektroden). Die opt. Weglänge im Absorptionsgefäß aus Quarz beträgt 12,41 cm. Der Gasdruck wird variiert u. der molekulare Absorptionskoeff. a in bekannter Weise berechnet. Er ist im ganzen untersuchten Frequenzbereich (30 500— 36 030 cm-1 ) für H J merklich größer als für D J. Ferner erstreckt sich die Absorption des H J nach kleineren Fre­ quenzen als die von DJ. Die beiden Absorptionskurven haben an der Stelle der maxi­ malen Absorption einen Abstand von etwas über 300 cm-1 , im Einklang mit der Differenz der Nullpunktsenergien (halben Grundschwingungsquanten) der beiden Moll. 1/a co„ (HJ) — l/2 <u„ (DJ) = 1135 — 805 cm- 1 = 330 cm-1 . Nach höheren Fre­ quenzen zu erstreckt sich die Absorption beider Gase bis weit ins U V, ohne Andeutung einer Intensitätsabnahme. Im Zusammenhang mit diesen Beobachtungen werden die Ergebnisse einiger anderer Autoren diskutiert. — Ferner werden die Dampfdrücke von festen u. fl. H J u. D J mit einem Quarzspiralmanometer zwischen dem Kp. u. — 82° gemessen. Die Tripelpunkte werden mit Hilfe von Erwärmungskurven bestimmt. Die Ergebnisse der Vff. für fl. H J stimmen mit den Literaturangaben gut überein, während sich für festes H J größere Abweichungen zeigen. Mit Hilfe der calorimetr. Daten von G ia u q u e u . W ie b e (C. 1 9 2 9 . II. 145) ergeben sieh aus den Messungen der Vff. die Dampfdruckgleichungen: log p (fl- H J) = 26,119 + 0,002 293-T — 7,111-log T — 1636/21 log p (festes H J) = 10,493 — 0,003 167-T — 0,377-log T — 1406/21 Durch Vergleich der gemessenen Dampfdrücke von D J mit den hiernach für H J bei denselben Tempp. berechneten Werten ergeben sich für D J die Gleichungen: log p (fl. DJ) = 26,129 — 0,002 293-T — 7,111-log T — 1636/i' log p (festes DJ) = 10,505 — 0,003 167- i 7 — 0,377-log T — 1406/21 Der n. Kp. liegt hiernach für H J bei 237,5° absol. u. für DJ bei 237,0° absol. Somit hat D J bei gegebener Temp. einen etwas höheren Dampfdruck als H J. Dos Verhältnis der Dampfdrücke ist nach jenen Gleichungen im ganzen Bereich des festen u. fl. Zu­ standes konstant. Mithin müssen die Verdampfungs-, Schmelz- u. Sublimationswärmen von H J u. D J bei derselben Temp. nahezu ident, sein. Tatsächlich ergibt eine A b ­ schätzung der Verdampfungswärmen nach der von Hildebrand abgeänderten l'ROUTONschen Regel für DJ 4709, für H J 4724 cal/Mol bei 237,5° absol. Die Dampf- druekunterschiede für H J u. D J liegen zwar in derselben Richtung, sind aber kleiner als die von H F u. D F nach Claussen u. Hildebrand (C. 1934. II. 3710), vielleicht infolge der kleineren Polarität von D J (bedingt durch den kleineren Anharmonizitäts- faktor im Bereich der Nullpunktsenergie) gegenüber D F. (J. ehem. Physics 3. 415— 20. 1935. Univ. of Michigan, Dep. of Chem.) Z e i s e . Nobuji Sasaki und Osamu Mabuchi, Die para-ortlio-Zusammensetzung des aus Wasserstoffatomen primär entstehenden Wasserstoffgases. Während nach der Annahme einiger Autoren der bei Rkk. entstehende H 2 stets die der jeweiligen Rk.-Temp. ent­ sprechende Gleichgewichtszus. haben sollte, muß nach P e l t z e r u. W lGNER (C. 1 9 3 2 . H . 6) auf Grund des Satzes von der Erhaltung des gesamten Kemspins der entstehende 1936. H. A. A l l g e m e in e u n d physikalische C h e m i e . 251 H 2 die o- u. p-Modifikationen immer im n. Verhältnis 3 : 1 gemischt enthalten.
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