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Some factors influencing the constancy of RF values in paper chromatography under australian field conditions
JoURXAL OF CHRO&IATOGRAPHY
SOME, IN
FACTORS PAPER
INFLUENCING
‘CHROMA’+OGRAPHY
THE
281
CONSTANCY
UNDER
OF
R,
AUSTRALIAN
VALUES FIELD
CONDITIONS .%.’S. RITCHIE Newcastbe Un.iversil_v College, NewcnstCe; N.S. IV. (Aztstradia)
INTROISUCTIOX
’ ., i 5
,. The application of paper chromatographic techniques to geological problems “‘required that, on some occasions, analyses had to be carried out in the field or under base-camp conditions. The methods of WARD AND MARRANZINO~, NZVILL AND LIZVER~,,, and RITCHIE~ certainly were designed ‘for use uiider these conditicns. Published data on Rp values generally relate to laboratory studies made~uxider,‘controlled conditions of temperature and humidity. The realization that the extremes’of ternper’&ture and humidity which were likely under .Australian field conditions, would influence seriously the Rp values prompted the investigations, the results of which are nbw reported. As far as possible the data presented have been compiled from field tests. Tithe technique used was by ascending development, using rectangles of Whatman Noi I paper (25 cm x 30 cm) standing in the solvents in screw-top 6-l polythene jars. Sometimes the ~“runs” were done in a small tent but mqre often, in & bos.trailer,,fitted with a canvas hood. In some cases the field conditions were simulated’in laboratory tests with good correlation. RRSULTS ,’
.,
i
The main results are shower in Table I. ‘. : ” .’ : ,‘I. . .~!;‘i1; Apart ,from the variations in the ,Z& values, the significance of which will be discussed. below, extreme humidity’ presents’ some special, problems. One important dmiculty is the maintenance of the paper in a workable condition overperiods of weeks in the field. This is a difficulty encountered.‘in,Africa by BURSILL~ ,as,well as in Australia. The ascent of the solvents by capillarity was almost stopped when.,the paper became ,moist. The vapour phase seemed to. react with the water .in the (paper and on occasions the metal: ions moved. downwards under ‘the influence. of .gravity.:,; I : Even on the : one chromatogram, 1inconsistent : results, were obtained when .the vessels were exposed to wind or direct sunlight:The problem was,overcome by placing boxes or cardboard cartons over the vessels. Apart from this effect, very consistent results were obtained on any one cl~rqmatogram. The variations which ‘are revealed, in Table I may be generalized as follows : I. Hot-dry,. conditions.: are .conducive :to. higher .Rp values;! Notable esception‘s ,... .( ,,(,‘,.: are Coa+ and Mna+ in solvent I. / ,’ : .’
:‘,
,..’
.”
i
/
,,
J. Chrothntog.,
10 (1963)
281-:$&
o.ss + c 0.Q + c
o.so + c 0.92
1.0
1.0
0.75 I.0
0.97 I.0
0.93 0.93
+
0.48 O-97 0.74 1.0
c
+ +
c c
:$
0.92 o*G2
+
&
+
q
0.94 0.97
0.93
:? ‘I :,i .. .’ i
s I,:‘+
o.ss
0.9s
AS”+
0.92
0.92
up to
17&l-l-
cua+
0.93
0.gG
o.so
0.59 o-34-0.92
0.34-0.Q7 0.40-o.so 0.72
Co2” Mn042-
O-53 0.42 0.73
Ni2.b
‘0.52
0.75 0.27
Mn2+
0.48
0.2s
0.33
i+-+
9.94
$\I””
o.Go 1
”
,..pt4+
: r
0.50
0.47’
!
c
0.62
O-77 0.92 + 0.40
c
0.83 0.8s 0.40
0.50
up to 0.75 o.jqc--I.0 0.30-0.3s 0.53 -I_ c 0.32
0.49
c-o.92
C-O.58
0.25
0.20
0.27
0.24
0.28
0.32
0.2s
o-33
0.30
0.93 +
c
1.0
+
c
0.44
0.67
o.$
0.‘70
0*7?
~olven ti
0.91
0.90 0.4 4. 0.64 0.4G
0.48 0.75 o.so
0.47
,..
Solvent2
0.4G
j-0
ILO + 0.35 o.Ga
&+ Tj4+
V"* WC@-
0.90
0.47
”
~tiop
0197
0.9s
0.92
sg
0.45 0.42 o.so 0.40 0.32
O.GI
0.52 3o.fxJ
,,
0.4G
. B.?2+, M&p? ~i\u:l+.
0.2s
+
c
0.93 0.90 0.40
1.0
o.so
0.
o.ss
+ +
c c
='Butahol-cone, HCl-cone'. HI?-water (ro0:go: 'A='Butanol fhction of butanol-cont. HRr-water
0.53 + cj; 0.59 ‘
1.0
o.s7
0.3G 0.60
0.
0.37
0.2s
o*s-r.0 I.0 +
as
:: 1:
0.94
0.55
c
o.3G 0.41 0.33
0
0
45).
(xoo:ro:go)
+
cont. I-IBr (40).
,’
:,’ ,,
:
,,CONCLUSION$’ ; .., I.
~‘,Rp+valties,of:,comm,on metal ions’vary ‘1; temperature,
considerably
;”
‘/
;
’
under the influence of: :
1:
,.
+
c
0.2s
2. Hot-wet conditions produce values slightly lower than the hot-dry. 3. Cold-wet conditions produce lower lip values than the hot conditions but not always lower than the published results which were obtained near zoo. : I. ” Some.disadvantage is revealedin that, within the range of conditions experienced, identification’ of ions cannot be made by reference to- the published RF ~values ob.tained.~uncler~controlled .laboratory conditions. The disadvantage may ‘be overcome by running parallel chromatograms’in such a way ‘that known and unknown ions may be.compared3. ” .’ : Advantageous features appear to be a better separation. at temperatures from 359 to 40” with :less variation, of Rp over small ,temperature ranges. Further results obtained at .niore critical temperatures might reveal that, for the solvents used, 2oP. 2.1" is an unfavourable.temperature for J?p determinations. .. . ,‘$ ,’ 1’.‘. ,/. ! ;.. ” 3 ,,,‘.,II;‘, ,, :<,, I”
:I
0.4G
0.23 0.43 0.37-0.43 0.43
2:
,,j
.”
$1
.,,
.'
:
FACTORS
0.13 + 0.45 +
C C
0.90
0.8s ‘X.0 ’
0.80 0.92
+
c
0.73
0.12
+
0.81 -j- c 0.93 o.sg I.0
c
0.72 0.90 o.ss 0.95
+
c
0.95 o.ss
o.ss + c
o.G7
O.SG
0.71
+
c
0.80 0.77
0.65 0.70 0.60
up to 0.67 0.70
o-74 o-55 0.77 0.72
0.91 0.90 0.73 0.7G 0.76 0.74
+
0.95 0.w
c
0.82 o.so
1.0
Solvent Solvent
1.0
3 = -( =
“0.85
O,G2
0.72 0.72
0.73 o.GG
0.65
0.5s 0.72
0.70
0.7s
0.92 +
c
0.86 0.73 0.7s 0.75 o.i.‘, I.0
+ +
THE
c c
COXSTAXCY
+ 0.59 0.4s + 0.77-0.83 o.s5
+
c
0.57 0.73 o.Gg
fz c
1.0
0.7G 0.51 0.94 0.58 0.95
RF
OF
+ +
c c
0.70 0.76
+ +
c c
0.82 0.92
+ +
c c
o.sg
0.9-t
0.92 0.92
0.45-,O-55 0.S3~0.92 0.03
0.97 0.Y7 0.$3 0.90 0.02
0.25
0.27
c
0.s3 0.6-i 0.530
+
c
0.5G
0.55 0.54 0.5s 0.56 0.94
0.42
c
0.90 0.02
f +
c c
:
+ +
c c
0.74 0.45 o.zG T.0
^t
c
0.25
+
c
“I
0.15
0.1.5
I
"
0.75
0
,
0.26
0.97
0.90 0.91 + 0.10
c
0.95 0.90
0.0tj
0.10
0.84
0.61
o.G4 o.5&-064 o.Gq
1.0
I.0
+c
+
c
0.76 0.4s 0.02 I.0
0.52
0.(15 I.0
+c
‘,,
0
0.3_6
+
c
-t_ c o.so + c
o.so +
+
0.90
0.03
0.93
283
VALUES
0.90
+
o.qKl 0.02 0.22
0.95 o.so o.SG 0 *$3a
0.S‘~ o.ss 0:7s
1.0
0.13 0.45 o-77 0.7G 0.90
O.jO
0.9-+ 0.75 o.SG
INFLUENCIXG
,0.28
;
0,‘4
c
/
;:“,7,‘$
.’
c
0.08 o.G2 0.92 0.97 +
c’c
: C ;
Etlianol-methanol-2 N HCl (Go : Go: So): Acetone-cont. HCl-cont. I-IF-water ( I Yo : 10 : 2 : 8). .I
humidity (which affects the moisture content of thd paper), . : 3. temperature variations from one side of the vessel to the other. The difficulties thus created can be overcome to some extent by using a comparai tive method in which known metal ions are chrornatographed alongside the unknown ions. An air-tight container kept dry by silica gel should overcome the moisttire ,/ problem. 2.
SUNMARY
.’
,.L’
Rp values of metal ions obtained under Australian field conditions are reeorted; Tlie effects of temperature and humidity are shown. Precautions leading to effective use’ ,, of the technique in the field are mentioned. .’ REFERENCES .’ ‘. 1 F. 2 H.’ 3’A. J C.
N.-WARD AND A. 17. C. NE&LL.AND S. R%.ZHIE, &on'; BURSILL, personal /
’
‘:
‘,
,. ‘.I
; , : :,
, Ik ) i 1’. IMARRANZINO, U.S. Gaol. SUYV., Brtll., ,No. 1036-J. 1957. R. R., LEVER, Acrsfra/as,i~tr I?!&., ,nlhr~ug & Met. Proc,,~ NC+ I?!’ (1959). r4.r,,.. .“,,I, Geol., sy (1962) 23s. ., .’ , ‘: ‘. communication, rgbr. ’ : J.
Chrormdog.,
10 (xgG3)
2St-2S3
:
SOME, IN
FACTORS PAPER
INFLUENCING
‘CHROMA’+OGRAPHY
THE
281
CONSTANCY
UNDER
OF
R,
AUSTRALIAN
VALUES FIELD
CONDITIONS .%.’S. RITCHIE Newcastbe Un.iversil_v College, NewcnstCe; N.S. IV. (Aztstradia)
INTROISUCTIOX
’ ., i 5
,. The application of paper chromatographic techniques to geological problems “‘required that, on some occasions, analyses had to be carried out in the field or under base-camp conditions. The methods of WARD AND MARRANZINO~, NZVILL AND LIZVER~,,, and RITCHIE~ certainly were designed ‘for use uiider these conditicns. Published data on Rp values generally relate to laboratory studies made~uxider,‘controlled conditions of temperature and humidity. The realization that the extremes’of ternper’&ture and humidity which were likely under .Australian field conditions, would influence seriously the Rp values prompted the investigations, the results of which are nbw reported. As far as possible the data presented have been compiled from field tests. Tithe technique used was by ascending development, using rectangles of Whatman Noi I paper (25 cm x 30 cm) standing in the solvents in screw-top 6-l polythene jars. Sometimes the ~“runs” were done in a small tent but mqre often, in & bos.trailer,,fitted with a canvas hood. In some cases the field conditions were simulated’in laboratory tests with good correlation. RRSULTS ,’
.,
i
The main results are shower in Table I. ‘. : ” .’ : ,‘I. . .~!;‘i1; Apart ,from the variations in the ,Z& values, the significance of which will be discussed. below, extreme humidity’ presents’ some special, problems. One important dmiculty is the maintenance of the paper in a workable condition overperiods of weeks in the field. This is a difficulty encountered.‘in,Africa by BURSILL~ ,as,well as in Australia. The ascent of the solvents by capillarity was almost stopped when.,the paper became ,moist. The vapour phase seemed to. react with the water .in the (paper and on occasions the metal: ions moved. downwards under ‘the influence. of .gravity.:,; I : Even on the : one chromatogram, 1inconsistent : results, were obtained when .the vessels were exposed to wind or direct sunlight:The problem was,overcome by placing boxes or cardboard cartons over the vessels. Apart from this effect, very consistent results were obtained on any one cl~rqmatogram. The variations which ‘are revealed, in Table I may be generalized as follows : I. Hot-dry,. conditions.: are .conducive :to. higher .Rp values;! Notable esception‘s ,... .( ,,(,‘,.: are Coa+ and Mna+ in solvent I. / ,’ : .’
:‘,
,..’
.”
i
/
,,
J. Chrothntog.,
10 (1963)
281-:$&
o.ss + c 0.Q + c
o.so + c 0.92
1.0
1.0
0.75 I.0
0.97 I.0
0.93 0.93
+
0.48 O-97 0.74 1.0
c
+ +
c c
:$
0.92 o*G2
+
&
+
q
0.94 0.97
0.93
:? ‘I :,i .. .’ i
s I,:‘+
o.ss
0.9s
AS”+
0.92
0.92
up to
17&l-l-
cua+
0.93
0.gG
o.so
0.59 o-34-0.92
0.34-0.Q7 0.40-o.so 0.72
Co2” Mn042-
O-53 0.42 0.73
Ni2.b
‘0.52
0.75 0.27
Mn2+
0.48
0.2s
0.33
i+-+
9.94
$\I””
o.Go 1
”
,..pt4+
: r
0.50
0.47’
!
c
0.62
O-77 0.92 + 0.40
c
0.83 0.8s 0.40
0.50
up to 0.75 o.jqc--I.0 0.30-0.3s 0.53 -I_ c 0.32
0.49
c-o.92
C-O.58
0.25
0.20
0.27
0.24
0.28
0.32
0.2s
o-33
0.30
0.93 +
c
1.0
+
c
0.44
0.67
o.$
0.‘70
0*7?
~olven ti
0.91
0.90 0.4 4. 0.64 0.4G
0.48 0.75 o.so
0.47
,..
Solvent2
0.4G
j-0
ILO + 0.35 o.Ga
&+ Tj4+
V"* WC@-
0.90
0.47
”
~tiop
0197
0.9s
0.92
sg
0.45 0.42 o.so 0.40 0.32
O.GI
0.52 3o.fxJ
,,
0.4G
. B.?2+, M&p? ~i\u:l+.
0.2s
+
c
0.93 0.90 0.40
1.0
o.so
0.
o.ss
+ +
c c
='Butahol-cone, HCl-cone'. HI?-water (ro0:go: 'A='Butanol fhction of butanol-cont. HRr-water
0.53 + cj; 0.59 ‘
1.0
o.s7
0.3G 0.60
0.
0.37
0.2s
o*s-r.0 I.0 +
as
:: 1:
0.94
0.55
c
o.3G 0.41 0.33
0
0
45).
(xoo:ro:go)
+
cont. I-IBr (40).
,’
:,’ ,,
:
,,CONCLUSION$’ ; .., I.
~‘,Rp+valties,of:,comm,on metal ions’vary ‘1; temperature,
considerably
;”
‘/
;
’
under the influence of: :
1:
,.
+
c
0.2s
2. Hot-wet conditions produce values slightly lower than the hot-dry. 3. Cold-wet conditions produce lower lip values than the hot conditions but not always lower than the published results which were obtained near zoo. : I. ” Some.disadvantage is revealedin that, within the range of conditions experienced, identification’ of ions cannot be made by reference to- the published RF ~values ob.tained.~uncler~controlled .laboratory conditions. The disadvantage may ‘be overcome by running parallel chromatograms’in such a way ‘that known and unknown ions may be.compared3. ” .’ : Advantageous features appear to be a better separation. at temperatures from 359 to 40” with :less variation, of Rp over small ,temperature ranges. Further results obtained at .niore critical temperatures might reveal that, for the solvents used, 2oP. 2.1" is an unfavourable.temperature for J?p determinations. .. . ,‘$ ,’ 1’.‘. ,/. ! ;.. ” 3 ,,,‘.,II;‘, ,, :<,, I”
:I
0.4G
0.23 0.43 0.37-0.43 0.43
2:
,,j
.”
$1
.,,
.'
:
FACTORS
0.13 + 0.45 +
C C
0.90
0.8s ‘X.0 ’
0.80 0.92
+
c
0.73
0.12
+
0.81 -j- c 0.93 o.sg I.0
c
0.72 0.90 o.ss 0.95
+
c
0.95 o.ss
o.ss + c
o.G7
O.SG
0.71
+
c
0.80 0.77
0.65 0.70 0.60
up to 0.67 0.70
o-74 o-55 0.77 0.72
0.91 0.90 0.73 0.7G 0.76 0.74
+
0.95 0.w
c
0.82 o.so
1.0
Solvent Solvent
1.0
3 = -( =
“0.85
O,G2
0.72 0.72
0.73 o.GG
0.65
0.5s 0.72
0.70
0.7s
0.92 +
c
0.86 0.73 0.7s 0.75 o.i.‘, I.0
+ +
THE
c c
COXSTAXCY
+ 0.59 0.4s + 0.77-0.83 o.s5
+
c
0.57 0.73 o.Gg
fz c
1.0
0.7G 0.51 0.94 0.58 0.95
RF
OF
+ +
c c
0.70 0.76
+ +
c c
0.82 0.92
+ +
c c
o.sg
0.9-t
0.92 0.92
0.45-,O-55 0.S3~0.92 0.03
0.97 0.Y7 0.$3 0.90 0.02
0.25
0.27
c
0.s3 0.6-i 0.530
+
c
0.5G
0.55 0.54 0.5s 0.56 0.94
0.42
c
0.90 0.02
f +
c c
:
+ +
c c
0.74 0.45 o.zG T.0
^t
c
0.25
+
c
“I
0.15
0.1.5
I
"
0.75
0
,
0.26
0.97
0.90 0.91 + 0.10
c
0.95 0.90
0.0tj
0.10
0.84
0.61
o.G4 o.5&-064 o.Gq
1.0
I.0
+c
+
c
0.76 0.4s 0.02 I.0
0.52
0.(15 I.0
+c
‘,,
0
0.3_6
+
c
-t_ c o.so + c
o.so +
+
0.90
0.03
0.93
283
VALUES
0.90
+
o.qKl 0.02 0.22
0.95 o.so o.SG 0 *$3a
0.S‘~ o.ss 0:7s
1.0
0.13 0.45 o-77 0.7G 0.90
O.jO
0.9-+ 0.75 o.SG
INFLUENCIXG
,0.28
;
0,‘4
c
/
;:“,7,‘$
.’
c
0.08 o.G2 0.92 0.97 +
c’c
: C ;
Etlianol-methanol-2 N HCl (Go : Go: So): Acetone-cont. HCl-cont. I-IF-water ( I Yo : 10 : 2 : 8). .I
humidity (which affects the moisture content of thd paper), . : 3. temperature variations from one side of the vessel to the other. The difficulties thus created can be overcome to some extent by using a comparai tive method in which known metal ions are chrornatographed alongside the unknown ions. An air-tight container kept dry by silica gel should overcome the moisttire ,/ problem. 2.
SUNMARY
.’
,.L’
Rp values of metal ions obtained under Australian field conditions are reeorted; Tlie effects of temperature and humidity are shown. Precautions leading to effective use’ ,, of the technique in the field are mentioned. .’ REFERENCES .’ ‘. 1 F. 2 H.’ 3’A. J C.
N.-WARD AND A. 17. C. NE&LL.AND S. R%.ZHIE, &on'; BURSILL, personal /
’
‘:
‘,
,. ‘.I
; , : :,
, Ik ) i 1’. IMARRANZINO, U.S. Gaol. SUYV., Brtll., ,No. 1036-J. 1957. R. R., LEVER, Acrsfra/as,i~tr I?!&., ,nlhr~ug & Met. Proc,,~ NC+ I?!’ (1959). r4.r,,.. .“,,I, Geol., sy (1962) 23s. ., .’ , ‘: ‘. communication, rgbr. ’ : J.
Chrormdog.,
10 (xgG3)
2St-2S3
: