(Ultraviolet and Visible Spectrophotometry, UV-Vis)

1

• ??? ??-???????
• (Ultraviolet and Visible Spectrophotometry,
  UV-Vis)
•  
• 2.1 ??-??????
• 2.2 ???????-----Lambert-Beer ??
• 2.3 ??-?????????
• 2.4 ??????
• 2.5 UV-Vis????????
• UV-Vis?????????,???????????????????
• UV-Vis?????????????????160780nm.
• UV-Vis???????????,?????(UV)???????,???
• ?????,??????????????????

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2.1 ??-?????? ??????????? 1.
???????????--------??????------????????-----?????
? 2. ??????????(Electron energy
level)?,??????????????????,????????(Vibration)????
?(Rotation)?????!???????,????-????????????????????
??,????????E???????????? ???Ee??1-20 eV
?Ev??0.05-1 eV ?Er???0.05 eV
??,???????????????????12????,??????????,???-?????
?,??????????
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???????????????????(????????)???????,?????
????????????????????,??UV-Vis????????
?????????????????????,???????,??????????????(???A)
,????A????,??????????,???????????????,????????(???
???????)???????
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????????????? n????(??????????) ????????-??
-??-?n-??-?n-?
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?-?C-H???,?CH4(125nm)C-C?,?C2H6(135nm),??
????? ?-? ??-?????????????-??????,?????
? ????? n-??????????,?H2O(167nm)CH3
OH(184nm)CH3Cl (173nm)CH3I(258nm)
(CH3)2S(229nm)(CH3)2O(184nm)
CH3NH2(215nm)(CH3)3N(227nm),??,????????
200nm,??????? ??????????????????(?-?,?
-?,?-??n-?),??????,???????????????????,????????
? ???-??n-?????????,?????????????????,??
??????,?????????
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?? 1)?????160, 180,290nm?????,??????????????
2)???(190nm)???(185nm)????(195nm)?????????? 3)??
?????N-CH2-CH2-CH3?N-CH2-CHCH2???????? ?
??????????
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2. ???? ???(Chromogenesis group)
???????????????,?????????????n-?
??-???,???????????????,?????? ???(Auxochromous
group) ??????,??????????????????????????
??,????????????????? -Flt-CH3lt-Brlt-OHlt-OCH3lt-NH2lt-
NHCH3lt-NH(CH3)2lt-NHC6H5lt-O- ?????(Redshift or
blueshift) ??????????????????????,???????
?(??)???????(??)???? ?????????????????????
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1)???????----?? ?CH2CH2??-???,?max16520
0nm?1,3-???,?max217nm 2)???????????????
?CH3CHO?????????????CH3CHO-H2O?CH3CH(OH)2
???,?max290nm,???????,???????????,????,?????? 3)
??????---?? ?CH3I(258nm), CH2I2(289nm),
CHI3(349nm) 4)????????? ?????????,?-NH2?-OH
?-Cl,??????????????,?-R,-OCOR,???????
???????H????????,??????
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5)pH?????? ????????????,?210.5nm?270nm?????
???????,??????235nm? 287nm(p- ???). 6)?????????
?n-?????????,???????,?? H
??????,??????-?????????,???????,??????????????,?
???? ???????,????????,???????
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????????? ??????????-??????,??????? p-d
???????????? d-d, f-f ????????? 1. ??????
(Charge transfer transition)
??????????(???)???(????)?????,????????,???????????
?????? ?max ?? (104??),????????
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2. ????(Ligand field transition) ?????
d ? f ???????(Degeneration orbit),????????,??????,
d ? f ????????????????,?????????????????,????????
? d ? f ??,????????? ???? ?max ??
(102),?????????????????????????
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2.2 ???????-----Lambert-Beer ?? ??  ????
????I0?????(Incident beam)
?????????????,?????????,?????????(Emergent)???????
????(Scattering)???(Reflection),?????????????)???,
????????10,??, I0Ie Is I r
??,??????????????????????????!
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??Lambert-Beer ?? ?????????,????????A?????
???????,? k ?????,???????????????? ?
???? g/L ???,? k ?????,? a ??,? ?
????mol/L???,? k ???????,?? ??,? ? ? a ?????
??,???????????? ?????,??,? ???????
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???? L-B ????? ????? A ??? b ???????? b
???,A ? c ???????,??? L-B ??!??????????????? 1.
?????? a)??????--????????????????????
?????????---? ?? b)???????????,?????????????????
??????,?????????????? c)?????????????????
??????? d)??????????????????
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b)??????????????????,????????????????????????
????(?????)??????????????,????,???????????,?????
?
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2.3 ??-????????? ??-????????????????????????
???? ???? ????????????????????????????? 1.
?????3402500 nm,??????? 2. ?????160375nm,????
??? ?????(Mnochromator) ??????????,?UV-Vis?
???,?????????????!(????????????????????) ?????(Cel
l,Container) ????????????????????,????????
?????????????????????????????? ??????????PMT?PDA
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2. ???????
?????????????????????,???????A? ?AB1??AB2?????1
??2??????,??1??2 ???,?????????????,? ???,???????
?????????????? ??????????????????????????????(???
?????????????????????)??????????????,?????
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3. ???????? ???????????????????????,??????
????? ?????? ???-???(????)????(????)????
????????????????? ??????? ?? K2CrO4
?????(?25oC?,????????0.04000g/L? KOH
??(0.05mol/L)???? A,???????A ???? P31 ?? 2.1
???????
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• ????????
• ????????
• ???????? ? ????????????????????????????????
  ???????
• 2. ?????
• ???????????????????,??????????
• 3. ???????????? pH ???
• 4. ??????????????
• ???????
• ????????????????(?????)????????,?
• ?????(?????)???
• 2. ???????????????????????,???????(?
• ????)
• 3. ??????????????????,?????????,????
• ???(??????)?

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?????? 1. ???? ???????pH??,???????????????
,?????,???????????0.5MH2SO4???,????Hg2?????????,?
?Pb2?Cu2?Ni2?Cd2????????????? 2. ????? 3.
?????? 4. ????? 5. ??????????
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?????? 1. ??????? 1)?????(?) 2)?????
???????????,?????????cs?????,???????,??????k,???Ax
kcx??cx ??????????????L-B??,?cx?cs?????,???
??????
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2. ??????? ??????????,?????????????????
???????? X ? Y,?????,????????,????????????  
?a)X,Y ???????????,?????,???????????? ?b)?c)
X,Y ????,?????????????X?Y??? ??,X,Y ????? ?1
? ?2 ???????? ? ??????? X, Y ??????????????? cx ?
cy?
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4. ????? ???3?????????? b
?????????????,???????????????? ????????????, A1A
1a A1b A2 A2a A2b ????????k1?k2???,??, Sk2(A
2aA2b)-k1(A1aA1b)(k2A2b-k1A1b)(k2A2a-k1A1a) ??
?????,????k2/k1A1b/A2b,? S(k2A2a-k1A1a)(k2?2-k1
?1)lca ??,?????? ca ??,???? ca??????cb?
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3)???????? ??????,??? ??????(?????
)??????????(?????)???d ????????(?????)????p1?p2
??????????????
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7. ???????????? 1)????(???) ?????????? ??????cM,
??cR,??????MRn????A,?cR/cM???A??,??????????,??????
??????? n?
?MRn ??????,?
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2)????????(Job?) ??????cRcMc
??,???cM?cR?????,??cM/c????A??,????????cM/cR??????
???????????????cM/c????????????0.5,????n?11????0
.33,????n?12??n(1-cM/c)/(cM/c)

?cM/cf,?


??????????????????????
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8. ????????? ??????HB,??????? ???B-
?HB,????Ka? ???,??????pH???????????,???
???,???B-?HB?????????????,??????????????????pH????
??,???B-?HB??????????????,???????B-?HB,???????
pKa?Ka?