气相色谱法测定1,2-丙二胺的含量

附件10化妆品中乙醇胺等5种有机胺的检测方法1 适用范围本方法规定了测定化妆品中乙醇胺、二乙醇胺、三乙醇胺、二甲胺、二乙胺的离子色谱法。

本方法适用于膏霜、乳、液、粉类化妆品中乙醇胺、二乙醇胺、三乙醇胺、二甲胺、二乙胺的含量测定。

2 方法提要化妆品中乙醇胺等5种有机胺用流动相提取后，经含羧酸功能基的阳离子交换柱分离，电导检测器检测，以保留时间定性，峰面积定量。

对于阳性结果，可用气相色谱-质谱进行进一步确证。

本方法中乙醇胺、二乙醇胺、三乙醇胺、二甲胺、二乙胺的检出限、定量下限及取0.5g样品时的检出浓度和最低定量浓度见表1。

表1 5种有机胺的检出限、定量下限、检出浓度和最低定量浓度物质名称乙醇胺二乙醇胺三乙醇胺二甲胺二乙胺检出限（ng）9定量下限（ng）15 15 30 15 15检出浓度（μg/g）18 18 36 18 18最低定量浓度（μg/g）60 60 120 60 603 试剂和材料除另有规定外，所用试剂均为分析纯，水为一级实验用水。

甲烷磺酸，优级纯。

正已烷。

乙腈，优级纯。

无水乙醇，优级纯。

无水硫酸钠。

乙醇胺，优级纯，纯度≥99%。

二乙醇胺，优级纯，纯度≥99%。

三乙胺，优级纯，纯度≥99%。

二甲胺水溶液，纯度33%。

二乙胺，优级纯，纯度≥99%。

流动相：取甲烷磺酸、50mL乙腈，加水稀释至1L，过滤后备用。

混合标准溶液：分别称取0.1g（精确到0.0001g）乙醇胺、二乙醇胺、二乙胺，及0.2g（精确到0.0001g）三乙醇胺、0.3g（精确到0.0001g）二甲胺水溶液于100mL容量瓶中，用乙腈定容，配成如表2所示浓度的混合标准储备溶液。

吸取储备溶液于100mL容量瓶中，用流动相定容至刻度，摇匀，得到50mg/L乙醇胺、二乙醇胺、二甲胺、二乙胺和100mg/L三乙醇胺混合标准使用溶液，再用流动相稀释混合标准使用溶液配成系列浓度混合标准工作溶液。

表2 5种有机胺混合标准储备溶液及工作溶液浓度物质名称乙醇胺二乙醇胺三乙醇胺二甲胺二乙胺混合标准储备溶液浓度（mg/L）1000 1000 2000 1000 1000混合标准工作溶液浓度（mg/L）12 2 4 2 2 10 10 20 10 10 25 25 50 25 25 50 50 100 50 504 仪器和设备离子色谱仪，具有电导检测器，配色谱工作站。

催化合成1，2—丙二胺研究进展摘要：综述了1，2-丙二胺的催化合成研究进展，详细介绍了二卤丙烷法、醇的催化胺化法、1，2-二甲基乙二肟还原法、氮丙啶法和丙烯腈法制备1，2-丙二胺工艺和催化剂方面的研究进展。

指出了传统1，2-丙二胺合成工艺在现代化学工业发展中面临的困境，认为醇的催化胺化法是1，2-丙二胺合成最有应用潜力的发展方向。

关键词：1，2-丙二胺；选择性；胺化；催化；合成有机脂肪胺及其衍生物是一类重要的化工原料，广泛应用于日用化学品及石油化工等众多领域，在国民经济中占有十分重要的地位。

1，2-丙二胺作为有机胺类化合物重要一员，在有机合成、油品钝化剂、环氧树脂固化促进剂、氨纶、改性虫胶涂料等领域有重要应用，其衍生物还能作为橡胶、涂料的原料和螯合剂、选矿剂等使用，需求量大。

1，2-丙二胺是具有邻位二胺结构的双官能团化合物，性质比较活泼，易于发生反应。

经过不断探索研究，形成了很多1，2-丙二胺的制备方法，大体可以分为两类，一是对传统的1，2-二卤丙烷催化胺化法的深入研究和工艺改进，二是探索以环氧化合物、醇、肟等为原料的催化还原胺化法。

二卤丙烷催化胺化制备1，2-丙二胺反应过程简单，胺化反应成熟，通过控制反应条件可控制反应深度，收率较高。

环氧化合物、氨基醇等的催化还原胺化制备胺类化合物是目前发展比较迅速的活跃领域之一，取得了令人瞩目的成果。

其原料来源十分广泛，工艺简单清洁，除目的产物外，生成的多胺类化合物可分离利用，无其他废弃物。

本文就催化胺化合成1，2-丙二胺综述其研究发展状况。

1 催化合成1，2-丙二胺研究进展1.1 二卤丙烷法以二溴丙烷为原料可以胺化制备1，2-丙二胺，但价格昂贵严重限制了该法的发展。

二氯丙烷是环氧氯丙烷和环氧丙烷生产过程中的副产物，部分用于配制农药外，其余则需要寻找合适的转化途径加以利用。

二氯丙烷的转化利用途径中氨解制备线性胺类和多胺类化合物是十分重要的方法。

俞章森等以二氯丙烷废液和氨为原料对1，2-丙二胺合成工艺进行研究发现，从收率和工业成本考虑采用CuO为催化剂，水为反应溶剂较好。

气相色谱法测定新型卷烟气溶胶中水、烟碱、1,2-丙二醇和丙三醇的含量张丽;王维维;张小涛;胡硕;姬厚伟;万强;陈永芳;刘剑【摘要】提出了同时测定新型卷烟气溶胶中水、烟碱、1,2-丙二醇和丙三醇的气相色谱双柱双检测器法.采用Φ44 mm剑桥滤片捕集5支新型卷烟中气溶胶总粒相物,剑桥滤片用20 mL含3种内标的异丙醇溶液(乙醇为水的内标,2-甲基喹啉为烟碱的内标,1,4-丁二醇为1,2-丙二醇和丙三醇的内标)振荡萃取10 min,萃取液过0.22μm滤膜后进行气相色谱分析.采用Porapak Q2填充柱和热导检测器检测水,采用DB-ALC色谱柱和氢火焰离子化检测器检测烟碱、1,2-丙二醇和丙三醇,内标法定量.结果表明:水、烟碱、1,2-丙二醇和丙三醇的质量浓度在一定范围内与其峰面积和内标峰面积的比值呈线性关系,检出限(3S/N)分别为0.08,0.01,0.02,0.05 mg·支-1.按标准加入法进行回收试验,回收率为92.3％～103％,测定值的相对标准偏差(n=6)为2.4％～9.8％.【期刊名称】《理化检验-化学分册》【年(卷),期】2018(054)010【总页数】6页(P1188-1193)【关键词】气相色谱法;新型卷烟;气溶胶;水;烟碱;1,2-丙二醇;丙三醇【作者】张丽;王维维;张小涛;胡硕;姬厚伟;万强;陈永芳;刘剑【作者单位】贵州中烟工业有限责任公司技术中心,贵阳 550009;贵州中烟工业有限责任公司技术中心,贵阳 550009;贵州中烟工业有限责任公司技术中心,贵阳550009;贵州中烟工业有限责任公司技术中心,贵阳 550009;贵州中烟工业有限责任公司技术中心,贵阳 550009;贵州中烟工业有限责任公司技术中心,贵阳 550009;贵州中烟工业有限责任公司技术中心,贵阳 550009;贵州中烟工业有限责任公司技术中心,贵阳 550009【正文语种】中文【中图分类】O657.7与传统卷烟不同，新型卷烟主要是通过低温加热的方式(400℃以下)将烟草烟碱和香味成分释放出来［1］，从而减少了烟草因高温燃烧裂解所产生的化学成分，使得卷烟烟气中有害成分大幅度降低且无侧流烟气的释放［2-3］。

气相色谱法同时检测加热不燃烧卷烟芯材中的1,2-丙二醇、烟碱与甘油含量赵光飞;张一扬;周桂园;刘静;屠彦刚;陈华;任俞澄;吴建霖;陈绍全;陈宇超;李锐【摘要】为准确测量加热不燃烧卷烟芯材中的1,2-丙二醇、烟碱与甘油含量,将加热不燃烧卷烟芯材样品切丝,以1,4丁二醇、正十七碳烷为内标,异丙醇内标溶液振荡萃取2 h,建立气相色谱法同时测定1,2-丙二醇、烟碱和甘油含量,并利用卡尔费休水分电位滴定仪检测样品中水分,计算得到样品中1,2-丙二醇、烟碱和甘油的绝干含量.结果表明1,2-丙二醇、烟碱、甘油分别在1.0～10.0 mg/mL、0.1～1.0 mg/mL、1.0～10.0 mg/mL范围内,工作曲线线性良好,相关系数均高于0.999,相对标准偏差分别为1.50％、2.62％、0.70％,加标回收率在97.11％～102.62％之间,检出限分别为0.019 mg/mL、0.009 mg/mL、0.011 mg/mL,定量限分别为0.064 mg/mL、0.030 mg/mL、0.039 mg/mL.该方法前处理简单、安全,定量结果准确可靠、重现性好,适用于加热不燃烧卷烟芯材中1,2-丙二醇、烟碱、甘油定量分析.【期刊名称】《中国测试》【年(卷),期】2019(045)003【总页数】6页(P69-74)【关键词】气相色谱法;加热不燃烧卷烟芯材;1,2-丙二醇;烟碱;甘油【作者】赵光飞;张一扬;周桂园;刘静;屠彦刚;陈华;任俞澄;吴建霖;陈绍全;陈宇超;李锐【作者单位】湖南农业大学烟草研究院,湖南长沙 410128;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;湖南农业大学烟草研究院,湖南长沙 410128;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100;中烟施伟策(云南)再造烟叶有限公司,云南玉溪 653100【正文语种】中文【中图分类】TS411;O657.710 引言加热不燃烧型烟草制品具有“加热烟草而不燃烧烟草”的特点，在感官质量及吸食方式上与传统烟草制品最为相似[1]，在满足消费者吸烟体验的同时，能够有效降低有害成分的释放量[2-4]。

直接进样气相色谱法测定水中的1，2-环氧丙烷易睿，高娟，鲁宝权扬州市环境监测中心站，江苏扬州225009摘要：建立了气相色谱法测定水中1，2-环氧丙烷的方法。

采用小体积直接进样，键合交联毛细管柱分离，氢火焰离子化检测器，在几分钟内完成了测定。

该方法线形测定范围为0.859～17.18mg/L，相对标准偏差不大于8%，加标回收率为97.0%～104%，标准曲线相关系数为0.9996，检出限为0.01mg/L，可用于水中1，2-环氧丙烷的分析测定。

关键词：直接进样气相色谱1，2-环氧丙烷水Determination of Propylene Oxide in Water by GC with Direct InjectionYI Rui , Gao Juan, LU Bao-Quanyangzhou environmental monitoring central station ,yangzhou ,jiangsu 225009,china Abstract：A new method for determination of propylene oxide in water by GC was established. Propylene oxide was quickly determined within several minutes by capillary gas chromatography with hydrogen FID and small volume direct injection. The linear range of the method was 0.859～17.18mg/L.The relative standard deviations was no more than 8%.The average recovery was 97.0%～104%.The correlation coefficient of the standard curve was 0.9996 and the lowest limit of detection was 0.01mg/L.The method can be used for monitoring of propylene oxide in water. Keywords: direct injection, gas chromatography, propylene oxide, water1 前言1，2-环氧丙烷（Propylene oxide）是石油化工重要中间体之一，是仅次于聚丙烯和丙烯腈的第三大丙烯类衍生物。

METHOD 80111,2-DIBROMOETHANE AND 1,2-DIBROMO-3-CHLOROPROPANEBY MICROEXTRACTION AND GAS CHROMATOGRAPHY1.0SCOPE AND APPLICATION1.1This method is applicable to the determination of the following compounds in drinking water and ground water:_________________________________________________________________Compound Name CAS No.a1,2-Dibromoethane (EDB) 106-93-41,2-Dibromo-3-chloropropane (DBCP) 96-12-8_________________________________________________________________aChemical Abstract Services Registry Number.1.2For compounds and matrices other than those listed in Section 1.1, the laboratory must demonstrate the usefulness of the method by collecting precision and accuracy data on actual samples and provide qualitative confirmation of results by gas chromatography/mass spectrometry (GC/MS).1.3The experimentally determined method detection limits (MDL) for EDB and DBCP were calculated to be 0.01 µg/L. The method has been shown to be useful for these analytes over a concentration range of approximately 0.03 to 200 µg/L. Actual detection limits are highly dependent upon the characteristics of the gas chromatographic system, sample matrix, and calibration.1.4This method is restricted to use by or under the Supervision of analysts experienced in the use of gas chromatography and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.1.51,2-Dibromoethane and 1,2-Dibromo-3-chloropropane have been tentatively classified as known or suspected human or mammalian carcinogens. Pure standard materials and stock standard solutions of these compounds should be handled in a hood. A NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles high concentrations of these toxic compounds.2.0SUMMARY OF METHOD2.1Thirty five mL of sample are extracted with 2 mL of hexane. Two µL of the extract are then injected into a gas chromatograph equipped with a linearized electron capture detector for separation and analysis. Aqueous matrix spikes are extracted and analyzed in an identical manner as the samples in order to compensate for possible extraction losses.2.2The extraction and analysis time is 30 to 50 minutes per sample depending upon the analytical conditions chosen. See Table 1 and Figure 1.2.3Confirmatory evidence is obtained using a different column (Table 1).3.0INTERFERENCES3.1Impurities contained in the extracting solvent (hexane) usually account for the majority of the analytical problems. Reagent blanks should be analyzed for each new bottle of hexane before use. Indirect daily checks on the hexane are obtained by monitoring the reagent blanks. Whenever an interference is noted in the method or instrument blank, the laboratory should reanalyze the hexane. Low level interferences generally can be removed by distillation or column chromatography, however, it is generally more economical to obtain a new source of hexane solvent. Interference-free hexane is defined as containing less than 0.01 µg/L of the analytes. Protect interference-free hexane by storing it in an area known to be free of organochlorine solvents.3.2Several instances of accidental sample contamination have been attributed to diffusion of volatile organics through the septum seal into the sample bottle during shipment and storage. Trip blanks must be used to monitor for this problem.3.3This liquid/liquid extraction technique extracts a wide boiling range of non-polar organic compounds and, in addition, extracts some polar organic compounds.3.4EDB at low concentrations may be masked by very high concentrations of dibromochloromethane (DBCM), a common chlorinated drinking water contaminant, when using the confirmation column.4.0APPARATUS AND MATERIALS4.1Microsyringe - 10, 25, and 100 µL with a 2 in. x 0.006 in. needle (Hamilton 702N or equivalent).4.2Gas Chromatograph4.2.1The GC must be capable of temperature programming and shouldbe equipped with a linearized electron capture detector and a capillary column splitless injector.4.2.2Columns4.2.2.1Column A - 0.32 mm ID x 30 m fused silicacapillary with dimethyl silicone mixed phase (Durawax-DX 3, 0.25 µmfilm, or equivalent).4.2.2.2Column B (confirmation column) - 0.32 mm ID x 30 mfused silica capillary with methyl polysiloxane phase (DB-1, 0.25 µmfilm, or equivalent).4.3Volumetric flasks, Class A - 10 mL.4.4Glass bottles - 15 mL, with Teflon lined screw caps or crimp tops.4.5Analytical balance - 0.0001 g.4.6Graduated cylinder - 50 mL.4.7Transfer pipet.5.0REAGENTS5.1Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination.5.2Organic-free reagent water - All references to water in this method refer to organic-free reagent water, as defined in Chapter One.5.3Hexane, C H - UV grade (Burdick and Jackson #216 or equivalent).6145.4Methyl alcohol, CH OH - Demonstrated to be free of analytes.35.5Sodium chloride, NaCl - Pulverize a batch of NaCl and place it in ao muffle furnace at room temperature. Increase the temperature to 400C for 30 minutes. Store in a capped bottle.5.61,2-Dibromoethane (99%), C H Br, (Aldrich Chemical Company, or242equivalent).5.7 1,2-Dibromoe-3-chloropropane (99.4%), C H Br C1, (AMVAC Chemical352Corporation, Los Angeles, California, or equivalent).5.8Stock standards - These solutions may be purchased as certified solutions or prepared from pure standards using the following procedures:5.8.1Place about 9.8 mL of methanol into a 10 mL ground glassstoppered volumetric flask. Allow the flask to stand, unstoppered, for about 10 minutes and weigh to the nearest 0.0001 g.5.8.2Use a 25 µL syringe and immediately add two or more drops(. 10 µL) of standard to the flask. Be sure that the standard falls directly into the alcohol without contacting the neck of the flask.5.8.3Reweigh, dilute to volume, stopper, and then mix by invertingthe flask several times. Calculate the concentration in milligrams per liter (mg/L) from the net gain in weight. When compound purity is assayed to be 96% or greater, the weight may be used without correction to calculate the concentration of the stock standard.5.8.4Store stock standards in 15 mL bottles equipped with Teflonlined screw-caps or crimp tops. Stock standards are stable for at leastofour weeks when stored at 4C and away from light.5.9Intermediate standard - Use stock standards to prepare an intermediate standard that contains both analytes in methanol. The intermediate standard should be prepared at a concentration that can be easily diluted to prepare aqueous calibration standards that will bracket the working concentration range. Store the intermediate standard with minimal headspace and check frequently for signs of deterioration or evaporation, especially just before preparing calibration standards. The storage time described for stock standards also applies to the intermediate standard.5.10Quality control (QC) reference sample - Prepare a QC reference sample concentrate at 0.25 mg/L of both analytes from standards from a different source than the standards used for the stock standard.5.11Check standard - Add an appropriate volume of the intermediate standard to an aliquot of organic-free reagent water in a volumetric flask. Do not add more than 20 µL of an alcoholic intermediate standard to the water or poor precision will result. Use a 25 µL microsyringe and rapidly inject the alcoholic intermediate standard into the expanded area of the almost filled volumetric flask. Remove the needle as quickly as possible after injection. Mix by inverting the flask several times. Discard the contents contained in the neck of the flask. Aqueous calibration standards should be prepared every 8 hours.6.0SAMPLE COLLECTION, PRESERVATION, AND STORAGE6.1See the introductory material to this chapter, Organic Analytes, Section 4.1.7.0PROCEDURE7.1Recommended Chromatographic ConditionsTwo gas chromatography columns are recommended. Column A is a highly efficient column that provides separations for EDB and DBCP without interferences from trihalomethanes. Column A should be used as the primary analytical column unless routinely occurring analytes are not adequately resolved. Column B is recommended for use as a confirmatory column when GC/MS confirmation is not available. Retention times for EDB and DBCP on these columns are presented in Table 1.Column A:oInjector temperature: 200C.oDetector temperature: 290C.Carrier gas (Helium)Linear velocity: 25 cm/sec.Temperature program:oInitial temperature: 40C, hold for 4 min.o o oProgram: 40C to 190C at 8C/min.oFinal temperature: 190C, hold for 25 min., or until all expected analytes have eluted.See Figure 1 for a sample chromatogram and Table 1 for retention data.Column B:oInjector temperature:200C.oDetector temperature:290C.Carrier gas (Helium)Linear velocity:25 cm/sec.Temperature program:oInitial temperature:40C, hold for 4 min.o o oProgram:40C to 270C at 10C/min.oFinal temperature:270C, hold for 10 min., or untilall expected analytes have eluted.See Table 1 for retention data.7.2Calibration7.2.1Prepare at least five calibration standards. One shouldcontain EDB and DBCP at a concentration near, but greater than, the method detection limit (Table 1) for each compound. The others should be at concentrations that bracket the range expected in the samples. For example, if the MDL is 0.01 µg/L, and a sample expected to contain approximately 0.10 µg/L is to be analyzed, aqueous calibration standards should be prepared at concentrations of 0.03 µg/L, 0.05 µg/L, 0.10 µg/L,0.15 µg/L, and 0.20 µg/L.7.2.2Analyze each calibration standard and tabulate peak height orarea response versus the concentration in the standard. Prepare a calibration curve for each compound. Alternatively, if the ratio of response to concentration (calibration factor) is a constant over the working range (< 10% relative standard deviation), linearity can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.7.3Sample preparation7.3.1Remove samples and standards from storage and allow them toreach room temperature.7.3.2For samples and field blanks contained in 40 mL bottles,remove the container cap. Discard a 5 mL volume using a 5 mL transfer pipet. Replace the container cap and weigh the container with contents to the nearest 0.1 g and record this weight for subsequent sample volume determination.7.3.3For calibration standards, check standards, QC referencesamples, and blanks, measure a 35 mL volume using a 50 mL graduated cylinder and transfer it to a 40 mL sample container.7.4Extraction7.4.1Remove the container cap and add 7 g of NaCl to all samples.7.4.2Recap the sample container and dissolve the NaCl by shaking by hand for about 20 seconds.7.4.3Remove the cap and using a transfer pipet, add 2.0 mL of hexane. Recap and shake vigorously by hand for 1 minute. Allow the water and hexane phases to separate. If stored at this stage, keep the container upside down.7.4.4Remove the cap and carefully transfer a sufficient amount (0.5-1.0 mL) of the hexane layer into a vial using a disposable glass pipet.7.4.5Transfer the remaining hexane phase, being careful not to include any of the water phase, into a second vial. Reserve this second ovial at 4C for reanalysis if necessary.7.5Analysis7.5.1Transfer the first sample vial to an autosampler set up to inject 2.0 µL portions into the gas chromatograph for analysis. Alternately, 2 µL portions of samples, blanks and standards may be manually injected, using the solvent flush technique, although an auto sampler is strongly recommended.7.6Determination of sample volume7.6.1For samples and field blanks, remove the cap from the sample container. Discard the remaining sample/hexane mixture. Shake off the remaining few drops using short, brisk wrist movements. Reweigh the empty container with original cap and calculate the net weight of sample by difference to the nearest 0.1 g. This net weight is equivalent to the volume of water extracted.7.7Calculations7.7.1Identify EDB and DBCP in the sample chromatogram by comparing the retention time of the suspect peak to retention times generated by the calibration standards and the check standard.7.7.2Use the calibration curve or calibration factor to directlycalculate the uncorrected concentration (C) of each analyte in the samplei(e.g. calibration factor x response).7.7.3Calculate the sample volume (V) as equal to the net samplesweight:V (mL) = gross weight (grams) - bottle tare (grams)s7.7.4Calculate the corrected sample concentration as:Concentration (µg/L) = C x 35iVs7.7.5Report the results for the unknown samples in µg/L. Round theresults to the nearest 0.01 µg/L or two significant figures.8.0QUALITY CONTROL8.1Each laboratory that uses this method is required to operate a formal quality control program.8.1.1The laboratory must make an initial determination of themethod detection limits and demonstrate the ability to generate acceptable accuracy and precision with this method. This is established as described in Section 8.2.8.1.2In recognition of laboratory advances that are occurring inchromatography, the laboratory is permitted certain options to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 7.1 and 8.2.8.1.3The laboratory must analyze a reagent and calibration blank todemonstrate that interferences from the analytical system are under control every twenty samples or per analytical batch, whichever is more frequent.8.1.4The laboratory must, on an ongoing basis, demonstrate throughthe analyses of QC reference samples and check standards that the operation of the measurement system is in control. The frequency of the check standard analyses is equivalent to 5% of all samples or every analytical batch, whichever is more frequent. On a weekly basis, the QC reference sample must be run.8.2To establish the ability to achieve low detection limits and generate acceptable accuracy and precision, the analyst must perform the following operations:8.2.1Prepare seven samples each at a concentration of 0.03 µg/L.8.2.2Analyze the samples according to the method beginning inSection 7.0._8.2.3Calculate the average concentration (X) in µg/L and thestandard deviation of the concentrations (s) in µg/L, for each analyte using the seven results. Then calculate the MDL at 99% confidence level for seven replicates as 3.143s._8.2.4For each analyte in an aqueous matrix sample, X must bebetween 60% and 140% of the true value. Additionally, the MDL may not exceed the 0.03 µg/L spiked concentration. If both analytes meet the acceptance criteria, the system performance is acceptable and analysis of actual samples can begin. If either analyte fails to meet a criterion, repeat the test. It is recommended that the laboratory repeat the MDL determination on a regular basis.8.3The laboratory must demonstrate on a frequency equivalent to 5% of the sample load or once per analytical batch, whichever is more frequent, that the measurement system is in control by analyzing a check standard of both analytes at 0.25 µg/L.8.3.1Prepare a check standard (0.25 µg/L) by diluting theintermediate standard with water to 0.25 µg/L.8.3.2Analyze the sample according to Section 7.0 and calculate therecovery for each analyte. The recovery must be between 60% and 140% of the expected value for aqueous matrices. For non-aqueous matrices, the U.S. EPA will set criteria after more interlaboratory data are gathered.8.3.3If the recovery for either analyte falls outside thedesignated range, the analyte fails the acceptance criteria. A second calibration verification standard containing each analyte that failed must be analyzed. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test.8.4On a weekly basis, the laboratory must demonstrate the ability to analyze a QC reference sample.8.4.1Prepare a QC reference sample at 0.10 µg/L by diluting the QCreference sample concentrate (Section 5.9).8.4.2For each analyte in an aqueous matrix, the recovery must bebetween 60% and 140% of the expected value. When either analyte fails the test, the analyst must repeat the test only for that analyte which failed to meet the criteria. Repeated failure, however, will confirm a general problem with the measurement system or faulty samples and/or standards.If this occurs, locate and correct the source of the problem and repeat the test. For non-aqueous matrices, the U.S. EPA will set criteria after more interlaboratory data are gathered.8.5Instrument performance - Check the performance of the entire analytical system daily using data gathered from analyses of blanks, standards, and replicate samples.8.5.1Peak tailing significantly in excess of that shown in thechromatogram (Figure 1) must be corrected. Tailing problems are generally traceable to active sites on the GC column or to the detector operation.8.5.2Check the precision between replicate analyses. A properlyoperating system should perform with an average relative standard deviation of less than 10%. Poor precision is generally traceable to pneumatic leaks, especially at the injection port.9.0METHOD PERFORMANCE9.1Method detection limits are presented in Table 1. Single laboratory accuracy and precision at several concentrations in tap water are presented in Table 2.9.2In a preservation study extending over a 4 week period, the average percent recoveries and relative standard deviations presented in Table 3 were observed for organic-free reagent water (acidified), tap water and ground water. The results for acidified and non-acidified samples were not significantly different.10.0 REFERENCES1.Optimization of Liquid-Liquid Extraction Methods for Analysis of Organicsin Water, EPA-600/S4-83-052, 1984.2.Henderson, J.E.; Peyton, G.R.; Glaze, W.H. Identification and Analysis ofOrganic Pollutants in Water; Keith, L.H., Ed; Ann Arbor Sci.: Ann Arbor, MI; 1976.3.Richard J.J.; Junk, G.A. Journal AWWA 1977, 69, 62.4.Budde, W.L.; Eichelberger, J.W. Organic Analyses Using Gas Chromatography-Mass Spectrometry; Ann Arbor Science: Ann Arbor, MI; 1978.5.Glaser, J.A.; et al. Environmental Science and Technology 1981, 15, 1426.6.Methods for the Determination of Organic Compounds in Finished DrinkingWater and Raw Source Water; U.S. Environmental Protection Agency. Office of Research and Development. Environmental Monitoring and Support Laboratory. ORD Publication Offices of Center for Environmental Research Information: Cincinnati, OH 1986.TABLE 1.CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTIONLIMITS (MDL) FOR 1,2-DIBROMOETHANE (EDB) AND1,2-DIBROMO-3-CHLOROPROPANE (DBCP)______________________________________________________________________________ Retention Time, Minutes Analyte Column A Column B MDL (µg/L) EDB 9.5 8.9 0.01 DBCP 17.3 15.0 0.01 Column A: Durawax-DX 3Column B: DB-1______________________________________________________________________________ TABLE 2.SINGLE LABORATORY ACCURACY AND PRECISIONFOR EDB AND DBCP IN TAP WATER______________________________________________________________________________RelativeNumber Spike Average Standardof Concentration Recovery DeviationAnalyte Samples(µg/L) (%) (%)EDB 7 0.03 114 9.57 0.24 98 11.87 50.0 95 4.7DBCP 7 0.03 90 11.47 0.24 102 8.37 50.0 94 4.8______________________________________________________________________________TABLE 3.ACCURACY AND PRECISION AT 2.0 µg/LOVER A 4-WEEK STUDY PERIOD______________________________________________________________________________ Average RelativeNumber Accuracy Std. Dev.1Analyte Matrix of Samples (% Recovery) (%)EDB RW-A 16 104 4.7GW 15 101 2.5GW-A 16 96 4.7TW 16 93 6.3TW-A 16 93 6.1DBCP RW-A 16 105 8.2GW 16 105 6.2GW-A 16 101 8.4TW 16 95 10.1TW-A 16 94 6.91RW-A=Organic-free reagent water at pH 2GW=Ground water, ambient pHGW-A=Ground water at pH 2TW=Tap water, ambient pHTW-A=Tap water at pH 2SAMPLE CHROMATOGRAM FOR EXTRACT OF WATER SPIKED AT 0.114 µg/L WITH EDB AND DBCP1,2-DIBROMOETHANE AND 1,2-DIBROMO-3-CHLOROPROPANE BY MICROEXTRACTION AND GAS CHROMATOGRAPHY。

气相色谱内标法测定乙二胺、哌嗪及三乙烯二胺含量刘文;马平;李平;田红丽;刘荣杰【摘要】利用气相色谱内标法定量分析乙二胺、哌嗪及三乙烯二胺的含量.以正癸醇为内标,结合气相色谱内标法原理及色谱工作站特点,用峰面积比代替以往峰面积记录数据,测定乙二胺、哌嗪及三乙烯二胺的含量.确立了乙二胺、哌嗪、三乙烯二胺的内标标准曲线,各标准曲线方程的线性相关系数r≥0.999,标准偏差0.56％～1.36％,精密度高,重复性好,可用于乙二胺、哌嗪及三乙烯二胺的含量测定.实验表明内标定量分析法准确度高、精密度好,可用于哌嗪合成体系中上述组分的定量和研究.【期刊名称】《应用化工》【年(卷),期】2014(043)003【总页数】3页(P554-556)【关键词】气相色谱;内标法;哌嗪合成体系;正癸醇【作者】刘文;马平;李平;田红丽;刘荣杰【作者单位】西北大学化工学院,陕西西安710069;银川大学石油化工学院,宁夏银川750105;银川大学石油化工学院,宁夏银川750105;银川大学石油化工学院,宁夏银川750105;银川大学石油化工学院,宁夏银川750105【正文语种】中文【中图分类】TQ207+.4乙二胺催化合成无水哌嗪反应中，三乙烯二胺为反应的主要副产物，为获得反应的转化率和收率，需要对产物中乙二胺、哌嗪及三乙烯二胺的含量进行测定。

在以往的定量过程中，大多采用外标法，但对于易挥发的乙二胺来说，用气相色谱外标法分析其含量，很难控制进样量，因此定量不准确。

而内标法在一定程度上可以消除操作条件变化所引起的误差，较之外标法具有受色谱条件影响小、定量准确等优点［1-2］。

故本研究采用内标法对哌嗪合成体系中的上述组分进行定量和研究，结果满意，方法可行。

聚乙二醇为氢键型固定液，用于分离醇、酮、醛等含氧化合物及一般应用［2］。

乙二胺、哌嗪、三乙烯二胺均为二胺类有机化合物，与醛、酮可发生加成缩合反应(排除醛、酮类溶剂);甲醇、乙醇与乙二胺极性相似，在该填充柱上不能完全分离。

气相色谱法测定依托咪酯注射液中丙二醇的含量作者：赵鑫来源：《科学与财富》2018年第11期摘要：目的：为医疗业的健康有序发展，为以后的医疗科研和临床研究提供依据。

进行对于依托咪酯注射液的测定，以确定这种测定方法是否能够测定出其中1，2一丙二醇含量。

方法：主要采用的是气相色谱法，以正辛醇为内标，色谱柱为毛细管柱（30m×0.53mm×1μm），汽化室温度220℃，程序升温：初始温度为120℃，维持3分钟；以每分钟10℃的速度升至250℃，保持5min。

载气：氮气，流速为4mL·min-1；检测室温度250℃，尾吹30mL·min-1，进样量1μL。

结果：上述测定方法能使内标（正辛醇）、1，2一丙二醇、1，3～丙二醇和二甘醇良好分离，1，2一丙二醇在50～1500μg·mL-1的范围内丙二醇浓度（C）与峰面积响应值有良好的线性关系，r=O.9999；进样精密度、日内测定精密度、日间精密度的RSD分别为1.5%、1.5%、1.3%；平均回收率（n=9）为100.6%，RSD为1.4%：方法定量限和检测限分别为2.0、0.62μg·m L-1。

结论：在进行依托咪酯注射液中丙二醇的含量测定时，气相色谱法具有明显的效果，可以控制其中具体丙二醇的含量。

关键词：丙二醇；含量测定；气相色谱法依托咪酯注射液简单来说就是能够进行全身麻醉的药物，在临床上具有广泛的用途，其催眠效果是正常麻药的好几倍，而且还对人身体的其他部位没有重大影响，值得被人们进行研究。

它的实际用途也是非常广泛，其优点多，因此深受大家的喜爱。

而气相色谱法是一种先进的医疗中的技术，是现代科技发展的产物，具有方便、快捷且有效的特点，在医疗的其他研究方面也都有广泛应用，能够帮助医疗工作人员对化合物进行分离，从而在科研上具有极大的应用价值，是良好的技术使用工具，对医生的研究工作起到了不少作用。

其中咪酯注射液的分离工作主要应用的工具手段就是气相色谱法。