氮气中六氟化硫气体标准物质的研制

建立了制备氮气中六氟化硫气体标准物质的方法。以称量法制备气体标准物质并计算定值,采用气相色谱法对制备的气体标准物质的均匀性和稳定性进行考察。将所制备的标准物质与中国计量院提供的氮气中六氟化硫气体标准物质进行比对分析验证,确保了气体标准物质量值的准确可靠。结果表明,所研制的浓度为10μL/L的氮气中六氟化硫气体标准物质定值的扩展不确定度为2%,贮存有效期为1年,完全能够满足电力部门仪表的检定与校准要求。     

二氧化碳中一氧化氮气体标准物质研制

研制二氧化碳中一氧化氮气体标准物质。以高纯二氧化碳和一氧化氮气体标准物质为原料,采用称量法制备二氧化碳中一氧化氮气体标准物质,用气体分析仪对制备的标准物质浓度进行检测,并对该标准物质定值结果的不确定度进行评定。研制的二氧化碳中一氧化氮气体标准物质中一氧化氮的浓度为5,25,50 μmol/mol,相对扩展不确定度为3.0% (k=2)。该气体标准物质具有良好的均匀性和稳定性,可用于食品级二氧化碳分析方法的确认和评价。     

空气中偏二甲肼气体标准物质的研制

采用称量法制备空气中偏二甲肼气体标准物质,分别用F检验和回归曲线法对研制的标准物质进行均匀性和稳定性检验。结果表明,研制的空气中偏二甲肼气体标准物质具有良好的均匀性和稳定性,定值结果分别为10,500μmol/mol,定值结果的相对扩展不确定度为2%(k=2)。该标准物质可用于偏二甲肼报警器的检定或校准。     

电力变压器油中溶解气体分析用标准物质的研制

采用称量法制备了电力变压器油中溶解气体分析用气体标准物质,分别用F检验和回归曲线法对研制的标准物质进行了均匀性和稳定性检验。结果表明,研制的电力变压器油中溶解气体分析用标准物质具有良好的均匀性和稳定性,标准物质定值结果为5 000μmol/mol,定值结果的相对扩展不确定度为1%(k=2)。该标准物质可用于电力部门变压器油中溶解气体的分析及测试。     

氦离子化气相色谱仪校准用混合物中甲烷气体标准物质研制

介绍氦中甲烷气体标准物质的制备方法.以超纯氦气和高纯甲烷为原料,采用称量法制备特性值为10μmol/mol的氦中甲烷气体标准物质.采用气相色谱法(DID检测器)对制备的标准物质进行均匀性、稳定性检验,并对定值结果的不确定度进行评定.研制的气体标准物质均匀性和稳定性良好,有效期为12个月,相对扩展不确定度为2％(k=2)...     

氦气分析用杂质成分气体标准物质研制

采用称量法研制了氦气中微量氖、氢、氧、氮、甲烷、二氧化碳和一氧化碳7种杂质成分气体标准物质,介绍了称量法制备技术、稀释气中相关杂质的定量等过程,并分别用F检验和回归曲线法对研制的气体标准物质进行了均匀性和稳定性检验.结果表明,研制的氦气分析用杂质成分气体标准物质具有良好的均匀性和稳定性,气体标准物质定值结果为10μmo...     

甲烷中微量噻吩气体标准物质研制

研制了甲烷中噻吩气体标准物质。以高纯噻吩、高纯甲烷为原材料，包装容器为4 L内壁经抛光处理的铝合金瓶，通过微量转移与常规相结合的方法完成了甲烷中微量噻吩气体标准物质制备。利用气相色谱法对标准物质进行了均匀性检验及稳定性考察。F检验和回归曲线法实验结果表明，该气体标准物质在压力为0.5～10 MPa范围内，均匀性良好，在常温条件下保存12个月稳定。采用称量法对该气体标准物质进行了定值，并对定值、均匀性和稳定性引入的不确定度进行了评定，该系列甲烷中微量噻吩气体标准物质标称摩尔分数为1.00～10.0μmol/mol，定值结果的相对扩展不确定度为2%(k=2)。     

PE熔体流动速率标准物质的研制

介绍PE熔体流动速率标准物质的研制过程。采用聚合物共混技术制备标准物质,6家实验室协作定值,定值方法采用GB／T3682—2000标准。研制的PE熔体流动速率标准物质的均匀性、稳定性良好,定值结果准确、可靠。标准物质的稳定期大于1a,标准值为20．10g／(10min),扩展不确定度为0．46g／(10min)。     

超高强度钢（35CrNi3Mo）化学成分标准物质研制

采用与超高强度钢,台炼过程相同的工艺制备了35CrNi3Mo化学成分标准物质。对标准物质的制备技术、均匀性检验、稳定性考察进行了分析。研制的35CrNi3Mo化学成分标准物质具有良好的均匀性和稳定性。采用8家实验室进行协作定值,对定值结果的不确定度进行评定,各组分定值结果的相对扩展不确定度小于13％。     

《化学分析计量》2005年总目次

标准物质氧弹燃烧-离子色谱法测定原油标准物质中硫含量………(1-4)碳素钢氧氮气体标准样品的研制……………………………(2-4)吡虫啉标准样品的研制………………………………………(3-4)纳米二氧化硅标准物质候选物的制备………………………(3-8)氮中二氧化硫标准气体定值方法的研究……………………(4-4)高纯硅溶胶成分标准物质的制备……………………………(5-4)不确定度聚氯化铝中氧化铝含量的测量不确定度评定………………(1-8)粘油类产品中钠快速测定方法测量不确定度的评定………(1-12)果蔬类农产品中农药残留量检测的不确定度评定……     

低浓度氮中二氧化硫气体标准物质的制备

以二氧化硫纯度标准物质和高纯氮气为原料,采用与一级标准物质比较法制备了摩尔分数为10~100μmol/mol的氮中二氧化硫标准物质。用二氧化硫分析仪对配制的标准物质进行了机械混匀试验、压力均匀性和时间稳定性试验。结果表明,滚动30~80 min后该标准物质机械混匀良好;经F检验,在10~0.5 MPa范围内该标准物质量随压力变化无显著差异,具有较好的压力均匀性;在–20℃和40℃条件下保存7 d,其量值无显著变化,可满足运输环节量值稳定性要求;在常温下贮存11个月,量值无显著性变化,满足国家二级标准物质稳定性要求。采用与一级标准物质比较法定值,并对定值结果的不确定度进行了评定。研制的低浓度氮中二氧化硫气体标准物质的标准值分别为9.89,55.4,101.2μmol/mol(U_(rel)=2%,k=2),该标准物质满足国家二级标准物质的相关技术要求,可用于仪器校准、测量过程质量控制及分析方法的确认和评价。     

压力对加压煤气化过程中氮释放的影响

为了解大型加压煤气化过程中污染物分布状态及其影响因素,着重研究了压力对加压大型煤气化过程中氮释放的影响。对晋城无烟煤在φ800 mm加压灰熔聚流化床煤气化实验进行跟踪采样分析,水蒸气和氧气作为气化介质(Steam/O₂≈3/1, 体积比),气化炉内反应温度为1 000℃,考察0.6、1.0、1.5、2.0 MPa四种气化压力下氮化物在产物中的分布。结果表明,氮元素主要分布在气相产物中,随着气化压力增大固相产物中的氮含量增加,气相产物的氮含量先增加,在1.0 MPa以后呈现略微下降的趋势,并通过对比分析晋城无烟煤和气化底渣的氮赋存形态,从微观层面进一步探讨压力对氮分布规律的影响方式。     

Determination of trace organic carbon and nitrogen in the presence of carbonates in anorganic bovine bone graft materials

The widespread concern of bovine spongiform encephalopathy (mad cow disease) has raised questions about the possibility of residual organic material in bovine-derived bone graft materials. Conflicting reports have shown both the presence and the absence of organic materials in bone derived products. This study compared residual organic levels in two commercial bone graft products: a bovine bone product treated chemically and at low temperature, and a bovine bone product treated at high temperature. In this study, organic carbon, the primary constituent of organic materials, is defined as carbon that is not liberated as CO₂ upon acidification (i.e. non-carbonate carbon). Three approaches to the determination were used: (1) organic carbon was calculated as the difference between total carbon determined by high temperature combustion and carbonate carbon determined by acid evolution of CO₂. (2) Organic carbon was determined by measuring total carbon by high temperature combustion of a sample that had been pretreated with acid to remove all carbonate. (3) The total organic carbon remaining in solution after acid dissolution was determined. In addition, organic nitrogen was determined as the difference between total Kjeldahl and ammonia nitrogen. Total nitrogen values were confirmed using an instrumental nitrogen analyzer. No detectable organic carbon or organic nitrogen was observed in the high temperature bone product. In the low temperature treated bovine product, however, approximately 2000 μg/g organic carbon was measured by all three methods, as well as 15 μg/g organic nitrogen.     

三氟化氮纯度的分析

介绍三氟化氮中主要杂质组分含量的分析方法、标准物质的正确使用方法、杂质含量分析结果以及三氟化氮纯度测量结果不确定度的评价。     

Certified Reference Materials for Micro-Analysis of Carbon and Nitrogen

Quantitative analysis by electron probe micro analysis (EPMA) is usually carried out by reference to materials of known composition (standards) but because of the low X-ray yield arising from electron bombardment of low atomic number elements there is a particular problem when analysing these elements. This paper addresses the problem by describing briefly the production and certification of reference materials for two elements, carbon and nitrogen. Cementite (Fe₃C), a line compound, was chosen as a suitable material for carbon and -Fe₄N for nitrogen. The compounds were produced by, respectively, carburising or nitriding pure iron under carefully controlled conditions. Particular emphasis is placed on a homogeneity study, background correction methods and methodology validation using these reference materials. A linear relationship was established between the certified content of the material and zero. Certified values (6.69±k 0.13wt% C and 5.77±k 0.094wt% N) were assigned for the composition, where k is the coverage factor.     

载Na胜利褐煤热解过程中氮的迁移转化

采用具有流化床/固定床特征的石英反应器进行不同Na负载量的胜利褐煤热解实验,考察不同Na负载量对煤热解过程中氮迁移的影响。用紫外可见分光光度计分析气相的NH_3和HCN,用X光电子能谱仪(XPS)表征固体半焦中有机氮的存在形式。结果表明,低温热解时,增加Na的含量对煤中氮转化为NH_3起促进作用;高温热解时,Na抑制煤中氮转化为NH_3。Na对煤中氮转化为HCN表现为抑制作用,这种影响规律不随温度而变化。载Na量增加降低半焦氮含量,促进半焦中季氮的生成,但这种影响在低温时不明显。     

气相色谱-氮化学发光检测法分析催化汽油中含氮化合物类型的分布

建立了催化汽油馏分中各种含氮化合物类型分布的气相色谱-氮化学发光检测分析方法,考察了各种色谱条件对含氮化合物分离的影响。采用化学预处理的方法浓缩了催化汽油中的含氮化合物,并结合气相色谱-质谱检测以及部分含氮化合物标准样品,对某催化汽油中的20多个含氮化合物进行了定性(或归类)。催化汽油中几种主要含氮化合物(苯胺、2-甲基苯胺、二甲基苯胺)含量测定值的相对标准偏差(RSD)均不大于2.5%。当信噪比(S/N)为3时,苯胺氮的检出限为1.0 mg/L。该方法可用于不同来源和不同加工工艺的汽油馏分中各种含氮化合物类型分布的研究。     

High-performance ion chromatography assessment of inorganic and organic nitrogen fractions in potatoes

A new high-performance ion chromatography assay for organic and inorganic nitrogen analysis has been proposed and examined. In the devised protocol, inorganic sample constituents were measured after ultrasonically assisted water extraction. The amine and amide nitrogen content was assessed after modified Kjeldahl digestion and determined as NH₄⁺, and the total nitrogen content was quantified as NO₃⁻ after microwave-facilitated digestion. Finally, the nitro, azo, azoxy nitrogen was calculated by comparison of the total nitrogen content and all measured nitrogen species. The detection limits of the measured ions were 2.0, 0.82 and 0.17 mg L⁻¹ for nitrate, nitrite and ammonium, respectively. For samples of potatoes, the average shares of the nitrogen species found in the total nitrogen content were: 0.83% of nitrate nitrogen, <0.03% of nitrite nitrogen, 2.1% of ammonium nitrogen, 71% of nitro, azo, azoxy nitrogen, and 26% of amine, amide nitrogen. We expect the method to be applicable to different vegetable samples. The quality of the results obtained was verified by analyzing certified reference material and comparing to another analytical method.     

Mass spectrometric method for the absolute calibration of the intramolecular nitrogen isotope distribution in nitrous oxide

A mass spectrometric method to determine the absolute intramolecular (position-dependent) nitrogen isotope ratios of nitrous oxide (N₂O) has been developed. It is based on the addition of different amounts of doubly labeled ¹⁵N₂O to an N₂O sample of the isotope ratio mass spectrometer reference gas, and subsequent measurement of the relative ion current ratios of species with mass 30, 31, 44, 45, and 46. All relevant quantities are measured by isotope ratio mass spectrometers, which means that the machines inherent high precision of the order of 10^–5 can be fully exploited. External determination of dilution factors with generally lower precision is avoided. The method itself can be implemented within a day, but a calibration of the oxygen and average nitrogen isotope ratios relative to a primary isotopic reference material of known absolute isotopic composition has to be performed separately. The underlying theoretical framework is explored in depth. The effect of interferences due to ¹⁴N¹⁵N¹⁶O and ¹⁵N¹⁴N¹⁶O in the ¹⁵N₂O sample and due to ¹⁵N ₂ ⁺ formation are fully accounted for in the calculation of the final position-dependent nitrogen isotope ratios. Considering all known statistical uncertainties of measured quantities and absolute isotope ratios of primary isotopic reference materials, we achieve an overall uncertainty of 0.9 (1). Using tropospheric N₂O as common reference point for intercomparison purposes, we find a substantially higher relative enrichment of ¹⁵N at the central nitrogen atom over ¹⁵N at the terminal nitrogen atom than measured previously for tropospheric N₂O based on a chemical conversion method: 46.3±1.4 as opposed to 18.7±2.2. However, our method depends critically on the absolute isotope ratios of the primary isotopic reference materials air–N₂ and VSMOW. If they are systematically wrong, our estimates will also necessarily be incorrect.     

基于氦离子化气相色谱法测定微量氧、氮的影响因素

探讨氦离子化气相色谱法测定样品中微量氧、氮含量的影响因素。采用控制变量法,对色谱柱温度、进样流量、进样管道环境及极化电压等因素对微量氧、氮测定结果的影响进行讨论和分析。结果表明,当色谱柱温度为25~45℃时,色谱柱对氧、氮吸附量最小;当进样流量不小于70 mL/min时,微量氧、氮测定结果受外界干扰最小;当极化电压为80~160 V时,氧、氮具有最佳的响应值;初次测定样品中微量氧、氮含量时,需使进样管道表面吸附的氧、氮处于饱和状态,以便获得理想的测定结果。讨论的结果可为氦离子化气相色谱法测定相关样品中微量氧、氮含量时提供技术参考。