Chapter 26 Atomic Spectroscopy

＊ atomic spectroscopy
→ qualitative ; quantitative
→ more than 70 element ; ppm ; ppb
→ rapid ; convenient ; high selectivity
＊ atomic spectrometer → two type :
․ optical atomic spectrometer
․ atomic mass spectrometer (Ch.27)
Q:為什麼原子光譜儀
與分子光譜儀要分
成兩種儀器？
A:原子光譜儀
1. 提 供 高 能 量 環 境。
2. 光 譜 線 10 寬 度。
-3
1. 提供高能量環境。
․ 原子光譜儀 → 高溫環境 → 破壞化學鍵
→ 形成原子 → 檢測原子光譜
․ 分子光譜儀 → 常溫 → 保持化學鍵
→ 維持分子結構 → 檢測分子光譜
2. 光 譜 線 10-3 寬 度。
․ 原子光譜 → line spectrum → 0.001 nm
․ 分子光譜 → band spectrum → ~ 1 nm
 原子
分
子
P0 P
1 nm
光 0.001 nm
源
P0 ≈ P
無法分析
原子
原
子 P0 P
光 0.001 nm
源
A = - log (P/P0) = ε b c
A ∞ 濃度、可進行分析
＊ atomic spectrometry → perform
→ gaseous medium → individual
→ atom → well separate gas-phase
＊ atomization → convert sample
→ gas-phase atom
＊ efficiency ; reproducibility
→ atomization critical step influence
→ sensitivity ; precision ; accuracy
Q : 圖表問答題
請問由 Table 26-1 可以得到什麼資訊？
＊ table 26-1 → atomization method :
․ flame ; electrothermal → widely used
→ atomic absorption spectrometry
․ inductively coupled plasma → employ in
→ optical emission spec.; atomic mass spec.
․ direct-current plasma ; e- arc ; e- spark
→ not widely use ; replace by ICP or other
 26A Origin of Atomic Spectra
＊ sample → atomization → gas-phase
․ atom → detected by → optical
→ atomic spectroscopy (chap. 26)
․ ions → detected by → atomic
→ mass spectroscopy (chapter 27)
＊ gas-phase atom → no vibrational
→ no rotational energy → only
→ electronic transition (line spectra)
26A-1 Emission Spectra
＊ atomic emission spectrometry
→ sample → atom → excited by
→ heat or electric eng. → atom*
․ plasma
․ flame
․ low-pressure discharge
․ laser
＊ figure 26-1 → energy-level diagram

→ Na atom → ground state → applied

→ energy → heat; electric → excited state

→ a few nanosecond → relaxation

→ 3 emission line → 285 ; 330 ; 590 nm

＊ resonance transition → resonance line

→ absorption eng. → equal emission eng.

26A-2 Absorption Spectra
＊ atomic absorption spec.
→ figure 26-3 → Na vapor
→ ground state → 3s electron
→ absorb 285 ; 330 ; 590 nm
→ excited to → 3p ; 4p ; 5p
→ selection rule → Δ l = ± 1
26A-3 Fluorescence Spectra
＊ atomic fluorescence spec.
→ ground state atom
→ selected λ radiation
→ excited atom → relax
→ emit radiation → 90 o

→ detect → fluo. spec.

＊ resonance fluorescence
→ source radiation
→ same λ
→ emission radiation
→ fluorescence
26A-4 Width of Atomic
Spectral Line
＊ factor influence line width :
․ natural broadening
․ collision broadening
․ Doppler broadening
Q : 請問原子光譜的光譜線寬度
(line width)，會受到那三種
因素的影響？簡要說明之。
＊ natural broadening
→ Heisenbergs uncertainty
→ Δt ․ Δv > 1
→ excited state → lifetime ↓
→ 10 -8 s → Δv↑
→ line width ↑ → 10 -5 nm
＊ collisional broadening
→ pressure ↑ ; temperature ↑
→ collision ↑ → energy
→ transfer → absorb / release
→ ΔE spread ↑ → spectra line
→ broadening ↑ → 3 x 10-3 nm
→ pressure broadening
Q :參考圖(26-4)，請問 Doppler Broadening

如何影響原子光譜的 line width？

＊ Doppler broadening → atom rapid motion

→ moving toward detector → shorter λ

→ moving away from → detector

→ longer λ → figure 26-4 → Doppler shift

→ atom velocity↑; line broaden↑ 0.005 nm

26B Production of Atom and Ion
＊ solid ; solution ; gas
→ sample → atomizer
․ atom → measured by
→ optical spectrometry
․ ion → measured by
→ mass spectrometry
26B-1 Sample Introduction
System
(連續進樣)
＊ continuous atomizer
→ plasma ; flame
→ sample introduced
→ continuously
 (不連續進樣)
＊ discrete atomizer (一次進樣)

→ electrothermal
→ sample introduced
→ discretely
→ syringe ; autosampler
＊ figure 26-5
→ solution sample
→ continuous introduction
→ plasma or flame
＊ solution sample
→ nebulizer → nebulization
→ fine spray → aerosol
→ plasma ; flame
Q : 圖(26-6)為樣品原子化的過程
配合以下提示回答圖中(a)~(g)
＊ figure 26-6 → process
→ solution sample
→ nebulization → desolvation
→ volatilization ; atomization
→ gas-phase → atom or ion
Q : 問答題 (沒有圖表)

請問原子光譜儀的原子

化方法，有哪些類型？
26B-2 Plasma Source
＊ plasma atomizer → 1970 s
→ several advantage used for
→ atomic emission spec.
→ atomic fluorescence spec.
→ atomic mass spectrometry
＊ plasma → hot gas → contain
→ high conc. → cation ; anion
→ temp. > 6000℃ → sample
→ obtain → sufficient energy
→ bond dissociate → atom form
→ detect → atomic spectroscopy
＊ energy supply → maintain
→ high temperature plasma
＊ three power source :
․ dc electrical
․ microwave-frequency
․ radio-frequency
＊ radio-frequency
→ inductive couple plasma
→ greatest advantage
→ sensitivity
→ less interference
＊ dc electrical source
→ dc plasma
→ simple ; low cost
Q : 參考圖26-7，請說明 inductively coupled

plasma的原理。圖中 inner tube, central

tube 以及 outer tube 分別具有什麼功能

(1) inductive couple plasma

＊ figure 26-7 → ICP source

→ three concentric tube

→ inner tube ; center tube ; outer tube

․ inner tube → sample aerosol
→ carry by → 1 L/min Ar
→ into plasma → 6000~104 K
→ atomized
․ outer tube → coolant gas
→ Ar flow → cooling
․ center tube → Ar flow → 11~17 L/m.
→ Tesla coil → spark → Ar ionization
→ produce Ar+ and e- → radio-frequency
→ current in coil → induce magnetic field
→ Ar+ accelerated → collide neutral Ar
→ chain reaction → more Ar+ & e- produce
→ form Ar plasma → lot of Ar+ and e-
→ flow in the coil → resistance → cause
→ ohmic heating → temperature ↑ (~104 K)
 spark + -
Ar Ar + e
磁場誘導Ar+
加速碰撞Ar + -
Ar Ar + e
磁場誘導2Ar+
加速碰撞Ar + -
Ar Ar + e
磁場誘導3Ar+
加速碰撞Ar + -
Ar Ar + e
磁場誘導nAr+
加速碰撞Ar + -
Ar Ar + e
(chain reaction) lots of Ar+ and e-
＊ figure 26-8 (略)
(a) radial geometry
→ stable ; precise
(b) axial geometry
→ lower
→ detection limit
Q : 問答題 (沒有圖表)
請問 inductively coupled plasma
比 flame atomizer具有哪些優點？

【提示】 inert environment,

uniform temperature, thin path
length, linear range↑, atomization
efficiency ↑, less interference
＊ advantage
→ plasma over flame :
1. chemically inert environment
→ better than flame
→ less reactive
2. uniform temperature
→ better reproducibility
3. thin path length
→ minimize
→ self-absorption
4. concentration
→ calibration curve
→ linear range
→ several order ↑
 A* A + hv
(emission)

hv + A A*
(self-absorption)
 A AA
A*
A AA A
hv

(self-absorption)
5. analyte → 2 ms in plasma
→ longer than → flame
→ desolvation ; vaporization
→ more complete → higher
→ atomization efficiency ↑
→ fewer interference
6. plasma → 6000 ~10 4 K
→ molecular structure
→ not exist
→ nonvolatile complex
→ eliminate → no
→ molecular spectrum
→ less interference
(2) direct current and (略)
other plasma source
＊ not widely used
→ replaced by
→ ICP or other
26B-3 Flame Atomizer
＊ figure 26-10 → 圖形配合題
→ laminar-flow burner → sample sol.
→ flow through → sample capillary
→ nebulizer → aerosol → baffle
→ flow spoiler ; uniform fine droplet
→ fuel oxidant → produce flame
→ table 26-2 → pressure relief vent
→ prevent explosion
＊ advantage
→ laminar-flow burner
→ quiet flame
→ reproducibility ↑
→ long path length
→ sensitivity ↑
26B-3 Flame Atomizer
(1) property of flame
(2) type of flame used in
atomic spectroscopy
(3) effect of flame temp.
(4) absorption/emission
spectra in flame
(5) ionization in flame
(1) property of flame
＊ figure 26-11
→ nebulize sample → into flame
→ primary combustion zone
→ desolvation → solid particle
→ inner cone → hottest part
→ vaporized atom; ion; molecule
→ outer cone oxidation into atm
＊ fuel / oxidant mixture
→ through flame
→ high velocity → sample
→ only fraction → atomized
→ flame → atomizer
→ not very efficient
(2) type of flame used in
atomic spectroscopy
＊ table 26-2 → flame
→ fuel ; oxidant → temp.
＊ IA ; IIA metal → easily
→ excited → 1700 ~ 2400 ℃
＊ heavy metal → less readily
→ excited → 2500 ~ 3100 ℃
(3) effect of flame temperature
＊ emission ; absorption spectra
→ affect by → variation in
→ flame temperature
․ higher temp. → atomization ↑
․ but → IA metal
→ temp. ↑ → ionization ↑
→ atomization ↓
＊ flame temp. → determine
→ fraction → analyte
→ desolvated ; vaporized
atomized ; ionized
→ efficiency
→ atomization; ionization
＊ flame temp. → determine
→ ratio → atom* / atom
→ unexcited atom
→ absorption spectra
→ excited → atom
→ emission spectra
＊ C2H2 / air → flame
→ 2400 ℃
→ Mg* / Mg = 10 -8

＊ C2H2 / O2 → flame
→ 3100 ℃
→ Mg* / Mg = 10 -6
＊ Mg* → 102 ↑
→ emission spectroscopy
→ intensity → 10 2 ↑
→ control of temperature
→ important for
→ emission spectroscopy
＊ Na atom → from 2500 ℃ → 2510 ℃
→ 10 ℃ ↑ → Na* (3p e-) → population
→ 3 % ↑ → Na (3s e-) → 0.002 % ↓
→ temp. control → more important
→ emission → than absorption method
＊ ICP → uniform temperature → better
→ temperature control → used for
→ atomic emission / fluorescence spec.
＊ analyte in flame → # of atom/atom*
→ 103 ~ 1010 → ground state atom ↑
→ absorption ↑ → abs. method
→ lower → detection limit
→ than → emission method
＊ in fact → other factor → influence
→ detection limit → abs. / emission
→ comparable → table 26-3 (略)
(4) absorption / emission spectra in flame

＊ flame emission spectrum → figure 22-19

→ Na(330 nm); K(404 nm); Ca(423 nm)

→ line spectra → emission band

→ MgOH ; MgO ; CaOH → vib. ; rot.

→ superimpose → electronic transition

→ molecular spectra → band spectra

＊ flame absorption spectrum

→ seldom record

→ line spectra → very small

→ line width → require

→ high-resolution spectrometer
 (5) ionization in flame
＊ Ba ⇋ Ba+ + e-
→ flame temperature ↑
→ ionization ↑ → Ba ↑ +

→ Ba ↓ → atomic spectra
→ sensitivity ↓ (略)
28B-4 Electrothermal Atomizer
28B-5 Other Atomizer (略)
26C Atomic Emission
Spectrometry
26C-1 Instrumentation
＊ figure 26-13 (圖形配合題)
→ diagram → ICP
→ atomic emission spec.
 26C-2 Source of Nonlinearity
in Atomic Emission
＊ self-absorption → high concentration
→ atom* → emit radiation → absorb
→ ground state atom → emit radiation
→ intensity ↓ → error quantitative
＊ self-reversal → self-absorption
→ produce radiation band→ min. center
26C-3 Interference in Plasma

and Flame in Emission

＊ interference effect → similar

→ plasma ; flame → two type

→ blank or analyte interference

(1) blank interference
＊ blank interference
→ additive interference
→ indepent analyte conc.
→ perfect blank solution
＊ spectral interference
→ other species
→ spectra overlap
＊ determination
→ Mg → at 285.21 nm
→ blank interference
→ Na → at 285.28 nm
＊ How to reduce Na
interference ?
․ improve → instrument
→ resolution → 0.01 nm
→ no opportunity
․ prepared → blank solution
→ same amount → Na
→ not easy prepared
․ record Mg → another λ
→ Na → can be reduced
(2) analyte interference
＊ analyte interference
→ change magnitude
→ analyte signal
→ not spectral interference
→ physical ; chemical effect
＊ physical interference :
alter the efficiency of nebulization
such as :
․ nebulization ; desolvation ;
volatilization
․ change solution viscosity
․ alter sample flow rate
․ change temperature → combustion
→ organic species → affect
→ efficiency of nebulization
＊ chemical interference :
․ PO43- → react with → analyte Ca2+
․ form nonvolatile complex Ca3(PO4)2
․ alter concentration of Ca in flame
․ such effect can be eliminated by the
use of higher temperature → complex
→ Ca3(PO4)2 dissociate → obtain Ca
＊ releasing agent (Sr) :
․ addition of excess Sr
․ Sr → react with → interference PO43-
․ form → strong phosphate complex
→ Sr3(PO4)2 → than Ca3(PO4)2
․ prevent PO43- react with analyte (Ca)
․ minimize → PO43- interference
＊ protective agent :

․ presence of EDTA ; 8-hydroxyquinoline

․ react with → analyte Ca → form stable

→ but volatile complex → Ca-EDTA

․ prevent → formation of Ca3(PO4)2

→ nonvolatile complex → interference

＊ ionization suppressant (K) :
․ Ba ⇋ Ba+ + e- (往右反應)
→ ionization ↑ → analyte Ba ↓
․ add K → easily ionized element
․ K ⇋ K+ + e- → produce electron
․ 勒沙特列原理 → # of electron ↑
→ Ba ⇋ Ba + e → 往左反應
+ -

→ Ba ↑ → favor atomic spectra

26C-4 Application
＊ inductively coupled plasma (ICP)
→ most widely used
→ emission spectroscopy
→ low background ; low noise
freedom from interference
high sensitivity; but expensive
＊ ICP application
→ determining trace metal
→ environment
petroleum product
foodstuffs ; geological
biological materials
26D Atomic Absorption
Spectrometry ( AAS )
＊ AAS → most widely used
→ all atomic method
→ simplicity ; low cost
effectiveness
26D-1 Line Width Effect in
Atomic Absorption
＊ atomic absorption → line spectra
→ 0.002 ~ 0.005 nm → continuous
→ monochromator → λ > 1 nm
→ departure from → Beer’s law
＊ line source → narrow λ
→ atomic abs.→ obey Beer’s law
Figure 26-15
(a) line source
→ band width → narrow
(b) atom absorption line
→ absorb → source radiant
(c) source radiant
→ attenuate → Beer’s law
26D-2 Instrumentation
＊ figure 26-16 → 圖形配合題
→ single beam → AAS
Q : 圖形配合題
圖26-16為 single-beam atomic
photometer 的儀器構造圖，配
合以下提示回答圖中 (a) ~ (f)。
(1) line source
Q : 請說明hollow-cathode lamp原理
＊ figure 26-17 → 圖表問答題
→ hollow-cathode lamp
→ Ar → 1 ~ 5 torr → 300 V
→ ionized → Ar+ → accelerated
→ cathode surface coating metal
→ sputtering → atom* → relax
→ emit radiant → line source
＊ hollow-cathode lamp 的原理
電游離 + -
Ar Ar + e
+ 電場加速
Ar 撞擊cathode表面

sputtering
M(s) M(g) ; M(g)*
relax
M(g)* M(g) + h v
(光譜寬度 0.001 nm)
(2) source modulation
＊ figure 26-18 → 圖形配合題
→ double-beam AAS
(3) atomic abs. instrument (略)
(4) background correction (略)
․ continuum source (略)
․ pulse hollow-cathode lamp
․ Zeeman effect (略) (略)
Q : 圖形配合題
圖26-18為 double-beam atomic
absorption spectrophotometer
的儀器構造圖，配合以下提示
回答圖中 (a) ~ (g)。
26D-3 Flame Atomic Absorption (略)
(1) quantitative measurement (略)
(2) quantitative analysis (略)
(3) detection limit / accuracy (略)
26D-4 Abs./Electrothermal Atomizer(略)
26D-5 Interference in Atomic Abs. (略)
26E Atomic Fluorescence Spec. (略)