錳礦石和錳精礦 鋁含量的測定 光度法和重量法 編制說明

1《錳礦石和錳精礦鋁含量的測定光度法和重量法》標(biāo)準(zhǔn)編制說明關(guān)于下達(dá)2023年第二批推薦行國家標(biāo)準(zhǔn)計劃及相關(guān)和重量法》（計劃編號為2023-0638本標(biāo)準(zhǔn)《錳礦石和錳精礦鋁含量的測定光作指導(dǎo)、反復(fù)整理修訂等一系列過程后形成了標(biāo)準(zhǔn)草案。標(biāo)準(zhǔn)制定嚴(yán)1.1-2020《標(biāo)準(zhǔn)化工作導(dǎo)則第1部分樣品中的鋁含量進(jìn)行了較為全面、系統(tǒng)的試驗(yàn)和驗(yàn)證，經(jīng)過實(shí)驗(yàn)優(yōu)化2在化學(xué)工業(yè)方面，錳礦石還是制取二氧化錳、硫酸錳、高錳酸出口錳礦石中錳、鐵、硅、鋁、鈣、鎂、鈦、鉀和磷元素的測定波長色散X射線熒光射光譜法。未檢索到采用光度法和重量法測定錳礦石和錳精礦方法標(biāo)準(zhǔn)》進(jìn)行編寫，此標(biāo)準(zhǔn)修改采用國際標(biāo)準(zhǔn)ISO4andconcentrates–Determinationofaluminiumcontent–Photometricand灼燒溫度，增加了重量法殘留鋁的檢查，改寫了重量法精密度，增加了試驗(yàn)報告要求，3法，適用于鋁含量為0.1%～1.5%（m/m）的樣品；方法B為重量法，適用于鋁含量大處理后的殘渣用碳酸鈉熔融，熔體在鹽酸中在氯化鋅和硼酸存在下，用強(qiáng)氫氧化鉀溶液沉淀氫氧化物，a)修改了前言部分（見前言）；）；4c)修改了規(guī)范性引用文件（見2）；）；），）；f)增加了試劑描述，修改了鉻天青S溶液的濃度（見4.2），增加了采用市）；）；），），）；i)降低了殘渣熔融溫度（見，），修改氫氧化增加了加熱煮沸、流水冷卻、立即過濾、計時開始的要求（見），）；）；）；）；）；）；p)本文件與ISO4295:1988(E)相比，在結(jié)構(gòu)上有較多調(diào)整，附錄C中列出了q)本文件與ISO4295:1988(E)相比存在技術(shù)性差異，附錄D中給出了相應(yīng)技r)本文件增加了附錄E，殘留鋁的測定---電感耦合等離子體原子發(fā)驗(yàn)證時發(fā)現(xiàn)，部分ISO4295:1988(E)的規(guī)定不完全滿足準(zhǔn)確性要求，為此進(jìn)行了條5ISO4295:1988(E)的規(guī)定為：加入30mL氫氧化鉀后未要求煮沸，未要求流水快速冷卻，未要求即時干過濾，要求根據(jù)鋁含量進(jìn)行稀釋。試驗(yàn)發(fā)現(xiàn)按照ISO4295:1988(E)標(biāo)樣試驗(yàn)結(jié)果/%標(biāo)稱值/%GBW07262GBW072650.6690，0.73210.89標(biāo)樣上清液中鋁/%溶液沉淀混合中鋁/%GBW072621.3070，1.31321.4843，1.4763GBW072650.2895，0.33300.9283，0.9022試驗(yàn)，規(guī)定以比色溶液定容至刻度并搖勻開始計時采用2個錳礦石標(biāo)準(zhǔn)樣品進(jìn)行驗(yàn)證，根據(jù)本方法對試樣進(jìn)行鋁含量的測定。驗(yàn)證結(jié)/% /%t值123458AMnOre-90.23010.21230.23760.20860.22220.01210.212.01363.182GBW072621.53141.56691.56241.61421.56870.02961.43753.1826協(xié)同實(shí)驗(yàn)5個水平的樣品均是標(biāo)準(zhǔn)樣品，使用MEF方法評價正確性。將5個標(biāo)準(zhǔn)有顯著性差異，截距與0沒有顯著性差異，測量結(jié)果的正確性得到驗(yàn)證。利用linest函數(shù)進(jìn)行擬合，斜率k=0.9559、標(biāo)準(zhǔn)偏差s(k)=0.0395，截距b=0.0288%、標(biāo)準(zhǔn)偏差k：0.9559，t(k)=1.116）：）：組織了8家實(shí)驗(yàn)室參加5個水平的精密度協(xié)同實(shí)驗(yàn)，每家每水平報出2個結(jié)果。根實(shí)驗(yàn)室編號水平結(jié)果2/%實(shí)驗(yàn)室編號水平結(jié)果2/%11512233744552161223344553171223344554181223344558123451234567812345123456789跟濃度沒有依賴關(guān)系。實(shí)驗(yàn)室5濃度水平2、實(shí)驗(yàn)室8濃度水平5超出顯著性水平5%實(shí)驗(yàn)室水平/方差1234516.47998E-062.20499E-041.89728E-031.80000E-072.53125E-0421.40450E-055.00000E-071.65312E-031.80499E-046.84503E-0634.90050E-054.51249E-053.52800E-032.76024E-035.32512E-0348.19201E-055.44499E-062.22444E-031.40981E-032.92821E-0451.68200E-054.86719E-043.59121E-048.82001E-041.69362E-0365.44499E-064.14050E-051.88181E-042.56328E-033.56447E-0471.56800E-051.24820E-044.17606E-042.20499E-062.96450E-0388.45000E-054.41800E-052.81250E-031.31585E-039.77201E-03方差和2.73895E-049.68693E-041.30802E-029.11406E-032.06645E-02最大方差8.45000E-054.86719E-043.52800E-032.76024E-039.77201E-03C0.3090.5020.2700.3030.473C（8，2）臨界值0.794（1%），0.680（5%）12345123456781234512345678實(shí)驗(yàn)室水平1234510.20790.51040.79761.09321.461320.22780.56460.89541.04861.559830.22490.56050.8211.13781.472940.20940.56550.82141.15101.522650.23720.57850.79011.11801.611560.23380.58960.80181.12781.580470.23940.60880.82891.13681.583880.26200.61670.82911.16551.5497平均值/%0.230300.574330.823161.122341.54275標(biāo)準(zhǔn)偏差/%0.017410.033130.032730.036780.05357最大值/%0.262000.616700.895401.165501.61150最小值/%0.207900.510400.790101.048601.46130GMAX1.8211.2792.2071.1731.283GMIN1.2871.9301.0102.0051.520G（8）臨界值2.274（1%），2.126（5%）序號水平1234510.20790.51040.79011.04861.461320.20940.56050.79761.09321.472930.22490.56460.80181.11801.522640.22780.56550.82101.12781.549750.23380.57850.82141.13681.559860.23720.58960.82891.13781.580470.23940.60880.82911.15101.583880.26200.61670.89541.16551.6115方差3.03077E-041.09785E-031.07102E-031.35252E-032.86962E-03除去兩個最大值的方差1.51280E-047.43286E-042.45015E-041.18466E-032.33327E-03除去兩個最小值的方差1.74098E-044.79974E-041.03555E-032.83514E-049.51787E-04GMAX,20.4990.6770.2290.8760.813GMIN,20.5740.4370.9670.2100.332G(8)臨界值0.0563(1%),0.1101(5%)水平1X1/%X2/%檢測次數(shù)平均值/%方差實(shí)驗(yàn)室10.20610.209720.207906.47998E-06實(shí)驗(yàn)室20.22510.230420.227751.40450E-05實(shí)驗(yàn)室30.22980.219920.224854.90050E-05實(shí)驗(yàn)室40.21580.203020.209408.19201E-05實(shí)驗(yàn)室50.23430.240120.237201.68200E-05實(shí)驗(yàn)室60.23540.232120.233755.44499E-06實(shí)驗(yàn)室70.24220.236620.239401.56800E-05實(shí)驗(yàn)室80.26850.255520.262008.45000E-05總平均值0.23028（單元均值間方差*檢測次數(shù)）總和6.06281E-04平均檢測次數(shù)2重復(fù)性方差3.42369E-05實(shí)驗(yàn)室間方差2.86022E-04再現(xiàn)性方差3.20259E-04水平2X1/%X2/%檢測次數(shù)平均值/%方差實(shí)驗(yàn)室10.52090.499920.510402.20499E-04實(shí)驗(yàn)室20.56410.565120.564605.00000E-07實(shí)驗(yàn)室30.55570.565220.560454.51249E-05實(shí)驗(yàn)室40.56380.567120.565455.44499E-06實(shí)驗(yàn)室50.56290.594120.578504.86719E-04實(shí)驗(yàn)室60.59410.585020.589554.14050E-05實(shí)驗(yàn)室70.61670.600920.608801.24820E-04實(shí)驗(yàn)室80.62140.612020.616704.41800E-05總平均值0.57431（單元均值間方差*檢測次數(shù)）總和2.19590E-03平均檢測次數(shù)2重復(fù)性方差1.21087E-04實(shí)驗(yàn)室間方差1.03741E-03再現(xiàn)性方差1.15850E-03水平3X1/%X2/%檢測次數(shù)平均值/%方差實(shí)驗(yàn)室10.76680.828420.797601.89728E-03實(shí)驗(yàn)室20.86660.924120.895351.65312E-03實(shí)驗(yàn)室30.86300.779020.821003.52800E-03實(shí)驗(yàn)室40.78800.854720.821352.22444E-03實(shí)驗(yàn)室50.80350.776720.790103.59121E-04實(shí)驗(yàn)室60.81150.792120.801801.88181E-04實(shí)驗(yàn)室70.84330.814420.828854.17606E-04實(shí)驗(yàn)室80.86660.791620.829102.81250E-03總平均值0.82314（單元均值間方差*檢測次數(shù)）總和2.13986E-03平均檢測次數(shù)2重復(fù)性方差1.63503E-03實(shí)驗(yàn)室間方差2.52415E-04再現(xiàn)性方差1.88745E-03水平4X1/%X2/%檢測次數(shù)平均值/%方差實(shí)驗(yàn)室11.09351.092921.093201.80000E-07實(shí)驗(yàn)室21.03911.058121.048601.80499E-04實(shí)驗(yàn)室31.10061.174921.137752.76024E-03實(shí)驗(yàn)室41.12441.177521.150951.40981E-03實(shí)驗(yàn)室51.09701.139021.118008.82001E-04實(shí)驗(yàn)室61.16361.092021.127802.56328E-03實(shí)驗(yàn)室71.13571.137821.136752.20499E-06實(shí)驗(yàn)室81.13981.191121.165451.31585E-03總平均值1.12231（單元均值間方差*檢測次數(shù)）總和2.70214E-03平均檢測次數(shù)2重復(fù)性方差1.13926E-03實(shí)驗(yàn)室間方差7.81440E-04再現(xiàn)性方差1.92070E-03水平5X1/%X2/%檢測次數(shù)平均值/%方差實(shí)驗(yàn)室11.45001.472521.461252.53125E-04實(shí)驗(yàn)室21.55791.561621.559756.84503E-06實(shí)驗(yàn)室31.42131.524521.472905.32512E-03實(shí)驗(yàn)室41.53471.510521.522602.92821E-04實(shí)驗(yàn)室51.58241.640621.611501.69362E-03實(shí)驗(yàn)室61.59371.567021.580353.56447E-04實(shí)驗(yàn)室71.54531.622321.583802.96450E-03實(shí)驗(yàn)室81.47981.619621.549709.77201E-03總平均值1.54273（單元均值間方差*檢測次數(shù)）總和5.74001E-03平均檢測次數(shù)2重復(fù)性方差2.58306E-03實(shí)驗(yàn)室間方差1.57848E-03再現(xiàn)性方差4.16154E-03統(tǒng)計項(xiàng)水平12345總平均值0.230280.574310.823141.122311.54273（單元均值間方差*檢測次數(shù)）總和6.06281E-042.19590E-032.13986E-032.70214E-035.74001E-03重復(fù)性方差3.42369E-051.21087E-041.63503E-031.13926E-032.58306E-03實(shí)驗(yàn)室間方差2.86022E-041.03741E-032.52415E-047.81440E-041.57848E-03再現(xiàn)性方差3.20259E-041.15850E-031.88745E-031.92070E-034.16154E-03重復(fù)性標(biāo)準(zhǔn)偏差0.0058510.0110040.0404360.0337530.050824實(shí)驗(yàn)室間標(biāo)準(zhǔn)偏差0.0169120.0322090.0158880.0279540.039730再現(xiàn)性標(biāo)準(zhǔn)偏差0.0178960.0340370.0434450.0438260.064510重復(fù)性限0.0163830.0308110.1132210.0945080.142307再現(xiàn)性限0.0501090.0953040.1216460.1227130.180628統(tǒng)計項(xiàng)水平12345N=0，迭代初始m/%TT1=39345.49，T2=13555.30，T3=6714.28，T4=335.82，T5=175.51函數(shù)方程s=-0.001545+0.029260mm/%TT1=44892.46，T2=14583.76，T3=7255.11，T4=405.03，T5=222.56函數(shù)方程s=-0.002718+0.036141mN=2，迭代2次m/%TT1=37326.69，T2=11553.78，T3=5354.59，T4=317.04，T5=162.19函數(shù)方程s=-0.002656+0.036020m統(tǒng)計項(xiàng)水平12345N=0，迭代初始m/%TT1=5276.32，T2=2605.90，T3=2036.96，T4=146.60，T5=98.21函數(shù)方程s=0.010789+0.034411mm/%TT1=5235.38，T2=2648.76，T3=2046.95，T4=149.73，T5=100.63函數(shù)方程s=0.010794+0.035193mN=2，迭代2次m/%TT1=5104.15，T2=2570.70，T3=1979.92，T4=145.55，T5=97.43函數(shù)方程s=-0.010784+0.035208m將標(biāo)準(zhǔn)差迭代方程兩邊乘以2.8，可得重復(fù)性限和再現(xiàn)性限與含量的關(guān)系，精密度σr=0.0360×m?0.0027σR=0.0352×m+0.0108（2）r=0.1009×m?0.0074R=0.0986×m+0.0302（4）式中：m—樣品的鋁含量；σr—重復(fù)性