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Quantitative Analysis of Silicon Tetrachloride, Carbon Disulfide, and Dichloroethane Concentration by Raman Spectroscopy

Quantitative Analysis of Silicon Tetrachloride, Carbon Disulfide, and Dichloroethane... Hindawi Journal of Analytical Methods in Chemistry Volume 2023, Article ID 1894505, 11 pages https://doi.org/10.1155/2023/1894505 Research Article Quantitative Analysis of Silicon Tetrachloride, Carbon Disulfide, and Dichloroethane Concentration by Raman Spectroscopy 1,2 3 2 2 2 Xiaoyan Xiang , Yufeng Shao, Yanfang Wei, Wentang Xia, and Xiaoli Yuan College of Communication Engineering, Chongqing University, Chongqing 400040, China School of Metallurgical and Materials Engineering, Chongqing University of Science and Technology, Chongqing 401331, China College of Electronic and Information Engineering, Chongqing Tree Gorges University, Chongqing 404100, China Correspondence should be addressed to Xiaoyan Xiang; xxycsu@126.com Received 13 May 2022; Revised 2 July 2022; Accepted 26 October 2022; Published 16 February 2023 Academic Editor: Boryana M. Nikolova Damyanova Copyright © 2023 Xiaoyan Xiang et al. Tis is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Quantitative analysis of silicon tetrachloride, carbon disulfde, and dichloroethane concentrations to obtain vapor-liquid equilibrium data of the SiCl -CS and SiCl -C H Cl binary systems was established by Raman spectroscopy. Te cheap 4 2 4 2 4 2 glass sampling pipe was used as a carrier for Raman spectroscopy measurements. Te Raman peak height of the internal standard was used to remove interference factors such as sampling pipe diameter, temperature, laser power, and other efects from the instrument. Te peak height ratio between the Raman characteristic peak of the analyte and that of the internal standard was proportional to the analyte concentration. During the measuring process of vapor-liquid equilibrium data for the SiCl -C H Cl 4 2 4 2 binary system, the linear equation of y � 0.0068 + 0.75x with R of 0.9939 was used for the determination of SiCl concentration at −1 2 the 422 cm band. Te linear equation of y � 0.0019 + 0.2266x with R of 0.9966 was used for the determination of C H Cl 2 4 2 −1 2 concentration at the 754 cm band. For the SiCl -CS binary system, the linear equation of y � 0.0494 + 4.7535x with R of 0.9962 4 2 −1 2 was used for the determination of SiCl concentration at the 422 cm band. Te linear equation of y � 0.8139 + 8.7366x with R of −1 0.9973 was used for the determination of CS concentration at the 654 cm band. Te concentration of standard samples calculated by these standard curves was compared with the actual value to verify the accuracy of this method. Te reproducibility is good when determining silicon tetrachloride and dichloroethane concentrations for the SiCl -C H Cl binary system, with RSEP 4 2 4 2 values of 2.81% and 2.17%, respectively. Meanwhile, the RSEP values are 3.55% and 4.16%, respectively, when determining silicon tetrachloride and carbon disulfde concentrations for the SiCl -CS binary system. 4 2 made to extract SiCl from the liquid waste for a long time 1. Introduction [7–9]. Besides SiCl and TiCl , there are also a small amount 4 4 Titanium-containing liquid waste coming from the recti- of impurities in the liquid waste such as FeCl , MgCl , CS , 3 2 2 fying process is the major waste in the titanium metallurgy C H Cl , and so on. In order to extract purifed SiCl , these 2 4 2 4 industry. Generally speaking, the concentration of SiCl and impurities must be removed. Te method to obtain high- TiCl in the titanium-containing liquid waste is 15∼20% and grade SiCl includes adsorption, rectifcation, partial hy- 4 4 60∼70%, respectively [1]. Te liquid waste containing TiCl drolysis, and photochlorination [10–13]. Among all these and SiCl is a valuable resource, but it is hydrolyzed easily in methods, rectifcation may be the best way to extract purifed a moist environment, producing a large amount of HCl, SiCl from the liquid waste because no additional impurities which is a toxic gas [2–4]. Terefore, improper disposal of are introduced. Unfortunately, due to the little diference in titanium-containing liquid waste would lead to waste of SiCl and CS or C H Cl in boiling point, the rectifcation 4 2 2 4 2 resources and destruction of the eco-environment [5, 6]. process is energy-sucking. In order to reduce energy con- Resource utilization of the titanium-containing liquid waste sumption, the accurate vapor-liquid equilibrium data for the is always of great importance in China, and efort has been SiCl -CS and SiCl -C H Cl binary systems must be 4 2 4 2 4 2 2 Journal of Analytical Methods in Chemistry measured to optimize the design of the rectifying column. sample containing SiCl will be sealed before it was sub- During the measurement, the content of SiCl , CS , and mitted for Raman detecting according to our previous work 4 2 C H Cl in the sample must be analyzed to obtain accurate [31]. Te liquid sample stored in a sealed colorimetric tube 2 4 2 gas-liquid equilibrium data. was frst moved into a drying oven. Te colorimetric tube Generally, inorganic substances could be detected by was then opened, and a little glass sampling pipe was inductively coupled plasma-atomic emission spectrometry inserted into the colorimetric tube. After the liquid sample (ICP-AES) by dissolving in acid solution. Organic com- entered the little glass sampling pipe by capillary action, the pounds could be analyzed by gas or liquid chromatography little glass sampling pipe was taken out and moved to the and infrared (IR) spectroscopy [14–17]. However, these alcohol lamp. Te both ends of the glass sampling pipe were methods could not be used for simultaneous analysis of heated and melted to allow the liquid sample to get sealed in inorganic and organic compounds. Recently, quantitative it. Te preparation process is convenient, and the material is analysis of components in solution by Raman spectroscopy inexpensive. has been reported, and there are several advantages to using Raman spectra for quantitative analysis [18–22]. For ex- 2.3. Preparation of Standard Samples. SiCl , C H Cl , and ample, it is a nondestructive technology that is usually 4 2 4 2 CS were purchased from Coron Chemical Industry Co., applicable without any sample preparation process, which is Ltd. Tere is often little water remaining in the purchased convenient for online quantitative determination [23, 24]. C H Cl and CS , which may lead to the hydrolysis of SiCl . Tis analytical method may also be applied to samples 2 4 2 2 4 Hence, the purchased C H Cl and CS were dehydrated containing SiCl , CS , and C H Cl . Creighton and Sinclair 2 4 2 2 4 2 2 4 2 frst. Te dehydration process is also similar to our previous studied the Raman spectra of liquid SiCl and CS as early as 4 2 work [31], just with a diferent distillation temperature: 1973 [25], Gong studied the Raman scattering from liquid frstly, anhydrous calcium chloride (stored in a vacuum CS for diferent concentrations of benzene [26], and Stefen drying oven at 105 C for 24 h before use) and C H Cl or CS gave information about the 2D Raman response of liquid 2 4 2 2 were put into a desiccative conical fask with a stopper. Ten, CS [27]. Meanwhile, the spectral information of C H Cl 2 2 4 2 the mixture was magnetically stirred at room temperature could also be found in literature [28–30], but there is nearly for 12 h. Finally, the fltrate from the mixture was distilled at no study on the quantitative determination of CS , C H Cl , 2 2 4 2 ° ° certain temperature (90 C for C H Cl and 50 C for CS ), and SiCl in liquid samples by using Raman spectra. 2 4 2 2 and the distillate was collected for the preparation of Terefore, the purpose of the present study is to establish standard samples. In the measurement of vapor-liquid a rapid and accurate method to determine the concentration equilibrium data for the SiCl -CS and SiCl -C H Cl bi- of CS , C H Cl , and SiCl simultaneously in liquid samples. 4 2 4 2 4 2 2 2 4 2 4 nary systems, the concentrations of SiCl , CS , and C H Cl During the analysis procedure, the standard solutions with 4 2 2 4 2 in liquid samples should be analyzed simultaneously. Tus, internal standards were sealed in cheap glass capillaries for CS was used as an internal standard during the concen- the Raman spectrometer. Ten, the peak height ratio be- tration determination of SiCl and C H Cl for the SiCl - tween the Raman characteristic peak of the analyte and that 4 2 4 2 4 C H Cl binary system, while C H Cl was used as an in- of the internal standard was calculated to establish the 2 4 2 2 4 2 ternal standard during the concentration determination of calibration curves of CS , C H Cl , and SiCl . After that, the 2 2 4 2 4 SiCl and CS for the SiCl -CS binary system. Ten, the Raman spectrometries of standard samples were measured, 4 2 4 2 working standard solutions at several concentration levels of and the concentration of the analyte was calculated using the SiCl , C H Cl , and CS were prepared. standard curves to confrm the availability of this method. 4 2 4 2 2 2. Materials and Methods 2.4. Establishment of Calibration Curves. Working standard solutions with diferent concentrations of SiCl , C H Cl , 4 2 4 2 2.1. Raman Spectrometer. Raman spectrometry of all sam- and CS were prepared for Raman detecting. Te baselines of ples was detected by the LabRAM HR Evolution spec- the obtained Raman spectra were taken out by using Origin trometer, equipped with an Olympus BX41 microscope with 8.5 to avoid noise and fuorescence efects. After that, the a 10X objective lens (NA � 0.25), which was used for fo- characteristic peak heights of SiCl , C H Cl , and CS were 4 2 4 2 2 cusing the laser beam on the sample. A 532 nm Ar ion laser extracted from the revised Raman spectra, respectively. Te (Spectra Physics 2017) was used for excitation with power of peak height ratio between the Raman characteristic peak of ∼50 mW. Te back scattering light was passed into the analyte and the internal standard was subsequently a monochromator and detected with a charge coupled device calculated according to the following equation: (CCD) detector. Te Raman spectrum between 100 and −1 3200 cm was collected with an exposure time of 30 s and 2 I R � , (1) accumulations for each spectrum. where I is the Raman intensity of analyte and I is the A S 2.2. Sample Preparation for Raman Analysis. Te sample Raman intensity of internal standard. Te calibration curve containing SiCl is easily hydrolyzed to release HCl in the air, was generated by plotting the characteristic peak height ratio which is not convenient for Raman detecting. Terefore, the against the concentration of analytes. Journal of Analytical Methods in Chemistry 3 It can be seen from Figure 2(a) that the intensity of carbon 3. Results and Discussion −1 disulfde at 654 cm is not changed with the variation of 3.1. Raman Spectra of the Mixed Solution Containing SiCl , 4 silicon tetrachloride and dichloroethane concentration. Te C H Cl , and CS . In order to obtain the characteristic 2 4 2 2 slight increase or decrease in intensity may be due to the peaks of SiCl , C H Cl , and CS for quantitative analysis, 4 2 4 2 2 change in laser power. the Raman spectra of a mixed solution containing SiCl , 4 Te Raman spectra of standard solutions on the charac- −1 C H Cl , and CS are detected, as shown in Figure 1. 2 4 2 2 teristic peak of silicon tetrachloride at 422 and 480 cm are Figure 1(a) shows the full spectrum of the mixed solution presented in Figure 2(b). Te Raman spectra of standard so- −1 −1 from 200 cm to 3200 cm . Te full spectrum is partly lutions around the characteristic peak of dichloroethane at 754 −1 displayed in Figures 1(b) and 1(c) so that the charac- and 2968 cm are shown in Figures 2(c) and 2(d), respectively. teristic peaks of SiCl , C H Cl , and CS can be clearly 4 2 4 2 2 It can be seen from Figure 2(b) that the Raman intensity −1 observed. Figure 1(b) shows the spectrum of the mixed of silicon tetrachloride at 422 cm increases with the rising −1 −1 solution from 200 cm to 1000 cm band, and SiCl concentration in standard solutions, while the Raman −1 −1 Figure 1(c) shows the spectrum from 1000 cm to intensity of silicon tetrachloride at 480 cm is irregular with −1 1600 cm band. In order to rapidly and conveniently fnd the SiCl concentration. Tus, the characteristic peak of −1 the Raman band of SiCl , C H Cl , and CS , the details of 4 2 4 2 2 silicon tetrachloride at 480 cm is not suitable for quanti- the Raman peaks in Figure 1 are shown in Table 1. Te C-S tative analysis. In addition, although the Raman intensity of −1 vibrating mode of carbon disulfde [25] is found at the silicon tetrachloride at 422 cm increases with the increase −1 654 cm band in Figure 1(b), and the intensity reaches up in SiCl concentration, the linear relationship between to 5368. Two obvious bands with the maximum intensity Raman intensity and SiCl concentration is not good. It can −1 at 422 and 480 cm appeared, respectively, in Figure 1(b), be verifed from Figure 3 that the equation is which is attributed to the Si-Cl vibrating modes of silicon y � 32.74 + 23883.45x with R of 0.9719, where y and x de- tetrachloride [32]. Te vibrating mode of liquid di- note the Raman intensity and the mole fraction of silicon chloroethane is found in Figures 1(a)–1(c). Te band at tetrachloride, respectively. Tis indicates a bad linear re- −1 2968 cm shown in Figure 1(a) belongs to the symmet- lationship. Terefore, Raman absolute intensity cannot be rical stretching vibration of C-H . Te bands at 300 and 2 used to calculate the SiCl concentration accurately. −1 754 cm in Figure 1(b) are ascribed to deformation vi- bration of C-C-Cl and stretching vibration of C-Cl, re- −1 3.2.2. Standard Curves for the SiCl -C H Cl Binary System. 4 2 4 2 spectively [33]. Te peak at 1053 cm band in Figure 1(c) Generally, the Raman intensity of SiCl at characteristic peak is assigned to stretching vibration of C-C, and the peaks at −1 −1 (422 cm )indicated as I can be given by the following 1204, 1301, and 1431 cm band are due to the twisting equation [34]: vibration, wagging vibration, and scissoring vibration of C-H , respectively [33]. 2 I � K VC P , (2) A A A L In order to reduce the background noise interference, where C is the SiCl concentration, P is the density of laser a characteristic peak with high intensity should be used for A 4 L power, and K is the Raman signal constant of SiCl at quantitative analysis. Tus, the characteristic peak of di- A 4 −1 −1 422 cm , which can be afected by instrumental throughput chloroethane at 300, 1053, 1204, 1301, and 1431 cm with and the apparent Raman-scattering efciency. V is the weak intensity could be excluded during the analysis while volume of sample illuminated by the laser and viewed by the the characteristic bands of dichloroethane at 754 and −1 spectrometer. According to equation (2), the Raman in- 2968 cm with high intensity could be used for quantitative tensity of SiCl (I ) will change with the variation of K and analysis. Meanwhile, C-S vibrating mode of carbon disulfde 4 A A −1 P . Tere is often inevitable fuctuation of laser power, test at 654 cm band and Si-Cl vibrating modes of silicon tet- L −1 temperature, and instrument during the measurement of the rachloride at 422 and 480 cm band are clearly observed Raman spectrum. Tus, it is easy to understand the bad with high intensity. Terefore, these characteristic bands linearity between the Raman intensity and the mole fraction may be used for quantitative determination. of SiCl . In order to remove the efect of laser power, test temperature, and instrument, the characteristic peak height ratio was introduced: 3.2. Standard Curves for the SiCl -C H Cl Binary System 4 2 4 2 K VC P K C A A L A A R � � � kC , (3) A A 3.2.1. Raman Spectra of the Standard Solutions for the SiCl - K VC P K C IS IS L IS IS C H Cl Binary System. In order to obtain the standard 2 4 2 curves for the SiCl -C H Cl binary system, the Raman where R is the peak height ratio between SiCl and the 4 2 4 2 A 4 spectrums of the standard solutions with diferent SiCl and internal standard CS , C is the concentration of CS , which 4 2 IS 2 C H Cl concentrations were detected when carbon disul- is considered as invariable in all standard solutions, and K 2 4 2 IS −1 fde was added as an internal standard, and the results are is the Raman signal constant of CS at 654 cm . Tus, the shown in Figure 2. Te Raman spectrum around the characteristic peak height ratio is proportional to the con- −1 characteristic peak of carbon disulfde at 654 cm in the centration of SiCl , which is verifed in Figure 3. Te result in standard solutions is shown in Figure 2(a), which could be Figure 3 indicates that the linearity between the mole used to calculate the peak height ratio for the standard curve. fraction of SiCl and the Raman peak height ratio at 4 4 Journal of Analytical Methods in Chemistry Table 1: Details of Raman peaks in Figure 1. Raman peak in Figure 1 Attribution Substance −1 (cm ) 654 Vibrating mode of C-S CS 422 and 480 Vibrating modes of Si-Cl SiCl 300 Deformation vibration of C-C-Cl 754 Stretching vibration of C-Cl 1204 Twisting vibration of C-H C H Cl 2 4 2 1301 Wagging vibration of C-H 1431 Scissoring vibration of C-H 2968 Symmetrical stretching vibration of C-H -1 2968 cm 500 1000 1500 2000 2500 3000 -1 Raman shift (cm ) (a) -1 654 cm -1 754 cm -1 300 cm -1 422 cm -1 480 cm 200 400 600 800 1000 -1 Raman shift (cm ) (b) Figure 1: Continued. Raman intensity Raman intensity Journal of Analytical Methods in Chemistry 5 -1 1301 cm -1 1431 cm -1 1204 cm -1 1053 cm 1000 1200 1400 1600 -1 Raman shift (cm ) (c) Figure 1: Raman spectra of the mixed solution containing SiCl , C H Cl , and CS . 4 2 4 2 2 30000 2500 600 620 640 660 680 700 400 420 440 460 480 500 -1 -1 Raman shift (cm ) Raman shift (cm ) C H Cl :0; C H Cl :7.99%; C H Cl :0; C H Cl :7.99%; 2 4 2 2 4 2 2 4 2 2 4 2 SiCl :9.52% SiCl :3.72% SiCl :9.52% SiCl :3.72% 4 4 4 4 C H Cl :2.71%; C H Cl :10.57%; C H Cl :2.71%; C H Cl :10.57%; 2 4 2 2 4 2 2 4 2 2 4 2 SiCl :7.56% SiCl :1.84% SiCl :7.56% SiCl :1.84% 4 4 4 4 C H Cl :5.37%; C H Cl :13.10%; C H Cl :5.37%; 2 4 2 2 4 2 2 4 2 SiCl :5.62% SiCl :0 SiCl :5.62% 4 4 (a) (b) Figure 2: Continued. Raman intensity Raman intensity Raman intensity 6 Journal of Analytical Methods in Chemistry 700 720 740 760 780 2900 2920 2940 2960 2980 -1 Raman shift (cm ) -1 Raman shift (cm ) C H Cl :2.71%; C H Cl :10.57%; 2 4 2 2 4 2 C H Cl :2.71%; C H Cl :10.57%; 2 4 2 2 4 2 SiCl :7.56% SiCl :1.84% 4 4 SiCl :7.56% SiCl :1.84% 4 4 C H Cl :5.37%; C H Cl :13.10%; 2 4 2 2 4 2 C H Cl :5.37%; C H Cl :13.10%; 2 4 2 2 4 2 SiCl :5.62% SiCl :0 4 4 SiCl :5.62% SiCl :0 4 4 C H Cl :7.99%; 2 4 2 C H Cl :7.99%; 2 4 2 SiCl :3.72% SiCl :3.72% (c) (d) Figure 2: Raman spectra of the standard solutions for the SiCl -C H Cl binary system: (a) the characteristic peak of carbon disulfde at 4 2 4 2 −1 −1 −1 654 cm , (b) the characteristic peak of silicon tetrachloride at 422 and 480 cm , (c) the characteristic peak of dichloroethane at 754 cm , −1 and (d) the characteristic peak of dichloroethane at 2968 cm . 0.08 0.06 y = 0.0068+0.75x R = 0.9939 0.04 1500 y = 32.74+23883.45x R = 0.9719 0.02 0.00 0.00 0.02 0.04 0.06 0.08 0.10 Mole fraction of silicon tetrachloride −1 Figure 3: Calibration curve for the determination of silicon tetrachloride for the SiCl -C H Cl binary system at 422 cm (■: standard 4 2 4 2 solution used to establish calibration curve; □: standard solution used to verify the accuracy of the calibration curve). −1 −1 422 cm is good, and the equation is y � 0.0068 + 0.75x with Te Raman intensity of C H Cl at 754 and 2968 cm 2 4 2 R of 0.9939, where y and x denote the Raman peak height also increases with the increase in C H Cl concentration in 2 4 2 ratio and the mole fraction of SiCl , respectively. Terefore, standard solutions, which could be clearly observed in the characteristic peak height ratio will be used for the Figures 2(c) and 2(d). It can be seen from Figure 2(d) that the −1 following standard curves. characteristic peak of dichloroethane at 2968 cm divides Raman intensity Peak height ratio Raman intensity Raman intensity Journal of Analytical Methods in Chemistry 7 0.035 0.035 y = 0.0019+0.2266x 0.028 0.028 y = 0.00046+0.2334x R = 0.9966 2 R = 0.9995 0.021 0.021 0.014 0.014 0.007 0.007 0.000 0.000 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.00 0.03 0.06 0.09 0.12 Mole fraction of dichloroethane Mole fraction of dichloroethane (a) (b) −1 −1 Figure 4: Calibration curve for the determination of dichloroethane for the SiCl -C H Cl binary system at (a) 754 cm and (b) 2968 cm 4 2 4 2 (■: standard solution used to establish calibration curve; □: standard solution used to verify the accuracy of the calibration curve). 􏽶������������� into two peaks, so the mean Raman intensity of the two 􏽐 􏼐C − C 􏼑 peaks was used for quantitative determination of di- i�1 i (4) RSEP(%) � × 100, chloroethane. Similarly, the characteristic peak height ratio n 􏽐 􏼐C 􏼑 −1 i�1 i at 754 and 2968 cm was used to establish a standard curve for the determination of C H Cl concentration, and the 2 4 2 where C is the actual concentration of silicon tetrachloride or result is presented in Figure 4. It can be seen from Figure 4(a) dichloroethane, C is the concentration calculated from the that the linearity between the mole fraction of di- −1 Raman spectrum, and n is the number of samples. Te result in chloroethane and the Raman peak height ratio at 754 cm is Table 2 shows that the RSEP value for the concentration of SiCl good, and the equation is y � 0.0019 + 0.2266x with R of −1 is 2.81% when the 422 cm band is used. Te RSEP value for the 0.9966, where y and x denote the Raman peak height ratio −1 concentration of C H Cl is 2.17% at 754 cm band and 7.32% 2 4 2 and the mole fraction of dichloroethane, respectively. Te −1 at 2968 cm band. Tis means the band of dichloroethane at result in Figure 4(b) indicates that the characteristic peak −1 −1 754 cm may be the better choice for quantitative analysis. height ratio at 2968 cm is also proportional to the con- centration of dichloroethane, and the equation is y � 0.00046 + 0.2334x with R of 0.9995. 3.3. Standard Curves for the SiCl -CS Binary System. 4 2 Similarly, C H Cl was used as an internal standard during the 2 4 2 3.2.3. Te Veracity of the Standard Curves. To verify the quantitative determination of SiCl and CS for the SiCl -CS 4 2 4 2 accuracy of these standard curves, the Raman spectra of binary system. Te Raman spectrum of the standard solutions −1 standard samples with known concentrations of silicon around the characteristic peak of C H Cl (754 cm ) is shown 2 4 2 tetrachloride and dichloroethane were measured. Te peak in Figure 5, which could be used to calculate peak height ratio. height ratios calculated from the spectra were obtained and Te Raman spectra of standard solutions around the charac- are shown by hollow squares in Figures 3 and 4. Tese teristic peak of silicon tetrachloride and carbon disulfde −1 −1 hollow squares lie on the standard curve, though the (422 cm and 654 cm , respectively) are presented in Figures 6 measurement condition and target concentration are dif- and 7. First, the characteristic peak heights of silicon tetra- ferent from the standard curve. Tese results suggest that the chloride, carbon disulfde, and dichloroethane were taken from characteristic peak height ratio method is credible for the these Raman spectrums, which are shown in Figures 5–7. Ten, determination of silicon tetrachloride and dichloroethane. the peak height ratio was calculated according to the peak height To compare the diferent characteristic peaks applied, the of the solute and the internal standard. Finally, the peak height relative standard error of prediction, RSEP, is calculated ratio was plotted against the mole fraction of silicon tetrachloride according to the following equation: and carbon disulfde, which is also shown in Figures 6 and 7. Peak height ratio Peak height ratio 8 Journal of Analytical Methods in Chemistry Table 2: RSEP of SiCl and C H Cl concentration for the SiCl -C H Cl binary system by quantitative analysis at diferent 4 2 4 2 4 2 4 2 characteristic peaks. −1 −1 −1 SiCl (422 cm ) C H Cl (754 cm ) C H Cl (2968 cm ) 4 2 4 2 2 4 2 Actual concentration (%) 2.78 6.59 9.28 4.04 9.28 4.04 Estimated concentration (%) 2.69 6.41 9.19 4.24 9.91 4.43 RSEP (%) 2.81 2.17 7.32 700 720 740 760 780 800 -1 Raman shift (cm ) CS :0;SiCl :12.25% CS :13.10%;SiCl :4.60% 2 4 2 4 CS :4.55%;SiCl :9.59% CS :17.11%;SiCl :2.25% 2 4 2 4 CS :8.92%;SiCl :7.04% CS :20.96%;SiCl :0 2 4 2 4 −1 Figure 5: Raman spectra of the standard solutions for the SiCl -CS binary system at the characteristic peak of dichloroethane (754 cm ). 4 2 0.60 y = 0.0494+4.7535x R = 0.9962 1200 0.45 0.30 0.15 0.00 0.00 0.03 0.06 0.09 0.12 400 410 420 430 440 450 460 Mole fraction of SiCl -1 Raman shift (cm ) SiCl :12.25% SiCl :4.60% 4 4 SiCl :9.59% SiCl :2.25% 4 4 SiCl :7.04% (a) (b) −1 Figure 6: Raman spectra of standard solutions at the characteristic peak of silicon tetrachloride (422 cm ) and the standard curve for determination of silicon tetrachloride for the SiCl -CS binary system. (a) Raman spectrum and (b) calibration curve (■: standard solution 4 2 used to establish calibration curve; ○: standard solution used to verify the accuracy of the calibration curve). Raman intensity Raman intensity Peak height ratio Journal of Analytical Methods in Chemistry 9 2.8 y=0.8139+8.7366x R =0.9973 2.4 2.0 1.6 1.2 0.8 0.00 0.04 0.08 0.12 0.16 0.20 0.24 600 620 640 660 680 700 Mole fraction of CS -1 Raman shift (cm ) CS :4.55% CS :17.11% 2 2 CS :8.92% CS :20.96% CS :13.10% (a) (b) −1 Figure 7: Raman spectrum of standard solutions at the characteristic peak of carbon disulfde (654 cm ) and the standard curve for determination of carbon disulfde for the SiCl -CS binary system. (a) Raman spectrum and (b) calibration curve (■: standard solution used 4 2 to establish calibration curve; ○: standard solution used to verify the accuracy of the calibration curve). Table 3: RSEP of SiCl and CS concentration for the SiCl -CS Te results in Figure 6 show that the linearity between 4 2 4 2 binary system by quantitative analysis at diferent the mole fraction of silicon tetrachloride and the Raman −1 characteristic peaks. peak height ratio at 422 cm is good, and the equation is y � 0.0494 + 4.7535x with R of 0.9962, where y and x denote SiCl CS 4 2 −1 −1 the Raman peak height ratio and the mole fraction of silicon (422 cm ) (654 cm ) tetrachloride, respectively. Similarly, there is also a good Actual concentration (%) 3.41 8.30 15.12 6.76 linearity between the mole fraction of carbon disulfde and Estimated concentration (%) 3.63 8.53 15.74 7.06 −1 the Raman peak height ratio at 654 cm Te equation is RSEP (%) 3.55 4.16 y � 0.8139 + 8.7366x with R of 0.9973, which is shown in Figure 7. In order to verify the accuracy of these standard 4. Conclusion curves, the Raman spectra of standard samples with known Raman spectroscopy was applied to quantitatively determine concentrations of silicon tetrachloride and carbon disulfde were also measured. Te peak height ratios calculated from the concentration of silicon tetrachloride, carbon disulfde, these spectra are shown by hollow squares in Figures 6 and 7. and dichloroethane during the resource utilization of the Tese hollow squares lie on the standard curve, which also titanium-containing liquid waste. Te liquid sample was confrms that the characteristic peak height ratio method is sealed in a glass sampling pipe with an internal standard, and credible for the determination of silicon tetrachloride and the whole preparation process is convenient and in- carbon disulfde concentrations for the SiCl -CS binary expensive. Te peak height ratio between the Raman in- 4 2 system. tensities of the target substance and those of the internal Te relative standard error of prediction (RSEP) of the standard is proportional to the concentration of the target substance with a good linear relationship. Tis method standard curve for the SiCl -CS binary system is also cal- 4 2 culated according to equation (4), and the results are shown shows good accuracy when the standard samples are de- tected and the calculated concentration is compared with the in Table 3. Te result in Table 3 shows that the RSEP value of the SiCl concentration for the SiCl -CS binary system is actual concentration. Te relative standard error of pre- 4 4 2 −1 diction (RSEP) is 2.81% and 2.17%, respectively, when de- 3.55% when the peak height ratio at the 422 cm band is used. Te RSEP value of the CS concentration for the SiCl - termining silicon tetrachloride and dichloroethane 2 4 −1 CS binary system is 4.16% at the 654 cm band. Tese concentrations for the SiCl -C H Cl binary system. Te 2 4 2 4 2 results also indicate that these standard curves are reliable RSEP values are 3.55% and 4.16%, respectively, when de- during the determination of SiCl and CS concentrations termining silicon tetrachloride and carbon disulfde con- 4 2 for the SiCl -CS binary system. centrations for the SiCl -CS binary system. Tese results 4 2 4 2 Raman intensity Peak height ratio 10 Journal of Analytical Methods in Chemistry [11] E. Mueh, H. Rauleder, J. Monkiewicz, and R. Schork, “Process indicate that Raman spectroscopy can quantitatively de- and use of amino-functional resins for dismutating hal- termine the concentration of silicon tetrachloride, carbon osilanes and for removing extraneous metals,” disulfde, and dichloroethane when measuring vapor-liquid US20120183464, 2012. equilibrium data for the SiCl -CS and SiCl -C H Cl binary 4 2 4 2 4 2 [12] Y. Wan, X. Zhao, S. Guo, D. Yan, and D. Yang, “Te prep- systems. aration and detection of high purity silicon tetrachloride with optical fbres level,” Materials Science and Engineering Con- Data Availability ference Series, vol. 207, pp. 12–18, 2017. [13] R. L. Barns, E. A. Chandross, D. L. Flamm, L. T. Manzione, All the data are included in the manuscript. and L. F. Tompson, “Purifcation process for compounds useful in optical fber manufacture,” US4372834, 1983. [14] G. A. Zachariadis and E. Sahanidou, “Multi-element method Conflicts of Interest for determination of trace elements in sunscreens by ICP- Te authors declare that they have no conficts of interest. AES,” Journal of Pharmaceutical and Biomedical Analysis, vol. 50, no. 3, pp. 342–348, 2009. [15] E. Borras, ´ M. Rodenas, ´ J. J. Dieguez et al., “Development of Acknowledgments a gas chromatography-mass spectrometry method for the determination of carbon disulfde in the atmosphere,” Tis study was fnancially supported by the National Natural Microchemical Journal, vol. 101, pp. 37–42, 2012. Science Foundation of China (grant nos. 51604055 and [16] C. M. Liu, Y. Han, S. G. Min, W. Jia, X. Meng, and P. P. Liu, 51674057), the National Science Foundation for Post- “Rapid qualitative and quantitative analysis of metham- doctoral Scientists of China (grant no. 2018M643409), and phetamine, ketamine, heroin, and cocaine by near-infrared the “China Scholarship Council” fellowship (grant no. spectroscopy,” Forensic Science International, vol. 290, CSC201802075009). pp. 162–168, 2018. [17] D. M. Musingarabwi, H. H. Nieuwoudt, P. R Young, H. A. Eyegh ´ e-Bickong, ` and M. A. Vivier, “A rapid qualitative References and quantitative evaluation of grape berries at various stages [1] G. Z. 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Westerhuis, “Quantitative Raman reaction monitoring using the solvent as internal standard,” Analytical Chemistry, vol. 77, no. 5, pp. 1228–1236, 2005. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Journal of Analytical Methods in Chemistry Hindawi Publishing Corporation

Quantitative Analysis of Silicon Tetrachloride, Carbon Disulfide, and Dichloroethane Concentration by Raman Spectroscopy

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10.1155/2023/1894505
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Hindawi Journal of Analytical Methods in Chemistry Volume 2023, Article ID 1894505, 11 pages https://doi.org/10.1155/2023/1894505 Research Article Quantitative Analysis of Silicon Tetrachloride, Carbon Disulfide, and Dichloroethane Concentration by Raman Spectroscopy 1,2 3 2 2 2 Xiaoyan Xiang , Yufeng Shao, Yanfang Wei, Wentang Xia, and Xiaoli Yuan College of Communication Engineering, Chongqing University, Chongqing 400040, China School of Metallurgical and Materials Engineering, Chongqing University of Science and Technology, Chongqing 401331, China College of Electronic and Information Engineering, Chongqing Tree Gorges University, Chongqing 404100, China Correspondence should be addressed to Xiaoyan Xiang; xxycsu@126.com Received 13 May 2022; Revised 2 July 2022; Accepted 26 October 2022; Published 16 February 2023 Academic Editor: Boryana M. Nikolova Damyanova Copyright © 2023 Xiaoyan Xiang et al. Tis is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Quantitative analysis of silicon tetrachloride, carbon disulfde, and dichloroethane concentrations to obtain vapor-liquid equilibrium data of the SiCl -CS and SiCl -C H Cl binary systems was established by Raman spectroscopy. Te cheap 4 2 4 2 4 2 glass sampling pipe was used as a carrier for Raman spectroscopy measurements. Te Raman peak height of the internal standard was used to remove interference factors such as sampling pipe diameter, temperature, laser power, and other efects from the instrument. Te peak height ratio between the Raman characteristic peak of the analyte and that of the internal standard was proportional to the analyte concentration. During the measuring process of vapor-liquid equilibrium data for the SiCl -C H Cl 4 2 4 2 binary system, the linear equation of y � 0.0068 + 0.75x with R of 0.9939 was used for the determination of SiCl concentration at −1 2 the 422 cm band. Te linear equation of y � 0.0019 + 0.2266x with R of 0.9966 was used for the determination of C H Cl 2 4 2 −1 2 concentration at the 754 cm band. For the SiCl -CS binary system, the linear equation of y � 0.0494 + 4.7535x with R of 0.9962 4 2 −1 2 was used for the determination of SiCl concentration at the 422 cm band. Te linear equation of y � 0.8139 + 8.7366x with R of −1 0.9973 was used for the determination of CS concentration at the 654 cm band. Te concentration of standard samples calculated by these standard curves was compared with the actual value to verify the accuracy of this method. Te reproducibility is good when determining silicon tetrachloride and dichloroethane concentrations for the SiCl -C H Cl binary system, with RSEP 4 2 4 2 values of 2.81% and 2.17%, respectively. Meanwhile, the RSEP values are 3.55% and 4.16%, respectively, when determining silicon tetrachloride and carbon disulfde concentrations for the SiCl -CS binary system. 4 2 made to extract SiCl from the liquid waste for a long time 1. Introduction [7–9]. Besides SiCl and TiCl , there are also a small amount 4 4 Titanium-containing liquid waste coming from the recti- of impurities in the liquid waste such as FeCl , MgCl , CS , 3 2 2 fying process is the major waste in the titanium metallurgy C H Cl , and so on. In order to extract purifed SiCl , these 2 4 2 4 industry. Generally speaking, the concentration of SiCl and impurities must be removed. Te method to obtain high- TiCl in the titanium-containing liquid waste is 15∼20% and grade SiCl includes adsorption, rectifcation, partial hy- 4 4 60∼70%, respectively [1]. Te liquid waste containing TiCl drolysis, and photochlorination [10–13]. Among all these and SiCl is a valuable resource, but it is hydrolyzed easily in methods, rectifcation may be the best way to extract purifed a moist environment, producing a large amount of HCl, SiCl from the liquid waste because no additional impurities which is a toxic gas [2–4]. Terefore, improper disposal of are introduced. Unfortunately, due to the little diference in titanium-containing liquid waste would lead to waste of SiCl and CS or C H Cl in boiling point, the rectifcation 4 2 2 4 2 resources and destruction of the eco-environment [5, 6]. process is energy-sucking. In order to reduce energy con- Resource utilization of the titanium-containing liquid waste sumption, the accurate vapor-liquid equilibrium data for the is always of great importance in China, and efort has been SiCl -CS and SiCl -C H Cl binary systems must be 4 2 4 2 4 2 2 Journal of Analytical Methods in Chemistry measured to optimize the design of the rectifying column. sample containing SiCl will be sealed before it was sub- During the measurement, the content of SiCl , CS , and mitted for Raman detecting according to our previous work 4 2 C H Cl in the sample must be analyzed to obtain accurate [31]. Te liquid sample stored in a sealed colorimetric tube 2 4 2 gas-liquid equilibrium data. was frst moved into a drying oven. Te colorimetric tube Generally, inorganic substances could be detected by was then opened, and a little glass sampling pipe was inductively coupled plasma-atomic emission spectrometry inserted into the colorimetric tube. After the liquid sample (ICP-AES) by dissolving in acid solution. Organic com- entered the little glass sampling pipe by capillary action, the pounds could be analyzed by gas or liquid chromatography little glass sampling pipe was taken out and moved to the and infrared (IR) spectroscopy [14–17]. However, these alcohol lamp. Te both ends of the glass sampling pipe were methods could not be used for simultaneous analysis of heated and melted to allow the liquid sample to get sealed in inorganic and organic compounds. Recently, quantitative it. Te preparation process is convenient, and the material is analysis of components in solution by Raman spectroscopy inexpensive. has been reported, and there are several advantages to using Raman spectra for quantitative analysis [18–22]. For ex- 2.3. Preparation of Standard Samples. SiCl , C H Cl , and ample, it is a nondestructive technology that is usually 4 2 4 2 CS were purchased from Coron Chemical Industry Co., applicable without any sample preparation process, which is Ltd. Tere is often little water remaining in the purchased convenient for online quantitative determination [23, 24]. C H Cl and CS , which may lead to the hydrolysis of SiCl . Tis analytical method may also be applied to samples 2 4 2 2 4 Hence, the purchased C H Cl and CS were dehydrated containing SiCl , CS , and C H Cl . Creighton and Sinclair 2 4 2 2 4 2 2 4 2 frst. Te dehydration process is also similar to our previous studied the Raman spectra of liquid SiCl and CS as early as 4 2 work [31], just with a diferent distillation temperature: 1973 [25], Gong studied the Raman scattering from liquid frstly, anhydrous calcium chloride (stored in a vacuum CS for diferent concentrations of benzene [26], and Stefen drying oven at 105 C for 24 h before use) and C H Cl or CS gave information about the 2D Raman response of liquid 2 4 2 2 were put into a desiccative conical fask with a stopper. Ten, CS [27]. Meanwhile, the spectral information of C H Cl 2 2 4 2 the mixture was magnetically stirred at room temperature could also be found in literature [28–30], but there is nearly for 12 h. Finally, the fltrate from the mixture was distilled at no study on the quantitative determination of CS , C H Cl , 2 2 4 2 ° ° certain temperature (90 C for C H Cl and 50 C for CS ), and SiCl in liquid samples by using Raman spectra. 2 4 2 2 and the distillate was collected for the preparation of Terefore, the purpose of the present study is to establish standard samples. In the measurement of vapor-liquid a rapid and accurate method to determine the concentration equilibrium data for the SiCl -CS and SiCl -C H Cl bi- of CS , C H Cl , and SiCl simultaneously in liquid samples. 4 2 4 2 4 2 2 2 4 2 4 nary systems, the concentrations of SiCl , CS , and C H Cl During the analysis procedure, the standard solutions with 4 2 2 4 2 in liquid samples should be analyzed simultaneously. Tus, internal standards were sealed in cheap glass capillaries for CS was used as an internal standard during the concen- the Raman spectrometer. Ten, the peak height ratio be- tration determination of SiCl and C H Cl for the SiCl - tween the Raman characteristic peak of the analyte and that 4 2 4 2 4 C H Cl binary system, while C H Cl was used as an in- of the internal standard was calculated to establish the 2 4 2 2 4 2 ternal standard during the concentration determination of calibration curves of CS , C H Cl , and SiCl . After that, the 2 2 4 2 4 SiCl and CS for the SiCl -CS binary system. Ten, the Raman spectrometries of standard samples were measured, 4 2 4 2 working standard solutions at several concentration levels of and the concentration of the analyte was calculated using the SiCl , C H Cl , and CS were prepared. standard curves to confrm the availability of this method. 4 2 4 2 2 2. Materials and Methods 2.4. Establishment of Calibration Curves. Working standard solutions with diferent concentrations of SiCl , C H Cl , 4 2 4 2 2.1. Raman Spectrometer. Raman spectrometry of all sam- and CS were prepared for Raman detecting. Te baselines of ples was detected by the LabRAM HR Evolution spec- the obtained Raman spectra were taken out by using Origin trometer, equipped with an Olympus BX41 microscope with 8.5 to avoid noise and fuorescence efects. After that, the a 10X objective lens (NA � 0.25), which was used for fo- characteristic peak heights of SiCl , C H Cl , and CS were 4 2 4 2 2 cusing the laser beam on the sample. A 532 nm Ar ion laser extracted from the revised Raman spectra, respectively. Te (Spectra Physics 2017) was used for excitation with power of peak height ratio between the Raman characteristic peak of ∼50 mW. Te back scattering light was passed into the analyte and the internal standard was subsequently a monochromator and detected with a charge coupled device calculated according to the following equation: (CCD) detector. Te Raman spectrum between 100 and −1 3200 cm was collected with an exposure time of 30 s and 2 I R � , (1) accumulations for each spectrum. where I is the Raman intensity of analyte and I is the A S 2.2. Sample Preparation for Raman Analysis. Te sample Raman intensity of internal standard. Te calibration curve containing SiCl is easily hydrolyzed to release HCl in the air, was generated by plotting the characteristic peak height ratio which is not convenient for Raman detecting. Terefore, the against the concentration of analytes. Journal of Analytical Methods in Chemistry 3 It can be seen from Figure 2(a) that the intensity of carbon 3. Results and Discussion −1 disulfde at 654 cm is not changed with the variation of 3.1. Raman Spectra of the Mixed Solution Containing SiCl , 4 silicon tetrachloride and dichloroethane concentration. Te C H Cl , and CS . In order to obtain the characteristic 2 4 2 2 slight increase or decrease in intensity may be due to the peaks of SiCl , C H Cl , and CS for quantitative analysis, 4 2 4 2 2 change in laser power. the Raman spectra of a mixed solution containing SiCl , 4 Te Raman spectra of standard solutions on the charac- −1 C H Cl , and CS are detected, as shown in Figure 1. 2 4 2 2 teristic peak of silicon tetrachloride at 422 and 480 cm are Figure 1(a) shows the full spectrum of the mixed solution presented in Figure 2(b). Te Raman spectra of standard so- −1 −1 from 200 cm to 3200 cm . Te full spectrum is partly lutions around the characteristic peak of dichloroethane at 754 −1 displayed in Figures 1(b) and 1(c) so that the charac- and 2968 cm are shown in Figures 2(c) and 2(d), respectively. teristic peaks of SiCl , C H Cl , and CS can be clearly 4 2 4 2 2 It can be seen from Figure 2(b) that the Raman intensity −1 observed. Figure 1(b) shows the spectrum of the mixed of silicon tetrachloride at 422 cm increases with the rising −1 −1 solution from 200 cm to 1000 cm band, and SiCl concentration in standard solutions, while the Raman −1 −1 Figure 1(c) shows the spectrum from 1000 cm to intensity of silicon tetrachloride at 480 cm is irregular with −1 1600 cm band. In order to rapidly and conveniently fnd the SiCl concentration. Tus, the characteristic peak of −1 the Raman band of SiCl , C H Cl , and CS , the details of 4 2 4 2 2 silicon tetrachloride at 480 cm is not suitable for quanti- the Raman peaks in Figure 1 are shown in Table 1. Te C-S tative analysis. In addition, although the Raman intensity of −1 vibrating mode of carbon disulfde [25] is found at the silicon tetrachloride at 422 cm increases with the increase −1 654 cm band in Figure 1(b), and the intensity reaches up in SiCl concentration, the linear relationship between to 5368. Two obvious bands with the maximum intensity Raman intensity and SiCl concentration is not good. It can −1 at 422 and 480 cm appeared, respectively, in Figure 1(b), be verifed from Figure 3 that the equation is which is attributed to the Si-Cl vibrating modes of silicon y � 32.74 + 23883.45x with R of 0.9719, where y and x de- tetrachloride [32]. Te vibrating mode of liquid di- note the Raman intensity and the mole fraction of silicon chloroethane is found in Figures 1(a)–1(c). Te band at tetrachloride, respectively. Tis indicates a bad linear re- −1 2968 cm shown in Figure 1(a) belongs to the symmet- lationship. Terefore, Raman absolute intensity cannot be rical stretching vibration of C-H . Te bands at 300 and 2 used to calculate the SiCl concentration accurately. −1 754 cm in Figure 1(b) are ascribed to deformation vi- bration of C-C-Cl and stretching vibration of C-Cl, re- −1 3.2.2. Standard Curves for the SiCl -C H Cl Binary System. 4 2 4 2 spectively [33]. Te peak at 1053 cm band in Figure 1(c) Generally, the Raman intensity of SiCl at characteristic peak is assigned to stretching vibration of C-C, and the peaks at −1 −1 (422 cm )indicated as I can be given by the following 1204, 1301, and 1431 cm band are due to the twisting equation [34]: vibration, wagging vibration, and scissoring vibration of C-H , respectively [33]. 2 I � K VC P , (2) A A A L In order to reduce the background noise interference, where C is the SiCl concentration, P is the density of laser a characteristic peak with high intensity should be used for A 4 L power, and K is the Raman signal constant of SiCl at quantitative analysis. Tus, the characteristic peak of di- A 4 −1 −1 422 cm , which can be afected by instrumental throughput chloroethane at 300, 1053, 1204, 1301, and 1431 cm with and the apparent Raman-scattering efciency. V is the weak intensity could be excluded during the analysis while volume of sample illuminated by the laser and viewed by the the characteristic bands of dichloroethane at 754 and −1 spectrometer. According to equation (2), the Raman in- 2968 cm with high intensity could be used for quantitative tensity of SiCl (I ) will change with the variation of K and analysis. Meanwhile, C-S vibrating mode of carbon disulfde 4 A A −1 P . Tere is often inevitable fuctuation of laser power, test at 654 cm band and Si-Cl vibrating modes of silicon tet- L −1 temperature, and instrument during the measurement of the rachloride at 422 and 480 cm band are clearly observed Raman spectrum. Tus, it is easy to understand the bad with high intensity. Terefore, these characteristic bands linearity between the Raman intensity and the mole fraction may be used for quantitative determination. of SiCl . In order to remove the efect of laser power, test temperature, and instrument, the characteristic peak height ratio was introduced: 3.2. Standard Curves for the SiCl -C H Cl Binary System 4 2 4 2 K VC P K C A A L A A R � � � kC , (3) A A 3.2.1. Raman Spectra of the Standard Solutions for the SiCl - K VC P K C IS IS L IS IS C H Cl Binary System. In order to obtain the standard 2 4 2 curves for the SiCl -C H Cl binary system, the Raman where R is the peak height ratio between SiCl and the 4 2 4 2 A 4 spectrums of the standard solutions with diferent SiCl and internal standard CS , C is the concentration of CS , which 4 2 IS 2 C H Cl concentrations were detected when carbon disul- is considered as invariable in all standard solutions, and K 2 4 2 IS −1 fde was added as an internal standard, and the results are is the Raman signal constant of CS at 654 cm . Tus, the shown in Figure 2. Te Raman spectrum around the characteristic peak height ratio is proportional to the con- −1 characteristic peak of carbon disulfde at 654 cm in the centration of SiCl , which is verifed in Figure 3. Te result in standard solutions is shown in Figure 2(a), which could be Figure 3 indicates that the linearity between the mole used to calculate the peak height ratio for the standard curve. fraction of SiCl and the Raman peak height ratio at 4 4 Journal of Analytical Methods in Chemistry Table 1: Details of Raman peaks in Figure 1. Raman peak in Figure 1 Attribution Substance −1 (cm ) 654 Vibrating mode of C-S CS 422 and 480 Vibrating modes of Si-Cl SiCl 300 Deformation vibration of C-C-Cl 754 Stretching vibration of C-Cl 1204 Twisting vibration of C-H C H Cl 2 4 2 1301 Wagging vibration of C-H 1431 Scissoring vibration of C-H 2968 Symmetrical stretching vibration of C-H -1 2968 cm 500 1000 1500 2000 2500 3000 -1 Raman shift (cm ) (a) -1 654 cm -1 754 cm -1 300 cm -1 422 cm -1 480 cm 200 400 600 800 1000 -1 Raman shift (cm ) (b) Figure 1: Continued. Raman intensity Raman intensity Journal of Analytical Methods in Chemistry 5 -1 1301 cm -1 1431 cm -1 1204 cm -1 1053 cm 1000 1200 1400 1600 -1 Raman shift (cm ) (c) Figure 1: Raman spectra of the mixed solution containing SiCl , C H Cl , and CS . 4 2 4 2 2 30000 2500 600 620 640 660 680 700 400 420 440 460 480 500 -1 -1 Raman shift (cm ) Raman shift (cm ) C H Cl :0; C H Cl :7.99%; C H Cl :0; C H Cl :7.99%; 2 4 2 2 4 2 2 4 2 2 4 2 SiCl :9.52% SiCl :3.72% SiCl :9.52% SiCl :3.72% 4 4 4 4 C H Cl :2.71%; C H Cl :10.57%; C H Cl :2.71%; C H Cl :10.57%; 2 4 2 2 4 2 2 4 2 2 4 2 SiCl :7.56% SiCl :1.84% SiCl :7.56% SiCl :1.84% 4 4 4 4 C H Cl :5.37%; C H Cl :13.10%; C H Cl :5.37%; 2 4 2 2 4 2 2 4 2 SiCl :5.62% SiCl :0 SiCl :5.62% 4 4 (a) (b) Figure 2: Continued. Raman intensity Raman intensity Raman intensity 6 Journal of Analytical Methods in Chemistry 700 720 740 760 780 2900 2920 2940 2960 2980 -1 Raman shift (cm ) -1 Raman shift (cm ) C H Cl :2.71%; C H Cl :10.57%; 2 4 2 2 4 2 C H Cl :2.71%; C H Cl :10.57%; 2 4 2 2 4 2 SiCl :7.56% SiCl :1.84% 4 4 SiCl :7.56% SiCl :1.84% 4 4 C H Cl :5.37%; C H Cl :13.10%; 2 4 2 2 4 2 C H Cl :5.37%; C H Cl :13.10%; 2 4 2 2 4 2 SiCl :5.62% SiCl :0 4 4 SiCl :5.62% SiCl :0 4 4 C H Cl :7.99%; 2 4 2 C H Cl :7.99%; 2 4 2 SiCl :3.72% SiCl :3.72% (c) (d) Figure 2: Raman spectra of the standard solutions for the SiCl -C H Cl binary system: (a) the characteristic peak of carbon disulfde at 4 2 4 2 −1 −1 −1 654 cm , (b) the characteristic peak of silicon tetrachloride at 422 and 480 cm , (c) the characteristic peak of dichloroethane at 754 cm , −1 and (d) the characteristic peak of dichloroethane at 2968 cm . 0.08 0.06 y = 0.0068+0.75x R = 0.9939 0.04 1500 y = 32.74+23883.45x R = 0.9719 0.02 0.00 0.00 0.02 0.04 0.06 0.08 0.10 Mole fraction of silicon tetrachloride −1 Figure 3: Calibration curve for the determination of silicon tetrachloride for the SiCl -C H Cl binary system at 422 cm (■: standard 4 2 4 2 solution used to establish calibration curve; □: standard solution used to verify the accuracy of the calibration curve). −1 −1 422 cm is good, and the equation is y � 0.0068 + 0.75x with Te Raman intensity of C H Cl at 754 and 2968 cm 2 4 2 R of 0.9939, where y and x denote the Raman peak height also increases with the increase in C H Cl concentration in 2 4 2 ratio and the mole fraction of SiCl , respectively. Terefore, standard solutions, which could be clearly observed in the characteristic peak height ratio will be used for the Figures 2(c) and 2(d). It can be seen from Figure 2(d) that the −1 following standard curves. characteristic peak of dichloroethane at 2968 cm divides Raman intensity Peak height ratio Raman intensity Raman intensity Journal of Analytical Methods in Chemistry 7 0.035 0.035 y = 0.0019+0.2266x 0.028 0.028 y = 0.00046+0.2334x R = 0.9966 2 R = 0.9995 0.021 0.021 0.014 0.014 0.007 0.007 0.000 0.000 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.00 0.03 0.06 0.09 0.12 Mole fraction of dichloroethane Mole fraction of dichloroethane (a) (b) −1 −1 Figure 4: Calibration curve for the determination of dichloroethane for the SiCl -C H Cl binary system at (a) 754 cm and (b) 2968 cm 4 2 4 2 (■: standard solution used to establish calibration curve; □: standard solution used to verify the accuracy of the calibration curve). 􏽶������������� into two peaks, so the mean Raman intensity of the two 􏽐 􏼐C − C 􏼑 peaks was used for quantitative determination of di- i�1 i (4) RSEP(%) � × 100, chloroethane. Similarly, the characteristic peak height ratio n 􏽐 􏼐C 􏼑 −1 i�1 i at 754 and 2968 cm was used to establish a standard curve for the determination of C H Cl concentration, and the 2 4 2 where C is the actual concentration of silicon tetrachloride or result is presented in Figure 4. It can be seen from Figure 4(a) dichloroethane, C is the concentration calculated from the that the linearity between the mole fraction of di- −1 Raman spectrum, and n is the number of samples. Te result in chloroethane and the Raman peak height ratio at 754 cm is Table 2 shows that the RSEP value for the concentration of SiCl good, and the equation is y � 0.0019 + 0.2266x with R of −1 is 2.81% when the 422 cm band is used. Te RSEP value for the 0.9966, where y and x denote the Raman peak height ratio −1 concentration of C H Cl is 2.17% at 754 cm band and 7.32% 2 4 2 and the mole fraction of dichloroethane, respectively. Te −1 at 2968 cm band. Tis means the band of dichloroethane at result in Figure 4(b) indicates that the characteristic peak −1 −1 754 cm may be the better choice for quantitative analysis. height ratio at 2968 cm is also proportional to the con- centration of dichloroethane, and the equation is y � 0.00046 + 0.2334x with R of 0.9995. 3.3. Standard Curves for the SiCl -CS Binary System. 4 2 Similarly, C H Cl was used as an internal standard during the 2 4 2 3.2.3. Te Veracity of the Standard Curves. To verify the quantitative determination of SiCl and CS for the SiCl -CS 4 2 4 2 accuracy of these standard curves, the Raman spectra of binary system. Te Raman spectrum of the standard solutions −1 standard samples with known concentrations of silicon around the characteristic peak of C H Cl (754 cm ) is shown 2 4 2 tetrachloride and dichloroethane were measured. Te peak in Figure 5, which could be used to calculate peak height ratio. height ratios calculated from the spectra were obtained and Te Raman spectra of standard solutions around the charac- are shown by hollow squares in Figures 3 and 4. Tese teristic peak of silicon tetrachloride and carbon disulfde −1 −1 hollow squares lie on the standard curve, though the (422 cm and 654 cm , respectively) are presented in Figures 6 measurement condition and target concentration are dif- and 7. First, the characteristic peak heights of silicon tetra- ferent from the standard curve. Tese results suggest that the chloride, carbon disulfde, and dichloroethane were taken from characteristic peak height ratio method is credible for the these Raman spectrums, which are shown in Figures 5–7. Ten, determination of silicon tetrachloride and dichloroethane. the peak height ratio was calculated according to the peak height To compare the diferent characteristic peaks applied, the of the solute and the internal standard. Finally, the peak height relative standard error of prediction, RSEP, is calculated ratio was plotted against the mole fraction of silicon tetrachloride according to the following equation: and carbon disulfde, which is also shown in Figures 6 and 7. Peak height ratio Peak height ratio 8 Journal of Analytical Methods in Chemistry Table 2: RSEP of SiCl and C H Cl concentration for the SiCl -C H Cl binary system by quantitative analysis at diferent 4 2 4 2 4 2 4 2 characteristic peaks. −1 −1 −1 SiCl (422 cm ) C H Cl (754 cm ) C H Cl (2968 cm ) 4 2 4 2 2 4 2 Actual concentration (%) 2.78 6.59 9.28 4.04 9.28 4.04 Estimated concentration (%) 2.69 6.41 9.19 4.24 9.91 4.43 RSEP (%) 2.81 2.17 7.32 700 720 740 760 780 800 -1 Raman shift (cm ) CS :0;SiCl :12.25% CS :13.10%;SiCl :4.60% 2 4 2 4 CS :4.55%;SiCl :9.59% CS :17.11%;SiCl :2.25% 2 4 2 4 CS :8.92%;SiCl :7.04% CS :20.96%;SiCl :0 2 4 2 4 −1 Figure 5: Raman spectra of the standard solutions for the SiCl -CS binary system at the characteristic peak of dichloroethane (754 cm ). 4 2 0.60 y = 0.0494+4.7535x R = 0.9962 1200 0.45 0.30 0.15 0.00 0.00 0.03 0.06 0.09 0.12 400 410 420 430 440 450 460 Mole fraction of SiCl -1 Raman shift (cm ) SiCl :12.25% SiCl :4.60% 4 4 SiCl :9.59% SiCl :2.25% 4 4 SiCl :7.04% (a) (b) −1 Figure 6: Raman spectra of standard solutions at the characteristic peak of silicon tetrachloride (422 cm ) and the standard curve for determination of silicon tetrachloride for the SiCl -CS binary system. (a) Raman spectrum and (b) calibration curve (■: standard solution 4 2 used to establish calibration curve; ○: standard solution used to verify the accuracy of the calibration curve). Raman intensity Raman intensity Peak height ratio Journal of Analytical Methods in Chemistry 9 2.8 y=0.8139+8.7366x R =0.9973 2.4 2.0 1.6 1.2 0.8 0.00 0.04 0.08 0.12 0.16 0.20 0.24 600 620 640 660 680 700 Mole fraction of CS -1 Raman shift (cm ) CS :4.55% CS :17.11% 2 2 CS :8.92% CS :20.96% CS :13.10% (a) (b) −1 Figure 7: Raman spectrum of standard solutions at the characteristic peak of carbon disulfde (654 cm ) and the standard curve for determination of carbon disulfde for the SiCl -CS binary system. (a) Raman spectrum and (b) calibration curve (■: standard solution used 4 2 to establish calibration curve; ○: standard solution used to verify the accuracy of the calibration curve). Table 3: RSEP of SiCl and CS concentration for the SiCl -CS Te results in Figure 6 show that the linearity between 4 2 4 2 binary system by quantitative analysis at diferent the mole fraction of silicon tetrachloride and the Raman −1 characteristic peaks. peak height ratio at 422 cm is good, and the equation is y � 0.0494 + 4.7535x with R of 0.9962, where y and x denote SiCl CS 4 2 −1 −1 the Raman peak height ratio and the mole fraction of silicon (422 cm ) (654 cm ) tetrachloride, respectively. Similarly, there is also a good Actual concentration (%) 3.41 8.30 15.12 6.76 linearity between the mole fraction of carbon disulfde and Estimated concentration (%) 3.63 8.53 15.74 7.06 −1 the Raman peak height ratio at 654 cm Te equation is RSEP (%) 3.55 4.16 y � 0.8139 + 8.7366x with R of 0.9973, which is shown in Figure 7. In order to verify the accuracy of these standard 4. Conclusion curves, the Raman spectra of standard samples with known Raman spectroscopy was applied to quantitatively determine concentrations of silicon tetrachloride and carbon disulfde were also measured. Te peak height ratios calculated from the concentration of silicon tetrachloride, carbon disulfde, these spectra are shown by hollow squares in Figures 6 and 7. and dichloroethane during the resource utilization of the Tese hollow squares lie on the standard curve, which also titanium-containing liquid waste. Te liquid sample was confrms that the characteristic peak height ratio method is sealed in a glass sampling pipe with an internal standard, and credible for the determination of silicon tetrachloride and the whole preparation process is convenient and in- carbon disulfde concentrations for the SiCl -CS binary expensive. Te peak height ratio between the Raman in- 4 2 system. tensities of the target substance and those of the internal Te relative standard error of prediction (RSEP) of the standard is proportional to the concentration of the target substance with a good linear relationship. Tis method standard curve for the SiCl -CS binary system is also cal- 4 2 culated according to equation (4), and the results are shown shows good accuracy when the standard samples are de- tected and the calculated concentration is compared with the in Table 3. Te result in Table 3 shows that the RSEP value of the SiCl concentration for the SiCl -CS binary system is actual concentration. Te relative standard error of pre- 4 4 2 −1 diction (RSEP) is 2.81% and 2.17%, respectively, when de- 3.55% when the peak height ratio at the 422 cm band is used. Te RSEP value of the CS concentration for the SiCl - termining silicon tetrachloride and dichloroethane 2 4 −1 CS binary system is 4.16% at the 654 cm band. Tese concentrations for the SiCl -C H Cl binary system. Te 2 4 2 4 2 results also indicate that these standard curves are reliable RSEP values are 3.55% and 4.16%, respectively, when de- during the determination of SiCl and CS concentrations termining silicon tetrachloride and carbon disulfde con- 4 2 for the SiCl -CS binary system. centrations for the SiCl -CS binary system. Tese results 4 2 4 2 Raman intensity Peak height ratio 10 Journal of Analytical Methods in Chemistry [11] E. Mueh, H. Rauleder, J. Monkiewicz, and R. Schork, “Process indicate that Raman spectroscopy can quantitatively de- and use of amino-functional resins for dismutating hal- termine the concentration of silicon tetrachloride, carbon osilanes and for removing extraneous metals,” disulfde, and dichloroethane when measuring vapor-liquid US20120183464, 2012. equilibrium data for the SiCl -CS and SiCl -C H Cl binary 4 2 4 2 4 2 [12] Y. Wan, X. Zhao, S. Guo, D. Yan, and D. 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