IChO 2003 · Theory problem 15

Statements about Beer's law

Regarding Beer's law, are the following statements correct (Y) or not (N)?

(a) The absorbance is proportional to the concentration of the absorbing compound. (Y) (N)

(b) The absorbance is linearly related to the wavelength of the incident light. (Y) (N)

(c) The logarithm of transmittance is proportional to the concentration of the absorbing compound. (Y) (N)

(d) The transmittance is inversely proportional to the logarithm of absorbance. (Y) (N)

(e) The transmittance is inversely proportional to the concentration of the absorbing compound. (Y) (N)

Official English text of the problem.

Answers

  • (a) Y
  • (b) N
  • (c) Y
  • (d) N
  • (e) N

Solution

The Beer–Lambert law is \[ A=\log_{10}\!\left(\frac{I_0}{I}\right)=\varepsilon(\lambda)\ell c, \] where \(I_0\) and \(I\) are the incident and transmitted light intensities, \(\varepsilon(\lambda)\) is the molar absorption coefficient at wavelength \(\lambda\), \(\ell\) is the optical path length, and \(c\) is the concentration.

Transmittance is defined as \(T=I/I_0\), so \[ A=-\log_{10}T, \qquad T=10^{-A}=10^{-\varepsilon(\lambda)\ell c}. \] Both \(A\) and \(T\) are dimensionless. For example, with \(\ell\) in \(\mathrm{cm}\) and \(c\) in \(\mathrm{mol\,L^{-1}}\), \(\varepsilon\) has units of \(\mathrm{L\,mol^{-1}\,cm^{-1}}\).

(a) Correct (Y). At fixed wavelength and optical path length, within the conditions where Beer's law applies, \[ A=\bigl[\varepsilon(\lambda)\ell\bigr]c. \] Thus absorbance is proportional to concentration.

(b) Incorrect (N). The wavelength dependence of absorbance comes through \(\varepsilon(\lambda)\), which varies according to the absorption spectrum. Beer's law does not imply a linear relationship between absorbance and wavelength.

(c) Correct (Y). Rearranging the law gives \[ \log_{10}T=-\varepsilon(\lambda)\ell c. \] Thus the logarithm of transmittance is proportional to concentration, with a negative proportionality constant. Choosing another logarithm base only changes that constant.

(d) Incorrect (N). The actual relationship is \[ T=10^{-A}, \] rather than \(T\propto 1/\log A\).

(e) Incorrect (N). At fixed wavelength and optical path length, \[ T=10^{-\varepsilon(\lambda)\ell c}. \] Transmittance decreases exponentially with concentration; it is not inversely proportional to concentration.

The answers were checked against the official answers published by the organisers.