Mikrochimica Aeta [Wien] 1971, 464--470

9 by Springer-Verlag 1971

Department of Chemistry, Indian Institute of Technology, Bombay-76, India

Diluted Tributyl Phosphate as an Extraetant for Silver

By
A. A. gadav and S.M. Khopkar
(Received October 22, 1970)

Pure tributyl phosphate (TBP) has been used for the solvent extraction
of silver from hydrochloric acid containing sodium chloride 1-~. The
iodide complex of silver has also been extracted with pure TBP. Other
trialkyl phosphates or their salts 5-7 have been used for the extraction
of silver but in all cases the extraction coefficient was small and the
method not selective. We have developed a method for the quantitative
extraction of silver at trace concentration with diluted tributyl phosphate.
Thus 40% T B P in butanol extracts silver from 1 M nitric acid containing
2 M lithium nitrate as salting-out agent. I t is stripped from the organic
phase with dilute ammonia and is determined photometrically as its
complex with p-diethylaminobenzylidenerhodanine.
Several chelating agents have been used for the extraction of silver
but only dithizone, oxine and cupral were found effective for its separation
at microgram concentrations s. The ion-association complex of silver
with salicylic acid and dibutylamine has been extracted with isobutyl
methyl ketone 9, but the ternary complex with o-phenanthroline/Bromo-
pyrogallol 1Red1~ proved to be most useful for selective extraction (into
nitrobenzene). Bis(2-ethylhexyl) phosphoric acid ( H D E H P ) 11 and
diethyldithiophosphoric acid 12 have also been used as extractants but
only inefficiently for the extraction of silver.
The method proposed b y us is simple, rapid and affords clean-cut
separation of silver at microgram concentrations. I t is also possible
to isolate silver from a large number of elements. The overall operation
of extraction and determination takes about 30 minutes.
Yadav et al. : Diluted Tributyl Phosphate as an Extractant for Silver 465

Experimental
Reagents
Tributyl phosphate, b. p. 143 ~ C.
p-Diethylaminobenzylidenerhodanine, 0.05~o solution in ethyl alcohol.
n-Butanol.
Stock solution of silver, prepared by dissolving 0.7874 g of silver nitrate
in 1 litre of distilled water containing 0.001% of nitric acid, standardized
gravimetricallyla as chloride, and further diluted tenfold.

General proced'~re
An aliquot of the silver solution (49.8#g of Ag) was made 1 M in
nitric acid and 2 M in lithium nitrate when diluted to 25 ml. I t was
then transferred to a separatory funnel, 10 ml of 40% TBP solution
in butanol were added and' the mixture was shaken for about 5 minutes.
The two phases were allowed to settle, and the aqueous layer was with-
drawn. Silver was. s~rippe4 from the T B P - b u t a n o l phase by shaking
it with 10 and 5 ml of ammonia solution. The aqueous phase containing
silver was neutralized with nitric acid and then more was added until
the solution was 0.05 M with respect to nitric acid, in a total volume
of 25ml. Then 1 ml of 0.05% p-diethylaminobenzylidenrhodanine
solution was added. The solution was diluted to the mark and allowed
to stand for 5 minutes. The red-violet complex was then measured
photometrically at 495 nm. I t is necessary to measure the absorbance
within 20 minutes of complexation. The sequence of operation and
control of acidity is important in getting reproducible results 14.

Results and Discussion

E//eet o/ acidity and T B P concentration
The concentration of nitric acid was varied from 0.1 to 3 M and
the concentration of TBP from 20 to 100% (0.73-3.66 M) with n-butanol
as the diluent (Table I).
For quantitative extraction of silver it is convenient to use 40%
TBP in butanol, the lowest concentration that gives 100% extraction.
The optimum nitric acid concentration is 1 M in the presence of 2 M
lithium nitrate. An attempt was made to establish the probable composi-
tion of the extractable species by using a plot of log D vs. log T B P
concentration (0.5 M nitric acid medium). The slope was 2.7 indicating
that the extractable species may be [AgNOa(TBP)3] or [ttAg(N03) 2.
9(TBP)3 ]. This confirms the findings of previous workers 3 who found
the extractable species in chloride system medium to be [HAgC12(TBP)a 9
9(H~O)2 ]. Study of different diluents such as aromatic hydrocarbons,
466 A. A. Y a d a v and S. M. Khopkar : [Mikrochim. Acto~

TableI. Distribution r a t i o as a f u n c t i o n of a . c i d i t y *

[TBP ] [I-INO z] Extraction Distribution

(M, initial) (%) ratio (D)

20% (0.73 M) 0.10 66.7 2.00

0.25 70.0 2.33
0.50 75.0 3.00
0.75 81.7 4.46
1.00 86.7 6.52
30% (1.09 M) 0.10 71.7 2.53
0.25 73.3 2.75
0.50 80.0 4.00
0.75 88.5 7.70
1.00 90.0 9.00
40~o (1.46 M) 0.10 76.7 3.30
0.25 81.7 4.46
0.50 86.7 6.52
0.75 95.0 19.00
1.00 100.0 co
409o (1.46_a/i) in absence 0.10 40.0 0.67
of salting-out agent. 0.25 46.7 0.88
0.50 55.0 1.22
0.75 60.0 1.50
1.00 66.7 2.00
2.00 63.3 1.73
3.00 43.3 0.76
759o (2.74 M) 0.10 78.5 3.65
0.25 83.3 4.99
0.50 88.5 7.70
0.75 95.0 19.00
1.00 100.0 co
100~o (3.66 M) 0.10 85.0 5.67
0.25 90.0 9.00
0.50 93.3 13.93
0.75 98.5 65.66
1.00 100.0
* Ag= 49.8#g; 1 M LiNO 3

isobutyl m e t h y l ketone, carbon tetrachloride, chloroform an d b u t a n o l

showed t h a t n - b u t a n o l is t h e m o s t suitable d i lu en t as it gives t h e highest
e x t r a c t i o n coefficient.

E//ect o] salting-out agent

S ev eral salting-out agents such as t h e n i t r a t e s of lithium, sodium,
a m m o n i u m an d m a g n e s i u m were studied (Table II). Th e results show
t h a t only 2 M l i t h i u m n i t r a t e is effective for q u a n t i t a t i v e e x t r a c t i o n of
silver f r o m 1 M nitric acid.
1971/3] D i l u t e d T r i b u t y l P h o s p h a t e as a n E x t r a c t a n . t for Silver 467

TableII. Effect of Salting-out Agents*

Salting-out agent [ttNOs] Extraction Distribution

(M, initial) (%) r a t i o (D)

LiNO3 1M 0.10 60.0 1.50

0.25 66.7 '2.00
0.50 73.3 2.75
0.75 80.0 4.00
1.00 86.7 6.52
2M 0.10 76.7 3.30
0.25 81.7 4.46
0.50 86.7 6.52
0.75 95.0 19.00
1.00 100.0 cc
NaNO3 1M 0.10 50.0 1.00
0.25 55.0 1.22
0.50 60.0 1.50
0.75 63.3 1.73
1.00 67.7 2.10
2M 0.10 61.7 1.61
0.25 68.5 2.18
0.50 73.3 2.75
0.75 76.7 3.30
1.00 80.0 4.00
NH4NO 3 1M 0.10 50.0 1.00
0.25 56.7 1.31
0.50 63.3 1.73
0.75 68.5 2.]8
1.00 73.3 2.75
2M 0.10 63.3 1.73
0.25 70.0 2.33
0.50 75.0 3.00
0.75 80.0 4.00
1.00 83.3 4.99
Mg(NO3)2 1 M 0.10 53.3 1.14
0.25 60.0 1.50
0.50 66.7 2.00
0.75 73.3 2.75
1.00 80.0 4.00
2M 0.10 60.0 1.50
0.25 68.5 2.18
0.50 76.7 3.30
0.75 83.3 4.99
1.00 90.0 9.00
* A g = 49.8/~g; 1 M t t N O 3 ; 4 0 % T B P in b u t a n o l .

Period o] ahakinq
T h e p e r i o d of e q u i l i b r a t i o n w a s v a r i e d f r o m 1 t o 20 m i n u t e s . The
r e s u l t s s h o w e d t h a t 5 m i n u t e s e q u i l i b r a t i o n is a d e q u a t e .
 468 A . A . Y a d a v a n d S. M. K h o p k a r : [Mikrochim. A c t a

Inter/erences
V a r i o u s i o n s w e r e t e s t e d f o r i n t e r f e r e n c e i n t h e e x t r a c t i o n of s i l v e r
( T a b l e I I I ) . T h e t o l e r a n c e l i m i t w a s s e t a s t h e a m o u n t of f o r e i g n i o n
t h a t w o u l d c a u s e =~ 2 % e r r o r i n r e c o v e r y of silver 9 I t w a s s e e n t h a t
s i l v e r c a n b e e x t r a c t e d q u a n t i t a t i v e l y i n t h e p r e s e n c e of t h a l l i u m ( I ) ,
b i s m u t h , c o p p e r ( I I ) , c a d m i u m , zinc, n i c k e l , a l k a l i m e t a l s a n d a l k a l i n e
earths, arsenite, bromide, fluoride, selenite, tellurite, phosphate, and
o r g a n i c c o m p l e x i n g a n i o n s i n 100-fold r a t i o r e l a t i v e t o s i l v e r , a n d
thorium, uranium(VI), cobalt(II) and antimony(III) are tolerated in
50-fold ratio. Platinum(IV), palladium(II), gold(III), iridium(III) and

TableIII. Effect of diverse ions

Ag(I) = 49.8/~g; 1 ~,~/ I-INO a @ 2 M LiNO2; 4 0 % T B P in b u t a n o l

Ion A d d e d as Tolerance Ion A d d e d as Tolerance

limit, m g limit, nag

p b 2+ Pb(NO3) e 5.0 Z n 2+ Zn(NO~)2 - 59

Fig2 + ttg(NOs) 2 None 9 6 H20

TI+ T1NOs 5.0 M n 2+ MnSO 4. 4 H~O 0.5

CuS+ Cu(NO3) 3' 5.0 Co ~ Co(NQ)~- 2.5
9 6 Hs0 9 6H20
Cd2+ Cd(NO2) 2 9 5.0 Ni 2+ Ni(NO3) 2 9 5.0
9 4 H20 9 6 H20
Bi s+ Bi(NOs) ~ 9 5.0 Ca 2+ Ca(NO3)2 - 5.0
9 5tt20 9 4 H20

Sba+ C~I-I4KOTSb - 5.0 Sr 2+ Sr(NO3)~ 5.0

- 1/2 H20 Ba s+ Ba(NO3)2 5.0
Ru s Ru(NOa)2 0.5 AsO4 s Na~AsO 4 5.0
pd2+ Pd(NO3) 2 0.5 CrO42- K2CrO~ 0.25
Rh2+ Rh(NO3) 2 1.0 Mo702~ 6 (NH4)~Mo6024 - 0.5
I r ~+ Ir(N08) 2 0.5 9 4 H~0
p t 4+ Pt(NO2) 4 1.0 S e e s ~- Na2SeO 3 5.0
Au2+ Au(NOz) 3 1.0 Te032- Na~TeO 3 5.0
R e 6+ K21~,eO ~ 0.5 P043- NaaPO 4 5.0
FeS+ F%(804) s 9 5.0 F- NaF 0.5
9 12 I-I20 CHaCOO- Acetic acid 5.0
Ce4+ C%(SO~)s 5.0 Tart s- T a r t a r i c acid 5.0
Tha+ Th(N03) ~- 2.0 C20~ ~ Oxalic acid 5.0
9 4 H20 :?r 2- Malonic acid 5.0
Be2+ Be(NOs) 2" 59 Cit 2- Citric acid 5.0
9 4 I-I~O Ascorb- A s c o r b i c acid 5.0
Ti4+ Ti(SO4) 2 0.5 E D T A 4- EDTA 5.0
Z r ~+ Zr(NOs)4 5.0 ( d i s o d i u m salt)
U~+ U0~(NOs)2 " 1.0
9 6 tt~O
1971/3] Diluted Tributyl Phosphate as an Extraetant for Silver 469

ruthenium(III) are tolerated only in tenfold ratio. Mercury, chlorate,

cyanide, thiocyanate and w n a d a t e interfere at ~ny ratio.
The separation of silver ~rom copper, zinc and nickel is importan~
as they ~re associated in common alloys, and separation from antimony,
bismuth, arscnite, iron and copper is useful as they are associated with
silver in minerals. I t is possible to separate silver by this method ~rom
most of the noble metals. I t is also separated from thallium, thorium,
uranium, strontium and barium, with which, it is associated in fission
products. The relative standard deviation of the method was ~ 1.1% .

Summary
Diluted Tributyl Phosphate as an Extractant ]or Silver
A new method is devised for the rapid solvent extraction of silver
with diluted tributyl phosphate. Thus 40% TBP in butanol quanti-
tatively extracts silver (49.8#g) from 1 M nitric ~cid that is 2 M in
lithium nitrate as salting-out agent. Silver is stripped with dilute ammonia
and is determined photometrically at 495 nm as its red-violet complex
with p-diethylaminobenTylidenerhodanine. The effect of acidity, varying
TBP concentration and salting-out agent was studied. The probable
composition of the extractable species is thought to be AgNO 3 9 (TBP)3
or HAg(NO3)~(TBP)~. Silver can be extracted in presence of a large
number o~ elements with which it is associated in alloys, minerals or
fission products. The method is simple, selective and rapid and needs
only 30 minutes for the separation and determination.

Zusammenfassung
Eine neue Methode der Silberextraktion mit verd. Tributylphosphat
(TBP) wurde angegeben. Mit 40% TBP in Butanol wird Silber (49,8 #g)
BUS 1-m Salpeters~ure, die 2 Mole Lithiumnitrat pro Liter Ms Aussalzmittel
enth~lt, quantitativ extrahiert. Das Silber wird dann mit verd. Ammoniak
abgeschieden und photometrisch bei 495 n m a l s rotvioletter Komplex mit
p-Di~thylbenzylidenrhodanin gemessen. Der Einflul~ der Acidit~t, ver-
schiedener TBP-Konzentration und des Aussalzmittels wurde untersucht.
Die extrahierbare Verbindung hat wahrscheinlich die Zusammensetzung
AgNO~- (TBP)~ oder HAg(NO3)2(TBP)3. Silber kann in Gegenwart vieler
Elemente extrahiert werden, mit denen es in Legierungen, Mineralen oder
Spaltprodukten vergesellschaftet ist. Das Verfahren ist einfach, selektiv
und rasch. Fi~r Trennung m~d Bestimraung sind 30 Minuten erforderlich.

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470 Yad av et al. : Diluted Tributyl Phosphate as an E x t r a e t a n t for Silver

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