Varian Technologies korea Ltd Introduction to Atomic Absorption

Varian Technologies korea. , Ltd.

Introduction to Atomic Absorption Spectrometer 조 창 래

Varian Australia, Melbourne

AA 280 Configurations Available AA 280 FS (Flame) AA 280 Zeeman or D 2 (graphite furnace)

Measurement Range ICP-MS Price $k 200 150 ICP-OES 100 80 GF-AAS 40 Flame AA 100% 0. 1 % ppm ppb ppt ppq

주기율표 H Li Be Na Mg Flame Only Al Si P S Ne Cl Ar Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Cs Ba La Hf Ta W Re Os Ir Fr Ra Ac B C N O F Flame & Furnace K Ca Sc Ti V Rb Sr Y He Xe Pt Au Hg Tl Pb Bi Po At Rn Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th Pa U Np Pu Am. Cm. Bk Cf Es Fm Md No Lr

Radio waves Microwaves Gamma rays X rays 1 nm UV Infrared 100 nm 1 m Visible Region 430 500 560 600 650 750 nm

바닥상태 원자 Orbitals Neutrons Protons Electrons

Energy Level Diagram for Pb E 4 E 3 E 2 E 1 Eo 202. 2 217. 0 261. 4 Wavelength in Nanometers 283. 3

Absorption Energy Diagram (Few Lines/Element) Energy Excitation E¥ 이온화 E 3 } E 2 E 1 a b c d Eo 들뜬상태 c b a 바닥상태

Emission Energy Diagram (Many Lines/Element) Energy 방출 E¥ 이온화 E 3 } E 2 E 1 a b c d Eo 들뜬상태 c b a 바닥상태

원자흡수 과정 Io Resonance Non-resonance Fill Gas It Resonance

Beer-Lambert 법칙 이론 선 A b s A = abc 실제선 A ¹ abc Conc

Reasons for Non-linearity for Calibration Graphs m Unabsorbed radiation, stray light m Hollow cathode lamp line width broadening m Monochromator slit is too wide m Disproportionate decomposition of molecular species

Slit Width

Single Beam Configuration

Double Beam Configuration

The First AAS

Fast Sequential Lamp Selection

Atomizers m Flame atomization m Graphite furnace atomization m Vapor generation

Flame Atomization

Flame Types m Air - C 2 H 2 flame / 2125 ~ 2400(o. C) : Cu, Pb, K, Na, etc. m (Air) - N 2 O - flame / 2600 ~ 2800(o. C) m : Al, Si, W m Both : As, Ca, Cr, Mg, Os, Se, Sr m Fuel - C 2 H 2 m Oxidant - Air in Air/C 2 H 2 N 2 O in N 2 O/C 2 H 2 m Fuel rich flame = Reductant flame m Fuel thin flame = Oxidant flame

Flame Atomization m 1) Nebulization m 2) Desolvation m 3) Liquefation m 4) Vaporization m 5) Atomization m 6) Excitation m 7) Ionization M+ + A- (Solution) M+ + A- (Aerosol) MA (Solid) MA (Liquid - Gas) M 0 + A 0 (Gas) M* (Gas) M+ + e- (Gas)

Flame Atomizer - Burner

Spraychamber Kits

Nebulizer Assembly

Nebulization

Sample Introduction Pump System SIPS - 10 / 20

What is SIPS? m SIPS-20 dual pump system provides additional benefits: m On-line addition of chemical modifiers e. g. q Ionization suppressants q Internal standard correction m On-line Standard Additions calibration from one standard m On-line preparation of analytical spikes from 1 Std.

Schematic of SIPS-10 Operation m Sample is pumped to a Tee m Tee is also connected to diluent and outlet flows to nebulizer m Stop pump, only diluent is aspirated through nebulizer m Start pump, sample is pumped and mixed with diluent as it flows to the nebulizer m Pump speed controls dilution ratio applied - balance of nebulizer flow made-up of diluent m Typical dilution error < 2 %

Schematic of SIPS-20 Operation m SIPS-20 with 2 pumps allows sample to be introduced with another solution e. g. standard, modifier, internal standard m Proportion of solution added to sample is controlled by relative pup speed m Can “spike” sample with varying amounts of modifier – providing new capabilities e. g. on-line standards additions, internal standarization m Sample pump speed is reduced, compared with SIPS-10 operation, to prevent flooding of nebulizer

Graphite Furnace Atomizer

Typical Graphical Representation from ATOM

Steps in Running SRM Wizard Examine the results (30 to 40 mins. later) Shape maximum is the optimum setting Pressing OK creates a method with the optimum settings

Enhanced Tube Lifetimes – Precision Comparison Signal graphics for sample at 400 th & 4, 000 th firing Based on 10 replicates per sample for a 30 ug/L Cu Ave precision < 0. 5% RSD

Furnace Atomization m 1) Drying m 2) Ashing(Pyrolysis) m 3) Cool down(optional) m 4) Atomization m 5) Clean out m 6) Cool down

Workhead Water Cooling Gas Out Sealed Quartz Window Optical Path Gas Inlet Flexible Seal

비불꽃 원자화 과정 Atomize Clean Out Cool Down Ash Dry T I M E T E M P

Interferences m 1) Spectral interference m 2) Chemical interference m 3) Ionization interference m 4) Matrix interference m 5) Non-specific interference

Chemical Modifier

Chemical Modifier

Vapor Generation Atomizer - As, Se, Sn, Sb, Te, Bi, Hg

Light Sources m Hollow cathode lamps - HCL m Multi-element lamps m Ultra lamps m Electrodeless discharge lamps - EDL m Deuterium lamp - D 2

Hollow Cathode Lamp Process m Sputtering m Collision and Exitation m Emission and Stabilization

Background Correction m Deuterium technique m Smith - Heiftje technique m Zeeman technique: DC Zeeman design AC Zeeman design Longitudinal Zeeman Design Transverse Zeeman Design

D 2 Background Correction

Smith - Heiftje Technique

Zeeman Technique

Longitudinal Zeeman Design

Transverse Zeeman Design

Monochromator Czerny - Turner Type Ebert - Fastie Monochromator Littrow Monochromator Design

Czerny - Turner Type

Ebert - Fastie Monochromator

Littrow Monochromator Design

Gratings

Detectors m Photomultiplier tube(PMT)

불꽃 vs 비 불꽃 AAS Criteria Flame Furnace 분석원소 감 도 정밀도 간 섭 속 도 사용하기 불꽃에대한위험 자동화 분석비용 67 ppm-% good few rapid easy yes low 48 ppt-ppb fair many slow more complex no yes medium

불꽃 vs 비 불꽃 검출한계 비교 Element Ag As Bi Cd Cr Pb Zn 3 450 50 3 9 15 1. 5 Flame (ppb) Furnace(ppb)* 0. 035 0. 25 0. 45 0. 01 0. 075 0. 2 0. 0075 *Note: 20 L Volume & D 2 Peak Height Abs

불꽃 vs 비 불꽃 감도 100 g/L Pb @ 217. 0 nm Absorbance 0. 936 0. 004 비불꽃 시그날 for 10 L 불꽃 시그날

Terminology m 1) Sensitivity m 2) Detection limit m 3) Quantitation limit m 4) Accuracy m 5) Precision m 6) Standard Deviation

Spectr. AA 50/55

Spectr. AA 220 FS

New SPS 2 & SPS 3 Flame Autosamplers m SPS 2 & SPS 3 Autosamplers

Schematic of Traveling Rinse Probe Housing for Traveling Rinse Inlet for rinse solution (from pump) Outlet to waste

D. L Using Ultr. AA Lamps Element Wavelength Slit Width Conventional lamp D. L As 193. 7 nm 0. 5 1. 4 0. 25 Pb 283. 3 nm 0. 5 0. 8 0. 20 Se 196. 0 nm 1. 0 1. 1 0. 30 Ultra Lamp D. L

Spectr. AA 220 Z

What is ICP – AES ?

AAS 와 ICP-AES 비교

Sequential 과 Simultaneous 비교

What is ICP – MS ?

Varian ICP-MS Design Highlights m 90 degree ion mirror for the highest sensitivity and low background m. Peltier cooled spraychamber and low sample uptake for low oxides and reduced sample usage m. High speed, low noise/background quadrupole with curved fringe rods m. Optimized interface for high transmission, good matrix tolerance and low oxides m. Robust, high efficiency, solid state 27 MHz balanced plasma system m(no torch shield required) m 9 orders, all digital detector for easy setup and operation

Varian ICP-MS 개선된 Ion Optics Design m. High efficiency q >1000 Mcps/ppm in high sensitivity mode m. Low background q 90 degree ion mirror q Double off axis quad m. Low oxides q <1% Ce. O

Comparison of Techniques

Question