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For each analysis using coulometric titration and after preliminary studies,

chitosan (0.20~0.25 g) was dissolved in 25.00 mL of 0.10 mol/L standard

hydrochloric acid aqueous solution, stirred about 1 hour at 25 C, and diluted
to 100 mL in a volumetric flask. Then 5.00 mL sample solution was accurately
pipetted to 50 mL of 1.0 mol/L KCl supporting electrolyte. Double platinum
electrode (2 20 mm 30 mm, Jiangsu analysis instrument factory, China),
platinum wire auxiliary electrode ( 1 mm 120 mm, Jiangsu analysis
instrument factory, China) and E-201-C composite glass electrode (REX,
Shanghai) were inserted into the supporting electrolyte, and pure nitrogen gas
was purged into the solution. The electrolysis was started by clicking on the start
button and stopped automatically at the titration end-point. The DD (chitosan)
could be calculated by the software according to the electrolytic time, the
intensity of constant current and the mass of chitosan (after removing water).
The calculation formulae are as follow:
investigated, such as the composite glass electrode (CGE) (REX, Shanghai), the
electrode (GE) (REX, Shanghai)-saturated calomel electrode (SCE) (REX, Shanghai),
the tungsten electrode (TE) (RUOSULL, Shanghai)-antimony electrode (AE)
(RUOSULL, Shanghai) and the antimony electrode-saturated calomel electrode.
Selection of indicating electrode couples

Indicating electrode couples are very important for indicating system of

coulometric titration. They should have a quick response to the change of H+
and the obvious titration jump of pH. Four different indicating electrode couples
Since all four electrodes have similar characteristics,
the composite glass electrode is selected as the indicating electrode couple in this
study due to its simplicity and easy to use.
Selection of supporting electrolytes
and their concentrations
The supporting electrolyte provides the necessary ions
for the current flow through
the sample solution. Na2SO4, K2SO4, KNO3 and KCl
were considered as supporting
electrolytes. After investigation of the current
efficiency during electrolysis, KCl was
selected as the supporting electrolyte.
1.0 mol/L
KCl was chosen as supporting electrolyte solution.

Selection of Intensity of constant current

If the current intensity is too high, the time of titration will be sharply shortened,
and the current efficiency will be unable to reach 100%, resulting in low accuracy
the results. On the other hand, when the current intensity is too low, the time of

titration will be too long. Therefore, 15.00 mA is selected as the intensity of

electrolysis current in this research to ensure the time of titration is about 400 s,
the system accomplished titration within 7 min.
Selection of coulometric titration end-point

The sample solution is the mixture of strong acid and weak

acid because the sample
was dissolved in the excessive hydrochloric acid standard
solution. When the residual
hydrochloric acid standard solution is titrated, it is
necessary to know the titration
essence for the determination of the titration end-
at pH 3.80, thus this point is used as the titration end-point
in the solution.
The results using coulometric titration method for the determination of the
degree of deacetylation of chitosan show good agreement with the values obtained by
1H NMR method. The maximal discrepancy is found to be only 0.8% in the outcomes,
while large discrepancies are shown between the result of 1H NMR and other methods,
indicating that the coulometric titration has good accuracy. Also, the method
robustness for DD (chitosan) determination was considered by the research. The
samples were measured by different testing environment and all samples were
prepared freshly daily. The results are presented in the Table 4. The standard
deviations from coulometric titrations are below 0.5% and there are no obvious
discrepancy in the comparison between different occasions, which reveals promising
precision in this method and shows it possesses better robustness.