金化學(xué)分析方法 第12 部分 銀、銅、鐵、鉛、鉍、銻、鎂、鎳、錳、鈀、鉻、鉑、銠、鈦、鋅、砷、錫、硅、鈷、鈣、鉀、鋰、鈉、碲、釩、鋯、鎘、鉬、錸、鋁含量的測(cè)定 電感耦合等離子體原子發(fā)射光譜法 編制說明

銀、銅、鐵、鉛、鉍、銻、鎂、鎳、錳、鈀、鉻、鉑、銠、鈦、鋅、砷、錫、硅、鈷、鈣、鉀、鋰、鈉、碲、釩、鋯、鎘、鉬、錸、鋁含量的測(cè)定電感耦合等離子體原子發(fā)射光譜法編制說明（征求意見稿）紫金礦業(yè)集團(tuán)股份有限公司2023.042銀、銅、鐵、鉛、鉍、銻、鎂、鎳、錳、鈀、鉻、鉑、銠、鈦、鋅、砷、錫、硅、鈷、鈣、由全國(guó)有色金屬標(biāo)準(zhǔn)化技術(shù)委員會(huì)歸口，紫金礦業(yè)集團(tuán)股份有限公司牽頭起草，項(xiàng)目計(jì)劃編本文件起草單位有：紫金礦業(yè)集團(tuán)股份有限公司、北礦檢測(cè)技術(shù)有限公司、大冶有色金屬集團(tuán)控股有限公司、深圳市中金嶺南股份有限公司韶關(guān)冶煉廠、山東恒邦冶煉股份有限公其中紫金礦業(yè)集團(tuán)股份有限公司負(fù)責(zé)統(tǒng)一樣品的收集和分發(fā)，分析方法的實(shí)驗(yàn)研究，樣品測(cè)試結(jié)果的收集和處理，標(biāo)準(zhǔn)文本、試驗(yàn)報(bào)告和編制說明的撰寫。北礦檢測(cè)技術(shù)有限公司、大冶有色金屬集團(tuán)控股有限公司、深圳市中金嶺南股份有限公司韶關(guān)冶煉廠為一驗(yàn)單位，負(fù)責(zé)對(duì)試驗(yàn)報(bào)告中的條件實(shí)驗(yàn)進(jìn)行驗(yàn)證，提供精密度和準(zhǔn)確度測(cè)試數(shù)據(jù)，并對(duì)標(biāo)準(zhǔn)文本提出修改意見。山東恒邦冶煉股份有限公司、紫金銅業(yè)有限公司、華津國(guó)檢（深圳）金銀珠寶檢驗(yàn)中心有限公司、東北大學(xué)為二驗(yàn)單位，負(fù)責(zé)提供精密度試驗(yàn)數(shù)據(jù)，并對(duì)標(biāo)準(zhǔn)文本提出紫金礦業(yè)集團(tuán)股份有限公司是以金銅等金屬礦產(chǎn)資源勘查和開發(fā)及工程技術(shù)應(yīng)用為主的大型跨國(guó)礦業(yè)集團(tuán)，運(yùn)營(yíng)管理著紫金礦業(yè)集團(tuán)分析測(cè)試中心和國(guó)家重點(diǎn)實(shí)驗(yàn)室，擁有一支基礎(chǔ)理論扎實(shí)、實(shí)踐經(jīng)驗(yàn)豐富的研究和服務(wù)隊(duì)伍。目前，紫金礦業(yè)集團(tuán)股份有限公司測(cè)試中心取得了“中國(guó)計(jì)量認(rèn)證（CMA）”、“中國(guó)合格評(píng)定國(guó)家認(rèn)可委員會(huì)（CNAS）”、“THE國(guó)有色金屬工業(yè)協(xié)會(huì)、中國(guó)有色金屬學(xué)會(huì)有色金屬工業(yè)科學(xué)技術(shù)獎(jiǎng)一等獎(jiǎng)2項(xiàng)、二等獎(jiǎng)2項(xiàng)、三等獎(jiǎng)1項(xiàng)，全國(guó)有色金屬標(biāo)準(zhǔn)化技術(shù)委員會(huì)技術(shù)標(biāo)準(zhǔn)優(yōu)秀獎(jiǎng)二等獎(jiǎng)6項(xiàng)、三等獎(jiǎng)6學(xué)紫金礦業(yè)集團(tuán)股份有限公司在接到本標(biāo)準(zhǔn)制訂任務(wù)后，立即組織骨干人員成立了標(biāo)準(zhǔn)編制組，制定了該標(biāo)準(zhǔn)的研究?jī)?nèi)容、技術(shù)路線、任務(wù)分工和進(jìn)度安排。主要工作過程經(jīng)歷以下鉍、銻、鎂、鎳、錳、鈀、鉻、鉑、銠、鈦、鋅、砷、錫、硅、鈷、鈣、鉀、鋰、鈉、碲、實(shí)，確定了由紫金礦業(yè)集團(tuán)股份有限公司負(fù)責(zé)起草工作，北礦檢測(cè)技術(shù)有限公司、大冶有色金屬集團(tuán)控股有限公司、深圳市中金嶺南股份有限公司韶關(guān)冶煉廠、紫金銅業(yè)有限公司、山東恒邦冶煉股份有限公司等單位、華津國(guó)檢（深圳）金銀珠寶檢驗(yàn)中心有限公司協(xié)助起草。Fe：0.0002~0.05%、Pb：0.0002~0.05%、Bi：0.0003~0.05%、Sb：0.0005~0.05%、Mg：0.0002~0.05%、Mo：0.0002~0.05%、Re：0.0002~0.05%、Al：0.0002~0.05%雜質(zhì)元素和測(cè)定4中銀、銅、鐵、鉛、鉍、銻、鎂、鎳、錳、鈀、鉻、鉑、銠、鈦、鋅、砷、錫、硅、鈷、鈣、鉀、鋰、鈉、碲、釩、鋯、鎘、鉬、錸、鋁含量不同梯度的4種試驗(yàn)樣品，另通過標(biāo)準(zhǔn)實(shí)驗(yàn)、試樣量的確定實(shí)驗(yàn)、試樣介質(zhì)實(shí)驗(yàn)、定容酸度實(shí)驗(yàn)、標(biāo)準(zhǔn)基體的選擇實(shí)驗(yàn)、干擾實(shí)驗(yàn)、雜質(zhì)元素的檢出限試驗(yàn)、方法比對(duì)實(shí)驗(yàn)、樣品全過程加標(biāo)回收以及精密度試驗(yàn)，形成了3）調(diào)整測(cè)定范圍下限。綜合各驗(yàn)證單位提交的定量下限試驗(yàn)數(shù)據(jù)，將Te測(cè)定下限由反饋及查找各大品牌ICP廠家資料，安捷倫、賽默飛、斯派5）條件實(shí)驗(yàn)中“方法比對(duì)實(shí)驗(yàn)”可增加低含量2.2適用性和先進(jìn)性通過結(jié)合金錠生產(chǎn)和應(yīng)用的實(shí)際需求，確定測(cè)定方法和測(cè)定范圍，提高了本標(biāo)準(zhǔn)的適用性。經(jīng)充分調(diào)研，采用操作簡(jiǎn)便、靈敏度高、精密度和準(zhǔn)確好、在行業(yè)內(nèi)普及的分析方法（電感耦合等離子體發(fā)射光譜法），能很好地滿足行業(yè)對(duì)金錠中銀、銅、鐵、鉛、鉍、銻、鎂、鎳、錳、鈀、鉻、鉑、銠、鈦、鋅、砷、錫、硅、鈷、鈣、鉀、鋰、鈉、碲、釩、鋯、本文件是首次制定，并且是在充分調(diào)研金錠中銀、銅、鐵、鉛、鉍、銻、鎂、鎳、錳、鈀、鉻、鉑、銠、鈦、鋅、砷、錫、硅、鈷、鈣、鉀、鋰、鈉、碲、釩、鋯、鎘、鉬、錸、3.1測(cè)定范圍的確定本標(biāo)準(zhǔn)適用于金錠中銀、銅、鐵、鉛、鉍、銻、鎂、鎳、錳、鈀、鉻、鉑、銠、鈦、鋅、砷、錫、硅、鈷、鈣、鉀、鋰、鈉、碲、釩、鋯、鎘、鉬、錸、鋁含量的測(cè)定。高純度的金錠雜質(zhì)含量很低，為了適用于較高純度金錠需求，故本標(biāo)準(zhǔn)的測(cè)定范圍確定為Ag：3.2測(cè)定方法的確定現(xiàn)有檢測(cè)金中雜質(zhì)元素的方法主要有火焰原子吸收光譜法、火花原子發(fā)射光譜法、乙酸乙酯萃取-ICP-AES法、砷和錫量測(cè)定氫化物-原子熒光光譜法、硅量的測(cè)定鉬藍(lán)分光光度法6等。高純金測(cè)定雜質(zhì)元素的主要方法有：乙酸乙酯萃取分校正-內(nèi)標(biāo)法、乙醚萃取分離-ICP-AES法。萃取法檢測(cè)元素較多但操作繁瑣、毒性大、時(shí)間長(zhǎng)，原子吸收法消解時(shí)間短但檢測(cè)元素較少。本方法選擇使用王水消解試料，基體匹配后電3.3儀器條件選擇測(cè)試條件的不同，會(huì)直接影響實(shí)驗(yàn)的測(cè)試結(jié)果，需確認(rèn)儀器的最優(yōu)測(cè)試條件。配制金冷卻氣、輔助氣、進(jìn)樣速率、觀測(cè)高度不變的條件下，按不同分析功率、霧化氣流量等儀器由于測(cè)定微量元素時(shí)存在金基體的影響，在廠家推薦的儀器工作條件下，每個(gè)待測(cè)元素一條譜線測(cè)得的強(qiáng)度值、波峰形狀和基線情況，波峰尖銳、基線平滑、無干擾峰或干擾峰較重疊干擾峰影響，檢測(cè)結(jié)果異常偏高，應(yīng)選擇610.362nm。各雜質(zhì)元素測(cè)定推薦譜線波長(zhǎng)見NaKVNi光譜儀有自動(dòng)背景校正功能，檢測(cè)試樣，參照計(jì)算機(jī)屏幕上所顯示的每條譜線子陳列圖及標(biāo)識(shí)的譜線，背景與校正后的強(qiáng)度值，在譜線峰兩側(cè)選擇背景扣除的最低值波長(zhǎng)位置，并73.4試樣量的確定/%1121314151617181911K1111Ni1Na111V111111111111而影響溶液霧化效果，樣品檢測(cè)信號(hào)凈強(qiáng)度有所下降。試樣量少，試液中各元素濃度過低。3.5試樣介質(zhì)8酸度影響試液提升速率和譜線強(qiáng)度。在其他條件一定的情況下，分別用鹽酸（1+9）、混合酸（1+9）沖洗表面皿和杯壁，移入50mL塑料容量瓶中，加入含1.00μg/mL混合標(biāo)準(zhǔn)溶序號(hào)元素量L（1+9）鹽酸(μg/mL）（1+9）混合酸(μg/mL）%/%值%1121314151617181911K1111Ni1Na111V111111111111表5結(jié)果表明：在（1+9）稀鹽酸介質(zhì)下，回收率在96.85%~108.45%，RSD在元素%/%%/%%/%1121314151617181911K1111Ni1Na111V1111111111113.7標(biāo)準(zhǔn)基體的選擇用無金基體標(biāo)準(zhǔn)曲線和金基體標(biāo)準(zhǔn)曲線測(cè)定各元素的濃度，分析對(duì)各雜質(zhì)元素回收率的影表7無金基體標(biāo)準(zhǔn)曲線測(cè)定各元素的濃度回收率1121314151617181911K11111Ni1Na11111111111V1111121314151617181911K11111Ni1Na11111111111V111素回收率分別為70.10%~117.70%、70.35%~113.70%、68.30%~117.65%。采用金基體標(biāo)準(zhǔn)曲92.50%~115.25%、85.90%~108.05%。試驗(yàn)數(shù)據(jù)表明：鉀、鉬、銻、釩等）回收率偏低。標(biāo)準(zhǔn)溶液含金基體時(shí)，一定程度上降低儀器靈敏度，消除針對(duì)金錠中所含雜質(zhì)元素之間的相關(guān)干擾，分別對(duì)三十種待測(cè)元素（0.1μg/mL）加入其他二十九種元素（20mg/L）檢測(cè)目標(biāo)元素鋅、碲等元素回收率偏低，鉑、鉬、硅等元素回收率偏學(xué)前處理方法進(jìn)行分離。采用金基體匹配、調(diào)整背景校正后能消除大部分干擾，大部分元素續(xù)處理。ICP測(cè)定中多譜擬合法（MSF法）是基于建立待測(cè)元素和共存元素光譜的數(shù)學(xué)模型，并通過數(shù)學(xué)模型把待測(cè)元素光譜從干擾背景光譜中剝離出來，從而校正干擾元素光譜干擾的一種方法，將MSF模型建立完成后，后續(xù)實(shí)驗(yàn)可直接使用，方便批量處理。對(duì)部分譜線其存在負(fù)干擾、當(dāng)選用波長(zhǎng)Mo202.031nm進(jìn)行鉬含量測(cè)定時(shí)，Pt對(duì)其存在正干擾。使用3.9雜質(zhì)元素的檢出限試驗(yàn)表9金基體標(biāo)準(zhǔn)曲線測(cè)定各元素的回收率元素濃度(μg/mL）123456789KNiNaVKVNiNa3.10方法比對(duì)實(shí)驗(yàn)NiNiNi測(cè)定范圍為0.00002~0.001%，選擇低含量段范圍進(jìn)行比對(duì)結(jié)果符合金錠產(chǎn)品標(biāo)準(zhǔn)中相關(guān)質(zhì)量元素/%/%/%KNiNaV3.12起草及驗(yàn)證單位精密度試驗(yàn)為了考察本方法的精密度，7家驗(yàn)證單位按照起草單位制定的實(shí)驗(yàn)方案進(jìn)行了驗(yàn)證試n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n12345671234567n123456712345673.13試樣量的確定-補(bǔ)充試驗(yàn)1121314151617181911K1111Ni1Na111V111111111111量大，不利于測(cè)定、稱樣量少，所含雜質(zhì)元素會(huì)達(dá)不到測(cè)定工作曲線的3.14基體殘留情況分析123456789123456789/ug/ml含量/ug/ml1234567897家實(shí)驗(yàn)室精密度數(shù)據(jù)進(jìn)行統(tǒng)計(jì)、分析和處理。以一個(gè)實(shí)驗(yàn)室和一個(gè)水平組合為精密度試驗(yàn)的一個(gè)單元，進(jìn)行測(cè)試結(jié)果的一致性和離群值檢實(shí)驗(yàn)室i水平j(luò)1AgAsBiCdCoCuFeLiMgMnNiPbPdPtReRhSbSnTeVZn10.0010230.0005760.0008990.0008100.0009010.0011040.0017270.0007640.0002060.0010630.0009940.0009440.0008600.0009140.0001670.0008240.0006800.0007770.0006690.0001910.00091720.0010210.0006310.0009030.0007830.0008140.0011890.0016090.0007690.0002710.0010200.0009800.0009210.0008930.0009570.0002540.0008710.0007760.0007710.0007290.0001970.00090430.0010510.0005540.0007830.0007730.0008080.0010930.0017780.0007640.0002060.0010030.0009670.0009230.0007790.0008360.0002990.0008290.0006630.0007530.0006990.0001540.00091340.0010210.0005670.0007810.0006860.0007560.0009500.0016610.0008610.0002700.0009170.0009190.0008600.0008960.0007100.0002060.0008860.0005900.0008570.0004640.0001500.00079750.0010390.0005290.0006060.0007230.0007960.0011730.0017860.0007430.0001860.0008660.0009340.0009630.0008730.0008110.0001410.0008040.0007190.0007640.0007560.0001260.00080460.0009690.0005870.0009010.0007430.0007130.0010560.0016160.0005640.0002510.0008530.0008810.0008740.0008400.0007590.0001570.0008130.0006630.0007660.0007590.0001390.0007967-0.0004070.0009060.0006110.0008070.0011060.0018110.0009110.0001030.0008130.0009200.0009360.0007300.0009390.0002090.0008100.0007510.000804-0.0001290.000910總平均值0.0010210.0005500.0008260.0007330.0007990.0010960.0017210.0007680.0002130.0009330.0009420.0009170.0008390.0008470.0002050.0008340.0006920.0007850.0006790.0001550.000863實(shí)驗(yàn)室i水平j(luò)2AgBiCdCoCrCuFeLiMnNiPbPdPtRhSbSnTeZn10.0095390.0081800.0081130.0085160.0093810.0099470.0165240.0099440.0095430.0095960.0090210.0082200.0083160.0080840.0072810.0073060.0079360.00857720.0097310.0080100.0080790.0084340.0099370.0099090.0165570.0104390.0095390.0093560.0088630.0086910.0085040.0087530.0070740.0070340.0079570.00834430.0089200.0079970.0077960.0083710.0090240.0093760.0163960.0099430.0092570.0094500.0086610.0082130.0080840.0080730.0068510.0075700.0077210.00877940.0089030.0074990.0075610.0078990.0088440.0092640.0163070.0099070.0086410.0090130.0095440.0085840.0078070.0083610.0074810.0075490.0070360.00806050.0103590.0076230.0073690.0079660.0088560.0092740.0152440.0106310.0084630.0085510.0083830.0082640.0083370.0079490.0072870.0073460.0074960.00786960.0087790.0081590.0075560.0075700.0087690.0092430.0152570.0102360.0091800.0094970.0089410.0081470.0080610.0083900.0075170.0070610.0078190.00842470.0095140.0090130.0091800.0086360.0105670.0098960.0176490.0103610.0098160.0101390.0104000.0081440.0081070.0084470.0071440.0072500.0074400.009007總平均值0.0093920.0080690.0079500.0081990.0093400.0095580.0162710.0102090.0092060.0093720.0091160.0083240.0081740.0082940.0072340.0073020.0076290.008437水平j(luò)34Ni1234567實(shí)驗(yàn)室i水平j(luò)56VAlKNaV1234567總平均值水平j(luò)78AlKNaAlKNa1234567水平j(luò)1NiV1234567和實(shí)驗(yàn)室i水平j(luò)2AgBiCdCoCrCuFeLiMnNiPbPdPtRhSbSnTeZn10.00017620.00025570.00018140.00029580.00017790.00025460.00055360.00033280.00024270.00021470.00016890.00022790.00028250.00027580.00018050.00033230.00016430.000226120.00063490.00049470.00025180.00022000.00042710.00046290.00061060.00041860.00029620.00037260.00019340.00030260.00039760.00023900.00033510.00051280.00015120.000869330.00066690.00057940.00032930.00019990.00027790.00049810.00092380.00046950.00016160.00040900.00034750.00012150.00042820.00054810.00033140.00043240.00020190.000325840.00006820.00014170.00010610.00023210.00013750.00013530.00055280.00036650.00021800.00016480.00017920.00011390.00013670.00010620.00020070.00013660.00013020.000144750.00077810.00007830.00005010.00007110.00008830.00025530.00041140.00012850.00008180.00007060.00021320.00024460.00028650.00022130.00027540.00023700.00048060.000057060.00016990.00067050.00020660.00016690.00064100.00042910.00051800.00044370.00018080.00015220.00021260.00023160.00017030.00038610.00023160.00023430.00034810.000240770.00006550.00006470.00005480.00023170.00010550.00013820.00010350.00044520.00008890.00007650.00004620.00006240.00067340.00003900.00011190.00030010.00006610.0000559聯(lián)合單元內(nèi)標(biāo)準(zhǔn)差0.00046630.00040100.00019430.00021260.00032510.00034100.00057150.00038770.00019550.00024300.00021100.00020300.00037880.00030340.00024990.00033380.00025750.0003776標(biāo)準(zhǔn)偏差平方和（10）15221761125667264224316310739995813876228643810523142675934133333115522885831004505644429437014780081464038998167實(shí)驗(yàn)室i水平j(luò)34CdCuLiMnMoPbPtRhAgBiCoNiPdSbSnTeZn10.00096040.00133650.00112420.00062310.00091590.00056090.00133380.00080650.00190070.00204440.00092090.00092350.00174320.00107180.00084760.00187260.002081820.00102610.00175950.00105290.00096000.00118930.00143180.00090050.00100560.00180990.00186600.00127670.00088480.00173450.00086410.00135910.00070830.001743930.00131740.00110910.00075540.00130250.00142210.00161670.00109410.00192170.00198240.00193170.00103400.00127810.00090540.00168280.00161520.00162520.001566440.00047300.00028120.00021380.00032700.00150070.00032140.00018610.00035650.00062490.00057480.00077060.00063650.00078490.00084230.00099080.00086060.000473650.00032420.00035200.00067700.00035030.00056520.00051980.00028380.00120390.00134340.00116430.00075550.00028010.00093070.00108120.00109580.00141610.000735860.00085380.00112800.00059470.00090120.00075920.00035530.00065100.00138190.00123890.00147760.00132420.00051940.00065530.00086540.00104810.00092470.001336170.00024590.00042780.00021860.00034120.00026810.00104340.00069710.00031340.00051050.00066530.00044260.00022210.00027640.00038210.00026080.00046550.0002157聯(lián)合單元內(nèi)標(biāo)準(zhǔn)差0.00083060.00105360.00074150.00077130.00103480.00096850.00082910.00113000.00145450.00149790.00097550.00076270.00112470.00103510.00110350.00122290.0013324標(biāo)準(zhǔn)偏差平方和（10）482890577704763848605416458674954956566452481195289389051480931015704995666102440717528855172750056785235951046757112426395實(shí)驗(yàn)室i水平j(luò)56AsCaCrFeMgVAlAsCaKMgMoNaReTiVZr10.00119750.00192280.00095810.00166510.00139300.00161100.00056260.00062960.00074880.00071990.00031290.00027140.00097330.00039200.00039400.00034670.00040170.000308820.00278680.00194980.00162350.00119390.00250420.00121030.00056160.00063690.00036940.00043060.00018130.00100410.00103050.00042200.00039280.00044100.00036890.000391230.00323200.00206110.00064980.00141110.00135700.00133080.00054860.00040770.00078070.00045910.00025110.00034490.00078410.00037250.00028850.00020470.00060240.000317740.00057220.00049080.00036230.00120110.00031520.00029060.00013850.00013440.00019720.00019360.00019230.00013670.00014670.00020440.00017660.00012190.00012190.000176450.00067620.00097750.00137250.00064240.00059760.00051100.00014950.00006430.00014590.00021010.00008930.00022680.00043220.00009500.00012000.00010270.00010820.000086460.00112370.00136800.00106210.00091070.00143570.00066360.00017510.00048720.00051550.00082990.00032150.00026610.00023010.00029550.00036460.00035890.00036800.000209270.00034750.00063600.00027980.00024040.00055750.00048790.00017610.00009580.00014580.00029000.00005890.00012070.00046880.00011040.00023410.00014070.00017730.0001296聯(lián)合單元內(nèi)標(biāo)準(zhǔn)差0.00176530.00147450.00101400.00103430.00135650.00098960.00038470.00042040.00048610.00050270.00022220.00044020.00066600.00029780.00029910.00027530.00034920.0002531標(biāo)準(zhǔn)偏差平方和（10）218141761521937671970867488848128812906855043103611312368991653752176905234565213563193105061620771626045530571853705448510水平j(luò)78KNaKNa1234567和）3.14.1測(cè)試結(jié)果一致性檢查1NiV12342.028185567實(shí)驗(yàn)室i水平j(luò)2AgBiCdCoCrCuFeLiMnNiPbPdPtRhSbSnTeZn10.2587460.2271150.2668080.8109600.0612661.1483620.298420-0.9282530.6814710.453949-0.142000-0.4684110.618475-0.7569810.2038790.0164530.9305710.35457820.599296-0.1193810.2104970.6026060.8790461.0344300.3379630.8064920.672813-0.032248-0.3792771.6649271.4407351.657693-0.684263-1.2707350.995599-0.2351793-0.833536-0.145586-0.2540710.441772-0.464300-0.5395190.143684-0.9332670.1045560.158758-0.680683-0.499441-0.390662-0.798258-1.6397801.2697680.2776970.8647364-0.863808-1.161780-0.638865-0.768140-0.729185-0.8686560.037088-1.058610-1.139606-0.7268140.6403741.180077-1.5991350.2439741.0613951.168148-1.800575-0.95518951.706714-0.908460-0.955616-0.596340-0.712367-0.839118-1.2420651.483343-1.500358-1.661584-1.097522-0.2680060.711913-1.2471390.2283790.206144-0.404656-1.4400206-1.0832730.183439-0.648250-1.608865-0.840605-0.931952-1.2265910.094544-0.0515770.254261-0.261707-0.798108-0.4903300.3471651.214523-1.1420170.575089-0.03256370.2158621.9246532.0194981.1180071.8061440.9964531.6515010.5357511.2327011.5536791.920816-0.811038-0.2909950.553547-0.384132-0.247760-0.5737261.44363834Ni1234567實(shí)驗(yàn)室i水平j(luò)56AsCaCrFeMgVAlAsCaKMgMoNaReTiVZr10.295918-0.2461180.519060-1.315507-0.593965-0.0426640.0970620.170625-0.5421090.310450-0.007291-0.435851-0.077066-0.548298-0.3073880.1729110.6576850.57217120.353754-0.6076490.346801-0.842750-0.579628-0.145767-0.121719-0.559524-0.5932641.8050620.2148571.0964902.2108550.838673-0.0362580.861712-0.1987380.33657130.8627121.7069561.0791891.5195771.0429931.601659-0.8692200.954705-0.444450-0.947592-0.3795370.648223-0.464001-0.8292790.0543690.742267-0.9674291.0371714-1.906305-1.029771-0.6057600.6616101.6923790.3804160.9126290.262308-0.3607420.2224230.5240610.817467-0.142569-0.5602541.9696021.036898-0.2488701.11157150.105503-0.324887-0.1049530.649937-0.841913-1.1856901.6467610.3490131.080896-1.3015311.691835-1.140271-0.591731-1.176022-0.520778-0.762743-0.486997-1.1886286-0.679289-0.575333-1.902840-0.050444-0.802275-1.219465-0.4529290.801208-0.890892-0.048991-0.481605-1.423869-0.6712701.0299800.154537-1.702378-0.704236-1.14522870.9677071.0768020.668504-0.6224220.0824080.611510-1.212585-1.9783351.750560-0.039821-1.5623210.437812-0.2642171.245200-1.314084-0.3486661.948585-0.723629水平j(luò)78KNaKNa12345671NiV1234567--2Ni123456734Ni123456756VKNaV123456778KNaKNa1234567采用科克倫（Cochran）檢驗(yàn)法對(duì)實(shí)驗(yàn)室間標(biāo)準(zhǔn)方差的檢驗(yàn)。先計(jì)算m組數(shù)據(jù)1NiV1234567--2Ni123456734Ni123456756VKNaV123456778KNaKNa1234567經(jīng)查，對(duì)于p=7，n=7,柯克倫檢驗(yàn)值的臨界值在顯著性實(shí)驗(yàn)室i水平j(luò)1AgAsBiCdCoCuFeLiMgMnNiPbPdPtReRhSbSnTeVZn10.0246940.1382920.1152420.1711250.1447490.0282190.3085880.1642340.0794610.1370110.1185890.0190250.1686430.0128100.1264540.1502800.1817770.1414060.3713950.1791140.14923720.0577800.3485240.2061270.1100090.1623460.3447110.1697650.1323270.3367000.1897460.1532180.3158150.1209720.1850270.3500250.2772210.2116850.1486770.3974680.16563030.3145530.1002440.2731890.2552520.2409600.0842480.3408360.1407410.1419550.2783400.1196200.1019390.4123260.2316640.4500400.0888380.1049660.1588610.12945240.0812750.0177700.0326880.1438580.1186370.0118280.1222310.0509520.0565660.1128620.0581510.1032100.1178960.0079700.0101160.1167070.0430520.0969520.0767170.0177220.24420650.3111960.1779880.2941930.0573550.0471140.1049340.0641260.1207020.0087540.1823530.1140150.3218790.0779140.1189870.0227620.1894480.0501140.1833190.1433240.0037970.05483360.2105010.3157070.2489420.2350620.1975400.2671510.2483820.1642340.3744110.2094600.2456710.0464920.1363490.0811270.2043500.0767390.1382690.3640980.1549210.1746840.24477170.0017200.0025640.0094020.0743610.0021970.0026600.0267130.0033670.0266140.0320160.0739600.2762870.1817530.0546280.0167870.2207290.0025400.0683540.0118712Ni123456734Ni123456756VKNaV123456778KNaKNa12345671NiV12345672Ni123456734Ni123456756VKNaV1234567水平j(luò)78KNaKNa1234567表25組內(nèi)格拉布斯（Grubbs）一個(gè)離群值檢驗(yàn)結(jié)果（1）1NiV1234567實(shí)驗(yàn)室i水平j(luò)2AgBiCdCoCrCuFeLiMnNiPbPdPtRhSbSnTeZn10.2587460.2271150.2668080.8109600.0648641.1483620.298420-0.9282530.6814710.453949-0.142000-0.4684110.524651-0.8680310.2038790.0164530.8226840.28946320.599296-0.1193810.2104970.6026061.0344300.3379630.8064920.672813-0.032248-0.3792771.6649271.2815251.486974-0.684263-1.2707350.8781413-0.833536-0.145586-0.2540710.441772-0.429527-0.5395190.143684-0.9332670.1045560.158758-0.680683-0.499441-0.404240-1.6397801.2697680.2658970.7576964-0.863808-1.161780-0.638865-0.768140-0.678699-0.8686560.037088-1.058610-1.139606-0.7268140.6403741.180077-1.5166150.1081891.0613951.168148-1.506505-0.91266751.706714-0.908460-0.955616-0.596340-0.662879-0.839118-1.2420651.483343-1.500358-1.661584-1.097522-0.2680060.610660-1.3460770.2283790.206144-1.3576546-1.0832730.183439-0.648250-1.608865-0.931952-1.2265910.094544-0.0515770.254261-0.261707-0.798108-0.4959820.2088311.214523-1.142017-0.06586370.2158621.9246532.0194981.1180071.7062410.9964531.6515010.5357511.2327011.5536791.920816-0.8110380.410113-0.384132-0.247760-0.4602181.28902434Ni1234567實(shí)驗(yàn)室i水平j(luò)56AsCaCrFeMgVAlAsCaKMgMoNaReTiVZr10.490464-0.2461180.519060-1.315507-0.652060-0.0426640.0970620.170625-0.5421090.310450-0.007291-0.263955-0.077066-0.548298-0.3073880.1729110.6576850.5721712-0.6076490.346801-0.842750-0.145767-0.121719-0.559524-0.5932641.8050620.2148572.2108550.838673-0.0362580.861712-0.1987380.33657131.7069561.0791891.5195770.8936121.601659-0.8692200.954705-0.444450-0.947592-0.3795370.866599-0.464001-0.8292790.0543690.742267-0.9674291.0371714-1.512668-1.029771-0.6057600.6616101.5067850.3804160.9126290.262308-0.3607420.2224230.5240611.043099-0.142569-0.5602541.9696021.036898-0.2488701.11157150.317264-0.324887-0.1049530.649937-0.886180-1.1856901.6467610.3490131.080896-1.3015311.691835-0.998577-0.591731-1.176022-0.520778-0.762743-0.486997-1.1886286-0.396580-0.575333-1.902840-0.050444-0.848753-1.219465-0.4529290.801208-0.890892-0.048991-0.481605-1.294333-0.6712701.0299800.154537-1.702378-0.704236-1.14522871.1015201.0768020.668504-0.622422-0.0134050.611510-1.212585-1.9783351.750560-0.039821-1.5623210.647167-0.2642171.245200-1.314084-0.3486661.948585-0.72362978KNaKNa1234567p=5p=6p=7表26組內(nèi)格拉布斯（Grubbs）一個(gè)離群值檢驗(yàn)結(jié)果（2）1NiV1234567實(shí)驗(yàn)室i水平j(luò)2AgBiCdCoCrCuFeLiMnNiPbPdPtRhSbSnTeZn10.2587460.2271150.2668080.8109600.0648641.1483620.298420-0.9282530.6814710.453949-0.142000-0.4684110.524651-0.8680310.2038790.0164530.8226840.28946320.599296-0.1193810.2104970.6026061.0344300.3379630.8064920.672813-0.032248-0.3792771.6649271.2815251.486974-0.684263-1.2707350.8781413-0.833536-0.145586-0.2540710.441772-0.429527-0.5395190.143684-0.9332670.1045560.158758-0.680683-0.499441-0.404240-1.6397801.2697680.2658970.7576964-0.863808-1.161780-0.638865-0.768140-0.678699-0.8686560.037088-1.058610-1.139606-0.7268140.6403741.180077-1.5166150.1081891.0613951.168148-1.506505-0.91266751.706714-0.908460-0.955616-0.596340-0.662879-0.839118-1.2420651.483343-1.500358-1.661584-1.097522-0.2680060.610660-1.3460770.2283790.206144-1.3576546-1.0832730.183439-0.648250-1.608865-0.931952-1.2265910.094544-0.0515770.254261-0.261707-0.798108-0.4959820.2088311.214523-1.142017-0.06586370.2158621.9246532.0194981.1180071.7062410.9964531.6515010.5357511.2327011.5536791.920816-0.8110380.410113-0.384132-0.247760-0.4602181.28902434Ni1234567實(shí)驗(yàn)室i水平j(luò)56AsCaCrFeMgVAlAsCaKMgMoNaReTiVZr10.490464-0.2461180.519060-1.315507-0.652060-0.0426640.0970620.170625-0.5421090.310450-0.007291-0.2639551.194711-0.548298-0.3073880.1729110.6576850.5721712-0.6076490.346801-0.842750-0.145767-0.121719-0.559524-0.5932641.8050620.2148570.838673-0.0362580.861712-0.1987380.33657131.7069561.0791891.5195770.8936121.601659-0.8692200.954705-0.444450-0.947592-0.3795370.866599-0.391630-0.8292790.0543690.742267-0.9674291.0371714-1.512668-1.029771-0.6057600.6616101.5067850.3804160.9126290.262308-0.3607420.2224230.5240611.0430990.926165-0.5602541.9696021.036898-0.2488701.11157150.317264-0.324887-0.1049530.649937-0.886180-1.1856901.6467610.3490131.080896-1.3015311.691835-0.998577-0.915295-1.176022-0.520778-0.762743-0.486997-1.1886286-0.396580-0.575333-1.902840-0.050444-0.848753-1.219465-0.4529290.801208-0.890892-0.048991-0.481605-1.294333-1.2413871.0299800.154537-1.702378-0.704236-1.14522871.1015201.0768020.668504-0.622422-0.01