M. TSCHAPEK
76
mit 20 bis 30 ccm trockenem Methylenchlorid aufge­
nommen. Die entstehende tiefrote Lösung wird jetzt
noch etwas eingeengt und schließlich mit 100 bis
150 ccm Petroläther (Siedebereich 60 —80°) versetzt.
Die Komplexe scheiden sich kristallin ab und werden
abfiltriert. Die Ausbeuten betragen bis 85% der Th.
bez. auf eingesetztes Durochinon.
Ni(0)-Durochinonkomplex mit
a) Cyclooctadien- (1.5) :
NiC18H240 2 Ber. Ni 17,73 C 65,30
Gef. Ni 17,87 C 65,45
Mol.-Gew. Ber. 331. Gef. (kyroskopisch
zol) 331.
b) Bicyclo(2.2.1)heptadien:
NiC17H20O2 Ber. Ni 18,61 C 64,81
Gef. Ni 18,52 C 64,24
c) Dicyclopentadien:
NiC20H24O2 Ber. Ni 16,53 C 67,65
Gef. Ni 16,88 C 67,16
H 7,31 .
H 7,25 .
in Ben­
H 6,40 .
H 6,50.
H 6,81 .
H 6,67.
Der Ni(0)-xylochinonkomplex mit Cyclooctadien 1.5
wurde nach der gleichen Vorschrift erhalten. Zers.P.
10 Nach Me&sungen von Herrn A.
S e p p , Technische Hoch­
schule München.
11 Eine gesättigte Lösung von Bis-durochinon-nickel (0) in
DCC1S zeigt das Signal der Protonen des Durochinons bei
1,80 ppm (40 mHz) auf der low-field-Seite von Tetra­
150°. Ber. Ni 19,38. Gef. Ni 19,20. Mol.-Gew. Ber. 303.
Gef. (kryoskopisch in Benzol) 308.
Magnetische Messung: Cyclooctadien-Ni(O)-Duro­
chinon ist diamagnetisch
(XM= ( - 148 ± 66) • IO "6 cm3 g“ 1] 10.
Einen einfachen und eindeutigen Beweis für die an­
genommene „Sandwich“-Struktur des CyclooctadienNi(0)-Durochinons ergibt das kernmagnetische Reso­
nanz-Spektrum. Es treten bei 40 mHz auf der lowfield-Seite von Tetramethylsilan drei Signale bei 3,70,
2,37 und 2,17 ppm auf (in DCC13), deren Intensitäts­
verhältnis 4 : 8 : 12 beträgt. Die ersten beiden Signale
sind dabei den Protonen des symmetrisch an das Nik­
keiatom gebundenen Cyclooctadiens zuzuordnen. Das
Signal bei 2,17 ppm entspricht den 12 Protonen des
metallgebundenen Durochinons n ’ 12.
Herrn Prof. Dr. Dr. h. c. E. W ib e r g danken wir
für das dieser Arbeit entgegengebrachte Interesse und
deren großzügige Förderung. Der B a d i s c h e n
A n i l i n - u. S o d a f a b r i k A.G. sind wir für eine
wertvolle Chemikalienspende zu großem Dank ver­
pflichtet.
methylsilan. Die Durochinonmoieküle sind somit gleich­
artig an das Nickelatom gebunden.
12 Für die Durchführung der kernmagnetischen Untersuchun­
gen sind wir Herrn Dr. W. Brügel (BASF, Ludwigshafen)
zu großem Dank verpflichtet.
Selective permeability of the rocks w ith respect to ions
By M. T schapek
From Instituto de Suelos y Agrotecnia, Cervino 3101, Buenos Aires
(Z. Naturforschg. 17 b, 76— 78 [1962] ; eingegangen am 12. August 1961)
1. The Dialysepotential (or “Membrane concentration potential”) was investigated and the
transference numbers of an ion was calculated for the diaphragm of different rocks.
2 . Most of the rocks have a selective permeability with respect to the ions.
3. Alumstone and shale showed greatest selective permeability.
It is a well known fact most of the rocks are
porous, that is to say contain free pores (and inter­
stices) full of air and water. While the porosity
varies from 0 to 50% the size of the pores varies
m udi more: from A up to cm. The fine pores
( < 1 0 ~ 5 cm) due to their low permeability offer
a greater interest coupled with a much greater dif­
ficulty for their determination.
The perm eability of a porous body with reference
to the ions depends in addition on the size of the
1 L.
2 K.
M ic h a e l is ,
M eyer,
J.
A.
F u jit a ,
S ie v e r s ,
Biochem. Z. 142, 398 [1923].
Helv. chim. Acta 19, 649, 665
pores as well as on the charges upon their surface.
It is a fact, that charged pores of a size of < 1 0 Ä
are impermeable to one kind of ion (anion or
cation) whereas if the size is > 1 0 ~ 6 cm they are
permeable to both kinds of ions. The selective per­
m eability of a porous body with respect to the ions
is determined by the Dialysepotential (or “Mem­
brane concentration potential” ).
The method of measuring the Dialysepotential
developed by M ichaelis \ M eyer 2, M anegold 3,
3 E.
M a n e g o l d , Kapillarsysteme Bd. 1, Straßenbau, Chemie
und Technik Verlagsgesellschaft, Heidelberg 1955.
[1936].
Unauthenticated
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SELECTIVE PERMEABILITY OF THE ROCKS WITH RESPECT TO IONS
S ollner 4, C larke 5, etc., consists in the following.
Two solutions of different concentration of KC1
(e. g. 0,1 N and 0,01 N) are brought into contact
in an apparatus for dialysis through the diaphragm
of a porous body under consideration. The poten­
tial which appears, due to the change of the m igra­
tion velocities of ions in the diaphragm can be
measured with two calomel electrodes submerged
in two sections of apparatus for dialysis. From
these determinations the transference num bers (t +
and t _ ) can be calculated and conclusions can be
arrived at as to the size of the pores The final
conclusion can be obtained by assuming that the
relation between the sizes of the pores and the
transference numbers established for membranes by
M anegold 3, Zhukov 6, Grigorov 7 and oth. is also
valid for inorganic diaphragm s (in this case for
rocks). It is to be understood that a values of the
pores is not a mean but a maximum, because as
shown by M ichaelis in the presence even of a
microscopic orificie the Dialysepotential diminishes.
For uni-univalent electrolyte and a negative
membrane we may write:
E=
E max —
t+ —t.
-M R T
R T , a.
— =— In
F
a
In
E — (2 t+ —l)-£<max5
t+ = 0,5 +
E
2£n
= 0,5 —
E_
2 £m ax
where:
- Dialysepotential at 0 <C t+ <C 1;
- Dialysepotential at t+ = 1 (t - = 0) ;
Em ax
t + , t — — transference numbers of cation and anion;
a", a'± — activities of the electrolyte in two sections
of apparatus for dialysis;
R
— Gas constant;
T
— Absolute temperature;
F
— Faraday constant.
E
It is known that some clays under certain con­
ditions possess the properties m em brane of selective
permeability. M arshall 8 showed that when clays
are heated to a high tem perature they can be used
as reversible electrodes with respect to cations.
W yllie 9 and form erly S chlumberger 10 et al.
4 K. S o l l n e r , Ann. N. Y. Acol. S e i . 57 (3 ), 177 [1 9 5 3 ].
5 J. C l a r k e et al., J. physic. Chem. 56, 78 [1 9 5 2 ].
6 I . Z h u k o v , Uspekhi Khimii 12, 265 [1 9 4 3 ].
7 O . G r i g o r o v u . N. P r i k h o d ’k o , Koll-Zh. 11, 141 [1 9 4 9 ].
8 C. E.
M a rsh a ll,
The colloidchemistry of the silicate mine­
77
showed that in the presence of layers of shale in
nature, a Dialysis potential is observed, which those
authors call “ Self-Potential” (S-P).
The appearance of S-P in nature probably
depends not on the diameter of the pores, but on
the thickness of the water film. T schapek 11 proved
that in very thin films of water there appears a dif­
fusion potential, due to surface charges. This indi­
cates that in nature there must be a S-P (or Dialyse­
potential) independent of the size of the pores, al­
ways provided that the disperse system is not
saturated with water. Even in the laboratory no
process (vacuum or boiling) can assure a perfect
elimination of the air. If the pores contain air then
the Dialysepotential is a function not of the dia­
m eter of the pore, but of the thickness of the film
on the surface.
Pores > 10-6 cm
1. K aolin (paste)
2. Marble
Pores < 10 ~6 cm
1 . Orthoquarzite
2. A ctinolite
3. Sandstone
4. Spessarzite
5. M icazite
6 . Diorite
7. Granite
8 . Lim estone
9. Quarzite
10. Gneiss
11. Conglomerate
12. Opal
13. B entonite
W yom ing
(air-dried)
14. Shale
15. A lum stone
W ithout Pores
1. Quarz
2. Calcite
3. Mica
E
*cr
0
0
0,51
0,51
3,8
4,6
5,0
0,47
0,46
0,45
0,38
0,36
0,33
0,33
0,32
0,25
0,25
12,8
15,4
19,0
19,6
20,2
27,6
27,6
31,2
37,8
0.21
0,15
38,0
41,6
43,6
0,15
0
0
0
—
N otes
1. A dilute solu­
tion always
had a positive
charge which
means th at the
pores are nega­
tively charged.
2. E determined
after the dis­
appearance o f
A sym m etry
potential.
3. From 4 differ­
ent classes o f
opal, only 1
contained
pores.
0,12
0,10
—
—
Dialysepotential (E ) and transference numbers
0,1 N Cl - 0,01 N KC1.
(<cr)
To facilitate the elimination of the air from the
diaphragm s of rocks, the latter were carved to a
9 M. R. J.
W y l l i e , Sympos. „Clays and clay technology“
(1955). S-Francisco.
10 C. S c h l u m b e r g e r et al., Amer. Inst. Mining Engr., Trans.
110, 273 [1934].
11 M. T s c h a p e k , Naturwissenschaften 48, 96 [1961].
rals (1 9 4 9 ).
Unauthenticated
Download Date | 6/19/17 12:55 AM
78
H. NISHIKAWA, S. YAMADA AND R. TSUCHIDA
thickness of 1 —2 mm. So plates of 2 cm diameter
prepared from the rocks were evacuated and held
in boiling water and afterwards glued over orifice
of the dividing wall of the dialisis apparatus. In
the table will be found the data of the values of
Dialysepotential and transference numbers of anion.
As can be seen most of the rocks, with some
exceptions, possess a selective permeability with
respect to the ions i. e. that the size of the pores
< 1 0 -6 cm. Alumstone and shale gave the highest
values.
It would be particularly interesting to consider
the data on the Wyoming bentonite which is montmorillonitic. The plug was 1 cm thick. The solutions
of both sections do not change the hum idity of the
plug, because after wetting 1 mm on both sides the
perm eability disminishes in such a way that many
hours are reguired to put both KC1 solutions into
contact. As demonstrated by B a r s h a d 12 at low
water content the total surface does not participate
in interaction with the water. Bentonite with a 12%
water content has t c l— equal 0,14, which shows
that not all the surface (800 m2g_1) is covered
with this water, because then we would have a layer
thinner than a molecular diameter, while to this
<CL—would correspond a pores diameter of approxi­
mately 25 Ä.
Sympos. „Clays and clay Technology“ (1955).
S-Francisco.
12 I . B a r s h a d ,
Di- andT ervalent C obalt C om p lexes w ith N-alkyl-salicylideneimines
B y H . N is h ik a w a ,
S.
Y am ada
and
R . T s u c h id a
Department of Chemistry, Faculty of Science, Osaka University, Nakanoshima, Osaka, Japan
(Z. Naturforschg. 17 b, 78—81 [1962] ; eingegangen am 21. August 1961)
There have been reported a number of cobalt complexes of A-aryl-salicylideneimines, but
systematic study of the cobalt complexes of most iV-alkyl-salicylideneimines has not been reported.
Recently we have succeeded in preparing a series of cobalt (II ) 1 and cocalt(III)2>3 complexes with
TV-alkyl-salicylideneimines. The present communication is mainly concerned with a brief account
of the systematic study about the preparation and relative stability of these complex compounds.
One of the principal procedures employed in the
present work is to reflux cobaltous acetate tetrahydrate, salicylaldehyde and one of the amines in
ethanol, followed by addition of a small am ount of
a sodium carbonate solution. The amines used in
the present work include methyl, ethyl, n- and isopropyl, an n- and sec-butyl amine.
Black crystals, which have been found to cor­
respond to the sexa-co-ordinate cobalt (III) com­
plexes, C o ( 0 ’C6H4-C H :N ‘R )3 , are obtained when
one of the n-alkyl amines is used as the am ine in
the procedure (Table I).
This result is readily explained, since it is well
known that with many strongly co-ordinating
ligands the sexa-co-ordinate cobalt (III) complex
is made more stable rather than the quadri-coordinate co balt(II) complex. Thus in the above
reaction, the quadri-co-ordinate complex of cobalt
(II) may most probably form at first, but be readily
oxidized to give the sexa-co-ordinate cobalt (III)
compound, which has been obtained as black green
crystals in the present work.
Following a similar procedure in the atmosphere,
however, red crystals of the quadri-co-ordinate co­
balt (II) complex, C o ( 0 ’C6H 4, C H :N ‘R )2 , are
obtained with zso-propyl and 5ec-butyl amine
(Table I). W ith these amines, all attemps to pre­
pare sexa-co-ordinate cobalt (III) complexes, even
using oxidizing agents, have so far been unsuccess­
ful. This indicates, at least qualitatively, that ,/V-isopropyl- and sec-butyl-salicylideneimine are more
difficult to form sexa-co-ordinate complexes of co­
balt (III) than quadri-co-ordinate complexes of
c o b a lt(II). This may be ascribed mainly to the
steric factor in the following way.
F or one thing, as the S t u a r t model shows, an
1 The iso-propyl derivative was reported by H.
3 The ethyl derivative was reported by B. 0 .
D ie h l and
T. S. C hao, Io w a State C oll. J. Sc., 22, 126 [1947].
2 The methyl derivative was reported by J. E n d o , J. diem. Soc.
Japan 65, 428 [1944]; C. A. 42, 1576 d [1948].
W est,
Soc. [London] 1960, 4944.
Unauthenticated
Download Date | 6/19/17 12:55 AM
J. diem.