The temperature dependence of derivative ultraviolet absorption spectra

The effects of variation of temperature in the range 0 degrees -40 degrees C on the zero and second derivative ultraviolet absorption spectra of ten compounds have been investigated. When the temperature of the solutions was increased, most of the substances showed a linear reduction of maximum absorbance (A(max)), with temperature coefficients of -0.07 +/- 0.03% per degree. The second derivative amplitudes of all the substances were reduced, with temperature coefficients (-0.1 to -0.5% per degree) that bore no significant relationship to those of the corresponding A(max) values. These effects on the extrema of the derivative spectra are explained by the small reduction in curvature at the corresponding wavelengths of the fundamental spectra, that occurs with increasing temperature. The precise and accurate assay of substances by derivative UV spectrophotometry requires that the temperatures of the standard and sample solutions are identical at the time of measurement.