BRITISH CHEMICAL ABSTRACTS
A . - P U R E CHEMISTRY
MAY, 1931.
G en eral, P h y sic a l, and
N e w b a n d s in th e s e c o n d a r y s p e c t r u m of h y d ro g e n . D . S. Jo g (Phil. Mag., 1931, [vii], 41, 761—7S6; cf. R ichardson, A., 1930, 387).—The known electronic levels of hydrogen are su m m ar
ised, a n d are in te rp re te d on H u n d ’s th e o ry of axial q u a n tisa tio n ; th e m ethod is applied to th e calculation of th e electronic term s of th e hydrogen molecule.
N . M. Bl i g h. F in e s t r u c t u r e i n h y d r o g e n b a n d lin e s . 0 . W . Ri c h a r d s o n an d W . E. Wi l l i a m s (N ature, 1931, 127, 481).—A n ex am in atio n of th e sp ectru m of hydrogen in a large H ilger q u a rtz spectrograph crossed by a reflexion echelon establishes th e corre
lation betw een th e spectrum of m olecular hydrogen and atom ic helium . L. S. Th e o b a l d.
G a s e o u s d is c h a r g e s . I. C h a r a c te r is tic s of th e d is c h a r g e s i n h y d r o g e n a n d n i t r o g e n a t re d u c e d p r e s s u r e s w i t h a n in c a n d e s c e n t c a th o d e . II. In flu e n c e of th e t h e r m a l t r e a t m e n t of th e e le c tro d e o n t h e g lo w d is c h a r g e . I I I . In flu e n c e of g a s - l o a d i n g of th e c a th o d e o n th e ig n itio n p o te n tia l o f th e g lo w d is c h a r g e in h y d r o g e n . E. Ba d a r e u (Bull. F a c. S tiin te C ernauti, 1929, 3, 221—236, 304—306, 1— 8 ; Chem. Z entr., 1930, ii,
1043). L. S. Th e o b a l d.
C old e m is s io n f r o m u n c o n d itio n e d s u r f a c e s . W. H. Be n n e t t (Physical Rev.,' 1931, [ii], 37, 582—
590).—Em ission from unconditioned m etals in high electric fields an d th e effect on th e em ittin g surfaces of discharges th ro u g h hydrogen were investigated.
Loose fine p articles have a g rea ter influence on th e quantity' of em ission th a n n a tu re an d conditioning of
cathode. N . M. Bl i g h.
C le a n -u p p h e n o m e n o n i n h y d r o g e n . E . Hi e d e- mann (Ann. Physik, 1931, 8, [v], 456—474).—The clean-up phenom enon in hydrogen follows a norm al (in essentials sim ilar to t h a t described b y Johnson) or an abnorm al (observed by' Mierdel) course d epend
ing on th e tre a tm e n t to w hich th e discharge tu b e has Lcen previously' subjected. The norm al clean-up is characterised b y adsorption of hydrogen, w hilst th e abnormal appeal's to be th e resu lt of condensation of a mixture of silicon hydrides. W . Go o d.
V isible s p e c t r u m of h e liu m . J . S. To w n s e n d
and F . L. Jo n e s (Phil. Mag., 1931, [vii], 11, 679—
685; cf. A ., 1930, 973).—The relatio n betw een the
% h | em itted b y a discharge in a gas a n d th e energy' o£ the electrons causing ionisation by collision w ith the gas molecules w as in v estig ated by observations
o o 539
In o r g a n ic C h em istry.
on th e change in in te n sity of th e light due to changes of pressure in helium over th e range 20— 2 m m ., an d electron energies 3— 4 volts. B o h r’s m odel of th e helium atom , requiring a m inim um of 20 volts for ra d ia tio n emission, is n o t supported.
N. M. Bl i g h. H y p e r f in e s t r u c t u r e of L i +. I I . P . Gü t- t i n g e r an d W . Pa u l i (Z. Physik, 1931, 67, 743—
765).—T heoretical (cf. A., 1930, 1487). H yperfine separations in th e L i 1- lines, 3Fo.i,2'“3‘8ij are com p ar
able w ith fine stru c tu re separations.
A. B. D. Ca s s i e. V a c u u m s p a r k s p e c t r a to 4 0 Á . : s p e c t r a of B e I I I , B e IV , B I V , B v , a n d C v . B. E d l é x (N ature, 1931, 127, 405— 406).—T he hydrogen- an d helium -like sp ectra previously tra c e d to Be rv (A., 1930, 263) have been com pleted w ith B rv- B v, and C v , and the lim it of optical spectra has been b ro u g h t dow n to 40-28 Á. W ave-lengths of th e series 1W — n~P an d 12,S'—32P , an d 11S —n 1P are ta b u la te d . T he calculated q u a n tu m defect from th e series of Be i n is n —n * = —0-013±0-001. L. S. Th e o b a l d.
I n te n s ity m e a s u r e m e n t s i n th e a t m o s p h e r i c o x y g e n b a n d a t 7 6 0 0 Á . W . H . J . Ch i l d s an d R . Me c k e (Z. P h y sik , 1931, 6 8, 344— 361).—T he in ten sity of absorption due to th e A -group of oxy-gen near 7600 A. w as determ ined b y F rerich s’ m ethod (ibid., 1925, 31, 305), using a dispersion of 2-6 Á. p er m m ., and colum ns of air 14, 33, an d 62 m etres long.
D eviations from L a m b e rt’s law were investigated and a I lowed for, an d th e sta tistic a l w eights of th e ro tatio n al levels were determ ined.
A. B. D. Ca s s i e. S t a r t i n g p o te n tia ls of th e c o r o n a d is c h a r g e in n e o n . F . M. Pe n n i n g (Phil. Mag., 1931, [vii], 11, 961— 980),— C ontrary to th e results of Huxley' (cf.
A., 1928, 567), th e sta rtin g p o te n tia l of a positive discharge in pu re neon was found to be higher th a n th a t of a negative discharge. The form er could, how ever, be decreased below th e la tte r by the a d d itio n of traces of argon. N. M. Bl i g h.
P h o t o m e t r y of t h e n e o n la m p . M. J . Dr u y v e s- t e y n an d N. Wa r m o l t z (Z. Physik:, 1931, 6 8, 378—
394).— L ig h t em itted norm ally to th e cathode of a neon lam p w as investigated visually b y m eans of a ro ta tin g sector photom eter. F ifteen in tern atio n al candles are e m itte d per a m p , passing th ro u g h th e la m p ; th is intensity' is proportional to th e c u rren t an d indep en d en t of cathode fall an d gas pressure.
A stu d y of th e influence of helium and argon suggests
5 4 0 B R I T IS H C H E M IC A L A B S T R A C T S .— A .
th a t ex citatio n is due to slow electrons of 25 volts
energy. A. B. D. Ca s s i e.
N e w r e s o n a n c e s e r ie s of s u l p h u r v a p o u r . I I I . J . G e n a r d (Bull. Acad. roy. Belg., 1931, [v], 17, 184— 190).—The e x te n t of th e ex citatio n region of th e resonance spectrum of S2 w as investigated. Con
ditions used were o th er th a n those giving the optim um fluorescence; e xcitation was by m eans of m agnesium spark. The lower lim it of th e e x citatio n spectrum is betw een 2890 an d 2850 A. A. J . M e e .
R o ta tio n a l a n a ly s is of th e S 2 b a n d s . S. M.
Na h d ć and A. Ch r is t y (Physical R ev., 1931, [ii], 3 7 , 490—506; cf. R osen, A., 1927, 608).—The emission spectrum of S2 was obtained b y m eans of a Geissler tube, an d th e bands 9—1 (X 2857-36), 7—0 (X 2860-13), 8— 1 (X 2887-84), 9— 1 (X 2917-38), a n d 7— 1 (X 2920-28) were investigated. E ach b a n d consists of th ree R and th ree P b ran ch es; th e stru c tu re is sim ilar to t h a t of th e S ch u m an n -R u n g e bands of oxygen.
W ave num bers an d in terv als for th e lines of each band are tab u la te d , an d th e ro ta tio n a l analysis is
obtained. N. M. Bl ig h.
S p a r k s p e c t r a of c h lo r in e . K Mu r a k a w a
(Sci. P ap ers In st. Phys. Chem. Res. Tokyo, 1931, 1 5 , 105— 109; cf. th is vol., 276).— The spectrum of Cl i i i was excited by increasing th e spark g ap and c u rre n t in a Geissler tu b e w ith tu n g sten electrodes, one containing a little sodium chloride. Intensities, w ave-lengths, an d term com binations are ta b u la te d for 29 newly-classified lines. The classification of Cl i i lines is extended. N. M. Bl ig h.
B a n d s p e c t r a of s c a n d iu m , y t t r i u m , a n d l a n t h a n u m m o n o x id e s . W . F . M e g g e r s and J . A. W h e e l e r (Bur. S tan d . J . Res., 1931, 6, 239—
275).—T he b and spectrum of scandium oxide con
tain s 139 b an d heads, all degraded tow ards th e red.
T hey are divided in to five system s, th e 0 -0 tr a n sitions having heads a t 4857-79 an d 4858-09, 6017-07, 6036-17, 6064-31, 6079-30 A. Y ttriu m oxide gives 120 b an d heads degraded to w ard s th e red, th e five 0 -0 tran sitio n s being 4817-38 an d 4818-20, 5939-08, 5972-04, 6096-78, 6132-06 A, L an th an u m m onoxide gives 300 b and heads, divided in to nine system s, seven of w hich include all bands shaded tow ards th e red, a n d th e o th er tw o of groups of w eaker bands shaded aw ay from th e red. C. W . G ib b y .
I n t e n s i t y m e a s u r e m e n t s in t h e s p e c t r u m of m a n g a n e s e . R . S . Se w a r d (Physical R ev., 1931, [ii], 37, 344— 361; cf. M cLennan, A., 1926, 766;
D uffendack, A., 1929, 966).— R elativ e in ten sity m easurem ents were m ade, an d full d a ta ta b u la te d for 150 lines of 23 m ultiplets of Mn i, an d 3 of Mn i i.
N. M. Bl ig h. F lu o r e s c e n c e of z in c v a p o u r . W . K a p u ś c i ń s k i (Bull. A cad. Polonaise, 1930, A, 453— 459).—The fluorescence spectrum of zinc v ap o u r extends from 2130 to 4900 A., an d consists of lines an d bands.
The trip le ts originate in levels n o t directly excited from th e ground level. A. B. D. C a s s ie .
O p tic a l e x c ita tio n f u n c tio n s of c a d m iu m a n d z in c lin e s . K . La r c h ć (Physikal. Z., 1931, 3 2 , 1 8 0—1 8 1 ).—A lecture. W . Go o d.
C r itic a l p o te n tia ls of th e s p a r k s p e c t r u m of c a d m iu m . D. Co l so n (Proc. Iow a Acad. Sci., 1929, 3 6 , 307).— E x c ita tio n b y electron im p act (8-8—200 volts) was em ployed. Ch e m ic a l Ab s t r a c t s.
S e c o n d s p e c t r u m of x e n o n . C. J . Hu m p h r e y s, T. L. d e Br u i n, an d W . F . Me g g e r s (Bur. S tand. J . R es., 1931, 6. 287— 293).—A p a rtia l list of identified term s an d th eir com binations is given.
C. W . Gi b b y. P r o b a b i l i t i e s of r e c o m b in a tio n in to th e 1 2S s t a t e of c æ s iu m . C. B o e c k n e r (Bur. S tand. J . Res., 1931, 6, 277— 285).— The in te n sity d istrib u tio n in th e Y2S series of cæsium has been m easured between 3184 an d 2750 A. F rom th is an d th e velocity dis
trib u tio n of th e discharge electrons th e relative prob
ab ility of recom bination of free electrons in to the l 2tS sta te is shown to fall n early as th e inverse fo u rth power of th e velocity for energies greater th a n 0-15 v olt. C. W . G ib b y .
M e a s u r e m e n ts in th e a r c s p e c t r u m of rh e n iu m . W . M e i d i n g e r (Z. P hysik, 1931, 68, 331— 343).—
A num ber of lines betw een 2600 a n d 3500 A. and betw een 4040 an d 5300 A. were m easured w ith ail accuracy of ¿ 0 - 1 A. in th e arc spectrum of rhenium.
A. B. D. Ca s s i e. A b s o r p tio n s p e c t r u m of d is s o lv e d m e r c u r y . H . R e i c h a r d t a n d K . F . B o n h o e f f e r (Z. Physik, 1931, 67, 780—789).—A furnace containing a quartz absorption vessel w hich could co n tain liquids a t 200 a tm . an d 250° is described. A double m ercury 2537 A. line, displaced tow ards th e red, appeared a t 120s w hen th e m ercury w as dissolved in w ater, a t 50°
when in m ethyl alcohol, a n d a t 15° w hen in hexane.
D oubling is a S ta rk effect due to th e electric field w ithin th e solution. The doublet sep aratio n dimin
ishes w ith rise of tem p e ra tu re or decreasing density of th e solvent. A n absorption edge a t 2200 A. is ascribed to ionisation of dissolved m ercury atom s.
A. B . D. Ca s s i e. F lu o r e s c e n c e of m e r c u r y v a p o u r u n d e r a to m ic a n d m o le c u la r a b s o r p tio n . H . Nie w o d n ic z a ń s k i
(N ature, 1931, 127, 406).—T he view th a t th e fluor
escence of m ercury v ap o u r is due m ainly to atomic a bsorption is su p p o rted by th e a u th o r’s w ork on the influence of a m agnetic field on fluorescence (A., 1929, 979; cf. R ayleigh, th is vol., 137).
L . S. Th e o b a l d. S p a r k s p e c t r a of m e r c u r y . B. Ric a r d (Compt.
rend., 1931, 192, 618— 620).—W ith th e electrodeless discharge new lines have been m easured belonging to th e H g II, H g m , a n d H g itv sp ec tra from 4000 to
2700 A . C. A . SlLBERRAD.
F in e s t r u c t u r e i n th e m e r c u r y s in g le t te r m s . S. To l a n s k y (Proc. R oy. Soc., 1931, A, 130, 55S—
578).— B y th e use of a low -pressure high-frequency electrodeless discharge in pure m ercury v ap o u r, which increases th e relativ e an d intrinsic intensities of the singlet an d inter-com bination lines involving upper singlet levels, num erous stru c tu re hav e been ex
am ined. An explanation, based on th e conception of nuclear spin, is suggested for th e origin of th e fine stru ctu res. This accounts for m o st of th e difficulties a n d explains th e a p p a re n t m u ltip licity of th e 7lS0
level. L. L. Bir c u m s h a w.
G E N E R A L , P H Y S I C A L , A N D IN O R G A N I C C H E M IS T R Y . 5 4 1
Resonance line of m ercury on addition of rare gases. P. Ku n z e (Ann. P hysik, 1931, 8, [v], 500— 520).— The effect of helium , neon, a n d argon on the emission an d ab so rp tio n of th e resonance line of m ercury (2537) has been experim entally investig
ated. A q u a n tita tiv e discussion of th e results is
given. W . Go o d.
Hyperfine structure of tbe m ercury resonance line 2537 A. I. S. Mr o z o w s k i (Bull. Acad.
Polonaise, 1930, A, 464— 503).— The Zeem an effect in absorption w as studied for th e m ercury 2537 A.
line w ith fields up to 8 kilogauss. A nom alies ob
served by M cNair (A., 1928, 807) betw een 1 and 3-5 kilogauss in emission ap p ear in absorption.
This hyperfine stru c tu re an d Zeem an effect can n o t be explained b y o rd in ary hypotheses.
A. B. D. Ca s s i e.
Hyperfine structure of certain m ercury lines.
B. V e n k a t e s a c h a r an d L. S i b a i y a (Mysore U niv.
J., 1930, 4, 145— 148).— Analyses of th e m ercury lines 6716, 6123, 6072, an d of 4916 A. are given.
C. W . Gi b b y.
Intensity of m ercury lines excited by positive ions. D. Fr i s o h e (Proc. Iow a A cad. Sei., 1929, 36, 307— 308).— T he results were com pared w ith those of investigation of th e electron spectrum .
Ch e m ic a l Ab s t r a c t s.
Life of the excited state and the fine structure of the m ercury arc spectrum. S. Mr o z o w s k i (Z.
Physik, 1931, 68, 278— 283).— I t is show n th a t th e times of life of different levels w hich ta k e p a r t in the production of a m u ltip le t are nearly equal to each other so far as tran sitio n s to o th e r levels belong
ing to th e sam e term system are concerned.
A . J . Me e.
Thallium -inert gas bands. H. Kr e f f t and R. Ro m p e (N aturw iss., 1931, 1 9 , 269).—M ixtures of thallium v ap o u r w ith in e rt gases give absorption bands in th e neighbourhood of th e strongest th alliu m lines (5350 an d 3776 A.). P ro b ab ly these arise from a th a lliu m -in e rt gas molecule. T he sep aratio n of the b and heads varies w ith th e in e rt gas.
W . R . An g u s.
Influence of ion density on the arc spectrum of thallium. H . Kr e f f t (N aturw iss., 1931, 1 9 , 269—
270).—Spectrogram s are given showing th e influence of different c u rre n t stren g th s on th e absorption spectrum ob tain ed from a discharge in m ix tu res of thallium w ith in e rt gases. The observed phenom ena
are discussed. W . R . An g u s.
Determination of energy of dissociation from predissociation spectra. L. A. T u r n e r (Z.
Physik, 1931, 68, 178— 183).— A n ex p lan atio n of th e existence of tw o ty p es of predissociation spectrum is given. I n th e one th e disappearance of fine stru c tu re 18 sharp, in th e o th e r g radual. A. J . Me e.
R e d u c tio n of in t e n s i t y of s p e c t r a l lin e s in stro n g e le c tr ic fie ld s . C. La n c z o s (Z. P hysik, 1931, 68, 204— 232).— The reduction of th e in te n sity
°1 the emission lines of th e hydrogen ato m is dis
cussed q u a n tita tiv e ly on th e basis of w ave m echanics, and ascribed to “ pre-ionisation.” The electric field sets the ato m in a sta te of spontaneous ionisation, so th a t radioactive disintegration can ta k e place. In
th e higher ex cited sta te s th is d isin teg ratio n takes place in a tim e which is less th a n th e life of th e excited atom , an d as ra d ia tio n tra n sitio n can n o t ta k e place the emission line disappears.
A. J . Me e.
Zeeman effect of forced radiation transitions produced by inner electric fields. G. P . It t m a n n
an d H . C. Br in k m a n (N aturw iss., 1931, 1 9 , 292).—•
The occurrence of a forbidden line in absorption or emission sp ectra m ay be due to tw o causes, which can be distinguished by a stu d y of th e Z eem an effect.
The Zeem an effect for tran sitio n s which are forced by electric fields by no m eans agrees w ith th a t p roduced for p erm itte d tran sitio n s. A. J . Me e.
After-glow and its life in discharge tubes.
D . B. De o d h a r (N ature, 1931, 1 2 7 , 485).—A strong after-glow persisting for 45 m in. has been observed in silica tu b es filled w ith gases a t low pressures and excited for 2 m in. b y induction coils giving a n o u tp u t of 400 volts. T he ra te of decay is extrem ely slow.
The flash phenom enon recorded by B raddick (this vol., 1) is seen in these after-glows. L. S. Th e o b a l d.
Sensitivity of photographic plates in tbe region between ultra-soft X-rays and tbe ultra
violet. M. S o d e r m a n (Z. P hysik, 1931, 6 7 , 790—
793).— S chum ann plates are b est su ited to p h o to g raphing sp ectra betw een 50 an d 500 A.
A. B. D. Ca s s i e.
Sources of illum ination for ultra-violet m icro
scopy. B. K . Jo h n s o n (Proc. P hysical Soc., 1931, 4 3 , 127— 137).— Q u a n tita tiv e m easurem ents have been m ade of th e relative intrinsic brightness of spectrum lines given b y various sources of rad iatio n . S park discharge betw een cadm ium electrodes is th e m ost suitable source of ra d ia tio n for q u a rtz rnono- ch ro m at microscope objectives com puted for a w ave
length in th e neighbourhood of 0-275 p. A special tran sfo rm e r an d condenser is described.
W . E. Do w n e y.
Influence of the crystal-orientation of the cathode on that of an electrodeposited layer.
W . A. Wood (Proc. P hysical Soc., 1931, 4 3 , 138—
141).— A '-Ray ex am in atio n shows t h a t th e o rien tatio n of a copper deposit for sm all cu rren ts is th e sam e as th a t of th e cathode. Nickel a t low c u rre n t densities assum es a d istin ct o rientation. As th e c u rre n t is increased th ere is a region of no o rientation, b u t a t still higher cu rre n ts th e o rien tatio n is th e sam e as th a t of th e cath o d e surface. W . E . Do w n e y.
Intensity of X-rays reflected from platinum, silver, and glass. H . W . E d w a r d s (Physical R ev., 1931, [ii], 3 7 , 339— 343).—T he in te n sity of a m ono
chrom atic beam of X -ray s of w ave-length 0-69 A., ob tain ed by reflexion from ealcite, was m easured on reflexion from platin u m , silver, and glass m irrors for angles of incidence varying from 0-75 to 1-25 tim es th e critical angle. N . M. B l i g h .
Frequencies of characteristic X-radiation for the elem ents 1 1 Na to 1 7 Cl, calculated more accurately than at present w ith hypotheses extending the classical theory. S. Bj o r c k (Z.
P hysik, 1931, 68, 133— 144).—Theoretical.
A. B. D. Ca s s i e.
542 B R I T I S H C H E M IC A L A B S T R A C T S .— A .
M a s s a b s o r p t i o n c o e ffic ie n t of t h e I i s h e ll a c c o r d in g t o t h e D ir a c r e l a t i v i s t i c t h e o r y of th e e le c tro n . L. C. Ro e ss (Physical R ev., 1931, [ii], 37, 532— 555).—M athem atical. W ith a m odel ato m containing tw o non-interacting electrons an d a fixed nucleus th e m ass absorption coefficient is calculated w ith th e help of th e D irac relativistic equation.
R esu lts fo r lead, tin , zinc, an d alum inium are ta b u l
a te d an d graphed for com parison w ith experim ental d a ta , an d w ith values calculated on a non-rclativistic basis (cf. Stobbe, th is vol., 138). N . M. Bl ig h.
D is tr ib u tio n of e le c tr ic ity i n th e l i t h i u m a to m . B. Ar a k a t z u a n d P. Sc h e r r e h (Helv. p h y s. A c ta , 1930, 3, 428— 135 ; Chem. Z entr., 1931, i,“ 13— 14).
—T he scatterin g of X -ray s b y lith iu m has been exam ined b y th e pow der ruothod, and th e electronic d istrib u tio n is discussed. A. A. El d r i d g e.
T h e i o n is a tio n f o r m u l a a n d th e n e w s t a t i s t i c s . W . An d e r s o n (Phil. Mag., 1931, [vii], 11, 6 8 5 — 6 86).
— R em arks on a p ap er by C handrasekhar (A., 1930,
83 3 ). N . M. Bl ig h.
I o n is a tio n of a r g o n , n e o n , a n d h e liu m b y v a r i o u s a lk a li io n s . R . M. Su t t o n a n d J . C.
Mo u z o n (Physical R ev., 1931, [ii], 37, 379— 382;
cf. A., 1930, 656).— Cæsium, ru b id iu m , potassium , a n d sodium positive ions from K u n sm an c a ta ly st sources an d lith iu m ions from spodum ene were used to produce ionisation in helium , neon, a n d argon.
M axim um ionisation was produced in each gas by th e alkali ion n earest to it in atom ic nu m b er (cf.
Beeck, A., 1930, 1494). N . M. Bl ig h. T h e o r y of t h e p h o to - e le c tr ic e ffe c t i n m e ta ls . I. Tam m a n d S. Sc h u b ln (Z. P hvsik, 1931, 68, 97—
113).—T heoretical. Photo-em ission is re la ted to the p o te n tia l b arrier a t th e m etal surface (surface effect) a n d to th e energy of binding of conduction electrons (volum e effect). T he influence of surface lay ers is
discussed. A. B. D. Ca s s i e.
P h o to - e le c tr ic e ffe c t a n d re f le x io n of e le c tr o n s a t h y d r o g e n is e d p o t a s s i u m s u r f a c e s . W . Kl u g e
a n d E. Rupp (Physikal. Z., 1931, 32, 163—172).—
A n experim ental arrangem ent is described w ith w hich parallel investigations of th e stru c tu re and photo-electric em ission of potassium surfaces were carried out. T he results su p p o rt th e view th a t th e selective photo-electric effect ex h ib ited b y th e potassium surface a fter a glow discharge in hydrogen a t low pressure is due to interspersion of potassium in potassium hydride. T he investigations of surface stru c tu re by electron reflexion lead to th e values 7-3 volts for th e m ean inner p o te n tia l of potassium a n d 5-4 A. ¿0-1 for th e lattice co n sta n t of potassium
hydride (cubic lattice). W . Go o d.
Q u a n t u m d y n a m ic s of th e e le c tr o n . E. S c h r ô -
d i n g e r (Sitzungsber. Prouss. A kad. W iss., B erlin, 1931, 12 p p .).— M athem atical.
D ir e c tio n s of e m is s io n o f p h o to - e le c tr o n s . P . Au g e r an d (Ml l e.) T. Me y e r (Compt. rend., 1931, 1 9 2 , 672—673).
E l a s t i c s c a t t e r i n g of s lo w e le c tr o n s i n a r g o n . E . C. Bu l l a r d an d H . S. W . Ma s s e y (Proc. R oy.
Soe., 1931, A, 1 3 0 , 579—590; cf. R am sauer an d
K o llath , A., 1930, 269, 1495).—W ith th e o bject of o btaining fu rth e r in sig h t in to th e R am sau er effect, experim ents have been carried o u t in w hich th e an g u lar d istrib u tio n of slow electrons (velocities from 4 to 40 volts) scattered elastically in argon have been m easured over th e an g u lar range 15— 125°. S c a tte r
ing curves are obtain ed showing pronounced m axim a an d m inim a. L . L. Bir o u m s h a w.
D if f r a c tio n of e le c tr o n s i n m e r c u r y v a p o u r . F . L. Ar n o t (Proc. R oy. Soc., 1931, A, 1 3 0 , 655—
667; cf. preceding a b stra c t).— B y m eans of th e a p p a ra tu s previously described (A., 1930, 6), th e ang u lar d istrib u tio n s of electrons of 15 different velocities (8-6— 800 volts) scattered in m ercury v ap o u r have been m easured over a n angular range of IS —
126°. L. L. Bir o u m s h a w.
S c a t t e r i n g of h ig h - v e lo c ity e le c tr o n s i n h y d r o g e n a s a t e s t of th e i n t e r a c t i o n e n e r g y of tw o e le c tr o n s . H . C. Wo l fe (Physical R ev., 1931,
[ii], 37, 591— 601).— M athem atical. N . M. Bl i g h. A b s o r p tio n c o e ffic ie n t f o r s lo w e le c tr o n s in t h a l l i u m v a p o u r . R . B. Br o d e (Physical R ev., 1931, [ii], 37, 570—573; cf. A., 1930, 657).—T he absorption coefficient w as obtained b y sending a beam of electrons th ro u g h th alliu m v ap o u r a n d m easuring th e decrease in in te n sity of th e beam as a fun ctio n of th e v ap o u r p re ssu re ; p lo tte d ag ain st th e velocity of th e electrons th ere is a m inim um a t 1-4 an d a m axim um a t 4-5 volts. IST. M. Bl ig h.
L ib e r a tio n of e le c tr o n s b y c o llis io n w ith p o s itiv e io n s a t lo w g a s p r e s s u r e s . I I . S ilv e r , a lu m in iu m , p o t a s s i u m , s o d iu m , a n d m e r c u r y in h y d r o g e n , n itr o g e n , m e r c u r y v a p o u r , a n d r a r e g a s e s . A. Gü n t h e r-Sc h u l z e an d F . Ke l l e r (Z.
P hysik, 1931, 68, 162— 173).—The yield of electrons due to collision in hydrogen an d nitrogen increases w ith th e am o u n t of gas, b u t in th e rare gases is inde
p e n d e n t of th is factor. I t increases w ith th e energy of collision, b u t above 1000 v o lts th e increase is small. I n general th e n u m b er of electrons se t free is g reater th e sm aller is th e m ass of th e ion colliding.
A. J . Me e. P y r o m e t r y a n d t h e r a d i a t i o n p r o p e r t i e s of h e a te d m e t a l s . R . Ha s e (Proc. P hysical Soc., 1931, 43, 212—216).— I t is experim entally shown th a t th e m axim um of th e energy e m itted b y a ra d ia tin g m etal is proportional to th e square ro o t of th e specific resistance a t zero a n d to th e six th pow er of th e absolute te m p eratu re, in stead of to th e fifth pow er as in th e case of a black body. The resu lts are in good agreem ent w ith theoretical predictions, based on M axwell’s th eo ry . W . E . Do w n e y.
D ir e c t m e a s u r e m e n t of m o le c u la r v e lo c itie s . I. F . Za r t m a n (Physical R ev., 1931, [ii], 37, 383—
391; cf. E ldridge, A., 1928, 108; L am m ert, A., 1929, 970).—A m ethod is described in w hich m ole
cules condense on a glass p late fasten ed to a rapidly revolving cylinder. A stream of bism uth molecules having velocities of 168— 673 m . per sec. w as spread over a b a n d 3 cm . w id e ; th e v ap o u r w as found to con
sist of 40% B i an d 60% Bi2 a t 851°. N . M. Bl ig ii. P o s itiv e io n e m is s io n f r o m t h i n p l a t i n u m f ilm s o n g la s s . R . A. Ne l s o n (Rev. Sei. In str.,
G E N E R A L , P H Y S IC A L , A N D IN O R G A N IC C H E M IS T R Y . 5 4 3
1931, [ii], 2, 173— 179; cf. th is vol., 26).—A n apjjar- atu s for th e p ro d u ctio n of N a + or K + ions from a n eq uipotential surface of controlled therm ionic ac tiv ity is described. T he positive ion c u rre n t from platinised glass w as g rea ter th a n th a t from u n platinised glass a t th e sam e tem p eratu re. A new effect, th e existence of a m axim um a n d m inim um in the positive therm ionic cu rren t-electro ly sis p o ten tial curves, w as m ore pronounced w ith th e eq u ip o ten tial
em itter. N . M. Bl i g h.
I n te r c h a n g e of t r a n s l a t i o n a l , r o t a t i o n a l , a n d v ib r a tio n a l e n e r g y in m o le c u la r c o llis io n s . C.
Ze n e r (Physical R ev., 1931, [ii], 37, 556— 569).—
M athem atical. T he change in in tern al energy of molecules on collisions is in vestigated. T he in te r
change of v ib ratio n al a n d tra n sla tio n a l energy for a collision in line of a n a to m a n d diatom ic molecule, and th e interchange of ro ta tio n a l a n d tran slatio n al energy for th e collision in a p lane of an ato m an d a rigid sym m etrical molecule are exam ined.
N . M . Bl i g h. A t. w t. of o x y g e n . R e la tiv e a m o u n t s of th e th r e e is o to p e s . R . Me c i c e an d W . H . J . Ch i l d s
(Z. P h y sik , 1931, 68, 362— 377).—T he in ten sities of absorption of th e A 0 160 1G b an d d ue to a few m etres of a ir a n d of th e A 'O 10O18 b and d ue to th e e a r th ’s atm osphere were com pared, a n d th e isotope ra tio 0 16: 0 17: 0 1S w as found to be G 30±20 : 0-2 :1 . The at. w t. of oxygen is accordingly 16-0035± 00003, and th e m ass spectrographic w t. of a n elem ent is 1-00022 tim es its chem ical a t. w t.
A. B. D . Ca s s i e. A t. w t. of io d in e . A n a ly s is of io d in e p e n to x id e . G. P . Ba x t e r a n d A. Q. Bu t l e r (J. A m er. Chem.
Soc., 1931, 53, 968— 977).—T herm al decom position of iodine p entoxide produced b y d eh y d ra tio n of iodic acid affords th e iodine : oxygen ra tio 3-17262, com pared w ith 3-17330 deduced from accepted a t. w t.
The discrepancy is a ttr ib u te d to abnorm al com position of the pentoxide. J . G. A. Gr i f f i t h s.
C h lo rin e is o to p e of n u c l e a r m a s s 39. G.
He t t n e r a n d J . Bö h m e (N a tu rwiss., 1931, 19, 252).
—An ex am ination of th e ro ta tio n -v ib ra tio n lines of hydrogen cliloride in th e v icin ity of 1-7 g has dem on
strated th e existence of a chlorine isotope w ith th e nuclear m ass 39 (cf. B ecker, A., 1930, 393).
R . Cu t h i l l. C o n n e x io n b e tw e e n r e la tiv e p r o p o r t i o n s of iso to p es a n d c o r e m o m e n t s of c e r t a i n e le m e n ts . H. Sc h ü l e r an d J . E . K e y s t o n (Z. P h y sik , 1931, 68, 174— 177).—A q u a n tita tiv e relatio n betw een th e relative proportions of th e isotopes of c e rtain elem ents
«an be found if th e isotopes arc considered as even and odd. T his classification is related to th e nuclear Moment for a given ato m , a n d in consequence th e relative proportions of isotopes are also re la te d to
this q u a n tity . A. J . Me e,
R a d io a c tiv e d e c o m p o s itio n a p p e a r a n c e s in flu o rite. L. Go e b e l (Z. K rist., 1931, 76, 457—4 5 S ;
«f- Leitm eier, A., 1926, 367).— The coloration of fluorite is duo to radioactive action liberating fluorine which escap es/leav in g free calcium in colloidal form . When th e particles of calcium are sm allest, a green
colour re su lts; blue, violet, or colourless m a terial arises from progressively larger particles. Changes in size of the particles, an d consequently in colour, can be effected by h e a t, pressure, or rad iatio n , a n d the changes cap be followed b y th e ultram icroscope.
T his change m ay, how ever, be due to th e lib erated calcium ato m s form ing a definite lattice, a view su p p o rted b y th e detectio n in a n X -ra y p h o tograph of fa in t indications of a line corresponding w ith th e calcium lattic e. C. A. Si l b e r r a d.
A b s o r p tio n cf (3-rays b y m a t t e r . G . Fo u r n i e r
an d M. Gu i l l o t (Compt. rend., 1931, 1 9 2 , 555—
557).— B y a slight m odification of th e m eth o d p rev iously described (cf. A ., 1926, 8S0) th e following m ass ab so rp tio n coefficients (¡i/p) fo r [3-rays from radium - D -\-li hav e been d e te rm in e d : boron 16-4; ph o s
phorus, w hite (solid or liquid) 20-9, red 20-2; v a n a d ium 19-7; arsenic 20-9; brom ine 23-0; sodium 16-8.
C. A. Si l b e r r a d. N u m b e r a n d i n t e r n a l a b s o r p tio n of y - r a y s f r o m r a d iu m - 7 ) . E . St a h e l (Z. P hysik, 1931, 68, 1— 11; cf. th is v o l.,,2 S l).—T he n u m b er of (3-rays e m itte d b j' in te rn a l conversion of the- 263 X u n its y -rad iatio n from d isin teg ratio n of 100 radium -D nuclei w as determ ined b y m eans of a Geiger counter.
A ssum ing a n in te rn a l conversion coefficient corre
sponding w ith 97 % absorption, th is gives a n emission of ono y -q u an tu m b y each d isintegrating nucleus.
A. B. D . Ca s s i e. I n i t i a l c h a r g e of t h e r e c o il a t o m s p r o d u c e d d u r i n g th e d i s i n t e g r a t i o n of r a d o n . W . Mu n d, P . Ca p r o n, an d J . Jo d o g n e (Bull. Soc. chirn. Belg., 1931, 40, 35—74).— T he in itia l charge on th e recoil ato m s of rad o n is p o sitiv e a n d approxim ates to 2e, corresponding w ith th e loss of tw o electrons. The charge originates in th e p rim a ry disintegration, an d is n o t a resu lt of subsequent collisions w ith o th er
particles. H . F . Gi l l b e.
E le c tr o n ic e n e r g y le v e ls of th e e l e m e n t s : s iz e s a n d e le c tr o n ic s t a t e s of a t o m s i n m e ta llic c r y s t a l s . W . Hu m e- Ro t h e r y (Phil. Mag., 1931, [vii], 11, 649—6 7 8 ; cf. A ., 1930, 1233).— T heoretical.
I f Z is th e atom ic n u m b er th e in terato m ic distances in th e crystals v a ry as 1/Z, l / Z 2, l / Z 3, and l / Z 5 for elem ents a t th e beginning of th e first, second, th ird , an d fo u rth periods, respectively, w hilst th e electronic energy levels v a ry linearly as Zfi, Z i , Z 6, a n d Z 10 fo r th e N 1 electrons of th e ou term o st group of electrons of th e atom ic core or ion. T his correspondence is exam ined in d etail an d p lo tte d fo r th e groups con
cerned, an d is applied to a discussion of th e in te r
atom ic distances in th e cry stals of th e tran sitio n al elem ents of th e long periods, an d a m eth o d is sug
gested for determ ining th e electronic sta te s of th e atom s in th e solid crystals. I t is concluded th a t th e tra n sitio n process begins in th e solid crystals a t group V I, an d in th e free ato m s a t group I I I . F o r th e valen cy electrons i t is show n th a t in groups 0, I a , and I I a a linear relatio n exists betw een nrV and Z 23 for th e m em bers of an y one group, w here V is th e ionisation p o ten tial a n d n th e electron q u an tu m num ber. I n group 0 th e interatom ic distances agree w ith th e law of th e sub-groups d /n —{l/a Z )x, prev
iously deduced. N . M. Bl i g h.
5 4 4 B R IT IS H CH EM ICA L A B STRA CTS.— A .
Statistics of nuclei. P. Eh r e n f e s t an d J . R.
"OpSe n h e im e r (Physical R ev., 1931, [ii], 3 7 , 333—
338)% pM atheniatical. N. M. Bltgh.
Statistics of com plex system s according to the new quantum m echanics. J . W i g h e r (M ath.
N aturw iss. Anz. U ngar. A kad. W iss., 1929, 46, 576—
5 8 2 : Chem. Z entr., 1930, ii, 3502—3503).
Arrangem ent of protons and electrons in the atom ic nucleus. W . M. La t im e r (J . Am er. Chem.
Soc., 1931, 5 3 , 981— 990).—T heoretical. F ro m a consideration of th e relative abun d an ce of elem ents and of th e num ber of protons an d electrons in atom ic species th e a t. w ts. of w hich are ap p ro x im ately in teg ral m ultiples of 4, a n arra n g em en t of electrons and protons in a geom etrical space lattic e in th e atom ic nuclei consistent w ith th e num bers of “ e x tra ” electrons in th e heavier elem ents is suggested.
E ach a-particle is situ a te d a t th e corner of a te tr a hedron, an d com bination of such te tra h e d ra leads to a face-centred cubic lattic e of a-particles. Since an a-particle is represented as a te tra h e d ra l arran g e
m e n t of 4 pro to n s a b o u t an electron pair, th e insertion of a n electron p air a t each p o in t a b o u t which four sp in vectors converge, as in th e a-particle, leads to a d iam ond-type lattic e of electron pairs.
J . G. A. Gr i f f it h s.
Band spectrum of tin oxide. I. A nalysis of the vibration system s of the bluish-violet bands.
P. C. Ma h a n t i (Z. P h y sik , 1931, 68, 114—125).—
T he w ave-lengths of th e heads of bands due to tin oxide betw een 3200 an d 4600 A. were d eterm ined by a concave g ratin g , 6—18 A. p er m m . M ost of the bands were fitted to th ree system s. T he h e a t of dissociation for th e ground s ta te is 3-66J;0-l volts.
A. B . I ) . Ca s s i e.
Sim ple relations between m olecular spectra and structure. H . De s l a n d r e s (Com pt. rend., 1931, 192, 521-4525; cf. this vol., 2S3).— F u rth e r exam ples of relations betw een th e frequencies of certa in lines or bands, th e “ fu n d a m e n tal frequency ” (1062-5), an d atom ic n u m b er are given in conform ity w ith th e form ula previously deduced.
C . A . S l L B E R R A D .
Absorption spectra of aqueous solutions of the coloured ions Cu, Cr, and Co. 51. Ka h a n o-
w icz and P. Or e c c h io n i (Z. P h y sik , 1931, 68, 126—
132).—T he e x tin ctio n coefficients for infinitely d ilute electrolytic solutions containing nickel, copper, chrom ium , and cobalt were determ ined th ro u g h o u t th e visible spectrum . T he p h otom etric curves show th ree phases of absorption w hich can be ascribed to molecules, free ions, and com plex ions, respectively.
A. B . D . Ca s s i e.
Absorption of light and constitution. II.
Heteropolar organic compounds. A, Bu r a w o y
(Ber., 1931, 64, [B], 462— 492; cf. th is vol., 144).—
The a bsorption of lig h t b y onium salts depends on conjugated system s. These, like those of hom opolar com pounds (loc. cit.), have polar co nstruction an d th e ir ab so rp tio n of light increases w ith th e ir length a n d degree of po larity . Positively-charged atom s function as negative term in al ato m s of th e con
ju g a te d system s in cations. I n harm ony, th e b atho- chrom ic a ctio n increases in th e sequence X R 2< 0 - R <
S-R, hence n o t w ith th e positive, b u t ivith th e negative ch aracter. I n hom opolar com pounds an d in cations, an d in c o n tra st to th e positively-charged groups, fu rth e r uncharged groups have increased batho- chrom ic action in th e sequence 0 - R < S - R < N R 2 when th e y are in conjunction w ith th e conjugated system causing absorption, th a t is, w hen th e y are term inal m em bers of th e chrom ophore group an d consequently increase th e p olarity. I f th e y are n o t term inal m em bers of th e chrom ophoro group, th e ir hypso- chrom ic effect is strong in case of d ire ct su bstitution b u t w eak in union to a ro m atic su b stitu e n ts. The com plete spectrum of a com pound is regarded as th e re su lta n t of th e absorption bands of different chrom ophoric groups a n d isolated bands as a conse
quence of p articu larly favoured chrom ophors. These different chrom ophors are n o t form ed in th e same molecule, b u t in different “ electron-isom eric ” mole
cules. Sm all persistence is n o t a specific property of R bands, b u t is to be a ttrib u te d to th e presence of only a v ery sm all am o u n t of radical-like molecules in a com pound.
A ddition of acid causes p r in c ip a l^ a change in th e degree of p o la rity of th e conjugated system in so far as i t alters only th e ncgativo term in al group.
T he groups C!NH2, C!OH, C!SH arise from th e groups C:NH, CIO, C.'S. P ositively-charged ato m s have a m ore strongly bathochrom ic action a n d are therefore m ore negative th a n th e corresponding uncharged atom s. I n th e conjugated system of a cation, the m ost positive ato m in v ariab ly gives th e electron to th e anion, an d is therefore th e negative term inal atom . A ddition of a n acid molecule to an R chromo- p h o r an nihilates th e corresponding b a n d s; conse
q u en tly R b an d s do n o t occur in th e sp ectra of cations.
The ab so rp tio n of lig h t of aci-salts or th e ir anions is a ttrib u te d to conjugated system s a n d subsidiarily to R chrom ophors. I n th is connexion, negatively- charged ato m s behave as positive groups (atom s);
in p articu lar, th e negatively-charged oxygen atom com ports itself as th e nitrogen of a n amino-group.
I t is bathochrom ic only w hen i t is th e term in al atom of a chrom ophor. I n anions in branchings of a con
ju g a te d system,- th e positive groups O-R, S-R, N IL have a hypsochrom ic effect.
A chrom ophor is an ato m or a group which is necessary for th e occurrence of a n absorption band, in d ep en d en tly of possible su b stitu e n ts w hich merely cause displacem ent of th e bands. T h e absorption of lig h t b y organic com pounds is a ttrib u ta b le (1) to u n sa tu ra te d individual ato m s ch aracteristic for the free radicals (R chrom ophors) a n d (2) to conjugated system s, therefore groups of atom s (K chromophors).
I t is proposed to replace th e conception of “ auxo- chrom ic groups ” by “ auxochrom ic ato m s.” The la tte r are th e term in al ato m s of th e chrom ophoric groups. The ato m s 0 , S, N of th e groups O-R, S-R, N R 2 an d all negatively-charged ato m s in anions are positive auxochrom ic a to m s; th e ato m s N , O, S of th e groups CIN, CIO, CIS, N iN , NIOj to g eth e r w ith all positively-charged ato m s in cations, are negatively auxochrom ic atom s, w hereas th e uncharged carbon
ato m is am photeric. H . Wr e n.
G E N E R A L , P H Y S IC A L , A N D IN O R G A N IC C H E M IS T R Y . 5 4 5
A b s o r p tio n of s y n th e tic s p in e ls c o lo u r e d b y m a n g a n e s e a n d c h r o m iu m . K . Sc h l o s s m a c h e r
(Z. K rist., 1930, 75, 399—409; Chern. Z en tr., 1931, i, 438).
C o lo u rs of in o r g a n ic s a l t s . M. N . Sa h a an d S. C. De b (N ature, 1931, 1 2 7 , 485; cf. A., 1930, 272).—A bsorption sp e ctra of chrom ic an d ferrous chlorides o b tain ed in a vacuum furnace a t 1000—
1400° show bands a t 4100 a n d 4350 Â., respectively.
These bands are ascribed to C r+~~ an d I'V an d are due to m agnetic tran sitio n s in th e d3 a n d d6 shells. C ontinuous absorption from 3000 to 2200 A., the lim it of th e a p p a ra tu s used, is also observed a n d is ascribed to th e CT ion. L. S. Th e o b a l d.
O p tic a l c o n n e x io n b e tw e e n th e p h o s p h o r escen ce of a l k a l i h a lid e s a n d s o lu tio n s of c o m p le x h a lid e s of le a d a n d th a l l i u m . H . Fr o m h e r z (Z.
Physik, 1931, 68, 233— 243).—A n extension to th e heavy m etals of earlier w ork on th e com plex halides of copper a n d silver (cf. A., 1929, 626).
A. J . Me e. C o lo u rin g a n d lu m in e s c e n c e b y B e c q u e r e l r a d ia tio n . I I I . K . Pr z i b r a m (Z. P hysik, 1931, 68, 403— 422 ; cf. A., 1924, ii, 8 5 ; 1927, 393).—
W ork on th e colouring of rock sa lt is sum m arised.
Colouring is due to tw o large classes of centres : neutralised cations, an d n eu tra l ato m s in irregular surroundings. M any different centres are d istin guished, an d como u n d er one of these tw o classes.
Pressure favours d isturbance of th e cry stal lattice, and so increases th e ra te of colouring of a crystal.
Radioluminescence an d th e actio n of B ecquerel radiation were studied ; m a n y n a tu ra l m inerals owe their colour to Becquerel radiation.
A . B . D . Ca s s i e. E x a c t s o lu tio n of th e H a r r i e s - H e r t z c o llis io n p ro b le m , a n d i t s a p p lic a tio n to e x p e r i m e n t a l a r r a n g e m e n t i n R a m a n e ffe c t e x p e r im e n ts . H. Ba r t e l s an d C. H . No r d s t r o m (Z. P hysik, 1931, 68, 42— 63).—Theoretical. T he num ber of collisions suffered by an electron in trav ersin g a given th ic k ness of gas is redeterm ined b y B a rte ls’ m ethod (A., 1930, 1336) in stead of th e original diffusion m ethod.
The earlier m ethod fails a t low densities of scatterin g material, w hen th e num ber of collisions depends on the direction of incidence of th e electrons. The results are applied to scatterin g of lig h t by tu rb id media, and i t is concluded th a t tu rb id m edia give no greater in te n sity of R a m a n rad iatio n th a n do clear
media. A. B. D. Ca s s i e.
T r a n s itio n p r o b a b i l i t y i n th e R a m a n e ffe ct.
L. S. Or n s t e i n an d J . Re k v e l d (Z. P h y sik , 1931, 68, 257—259).— A form ula is developed for th e relation betw een th e intensities of Stokes and an ti- Stokes lines. T here is some ground for a general formula for th e p ro b ab ility of a transition.
A. J . Me e. R a m a n s p e c t r u m of h y d r o g e n p e r o x id e . S.
Ve n k a t e s w a r a n(N ature, 1 9 3 1 ,1 2 7 ,4 0 6 ) .—A R am an frequency of 875 accom panied by a w eak com ponent at 903 c m r1 has been observed in th e R am a n spectrum of an aqueous solution of M erck’s perhydrol. O ther diffuse bands have been obtained.
L. S. Th e o b a l d.
M o d ifie d s c a t t e r i n g b y h y d r o g e n h a lid e s . E . 0 . Sa l a n t a n d A. Sa n d o w (Physical R ev., 1931, [ii], 37, 373— 378; cf. W ood, A ., 1930, 978).—
R a m a n lines of gaseous hydrogen chloride, brom ide, a n d iodide, an d liquid hydrogen chloride and brom ide were m easured. T he shifts of th e first tw o gases agree w ith th e infra-red b a n d s; th a t of hydrogen iodide does n o t agree, an d is considered th e m ore a ccu rate d eterm in atio n of th e (0,1) H I v ib ratio n al tran sitio n . In ten sities of scatterin g are in th e reverse order of those of absorption, in agreem ent w ith th e H ill-K em b le th eo ry of scatterin g by diatom ic gas molecules (cf. A., 1929, 865). T he lines scattered by th e liquids differ in appearance from , and show sm aller shifts th a n , those of th e g a se s; th e differences in th e shifts are too large to be a ttrib u te d to a L o re n tz - Lorenz force, an d a re evidence of quantum -m echanical m olecular interactio n s (cf. B reit and S alan t, A., 1930,
1496). N . M. Bl i g h.
R a m a n e ffe c t in w a t e r a n d i n s o m e s o lu tio n s . R . Br t t n e t t i an d Z. Ol l a n s (A tti R . Accad. Lincei, 1930, [vi], 12, 522— 529).—The effect w as studied w ith w ater, w ith solutions of n itric acid, of n itra te s of sodium , am m onium , potassium , barium , alum in
ium , lan th an u m , cerium , an d th o riu m , of h y d ro chloric acid, a n d cerium chloride. The effect of th e n itra te ion is to cause depolym erisation of th e w ater, w hich, however, does n o t become hom ogeneous.
E. G. Tr y h o r n. R a m a n e ffe c t a n d p r o b l e m s of c o n s titu tio n . I I . C y a n o -c o m p o u n d s . A. Da d i e u (Ber., 1931, 64, [B], 358— 361; cf. A., 1930, 1162).—M easure
m en ts of th e R a m an sp ectra of th e following com pounds are re c o rd e d : acetonitrile, o-toluonitrile, hydrogen an d potassium cyanide, m ethyl- an d ethyl- carbylam ine, phenyl- a n d a-naphthyl-carbim ide, eth y l th io cy an ate, eth y l-, fsobutyl-, phenyl-, an d p-tolyl- thiocarbim ide. T he presence of a treble linking is established in th e thiocarbim ides, to w hich th e con
s titu tio n R\NT<^!? is therefore ascribed, th u s indicating a stru c tu ra l difference from th e carbim ides, R-NICIO.
T he d a ta for th e carbylam ines do n o t accord w ith eith er of th e classical stru ctu res, b u t are in te rp re te d b y th e form ula R -N = C ; a n analogous co n stitu tio n appears ap p ro p riate to carbon m onoxide, fulm inic acid, an d all o th er com pounds containing “ b iv alen t ” carbon. I n hydrocyanic acid th e iso-form is calculated to be p resen t to th e e x te n t of a b o u t 0-5% . H . Wr e n.
R a m a n s p e c t r a of s o m e o r g a n ic h a lid e s . C. E . Cl e e t o n an d R . T. Du f f o r d (Physical R ev., 1931, [ii], 37, 362— 372).—R am an spectra obtained b y helium ex citatio n (cf. W ood, A ., 1929, 741) were photographed, a n d resu lts ta b u la te d and discussed for 19 sim ple organic halides n o t previously reported, including m agnesium m eth y l brom ide and iodide and ethylidene chloride an d iodide. I t is shown th a t in m an y cases th e observed frequencies can be expressed in term s of fo u r assum ed fundam entals (five in th e cyclic com pounds), tw o of w hich are n o t observed.
T he application of available th eo ry is discussed.
N . M. Bl i g h. R a m a n lin e s of c i/c /o p ro p a n e a n d v a le n c y p r o p e r t i e s of s o m e o r g a n ic c o m p o u n d s . R . C. Ya t e s
546 B R I T I S H C H E M IC A L A B S T R A C T S .— A .
(Physical R ev ., 1931, [ii], 37, 616—618; cf. A., 1930,. 1349).— M athem atical. T hree fu n d am en tal w ave-num bers for cyclopropane a re calculated from th e equations of m o tio n of a system of th ree particles v ib ra tin g in a plane. T he c h ara cter of a single linking actin g a d ja c e n t to a double linking in acet- aldehyde an d to a trip le linking in aceto n itrile is
studied. N . M. Bl i g h.
M ass spectra of glasses, salts, and m etals and construction of a circular mass-spectrograph..
H . Mitraw kxn' (Ann. P hysik, 1931, 8, [v], 353— 432;
cf. th is vol., 407).— T he m ethod of investigating m ass sp ectra is described. A stro n g em ission of sodium , potassium , m agnesium , calcium , a considerable em is
sion of silicon an d oxygen, a n d a n irregular w eak emission of heavy7 m etals from L indem ann, Je n a , T hüringen, lead, u ran iu m , an d silver glass, alundum cem ent, a n d com bustion glass have been in v estig ated m ass-spectrographically7 in th e tem p e ra tu re range 900— 1600° A bs. The m echanism of th e emission appears to be due both to electrolysis a n d to ionisation b y im pact. Mass spectrogram s of alum inium ph o s
p h a te , K u n sm a n ’s m ix tu re, tu n g sten , p latin u m , an d copper were also stu d ied . W . Go o d.
Transparency of glasses to ultra-violet rays.
P. Gi l a r d, P . Sw i n g s, a n d A. Ha u t o t (Bull. A cad, roy. Belg., 1931, [v], 17, 235— 248).—T he effect of differing concentrations of co n stitu en ts of glasses on th e ir ultra-v io le t transm ission is exam ined. T ran s
p arency increases w ith silica c o n te n t, b u t th ere is a n o p tim um concentration, depending on th e o th er substances present. T he co n centration of lime has little effect on th e tran sp aren cy . Increase in barium oxide o r alum ina is fa v o u ra b le ; increase in potassium is m ore favourable th a n a corresponding increase in sodium co ncentration. T he addition of boron trioxide ex ten d s th e tra n sp a ren cy . A. J . M ee.
Electrolytic valve action. I. Tantalum oxide layer. A. Gü n t h e r- Sc h u l z e a n d H . Be t z (Z.
P hysik, 1931, 68, 145— 161).— E x p e rim en t shows th a t th e layer responsible for valve actio n in th e case of ta n ta lu m consists of a com pact non-porous layer of T a 20 5. T he activ e layer has th e sam e dielectric co n sta n t when in th e electrolyte as w hen in th e dry7 s ta te , a n d th is value is know n. T his fact m a y be utilised to determ ine th e thickness of th e layer, and it is found th a t th is a m o u n ts to 82 m g w hen th e lay er is produced by a voltage of 100.
A. J . Me e.
Electric conductivity of liquid hydrocarbons in thin layers. L. Br ü n in g iia u s (J. P h y s. R adium . 1931, [vii], 2, 69— 85).-—A m ore d etailed account of w ork alread y n o ted (th is vol., 285).
M echanism of the “ e le c tr ic ” discharge in solid insulators. I. II. A. v o n Hi p f e l (Z.
P hysik, 1931, 67, 707—724; 68, 309— 324).—T he p a th s of electrons in cry stals during electrical d is
charges were stu d ied . R esults suggest th a t th e p o te n tia l v ariatio n s giving m echanical stre n g th to a cry stal also determ ine its electrical resistance.
A. B . D . Ca s s i e.
Reciprocal relations in irreversible processes.
I. L. On s a g k r (P hysical R ev., 1931, [ii], 37, 405—
426).—M athem atical. T herm oelectric phenom ena, transference phenom ena in electrolytes, an d h e a t conduction in a n anisotropic m edium are considered as exam ples of coupled irreversible processes, and a general class of reciprocal relatio n s is deduced by a new th eo retical tre a tm e n t from th e principle of microscopic reversibility. N . M. Bl i g h.
E .M .F . of dielectrics. K. La r k- Ho r o v it z
(N ature, 1931, 127, 440).— Previous w ork by7 the a u th o r is discussed. L. S. Th e o b a l d.
Dielectric constant and electric m om ent of som e am ines. P . N. Gh o s h a n d T. P. Ch a t t e r j e e
(Physical R ev., 1931, [ii], 37, 427— 429).— U sing a heterodyne n u ll-b eat m eth o d (cf. M ahanti, A., 1930, 841) th e dipole m om ent x lO 18 for m ethyl-, dim ethyl-, trim eth y l-, ethyl-, diethyl-, a n d trieth y l-am in es gave th e values 0-99, 0-90, 0-82, 0-99, 0-90, an d 0-82 e.s.u., respectively. V alues of th e dielectric co n sta n t are also given, and, except in th e case of m ethylam ine, increase w ith th e b. p. of th e com pound. T he polar groups N H ,, N H , an d N in th e respective am ines are mainly7 responsible for th e developm ent of th e dipole m om ent of th e molecule. N . M. Bl i g h.
Dielectric constant of w ater as determined by a resonance method. E . P . Li n t o n a n d 0.
Ma a s s (J. Am er. Chem. Soc., 1931, 53, 957— 964).—
Sources of error in th e m eth o d of C uthbertson and M aass (A., 1930, 523) hav e been investigated. With liquids of high dielectric c o n stan t, results are best o btain ed w ith a liigh-power oscillating circuit per
m ittin g th e determ in atio n of th e resonance point b y m eans of th e harm onic in stead of th e fundam ental.
Provided th e co n d u ctiv ity of th e m edium is less than a certain value (4 x 10~° ohm -1 in th e case of water), th e resonance p o in t is indep en d en t of th e conductivity.
T he dielectric co n stan ts a t 25° are : e th e r 4-255, ethylene dichloride 10-38, w ater 79-2, a n d hydrogen peroxide a t 0° 93-5 (cf. loc. cit.).
J . G. A . Gr e f f it h s.
Dependence of the m olecular polarisation of gaseous aß-dichloroethane on temperature. R-
Sä n g e r (Helv. phys. A cta, 1930, 3, 461— 463; Chem.
Z entr., 1931, i, 229).— A lecture (cf. th is vol., 147).
A. A. El d r i d g e.
Variations w ith tem perature and frequency of dielectric loss in a viscous m ineral insulating oil.
H . H . Ra c e (Physical R ev., 1931, [ii], 37, 430—
446).— F ro m m easurem ents of dielectric loss using a n open q u a rtz insulated cell over a w ide range of frequency a n d tem p e ratu re, D ebye’s th e o ry of polar molecules has been ex ten d ed to give sim ple expres
sions for conditions of m axim um loss p er cycle.
N . M. Bl i g h.
Theory of dielectrics. J . I I . J . Po o l e (Phil- Mag., 1931, [vii], 11, 995— 996).
Mol. volume and density at the absolute zero.
G. L, Ch a b o r s k i (Bui. Chim. p u ra appl., B ukarest, 1929, 31, 53—6 6 ; Chem. Z entr., 1930, ii, 1046).—
By7 th e use of Longinescu a n d C haborski’s “ molar co n centration ” C m —1000djM equations are derived fo r evalu atin g th e mol. volum e a n d d e n sity a t 0°
A b s .: F 0= 1000[Cth0 ; d0= M C m 0[1000; Cm0= C m f 1000(v—b)/b-, where v —b is th e covolum e an d b is
