(Key laboratory of analytical science and technology of Hebei province, College of Chemistry and Environmental Science, Hebei University, Baoding, 071002, China) Received Aug. 21, 2002. Abstract Based on the reversed phase ion-pair chromatography, the retention behaviour of thiourea, polysulfide, ammonium sulfide and ammonium thiocyanate were discussed under different conditions such as ion pair reagent and its concentration, ion intensity and organic reagent. It was testified that the concentration of ion pair reagent, pH and the volume ratio of tetramethylene-oxide in mobile phase played important roles in the retention behavior of ammonium sulfide and ammonium thiocyanate. The best analytical results were obtained by using a C18 column with a mobile phase comprising a 20:79:1 (% v/v) mixture of methanol-water-tetramethylene-oxide, pH 6.64, containing 3.0 mmolL-1 ammonium tetrabutyl bromide and 6 mmolL-1 KH2PO4-K2HPO4 buffer. Column temperature and detection wave were controlled at 25 ºC and 220nm, respectively. Linearity of the working curve was investigated with correlation coefficients of 0.9989-0.9999, and the relative standard deviation was below 4.9%. The proposed method had been successfully used in the samples determination.Keywords Reversed phase ion-pair chromatography, thiourea, polysulfide, ammonium sulfide, ammonium thiocyanate,retention behavior 1 INTRODUCTION Ammonium thiocyanate and thiourea were two kinds of important chemicals and medicine materials[1,2]. And the conventional production process to obtain them were[3,4] : CS2 + 2NH3 £½ NH4SCN + H2S [1] NH4SCN £½ NH2CSNH2 [2] The reaction [1] was often accompanied with a secondary reaction [3], which provided a by-product of polysulfied (NH4)2CS3. (NH4)2CS3 could be changed into ammonium thiocyanate described as equation [4] when heated[5]. 2NH3 + H2S + CS2 £½ (NH4)2CS3 [3] (NH4)2CS3 £½ NH4SCN + H2S [4] In the preparation of ammonium thiocyanate, the mixture of ammonium thiocyanate, ammonium sulfide, and polysulfide was often gained, and when thiourea was prepared through isomerization of ammonium thiocyanate, the mixture of thiourea and ammonium thiocyanate was obtained. So the development of the qualitative and quantitative method for simultaneous determination of the components would provide a powerful means for their kinetics and mechanism study. In the previous work, Pertunina gave the titrimetric method for the detection of NH4SCN, (NH4)2S, NH3 and H2S step by step[6]. While Berestetskii reported a potentiometric titration of S2-, SCN- and S2O32- using a carbon indicator electrode[7]. NH2CSNH2 was usually detected by its UV absorption spectrometry[8]. But none of these methods could be directly used for the simultaneous determination of the four components. Reversed ion pair HPLC had been well used in the determination of organic acid, heterpolyacid, inorganic compounds and specific analysis[9-12]. But it had not been employed in the determination of NH4SCN, (NH4)2S, (NH4)2CS3 and NH2CSNH2 at the same time. In this paper, the reversed phase ion pair chromatography method was developed and used for the simultaneous and direct determination of the four components. The optimal separation condition was obtained through the study of retention behavior of the components under different conditions. The method had been successfully used in the samples detection. 2 EXPERIMENTAL Ammonium sulfide was guarantee reagent (Tianjin, China). Polysulfide was prepared with carbon disulfide and ammonium sulfide according to the reference[13]. The yield of polysulfide was calculated according to the amount of carbon disulfide. All the reagents and solvents used were analytical grade. 3 RESULTS AND DISSCUSSION The pH value of mobile phase had no effect on thiourea and polysulfide, but in order to keep ammonium of thiocyanic acid and hydrogen sulfide in ionic state, it should be controlled at above 6.0. With the increasing of pH from 6.10 to 7.17, the retention times of the ammonium thiocyanate and ammonium sulfide decreased, the results were shown as Fig. 2. This might be caused by the increasing of negative charge of phosphate, which promoted the complexing of phosphate with TBA, then decreased the complexing of TBA with thiocyanate and sulfide[11,14]. In the separation of the four components, pH played an important role.
3.3 The influence of organic reagents
on the retention behavior 3.5 Optimization of the mobile phase With the modification of the TBA concentration, pH, ion intensity, the volume ratio of water, methanol and tetramethylene-oxide, the optimal separation conditions were gained through uniform design experiment U7 (76) provided by Fang[15]. The mobile phase was 20:79:1 of methanol-water-tetramethylene-oxide, containing 3.0 mmolL-1 TBA and 6 mmolL-1 KH2PO4-K2HPO4 buffer solution with pH 6.64. Under the proposed condition, the flow rate and column temperature were controlled at 1ml/min and 25ºC, respectively, the chromatogram of NH2CSNH2 (I), (NH4)2CS3 (II), (NH4)2S (III) and NH4SCN (IV) was obtained as Fig. 3. 3.6 The detection of linearity and recoveries The relation between the peak area and the mass of the four components was examined. The linearity regression equations along with linearity ranges and correlation coefficients for determination of the four components are given in Table 1. The calibration curve was linear for the four components with correlation coefficients of 0.9989-0.9999. A series of mixtures of the four components with different mole ratio, were determined, and the recoveries for the four components were examined. The results with relative standard deviation (RSD) were listed in Table 2. Recoveries and relative standard deviations were in the range of 94.0-106.0% and 0.76-4.9%, respectively, for the four components. Table 1. The regression equation and linear scopes
Y: area of peak, X: the mass of composition ( mg) Table 2. Recoveries of NH2CSNH2 (I), (NH4)2CS3 (II), (NH4)2S (III), NH4SCN (IV)
Fig. 4 The chromatogram of (NH4)2CS3, (NH4)2S and NH4SCN detected in synthesis mixture ¡¡
3.7 Sample analysis
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