銀化學分析方法 第7部分：金、鈀量的測定 電感耦合等離子體發(fā)射光譜法 征求意見稿

3銀化學分析方法第7部分：金和鈀量的測定電感耦合等離子體原子發(fā)射光譜法警示——使用本文件的人員應(yīng)有正規(guī)實驗室工作的實踐經(jīng)驗。本文件并未指出所有有可能的安全問題。使用者有責任采取適當?shù)陌踩徒】荡胧⒈ＷC符合國家有關(guān)法規(guī)規(guī)定的條件。本文件規(guī)定了銀中金和鈀含量的測定方法。本文件適用于銀中金和鈀含量的測定。測定范圍：金：0.0002%～0.050%，鈀:0.0002%~0.050%。2規(guī)范性引用文件下列文件中內(nèi)容通過文中的規(guī)范性引用而構(gòu)成本文件必不可少的條款。其中，注日期的引用文件，僅該日期對應(yīng)的版本適用于本文件；不注日期的引用文件，其最新版本（包括所有的修改單）適用于本文件。GB/T6682分析實驗室用水規(guī)格和試驗方法GB/T8170數(shù)值修約規(guī)則與極限數(shù)值的表示和判定3術(shù)語和定義本文件沒有需要界定的術(shù)語和定義。4方法原理試料用硝酸溶解，過濾分離金，將沉淀置于坩堝中，于馬弗爐中灼燒，加入王水沸水浴中溶解。濾液加鹽酸沉淀分離基體銀，合并兩種溶液，在鹽酸介質(zhì)中，于電感耦合等離子體原子發(fā)射光譜儀上,分別在242.7nm，340.458nm處測定試液中金和鈀的強度。5試劑和材料除非另有說明，在分析中僅使用確認為分析純及以上的試劑。5.1水，GB/T6682,二級水。5.2鹽酸(p=1.19g/mL)5.3硝酸(p=1.42g/mL)5.4鹽酸(1+1)5.5鹽酸(1+4)5.6鹽酸(5+95)5.7硝酸(1+5)5.8硝酸(2+98)5.9混合酸（鹽酸：硝酸=3:1）5.10混合酸（鹽酸：硝酸：水=3:1:4）5.11金標準貯存溶液:稱取純金0.1000g(質(zhì)量分數(shù)≥99.99%),置于100mL燒杯中,加入20mL王水(5.9),蓋上表面皿,低溫加熱溶解,取下用水洗表皿及杯壁,冷卻。移入100mL容量瓶中,用水稀釋至刻度,混4勻。此溶液1mL含1000μg金。5.12鈀標準貯存溶液:稱取0.1000g金屬鈀(質(zhì)量分數(shù)≥99.99%)于100mL燒杯中,加入20mL混合酸(5.9),低溫加熱溶解,驅(qū)趕氮的氧化物,冷卻至室溫,移入100mL容量瓶中,用水稀釋至刻度,混勻。此溶液1mL含1000μg鈀。5.13金和鈀混合標準溶液（100μg/mL):分別移取金標準貯存溶液(5.11)鈀標準貯存溶液(5.12)各10.0mL于100mL容量瓶中,加入10mL混合酸(5.10)，用水稀釋至刻度,混勻,此溶液1mL含有100μg金，100μg鈀。6儀器和設(shè)備6.1分析天平：分度值0.1mg。6.2瓷坩堝：容積為50mL。6.3電感耦合等離子體原子發(fā)射光譜儀。在儀器最佳工作條件下,凡能達到下列指標者均可使用：——分辨率:200nm時光學分辨率不大于0.010nm；400nm時光學分辨率不大0.020nm；——儀器穩(wěn)定性:在儀器的最佳工作條件下，用最低濃度的標準溶液（不是“零”濃度標準溶液）測量11次，各元素光強度的相對標準偏差不超過2.5%?！髟赝扑]的分析譜線見表1。表1測定元素推薦波長AuPd儀器推薦工作條件參數(shù)參見附錄A。7樣品試料用20mL鹽酸（5.5）微沸5分鐘，用水清洗至無氯離子后，再用無水乙醇沖洗兩次，自然晾干后備用。8分析步驟按表2稱取試料，精確至0.0001g。表2稱樣量及定容體積g55%3118.2空白試驗隨同試料做空白試驗。8.3測定58.3.1按表2稱取試料置于250mL燒杯中、按表2加入硝酸(5.7)，蓋上表面皿,低溫加熱溶解,取下,用水沖洗表皿及杯壁加熱煮沸。用定量慢速濾紙加少許濾紙漿過濾,用熱硝酸(5.8)洗滌燒杯及沉淀共6-7次，洗液用250mL燒杯承接。將沉淀連同濾紙一起放入50mL瓷坩堝中,在電熱板上烘干,置于馬弗爐中從低溫升至700℃,灼燒15min,取出放冷。加入10mL混合酸(5.9),在沸水浴上加熱溶解金,至體積約為1mL。8.3.2將7.3.1所得濾液(體積約70mL，如體積過大濃縮至70mL左右)置于電熱板上加熱煮沸,取下，按表2邊攪拌邊慢慢滴加鹽酸(5.5例如：25mL鹽酸溶液滴加時間控制在3~5min,加入速度約0.12mL/s~0.17mL/s），加熱并不斷攪拌至溶液清亮，于沸水浴保溫30min，保溫過程中每隔10min用玻璃棒攪拌沉淀。用慢速定量濾紙過濾,先將上清液倒入漏斗過濾完后，沉淀留于原杯中每次加入約10mL熱稀鹽酸(5.6)于杯中，用玻璃棒攪拌后將洗液倒入漏斗中過濾，沉淀留于原杯中重復上述動作5~6次后，連同沉淀一起倒入漏斗中，熱稀鹽酸(5.6)洗滌杯壁及沉淀3~4次,濾液收集于400mL燒杯中。8.3.3將7.3.1和7.3.2所得溶液合并，置于低溫電熱板上蒸至近干,取下冷卻后，用適量水吹洗杯壁及表面皿,按表2加入鹽酸(5.4),低溫溶解鹽類，取下冷卻。按表2移入相應(yīng)體積容量瓶中,用水稀釋至刻度,混勻。干過濾后，于電感耦合等離子體發(fā)射光譜儀上，波長267.59nm、340.458nm處,在選定的儀器工作條件下,測量分析試液及隨同試料空白中被測元素的譜線強度，扣除空白值,從工作曲線上確定被測元素的質(zhì)量濃度。8.4工作曲線的繪制8.4.1系列標準工作溶液配制移取0mL、0.25、0.50mL、1.00mL、200mL、5.00mL、10.00mL金和鈀混合標準溶液（5.13），置于一組100mL容量瓶中，加入10mL鹽酸（5.4），用水稀釋至刻度，混勻。8.4.2工作曲線的繪制在與試液測定相同條件下,以“零”標準溶液調(diào)零,測量系列標準工作溶液的光譜強度,以被測元素的濃度為橫坐標,譜線強度為縱坐標,由儀器自動繪制工作曲線。9試驗數(shù)據(jù)處理被測元素以質(zhì)量分數(shù)wx計，按公式（1）計算：wx100%…………（1）式中：c0——自工作曲線上查得空白溶液中金、鈀的質(zhì)量濃度，單位為微克每毫升(μg/mLc——自工作曲線上查得試液中金、鈀的質(zhì)量濃度，單位為微克每毫升(μg/mL）；v——測定試液的體積，單位為毫升（mL）;m——試料的質(zhì)量，單位為克（g）；計算結(jié)果表示到小數(shù)點后4位；若質(zhì)量分數(shù)小于0.0010%時，計算結(jié)果表示到小數(shù)點后5位。10精密度在重復性條件下獲得的兩次獨立測試結(jié)果的測定值，在以下給出的平均值范圍內(nèi)，這兩個測試結(jié)果的絕對值不超過重復性限（r），超過重復性限（r）的情況不超過5%，重復性限（r）按表3數(shù)據(jù)采用線性外延法求得。表3重復性限wAu/%wPd/%10.2再現(xiàn)性在再現(xiàn)性條件下獲得的兩次獨立測試結(jié)果的測定值，在以下給出的平均值范圍內(nèi)，這兩個測試結(jié)6果的絕對差不超過再現(xiàn)性限（R），超過再現(xiàn)性限（R）的情況不超過5%，再現(xiàn)性限（R）按表4數(shù)據(jù)采用線性外延法求得。表4再現(xiàn)性限wAu/%R/%wPd/%R/%11.試驗報告本章規(guī)定試驗報告所包括的內(nèi)容。至少應(yīng)給出以下幾個方面的內(nèi)容：——試驗對象；——使用的方法；——分析結(jié)果及其表示；——與基本分析步驟的差異；——觀察到的異常現(xiàn)象；——試驗日期。7電感耦合等離子體發(fā)射光譜儀，工作參數(shù)見表1。表1儀器工作參數(shù)霧化器氣體流量（L/min）觀測高度（mm）輔助氣體流量（L/min）泵穩(wěn)定時間分析泵速（rpm）0.70.58精密度試驗原始數(shù)據(jù)精密度數(shù)據(jù)是在2023年由18家實驗室對金、鈀含量的5個不同水平樣品進行試驗確定的。每個實驗室對每個水平的金、鈀含量在重復性條件下獨立測定7次。測量的原始數(shù)據(jù)見表A·2、A·3。表A·2金精密度原始數(shù)據(jù)實驗室次數(shù)Au-水平j(luò)123451、大冶有色設(shè)計研究院有限公司（牽頭起草）10.000200.001480.003020.01440.052620.000200.001480.003120.01500.049130.000210.001680.002960.01490.051540.000190.001410.002970.01360.052050.000200.00160.002940.01400.051660.000200.001510.003090.01440.055970.000200.001660.003060.01510.0516均值0.000200.001550.003020.014490.05204s0.000010.000100.000070.000560.002022、南京市產(chǎn)品質(zhì)量監(jiān)督檢查院（參與起草）10.00016*0.001490.003020.014600.03911**20.00015*0.001600.002720.014220.03755**30.00021*0.001470.002660.013990.03812**40.00020*0.001470.00230**0.013650.03779**50.00014*0.001470.002650.014030.03791**60.00015*0.001670.002660.014210.03879**70.00018*0.001700.002680.013710.03764**均值0.000170.001550.002670.014060.03813s0.000030.000100.000210.000320.000603、北京達博有色金屬焊料有限責任公司（一驗單位）10.000170.0009**0.00260.0126*0.047920.00026**0.0010**0.00270.0118*0.048630.000180.0009**0.00280.01380.046840.000230.0011**0.00260.01350.047050.00015**0.0010**0.00270.01330.0473860.000210.0011**0.00280.0130*0.046970.000170.0011**0.00270.01350.0476均值0.000200.00100.00270.01310.0474s0.000040.000090.000080.000680.000654、中船黃岡貴金屬有限公司（一驗單位）10.00027**0.001200.00260**0.014500.04720**20.00031**0.001400.00211**0.01290*0.0493030.00030**0.001150.00256**0.014740.04724**40.00024**0.001400.00223**0.013870.0482550.00025**0.001400.00250**0.01322*0.0540660.00024**0.001400.00212**0.01287*0.0508270.00026**0.001500.00234**0.014540.04982均值0.000270.001350.002350.013810.04953s0.000030.000130.000210.000810.002405、江西銅業(yè)股份有限公司（一驗單位）10.000190.00170.00310.01550.053920.000180.00170.00310.01540.055530.000180.00170.00310.01530.054640.000190.00180.00300.01540.054150.000200.00170.00300.01550.053460.000200.00160.00280.01510.054070.000200.00170.00300.01520.0534均值0.000190.00170.00300.01530.0541s0.000010.000060.000110.000150.000736、紫金礦業(yè)集團股份有限公司測試中心（二驗單位）10.000170.001690.003030.0160.055220.000170.001680.002950.01540.054130.000160.001610.002910.01540.054140.000170.001630.002950.01530.053750.000170.00160.003010.01510.053560.000180.001550.002810.01510.052770.000180.001570.002860.01510.0523均值0.000170.00160.00290.01530.0537s0.000010.000050.000080.000320.000967、金川集團股份有限公司檢測中心（二驗單位）10.000220.00160.00310.0150.0520.000230.00170.0030.0140.05230.000230.00170.0030.0150.05240.000210.00170.0030.0150.05150.000230.00160.0030.016*0.05160.000230.00160.00310.0140.052970.000240.00170.00290.016*0.053均值0.000230.00170.00300.0150.052s0.000010.000050.000070.000820.000988、山東招金金銀精煉有限公司（二驗單位）10.0001930.0014630.002940.01360.049120.0002010.0014920.002940.01400.048830.0002030.0014440.003030.01400.048540.0001960.0014670.003090.01380.049050.0001890.0014830.003020.01320.050260.0001940.0014430.003070.01440.048870.0001970.0014370.002940.01410.0484均值0.000200.001460.003000.01390.0490s0.000000.000020.000060.000380.000589、中國有色桂林礦產(chǎn)地質(zhì)研究院有限公司（二驗單位）10.000180.00160.00280.01480.051620.000170.00160.00290.01470.05230.000180.00150.00290.01460.051940.000180.00160.00280.01460.050850.000180.00160.00280.01480.050660.000180.00160.00290.01460.05170.000190.00160.00280.01450.0507均值0.000180.00160.00280.01470.0512s0.000010.000040.000050.000110.0005910、國標（北京）檢驗認證有限公司（二驗單位）10.00020.00160.00290.0130.04520.000210.00160.00290.0130.04530.00020.00150.0030.0130.04540.000190.00160.00310.0130.04550.00020.00160.00310.0140.04660.00020.00170.00310.0140.04670.00020.00160.00300.0140.046均值0.000200.00160.00300.01340.0454s0.000010.000060.000090.000530.0005311、北京有色金屬與稀土應(yīng)用研究所有限公司理化中心（二驗單位）10.000220.00160.00320.01310.0446**20.000170.0012**0.00320.01480.0444**30.000180.00140.00330.0150.0467**40.000190.0012**0.00330.0150.050450.000160.001**0.00340.01480.049160.00020.0012**0.00310.01420.05170.00020.00140.00310.01470.049均值0.000190.00130.00320.01450.0479s0.000020.000200.000110.000680.0026812、云南黃金礦業(yè)集團貴金屬檢測有限公司（二驗單位）10.000210.00170.00310.01460.054120.000190.00160.00300.01490.054530.000210.00160.00310.01510.052240.000210.00170.00310.01530.053050.000210.00170.00310.01510.052860.000210.00170.00320.01520.053570.000210.00180.00320.01510.0526均值0.000210.00170.00310.01500.0532s0.000010.000070.000070.000230.0008313、貴研檢測科技云南有限公司（二驗單位）10.000170.00160.00300.01510.051320.000190.00160.00300.01490.050630.000190.00160.00280.01480.050740.000200.00160.00280.01500.051250.000180.00160.00280.01540.051460.000170.00150.00290.01470.051170.000170.00160.00300.01470.0522均值0.000180.00160.00290.01490.0512s0.000010.000040.000100.000250.0005314、中金嶺南有色金屬股份有限公司（二驗單位）10.000170.001590.002940.01440.049620.000140.001630.0030.01430.04930.000160.001620.002980.01450.049640.000170.001560.00290.01430.049550.000180.001430.002920.01420.0560.000160.001520.002940.01420.049870.000150.001550.002920.01440.0495均值0.000160.001560.002940.01430.0496s0.000010.000070.000040.000110.0003115、銅陵有色金屬集團控股有限公司（二驗單位）10.000170.00160.00280.0150.04820.000160.00150.00280.0140.04630.000170.00160.00290.0140.04840.000170.00150.00290.0140.04750.000170.00160.00280.0140.04760.000180.00160.0030.0140.04770.000170.00170.0030.0150.046均值0.000170.00160.00290.0140.047s0.000010.000070.000090.000490.0008216、江蘇北礦金屬循環(huán)利用科技有限公司（二驗單位）10.000170.001330.002700.013910.0477120.000160.001400.002890.013650.0483830.000140.001620.002650.013630.0474840.000160.001550.002740.013590.0482950.000140.001570.002770.013990.0475360.000150.001470.002650.013560.0486570.000150.001530.002630.013770.04721均值0.000150.00150.00270.01370.0479s0.000010.000100.000090.000170.0005417、山東恒邦冶煉股份有限公司（二驗單位）10.000210.00170.00320.016*0.056**20.00020.00160.00310.016*0.055*30.00020.00150.0030.016*0.055*40.000210.00160.00310.0150.054*50.000190.00170.00310.0150.05160.000190.00170.00310.0140.05170.000190.00170.00310.0150.052*均值0.000200.00160.00310.01530.0534s0.000010.000080.000060.000760.0020718、云南銅業(yè)股份有限公司（二驗單位）10.000180.001560.002930.01280.049720.000190.001630.002850.01460.052030.000210.001580.002960.01380.053340.000200.001610.003110.01380.051750.000190.001650.003080.01330.049060.000170.001570.002830.01410.051270.000200.001570.002850.01370.0505均值0.000190.001600.002940.013730.05106s0.000010.000030.000110.000570.00146表A·3鈀精密度原始數(shù)據(jù)實驗室次數(shù)Pd-水平j(luò)123451、大冶有色設(shè)計研究院有限公司（牽頭起草）10.0001560.001480.002830.01360.04820.0001490.001530.002930.01380.048530.0001530.001480.002770.01360.048640.0001390.001450.00280.0140.048350.0001380.00150.002830.01440.049960.0001310.001460.002720.01340.050770.0001520.001490.002790.01330.0466均值0.000150.001480.002810.013730.04866s0.000010.000030.000070.000380.001332、南京市產(chǎn)品質(zhì)量監(jiān)督檢查院（參與起草）10.000037**0.001410.00330**0.012980.0498420.000031**0.001470.00368**0.012720.0476230.000022**0.001480.00362**0.012860.05336**40.000034**0.001490.00354**0.012900.05221**50.000029**0.001560.00333**0.012610.05413**60.000024**0.001490.00325**0.012080.05353**70.000023**0.001380.00328**0.012320.05294**均值0.000030.001470.003430.012640.05195s0.000010.000060.000180.000330.002363、北京達博有色金屬焊料有限責任公司（一驗單位）10.000110.0010**0.00260.0189**0.047620.000120.0010**0.00270.0185**0.047930.000100.0010**0.00260.0197**0.047440.000120.0010**0.00270.0185**0.046850.000100.0012**0.00270.0193**0.047360.000090.0011**0.00260.0195**0.04870.000100.0012**0.00270.0187**0.0488均值0.000110.00110.00270.01900.0477s0.000010.000100.000050.000490.000634、中船黃岡貴金屬有限公司（一驗單位）10.00018*0.001700.002800.013700.04588**20.00017*0.001600.002800.013200.04506**30.00018*0.001720.002870.014500.04231**40.00015*0.001770.002640.013500.04151**50.00020*0.001690.002450.014500.04278**60.00016*0.001760.00236**0.01150**0.04476**70.00019*0.001770.00214**0.01270**0.04532**均值0.000180.001720.002580.013370.04395s0.000020.000060.000270.001050.001715、江西銅業(yè)股份有限公司（一驗單位）10.000160.00170.0030.01470.051420.000170.00160.00310.01450.053130.000170.00170.0030.01460.052140.000180.00170.00310.01460.051550.000170.00170.0030.01470.052660.000150.00170.0030.01460.051570.000170.00170.0030.01450.0518均值0.000170.00170.00300.01460.0520s0.000010.000040.000050.000080.000646、紫金礦業(yè)集團股份有限公司測試中心（二驗單位）10.000180.001710.003020.01480.051720.000170.001670.002950.01440.05130.000160.001640.002870.01450.050840.000160.001680.003060.01460.051250.000170.001690.003030.01450.049960.000160.001640.002890.01470.051570.000170.001650.002930.01460.0503均值0.000170.001670.002960.01460.0509s0.000010.000030.000070.000130.000647、金川集團股份有限公司檢測中心（二驗單位）10.00024**0.00160.00280.0140.0520.00027**0.00160.00280.0140.04930.00026**0.00170.00280.0140.04940.00026**0.00160.00280.0150.04850.00024**0.00170.00270.0140.04960.00025**0.00180.00280.0140.04970.00027**0.00180.00290.016*0.050均值0.000260.00170.00280.0140.049s0.000010.000090.000060.000790.000698、山東招金金銀精煉有限公司（二驗單位）10.000210.001470.003070.01290.046220.000210.001470.002930.01340.047330.000210.001460.003030.01340.046840.000200.001440.003080.01320.048050.000190.001470.003020.01250.049360.000210.001470.002930.01370.047970.000210.001500.002940.01350.0477均值0.000200.001470.003000.01330.0476s0.000010.000020.000060.000400.000979、中國有色桂林礦產(chǎn)地質(zhì)研究院有限公司（二驗單位）10.000160.00150.00280.01370.048620.000170.00150.00290.01390.048830.000160.00160.00280.01360.048940.000160.00170.00280.0140.049750.000150.00170.00290.01410.049560.000170.00170.00280.01360.049670.000160.00160.00280.01380.0488均值0.000160.00160.00280.01380.0491s0.000010.000090.000050.000200.0004510、國標（北京）檢驗認證有限公司（二驗單位）10.000210.00170.0030.0140.04820.000210.00170.00310.0140.04830.000220.00170.0030.0140.04840.000210.00160.00310.0150.04950.000210.00170.00310.0140.04960.000210.00180.00320.0140.04970.000210.00180.0030.0140.049均值0.000210.00170.00310.01410.0486s0.000000.000070.000080.000380.0005311、北京有色金屬與稀土應(yīng)用研究所有限公司理化中心（二驗單位）10.000150.00140.00240.01360.0463**20.000140.00150.00260.01340.0473**30.000130.00150.00270.01350.050240.000160.00140.00260.01380.050850.000140.00150.00280.01410.050260.000130.00140.00260.01360.052**70.000140.00150.00270.01360.0513均值0.000140.00150.00260.01370.0497s0.000010.000050.000130.000230.0021212、云南黃金礦業(yè)集團貴金屬檢測有限公司（二驗單位）10.000160.00140.0024**0.0131*0.0458*20.000150.0012**0.0024**0.0133*0.0463*30.000170.0013**0.00270.0132*0.0460*40.000140.00160.00300.01460.049250.000170.00160.00300.01480.049860.000150.00150.00270.01430.049570.000150.00150.00270.01400.0500均值0.000160.00140.00270.01390.0481s0.000010.000150.000240.000700.0019413、貴研檢測科技云南有限公司（二驗單位）10.000200.00170.00300.01460.050020.000210.00170.00280.01450.050030.000180.00160.00280.01460.049840.000170.00160.00280.01450.047350.000180.00160.00280.01440.050260.000190.00160.00290.01410.049870.000200.00160.00280.01400.0509均值0.000190.00160.00280.01440.0497s0.000010.000050.000080.000240.0011314、中金嶺南有色金屬股份有限公司（二驗單位）10.00011**0.001550.002850.01350.047620.000140.001540.002840.01330.047730.00011**0.001530.00291