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Determination of Lower Acidity of Jet Fuel by Catalytic Thermometric Titration Using Paraformaldehyde as a Thermometric EndPoint Indicator

Quan Xi Zheng, Ji Xin Mao, Li Guo, Yong Liang Xin, Shi Zhao Yang, Jian Jian Zhang, Bing Hao Chen, Jian Qiang Hu, Xin Xu
Published: 20 July 2020
Progress in Petrochemical Science , Volume 3, pp 1-7; doi:10.31031/pps.2020.03.000564

Abstract: Ji Xin Mao1, Quan Xi Zheng1*, Xin Xu1,2, Li Guo1, Yong Liang Xin1, Shi Zhao Yang1, Jian Jian Zhang1, Bing Hao Chen1 and Jian Qiang Hu1* 1Department of Aviation Oil, China 2State Key Laboratory of Tribology, China *Corresponding author: Quan Xi Zheng, Department of Aviation Oil, China Jian Qiang Hu, Department of Aviation Oil, China Submission: April 07, 2020;Published: July 20, 2020 DOI: 10.31031/PPS.2020.03.000564 ISSN 2637-8035Volume3 Issue3 The effect of concentrations of titrant, delivery rates, stirring rates, and oil mass on catalytic thermometric titration for the determination of the lower acidity of jet fuel were investigated, using KOH in isopropanol and paraformaldehyde as titrant and a catalytic thermometric indicator respectively. The results show that paraformaldehyde used as a catalytic indicator exhibits strongly endothermic effects to reflect end point significantly. When the oil mass is from 10g to 30g, the titration concentration is 0.01mol/L and the delivery rate is 1.0mL/min with moderate stirring, the tested acid numbers have good reproducibility and accuracy. The linear coefficient R2 of the fitting curve is 0.995. Using benzoic acid as a standard acid with concentration of 0.0105mg KOH/g to verify the accuracy of catalytic thermometric titration, the verified acid number is 0.0115mg KOH/g and basically consistent with the actual acid number, indicating that catalytic thermometric titration has good agreement with standard potentiometric titration methods and can be used for determination of acid number of jet fuels. It can accurately determine the acid number of jet fuel as low as 0.015mg KOH/g or even lower at optimized test conditions. The procedure is fast, easy to use, accurate, and highly reproducible to measure lower acidity in jet fuel. It is very suitable for the routine process and quality control of many types of oils. Keywords: Acidity; Jet fuel; Catalytic thermometric titration; Paraformaldehyde As an important quality control index to evaluate corrosion, especially for fuel oil, aviation oil, and hydraulic oil, the acidity of oils is applied to estimate the properties and deterioration of oils during usage and storage [1-3], which is determined with the standard methods based either on visual indicators titration or potentiometric titration [4-7]. However, accuracy of visual titration is strongly influenced by the skills and color perception of the analyst, and especially differential color perception of analysts is considerable for coloured oils. Potentiometric titration, especially for oils containing trace weak polyacids, is subject to the noxious influence of the sample solutions and is always unreliable because of the weak change of potential during acid-base neutralization titration, which results in difficult detection of end-point and repeatability. In order to achieve more fast and efficient determination of the end-point in titrations, there is increasing attention for a simple, fast, accurate, and precise automatic titrimetric operation that is substantially independent of analysts’ skills and suitable for routine process and quality control. As a new method, catalytic thermometric titration has several attractive features: [1] the apparatus is simple, and all that required is a temperature measuring probe such as a thermometer or a thermistor as the sensing element; [2] the thermometric probes are inert to most solutions, and temperature changes in highly colored can be detected easily; [3] the range of indication reaction is unlimited because all of reactions are accompanied with temperature changes, the magnitude of which can be adjusted by changing reagents’ concentrations [8-11]. The basic principle of this method is catalytic initiation of an exothermic or endothermic reaction with an excess of titrant, as a consequence, the end-point can be indicated by obvious temperature changes of the solution [8-15]. It has been successfully applied for determining acidic substances in aluminum ion concentration of waste water and vegetable oils [16-19]. However, as so far, there are few reports on application of catalytic thermometric titration on lower acidity of jet fuels. When small amounts of weak acidic species are titrated in nonaqueous solution with a titrant of strong alkali, the heat produced from the neutralization reactions may be quite small and easy to be confused by solvent evaporation and the mixing heat of the titrant with sample solution [4-7]. If the special thermometric indicator is added to sample solution, excess hydroxide ions would react quickly with them in endothermic or exothermic reactions, the end-point can be easily determined by temperature increase or decrease of the solution [20,21]. However, practical experience has demonstrated that the endpoint in thermometric titration showed excessive rounding, with consequent loss of precision and accuracy for some oils with lower acidity, such as aviation oil, hydraulic oil and fuel oils. Many studies have shown that titration error or the sharpness of the endpoint can be related to the concentration and delivery rate of titrant, volumes, and types of thermometric indicator [22-27]. In our previous studies [9,10], the trace water in jet fuels, as well as the acidity of several coloured oils, could be accurately and rapidly determined by catalytic thermometric titration using the mixture of acetone and chloroform as the end-point indicator. In this paper, we report herein our results on the determination of the lower acidity of jet fuels with catalytic thermometric titration employing paraformaldehyde as the end-point indicator, which exhibits strongly endothermic effects to reflect end point significantly and can determinate much more lower acidity than ASTM thermometric titration, and compared with potentiometric titration, the accuracy and repeatability of the thermometric titration is further investigated. Materials Paraformaldehyde, potassium hydroxide...
Keywords: Concentration / Oils / Delivery Rate / Aviation Oil / Thermometric Titration Using / Thermometric Indicator / endpoint in thermometric

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