The electrokinetic sonic amplitude (ESA) technique and density measurements have been used to
determine the dynamic mobility of a cationic polyacrylamide, CPAM (mol wt 5 × 106), and two cationic
polyamines (mol wt 5 × 104 and 5 × 105). For all three polyelectrolytes, the ESA signal increased linearly
with increasing polymer concentration up to 4 mg/mL. The dynamic mobility was higher for the larger
polyamine than for the smaller, but after correction for its higher charge density, it was found that the
dynamic mobility was essentially independent of molecular weight for the polyamines. At low ionic strength
the dynamic mobility of the polyacrylamide was 5 and 6 times lower than those for the two polyamines,
in agreement with its 5 and 6 times lower charge density, respectively.The dynamic mobility decreased
with increasing ionic strength for all three polymers, as expected. However, the corresponding electrokinetic
charge fraction of the polymers, calculated by modeling the polyelectrolytes as cylinders, decreased with
increasing ionic strength. This in contrast to the constant charge fraction evaluated from the dynamic
mobility of DNA (Rasmusson, M.; Åkerman, B. Langmuir
1998, 14, 3512), which shows that the atypical
behavior of the polyacrylamide and the polyamines is not an inherent property of the dynamic mobility
of polymers. The apparent persistence length of the polyacrylamide was evaluated from viscosity
measurements. From comparison with the electrophoretic behavior of other polymers, it is concluded that
CPAM is free-draining in ESA measurements, which shows that the cylinder model is applicable. The
decreasing charge fraction thus most likely reflects a real change in the electrokinetic charge of the polymer
with increasing salt concentration.
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