Quantitative Diffuse Reflectance and Transmittance Infrared Spectroscopy of Nondiluted Powders

Abstract

An adaptation of Kubelka's general model of diffuse reflectance and diffuse transmittance of light to nonideal scattering samples is proposed. It is applied to quantitative Fourier transform infrared spectrometry of nondiluted surface-derivatized silica powders. Corrections of the measurements are introduced in order to take into account common problems that often prevent a truly quantitative application of the DRIFTS analytical method. Effects on the measured data due to the background absorption of the sample and to the specular reflection on its surface are discussed and quantitatively corrected for. The possible existence of gradients of the optical properties of the powder medium is taken into account by a numerical adaptation of the model to inhomogeneities of the phenomenological absorption and scattering coefficients K and S. Model systems constituted of two types of silica powders of very different morphology are prepared. Known concentrations of molecules carrying a cyano functional group as chromophore were covalently anchored on the powder surface. Application of the adapted model gives a quite good description of the measured diffuse reflectance and diffuse transmittance in these cases where the simple Kubelka-Munk function fails.

Keywords

Quantitative FT-IR spectroscopy Diffuse reflectance Diffuse transmittance Nondiluted powders Derivatized silica

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References

Griffiths

P. R.

and Fuller

M. P

, in Advances in Infrared and Raman Spectroscopy, Hester

R. E.

Ed. (Heyden, London, 1982), pp. 63–129.

Fuller

M. P.

and Griffiths

P. R

, Am. Lab. 10, 69 (1978).

Fuller

M. P.

and Griffiths

P. R

, Anal. Chem. 50, 1906 (1978).

Fuller

M. P.

Hamadeh

I. M.

Griffiths

P. R.

and Lauenhaupt

D. E

, Fuel 61, 529 (1982).

Hamadeh

I. M.

and King

, J. Catal. 88, 264 (1984).

Kuehl

D. T.

and Griffiths

P. R

, Anal. Chem. 52, 1394 (1980).

Shafer

K. H.

Pentoney

S. L.

Jr. , and Griffiths

P. R.

, High Resol. Chromatogr. Chromatogr. Commun. 7, 707 (1984).

Chalmers

J. M.

and Mackenzie

M. W

, Appl. Spectrosc. 39, 634 (1985).

Hamadeh

I. M.

Yeboah

S. A.

Trumball

K. A.

and Griffiths

P. R

, Appl. Spectrosc. 38, 486 (1984).

10.

Kortüm

, Reflectance Spectroscopy (Springer-Verlag, Berlin, 1969).

11.

Yeboah

S. A.

Wang

S. H.

and Griffiths

P. R

, Appl. Spectrosc. 38, 259 (1984).

12.

Christy

A. A.

Tvedt

J. E.

Karstang

T. V.

and Velapodi

R. A

, Rev. Sci. Instrum. 59, 423 (1988).

13.

Chalmers

J. M.

and Mackenzie

M. W

, in Advances in Applied Fourier Transform Infrared Spectroscopy, Mackenzie

M. W.

Ed. (Wiley, Chichester, 1988), pp 136–138.

14.

Brimmer

P. J.

Griffiths

P. R.

and Harrick

N. J

, Appl. Spectrosc. 40, 2581 (1986).

15.

Brimmer

P. J.

and Griffiths

P. R

, Appl. Spectrosc. 41, 791 (1987).

16.

Schuster

, Astrophys. J. 21, 1 (1905).

17.

Kubelka

and Munk

, Z. Tech. Phys. 12, 593 (1931).

18.

Kubelka

, J. Opt. Soc. Am. 38, 448 (1948).

19.

See for example: (a) Unger

K. K.

, Porous Silica, J. Chrom. Library, v. 16 (Elsevier, Amsterdam, 1979); (b) Nestrick

T. J.

Lamparski

L. L.

and Stehl

R. H

, Anal. Chem. 51, 2273 (1979); (c) Berendsen

G. E.

Pikaart

K. A.

and De Galan

, J. Liquid Chromatogr. 3, 1437 (1980).

20.

(a) Erard

J. F.

and Kováts

E. sz

, Anal. Chem. 54, 193 (1982); (b) Erard

J. F.

Nagy

and Kováts

E. sz

, Colloids Surfaces 9, 109 (1984); (c) Rudzinski

Montgomery

T. L.

Frye

J. S.

Hawkins

B. L.

and Maciel

G. E

, J. Chromatogr. 323, 281 (1985).

21.

(a) Moser-Boroumand

, Spectroscopie FTIR Quantitative de Reflectance et Transmittance Diffuses, Ph. D. thesis No. 926, EPFL, Lausanne (1991); (b) Boroumand

Van den Bergh

and Moser

J. E

, Anal. Chem. (submitted for publication, 1992).

22.

(a) Broese van Groenou

, Powder Technol. 28, 221 (1981); (b) Thompson

R. A.

, Am. Cer. Soc. Bull. 60, 237 (1981); (c) ibid. 60, 244 (1981); (d) ibid. 60, 248 (1981); (e) Beddow

J. K.

, Particulate Science and Technology (Chemical Publishing, New York, 1980).

23.

Lin

T. P.

and Kan

H. K. A

, J. Opt. Soc. Am. 60, 1252 (1970).

24.

Oelkrug

Honnen

Wilkinson

and Willsher

C. J

, J. Chem. Soc., Faraday Trans. 83, 2081 (1987).

25.

Kubelka

, J. Opt. Soc. Am. 44, 330 (1954).

26.

Coufal

and Mandelis

, in Photoacoustic and Thermal Wave Phenomena in Semiconductors, Mandelis

Ed. (North-Holland, New York, 1987), pp. 149–173.

27.

Coufal

H. J.

Grygier

R. K.

Harne

D. E.

and Fromm

J. E

, J. Vac. Sci. Technol. A5, 2875 (1987).

28.

(a) Mandelis

Boroumand

Solka

Highfield

and Van den Bergh

, Appl. Spectrosc. 44, 132 (1990); (b) Mandelis

Boroumand

and Van den Bergh

, Spectrochim. Acta 47A, 943 (1991).

29.

Brimmer

P. J.

and Griffiths

P. R

, Appl. Spectrosc. 42, 242 (1988).

30.

Bellamy

L. J.

, The Infrared Spectra of Complex Molecules (Chapman & Hall, London, 1975).

31.

Thomson

H. W.

and Steel

, Trans. Faraday Soc. 52, 1451 (1956).

32.

Marquardt

D. W.

, Chem. Eng. Progr. 55, 65 (1959).

33.

Marquardt

D. W.

, J. Soc. Ind. Appl. Math. 11, 431 (1963).

34.

Surles

Erickson

J. O.

and Priesner

, Amer. Lab. 7(3), 55 (1975).

35.

Depecker

Sombret

and Legrand

, Analysis 13, 349 (1985).

36.

Brimmer

P. J.

and Griffiths

P. R

, Anal. Chem. 58, 2179 (1986).

37.

Mandelis

Boroumand

and Van den Bergh

, Appl. Opt. 29, 2841 (1990).

38.

CRC Handbook of Chemistry and Physics, Weast

R. C.

Ed. (CRC Press, Cleveland, 1974) p. B-133. Refractive indexes in the mid-infrared are assumed to be close enough to the values reported for visible light radiation (n ≈ nD).