Chapter 22 Introduction to

Spectrochemical Methods
22A Property of Electromagnetic
Radiation (略)
22B Interaction of Radiation & Matter
◎ energy-level transition spectroscopy
→ chemical species → energy level
→ transition → quantum theory
→ radiation energy → spectroscopy
◎ other type of spectroscopy
․ reflection
․ refraction
․ diffraction
․ elastic scattering
22B-1 Electromagnetic Spectrum
◎ electromagnetic spectrum
→ enormous range of energy
◎ γ-ray → X-ray → UV → IR
→ microwave → ESR → NMR
◎ table 22-2 → region
→ UV ; Visible ; IR spectrum
◎ figure 22-3 → region of
→ electromagnetic spectrum
→ type of quantum change
→ type of spectroscopy
◎ visible region → spectrum extends
→ from about 400 nm to 700 nm
◎ optical method → spectrosc. method
→ based on UV and IR radiation
22B-2 Spectroscopic Measurement

◎ ground state → lowest energy level

◎ excited state → higher energy level

◎ emission spectroscopy → fig. 22-4

◎ absorption spectroscopy → fig. 22-5

◎ photoluminescence spec. → fig. 22-6

Q : 圖表問答題
․ 圖(22-4) 為 emission spectroscopy
示意圖，請問圖(a)、圖(b)、圖(c)
代表什麼意義？並簡要說明之。
․ 圖(22-5) 為 absorption spectroscopy
示意圖，請問圖(a)、圖(b)、圖(c)
代表什麼意義？並簡要說明之。
․ 圖(22-6)為fluorescence spectroscopy
示意圖，請問圖(a)、圖(b)、圖(c)
代表什麼意義？並簡要說明之。
◎ fig. 22-4 : emission spectroscopy
․ first step
→ electron → ground state
→ absorb energy
→ heat ; electrical or radiation
→ transition → excited state
․ second step → electron from
→ excited state → relaxation
→ return to → ground state
→ emitted radiation
․ spectroscopy → measure
→ emitted radiation
→ frequency → 橫 座 標
→ intensity → 縱 座 標
→ obtain → spectrum (c)
◎ chemiluminescence spectroscopy
→ excitation by chem. reaction
◎ spectrum :
→ plot of radiation power
→ intensity → 縱 座 標
→ as a function of frequency
→ or wavelength → 橫 座 標
◎ figure 22-4 :
(a) sample excited
→ thermal ; electric ; chem.
(b) energy level → dash line
→ nonradiative excitation
→ solid line → radiative
→ emit photon
(c) spectrum → measure PE vs. λ
◎ fig. 22-5 → absorption spectros.
→ sample stimulate by radiation
→ from ground to excited state
→ measure → amount of
→ radiation absorbed vs. λ
◎ absorption spectroscopy
→ UV / visible region
→ most widely used
◎ figure 22-5 :
(a) P0 → incident radiation
→ absorbed by sample
→ transmitted radiation (P)
(b) energy → incident beam
→ ν or λ → equal
→ energy level → Δ E
→ absorbed by → sample
◎ figure 22-5 :
(c) absorption spectrum → plot
→ 縱座標 → absorbance (A)
→ A = - log ( P / P0 )
→ as a function of → 橫座標
→ radiation energy
→ frequency or wavelength
◎ photoluminescence spectroscopy
→ figure 22-6 → radiation
→ selected energy → absorbed by
→ sample → from excited state
→ relaxation → return to
→ ground state → emit radiation
→ measured → spectrum
→ advantage → more selectively
◎ figure 22-6 :
(a) P0 → incident beam
→ PL → luminescence
→ 90° → less interference
(b) absorption process → ‘↑’
emission radiation → ‘↓’
nonradiative → dash line
(c) spectrum → measure PL vs. λ
22C Radiation Absorption
◎ molecular species → absorb
→ characteristic frequency
◎ incident beam → absorbed
→ decrease in intensity
→ attenuate → quantitative
→ measure → Beer’s law
→ A = - log ( P / P0 ) = a b c
◎ attenuate → decrease
→ energy of a beam
◎ Beer’s law → intensity
→ radiation → attenuated
→ absorbance (A) → related
→ conc. (c) ; path length (b)
→ if b fixed ( usually 1 cm )
→ measure (A) → Beer’s law
→ A = a b c → obtain conc.
◎ monochromatic radiation
→ single color ; ν ; λ
◎ transmittance → T = P / P0
◎ percent transmittance
→ % T = ( P / P0 ) x 100 %
◎ absorbance → figure 22-7
→ A = - log T = log ( P0 / P )
(1) measuring transmittance
and absorbance
＊ incident beam → absorb by
→ analyte → attenuated
→ not by reflection ;
scattering ; or else
＊ figure 22-9 → incident beam
→ radiation loss
Q : 圖表問答題

參考圖 Figure 22-9，請說明

由圖中可以得到什麼資訊 ？
＊ blank solution → compensate
→ these effect
→ A = log ( P0 / P )
= log ( Psolvent / Psolution )
＊ experimental → blank solution
→ sample concentration = 0
→ adjust → %T = 100%
→ reflec. ; scatter → corrected
(2) Beer’s law : A = a b c = ε b c
＊ absorbance(A) → proportional to
→ conc. (c) ; path length (b)
absorptivity (a)
＊ a = ε → call molar absorptivity
→ if → c = mol / L ; b = cm
(3) term used in absorption spectro.
＊ table 22-3 : P0 ; P ; A ; T ; b ; a ; ε
Q : 圖表問答題

參考表 Table 22-3，請說明

Beer’s law: A = - log (P/P0) = ε b c

的公式中，A、P、P0、ε、b 及 c

分別代表什麼意義？
(4) using Beer’s law
＊ known concentration sample calculate ε
＊ measure A → known b ; ε → obtain conc.
＊ ε → as a func. of solvent ; solution ; temp.
＊ standard sol. → known c → measure A
→ plot calibration curve → A vs. c
＊ standard addition eliminate matrix effect
(5) applying Beer’s law to mixture
＊ Atotal = A1 + … + An = ε1 b c1 + … + εn b cn
22C-2 Absorption Spectra
＊ absorption spectrum
→ a plot of → A vs. λ
＊ figure 22-10 → MnO4-

→ c = 4, 8, 12, 16, 20 ppm

→ c → proportional to A
Q : 圖表問答題

參考圖 Figure 22-10 ， 請問圖中

數字4, 8, 12, 16, 20代表什麼意義？

由此圖可得到什麼結論？為什麼？
(1) atomic absorption
＊ figure 22-11 → Na (g)
→ atomic absorption transition
→ blue arrow → ground state
→ 3s → excited to
→ 3p ; 4p ; 5p → absorption
→ photon energy → equal
→ ΔE = E3p – E3s
＊ electronic transition
→ transfer an electron from
→ one orbital to another
＊ atomic absorption spectra
→ abs. line → very narrow
→ difficult to scan → range
→ λ → not recorded
＊ monochromatic source
→ very narrow λ → equal
→ ΔE → atom absorption
＊ atomic absorption → measure
→ single λ → equal ΔE
＊ single λ → very narrow
→ λ range → produced by
monochromatic source (26D)
(2) molecular absorption
＊ molecule → excite by
→ UV / Vis / IR → 3 type
→ quantum transition
→ e - ; vib. ; rot. transition
＊ atom → no chemical bond
→ no vib/rot → only e - trans.
＊ fig. 22-12 → energy-level diagram
․ polyatoms → absorb IR ; Vis ; UV
․ from E0 → ground state → excite
→ electronic state → E1 ; E2
→ 1, 2, 3, 4 → different vib. state
․ rotational state → low energy
→ very close line → not show
Q : 圖形配合題

圖(22-13)為分子振動模式種類

(types of molecular vibrations)

配合以下提示回答圖中(a)~(h)
＊ figure 22-13
→ type of molecular vibration
＊ bonding characteristics
→ vibrational energy → IR
＊ IR instrument → vib. transition
→ IR energy → chemical bond
→ identify functional group
＊ total energy of molecule
→ E = Ee- + Evib + Erot
＊ IR absorption :

․ IR eng. → not sufficient → no e- trans. (UV/Vis)

→ IR eng. only induce → vibrational transition

＊ absorption UV/Vis Radiation

․ UV / Vis energy → electronic state transition

→ plus many vib. / rot. state → large # of line

→ closely line → overlapping absorption band

․ in solution → analyte
→ surrounded by solvent
→ analyte / solvent collision
→ transfer energy → change
→ energy level higher ; lower
→ blur absorption band
→ band overlapping
→ smooth / continuous peak
․ atom → only e- transition
→ line spectrum
․ molecule → vib. / rot.
→ line overlap → band spec.
․ solution → collision
→ band overlapping
→ continuous spectrum
 原子 分子
電子組態能階 電子 + 震動 + 轉動

(電子組態)
(轉動) (震動)
Q : 問答題：
․ 何謂 line spectrum？
何謂 continuum spectrum？
․ Line spectrum為分子或原子
所產生的圖譜？為什麼？
․ Band spectrum為分子或原子
所產生的圖譜？為什麼？
原子：line spectrum

330

285
590
電子組態能階

振動能階

轉動能階

分子
band spectrum
Q : 圖表問答題

參考圖 Figure 22-14， 請問由

圖中可得什麼結論？為什麼？
＊ figure 22-14 → visible spectra
→ 1 , 2 , 4 , 5-tetrazine
(a) gas phase → molecule separated
→ vibration / rotation freely
→ transition among
→ vibration / rotation state
→ many absorption peak
(b) liquid phase :
→ unable rotation freely
→ no individual rot. state
→ blur energy level
→ peak in (a) → overlap
→ band spectrum
＊ figure 22-14 (b) → condense state rotation
→ little freedom → rotation line disappear
→ solvent molecule → collision vib. energy
→ not uniform → vibration line disappear
→ spectrum single → broad peak
＊ (c) → H2O solution → frequent collision
→ tetrazine/H2O interaction → blur
→ energy level → continuous spectrum
＊ figure 22-14 (c)
→ polar solvent
→ solvent effect
→ more pronounce
→ broad peak → than
→ nonpolar solvent
22C-3 Limits to Beer’s Law (略)
22D Emission Electromagnetic Rad.
＊ electron / particle bombardment
plasma ; flame ; e- arc ; radiation
․ excite → atom ; ion ; molecule
․ higher energy level → return to
→ lower energy state
→ release → excess energy
․ radiative → emit radiation
→ record emission spectrum
․ nonradiative → produce heat
→ no radiation → no spec.
․ excited state → lifetime
→ 10-9 ~ 10-6 second
22D-1 Emission Spectra
＊ figure 22-19 → brine → O2/H2 flame
→ emission spectrum (line, band, conti.)
＊ line spectrum → sharp peaks
→ individual atom
＊ band spec. → group of line
→ overlapping → molecule
＊ continuous spectrum → blue dash line
→ blackbody radiation
(1) line spectra
＊ individual atom → gas phase
→ line spectra → width
→ 10-1 ~ 10-2 Å (10-2 ~ 10-3 nm)
→ figure 22-19 → line spectra
→ Na ; K ; Sr ; Ca ; Mg
＊ fig. 22-20 → ground state → Na (3s1)
→ excite by thermal;e-;radiation eng.
→ transition to → 3p ; 4p ; 5p orbital
→ selection rule → Δ l = ± 1
→ few nanosecond → 3p return to 3s
→ emit radiation → λ = h c / (E3p - E0)
→ 3p return to 3s → λ = 589.6 nm
→ 3p’ return to 3s → λ = 589.0 nm
＊ 3p orbital → electron spin
→ split into → 3p ; 3p’
＊ 4p ; 4p’ → return to → 3s
→ more eng. → 330 nm doublet
＊ 4d ; 4d ’ → return to 3p (not 3s)
→ Δ l = ± 1 → 568 nm doublet
＊ figure 22-19 → doublet
→ appear as single line
→ limit resolution of instrument
→ 23A-3 ; 26A-1
＊ transition allow / forbidden
→ law of quantum mechanism
→ selection rule
→ Δl = ± 1 → not discussion
(2) band spectra
＊ gas radical or molecule
→ many vib. / rot. state
→ closely space line
→ not resolve by instrument
→ overlap band spectra
→ fig. 22-19 → OH ; MgOH
(3) continuous spectra

＊ figure 22-21 → solid carbon ; tungsten

→ heat incandescence → thermal radiation

→ blackbody radiation (temp. dependence)

＊ blackbody radiation → innumerable

→ atom and molecule → oscillation excite

→ condense solid → thermal energy

＊ figure 22-21 → energy peak
→ temp. ↑ → shift to shorter λ
＊ continuous spectra → fig. 22-19
→ particle in flame incandescent
→ thermal emission
→ UV region → backgd intensity ↓
→ IR region → backgd intensity ↑
＊ heated solid → emit IR ; Vis ; UV
→ can be used as radiation source
(4) effect of concentration on
line and band spectra
＊ radiation power ( P )
→ proportional to
→ concentration ( c )
→ P = k c → section 26C
→ quantitative analysis
22D-2 Emission by Fluorescence
and Phosphorescence
＊ atom/molecule → excited by
→ beam of radiation → relax to E0
→ emission spectra
→ fluorescence or phosphorescence
＊ fluorescence → more rapidly (10-5s)
＊ phosphorescence → minute or hour
＊ phosphorescence
→ emission radiation
→ minute or hour after
→ excited radiation cease
＊ fluores. → more important
→ than phosphorescence
→ discuss fluorescence only
(1) atomic fluorescence
＊ gas atom → excited
→ absorption line → fluo.
＊ Na(g) → absorb → 589 nm
→ excite to E3p → relax to E0
→ emit radiation → same λ
→ resonance fluorescence
＊ nonresonance fluorescence
→ E0 → excite to
→ higher energy level
→ series of collision
→ with other species
→ loss energy
→ nonradiative relaxation
→ no radiation → no fluo.
(2) molecular fluorescence
＊ figure 22-22 → absorption
nonradiative ; fluorescence
＊ fluorescence
→ photoluminescence process
＊ 2 type of nonradiative relaxat.
․ vibrational relaxation
․ internal conversion
Q : 圖形配合題

圖(22-22)為 energy-level diagram

配合以下提示回答圖中 (a) ~ (f)。

․ vibrational relaxation
→ vibration to vibration state
→ molecule / solvent collision
→ excess vibration energy
→ transfer to solvent
→ in a series of steps
→ solvent temperature ↑
→ nonradiative process
→ vibration relaxation
→ efficient process → lifetime
→ excited vibration state
→ 10 -15 second → very fast
→ fluorescence → 10-5 second
․ internal conversion (fig. 22-22 b)
→ nonradiative relaxation
→ lowest vib. level of E2 relax to
→ upper vib. level of E1
→ less efficient → mechanism
→ not fully understand
→ lifetime → 10-9 ~ 10-6 second
→ net effect → temperature ↑
＊only small number of excited molecule
→ fluorescence → structure require
→ slow rate → nonradiative relax.
→ most molecule lack these structure
→ greater probability → undergo
→ nonradiative relaxation → no fluo.
＊ stokes shift → fluorescence λ
→ longer than → excited λ