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Beer's Law - Why Absorbance Depends (Almost) Linearly On Concentration
Beer's Law - Why Absorbance Depends (Almost) Linearly On Concentration
Abstract: Beer’s law assumes a strictly linear dependence of the wherein is the reduced mass of the charges and x their
absorbance from concentration. Usually, chemical interactions and displacement, and we have assumed that the restoring force is
instrumental imperfection are made responsible for experimental proportional to this displacement (Hook’s law). Furthermore,
deviations from this linearity. In this contribution we show that even in absorption is introduced via the damping of the vibration in form
the absence of such interactions and instrumental errors, absorbance of a term proportional to the velocity of the charged mass dx dt
should be only approximately proportional to concentration. This can and a damping constant . Finally, the vibration is forced by an
be derived from the quadratic dependence of the complex refractive applied electric field E0 exp it , which is varying in time with
index, and, by that, of the molar attenuation coefficient, from the the frequency and acts on the charge q . If the vibration were
dielectric constant and its frequency dispersion. Following dispersion unforced, its eigenfrequency would be 0 k , wherein k is
theory, it is the variation of the real and the imaginary part of the the force constant from Hook’s law.
dielectric function that depends linearly on concentration in the The solution for the displacement in dependence of time derived
absence of interactions between the oscillators. We show that this from eqn. (1) is well-known:
linear correlation translates into a linear dependence of the q
x t E t . (2)
absorbance for low concentrations or molar oscillator strengths based 0 2 i
2
c·d/(m·mol·l-1)
0.05·1000
In the next step, we use that for r the following relation holds, 1.5
0.5·100
r 2 n k , put this relation into eqn. (9) and divide both sides by
Absorbance
5·10
2n : 50
1.0
c S *2
2
k . (10)
n 2 2 2 2
2
0
0.5
0.00 References
0 10 20 30 40 50
c / (mol/l) [1] E. Hecht, Optics,4/e, Pearson Education, 2002.
[2] W. Sellmeier Annalen der Physik. 1872, 223, 386-403.
Figure 3. Concentration dependence of the absorbance at two wavenumbers [3] W. Sellmeier Annalen der Physik. 1872, 223, 525-554.
80 cm-1 away from the oscillator position (1700 cm-1) for the hypothetical [4] H. Helmholtz Annalen der Physik. 1875, 230, 582-596.
material based on the CDHO model (black/green curves) compared to the [5] E. Ketteler Annalen der Physik. 1887, 266, 299-316.
Lorentz simplification that leads to Beer’s law (red/blue line). [6] H. A. Lorentz Koninkl. Ned. Akad. Wetenschap. Proc. 1906, 8, 591-611.
[7] P. Drude Annalen der Physik. 1893, 284, 536-545.
To summarize, we have established the connection between [8] C. Schaefer, F. Matossi, Das Ultrarote Spektrum, Verlag von Julius
Springer, Berlin, 1930.
Maxwell’s equations, the dispersion relations and Beer’s law and [9] T. G. Mayerhöfer, J. Popp Journal of Optics A: Pure and Applied Optics.
derived the latter from the former employing an approximation 2006, 8, 657-671.
[10] T. G. Mayerhöfer, J. Popp Chemphyschem : a European journal of
introduced by Lorentz in 1906. While it is in theory known since chemical physics and physical chemistry. 2018, accepted, DOI:
then, though not well-known, that absorbance is not additive, the 10.1002/cphc.201800961.
intuitive assumption of a linear dependence of absorbance from [11] T. G. Mayerhöfer, H. Mutschke, J. Popp Chemphyschem : a European
journal of chemical physics and physical chemistry. 2016, 17, 1948-1955.
concentration is in wide concentration ranges justified. [12] T. G. Mayerhöfer, H. Mutschke, J. Popp Chemphyschem : a European
The advent of much brighter light sources (like quantum cascade journal of chemical physics and physical chemistry. 2017, 18, 2916-2923.
[13] T. G. Mayerhöfer, J. Popp Spectrochimica Acta Part A: Molecular and
lasers in the mid-infrared) and more sensitive detectors, as well Biomolecular Spectroscopy. 2018, 191, 283-289.
as methods to determine concentrations in the molar range with [14] T. G. Mayerhöfer, S. Pahlow, U. Hübner, J. Popp The Analyst. 2018, 143,
standard equipment, might, however, be a game changer and 3164-3175.
[15] W. Mäntele, E. Deniz Spectrochimica acta. Part A, Molecular and
demand an understanding of the dependence of the optical biomolecular spectroscopy. 2016.
properties way beyond the limits of Beer’s law. [16] A. Y. Tolbin, V. E. Pushkarev, L. G. Tomilova Chemical Physics Letters.
2018, 706, 520-524.
As a note after acceptance, it was hard to believe for us that the [17] L. C. Zhao, M. H. Guo, X. D. Li, Y. P. Huang, S. H. Wu, J. J. Sun
natural connection between dispersion and absorption had not Analytical chemistry. 2017, 89, 13429-13433.
been established previously. In fact, while this manuscript was [18] M. Planck Sitzungsberichte der Königlich Preussischen Akademie der
Wissenschaften. 1902, I, 470-494.
under review, we kept looking for an older work on this topic and, [19] M. Planck Sitzungsberichte der Königlich Preussischen Akademie der
finally, made a find. Accordingly, Max Planck derived his own kind Wissenschaften. 1903, I, 480-498.
[20] T. G. Mayerhöfer, J. Popp submitted. 2018.
of dispersion relation in 1902.18 One year later, he published a
paper where he discussed, among other things, the principal
influence of the number of dipole moments per unit volume
(“vertheilungsdichte”) on the shape of the bands of the absorption
index.19 He discussed limiting cases based on an analogue of eqn.
(14), and came to the same principal conclusions as we did, i.e.
Beer’s law should hold good for small “vertheilungsdichten” and
lose its justification for stronger absorptions and higher
concentrations. Even if Planck did neither derive Beer’s law
explicitly nor an expression for the molar attenuation constant, we
think that his insights should have deserved much more than
having gone unheeded for so long.
In addition, we recently succeeded in deriving Beer’s law in strict
form directly from basic electromagnetic theory without the detour
to dispersion theory. As a consequence, it is not necessary to
make any assumption about a specific model oscillator/lineshape
function and it can be seen as a generalization of this work.
Accordingly, the principle results, like the dependence of the
molar attenuation constant from the refractive index, and the
corresponding deviation from the empirical law for higher
concentrations, remain unchanged.20
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Entry for the Table of Contents
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Beer’s law – why absorbance Author(s), Corresponding Author(s)*
depends (almost) linearly on
concentration: Page No. – Page No.
Absorbance is, counterintuitively, not per
Absorbance
law
Title
se an additive quantity. This is a
's
hereditary from the absorption index,
which is a wave, rather than a materials
er
Be
property, and extends to a non-linear
concentration dependence. For weak
O
CDH
oscillators the deviations from linearity
are very weak, otherwise the non-
additivity may account for persistent
experimental errors.
Concentration