Determination of Carbonyl Groups in Pyrolysis Bio-oils Using Potentiometric Titration: Review and Comparison of Methods

Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. Some compounds such as carbohydrates are not measured by the traditional method (modified Nicolaides method), resulting in low estimations of the carbonyl content. Furthermore, we have shown that reaction completion for the traditional method can take up to 300 h. The new method presented here (the modified Faix method) reduces the reaction time to 2 h, uses triethanolamine (TEA) in the place of pyridine, and requires a smaller sample size for the analysis. Carbonyl contents determined using this new method are consistently higher than when using the traditional titration methods.