Diffusive mass transport in binary
mixtures of a liquid solvent
and dissolved helium (He) or krypton (Kr) close to infinite dilution
is investigated by determining the Fick diffusion coefficient D
11 experimentally with dynamic light scattering
(DLS). Equilibrium molecular dynamics (EMD) simulations are used to
access the solute self-diffusion coefficient D
1, which is equal to D
11 at the
limit of infinite dilution. To address how the molecular characteristics
of the solvent influence molecular diffusion, a wide range of different
solvents is considered, including n-decane, n-hexadecane, n-octacosane, ethanol, 1-decanol,
cyclohexane, benzene, 2-methylpentane, 2,2-dimethylbutane, ethyl butanoate,
and n-hexanoic acid. Mixtures are investigated between
(303 and 448) K and up to 6.5 MPa. The average expanded experimental
uncertainty (k = 2) of D
11 from DLS experiments is 8.6%, and the average expanded statistical
uncertainty (k = 2) of D
1 from EMD simulations is 5.8%. Solvent force fields (FF) used in
EMD simulations to describe interactions within and between molecules
are primarily based on the all-atom optimized potentials for liquid
simulation (OPLS) FF, and a temperature-dependent modification developed
within our research group is applied. The average absolute relative
deviation of the simulated D
1 with respect
to the experimental D
11 is 14%. Results
from DLS and EMD show that diffusive mass transport in mixtures containing
dissolved He for a given solvent is (20–50)% greater than in
those with Kr. In comparison to mixtures based on linear alkanes,
those based on branched alkanes have larger D
11, while mixtures based on oxygenated and cyclic components
have smaller D
11.