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Chapter 23 Instrument for

Optical Spectrometry
* analytical instrument
→ absorption / emission
→ UV / Vis / IR
→ basic component alike
* optical instrument → spectroscopy
→ in UV / Vis / IR → although
→ optic nerve → respond Vis only
→ lenses ; mirror ; prism ; grating
→ UV / Vis / IR → similar
→ comparable optical instrument
* this chapter → instrument
→ component ; design
Q : 問答題
光譜儀的儀器構造,是由
哪五項基本要件所組成?
(寫出名稱即可,不須說明)
23A Instrument Component
* UV / Vis / IR instrument
→ five basic component
1. radiation source
2. wavelength selector
3. sample container
4. radiation detector
5. signal processing
Q : 圖形配合題

Figure (23-1 a, b, c)為optical

spectroscopy的儀器構造圖,

配合提示回答圖中 (a) ~ (e) 。


* figure 23-1 → configuration
→ various types instrument
(a) absorption spectroscopy
→ source radiation
→ selected wavelength
→ measure attenuation
→ A = abc
(b) fluorescence spectroscopy
→ sample excite by
→ radiation source
→ relax emit radiation
→ measure 90°
(c) emission spectroscopy
→ plasma ; flame
→ thermal energy
→ excite sample
23A-1 Optical Material

* instrument element

→ transmit UV/Vis/IR

→ optical material
Q : 圖表問答題

參考圖 Figure 23-2,請問由

圖中可以得到什麼資訊?
* figure 23-2 → silica glass
→ visible region → low cost
→ UV region → glass absorb
→ quartz → IR region
→ glass ; quartz → absorb
→ halide slat
23A-2 Spectroscopic Source
* suitable radiation source
→ sufficient power → easy
→ detection and measure
→ output → stable
→ reasonable period of time
* two type → figure 23-3
․ continuum source
→ broad → λ range
․ line source → limit #
→ spectral line
* continuous source
→ emit radiation
→ continuous with time
* pulsed source → laser
→ emit burst radiation
Q : 問答題

常用的 UV/visible 光源有哪些種類?

常用的 infrared 光源有哪些種類?

(寫出名稱即可,不需說明)
(1) continuum source in UV / Vis

* table 23-1 → most widely used

→ UV / Vis source

* figure 23-4 → tungsten filament

→ 2900 °K → 350 ~ 2200 nm


Q : 問答題
․ 請說明 tungsten lamp 產生
continuum UV radiation原理
․ 請說明 D2 lamp 產生
continuum UV radiation原理
* tungsten / halogen lamp
→ quartz / halogen lamp
→ quartz envelop
→ house filament
→ some iodine → quartz
→ temp. 3500°K → higher
→ intensity → extent
→ λ range → UV region
→ lifetime → double
→ tungsten lamp → W
→ sublimate → react with I2
→ form WI2 → diffuse
→ back to → hot filament
→ advantage → extend λ
→ intensity ↑ → lifetime ↑
* D2 / H2 lamp → most often used
→ UV region → consist
→ cylindrical tube → low pressure
→ D2 → quartz window
→ radiation exit → figure 23-5
→ mechanism → D2 → absorb
→ electrical eng. → D2* dissociate
→ D’ ; D” atom + UV photon

→ ( D2 + Ee → D2* → D’ + D” + hv )

→ Ee = electrical energy

→ ( Ee = ED2* = ED’ + ED” + hv )

→ ED2* = energy D2*


→ ED’ ; ED” = kinetic eng. of D’; D”

→ ED’ + ED” → vary → 0 ~ ED2*

→ photon eng. → vary → ED2* ~ 0

→ D2 lamp → continuous

→ radiation → 160 nm → vis.


* figure 23-5 (a)
→ D2 lamp → low voltage
→ form arc → between
→ filament / electrode
→ provide Ee
* figure 23-5 (b)
→ D2 lamp spectrum
→ continuous radiation
→ 160 ~ 375 nm
* D2 lamp more widely used
→ more intense
→ than → H2 lamp
(2) other UV / Vis source
* line source → Hg arc lamp
→ 253.7 nm → Hg line
→ common source
→ liquid chromatography
→ detector
* hollow-cathode lamp (Ch.26)
→ common line source
→ atomic abs. spec.
* laser → line source
→ tunable dye laser
→ range of λ
(3) continuum source in IR (略)
23A-3 Wavelength Selector (略)
23A-4 Detecting and Measuring
Radiant Energy
* transducer → type of detector
→ light intensity ; pH ; mass ; temp.
→ convert → electric signal
→ amplified ; manipulated
→ proportional to original quantity
→ discuss → radiation transducer
(1) property of radiation
transducer
* ideal transducer → low level
→ radiant energy → respond
→ rapidly → broad λ range
→ electric signal G → easy
→ amplified → low e noise
-

→ proportional → power P
→ G = K P + K’
→ K = sensitivity
→ K’ = dark current
→ no radiation
→ small response
Q : 問答題

請寫出常用的UV/visible偵測器名稱?

請寫出常用的 infrared 偵測器名稱?

(寫出偵測器的名稱即可,不需說明)
(2) type of transducer
* table 23-2 → two type
→ photon ; thermal transducer
* photon transducer → base on
→ radiation → reactive surface
* photoemission → UV / Vis / IR
→ enough energy → produce e-
→ record → e signal (current)
-
* photoconduction → IR less eng.
→ reactive surface → unable
→ produce electron → only
→ promote e - → conduct band
→ record conductivity
→ proportion → radiation P
* IR radiation
→ photoconducting material
→ measure → conductivity ↑
→ detect P → or measure
→ blackened material
→ temperature ↑
(3) photon detector
* widely used type :
․ phototube
․ photomultiplier tube
․ silicon photodiode (略)
․ photodiode array (略)
Q : 圖表問答題 (圖形配合題):

․ 參考圖 Figure 23-12,請說明

phototube 的原理。

․ 參考圖 Figure 23-13,請說明

photomultipier 的原理。
* phototube → figure 23-12
→ photoelectric effect
→ photon beam → cathode
→ photoemissive material
→ emit photoelectron
→ apply voltage → 90 V
→ electron → attract to anode
→ record I → proportional P
* photomultiplier → PMT
→ similar phototube
→ more sensitive → fig. 23-13
→ photon beam → cathode
→ emit electron → accelerate
→ a series of → dynode
→ produce → more electron

→ D1 ~ D9 → amplification

→ 10 5 → collect at anode

→ measure → current signal

→ 10 5 ↑ → sensitivity ↑
* silicon photodiode (略)

* photodiode array (略)

* diode-array detector (略)

* charge transfer device (略)


(4) thermal detector
* photon detector → table 23-2
→ not be used → measure IR
* IR radiation → lack energy
→ produce → photoemission e-
* thermal detector → black surface
→ absorb IR → temp. ↑ (10-3°C)
→ convert → electric signal
* difficulty of measurement
→ 10-3 °C → source of error
→ surrounding background
* minimize noise → vacuum ;
shielded ; rotating disk
→ figure 23-20 → chopper
→ analyte → ac signal
→ noise → dc signal
* table 23-2 → four type
thermal detector for IR (略)
23A-5 Signal Process (略)
23A-6 Sample Containers (略)
23B UV / Vis Photometerd and
Spectrophotometer
* spectrometer ; photometer
spectrophotometer (略)
23B-1 Single-Beam Instrument
* figure 23-19
→ simple spectrophotometer
* spectronic 20 → visible region
→ first → mid-1950s
→ modify version widely sold
→ throughout the world
* light-emitting diode display
→ LED → readout
→ transmittance ( T ) or A
* occluder (遮光板) → block
→ beam → calibration 0%T
* blank sample → light control
→ calibrate → 100 % T
* spectronic 20

→ 340 ~ 950 nm → band-pass

→ 20 nm → λ accuracy

→ ± 2.5 nm → photometric

→ accuracy → ± 2 % T
* spectronic 20
→ single-beam instrument
→ single λ → quantitative
→ measure absorption
→ advantage :
simplicity of instrument ;
low cost ; easy maintain
Q : 圖形配合題

圖(23-20a,b,c)為 UV/visible

photometer的儀器構造圖,

配合提示回答圖中 (a)~(g)。
25B-2 Double-Beam
Instrument
* figure 23-20
→ modern spectrometer
→ double-beam design
(a) single-beam → sample
→ reference → separate
(b) double-beam-in-space
→ V-shape mirror
→ beam splitter → two beam
→ one beam → reference
→ other beam → sample
→ photodetector → measure
→ two output → log ratio
→ computer display output
(c) double-beam-in-time
→ rotating mirror
→ separate beam
→ reference / sample cell
* double-beam instrument
→ advantage :
1. compensate for fluctuation
in radiant source
2. compensate variation of
source intensity with λ
3. suited continuous record
absorption spectra
Q : 圖形配合題

圖 (23-21) 為 multichannel

spectrometer的儀器構造圖

配合提示回答圖中 (a) ~ (g)


23B-3 Multichannel Instrument
* multichannel instrument
→ fig. 23-21 ; no λ selector
→ photodiode array
→ measure → entire
→ spectrum → at a time
→ time ↓ → but
→ expensive detector
* single channel instrument
→ λ selector → single λ
→ rotate → λ selector
→ obtain → another λ
→ scan range of λ → time ↑
→ but → simple detector
23C IR Spectrophotometer
(略)
23C-1 Dispersive Infrared
Instrument (略)
23C-2 Fourier Transform
Instrument (略)

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