[ COVTRIBUrIOS F R O M THE O A K RIDGES A T I O N A L LABORATORY,
CHEMISTRY DIVISION]
Anion-exchange Studies. XVIII. Germanium and Arsenic in HC1 Solutions’n2
NELSOXAND RCRTA. KRAUS
BY FREDERICK
RECEIVED
FEBRUARY
The anion-exchange behavior of Ge(IV), As(II1) and As(V) in hydrochloric acid solutions was studied with a strong base
quaternary amine anion-exchange resin Both Ge(1V) and As(II1) show little adsorption at low ,M HCI and rapidly in-
creasing adsorption with increasing 31 HCl above ca 5 &’ HC1 Adsorption of As(V) was low throughout t h e HCI conceri-
tration range studied (0 1 t o 12 .lf) Application of these d a t a t o separations is discussed
I t was demonstrated in previous papers that an-
ion exchange is a powerful tool for the separation
of many elements. .I systematic study of essen-
tially all metals has been carried out in hydrochloric
acid solutions and the present paper summarizes the
results for Ge(IV), ,Is(III) and As(V). Distribu-
tion coefficients D have been measured in the range
0.1 to 12 HC1. Considerable differences in
adsorbability were found which may be used as the
basis of a number of separations.
Experimental
Adsorbabilities were measured by the equilibrium or
column technique^.^ In the equilibrium technique meas-
ured amounts of solution and resin were agitated for a t least
one day, after which the solution phase was analyzed.
From the change in concentration after equilibration, dis-
tribution coefficients D (amount per kg. d r y resin/amount
per liter solution) were calculated. All resin weights and
distribution coefficients refer to resin dried over “Anhy-
drone” a t 60” in a vacuum desiccator. The resin was from
the same batch of relatively highly cross-linked polystyrene
divinylbenzene quaternary amine resin (Dower-1 , 200-230
mesh) which was used in most of the earlier studies and
which was characterized previously.
Most concentrations were determined radiometrically
with the tracers Ge” ( T I / ?= 12 hr.); As7’ (Tils = 40 hr.)
and the mixed tracer AsT3-Asi4(T = 76 day and =
19 d a y ) . The Ge77-As77 tracer T s prepared by neutron
irradiation of GeOa in the ORNL Low Intensity Training
Reactor ( L I T R ) . Aliquots of a stock solution, prepared
by dissolving the irradiated oxide in 0.5 J 4 NaOH, were
used after appropriate acidification. Half-life determina-
tions indicated t h a t the tracer was of satisfactory purity.
All final counting in the Ge(IV) equilibration experiments
was carried out after secular equilibrium with the daughter
activity As77 had been reached. Since Ge(IV) is easily
volatilized from strong HC1 solutions, both the resin and
solution phases were counted t o ensure t h a t no serious loss of
Ge(I\.) had occurred during sampling. For this purpose the
shaking experiments were carried out in 2-1111. tubes.
Samples of the solution (1 ml.),were counted, a s well as
the remaining liquid-resin mixture. The fractiofl‘ of
germanium in the resin could then be computed and ma-
terial balance” checked. S o experiments arc recorded
where loss exceeded 2OY0 of the activity.
The As’3--As7; tracer in HC1 solution was obtained from the
Radioisotopes Division of ORKL and analyzed by them for
radiochemical purity. I t contained 2070 As“, 80%
and negligible amounts of other activities.
The adsorbabilities of As(I1I) and As(V) were determined
by the column method. I n this method elution bands
characteristic of only one oxidation state can be followed and
errors from possiblc oxidation-reduction reactions and result-
ing cross-contamination by the various oxidation states can
be avoided. The method is thus more reliable than the
equilibrium method which in the absence of separate oxida-
tion state analyses yields only average adsorbabilities.
Most experiments with As(II1) were carried out with
(1) This document is based on work performed for t h e U . S. Atomic
Energy Commission at the Oak Ridge Sational Laboratory.
(2) Previous communication: F . Pl’elson and K A . Kraus, THIS
J O U R N A I , , 7 7 , 3972 (195.5)
(3) See e.g., K. .I.Kraus, l?,Selson and G. \V Smith, J . P h y s . Cht‘n7 ,
68, 11 (1954).
( 4 ) K , A . K r a u s and G . 13, hloore, 1”ili J O U R N A I . , 7 5 , 1457 ( 1 9 5 3 ) .
23, 1955
properly acidified aliquots of a stock solution prepared
by dissolving C.P. As203 in 0.5 111 S a O H . The elution
maxima were located by spot testing successive aliquots of
the effluent (SnC12 method5). T h e experiments with
As(V) mere carried out with the arsenic tracer. It origin-
ally contained both As(II1) and As(\’). T o prepare essen-
tially pure As(V) solutions the tracer was oxidized with
chlorine and to avoid possible reduction, particularly at
high hydrochloric acid concentrations,e chlorine was added
t o all the solutions as a “holding oxidant.”
All experiments were carried o u t in a n air-conditioned
room at 25 & 2“. Further experimental details will be
given in connection with the discussion of the various
systems.
Results and Discussion
1. Adsorbability of Ge(IV), As(II1) and As(V).
-The observed distribution coefficients D (amount
per kg. dry resin/amount per liter of solution) are
summarized in Fig. 1. The adsorbability of
Ge(1V) is essentially negligible from 0.1 to ca. 4
M HC1 and then rises sharply with increasing M
HC1 to D = 185 in 10 M HC1. There is indication
that D continues to increase a t higher HC1 con-
centrations. However, the high volatility of Ge-
(IV) under these conditions precludes accurate
measurements. The adsorbability of As(II1) is es-
sentially negligible in the region 0.1 to ca. 4 *If
HC1. There is indication that a t lower HCl con-
centrations its adsorbability rises with decreasing
M HCl, possibly due to adsorption of arsenite ions.
*4t HCl concentrations larger than 4 M , adsorb-
ability of As(IT1) increases with increasing M HC1
( D = ca. 26 in 11 ,I6 HCl). The adsorbability of
-4s(V) is low throughout the entire range of HC1
concentrations studied. Distribution coefficients
increase slightly with J6 HC1 from D = ca. 1.8 in
0.1 111 HCl to D = ca. 4 near 10 -1IHCl.
The strong adsorption of Ge(1V) and As(II1) a t
high hydrochloric acid concentrations suggests that
both elements form negatively charged complexes.
In the case of Ge(1V) these negatively charged
complexes are apparently not yet completely formed
in 10 A6 HC1 since adsorption appears to continue
to increase with increasing Jf HC1 in this region.
For .4s(III), on the other hand, above 10 M HCI
negatively charged complexes may become domi-
nant since the distribution coefficients tend to level
off. Qualitatively the adsorption behavior of AS-
(111) and Ge(1V) is essentially in agreement with
the known continued increase in the volatilities of
both Ge(1V) and As(II1) with IIif HC1, and one
might further conclude by cornbination of the ob-
servations on volatility and anion exchange that
formation of the negatively charged complexes for
( 5 ) F. Feigl, “Qualitative Analysis b y Spot Tests,” Elsevier Pub-
lishing Co., Xew York, S . Y . , 1946.
(6) J. W. Mellor, “Inorganic and Theoretical Chemistry,” Vol. I X ,
Longmans, Green a n d Co , S e w York, N . V.,p , 1-14.
Sept. 5 , 1955 AND ARSENICIN HCl SOLUTIONS
GERMANIUM 4,509

0 4 2 3 4 5 6 7
2
COLUMN VOLUMES OF EFFLUENT,
Fig. 2.-Separations involving germanium and arsenic.
io erable, adsorption of As(II1) becomes sufficiently
large to necessitate inconveniently large volumes
0.5 I
I I 1 I for its elution, although separation is feasible. The
0 2 4 6 8 (0 12 separation of As(V) from Ge(IV), on the other hand,
MOLARITY OF HCI. readily can be achieved a t high HCl concentra-
Fig. 1.-Adsorption of Ge(IY), As(I1I) and As(V). tions. Even a t low HC1 concentrations, where
these elements proceeds through the neutral species Under D A ~ ( v>) D G e ( I V ) , this separation is still feasible.
these conditions D A ~ ( vthough), low, is high
(GeC14and XsC13). enough to delay appearance of the As(V) elution
It is interesting to note that both Ge(1V) and band until essentially all the Ge(1V) (or any other
As( 111) are extractable from strong hydrochloric "non-adsorbable" element) has been removed.
acid solutions by organic solvents,' which is in ac-
cordance with these considerations, although it is A typical separation involving Ge(1V) and As(V)
felt that for these elements the fact that solvent is illustrated in Fig. 2a. For this experiment, Fe-
extraction occurs cannot be taken as an indication (111)was added, as well as a typical non-adsorbable
that singly negatively charged complexes are element. For the latter Eu(II1) was chosen since
f~rmed.~ I t is likely that in these cases solvent its tracer (EulS5)was conveniently available. An
extraction involves the neutral species GeC14 and 0.5-ml. aliquot of a solution containing Eu(II1) lS5
AsCl3. As(V)'?, Ge(IV)77,0.01 M Fe(III), 6 M HC1 and
One might be tempted to conclude that the ad- chlorine was added to an 0.45 cm.2 X 9.0 cm. col-
sorption of Xs(V), though small, indicates existence umn of resin pretreated with 6.2 ilf HCl and Cl?.
of negatively charged complexes. However, this is Elution was carried out with 6.2 34 HCl(C12).
unlikely in view of the instability of AsC16 and the The non-adsorbable element, E u ( I I I ) , appeared in
apparent non-existence of As(V)-chloride com- a sharp band with a maximum near 0.4 column vol-
plexes8 More probably the slight adsorption is ume and was separated from As(V), Ge(1V) and
due to extraction of arsenic acid ( H a s o , ) by the Fe(II1). As(V) appeared in a reasonably sharp
resin. The small increase in adsorption with M band with a maximum near 2.2 column volumes.
HCl probably reflects a relatively minor change in Ge(1V) was removed with 3 ill HC1 and then Fe-
the ratio of the activity coefficients of the species (111)with 0.4 Jf HC1.
H3As04in the two phases. The differences in the adsorbability of As(II1)
2. Separations Involving Arsenic and Ger- and As(V), particularly a t high J4 HCl, permit sep-
manium.-The differences in adsorbability between aration of these oxidation states, as demonstrated
As(II1) and Ge(1V) a t low HCl concentrations are in Fig. 2b. -in 0.1-ml. aliquot of a solution con-
too small to permit separations with small col- taining .~s(III)~~-~~-As(V)~~-~~ tracer and 9 >If
umns. A t high HCl concentrations where the HC1 was added to an 0.24 cm.? X 7 . 2 cm. column
differences between these two elements are consid- of resin which had been pretreated with 9 M HC1.
Elution was carried out with 9 M HC1. As(V), as
(7) (a) K . Rohre, 2 . nwal. Chem., 65, 108 (1824), (extractability of expected, appeared in the effluent in a reasonably
AsC18 b y CClr f r o m HCI solutions); (h) H . 51. Irving, Q u a r t . Rens., I,
200 (1951). sharp band near 2.2 column volumes of emuent,
( 8 ) See e . g . , (a) Gmelin's "Handhuch der anorganischen Chemie," while As(II1) remained adsorbed. Removal of the
Eighth Edition, System No. 1 7 , Verlag Chemie, Weinheim. Germany, Xs(II1) was accomplished with 0.1 M HCI.
1 9 5 2 , p. 391; (b) N. 1'. Sidgwick, "The Chemical Elements and their
Compounds," Vul. 1 , Clarendon Press, Oxford 1950, p. 7 8 1 . OAK RIDGE,TBSN.