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Paper chromatographic separation ofsilver(I), lead(ll), mercury(ll) and thallium(l) with solvents containing chloroform
Paper
chromatographic and thallium(l)
separation of silver(l), lead(ll), mercury(ll) with solvents containing chloroform
Some (Jf the possihilitics of using chloroform and chloroform mixtures for inorganic paper cl~romatograpl~y have been dcscribcd previously*. In the present work, similar ion migration studies and measurements of Rfi- values for silver, lcad, mercury(I1) ant1 thnllium(1) were carried out with twenty different solvent mixtures each containing chloroform. IZCllgCdS
Silver(I), Icntl(II), mcrcury(I1) and thallium(I) solutions were prcparccl from tlic analytical re;tgent-graclc nitrates. All organic solvents used were twice-clistillccl ancl basis with the cxccption of their mixtures were prcparctl on a volume-volume Pure conccntratccl nitric acicl and glacial acetic acid (E:. Merck) phenol solutions. were used to acidify certain solvent mixtures. I-Voccdurc All studies were performed on 3 mm Whatman paper (xx cm cli;lmctcr) which was cut with wicks of 3-4 cm as clcscril>ccl previously1 12. For measurement of Ru vducs of individual ions, the paper discs were spottccl at the ccntrc with tlic solution containing 10-x5 pg of cation per drop of 0.02 ml using a micropipette. The wet spots wcrc outlined with pencil and the discs were clricd at room tcmpcraturc (cu. 25”). Thcsc were clcvclol~cd to obtain adequate migration of The solvent fronts were marked again and tile discs wet-c dried. the particular ion. A spray of yellow ammonium sulphidc was usccl to cletect the rings (Ag+, grcy ; l’b”‘, dark brown ; M@+, ldack; and Tl+, reddish brown, which faded gradually owing to oxidation of thallous sulphiclc to white sulphatc). All RF mcasurcmcnts were ma& with respect to inner (RF(~). aswell as outer (Xp(,,) eclgcs of the rings and the values in Table I arc the mean of several mcasurcmcnts at different points on a particular ring. Separations wcrc carried out similarly with more conccntratccl solutions of the ions (40 to 50 rug per drop) mixccl in quo1 volumes and then spotting with one drop of the mixture. Successful separations were obtained for the 4 ions studicd with solvents 2, 8, 12, and 18 (SW Table I for solvent composition). Good separations were obtained for Hg, Ag and ‘I’1 with solvents I, 4 and 14, for Hg, Pb and Tl with solvents 4 and 6, and for Ag, l-16’ ;cncl I’b with solvent 13. I>iscussiorc It W:LS lX>illtcd Out by l~IIh’l’NAGr\l~ANl) I’OONIA 1 that absolute cliloroform is not suitable for inorganic chromatography, but chloroform mixed with polar organic solvents allowed sufficient migration to give successful separations. LEUERER3, i’OLLARD d dJ and HAIMSAWA~ have also cmphasisccl the need for polar solvents for the effective separation of inorganic ions. The present stuclics with Ag+, PIG+, H@+ and Tl+ supports the use of mixed solvents containing chloroform for separation of inorganic species. The results in Table I show that the addition of polar solvents to
.drrrtl. Chh.
Acln.
30 (rg6.1) 310-312
=
50
49 50 49
I- f
zoo 100
49
50
2 ml I.
50
..“_
ml J q9ml J,amIL j0 ml Ii 49 ml Ii, 2 ml L
ml H, I ml I. Zig 1 jg I,rmiN
.@
j0 ml H
~9 ml E, 2 ml I,
49 ml D. j0 ml E
ml D
50
49
50 49
,-_,..
._-.--
X.j t.;ij
3
I.ij
3-75
-
0.00 O.lj 0.00 0.00
0.61 0.6) 0.11 0.00
0.61
0.00 0.00 0.60
2 2 2.j 3
O.&i 0.62 0.05
o-73 0.32 a.tir 0.54
3
3 I 2
^
-._._~-”
0.00 0.32 0.00 0.M
0.7s 0.16 0.10
0.73
0.00 0.00 0.Q 031
OS! 0.;; 0.00 0.00 O.jO
O.=J O.Oj 0.18 O‘.$
0.Sg 0.00 0.7; 0.7'
0.Q 0.00 o.tio
-,--
049
-
-._-
0.95
o.sj o.sq I.00
0.7-r
O.jS 0.2j
0.79
I .oo 0.96 o.gtt
o-95
0.q 0.97 0.00 0.90
0.90
0.7; 0.3;
Hrro,
.. .
.._ _ __._.._._.-..-_
-_-
0.00 0.00 0.00 0.14
O.&J 0.41 O.lf 0.00
---
-_-..--._--
0.00
0.00 --
0.00 0.00 0.00
O.jb 0.00
0.2s
0.00
O&l
0.00
0.89 O.jl
0.00
0.00
O.Oj
0.36
0.00
0.b.f
0.61 0.0s
0.22
a.07
0.00
O..?j
O.ff
o.Gt
0.95
0.Z.j
o.yo
0.70
0.00
0.35
0.00
o.og
0.00
O.JO
0.2” I
0.q Oh.1
0.i-l O.jS
0.43
0.00
0.12
0.73 O.fZ O.@
O.jS OA 0.67
O.Sj
OS9 0.33
UFW
0.00 0.00
O-35 0.00 O.?L
O.tiI
O.b3 o-35
0.2 1
0.70
1Zrccr .__-._ _..- .-.
.- ._.___ -___
1.00 O.()b
,- -_
lip --. _-__
. _-.._.~__
0.S3 0.45
P&r .-_ ..- ._ ._- --_. lk*) HHiJ . .._ _. . .-. ._. _ _..._ .
Diffusion
4.5 5
2
2.5
.?
3 * 2.3
fh) --.__.
._I_...._._.___ - _..._-_
.-_ ofrun
Tinrr
_..___.______-
I{, 2 ml I. C 49 ml C, 2 ml I.
49 ml j0 mt
j0 ml B
50
50 39
49
50
rrtl .f added ___- t. ._--
IS 19 20
13 14 I’3 I6
10 11 I1
9
ii
6
5
A-0.
--._-__
.._-__
Solrent
-__
chloroform, 12 = methanol. C = ethanol, D = ?-propanol, E = butanol, F = amyl alcohol, G = acetone. H = .?-butanone, I = ph~w4 J = methyl acetate, K = ethyl acetate, 1. = concentrated nitric acid, 11 = glacial acetic acid)
--__._.._-
(;I
i?Fb+ALt!ESFORISDX\'IDt-.\tChftOSSIS DIFFEREST SOLi’ESTS
3x2
SHORT
chloroform In
facilitutcs
gcmc’rd,
clecrc;Lscd ngrees
the
movement
wit11 solvent
mixtures
with
with
increase
earlier
um( I) migratd
in the
and
sliglitly
of ioIlS.
separntion
containing
molecular
*“*7. In
findings*
only
COMJIUNICATIOSS
alcohols
weight
ihc
of the
I
alcohol
;L chloroform-hutanol
; in a chloroform
- amyl
:~lcohol
of all
added
the
(‘L’itblc
system,
silver
system,
only
ions
I) ; this
and
thalli-
incrcury(
I I)
migrated. ‘I’hc
kctonic
systems
gz~ve
pl1cnol-chloroform
system
iron,
cobalt,
and
only
mcrcury(I1)
The
nickel
usccl ‘I’lic
of
by
many
in I)rcscnt
work
prcscncc
of
wl1crc lead
(
in acidic
I~lctllyl
:lcctzLtc.
tlic
it sc’cmS
Tllc
(except silver 0.
.]unc
could
bc
tllc
ions
studictl,
(contr:iry
to
containing
wlierc~zls
its effect
esters
rcfs.
with
the
with
the
chloroform,
separation
1963)
nitric
CilSC! of
usictl,
ncitl
tcntlcricics
it 1i;icl little tllc
liighcr).
on
I) were
tllc
h:is l,ccn
but
;LS tllc
\V;LS prcfcrrcd of
cffcct
tllc: ions
lligllcst
of
‘I’llc
scclucncc
of
ions here.
1.1nly for
\*alucs,
I\‘,.*
or
it dc-
the: 4 ions
cl~loroforrn-.L-l,utanonc
CiLSCS (solvents
SyStctll,
RF* \‘illUC!S \V;LS
2, 3, I I zind 13) tllc
rncrciiry
ant1
vducs
for
clcvclopccl
quite
Scpnrations solvents
;lny 8)
3 of the
close of
cac:h
above
togctlicr
to eucll
three
contzlining
wit11 solvents
4 mctds
from
otlicr
wcrc
satis-
illltl nlctll:tllc~l, I~Ilti~nOl, zicctonc
chloroform
scverd
of the
chloriclcs. niign~tion
silver
ohtnincd. of
cliromatogr;iI’hy
is normall_v
same.
the
7 :ind
in inorg:anic acid
little
a
In some lcncl,
with
sepriltions
Irtli,
WilS
Hg.
tliallium
plishcd.
(Rcceivcd
tlic:
use
for mcrcury(1
cont;iining
obtained
the
iii
IlCilrl~
illlcl
c.g.,
the c;iscs
I\‘,.* vil!ucS
of tliallium,
(SW,
thnt
nioclificcl in otlicr
for
Scvcral
literature
acid
Lcatl
1~
chloroform.
hncl insoluble
solvents
results
of ;tn acid
mostly
wcrc
scpz1rntions
coulcl
all
for
In systcnls
7, Hydrochloric
systems
thallium(I)
clUnlitiltiVc
presence
1% -=C Ag
filCtOl_y
c1tllcr
set’).
workers
I).
I\‘,.* vnluc Tl
:ind
‘1’1~
(Tnblc
solvent
tllc
gcncrdly
the
Syh!IllS;
them
in rill tile
copper
nitric
~!l!O~~~fO~Ill--~St~~
crci1Sed
migrntion
to 1~ of little
migriltctl.
clcsiral~ility
cmphasised
good
provccl
of
mctnls
:~lcol~ols
mc:t;ils not
the
other
have
or
lirls not
previously
Only
from
CilCll
ketones
been
contziining
or
So tllnt
with
reprtecl
chloroform, been
in but
accom-
chromatographic and thallium(l)
separation of silver(l), lead(ll), mercury(ll) with solvents containing chloroform
Some (Jf the possihilitics of using chloroform and chloroform mixtures for inorganic paper cl~romatograpl~y have been dcscribcd previously*. In the present work, similar ion migration studies and measurements of Rfi- values for silver, lcad, mercury(I1) ant1 thnllium(1) were carried out with twenty different solvent mixtures each containing chloroform. IZCllgCdS
Silver(I), Icntl(II), mcrcury(I1) and thallium(I) solutions were prcparccl from tlic analytical re;tgent-graclc nitrates. All organic solvents used were twice-clistillccl ancl basis with the cxccption of their mixtures were prcparctl on a volume-volume Pure conccntratccl nitric acicl and glacial acetic acid (E:. Merck) phenol solutions. were used to acidify certain solvent mixtures. I-Voccdurc All studies were performed on 3 mm Whatman paper (xx cm cli;lmctcr) which was cut with wicks of 3-4 cm as clcscril>ccl previously1 12. For measurement of Ru vducs of individual ions, the paper discs were spottccl at the ccntrc with tlic solution containing 10-x5 pg of cation per drop of 0.02 ml using a micropipette. The wet spots wcrc outlined with pencil and the discs were clricd at room tcmpcraturc (cu. 25”). Thcsc were clcvclol~cd to obtain adequate migration of The solvent fronts were marked again and tile discs wet-c dried. the particular ion. A spray of yellow ammonium sulphidc was usccl to cletect the rings (Ag+, grcy ; l’b”‘, dark brown ; M@+, ldack; and Tl+, reddish brown, which faded gradually owing to oxidation of thallous sulphiclc to white sulphatc). All RF mcasurcmcnts were ma& with respect to inner (RF(~). aswell as outer (Xp(,,) eclgcs of the rings and the values in Table I arc the mean of several mcasurcmcnts at different points on a particular ring. Separations wcrc carried out similarly with more conccntratccl solutions of the ions (40 to 50 rug per drop) mixccl in quo1 volumes and then spotting with one drop of the mixture. Successful separations were obtained for the 4 ions studicd with solvents 2, 8, 12, and 18 (SW Table I for solvent composition). Good separations were obtained for Hg, Ag and ‘I’1 with solvents I, 4 and 14, for Hg, Pb and Tl with solvents 4 and 6, and for Ag, l-16’ ;cncl I’b with solvent 13. I>iscussiorc It W:LS lX>illtcd Out by l~IIh’l’NAGr\l~ANl) I’OONIA 1 that absolute cliloroform is not suitable for inorganic chromatography, but chloroform mixed with polar organic solvents allowed sufficient migration to give successful separations. LEUERER3, i’OLLARD d dJ and HAIMSAWA~ have also cmphasisccl the need for polar solvents for the effective separation of inorganic ions. The present stuclics with Ag+, PIG+, H@+ and Tl+ supports the use of mixed solvents containing chloroform for separation of inorganic species. The results in Table I show that the addition of polar solvents to
.drrrtl. Chh.
Acln.
30 (rg6.1) 310-312
=
50
49 50 49
I- f
zoo 100
49
50
2 ml I.
50
..“_
ml J q9ml J,amIL j0 ml Ii 49 ml Ii, 2 ml L
ml H, I ml I. Zig 1 jg I,rmiN
.@
j0 ml H
~9 ml E, 2 ml I,
49 ml D. j0 ml E
ml D
50
49
50 49
,-_,..
._-.--
X.j t.;ij
3
I.ij
3-75
-
0.00 O.lj 0.00 0.00
0.61 0.6) 0.11 0.00
0.61
0.00 0.00 0.60
2 2 2.j 3
O.&i 0.62 0.05
o-73 0.32 a.tir 0.54
3
3 I 2
^
-._._~-”
0.00 0.32 0.00 0.M
0.7s 0.16 0.10
0.73
0.00 0.00 0.Q 031
OS! 0.;; 0.00 0.00 O.jO
O.=J O.Oj 0.18 O‘.$
0.Sg 0.00 0.7; 0.7'
0.Q 0.00 o.tio
-,--
049
-
-._-
0.95
o.sj o.sq I.00
0.7-r
O.jS 0.2j
0.79
I .oo 0.96 o.gtt
o-95
0.q 0.97 0.00 0.90
0.90
0.7; 0.3;
Hrro,
.. .
.._ _ __._.._._.-..-_
-_-
0.00 0.00 0.00 0.14
O.&J 0.41 O.lf 0.00
---
-_-..--._--
0.00
0.00 --
0.00 0.00 0.00
O.jb 0.00
0.2s
0.00
O&l
0.00
0.89 O.jl
0.00
0.00
O.Oj
0.36
0.00
0.b.f
0.61 0.0s
0.22
a.07
0.00
O..?j
O.ff
o.Gt
0.95
0.Z.j
o.yo
0.70
0.00
0.35
0.00
o.og
0.00
O.JO
0.2” I
0.q Oh.1
0.i-l O.jS
0.43
0.00
0.12
0.73 O.fZ O.@
O.jS OA 0.67
O.Sj
OS9 0.33
UFW
0.00 0.00
O-35 0.00 O.?L
O.tiI
O.b3 o-35
0.2 1
0.70
1Zrccr .__-._ _..- .-.
.- ._.___ -___
1.00 O.()b
,- -_
lip --. _-__
. _-.._.~__
0.S3 0.45
P&r .-_ ..- ._ ._- --_. lk*) HHiJ . .._ _. . .-. ._. _ _..._ .
Diffusion
4.5 5
2
2.5
.?
3 * 2.3
fh) --.__.
._I_...._._.___ - _..._-_
.-_ ofrun
Tinrr
_..___.______-
I{, 2 ml I. C 49 ml C, 2 ml I.
49 ml j0 mt
j0 ml B
50
50 39
49
50
rrtl .f added ___- t. ._--
IS 19 20
13 14 I’3 I6
10 11 I1
9
ii
6
5
A-0.
--._-__
.._-__
Solrent
-__
chloroform, 12 = methanol. C = ethanol, D = ?-propanol, E = butanol, F = amyl alcohol, G = acetone. H = .?-butanone, I = ph~w4 J = methyl acetate, K = ethyl acetate, 1. = concentrated nitric acid, 11 = glacial acetic acid)
--__._.._-
(;I
i?Fb+ALt!ESFORISDX\'IDt-.\tChftOSSIS DIFFEREST SOLi’ESTS
3x2
SHORT
chloroform In
facilitutcs
gcmc’rd,
clecrc;Lscd ngrees
the
movement
wit11 solvent
mixtures
with
with
increase
earlier
um( I) migratd
in the
and
sliglitly
of ioIlS.
separntion
containing
molecular
*“*7. In
findings*
only
COMJIUNICATIOSS
alcohols
weight
ihc
of the
I
alcohol
;L chloroform-hutanol
; in a chloroform
- amyl
:~lcohol
of all
added
the
(‘L’itblc
system,
silver
system,
only
ions
I) ; this
and
thalli-
incrcury(
I I)
migrated. ‘I’hc
kctonic
systems
gz~ve
pl1cnol-chloroform
system
iron,
cobalt,
and
only
mcrcury(I1)
The
nickel
usccl ‘I’lic
of
by
many
in I)rcscnt
work
prcscncc
of
wl1crc lead
(
in acidic
I~lctllyl
:lcctzLtc.
tlic
it sc’cmS
Tllc
(except silver 0.
.]unc
could
bc
tllc
ions
studictl,
(contr:iry
to
containing
wlierc~zls
its effect
esters
rcfs.
with
the
with
the
chloroform,
separation
1963)
nitric
CilSC! of
usictl,
ncitl
tcntlcricics
it 1i;icl little tllc
liighcr).
on
I) were
tllc
h:is l,ccn
but
;LS tllc
\V;LS prcfcrrcd of
cffcct
tllc: ions
lligllcst
of
‘I’llc
scclucncc
of
ions here.
1.1nly for
\*alucs,
I\‘,.*
or
it dc-
the: 4 ions
cl~loroforrn-.L-l,utanonc
CiLSCS (solvents
SyStctll,
RF* \‘illUC!S \V;LS
2, 3, I I zind 13) tllc
rncrciiry
ant1
vducs
for
clcvclopccl
quite
Scpnrations solvents
;lny 8)
3 of the
close of
cac:h
above
togctlicr
to eucll
three
contzlining
wit11 solvents
4 mctds
from
otlicr
wcrc
satis-
illltl nlctll:tllc~l, I~Ilti~nOl, zicctonc
chloroform
scverd
of the
chloriclcs. niign~tion
silver
ohtnincd. of
cliromatogr;iI’hy
is normall_v
same.
the
7 :ind
in inorg:anic acid
little
a
In some lcncl,
with
sepriltions
Irtli,
WilS
Hg.
tliallium
plishcd.
(Rcceivcd
tlic:
use
for mcrcury(1
cont;iining
obtained
the
iii
IlCilrl~
illlcl
c.g.,
the c;iscs
I\‘,.* vil!ucS
of tliallium,
(SW,
thnt
nioclificcl in otlicr
for
Scvcral
literature
acid
Lcatl
1~
chloroform.
hncl insoluble
solvents
results
of ;tn acid
mostly
wcrc
scpz1rntions
coulcl
all
for
In systcnls
7, Hydrochloric
systems
thallium(I)
clUnlitiltiVc
presence
1% -=C Ag
filCtOl_y
c1tllcr
set’).
workers
I).
I\‘,.* vnluc Tl
:ind
‘1’1~
(Tnblc
solvent
tllc
gcncrdly
the
Syh!IllS;
them
in rill tile
copper
nitric
~!l!O~~~fO~Ill--~St~~
crci1Sed
migrntion
to 1~ of little
migriltctl.
clcsiral~ility
cmphasised
good
provccl
of
mctnls
:~lcol~ols
mc:t;ils not
the
other
have
or
lirls not
previously
Only
from
CilCll
ketones
been
contziining
or
So tllnt
with
reprtecl
chloroform, been
in but
accom-