石灰石及白云石化学分析方法 第12部分：氧化钾和氧化钠含量的测定 火焰原子吸收光谱法 编制说明

12一、工作简况1、任务来源本项目是依据国家标准化管理委员会国标委综合[202053202020204780-T-605，项目名122022122、主要工作过程起草()阶段:11日全国钢标委非金属矿分委员会组（或方法和技术现状与1220222月形成了标准征求意见稿及其编制说明等相关附件，报全国钢标委非金属矿分委员会秘书处。征求意见阶段:XXXXXXXXXX分委员会秘书处将标准征XXXXXXXXXXXX个XXXXXX条意见或建议(见《意见汇总处理表》)。审查阶段:XXXXXXXXXX月完成了标准XXXXXXXXXXXXXXXXXX市召开了《XXXX》标准审查会，到会XX分委员会委员XXXXXX水平。报批阶段:工作组按照会议审查意见对标准送审稿作了进一步的修改、整理和完善，在XXXXXXXX分委员会XXXXXXXXXXXXXXXXXX（3/4以上3、主要参加单位和工作组成员及其所做的工作本标准由鞍钢股份有限公司、鞍钢集团北京研究院有限公司、冶金工业信息标准研究院共同起草。主要成员:所做的工作：朴志民任工作组组长，主持全面协调工作，唐艳秀负责对各阶段标准的二、标准编制原则本标准在制定/修订过程中，遵循“面向市场、服务产业、自主制定、适时推出、及时本标准在起草过程中主要按GB/T1.1—2020《标准化工作导则 第1部分：标准化文件的结构和起草规则的要求编写在确定本标准主要技术指标时综合考虑生产企业的能力和用户的利益寻求最大的经济社会效益充分体现了标准在技术上的先进性和合理性。三、主要内容说明1、标准主要内容仪器性能校准曲线线性10min后，调节气体流量和燃烧头位置，将仪器调766.5nm589.0nm处测定，以钾、钠的溶液浓度为横坐表1. 校准曲线吸光度钾，ug/mL0.0吸光度，A00.05170.10190.20510.31000.40610.5065钠，ug/mL0.0吸光度，A00.06010.11980.23620.34710.46390.5769钾、钠校准曲线线性方程式为：yK=0.1691x+0.0012 相关系数R=0.9999；yNa=0.1918x+0.0028 相关系数R=0.9999；图1.钾校准曲线 图2.钠校准曲线方法检出限和特征浓度

c0.0044=0.0044/k=0.0260ug/mLK AcNa

cA

=0.0044/k=0.0229ug/mL将工作曲线按浓度等分成五段，最高段吸光度的差值与最低段吸光度的差值之比为：0.5065K:0.1019

0.98>0.70；

0.57690.1198

0.94>0.70所以，钾、钠的特征浓度和工作曲线线性都满足要求。精密度最低要求用最高浓度的标准溶液，测量11次吸光度，计算吸光度的平均值和标准偏差，该标准偏差不应超过该吸光度平均值的1.0%。（不是零浓度的标准溶液110.5%。表2.最高浓度、最低浓度吸光度和标准偏差11次测定值平均值标准偏差K最高浓度吸光度（3ug/mL）0.50630.50640.5056、0.50590.50500.50780.5068、0.5059、0.5069、0.50720.50640.0008最低浓度吸光度（0.3ug/mL）0.05320.05170.05130.0506、0.05180.05090.05160.0511、0.0517、0.0534、0.05120.05170.0009Na最高浓度吸光度（3ug/mL）0.57690.57580.57460.5782、0.57690.57690.57570.5761、0.5769、0.5792、0.57740.57680.0013最低浓度吸光度（0.3ug/mL）0.06010.06130.05960.0604、0.06010.06080.06030.0593、0.0600、0.0601、0.06050.06020.0005方法检出限在选定的实验条件下，对空白实验连续测定11次，以3倍的标准偏差计算方法检出限，K2O的检出限为0.0011%，Na2O的检出限为0.0014%。样品前处理方法的分析选择有证石灰石、白云石标准物质置于聚四氟乙烯烧杯中，分别利用如下两种方法进行样品前处理，实验现象如下表1：1250mL10mL，5mL5mL5mL盐酸、30mL100mL聚四氟乙烯容量瓶中，用水稀释至刻度，混匀。2250mL10mL，5mL5mL30mL100mL表3.样品前处理方法的比较样品名称样品编号前处理方法溶解现象石灰石YSBC14771a方法1溶液浑浊，乳白色方法2溶液清亮，透明无色白云石YSBC14750a方法1溶液浑浊，乳白色方法2溶液清亮，透明无色石灰石YSBC11711-20方法1溶液浑浊，乳白色方法2溶液清亮，透明无色从样品前处理两种方法的试验可以看出，方法1制备的试样浑浊，溶液呈乳白色，试样22进行试样的制备。称样量的选择0.10g、0.50g（0.0001g），随同试料做空白2进行样品前处理，在原子吸收光谱仪上进行钾、钠测定，结果如下表。表4.不同称样量的检验结果样品名称标样编号标准值0.10g0.50gK2ONa2OK2ONa2OK2ONa2O石灰石YSBC14771a0.00620.00730.00600.00750.00630.0072白云石YSBC14750a0.0300.0330.02930.03230.03040.0334石灰石YSBC11711-200.2990.0140.2950.01360.3020.01400.1g0.5g0.5g称样量。共存元素干扰试验30%-55%（Ca：20%-40%），氧化镁含量约0.0*-20%（Mg：0.0*-12%）Ca、Mg、SiFe、Al、Mn、KNa为比较氧化钙、氧化镁对钾、钠含量测定的影响，试验分别溶解基准碳酸钙和氧化镁，10mg/mL的溶液。在钾、钠浓度为0.3ug/mL和3ug/mL的溶液中，分别加入不同含量的干扰元素，按试验方法及选定的仪器工作条件测定其浓度值，结果见表5。表5. 共存元素干扰试验基体溶液干扰元素钾标准溶液钠标准溶液0.30ug/mL3.00ug/mL0.30ug/mL3.00ug/mL100mgCa0.303.010.303.02200mgCa0.313.000.303.0130mgMg0.303.040.313.0060mgMg0.303.000.303.00100mgCa+30mgMg0.313.020.303.02100mgCa+60mgMg0.303.000.313.00200mgCa+30mgMg0.292.980.302.97200mgCa+60mgMg0.303.000.303.00残渣处理21261、22为高温碱融解法，碱熔融是个复杂的物理化学融解过1为溶液在消解罐中酸消解，快速、高效、洁净的微波消解处理残渣能够有效避免样品的污染、元素的损失。表6.不同残渣处理方法比较试 样方法1：将溶液其转移至聚四氟乙烯消解罐中在160℃消解45min。方法2：将残渣过滤，洗涤，灼烧，加0.3g（碳酸锂+950℃熔融15n5L1结果0.01330.0138现象充分溶解，溶液清亮充分溶解，溶液清亮2结果0.03150.0320现象充分溶解，溶液清亮充分溶解，溶液清亮实验室内验证工作组采用本标准方法对有证石灰石、白云石标准物质进行分析，分别对不同水平钾、78。结果表明，本标准方法检测结果与标表7.本方法检测结果与标准物质标准值对比结果K2O（单位：%）样品名称样品编号测定值(%)平均值标准值误差RSD(%)石灰石YSBC14771a0.0061、0.0059、0.0061、0.0062、0.0060、0.00610.00610.00620.00012.1014石灰石YSBC14772、0.0211、0.0197、0.0201、0.0198、0.02030.02010.0210.00092.6031白云石YSBC14750a0.0293、0.03010.0297、0.02980.0294、0.02970.02970.0300.00030.9692白云石YSBC28721a-20130.0849、0.08560.0852、0.08580.0853、0.08590.08550.0850.00050.4777石灰石YSBC11714-200.139、0.1320.137、0.1390.135、0.1330.13570.1370.00132.040石灰石YSBC11711-200.309、0.2960.307、0.2910.302、0.3040.30130.2990.00232.204石灰石VS3193-850.499、0.4930.497、0.4870.504、0.5010.49680.490.00681.219石灰石DK1b1.025、0.9820.984、1.0270.997、1.0331.0060.960.0482.1558Na2O（单位：%）样品名称样品编号测定值(%)平均值标准值误差RSD石灰石YSBC14771a0.0068、0.00750.0069、0.00720.0070、0.00730.00710.00730.00023.5058石灰石YSB147720.0157、0.01710.0162、0.01620.0158、0.01670.01630.0150.00133.2824白云石YSBC14750a0.0321、0.03250.0336、0.03220.0324、0.03370.03280.0330.00032.1742白云石YSBC28721a-2013、0.01190.0123、0.01290.0124、0.01210.01240.0120.00043.1441石灰石YSBC11714-200.0139、0.01320.0141、0.01390.0135、0.01400.01380.0140.00022.5023石灰石YSBC11711-200.475、0.4820.479、0.4880.476、0.4870.48120.480.00121.1415石灰石VS3193-850.141、0.1360.134、0.1400.132、0.1380.13680.130.00682.5491精密度实验：本标准的精密度试验是2021年由9个实验室，对8个水平的氧化钾和氧化钠含量的石灰3GB/T6379.1规定GB/T6379.2，对得到的试验数据进行统计分析，得到的统计分析结果的重复性（r）和再现性标准差（R）列于表。表9.参加精密度试验的实验室实验室i实验室名称1鞍钢股份鲅鱼圈分公司质检计量中心2首钢技术研究院检测中心3本溪钢铁（集团）有限责任公司技术中心4河南科技大学5鞍钢集团钢铁研究院6京唐钢铁质检监督部7自然资源部实物地质资料中心8舞阳钢铁有限责任公司9柳州钢铁公司表10. 参加精密度试验的样品及参考含量值水平j样品名称/编号K2ONa2O1石灰石YSBC14771a0.00620.00732石灰石YSB147720.0210.0153白云石YSBC14750a0.030.0334白云石YSBC28721a-20130.0850.0125石灰石YSBC11714-20200.137—6石灰石YSBC11711-20200.2990.0147石灰石VS3193-850.490.488石灰石DK1b0.960.13氧化钾精密度试验数据统计分析原始数据依据GB/T6379.2-2004将精密度试验原始数据汇总如下表3.表11.氧化钾含量精密度试验原始数据实验室i水平j1234567810.00470.01940.02780.08900.1510.3140.5071.0370.00480.01910.02810.08570.1490.3090.5031.0220.00550.02040.02920.08960.1430.3150.5041.01820.00710.02060.03160.08870.1350.2880.4810.9760.00640.02140.02930.08660.1390.2940.4630.9900.00650.02080.02790.08690.1360.2960.4660.98130.00590.02120.03310.09400.1280.2870.4761.0260.00600.02040.03540.09000.1300.2900.4791.0240.00580.02160.03460.09100.1310.2840.4851.03040.00580.02010.03230.08160.1310.2870.5340.9840.00610.01860.03210.08120.1290.2890.5370.9990.00590.01880.03220.08170.1360.2890.5360.99350.00580.01980.02930.08560.1380.3090.4991.0250.00620.01940.03010.08490.1320.2960.4971.0320.00610.02110.02970.08520.1370.3020.4931.02760.00650.02160.03540.09840.1440.3160.4991.0550.00620.02100.03430.09560.1370.3080.4861.0400.00610.02220.03240.09620.1430.3130.4881.04070.00650.02030.03020.09010.1500.3100.5201.0400.00600.02110.03130.08730.1430.3140.5131.0450.00630.02070.03200.09040.1390.3250.5081.0418—0.02420.02720.08900.1420.3110.5091.01—0.02360.02680.08720.1560.3190.5120.99—0.02500.02780.09020.1600.3150.5041.0390.00640.02090.03070.08480.1380.2990.4800.9860.00630.02060.03060.08550.1380.3010.4800.9830.00640.01920.03000.08500.1390.2980.4790.989y

的计算由表11按下式计算单元平均值，结果见表12。yij

1n

nk1

y

…………1）表12. 氧化钾含量的单元平均值实验室i水平j1实验室i水平j1234567810.005000.019630.028370.088100.14770.31270.50471.025720.006670.020960.029590.087370.13700.29270.46980.982230.005900.021070.034370.091670.12970.28700.48001.026740.005930.019170.032200.081510.13200.28840.53580.992150.006030.020100.029700.085240.13570.30230.49621.039360.006270.021600.034030.096730.14130.31230.49101.045070.006230.020700.031170.089270.14400.31630.51371.04208—0.024270.027270.088800.15270.31500.50831.010090.006370.020230.030430.085100.13830.29930.47970.9860由表11计算单元标准偏差，如下表13。表13.氧化钾含量的单元标准偏差实验室水平j1234567810.000460.0006810.0007370.0021000.0041630.0032150.0020820.01001720.000390.0004340.0018280.0011190.0020740.0043430.0095610.00736030.0001100.0006110.0011680.0020820.0015280.0030000.0045830.00305540.000180.0007760.0001210.0002510.0036060.0012290.0012290.00730150.000190.0008890.0004000.0003590.0032150.0064080.0029010.00665860.000210.0006000.0015180.0014740.0037860.0040410.0070000.00866070.000280.0004000.0009070.0017100.0055680.0077670.0060280.0026468—0.0007020.0005030.0015100.0094520.0040000.0040410.02000090.000020.0009070.0003790.0003610.0005770.0015280.0005770.003000一致性的检查hkhk统计量的计算公式分别见公式（2）和公式（3）。hij

1 p 1 1 p 1 y ij jpy2ji1

…………2）其中，hij为曼德尔统计量h；pj为j水平下的实验室数；yj为j水平下的总平均值。k

S

……………（3）Sp其中，kij为曼德尔统计量kSp图3.曼德尔统计量h 图4.曼德尔统计量k34hk异常值的检验柯克伦(Cochran)GB/T8个水平计算柯克伦检验统C14C5%柯克伦检验临界值则测定值为正确值；C5%1%临界值则测定值为歧离值，如果检验C1%临界值，则测定值为统计离群值。表14.柯克伦检验统计量水平j12345678Smax所属实验室i19218728Smax0.000460.000910.001830.002100.009450.007770.009560.02000柯克伦检验统计量C0.3700.1940.3740.2490.490*0.3430.3990.531*柯克伦检验临界值P=8，n=3p=9，n=3显著性水平5%0.5160.478P=8，n=3p=9，n=3显著性水平1%0.6150.573注：歧离值以单星号*标注，离群值以双星号**标注。由于水平1只得到了8P=8P=95和水平8柯克伦检验统计量虽大于显著性水平5%临界值0.478，但小于显著性水平1%临界值0.573，测定值为歧离值，该歧离值仍然参与后续计算。格拉布斯(Grubbs).根据公式计算得到单侧和双侧检验统计量，列于表15。表15. 格拉布斯检验统计量水平P单个低值单个高值两个低值两个高值检验类型182.138*1.2460.2000.637格拉布斯检验统计量291.1422.299*0.6820.168391.4631.4830.4970.356491.5441.9700.5470.298591.3721.7370.5190.343691.3621.1510.4550.615791.3671.8670.5790.362891.3881.1480.4470.619歧离值5%临界值82.1262.1260.11010.1101格拉布斯检验临界值92.2152.2150.14920.1492离群值1%临界值82.2742.2740.05630.056392.3872.3870.08510.0851注：歧离值以单星号*标注，离群值以双星号**标注。1%5%临1%5%临界值的为歧离值。125%1%5%临界值。r、Rm之间的回归方程统计得到各水平的平均值m及r和R的结果，如下表16。表16.各水平的平均值m、重复性r和再现性R的结果水平jPmrRlgmlgrlgR180.006060.0007410.001490-2.2176-3.1299-2.8268290.02090.0019250.004438-1.6807-2.7156-2.3528390.03080.0027920.007123-1.5116-2.5541-2.1473490.08820.0039260.012550-1.0545-2.4060-1.9014590.13980.0126020.023128-0.8544-1.8996-1.6359690.30290.0123740.034217-0.5187-1.9075-1.4658790.49770.0141140.058273-0.3031-1.8504-1.2345891.01660.0256030.0724980.0071-1.5917-1.13971、r与m之间回归方程a.r=a+bm的情形利用加权二次迭代回归求出a、b之值，a=0.000866b=0.0415r=0.000866+0.0415mSe1=0.000399b．lgr=lgc+dlgm的情形经计算得：lgc=-1.5616d=0.6838lgr=0.6838lgm-1.5616Se2=0.000045由于Se1>Se2，所以r与m之间为一次对数函数式：lgr=0.6838lgm-1.56162、RmR=a+bm的情形利用加权二次迭代回归求出a、b之值a=0.00132；b=0.1218R=0.00132+0.1218mSe1=0.00282lgR=lgc+dlgm的情形经计算得：lgc=-1.0556；d=0.7696lgR=0.7696lgm-1.0556Se2=0.00034由于Se1>Se2，所以R与m之间为一次对数函数式：lgR=0.7696lgm-1.0556图5.重复性拟合曲线 图6.再现性拟合曲线变异系数根据R=2.8×σ(R)，变异系数CV(R)=100×σ(R)/m目标变异系数AIMCV(R)：lgCVR=-0.3466lgm+lg1.47721MAXCV(R)：lgCVR=-0.3466lgm+lg3.2467017：0.005%~1.00%。表17.氧化钾各水平变异系数CV(R)结果水平mjRσ(R)CV(R)AIMCV(R)MAXCV(R)10.006060.00150.00058.788.6719.0620.02090.00440.00167.605.6512.4230.03080.00710.00258.264.9410.8540.08820.01250.00455.083.437.5350.13980.02310.00835.912.926.4260.30290.03420.01224.032.234.9170.49770.05830.02083.081.884.1481.01660.07250.02592.551.473.23结论本标准测试方法中氧化钾的精密度（以质量百分数表示）表18.重复性和再现性结果水平范围m重复性r再现性R0.005%~1.00%lgr=0.6838lgm-1.5616lgR=0.7696lgm-1.0556氧化钠精密度试验数据统计分析原始数据、单元平均值及单元标准差GB/T6379.2-200419。表19. 氧化钠含量精密度试验原始数据实验室i水平j123456710.00740.01350.03500.01060.01060.4550.1250.00720.01460.03460.01100.01120.4520.1310.00720.01660.03510.01230.01200.4670.12120.00850.01540.03280.01110.01210.4580.1540.00730.01480.03210.01540.01420.4870.1510.00700.01460.03400.01390.01480.4760.15530.00680.01700.03800.01180.01130.4840.1370.00680.01810.03640.01220.01310.4900.1410.00700.01670.03580.01210.01260.4860.14040.00730.01710.03430.01230.01110.4610.1360.00760.01730.03440.01200.01030.4580.1350.00740.01700.03490.01220.01130.4670.13350.00680.01570.03210.01280.01390.4750.1410.00690.01710.03250.01190.01320.4820.1360.00750.01620.03360.01240.01410.4790.13460.01040.02030.03150.01630.03390.4560.2040.01130.02090.03150.01820.03140.4700.2140.01080.02040.03230.01810.03220.4700.21170.00800.01530.03420.01430.01700.4650.1360.00760.01620.03510.01490.01650.4730.1430.00780.01590.03380.01510.01620.4660.1398—0.01720.03050.02400.02500.4970.153—0.01800.03030.02200.02300.4990.148—0.01740.02970.02500.02180.5050.14390.00790.01410.03280.01190.01300.4500.1520.00740.01400.03210.01200.01330.4520.1500.00800.01390.03300.01210.01380.4510.154表20. 氧化钠含量的单元平均值实验室i水平j123456710.007270.014890.034900.011300.011270.45800.125720.007600.014920.032970.013440.013730.47330.153230.006870.017270.036730.012030.012330.48670.139340.007430.017170.034530.012170.010890.46200.134450.007070.016330.032730.012370.013730.47870.137060.010830.020530.031770.017530.032500.46530.209770.007800.015800.034370.014770.016570.46800.13938—0.017530.030170.023670.023270.50030.148090.007770.014000.032630.012000.013370.45100.1520表21. 氧化钠含量的单元标准偏差实验室i水平j123456710.0001310.0015760.0002650.0008890.0007020.0079370.00503320.0007790.0004120.0009490.0021920.0014180.0147210.00205930.0001240.0007370.0011370.0002080.0009290.0030550.00208240.0001490.0001490.0003210.0001530.0005150.0045830.00147150.0003790.0007090.0007770.0004510.0004730.0035120.00360660.0004510.0003210.0004620.0010690.0012770.0080830.00513270.0002200.0004580.0006660.0004160.0004040.0043590.0035128—0.0004160.0004160.0015280.0016170.0041630.00500090.0002840.0001000.0004690.0001000.0004040.0010000.002000一致性的检查78hkh6h6k2图7.曼德尔统计量h 图8.曼德尔统计量k异常值的检验首先应用柯克伦检验对数据进行分析，得到下面结果见表22：进行格拉布斯(Grubbs)检验，结果见表23：表22.柯克伦检验统计量水平j1234567Smax所属实验室i2332826Smax0.000780.001580.001530.002190.001620.014720.00577柯克伦检验统计量C0.534*0.2560.3220.504*0.3100.510*0.226柯克伦检验临界值P=9,n=3p=8,n=3显著性水平5%0.4780.516P=9,n=3p=8,n=3显著性水平1%0.5730.615注：歧离值以单星号*标注，离群值以双星号**标注。表23. 格拉布斯检验统计量水平P单个低值单个高值两个低值两个高值检验类型180.7582.389**(1.145)291.1952.0320.2820.636391.6831.7120.4920.408格拉布490.7692.3370.0662**0.838斯检验590.7772.2670.0550**0.823统计量691.3441.9660.2940.585790.9422.486**(1.305)歧离值82.1262.1260.11010.1101格拉布92.2152.2150.14920.1492斯检验82.2742.2740.05630.0563离群值临界值92.3872.3870.08510.0851从柯克伦检验统计结果可以看出，P-2实验室在水平1，4，6的柯克伦检验统计量虽然大于5%概率水平的临界值，但是小于1%概率水平的临界值，故其单元方差为歧离值，没有离群值，该歧离值仍然参与后续计算。从格拉布斯(Grubbs)17的单个高值格拉P-61.14514，5的两个低值（P-6、P-8实验室）测试结果为离群值，数据剔除。r、Rm之间的回归方程表24.各水平的平均值m、重复性r和再现性R的结果水平jPmrRlgmlgrlgR170.0073980.0010220.001219-2.1309-2.9907-2.9141290.0164640.0013600.005777-1.7835-2.8665-2.2383390.0334220.0018720.005627-1.4760-2.7278-2.2497470.0125290.0026640.003869-1.9021-2.5745-2.4124570.0130800.0021640.004571-1.8834-2.6647-2.3400690.4711100.0192420.045484-0.3269-1.7158-1.3421780.1407890.0094130.027434-0.8514-2.0263-1.56171、r与m之间回归方程r=a+bm的情形利用加权二次迭代回归求出a、b之值，a=0.00123b=0.0506r=0.00123+0.0506mSe1=0.000036lgr=lgc+dlgm的情形经计算得：lgc=-1.4771；d=0.6689lgr=0.6689lgm-1.4771Se2=0.000006Se1>Se2rm之间为一次对数函数式：lgr0.6689lgm-1.47712Rm之间的回归方程R=a+bm的情形利用加权二次迭代回归求出a、b之值a=0.00169；b=0.1556R=0.00169+0.1556mSe1=0.000952lgR=lgc+dlgm的情形经计算得：lgc=-1.0167；d=0.7559lgR=0.7559lgm-1.0167Se2=0.000147由于Se1>Se2，所以R与m之间为一次对数函数式：lgR=0.7559lgm-1.0167图9.重复性拟合曲线 图10.再现性拟合曲线变异系数根据R=2.8×σ(R)，变异系数CV(R)=100×σ(R)/m目标变异系数AIMCV(R)：lgCVR=-0.3466lgm+lg1.47721最大变异系数MAXCV(R)：lgCVR=-0.3466lgm+lg3.24670算出如下变异系数表：表25.氧化钠各水平变异系数CV(R)结果水平Rσ(R)CV(R)AIMCV(R)MAXCV(R)10.007400.00130.000465.888.0917.7820.01650.00570.0020212.566.1413.4930.03340.00550.001956.014.8010.5440.01250.00400.0014210.986.7