Fresenius' Journal of
Fresenius J Anal Chem (1990) 338: 908- 911
Separation and determination of xanthates in mixtures as dixanthogens
by normal-phase HPLC on a diol-phase
Chunshan Zhou 1, Albert Bahr 2, and Georg Schwedt 3
1 Department of Chemistry, Central South University of Technology, Changsha, Peoples Republic of China
z Institute of Mineral Processing and Benefication, Technical University Clausthal, Erzstrasse 20, W-3392 Clausthal-Zellerfeld,
Federal Republic of Germany
3 Institute of Inorganic and Analytical Chemistry, Technical University Clausthal, Paul-Ernst-Strasse 4, W-3392 Clausthal-Zellerfeld,
Federal Republic of Germany
Summary. A normal-phase-HPLC method for determining
individual xanthates in mixtures is presented. The quan-
titative analyses have been carried out after separation on
a LiChrosorb-Diol column using the non-polar solvent n-
hexane as mobile phase and UV-detection at 254 nm. The
developed HPLC procedure possesses a high sensitivity and
high speed of analysis, especially for xanthates with longer
alkyl chains. This method was applied to the determination
of xanthates in technical flotation liquors. Relative standard
deviations for contents of 0.6 x 10 -5 tool/1 to 1.2 x 10 -5 tool/1
were 2.76 to 5.45%. The absolute limit of determination for
potassium octyl xanthate is 0.2 ng.
Introduction
Since the xanthates have been aplied in 1925 by Keller [1]
for mineral processing, alkyl xanthates have been widely
used as collectors in the froth flotation of minerals. Recently,
separation and determination of individual components in
xanthate mixtures have become especially necessary in the
study of the adsorption mechanisms of surfactants on mi-
ineral surfaces and the optimization of processing. A number
of methods that have been proposed and applied to the
determination of xanthates include gravimetric [2],
titrimetric [3], electrochemical [ 4 - 6 ] and spectrometric [7]
methods. However, these methods are suitable only for the
determination of total xanthates. HPLC methods developed
by Hasty et al. [8-10] have not been more widely investi-
gated due to the formation of complicated dixanthogens.
Recently, two reversed-phase-HPLC methods [11, 12]
have been suggested for the separation and determination
of xanthates in xanthate mixtures. Although the limits of
detection of these methods are as low as 3.1 • 10-8 mol/1 and
1.6 • 10 * mol/1, respectively, in some applications an even
greater sensitivity is necessary. In this paper, a normal-phase-
HPLC method in combination with UV-detection with
acceptably determination limits of xanthates is described.
Offprint requests to. G. Schwedt
@ Springer-Verlag 1990
Experimental
Chemicals and instrumentation
The purification of xanthates was accomplished by the
method used in a previous study [11]. n-Hexane used as the
eluent was of HPLC grade (Riedel-deHafin AG) and was
degassed immediately before use. Methanol (HPLC grade,
Merck) and distilled water were filtered (0.45 ~tm Millipore
Filter) before use.
All HPLC experiments were performed by means of
the following apparatus: HPLC pump, series 400; UV
spectrophotometer, LC-85B; integrator, LC-100 Laboratory
(all apparatus described above were purchased from Perkin-
Elmer). Chromatographic column, LiChrosorb-Diol (5 pro),
250 x 4.6 m m (Merck).
Procedure
All calibration solutions of xanthates were freshly prepared
with a methanol-water mixture (80: 20). Immediately before
injecting the sample or the calibration sample into the chro-
matographic system, the corresponding dixanthogen was
prepared by oxidizing the xanthate by dropwise addition of
potassium iodine until the triiodide solution (consisting of
0.01tool/1 iodine in 0.2tool/1 potassium iodide) colour
persisted. The dixanthogen was extracted from the aqueous
solution by n-hexane, and a fixed volume of this organic
solution containing dixanthogen was immediately injected
into the HPLC-column. The mobile phase used was
n-hexane. The determinations were accomplished at a wave-
length of 254 nm, with quantification by the LC-100 in-
tegrator.
Results and discussion
Selection of the chromatographic system
It was confirmed that the reversed-phase-HPLC on a C18-
column with water-methanol mixtures as mobile phases
could be successfully applied for the separation of
dixanthogens with different alkyl chains [11, 12]. A detection
limit of 2 ng for diethyl dixanthogen was obtained when
 909

3OO 100 ~1 of the sample solution were injected into the HPLC-
system in a previous study. However, this limit of detection
g is not sufficient for the study of adsorption mechanism in
.M
flotation and for environmental analysis. In addition, the
height of a chromatographic peak is variable with the pro-
-.~ 200 portion of water and methanol in the mobile phase (Fig. 1).
A normal-phase-HPLC system with LiChrosorb-Diol as a
stationary phase was selected in this work. n-Hexane was
used as mobile phase. This HPLC-system cannot only in-
I00 , , , ~ ' / . /. / crease the limit of detection by nearly one order or
magnitude (0.2 ng for diethyl dixanthogen), but also avoids
the instability caused by a change of the proportions of water
and methanol.
i I i • i . . . . i . . . . i . . . . i . . . . i . . . . A chromatogram of the mixture of six dixanthogens
70 75 80 85 90 95 I00
CH30H in H2O [ v % )
is shown in Fig. 2. These dixanthogens are the oxidation
products of a xanthate mixture consisting of sodium ethyl
Fig. 1. Dependence of peak height of xanthates on methanol-water- xanthate, sodium isopropyl xanthate and potassium octyl
ratio. Column HS-5 Ct8, 150x4.6 mm (5 gm); Mobile phase: xanthate. This chromatogram shows a good separation
methanol:water 90:t0 (V/V), t.0 ml/min; UV 240 nm; Concentra- efficiency and a high speed of analysis. When the reversed-
tion of each xanthate 0.20 mmol/1 (A Na-etx, [] Na-ipx, © K-ipx) phase-HPLC is used for this purpose, the separation of the

I 2

i i i i i i

t~ (min) tR (min) tR (rain) tR (min)

Fig. 2. C h r o m a t o g r a m of a xanthate mixture by normal-phase-HPLC. Column: LiChrosorb-Diol 250 x 4.6 m m (5 gm); Mobile phase: n-
hexane; U V 254 nm; 0.6 ml/min. Ocx 0.70x 10 .5 mol/1, Ipx 0.70x 10 s tool/l, Etx 0.11 x 10 s mol/1. 1 (ocx)z; 2 Ipx-Ocx; 3 Etx-Ocx; 4
(Ipx)2; 5 Etx-Ipx; 6 (Etx)2

Fig. 3. C h r o m a t o g r a m of three symmetric dixanthogens. Conditions as Fig. 2. K-ocx 1.21 x 10 -6 tool/l, Na-ipx 2.10 x 10 6 tool/l, Na-etx
2.50 × 10 -6 mol/1; 1 (Ocx)2; 2 (Ipx)2; 3 (Etx)2

Fig. 4. C h r o m a t o g r a m for the determination of Na-etx and Na-ipx in solution before floating Pb,Zn-sulfide ore. Conditions as Fig. 2.
Results: Na-etx 1.03 x 10 -5 mol/1, Na-ipx 0.85 x 10 - s mol/1. 1 (Ipx)2; 2 Ipx-Etx; 3 (Etx)

Fig. 5. C h r o m a t o g r a m for the determination of Na-etx and K-amx in solution after floating Cu,Pb,Zn-sulfide ore. Conditions as Fig. 2.
Results : Na-etx 2.35 × 10- 6 tool/I, K-amx 0.45 x 10 6 mol/1.1 (Amx); 2 Amx-Etx; 3 (Etx)2
910

Table 1. Retention parameter as a function of C-atoms Table 3. Determination of simulation samples and F-test

Dixanthogen Number of CtR (min) K' Component det. Na-ipx K-amx

atoms Anal. method
A B A B
Etx- Etx 4 7.20 8.18
Etx- Ipx 5 6.86 7.59 Results
Etx- Ibx 6 6.62 7.52 ( x 10- 5 tool/l) 1.23 1.25 0.61 0.58
I p x - Ipx 6 6.52 7.41 1.20 1.25 0.65 0.63
Ipx-Ibx 7 6.31 7.17 1.27 1.21 0.59 0.57
Ibx-Ibx 8 6.14 6.98 1.19 1.16 0.59 0.63
Etx- Ocx 10 6.24 7.09 1.17 1.20 0.64 0.61
Amx - Amx 10 6.18 7.02 1.24 1.24 0.60 0.57
I p x - Ocx 11 6.00 6.82 1.25 1.23 0.60 0.65
Ocx - Ocx 16 5.57 6.33 1.18 1.21 0.67 0.62
1.22 1.17 0.63 0.65
1.25 1.20 0.66 0.66
Table 2. Detection limits of a few dixanthogens Mean value (X) 1.220 1.212 0.624 0.617
Standard dev. (S) 0.03367 0.03120 0 . 0 2 9 8 9 0.03367
Compound log e (at 254 nm) Detection limit (ng) s/x (%) 2.76 2.57 4.79 5.45
Fexpt. 1.16 1.27
(CH3OCS2) 2 4.25 0.41 Fo.lo/2(9,9) 3.18 3./8
(C2H50CS2)2 4.31 0.38
(C3H70C82)2 4.33 0.38 Na-ipx: Sodium isopropyl xanthate; K-amx: Potassium amy1
(C4H90C82) 2 4.40 0.35 xanthate A: Normal-phase-HPLC; B: reversed-phase-HPLC:
(CsH11OCSz)2 4.40 0.31 column RP18, 150 x 4.6 mm (5 ~tm); methanol: water 90 : 10 (V/V);
(C8H170C82)2 4.45 0.20 UV 240 nm; 1.0 ml/min [11, 12]

six dixanthogens, as shown above, takes at least 20 min.
Because dixanthogens have larger solubility and good
stability in n-hexane, they can be rapidly eluted from the
chromatographic column. This is the basis for increasing the
sensitivity by this normal-phase-HPLC method.
HPLC-behaviour of dixanthogen
Since a direct HPLC-determination of xanthate is difficult
to achieve, the oxidation of xanthate to dixanthogen was
applied in this work. The separation of dixanthogen
compounds was approached by taking advantage of the
differences in the hydrophobic moiety of the molecules.
Namely, the separation of these species depends on the
number of carbon atoms of the alkyl groups in dixanthogen
molecules. The experiments show that the retention o f these
compounds can be described as a function of chain length
of the alkyl groups in the dixanthogen molecules (Table 1).
Table 1 shows a linear relationship between the retention
parameter (K') and the number of carbon atoms for a given
homologous series. These results give a corresponding re-
gression equation with a correlation coefficient of 0.9252,
an intersection of 8.29 and a slope of -0.13.
From Table 1 it was found that the retention is related
to the total number of carbon atoms for both chains and
the values of the retention parameter K' decrease with an
increase in the number of carbon atoms of the alkyl groups in
the dixanthogen molecules. This is contrary to the reversed-
phase-HPLC with the stationary phase RPI 8 and the system
water-methanol as the mobile phase.
The reason is obvious. In reversed-phase-HPLC, the
mobile phase is polar, the dixanthogens with shorter chains
of carbon atoms, and therefore with stronger polarity, were
eluted earlier from the column than those with longer chains.
In the normal-phase-HPLC method developed here the
mobile phase is a non-polar solvent (n-hexane). The
dixanthogens with longer chains of carbon atoms (with
weaker polarity) show increased solubility in this solvent.
Consequently, they are eluted earlier from the column than
those with shorter chains. The elution time of dioctyl
dixanthogen of 20 rain results in a weak signal in reversed-
phase-HPLC. In this work elution takes only 6 rain even at
a slow flow rate (0.6 tool/l). This is also a considerable
advantage of this method.
Quantitative analysis
When a mixture of xanthates is oxidized, symmetrical and
asymmetrical dixanthogens are formed simultaneously. The
asymmetrical compounds would also be formed even after
mixing several kind of symmetrical dixanthogens. Figure 3
shows a chromatogram of a mixture of three symmetrical
dixanthogens (diethyl-, diisopropyl- and dioctyldixantho-
gen) chromatographed immediately after mixing. The
chromatogram with six peaks shown in Fig. 2 was obtained
after mixing. The new peaks correspond to three
asymmetrical compounds: ethyl-isopropyl-, ethyl-octyl- and
isopropyl-octyl dixanthogen, respectively.
The qualitative and quantitative analysis of xanthate
by means of the oxidation method are complicated by the
formation of the asymmetrical dixanthogens. Because the
ratio between symmetrical and asymmetrical dixanthogens
in a given reaction mixture is continually changing and be-
cause the equilibration of the mixtures takes a long time,
the determination of xanthate in these mixtures only by
symmetrical or only by asymmetrical dixanthogens is impos-
sible.
The evaluation and calculation of analytical results of
xanthates [11, 12] was employed in this work.
The analysis of the mixture shown in Fig. 2 is taken as
an example for the calculation. The general formula of the
 911

Table 4. Comparison of the determination of xanthates in Pb. Zn-ore flotation solution

Sample group No. 1

Component det.
Anal. method Etx Ipx Ocx Ipx Amx

A B dev. A B dev. A B dev. A B dev. A B dev.

1 2.51 2.44 -0.07 1.23 1.15 -0.08 1.14 1.23 0.09 2.03 2.08 0.05 1.16 1.10 -0.06
2 2.62 2.65 0.03 1.30 1.36 0.06 1.10 1.03 -0.07 2.01 2.06 0.05 1.14 1.10 -0.04
3 2.08 2.04 -0.04 1.17 1.19 0.02 0.87 0.81 -0.06 1.78 1.72 -0.06 0.94 0.98 0.04
4 2.05 2.07 0.02 1.04 1.01 -0.03 0.76 0.71 -0.05 1.62 1.64 0.02 0.99 0.97 -0.02
Results 5 155 1.59 0.04 1.07 1.08 0.01 0.72 0.75 0.03 1.45 1.49 0.04 0.70 0.75 0.05
( × 10- s mol/1) 6 1.63 1.68 0.05 0.89 0.93 0.04 0.58 0.53 -0.05 1.50 1.44 -0.06 0.73 0.73 0
7 1.21 /.28 0.07 0.72 0.70 -0.02 0.58 0.61 0.03 1.06 1.01 -0.05 0.55 0.59 0.04
8 1.05 1.04 -0.01 0.64 0.59 -0.05 0.45 0.50 0.05 0.80 0.79 -0.01 0.44 0.40 -0.04
9 0.80 0.76 -0.04 0.51 0.47 -0.04 0.32 0.34 0.02 0.64 0.67 0.03 0.31 0.34 0.03
10 0.85 0.83 -0.02 0.35 0.38 0.03 0.21 0.18 -0.03 0.51 0.56 0.05 0.25 0.27 0.02

d 0.003 - 0.006 - 0.004 0.006 0.003

Sd 0.015 0.014 0.018 0.014 0.013
texpt. 0.63 1.36 0.70 1.36 0.73
To.05,9 2.26 2.26 2.26 2.26 2.26

d: Mean value of the deviation

etx: ethyl xanthate; ipx: isopropyl xanthate; ocx: octyl xanthate; amx: amy1 xanthate

calibration equation of various c o m p o u n d s can be described
as follows:
h=a+bc
where h, a, b and c represent the peak height, intersection,
slope and concentration, respectively. The determination of
the three xanthates can be calculated by the following
formulas:
Cocx = 2 / b l ( h l - a l ) + 1/bz(h2-a2) + l/b3(h3-a3)
C,px = 2 / b ~ ( h 4 - a 4 ) + l / b z ( h z - a 2 ) + l / b s ( h 5 - a s )
CEtx = 2 / b 6 ( h 6 - a 6 ) + l / b 3 ( h 3 - a 3 ) + l / b s ( h s - a s )
Some experimental results of practical samples are
compiled in Table 4 (A). The resulting chromatograms are
shown in Figs. 4 and 5. The results obtained by reversed-
phase-HPLC using a C 18 column with methanol-water as a
mobile phase are compared in Table 4 (B). The t-test results
of both these methods are given in Table 4, too. These data
show no significant difference and no systematic error be-
tween the methods. Therefore, the newly developed HPLC-
method is reliable for the determination of individual
xanthates in the mixtures.
This normal-phase-HPLC method is especially suitable
for the separation and determination of xanthates with
longer alkyl chains.

The calibration curves used for various symmetrical and

asymmetrical dixanthogens were all linear (r = 0.9910 to References
0.9955) in the concentration range from 1 . 5 x 1 0 - s to
1. Keller CH (1925) US Patent 1,554, 216
1.0 x 10 - 4 mol/1. The detection limits were obtained for six 2. Majumdar KK (1952) J Scient Ind Res 11B:260
symmetrical dixanthogens, as shown in Table 2. The limits of 3. Verma KK, Bose S (1975) Fresenius Z Anal Chem 274:126
detection increase slightly with increasing n u m b e r of carbon 4. Oktawiec M (1966) Bergakademie 18:239 (CA 65:1836)
atoms of the alkyl groups in the compound. 5. Maurice MJ (1956) Anal Chim Acta 14:583
6. Bond AM, Sztajer Z, Winter G (1976) Anal Chim Acta 84:37
7. Pomianousski A, Leja J (1963) Can J Chem 41:2219
Applications 8. Hasty RA (1976) Analyst 101:828
The above described normal-phase-HPLC method was 9. Hasty RA (1977) Analyst 102:519
I0. Eckhardt JG, Stezenbach K, Burke MF, Moyers JL (1978) J
applied to determine xanthates in technical flotation liquors.
Chromatogr Sci 16:510
Table 3 gives a group of analytical results of simulation 11. Zhou C (1989) Dissertation TU Clausthal
samples of the flotation liquors and corresponding F-test 12. Zhou C, Bahr A, Schwedt G (1989) Fresenius Z Anal Chem
data. Deviations were 2 . 7 6 - 5 . 4 5 % . It is confirmed from 334:527
this table that the normal-phase-HPLC method agrees with
the reversed-phase-HPLC method examined. Received June 21, 1990