Ions in the ion mobility spectrometry (IMS) are mostly
hydrated.
A single peak in the drift time spectrum is usually generated by a
mixture of ions differing in the number of attached water molecules.
Under real IMS detector operating conditions, ions change their composition
during movement in the drift region due to the changes in the number
of water molecules attached to the ion. The impact of water vapor
on the drift times of small ions at different temperatures was studied
experimentally using an ion mobility spectrometer. The experiments
were carried out for hydronium, ammonium, oxygen, chloride, bromide,
and iodide ions. A theoretical model was developed, allowing us to
calculate the effective mobility of ions for a given concentration
of water vapor and temperature. The basic assumption adopted in this
model was the linear dependence of the effective mobility coefficient
on the mobility of ions with a certain degree of hydration. The weighting
factors in this relationship are the abundances of individual types
of ions. These parameters were determined by calculations based on
the thermodynamics of the formation and disintegration of ionic clusters.
From the known values of temperature, pressure, and humidity, the
values of effective mobilities can be predicted quite accurately.
The dependencies of reduced mobilities on the average degree of hydration
were also determined. For these dependencies, the measurement points
on the graphs are gathered along specific lines. This means that the
average degree of hydration unambiguously determines the value of
reduced mobility for a given type of ions.