Cw-laser thermal lens spectrometry in binary mixtures of water and organic solvents: composition dependence of the steady-state and time-resolved signals

Abstract

The thermal lens effect obtained in binary liquid systems composed of water and ethanol, propanol and acetonitrile has been investigated. The dependence of d n/d T upon the solvent volume fraction follows polynomials up to sixth order and cannot be precisely predicted using the additive rule. The sensitivity of the thermal lens method upon the addition of organic solvent in water varies as the temperature-dependent refractive index gradient to thermal conductivity ratio of the mixture provided that the signal is sampled correctly. Otherwise, especially when steady-state experiments are carried out, the thermally induced concentration gradient, known as the Soret effect, can change the thermo-optical properties of the solution locally in the irradiated area and produce an additional signal. This effect depends on the solvent and is maximum at low solvent composition. At the critical solvent volume fraction of 0.1–0.15, the Soret component may represent up to 25% of the pure thermal lens signal and has a time constant which is 200–400 times greater than the characteristic time constant of the thermal lens.