Professional Documents
Culture Documents
0065-2393/93/0236-0351$07.25/0
© 1993 American Chemical Society
Theory
T h e r e are t w o general types o f reflected light: specular a n d diffuse. A
c o m m o n example o f specular reflection (also called front-surface, regular, o r
F r e s n e l reflection) is light reflected f r o m mirrors o r other p o l i s h e d surfaces.
Specular reflectance occurs at any interface between t w o materials w i t h
different refractive indices. Specularly reflected light is characterized b y the
rule that the angle o f reflection is equal to the angle o f incidence. C o m m o n
examples o f diffusely reflecting surfaces are the matte surfaces characteristic
o f certain types o f paper a n d powders. D i f f u s e l y reflected radiation is the
fight reflected f r o m a diffusely reflecting sample f o r w h i c h the angle o f
reflection does not equal the angle o f incidence.
ri = η + ik' (1)
I = I e- *
0
k
(2)
Jfc'=Jfc/4irv (3)
k = 2.303ac (4)
f(R )
œ = (l-R f/2R^-k/s
œ (5)
1 = I e~"
0 (6)
substituted f o r R i n e q 5, w h e r e
œ
R' = R (sample)/Β»
œ œ (standard) (7)
Incident Radiation
Analyzer
Radiation from
To detector
interferometer
Polarizer
[] Sample
(A)
U Sample
(B)
Radiation from
interferometer
Detector
Analyzer
(C)
Figure 2. Schematic diagram of three commonly used optical configurations that
eliminate to a great degree the contribution of Fresnel specular reflectance to
the collected radiation. The top diagram (A) represents the in-line configuration
in which polarizers are used to eliminate the specular component. The middle
diagram (B) shows the off-line configuration in which exclusion of the plane of
incidence from the collection optics is used to eliminate the specularly reflected
component. The bottom diagram (C) is a configuration built by Fuller and
Griffiths (3). (Reproduced with permission from reference 17. Copyright 1948.)
3800 3000
Cm" 1
solid solutions in KCl (1:50 weight ratio): PVPh~P2VP polymer complex formed
with 4:1 initial composition (A); pure PVPh (B); and pure P2VP (C). (Reproduced
with permission from reference 27. Copyright 1984.)
temperature.
O n e o f the limitations o f the D R I F T technique is the n e e d to dilute
strongly absorbing samples i n a nonabsorbing matrix to avoid reststrahlen
effects. I n their D R I F T studies, T h o m p s o n a n d P a l m e r u s e d N a C l as the
diluent (1:10 C a C 0 : N a C l ) , a n d i n their photoacoustic studies using p u r e
3
oxidation of N O to N O +
b y C o (III) through the infrared absorption o f the
nitrosyl cation at 2162 c m - 1
a n d coordinated nitrosyl at 1674 a n d 1562 c m - 1
.
T h e species adsorbed o n a silver catalyst d u r i n g the oxidation of acetalde-
hyde was analyzed b y K a n n o a n d Kobayashi (48) using D R I F T spectroscopy.
T h e D R I F T spectra obtained f r o m the reaction were c o m p a r e d w i t h similar
spectra for silver salts, such as silver acetate, silver lactate, silver ketenide,
a n d silver carbonate. T h e s e comparisons, facilitated assignment of observed
peaks i n the i n f r a r e d spectrum o f the catalyst as b e i n g due to silver acetate
intermediates, a strongly adsorbed acetaldehyde, a n d an adsorbed alcohol.
T h e spectra obtained w i t h the D R I F T technique were c o m p a r e d w i t h spectra
for similar samples obtained b y transmission methods; the D R I F T m e t h o d
y i e l d e d m u c h better spectra i n the lower frequency region (1100 c m - 1
> v).
A l t h o u g h K a n n o a n d Kobayashi d i d dilute their catalyst samples i n K B r
d u r i n g the actual oxidation reactions, w h i c h w e r e c a r r i e d out at elevated
temperature (160 °C), they d i d not address the possibility of perturbation o f
the catalysis results due to the h i g h concentration o f alkali halide.
D R I F T spectroscopy was u s e d b y F r i e s a n d M i r a b e l l a (49) to study
commercial T i C l - A l C l
3 3 catalysts used i n the polymerization of propylene.
T h e y were able to m o n i t o r the decay o f the 1 6 4 0 - c m " absorption due to the
1
M n ( C O ) , K [ H F e ( C O ) ] , a n d K [ F e M n ( C O ) ] . D R I F T spectroscopy
2 1 0 3 n 2 1 2
NAVENUMBER
shown in sequence from bottom to top representing metal loadings of 0.92, 1.7,
2.5, 3.8, 4.5, and 5.6% Cu on Si0 , respectively.
2
spectrum o f the overlayers; that is, the C u ( a c a c ) species not i n direct contact
2
Summary
D i f f u s e reflectance spectroscopy i n the m i d - i n f r a r e d range is a p o w e r f u l
technique for the study o f certain types o f samples, i n c l u d i n g polymers,
heterogeneous catalysts, a n d n o v e l materials. D R I F T has great potential f o r
the study o f a w i d e variety o f processing p r o b l e m s a n d for i n situ investiga
tions, b o t h as a stand-alone technique a n d i n conjunction w i t h G C a n d
G C - M S . W h a t must b e kept i n m i n d i f useful results are expected are the
approximations inherent i n the technique such as optically dilute samples, the
problems a n d the solutions associated w i t h specular a n d diffuse Fresnel
reflectance, a n d the n e e d f o r reproducible sample preparation.
References
1. Wendlandt, W. W.; Hecht, J. G. Reflectance Spectroscopy; Interscience: New
York; 1966.
2. Kortum, G. Reflectance Spectroscopy: Principles, Methods, Applications; Sprin
ger: New York, 1969.
3. Willey, R. R. Appl. Spectrosc. 1976, 30, 593.
4. Fuller, M . P.; Griffiths, P. R. Anal. Chem. 1978, 50, 1906.
5. Fuller, M . P.; Griffiths, P. R. Appl. Spectrosc. 1980, 34, 533.
6. Culler, S. R.; Ishida, H.; Koenig, J. L. Annu. Rev. Mater. Sci. 1983, 13, 363.
7. Blitz, J. P.; Shreedhara Murthy, R. S.; Leyden, D. E. Appl. Spectrosc. 1986, 40,
829; Leyden, D. E.; Shreedhara Murthy, R. S. Spectroscopy 1977, 2, 28.
8. Childers, J. W.; Palmer, R. A. Am. Lab. 1986, 18(3), 22.
9. Urban, M . W.; Chatzi, E . G.; Perry, B. C.; Koenig, J. L. Appl. Spectrosc. 1986,
40, 1103; Koenig, J. L. Pure Appl. Chem. 1985, 57, 971.
10. Story, W. C.; Masujima, T.; Liang, J.; Liu, G.; Eyring, Ε. M . ; Harris, J. M.;
Anderson, L. L. Appl. Spectrosc. 1987, 41, 1156.
11. Kubelka, P.; Munk, F. Z. Tech. Phys. 1931, 12, 593.
12. Kubelka, P.; Munk, F. J. Opt. Soc. Am. 1948, 38, 448.
13. Hecht, H . G. Appl. Spectrosc. 1980, 34, 161.
14. Fraser, D. J. J.; Griffiths, P. R. Appl. Spectrosc. 1990, 44, 193.
15. Brimmer, P. J.; Griffiths, P. R. Appl. Spectrosc. 1988, 42, 242.
16. Brimmer, P. J.; Griffiths, P. R.; Harrick, N . J. Appl. Spectrosc. 1986, 40, 258.
17. Yang, P. W.; Mantsch, H . J.; Baudais, F. Appl. Spectrosc. 1986, 40, 974.
18. Brimmer, P. J.; Griffiths, P. R. Appl. Spectrosc. 1987, 41, 791.
19. Hembree, D. M.; Smyrl, H . R. Appl. Spectrosc. 1989, 43, 267.
20. Martin, Κ. Α.; Ferraro, J. R. Appl. Spectrosc. 1987, 41, 45.
21. Hawranek, J. P.; Jones, R. N . Spectrochim. Acta, Part A 1976, 32, 111.
RECEIVED for review July 15, 1991. ACCEPTED revised manuscript September
25, 1992.