  Recently, continuum Microkinetic Rate Theory (cMRT) has been advanced as a
method of studying rates of systems, where deviations between observation and
cMRT theory have been found, and it hypothesized that these deviations are
linked either to oscillations or fluctuations. Multinomial probability theory
(MPT) is used to derive analytical expressions for concentration fluctuations,
giving the fluctuations as a function of average concentrations and sample
sizes. MPT predictions of fluctuations in kinetically constrained systems are
verified against kinetic Monte Carlo, and it analytically shown that MPT
predicts canonical and grand canonical ensemble fluctuations. These fluctuation
results are discussed in conjunction with cMRT deviations and it argued that
fluctuations are not responsible for the deviations.
