090704 100704

10-800 nm.(1) 10-200nm() (2) 200-400nm(3) 400-800nm -

2.1 -2.1.1

-Ultraviolet-Visible absorption Spectra(UV)----

E = E2 - E1 = h 2.1.2 M + h M *

E1 E E2

2.1.3 (T%)(A),

,;

(Bouguer)(Lambert)17291760 1852(Beer): A b A c-AT:b()cmcmolL-1Lmol-1cm-1A lgT lg It / I0)= b c2.1.4 ------.

A-lgT -lg(It/I0)= b cT 10 A=10- b cC..

3. ()maxmax c b b c/ A max >105 C= A/ b =0.01/105=10-7 mol/L =(610)104 C= A/ b =0.01/5 104= 210-7 mol/L

.

C ---mol / L--- L mol 1 cm -1C--g / La--- L g 1 cm -1. Beer .Lambert Beer -

.Beer(C < 10-2mol/L)C>10-2 mol/L e.g. Cr42- 2H = Cr272- H2 Cr42- Cr272-()pH . e.g. -.

()2.1.5

(chromophore)(Auxochrome)-OH, -OR, -NHR, -SH, -SR, -X

2.1.6

(3)(Red shift) (4)(Blue shift)(5)(Hyperchromic effect)(6)(Hypochromic effect)(7)104(8)1000

2.1.7 n

. n < < n <

(

1 2max1043 *max162nmmax: 1104Lmol-1cm1 K(konjugierte ) Kmax 210250nmmax104max

-*B(Benzienoid)E(Ethylenic)UVB >200 nm250-3000 E *> 10000EE1 E2 E1(max 10000) , max 184nm E2(2000max 10000),max 204nm

E1 max 184 nm ( 68000) E1 max 203.5 nm ( 8800)B max 254 nm ( 250) B (B230270nm)max2003000 (215)B

(4)n*R(Radikalartig) R max270nmmax100 max

E. max104

2.1.8 1

9-62

*n *max *n *

n *

pH3pH

2.2 -UV spectrometer

.

1. 320800 nm 185390 nm

: 2.

3. 0.1-10cm1cm

360 nm2.25 mm

200 nm2.5 mm

4. CCD5.

. 2.1.

2.2.

2.3. A = A1 + A2 = 1-2bc

2.3 1 * *n *

2 *165 nm *173 nm *150-170 nm n *270-300,

3 max

1253+5*4273253+5*4+5*2283

. 1. 2.4 -.2. max() maxA. maxmaxWoodward* Scott* -

Sadtler. Sdandard Spectra (Ultraviolet). Heyden, London, 1978. 46000R. A. Friedel and M. Orchin, Ultraviolet Spectra of Aromatic Compounds, Wiley, New York, 1951. 579Kenzo. Hirayama, Handbook of Ultraviolet and Visible Absorption Spectra of Organic Compounds, New York, Plenum, 1967.M. J. Kamlet, Organic Electronic Spectra Data, Vol. 1,1946~1952, Interscience,1960. B.- max()max

. UV-VIS

:

--n*-- *max=243nm maxmax=272nm max=16

B. . 1. A-lgT -lg(It/I0)= b cA.

C.

2 1 1259nmB 2 2299nm lg=4.1

3. e.g. n* MAX = 264.5 nm E =452.96 kJ/mol n* MAX = 279 nm E =429.40 kJ/mol E =452.96- 429.40= 23.56 kJ/molE = 6.021023hv =6.021023hc/ = (6.0210236.625610-342.9979108)/(264.510-9) = 452.07 kJ/mol