Volume 8, Issue 2, April 2020, Page: 31-54
Esterification Between Citric Acid and Callistemon citrinus, Rice-Husk, Garcinia dulcis Catalysed by Citric Acid’s-H+- Monomers and Polymers Formation Mechanism
Andry Tahina Rabeharitsara, Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar
Sedraniaina Domoina Marie Esperance, Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar
Ny Idealy Elite Randriamanantena, Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar
Raïssa Faneva Mampitefa, Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar
Nambinina Richard Randriana, Chemical Process Engineering Department (E. S. P. A), Antananarivo University, Antananarivo, Madagascar
Received: Mar. 25, 2020;       Accepted: Apr. 10, 2020;       Published: Apr. 28, 2020
DOI: 10.11648/j.ajac.20200802.11      View  176      Downloads  95
Abstract
Esterification between citric acid molecules and molecules of Callistemon citrinus, rice husk and Garcinia dulcis (pulp-peel and pips) were carried out such as the citric acid molecules quantities (moles) were negligible against to these raw materials’ reactive molecules quantities (moles). Results showed generally an important initial, total conversions (after 60 minutes) of citric acids molecules which confirmed the essential role of raw materials’ aromatics molecules characterized by their alkene organic-function titrated with HF-0.00261N (Hydrofluoric acid) as support of citric acid’s protonic acid H+ catalyst (a portion of the carboxylic acids’ citric acid molecules used), support of non-ionic citric acid’s carboxylic acid (a portion of the carboxylic acids’ citric acid molecules used) and support of raw materials molecules reagents. So, the citric acid partial order of esterification of these used raw materials (Callistemon citrinus, rice husk and Garcinia dulcis (pulp-peel and pips)) with citric acid molecules were determined. Also, the brown citric acid equivalent monomers formed during esterification were calculated and their evolution were followed for all raw materials and results allowed to determine the citric acid’s protonic acid activities. In the same time, relationship between raw materials’ external specific surfaces, estimated by calculated and measured densities, and conversion or brown citric acid equivalent formed were established to conduct finally at the catalyst turnover. The variation of alkene organic-function concentration and/or quantities not only in solution but also in all by-products allowed to an ionic mechanism of these esterification with citric acid catalyzed by citric acid’s protonic acid H+ (a portion of the carboxylic acids’ citric acid molecules used) supported on all raw materials’ aromatics molecules and fiber structures in glass-flask where not only carbonic acids molecules but also hydrogens molecules gas were emitted. Finally, seeing that a non-negligible alkene organic-function quantities were titrated on all by-products, their valorization as catalytic support of citric acid molecules polymerization were carried out and a procedure constituted principally with estimation of dichloromethane and hexane insoluble/soluble products, titration with HF-0.00261N of the unsaturated organic-function in hexane soluble products and titration with NaOH-0.05N of the black citric acid equivalent quantities evolutions were established and the results confirmed the ionic mechanism of esterification with citric acid molecules during which not only carbonic gas and hydrogen gas were emitted but also new monomers and each equivalent saturated products (characterized by their globally white color and unsaturated organic-function titrated with HF-0.00261N), new polymers and poly-polymers (characterized by their globally black color and titrated with NaOH-0.05N) different to that obtained with radical mechanism catalyzed by Lewis acid sites were formed.
Keywords
Esterification, Citric Acid’s Protonic Acid H+, Catalyst, Support, Callistemon citrinus, Rice-husk, Garcinia dulcis, Hexane, Dichloromethane, Soluble Products, Insoluble Products, Monomers, Polymers
To cite this article
Andry Tahina Rabeharitsara, Sedraniaina Domoina Marie Esperance, Ny Idealy Elite Randriamanantena, Raïssa Faneva Mampitefa, Nambinina Richard Randriana, Esterification Between Citric Acid and Callistemon citrinus, Rice-Husk, Garcinia dulcis Catalysed by Citric Acid’s-H+- Monomers and Polymers Formation Mechanism, American Journal of Applied Chemistry. Vol. 8, No. 2, 2020, pp. 31-54. doi: 10.11648/j.ajac.20200802.11
Copyright
Copyright © 2020 Authors retain the copyright of this article.
This article is an open access article distributed under the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Reference
[1]
Rabeharitsara Andry Tahina, Raharilaza Paulin Merix, Randriana Richard Nambinina – Chemical Process Engineering Department (E.S.P.A), Antananarivo University – Madagascar – “Esterification Between Citric Acid and Pumpkin Pips’ Organic Molecules – Esters Hydrolysis and Esters Used as Hydrocarbons Additives” - American Journal of Applied Chemistry in Vol. 6, Issue Number 3, June 2018.
[2]
M. Laffitte, F. Rouquerol La réaction chimique Tome 2. Aspects thermodynamiques (suite) et cinétiques, 1991, Eds. Masson p. 22.
[3]
Silva AM, Kong X, Hider RC, Pharmaceutical Sciences Research Division, King’s College London, London, UK « Determination of the pKa of the hydroxyl group in the alpha-hydroxycarboxylates citrate, malate and lactate by 13C NMR: implications for metal coordination in biological systems » http://www.ncbi.nlm.nih.gov/pubmed/19288211.
[4]
Citric acid/C6H8O7 – PubChem
[5]
Gougerot-Schwartz A. “Cosmétologie et dermatologie esthétique” Encyclopedie Méd. Chir. (2000) 7p.
[6]
Sammy Eric ANDRIAMBOLA « Valorisation de l’acide citrique en polymères et en sels de mono- di- et tri-ammonium ». Mémoire de fin d’étude en vue de l’obtention du diplôme d’Ingénieur en Génie Chimique. E.S.P.A. Université d’Antananarivo. 2013.
[7]
M. Laffitte, F. Rouquerol La réaction chimique Tome 2. Aspects thermodynamiques (suite) et cinétiques, 1991, Eds. Masson p. 30.
[8]
US Department of agriculture
[9]
Razafindratsimba Ranja Lara Prisca “ Contribution à la valorization de la balle de riz en traitement des eaux” Mémoire de fin d’étude en vue de l’obtention du diplôme d’Ingénieur en Génie Chimique- GPCI IESVA Antsirabe – Université d’Antananarivo.2019.
[10]
Silos de Tourtoulen
[11]
«Garcinia dulcis (Roxb.) Kurz», Plants of the world Online, Royal Botanic Gardens, Kew, retrieved 2019-01-27
[12]
“Plants profile for Garcinia dulcis. USDA Plants Database Retrieved 2007-11-12.
[13]
Nanthaphong Khamthong and Nougpora Hutadilok-Towatana – College of Oriental Medecine, Rangsit University, Pathum Thani 12000, Thailand “ Phytoconstituents and Biological Activities of Garcinia dulcis (Clusiaceae) – Natural Product Communications in Vol. 12, Issue Number 3, 2017 P453-460.
[14]
Jean-Claude Favier, Jayne Ireland-Ripert, Carole Laussucq, Max Feinberg: «Répertoire général des aliments» - Tome 3 – Table de composition des Fruits exotiques, Fruits de cueillette d’Afrique – CRSTOM-Editions; TECDOC-Editions; INRA-Editions.
[15]
Brophy, Joseph J.; Craven, Lyndley A.; Doran, John C. (2013). Melaleucas: their botany, essential oils and uses. Canberra: Australian Centre for International Agricultural Research.
[16]
Harvey, Rod. “Bottlebrush – Genus Callistemon”. Australian National Botanic Garden. Retrieved 22 July 2015.
[17]
Rabeharitsara Andry Tahina – Rabearimihaja Phandry Nomena Ndjiva “Betacarotenes Dosage by Hydrofluoric Acid Solution and Validation of This New Process by SPC” - Chemical Process Engineering Department (E.S.P.A), Antananarivo University – Madagascar - American Journal of Applied Chemistry in Vol. 4, Issue Number 3, June 2016.
[18]
Joe S. Hughes and Barry G. Swanson “Soluble and insoluble dietary fiber in cooked common bean (phaseolus vulgaris) seeds” – Department of Food Science and Human Nutrition Washington State University, Pullman, Washington 99164-6330 – Food Microstructure, Vol.8 (1989), pp. 15-21.
[19]
Swanson BG, Hughes JS, and Rasmussen HP. “Seed microstructure: Review of water imbibition in legumes”. Food Microstructure. Vol.4 (1985), pp. 115-124
[20]
Rabeharitsara Andry Tahina – Rabemananjara Marie Nicole – Randriana Nambinina Richard “Black Citric Acid Polymer (PN) Pozzolana Activated – Na-PN-Pozzolana-CE Material Synthesis Tested As Catuonic Exchanger” - Chemical Process Engineering Department (E.S.P.A), Antananarivo University – Madagascar - American Journal of Polymer Applied Chemistry in Vol. 7, Issue Number 6, December 2019, P. 145-160.
[21]
Rabeharitsara Andry Tahina – Rovatahianjanahary Behevitra – Randriana Nambinina Richard “Pine Wood Powder Treatment To Obtain BxH+ Homogeneous Catalyst (H+/H2SO4) Supported On Its Aromatics And Polynuclear Aromatics Alkenes – Application In Citric Acid Polymerization To Black Polymers (PN)” - Chemical Process Engineering Department (E.S.P.A), Antananarivo University – Madagascar - American Journal of Polymer Science and Technology in Vol. 4, Issue Number 1, March 2018.
[22]
Rabeharitsara Andry Tahina – Rabemananjara Marie Nicole – Nambinina Richard Randriana – Haritiana Jeannelle Rakotonirina – Edouard Andrianarison – André Razafimandefitra – Baholy Robijaona “Auto-Inflammation Test Of Black Citric Acid Polymer (PN) and Fuel Oil (FO) Mixes – Coke formation” Chemical Process Engineering Department (E.S.P.A), Antananarivo University – Madagascar - American Journal of Applied Chemistry in Vol.5, Issue Number 3, June 2017.
Browse journals by subject