KINETICS OF STARCH NITRATION PROCESS WITH NITRIC ACID

Authors

DOI:

https://doi.org/10.15421/jchemtech.v30i3.262889

Keywords:

nitration; kinetics of processes; starch; starch nitrate; nitric acid; dissolution

Abstract

This article is devoted to an experimental study of the process of starch nitration with nitric acid (its mixture with water). This nitration method has a number of advantages over the industrial method based on using nitric-sulfuric acid mixture. The aim of this work is to determine the kinetic regularities of nitration process necessary to justify its technological regimes. The research methodology consisted in treating starch with acid and determining the change of nitrogen content in resulting starch nitrate over time at different parameters of nitration process. The results of the study are shows that process of starch nitration with nitric acid proceeds at the same time with dissolution and includes two stages: fast, associated with the dissolution of amorphous substances of starch grains, and slow, associated with the dissolution of their crystalline regions. A nitrogen content in starch nitrate at second stage takes on a close to constant value due to incomplete dissolution of the most perfect crystal fragments. A study shows influence of nitration process parameters on its kinetics. In logarithmic coordinates, the kinetic dependences of nitration are linearize with a break in the transition from the first to the second stage, which allow using a power function as their mathematical description. The findings of experimental data processing allowed to obtain empirical equations for calculating kinetics of nitration process.

References

Liu, J. (2019). Nitrate esters chemistry and technology. Singapore: Springer Singapore.

https://doi.org/10.1007/978–981–13–6647–5

Department of the Army Technical Manual Military Explosives. (1995). TM9 – 1300 – 214. U. S. Government Printing Office, 388–421/140013.

Caesar, G. V. (1958). Starch nitrate. Advances in Carbohydrate Chemistry, 13, 331–345.

https://doi.org/10.1016/S0096–5332(08)60360–4

Skryhan, K., Gurrieri, L., Sparla, F., Trost, P., Blennow, A. (2018). Redox regulation of starch metabolism. Frontiers in plant science, 9, 1344.

https://doi.org/10.3389/fpls.2018.01344

Li, C., Wu, A., Yu, W., Hu, Y., Li, E., Zhang, C., Liu, Q. (2020). Parameterizing starch chain-length distributions for structure-property relations. Carbohydrate polymers, 241, 116390.

https://doi.org/10.1016/j.carbpol.2020.116390

Diop, A., Talouba, I. B., Balland, L., Mouhab, N. (2019). Thermal characterization of a biodiesel nitration: Bio-additive’s synthesis by calorimetric methods. Thermochimica Acta, 673, 138-146. https://doi.org/10.1016/j.tca.2019.01.024

Zhang, K., Budinská, A., Passera, A., Katayev, D. (2020). N-Nitroheterocycles: Bench-stable organic reagents for catalytic ipso-nitration of aryl-and heteroarylboronic acids. Organic letters, 22(7), 2714–2719. https://doi.org/10.1021/acs.orglett.0c00671

Marchenko, G. N. (Ed.). (2000). [Physico–chemical bases and instrumental design of technology for the pyroxylin gunpowders production. (Vol.1)]. Kazan, Russian Federation: FEN (in Russian).

Lukashov, V. K., Sereda, V. I., Tishchenko, S. D. (2019). [Technological aspects of nitration of starch with nitrogen–sulfur acid mixture]. Journal of Chemistry and Technologies, 27, 2, 169–178 (in Russian). https://doi.org/10.15421/081918

Panchenko, O. A., Titova, O. I. (2005). [Problems and achievements in the production of cellulose nitrates]. Khmiya rastitelʹnogo syrʹya. – Chemistry of plant raw materials, 3, 85–88 (in Russian).

Kuchurov, I. V., Zharkov, M. N., Fershtat, L. L., Makhova, N. N., Zlotin, S. G. (2017). Prospective symbiosis of green chemistry and energetic materials. Chem. Sus. Chem., 10(20), 3914-3946.

https://doi.org/10.1002/cssc.201701053

Murray, J. I., Brown, D. B., Silva Elipe, M. V., Caille, S. (2021). Hazard Evaluation and Safety Considerations for Scale-Up of a Fuming Nitric Acid Mediated Nitration of Aryl Boronic Acids. Organic Process Research & Development, 26(3), 657–660. https://doi.org/10.1021/acs.oprd.1c00131

Wu, J. W., Zhang, P., Guo, Z. X. (2021). Nitration of deactivated aromatic compounds via mechanochemical reaction. Tetrahedron Letters, 72, 153087. https://doi.org/10.1016/j.tetlet.2021.153087

Veretenikov, E. A. (2000). Nitration of chlorobenzene with nitric acid: reaction kinetics and development of a method for obtaining nitrochlorobenzene. (PHD dissertation).https://viewer.rusneb.ru/ru/000199_000009_000252728

Zimmermann, W., Muhldorf. K., Gustav, S., Reinhardt, L. (1961). US Pat. 2995549. Essen, Germany. Wasag–Chemie Aktiengesellschaft.

Grageroff, I. A. (1959). US Pat. 2883376. New York, USA. Amoretty, V. A.

Ostrovsky, V.A., Enin, A. S., Boyko,L. N., Trifonov, R. E., Popova, E. A., Pavlyukova, Yu. N. (2016). [Kinetics and mechanism of nitration of 1–phenyl–5–methyltetrazole in the HNO3–H2SO4 system]. Zhurnal organicheskoy khimii. – Journal of Organic Chemistry, 52, 11, 1679–1685 (in Russian).

Yudin, N.V., Kushtaev, A. A., Zbarsky, V. L. (2007). [Nitration kinetics of 4–hydroxy–6–oxo–2–methylpyrimidine in sulfuric–nitric acid mixtures]. Uspekhi v khimii i khimicheskoy tekhnologii. – Advances in chemistry and chemical technology, 5, 73, 28–30(in Russian).

Golod, E. L. (2006). [Kinetics and mechanism of nitration of polynitroalkanes] / Ros. khim. zh. (ZH. Ros. khim. ob–va im. D.I. Mendeleyeva). – Ros. chem. j. (J. of Russian Chemical Society named after D.I. Mendeleev), 50, 3, 115–123 (in Russian).

Stovbun, S. V., Nikolsky, S. N., Melnikov, V. P., Mikhaleva, M. G., Litvin, Ya. A., Shchegolikhin, A. N., Zlenko, D. V., Tverdislov, V. A., Gerasimov, D. S., Rogozin, A. D. (2016). [Chemical physics of cellulose nitration]. Khimicheskaya fizika. – Chemical Physics, 35, 4, 20–35 (in Russian).

https://doi.org/10.7868/S0207401X16040117

Repin, V.B., Balyberdin, A. S., Makhotkin, A. F., Sharafislamov, F. Sh. (2013). [Modeling the influence of the initial degree of substitution of cellulose nitrates on the process of polymer swelling in nitric acid]. Vestnik Kazanskogo gosud. tekhnol. un–ta. – Bull. Kazan State technol. University, T. 35, 4, 129–132 (in Russian).

Mikhailov, Yu. M., Romanova, L. B., Darovskikh, A. V., Barinova, L. S. (2019). [Study of the process of nitration of hyperbranched polyglycidols]. Zhurnal prikladnoy khimii. – Journal of Applied Chemistry, 92, 3, 401–408 (in Russian).

Sullivan, F., Simon, L., Ioannidis, N., Patel, S., Ophir, Z., Gogos, C., Jaffe, M., Tirmizi, S., Bonnett, P., Abbate, P. (2018). Nitration kinetics of cellulose fibers derived from wood pulp in mixed acids. Industrial and Engineering Chemistry Research, 57, 6, 1883–1893. https://doi.org/10.1134/S0044461819030162

Nikolsky, S. N., Zlenko, D. V., Melnikov, V. P., Stovbun, S. V. (2019) The fibrils untwisting limits the rate of cellulose nitration process. Carbohydrate Polymers, 204, 45, 232–237.

https://doi.org/10.1016/j.carbpol.2018.10.019

Tishchenko, S. D., Lukashov, V. K. (2018). [Development of a method for determining the content of nitrogen in nitrate of starch]. «Education, science and production: development and prospects» Abstracts of III All–Ukrainian scientific and methodological conference, 2–30 (in Ukrainian).

Klenin, V.I., Fedusenko, I. V., Klokhtina, Yu. I. (2003). [Structure of solutions of crystallizing polymers. Influence of dissolution methods]. Vysokomolekulyarnyye soyedineniya. – High molecular compounds, 45 (A), 12, 2054–2062 (in Russian).

Colombo, M., Michels, L. R., Teixeira, H. F., Koester, L. S. (2022). Flavonoid delivery by solid dispersion: a systematic review. Phytochem. Rev., 21, 783–808 https://doi.org/10.1007/s11101-021-09763-3

Ibrahim, A., Daood, H. G., Égei, M., Takács, S., Helyes, L. (2022). A Comparative Study between Vis/NIR Spectroradiometer and NIR Spectroscopy for the Non-Destructive Quality Assay of Different Watermelon Cultivars. Horticulturae, 8(6), 509. https://doi.org/10.3390/horticulturae8060509

Published

2022-10-31