ICP技术研讨会议.ppt

PerkinElmer,Presentation Power File,Second level,Third level,Fourth level,Fifth level,A,nalytical,&,B,io Science Instrument Co.LTD.,博 精 儀 器,A,&,B,instrument,ICP/OES,感應藕合電漿放射光譜儀訓練課程,博精儀器股份有限公司,技術專員楊日懷,13926808973,課程內容,無機分析儀器,之介紹說明及比較,ICP-,基本原理,A:,樣品進樣系統,B:,等離子,(,電漿,),系統,C:,光學系統,D:,偵測系統,ICP-OES,分析參數之設定及方法之開發,ICP-OES,分析之應用,討論,ICP-OES and Furnace&Flame AA,Flames AA-,火燄式原子吸收光譜儀,Furance,AA-,石墨式原子吸收光譜儀,感應藕合電漿放射光譜儀,感應藕合電漿質譜儀,原子光譜學原理,H,He,Li,M,能量,離子化,吸收,(,a,),發射,(,e,),Be,一般情况下，原子处于基态，通过电致激发、热致激发或光致激发,等激发光源作用下，原子获得能量，外层电子从基态跃迁到较高能,态变为激发态，约经10,-8,s，,外层电子就从高能级向较低能级或基,态跃迁，多余的能量的发射可得到一条光谱线。,原子光譜學原理,原子的外层电子由高能级向低能级跃迁，能量以电磁辐射的形式发射出去，这样就得到发射光谱。原子发射光谱是线状光谱。,不同元素的原子具有不同的能级构成，,E,不一样，各种元素都有其特征,的光谱线，从识别各元素的特征光谱线可以鉴定样品中元素的存在，,这就是光谱定性分析；,元素特征谱线的强度与样品中该元素的含量有确定的关系，所以可通过测,定谱线的强度确定元素在样品中的含量，这就是光谱定量分析,Ground state,Excitation level,Ionization,V:,Ionizsation,potential,En,Em,:Excitation potential,E=En-,Em,=h,En,Em,V,感應藕合電漿放射光譜儀與,AA,之比較,Flame,AA,Graphite AA,ICP/OES,ICP/MS,BeerS Law in AA and ICP,A=,吸光度,(,強度,),a=,吸光系數,b=,光距長,c=,樣品濃度,Quantitation,in Atomic Emission,樣品濃度,光強度,火焰式原子吸收光譜儀,原子吸收光谱仪原理：仪器从光源辐射出具有待测元素特征谱线的光，通过试样蒸气时被蒸气中待测原素基态原子所吸收，由辐射特征谱线光被减弱的程度来测定试样中待测原素的含量。,石墨爐式原子吸收光譜儀,Comparison of analytical range,Flame AA,GFAA,ICP-OES,ICP-MS,1,1000,0.001,10%,0.000001,Concentration Linear Dynamic Range(mg/L),Axial View,Flame AA+GFAA,Analysis speed and DL,偵測極限,V.S.,分析速度,Detection limit-3,in g/l using flow spoiler.Impact bead improves up to 4x,Flame Elements&Detection Limits,H,Li,0.04,Na,0.7,K,2,Rb,3,Cs,5,Fr,Be,0.05,Mg,0.03,Ca,0.06,Sr,0.03,Ba,0.04,Ra,Sc,0.06,Ti,0.2,V,0.3,Cr,0.2,Mn,0.08,Fe,0.1,Co,0.2,Ni,0.4,Cu,0.5,Zn,0.1,Al,1.5,Si,4.0,P,3,S,6,Cl,Ar,Ga,3.0,Ge,0.9,As,2,Se,3.0,Br,40000,Kr,B,1,C,N,O,F,Ne,In,1.0,Sn,1.0,Sb,2.0,Te,2.0,I,2.0,Xe,Tl,2.0,Pb,2.0,Bi,2,Po,At,Rn,Y,0.2,Zr,0.4,Nb,0.6,Mo,0.6,Tc,Ru,2,Rh,4,Pd,2.0,Ag,0.1,Cd,0.07,La,0.7,Hf,0.5,Ta,1.0,W,1.0,Re,0.2,Os,120,Ir,1.0,Pt,1.0,Au,0.8,Hg,2,Ac,Rf,Ha,Dy,0.5,Ho,60,Er,0.5,Tm,0.4,Yb,0.06,Lu,0.02,Ce,1.0,Pr,1.0,Nd,1.0,Pm,Sm,1.0,Eu,0.1,Gd,0.9,Tb,1.0,Cf,Es,Fm,Md,No,Lr,Th,2,Pa,U,8.0,Np,Pu,Am,Cm,Bk,He,Anthanides,Ctinides,EL,DL,I.D.L 0.1-1.0 ppb,Detection limit-3,in g/l using in ppb use Axial,GemCon,Cyclonic,ICP-OES Elements&Detection Limits,EL,DL,I.D.L 0.1 ppb,EL,DL,I,.D.L 1-10 ppb,Atomic Spectroscopy interference Table,Atomic Spectroscopy comparison Table,ICP-MS,ICP-OES,Flame AAS,GFAAS,检出限,绝大部分元素非常杰出,绝大部分元素很好,部分元素较好,部分元素非常杰出,样品分析能力,每个样品的所有元素,2-6,分钟,每分钟每个样品的,5-30,个元素,每个样品每个元素,15,秒,每个样品每个元素,4,分钟,线性动态范围,10,8,10,5,10,3,10,2,精密度,短期,长期（,4,小时）,1-1-3%,5%,使用内标可改善,0.3-2%,75,73,68,50,半定量分析,能,能,不能,不能,日常操作,容易,容易,容易,容易,方法试验开发,需要专业技术,需要专业技术,容易,需要专业技术,无人控制操作,能,能,不能,能,易燃气体,无,无,有,无,操作费用,高,高,低,中等,基本费用,很高,高,低,中等,高,发展的概况,ICP-OES Basic Concepts,一般认为原子发射光谱是1860年德国学者基尔霍夫,（,Kirchhoff,GR）,和本生（,Bunsen RW）,首先发现的，,他们利用分光镜研究盐和盐溶液在火焰中加热时所产,生的特征光辐射，从而发现了,Rb,銣和,Cs,銫两元素。,其实在更早时候，1826年泰尔博（,Talbot）,就说明某,些波长的光线是表征某些元素的特征。从此以后，原,子发射光谱就为人们所注视。,ICP,在市場上各個領域的應用,在发射原子发射光谱以后的许多年中，其发展很缓慢，主要是因为当时对有关物质痕量分析技术的要求并不迫切。到了二十世纪三十年代，人们已经注意了到浓度很低的物质，对改变金属、半导体的性质，对生物生理作用，对诸如催化剂及其毒化剂的作用是极为显著的，而且地质、矿物质的发展，对痕量分析有了迫切的需求，促使,OES,迅速的发展，成为仪器分析中一种很重要的、应用很广的方法。,ICP/OES,測試流程圖,ICP-OES,可檢元素和檢測極限,H,Li,0.04,Na,0.7,K,2,Rb,3,Cs,5,Fr,Be,0.05,Mg,0.03,Ca,0.06,Sr,0.03,Ba,0.04,Ra,Sc,0.06,Ti,0.2,V,0.3,Cr,0.2,Mn,0.08,Fe,0.1,Co,0.2,Ni,0.4,Cu,0.5,Zn,0.1,Al,1.5,Si,4.0,P,3,S,6,Cl,Ar,Ga,3.0,Ge,0.9,As,2,Se,3.0,Br,40000,Kr,B,1,C,N,O,F,Ne,In,1.0,Sn,1.0,Sb,2.0,Te,2.0,I,2.0,Xe,Tl,2.0,Pb,2.0,Bi,2,Po,At,Rn,Y,0.2,Zr,0.4,Nb,0.6,Mo,0.6,Tc,Ru,2,Rh,4,Pd,2.0,Ag,0.1,Cd,0.07,La,0.7,Hf,0.5,Ta,1.0,W,1.0,Re,0.2,Os,120,Ir,1.0,Pt,1.0,Au,0.8,Hg,2,Ac,Rf,Ha,Dy,0.5,Ho,60,Er,0.5,Tm,0.4,Yb,0.06,Lu,0.02,Ce,1.0,Pr,1.0,Nd,1.0,Pm,Sm,1.0,Eu,0.1,Gd,0.9,Tb,1.0,Cf,Es,Fm,Md,No,Lr,Th,2,Pa,U,8.0,Np,Pu,Am,Cm,Bk,He,Anthanides,Ctinides,EL,DL,I.D.L 0.1-1.0 ppb,Detection limit-3,in g/l using in ppb use Axial,GemCon,Cyclonic,EL,DL,I.D.L 0.1 ppb,EL,DL,I,.D.L 1-10 ppb,ICP-OES,的優點,化學干擾少,極好的動態顯性范圍,Up to 100-1000,ppm,良好的檢出極限,0.4-2 ppb,光譜干擾,通過控制,方法,設計,/,軟件,速度,根據光譜儀的設計和應用,進行樣品分析,在數秒至數分鐘,可同時進行軸向和縱向觀測,軸向觀測有好的檢出極限,縱向觀測有較高的線性范圍,Axial View,(down center),Radial View,(across center),ICP-OES,的缺點,檢出限不如,GFAA ICP/MS,一些,特別,的應用要求較低的檢測限,某些元素線富礦區譜,稀有元素,(,Dy,Eu,La,Ce,),干擾,Transuranics,(U,Am,Pu,Tc,),使用費用比,AA,高,ICP/OES,的消耗量為,16L/min,原子光譜學原理,H,He,Li,M,能量,光散射 發射,(,e),離子化 電離,吸收,(,a,),Be,離子線躍遷,注釋,:,氬氣等離子体可提供的激發能為,15.75ev(,電子伏特）,Ar,用,Ar,做工作气体的优点：,Ar,为单原子惰性气体，不与试样组份形成难离解的稳定化 物，也不象分子那样因离解而消耗能量，有良好的,激发性能，本身光谱简单。,ICP-OES,可測試元素和偵測極限,H,Li,0.04,Na,0.7,K,2,Rb,3,Cs,5,Fr,Be,0.05,Mg,0.03,Ca,0.06,Sr,0.03,Ba,0.04,Ra,Sc,0.06,Ti,0.2,V,0.3,Cr,0.2,Mn,0.08,Fe,0.1,Co,0.2,Ni,0.4,Cu,0.5,Zn,0.1,Al,1.5,Si,4.0,P,3,S,6,Cl,Ar,Ga,3.0,Ge,0.9,As,2,Se,3.0,Br,40000,Kr,B,1,C,N,O,F,Ne,In,1.0,Sn,1.0,Sb,2.0,Te,2.0,I,2.0,Xe,Tl,2.0,Pb,2.0,Bi,2,Po,At,Rn,Y,0.2,Zr,0.4,Nb,0.6,Mo,0.6,Tc,Ru,2,Rh,4,Pd,2.0,Ag,0.1,Cd,0.07,La,0.7,Hf,0.5,Ta,1.0,W,1.0,Re,0.2,Os,120,Ir,1.0,Pt,1.0,Au,0.8,Hg,2,Ac,Rf,Ha,Dy,0.5,Ho,60,Er,0.5,Tm,0.4,Yb,0.06,Lu,0.02,Ce,1.0,Pr,1.0,Nd,1.0,Pm,Sm,1.0,Eu,0.1,Gd,0.9,Tb,1.0,Cf,Es,Fm,Md,No,Lr,Th,2,Pa,U,8.0,Np,Pu,Am,Cm,Bk,He,Anthanides,Ctinides,EL,DL,I.D.L 0.1-1.0 ppb,Detection limit-3,in g/l using in ppb use Axial,GemCon,Cyclonic,EL,DL,I.D.L 0.1 ppb,EL,DL,I,.D.L 1-10 ppb,滷素（,F,Cl,Br),的應用,?,這些元素（,F,Cl,Br,）的,ICP,的測試結果通常不被認同。,(such as Ion Chromatography,X-ray or Ion Specific Electrodes).,It,s not just a problem with ICP-OES,ICP/MS also has problems determining these elements in,real samples.,和,ICP/OES,一樣,ICP/MS,也有同樣的問題,樣品進樣系統,Cl,Br&I,在混合腔中有殘余時間長,（兩個樣品間沖洗時間長（,810,分鐘），產生記憶效應）,所以,Cl,Br&I,通常單獨分析或者使用不同的技術,ICP/OES,的原理示意圖,進樣系統介紹,Section#2,樣品進樣系統,樣品進樣系統,把溶液轉變成氣溶膠，通入到電漿中,樣品進樣條件通過電腦控制,注重進樣品元件及選擇依據應用,蠕動泵,不同的進樣系統設定,不同的蠕動泵的速度,樣品進樣系統裝置,To ICP,霧化器,樣品,solution,氬氣,To generate sample droplets by,nebulization,and,to introduce only fine droplets in the plasma.,進樣系統,霧化器,Nebulizer,s,十字交叉霧化器,Cross flow,Nebulizer,s,同心圓霧化器,Gem-cone,Nebulizer,s,超音波霧化器,UltraSonic,Nebulizer,s,Sample,Ar,nebulizer gas,Concentric nebulizer,Sample,Ar,nebulizer gas,Cross flow nebulizer,Cross-Flow Nebulizer,PE,標准配備,適用所有的樣品,Oils/Organics,All acids(HNO3,HCL,)dilute and conc.,Up to 10%dissolve solids(100 micron),蠕動幫的速度通常設定為,1.5 ml/min.,Precision on the order of 1%,非常容易清洗，維護保養且耐用,噴霧器噴霧模式,Good,Concentric Pattern,Pulse evenly with pump,Bad,Skewed,Sputtering,Meinhard,Concentric Nebulizer,同心圓氣動霧化氣,Best Precision and Detection Limits,最好的精密度和偵測極限,0.5%Precision,D.L.40%lower than cross-flow,Pump rate of 2 ml/min.,Can clog easily,容易堵塞,Fairly fragile:Do not,ultrasonicate,非常脆弱，易碎,Clean with warm solution of 20%HNO3:Do not boil!,Gem-Cone High Solid Nebulizer,高鹽霧化器,Can be used for most applications,適合多種高鹽樣品,Oils,油類,Brines,鹵水,Viscous samples,粘稠樣品,Plating baths,電鍍液,Handles dissolved solids to 25%(1 mm),Totally inert,惰性材質抗腐蝕,Pump rate of 2 ml/min.,UltraSonic,Nebulizer,超音波霧化器,Uses 1.4 MHZ frequency to shatter droplets to less than 5 microns.,用,1.4,兆赫频率,可將樣品打碎到小于,5,微米,Extremely high efficiency,10 times standard system.,极高的效率,10,倍标准体系,Detection limits will improve 6-20 fold.,检测限将提高,6-2 0,倍,High cost(17K),費用高,Does not handle high solids.,不能處理溶解固體含量高的樣品,記億效應高,.,Spray Chambers,混合腔,Scott-Type Double Pass Chamber,經由霧化器所產生之旋浮物質顆粒較大，造成訊號跳動較大；因此在霧化器之後一般加有混合腔,(Spray chambers),其主要效果為可將某些尺寸以上之霧狀旋浮質擋掉，使其霧化效果更佳。,Scott Double-Pass Spray Chamber,Separates the small droplets(10 microns)from the larger droplets,將小顆粒,(10nm),和大顆粒區分開,Small droplets travel through center tube,large droplet drop out of center tube and into the drain,小顆粒進去，大顆粒排除,2-4%efficient,霧化效率,2-4%,Durable and inert,耐用抗腐蝕,Cleaned with 10-20%warm not boiling HNO3,Can run most any solvent,適合大部分試劑,Very efficient.,霧化效率非常好,40%higher efficiency than a Scott-Type,Excellent Rinse-out,沖出效果非常好,不易堵塞,Detection limits improve by a factor of 2 over a Scott-Type,檢測限比,Scott-Type,要好,Clean with hot mineral acids,用熱酸清洗,Cyclonic Spray Chamber,Cyclonic spray chamber,Injectors and End Cap,Injectors:,Alumina,陶瓷,Quartz,石英,Sapphire,寶石,ICP Injectors,Sample injectors have different IDs for use with different solvents.,根據試劑使用不同的規格,The more volatile,the solvent,use a smaller ID sample injector.,揮發性的試劑使用規格較小的,injector,0.8,1.2,1.6&2.0 mm internal diameter,維護,日常維護,分析後水溶液后，用去離子水沖洗，或2 的硝酸，其次是去離子沖洗,.,分析有機溶液后，沖洗使用清潔溶劑,Injectors,Spray Chambers,浸泡在5-20 的硝酸或王水：可使用超聲波清洗,O-Rings,用肥皂和水清潔，沖洗徹底,Torch Design,完全快速,-,可調式樣品進樣系統,注射器,样,品,雾化系统,火,炬,可調整的位置,进,气,口,電漿的形成,在有气体的石英管外套装一个高频感应线圈，感应线圈与高频发生器连接。当高频电流通过线圈时，在管的内外形成强烈的振荡磁场。管内磁力线沿轴线方向。,管外磁力线成椭圆闭合回路。一旦管内气体开始电离（如用点火器），电子和离子则受到高频磁场所加速，产生碰撞电离，电子和离子急剧增加，此时在气体中感应产生涡流。这个高频感应电流，产生大量的热能，又促进气体电离，维持气体的高温，从而形成等离子炬。,ELAN DRC Plasma,等離子氣體,霧化氣體,(,載氣,),+,樣品氣溶膠,輔助氣體,RF,感應線圈,磁場,渦電流,等離子體,(,電漿,),Temperature distribution in Plasma,等離子体,(,電漿,),的分布,环,状结构可以分为若干区，各区的温度不同，性状不同，辐射也不同。,（1）焰心区,感应线圈区域内，白色不透明的焰心，高频电流形成的涡流区，温度最高达10000,K，,电子密度高。它发射很强的连续光谱，光谱分析应避开这个区域。试样气溶胶在此区域被预热、蒸发，又叫,预热区,。,等離子体,(,電漿,),的分布,（,2）,内焰区,在感应圈上10-20,mm,左右处，淡蓝色半透明的炬焰，温度约为6000-8000,K。,试样在此原子化、激发，,然后发射很强的原子线和离子线。这是光谱分析所利用的区域，称为,测光区,。测光时在感应线圈上的高度称为观测高度。,（3）尾焰区,在内焰区上方，无色透明，温度低于6000,K，,只能发射激发电位较低的谱线。,Ionization Process in Plasma,Optical System and detector,光學系統,Optima 2,1,00DV,光學系統,Refraction Through Prism,Incident Light,(all wavelengths),l,=782nm,l,=388nm,Wavelengths from 388nm to 782nm hit detector,Wavelengths shorter than 388nm or longer than 782nm do not hit detector,Prism,Echelle,Grating,Traditional,傳統的光柵,Echelle,Grating,Echellogram,160nm,900 nm,Continuous spectrum,0.1mm,One,Subarray,(shown sideways),Image Pattern on UV SCD,Wavelength within the Order,High,Low,Order Number,Wavelength,High,Low,Low,High,130,120,110,100,90,80,70,60,Pb,220.353,Cu 221.458,P 177.433,Sc 357.635,Cross-Disperser Grating Dispersion,Echelle,Grating Dispersion,167nm,403nm,觀測視窗,觀測視窗,垂直觀測,可根据分析元素调整观测位置，,干扰比 水平观测低，动态线性,范围比水平也高,1-2,个数量级。,尤其是对于高盐度或者复杂基体,更为合适。,水平觀測,由于光通量大，灵敏度高，但是,相应的干扰也大些，因此尾焰去,除技术就相当关键。检出限一般,比,radial-viewing,观测灵敏度高,3-10,左右。,雙向觀測,-,軸向觀測,(,水平觀測,),DV Optics,(,只用于垂直觀測,),ICP,發射光源,軸向觀測,大環形反射鏡,孔徑光蘭,小環形反射鏡,入口狹縫,(part of Input Optics),Motorized adjustment aims Large,Toroidal,Mirror toward Axial Window for Axial View,雙向觀測,-,垂直觀測,球面鏡,Baffle,ICP,發射光源,平面鏡,(,軸向觀測,),大環形反射鏡,孔徑光蘭,小環形反射鏡,入口狹縫,Motorized adjustment aims Large,Toroidal,Mirror toward Flat Mirror for Radial View,觀測視窗,Axial viewing,Radial viewing,Radial View,Advantages,Higher concentration ranges,Reduced effects from easily ionized elements,Fewer spectral Interferences,Internal standardization may not be required,Disadvantages,Not as appropriate for trace analysis,Precision degrades at lower concentrations,Many wavelengths may be insensitive at concentration of interest,Radial Torch View,Axial View,Advantages,Best detection limits,Better precision than radial view at low concentrations,Better signal/background ratios,Ability to dilute sample to reduce matrix effects or lower total dissolved solids,Disadvantages,Nebulizer effects greatly enhanced,Easily ionized element effects are enhanced,requiring the need for buffers,Internal standardization is required,雙電漿觀測方向,(,Dual View),最佳方便性,同一方法可同時使用雙觀測方向,簡化樣品分析之稀釋,提高線性動力範圍,最小基質干擾,最佳偵測極限,等離子體剪切氣,Detailed View of Plasma Emission Zones,PHZ (Pre Heating Zone,預熱區,),IRZ (Initial Radiation Zone,初始輻射區,),NAZ (Normal Analytical Zone,正常分析區,),Dominantly Ionic Emission,Primary zone for excited states,Tail Plume,NAZ,Shear Gas Position,PHZ,IRZ,Concentration,Emission Intensity,Calibration With Tail Plume,Removed,焰尾,Decay to Ground State,形成氧化物,自吸,Emission Intensity,Concentration,Self Absorption,Calibration Viewed,Through Tail Plume,等離子體剪切氣,減少自吸帶,控制分析光路范圍,減少基質效應,剪切氣的位置,Shear,Gas,(,剪切氣,),ICP-OES,分析參數之設定,方法設定,在,File,的目錄下,New,Method,(,建立新方法,),如下圖,分析參數設定,選擇波長,1.,打開元素周期表,2.,選擇所需波長,進入方法編輯後可直接進入該頁面,(,如下圖,),可依序編列下列方法之次項目,波,長,表,Wavelength Selection,Choose Wavelengths,Sensitivity,Linear Range,Interferences,分析參數設定,Delay Time,延遲時間設定為,30,秒,Repicates,積分次數,設定為,2,次或,3,次,Page Gas flow:,該功能為當光學系統充填氣體之流速；一般而言當分析波長,190 nm,時可選則,high,，,否則一般皆可設定於,normal,Time(sec):,該時間表示訊號測量時間以秒為單位,1.,如作自動積分可選擇,Auto,，,軟體可依分析元素之強度作個別積分時間，可選擇最小及最大之時間,手動積分,Manual,可進入,set,由操作者自行設定,(,積分時間為偵測器收集光子,photons,再輸出訊號之時間，,Read Time,則為每一個重覆所需總測量時間,),How to Optima best Integration time,ICP Emission Measurement,RF Power,Higher power,hotter plasma,Higher power for,organic solution,for,higher excitation elements higher power,higher sensitivity,for easily excited elements,lower power,higher sensitivity,水溶液和有機物的條件設定,參數,水溶液,有機溶液,Plasma Flow,電漿流速,15L/Min,1.5L/min,Auxiliary Flow,輔助電漿流速,0.5L/min(3000,型,),1.0L/min,Nebulizer Flow,霧化氣,氣體流速,0.2(2000,或,0.80,40000),0.50,RF Power,電漿功率,1300,1400/1450,Sample Flow Rate,樣品流速,1.50ml/min,0.80ml/min,Peak Processing,分析參數設定,設定檢量線溶液,1.,檢量線空白,2.,標准溶液的個數,3.,試劑空白,Calibration Standards,Run an acid or prep blank,Corrects for contamination,Do not calibrate too low,Low standard should be about 50 times the IDL,Unless method specifies differently,Calibrate below the Linear Dynamic Range,Typically 500,ppm,for radial,Typically 50,ppm,for axial,Recommendations above are for the most sensitive lines,LDR can be extended by using a less sensitive line,Be careful of chemistry,Place unstable,analytes,in a separate solution,Ag,Ba,P,S,Sn,Sb,Pt,Pd,MATRIX MATCH IF YOU CAN,分析參數設定,設定檢量線濃度,分別輸入檢量線,溶液的濃度,Calibrate below the Linear Dynamic Rang,Typically 500,ppm,for radial,Typically 50,ppm,for axial,分析參數設定,稱量的固體樣品時，,將濃度,mg/L,改為,mg/kg,分析參數設定,保存方法,感應藕荷電將放射光譜儀 訓練課程,-,之二,A,nalytical&,B,io Science Instrument Co.Ltd,楊日懷,Robin,2008/06/12,干擾校正技朮,Robin Yang,ICP-OES Interference,Physical,物理效應,Spectral,光譜干擾,Chemical,化學干擾,Ionization,離子化效應,Physical Interferences,Physical Interferences are:,Differences between sample transport efficiencies between your standards and your samples,H3PO4 does not nebulizer the same as DI water.,酸的黏度,以下列的次序递增,HClHNO3HClO4H3PO4H2SO4。,由于,ICP,光谱分析的试样为溶液状态，因此溶液的粘度、比重及表面张力等均对雾化过程、雾滴粒、气溶胶的传输以及溶剂的蒸发等都有影响，而粘度又与溶液的组成，酸的浓度和种类及温度等因素相关。,物理效應之校正,Relative Sensitivity of Elements in HNO,3,PFA nebulizer(0.25 ml/min),Spike 1,ppm,Y and Sc in H,2,SO,4,Analysis result Optima 2100DV (Concentric Glass Nebulizer),Sample Matrix H,2,SO,4,Relative Sensitivity of Elements in H,2,SO,4,Physical Interference Compensation-1,基體匹配法,內標法,標准添加法,稀釋樣品,標准添加,法,标准加入法对于未知或对样品浓度知道不是很清的样品，可采用标准曲线法及加标分析法。,取若干份体积相同的试液（,cX,），,依次按比例加入不同量,cs,的待测物的标准溶液（,cO,），,定容后浓度依次为：,cX,，,cX,+,cO,，,cX,+2cO，,cX,+3cO，,cX,+4,cO,分别测得吸光度为：,AX，A1，A2，A3，A4。,以,A,对浓度,cs,做图得一直线，直线反向延长，交于,cs,负轴于一点,cX，cX,点即待测溶液浓度。,若你的样品稀释了，,cX,乘以倍数才是最终结果,0.1,Aqueous,Calibration,Orchard Leaves,Method of Addition,20 g/L,Orchard Leaves,40 g/L,Measurement Solution,5,0,5,10,10,20,0,20,Found,Added,Arsenic,Abs.,0.6,0.5,0.4,0.3,0.2,標准添加法,Methods of additionsin software,線性（,linear Bracketing,）,不扣除,Blank,，,需二點以上；,檢量線之濃度範圍限於抹,某一範圍中,Conc,.of sample,=Intercept/Slope,Physical Interference Compensation-2,基體匹配法,內標法,標准添加法,內標法,内标法是将一定量的纯物质作内标物，加入到的试样中,根据被测试样和内标物的质量比及其相应的強度比来计算被测组分的含量。,Sequence No.:1,Autosampler,Location:15,Sample ID:Blank Date Collected:12/15/99 7:48:09 AM,-,Mean Data:32,Mean Corrected,Calib,Sample,Analyte,Intensity Conc.Units Std.Dev.Conc.Units Std.Dev.RSD,Y 371.029 603223.8 100%,0.7 0.82%,Al 308.215 712.0 3.7 3.7 1.05%,Ca 315.887+955.4,ppm,19.7,ppm,19.7 0.66%,Cr 205.560 417.0,ppm,0.0,ppm,0.0 1.43%,Cu 324.752 23.0,ppm,0.2,ppm,0.2 1.51%,Fe 259.939 885.7,ppm,3.4,ppm,3.4 0.58%,K 766.490 645.8,ppm,1.6,ppm,1.6 1.10%,Mg 279.077 600.8,ppm,1.2,ppm,1.2 0.57%,Mo 203.845