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Extra info for Chromatography
16 for broadening in open tubes gets modified in two ways: 1. , dependent on the retention factor, k); and 2. , diffusion) that occurs in the stationary phase. 17) where df is the thickness of the stationary phase film and Ds is the diffusion coefficient of the solute in the stationary phase. 18) 2 2f ′ (k) d 2 where B = 2Dm , Cm = 24 DR , and Cs = 3 Df . m s The change in the second term compared to the equation for open tubes without a stationary phase results from the fact that solutes near the wall randomly sorb onto or into the stationary phase and thus temporarily stop moving down the column.
Solutes in the stationary phase are not moving down the column, while the solutes that are in the mobile phase move ahead of them. The higher the retention factor, the bigger the effect. 5 shows that the ﬁrst term due to longitudinal diffusion is the same. The second term, which incorporates the effects of retention and slow mass transfer in the mobile phase, is now the largest contributor to broadening, and slow mass transfer in the stationary phase adds a whole new term but not a signiﬁcant one because the given ﬁlm thickness is quite thin.
Here again, we see that smaller particles lead to smaller H values associated with narrower peaks. In fact, the particle size is squared, so using smaller particles leads to a significant reduction in broadening. This term is also dependent on the mobile phase velocity for the same reasons discussed above in association with broadening in open tubes. As the velocity increases, less time is allowed for the solutes to diffuse between and experience multiple velocities. Therefore, less averaging occurs and solutes elute over a larger range of times.