Differentiation between phenol- and amino-substances in voltammetry determination of synthetic antioxidants in oils

The paper describes a method of voltammetric determination of antioxidants in lubricating oils developed with the use of Linear Sweep Voltammetry (LSV) and Fast Scan Differential Pulse Voltammetry (FSDPV). Experimental conditions have been found for simultaneous determination of phenol-based antioxidants and amino-antioxidants: the phenols can be electrochemically oxidized using the polarisation of gold disc electrode (AuDE) in the potential range of 0–1400 mV in 0.2 M H₂SO₄ in the presence of ethanol and acetonitrile at the ratio of 3:1. Secondary aromatic amines can be determined directly in this supporting electrolyte; the presence of phenolic antioxidants does not interfere with this analysis. On the other hand, secondary aromatic amines interfere with the determination of phenolic substances; therefore, the amines present have to be eliminated in a suitable way. A procedure for masking the aromatic amines using their reaction with nitrous acid has been suggested and optimised. The nitrosamines thus formed can be used for sensitive and selective determination of amino-antioxidants by means of cathodic reduction on the hanging mercury drop electrode (HMDE) using Fast Scan Differential Pulse Voltammetry. The method was applied in analysis of real samples of lubricating oils.