Vol 1 Ne. 1 TRANSACTIONS OF NFsoc THE SEPARATION AND DETERMINATION OF XANTHATES USING HIGH PERFORMANCE LIQUID CHROMATOGRAPHY” Zhou Chunshan® Central South University of Technology, Changsha 410083, China Bahr Albert”, Schwedt Georg® Technical University of Clausthal, Clausthat-Zellerfeld, Germany ABSTRACT Three HPLC methods for the separation and determination of xanthate mixtures are described. The chromatographic behaviour , advantages and application ranges of various: methods have been discussed in etail. A calculation method for determining the results of individual xanthates from the complicated chromatographic peaks of xanthate mixtures is presented. The limits of detection are 0.15—2.0ng, Key words: 1 INTRODUCTION Xanthates are generally prepared by the reaction of a sodium or potassium alkoxide so- lution with carbon disulfidel"!. Since the intro- duction of alkyl xanthates in mineral flotation in 1925 by Keller!Ithey have been widely used for the flotation of sulfide minerals!*!. Recent- ly, the xanthates and related compounds have also been used in such fields as cellulose syn- thesis, pesticide manufacturing, engine oil additives, production of fireproofing agents and corrosion inhibitors. Because of the widespread application of xanthates, their separation and determination in mixtures are of great importance. Numer- 5), titrime- » potentiometric! ®!, ‘ous methods, including gravimetrio 67, conductometric! polarographic! "! and spectrometric! '" proce- dures have been proposed. These methods are tric! lanuscript received November 3, 1990 @Dr:s Professor xanthate, dixanthogen, collector, liquid chromatography suitable for the determination of the sum of xanthates, but not for the identification and determination of individual xanthates in mix- tures, because they are all based on the fune- tional group of dithiocarbonates, without con- sidering the difference of alkyl groups. Has- ty!?“Ifirst applied HPLC to the determination of xanthates. The xanthates are first oxidized to dixanthogens and then injected into the chromatographic system. With this method, the xanthates of various alkyl chains can be identified. However, the preparation of the dixanthogens from xanthate mixtures is com- plicated and a suitable method for calculating analytical results has not been found yet. Additionally, the extension of this method is limited by the low solubility of dixanthogens and by the excess injecton of oxidizing agents that shorten the life of the chromatographic column.+ 90° TRANSACTIONS OF NFsoc October 199) ‘Three HPLC methods which are suitable for the identification and determination of in- dividual xanthates in mixtures are described in this paper. They are : A, Reversed-phase chromatography by oxidation before the column; B, Reversed-phase chromatography by complexation before the column: C, Normakphase chromatography by oxidation before the column. Some of these methods are developed on the basis of our previous work". 2 EXPERIMENTAL Instrumentation, Following apparatus were used: LC pump, Series 400; UV spectro- photometer, LC—85B: Integrator, LC— 100 Laboratory; Column for methods A, B, HS— 5, C18Spm), 4.6% 150mm; Column for meth- od C, LiChrosorb-Diol (Sm), 4.6 x 250mm. Reagents; Standard-reagents of xanthates were prepared from raw xanthates (indu- strial-reagent grade) by the method described in the reference!'*!, The other reagents were of analytical grade. The solvents used as mobile phase were of HPLC grade and degassed be- fore use. Procedure: Method A: Xanthates were dissolved in water, and then oxidized by 0.01 mol / I iodine solution in 0.20 mol /1 potas- sium iodide. Dixanthogens formed were ex- tracted by n-hexane. Six yl of this extraction solution was injected into the HPLC-system (stationary phase RP18). A solution of me- thanol and water (90:10) was used as mobile phase. The determination was accomplished at a wavelength of 240 nm by the UV detector. Method B: Xanthates were dissolved in a ‘methanol-water solution (80:20), into which an excess of copper subchloride powder was added. The solution was fully stirred until completion of the complex reaction of Cu(1)— xanthates. The solutions of these compounds were filtered (0.45m millipore filter) before use. A 6-solution sample was injected into the chromatographic system (stationry phase RP 18). The mobile phase was a methanol. water (90:10)solution which contained 0.1% hydroxylammomium chloride. The wavelength of UV detector was set permanently at 301nm. Method C; The stationary phase was LiChrosorb-Diol and n-hexane was used as mobile phase. The rest procedure followed method A. 3 RESULTS AND DISCUSSION 3.1 Derivation before the Column and Selec- tion of Chromatographic System Since the xanthates have strong polarity, their adsorption and separation in the HPLC system become difficult, and a direct chroma- tographic determination has not been reported thus far. In this work, xanthates were oxidized to dixanthogens (methods A,C)and made into metal complexes (method B), respectively. ROO COR Sus, or Bee ek ss ROGS Gut ) SCOR s s RO ceo S| Ss In these molecules, the xanthate charge is screened partially, the polarity weakened, and the hydrophobicity increased. So, these mole- cules have a moderate adsorption at some common stationary phases, e. g. RP 18 andVol. 1 Ne. 1 Separation & Determrination of Xanthates <9 Diol. Furthermore, the difference of carbon atom numbers between the molecules increases owing to the increment of molecule groups; so chromatographic separation becomes easier. An oxidation of iodine was applied in method A. Dixanthogens were extracted with n-hexane. A higher chromatographic sensitivi- ty and a better distination were both obtained (Fig. 1). a a ene ter min Chromatogram of a xanthate mixture by method A. determining conditions, UV, 240 nm; column HS-S C18, 150% 4.6 mm (Sum); mobile phase, methanol: water 90 10; flow rate 1.0m / min: concentration of xanthates before oxidation in 10™?mol / 1, Na~Etx (sodium ethyl nanthate) 0.6, Nicipx(odium isopropyl xanthate) 0.7, K—Ibx(potassium isobutyl xanthate) 0.8 1-),) | 2B te-Ipi 4-Bvcpxi S—Ipxclbx: 3Utpx)s bv), Since the xanthate radical forms very sta- ble complexes with the elememts which have an affinity for sulfur. e.g.ions of heavy metals (Cu), both dixanthogens and complexes of metal-xanthates formed while the flotation so- lutions of heavy metals minerals’ (e. g. copper sulfide ore) were determined by method A. Consequently, the chromatogrphic separation and determination can not be carried out ow- ing to the formation of complicated peaks. To overcome this difficulty, a procedure of tom- plex Cu(1)xanthates (méthod B) was devel- oped. After derivation only one kind of com- plex Cu(1)-xanthates was formed. In addition to the Cu(I)-complexes, other metal com- plexes have been also investigated. The experi- showed that Cu(I)-complexes are better. Fig.2 describes a chromatogram of six ments complexes from three xanthates and Cu(). Thus it can be seen that method B has shorter retention time and maintains better distinc- tion tay min Fig.2 Chromatogram of a xamthate mixture by method B wavelength 301 om, conditions as method A: Concentra- tion of xanthates before complexation(10™mol / 1); Na~Etx 0.50, Na—Ipx 0.70, K—Ibx 0.60 IE W),Cur Baw 4-Ete-Curlba; §—ipx-Cu-tbx 3—UIps),Cu: 6—(lbw),Cu Usually, a detection limit of 2 ng was at- tained by mehtods A and B, but in some cases, e.g. in the study of the mechanism of mineral flotation and in environmental analysis q low- er detection limit is desirable. Besides, the re- tention times of xanthates with more than six alkyl carbon atoms are usually over 30 min. It is evident that the period is too long. These two problems can be resolved if the chro- matographic system of method C is applied (Fig.3),9 TRANSACTIONS OF NFsoc October 199) 3.2. Chromatographic Behaviour The retention time sequences of xanthate derivatives in both systems are the opposite (Tablé.1). The flow rate of reversed-phase chromatography is 1.0ml/ min, and the flow rate of normal phase chromatography is 0.6ml / min. ‘Table 1 Chromatographic system and retention time Form of Number of ‘Reiention time min) anata aa Method A Method B Method C Etx-Ex 4 4.00 3.81 ae Etipx s 4a 4.16 6.86 Tpx-Ipx 6 491 4.60 652 Euclbx 6 Sal 5.09 662 Ipx-Tbx 7 6.09 sm 631 Tox-Ibx 8 in 7.14 64 ‘Amx—Amx 10 6.18 Ets-Ocx 10 624 Ipx-Oez u 6.00 Oex-Oex 16 551 * Form of Cu(1)-xanthate-complexes: Etx—Cu-Etx, Etx—Cu-Ipx: The reason for the difference of retention ¥¢=1.3578-0.1197X re=0.9279 time is that the stationary phase ii reversed -phase chromatography (RP18) is non- polar, while the mobile phase is polar. Thus the deri- vatives of xanthtes with shorter alkyb chains (with stronger polarity) were eluated earlier from the column and those with longer chains (with weaker polarity) were eluated later. In normal-phase chromatography the stationary phase is polar (Diol) and the mobile phase is non-polar solvent (n-hexane). According to the principle of* like dissolve like” the derivatives of longer alkyl chains carbon atoms (with weaker polarity)are eluated earlier but those with shorter chains are eluated later. Therefore, the retention times of xanthate derivatives can be regarded as a function of the number of carbon atoms. The following three lineal regression formulas and their correlation coefficient were obtained from the data in Table I: ¥,=0.0410+0.9110X Yq=0.1590+0.8210X 7.=0.9595 750.9589 when a mixture of xanthates is oxidized, there exists a strong tendency for the forma- tion of asymmetrical dixanthogens. Thus the acquired chromatograms are not only chro- matographic peaks with symmetrical chains of carbon atoms, but also those with asymme- trical chains formed from different xanthates. The peaks 2, 4, 5 in Fig.1 and 2, 3, 5 in Fig.3 belong to the chromatographic peaks with asymmetrical chairs. When a few symmetrical ixanthogens or symmetrical complexes of Cu(1)-xanthates were immediately injected in- to the HPLC-system after mixing, a chroma- togram with only symmetrical peaks, as shown in Fig.4, can be observed first, but a few hours later part of these symmetrical derivatives would be automatically transformed into asymmetrical ones (Fig. 1-3). This is because xanthate groups with shorter chains of carbon atoms form easily asymmetrical dixanthogens or Cu-complexes with longer chains of xan- thate groups. These asymmetrical derivativesVol. Pox. 1 ‘Separation & Determrination of Xanthates 98 dissolve with more difficulty in.water and is stabler than the symmetrical derivatives with shorter chains. Bx Suajoiects Sag? yy min Fig.3 Chromatogram of a xanthate mixture by method C Conditions; Column, LiChrosorb-Diol, 250x 4.6mm (Summ); mobile phase, n—hexane; 0. 6ml / min; 254 nm. con- centration of xanthates (10"‘mol/ I); K-Oex (potassium ‘octy] xanthate)0.30; Na~Etx 0.30. 1 @cx);s 2 Ipx-Ocx; 3. Etx-Ocxs 4 pws 5 Euclpx; 6 (Ew), 3.3. Calculation of Analytical Results The chromatograms of either dixantho- gens or metal complexes would be complicated because of the formation of asymmetrical compounds. Furthermore, the heights (area) of peaks in the determination of the same mix- ture were changed by the undulation of deter- mination condition. It is quite evident that the analytical results calculated on only symmetri- cal or asymmetrical compounds are not accu- rate. In our study, a weighted addition for the calibration and calculation was proposed. The calibration curves of symmetrical peaks were plotted as in common analysis, and asymmet- rical peaks were calibrated by* subtraction” . The calibration formula of various peaks is as follows: =atbe where h, a, b and c represent the peak height, intersection, slope and the concentra- tion of substances to be determined. 3 3 5 - 9 ty» min Fig” Chromatogram of symmetric dialkyl dixanthogens Method and conditions as methed A, concentration of xanthates (10~*mol / 1): Ne-Eix 040, Na-Ipx 040, K-tbx 0.50 1 (Eto; 2 lpn -3. be, Fig. 3 describes the chromatogram of a mixture consisting of three xantates, and indi- cates that each xanthate involves three peaks. ‘The concentration calculations are as follows: Copx=2/ by(hy-a,}#1 / by(hy-a.)H1 / b3(hyas) Cig =2/ b4lhy—agyt / bx(by-a,}41 / bs(hy-as)94 TRANSACTIONS OF NFsoc October 1991 Core =2/ blla—ag)+1 / bs(hy—ay)41 / ‘b<(he—as). on where the numbers at angles correspond to the numbers of chromatographic peaks. In all three chromatographic methods the calibration curves of symmetrical and asym- metrical compounds were linear in the concen- tration range from 1.5 10% to 1.0% 10 mol /1 (correlation coefficients: r= 0.9900 to 0.9951) c 3.4 Analytical Application ‘The detection limits of three methods are listed in Table 2, which shows that the detec- tion limits of methods A and B are very close but that of method C is ten times lower. The detection limit of xanthates with long alkyl chains is lower, which shows that method C has a higher sensitivity for alkyl xanthates with large molecular weight. ‘Table 2 Detection limits of xanthates ‘detection limits(ng) compound hee Na-Ete 20 38 025 NavIpx 22 41 0.22 K-Ibx 27 $4 0.22 K-Ame 31 59 0.21 K-Ocx 40 75 0.15 ‘Table3 Determination of xanthate mixtures and test of the identity and systematic error of various methods. came FT FOW Coiponenisd———Re-B tee Nasi har (10% mol / 1) 1.20 0.60 1.00 0.40 pablus Indians — eae ido ara ga TNTERSTNE TO ang 02 1.206 | 069 0662 610 1007 1.00 10M 04M 04N8 O01 ‘S (x10) 1006 529 693 890 5.73 667 4:90 6.77 8.27 449 468° 5.87 e 190 sg batho apg ha ae 130 is ln as Fre vas 1a us 131 Fas2 @.0) 3.18 Qo/ig ORS oom 0s 005 1s o.oas oom oom oomsors Fon one ass oor 0.069 Fos 6.) 3.32 T test of identity; Il test of systematic error Because there is as yet no practically feasi- ble HPLC method for determining xanthates, it is impossible to test these new developed methods with a known method. In order to confirm their reliability, these three methods have been examined by the analysis of synthe- tic mixtures and statistical tests. Part of the re- sults are compiled in Table 3. F-test was used as the identity test of various methods (a: 0.10). Exp» Ep-c and E,_¢ represent the F— values calculated from experimental results of methods A and B, B and C as well as A and C. The test of the systematic errors between vari- ous methods were also performed by F-test. Qc/fg in Table3 represents the estimated values of the variance between methods, while Qc/ fe represents that of the experimental ef- fect, fg and fy are the corresponding degree of freedom. It is obvious ‘{fiat F—values from the experiments are less than the corresponding critical F—values. Therefore, the methods A, B and C’can be regarded as the identity forVol. 1 ye 1 Separation & Determrination of Xanthates 95+ Tabled Determination of xanthates in solution of mineral flotation zample Tolu, of Cu sulfide ore solu, of Pb, Zn sulfide ore components Now K-Amx Ne-Ew K-Ibx method fea lianits dow aha Bava sya lh Tat 17123083 0s) oes SS LST Se 14814 —1.50 remit, FOL «(203-104-049 4B DAD 123 241.28 we 9.59 043064 031 030 031 O71 0.73 075 O68 O71 0.75 Cx10%mol/) 931, 0.30 031 0140140144 045 O41 0.38 «60.37 (0.39 0.28 029 028 01S 0.14 0.13040 038 037 034035037 3 Saas Wana tye min Fig.S Determination of Na-Etx and K-Amx in flotation sloution of lead-zine sulfide ore Method and conditions as method C results: 0.2310-¢mol / 1, K—Amx 0.39 10%mol / I{Etx)y, 2—Etx-Amx, 3—(Amx), Na-Etx the determination of xanthates, but the sys- tematic errors between them do not exist. These methods were developed for the study of adsorption mechanism of mineral processing and the optimization of processing technology. Consequently. the three methods mentioned above were examined using a large number of real samples Fig. 5. is chromato- gram of the flotation solution for lead-zine sulfide ore by method C. Part of the results are given in’ Table 4. The chromatogram and datum show that these three HPLC methods are suitable for the practical separation and determination of xanthates, and they agree with each other quite well. REFERENCES, 1 Schubert H. Aufbersitung fester minerlischer Robstoffe nd ed. VFR Dentscer Verlag. Leipzig: 1977. 21s-216 2 Keller CH. US Patent 1.544,216(1928) 3. Hu Weibai et af, Flotation, Metallurgical Industry Press, 1983, 35 4 Ruo$ Ret Soc Mining Engincers, 1963, Sep: 243 5 Majumdar K K. Sei ind Res 1952, 115,260 6 = Verma K K, et al. Fersenius Z Anal ‘Chem. 1975, 274: 12s 2 Srivata A.J Indian Chem Soc. 1975, 5 214 8 Oktawiee M. Chem Abst. 1966, 65,1836 9 Maurice M.J Anal Chim Acta. 1956 14, $83 10. Bond AM. er a. Anal Chim Acta, 1976, 84 37 11 Winter. tnorg Nucl Chem Lett 1975, 1h 113 12. Hasty R A, Analyst 1976, 101, 828 13. Hasty R A. Analyst. 1977, 102: 519 14. Zhow Chunshan, Disertation. TU Clnusthal. 1989 15. Being Insitute of Mining and Metallurgy. Analysis of organic flotation regents. Beings Metall Industry Press, 1987, 87