Citation: Lixu LEI. Route map for 100% completion of solid-state reactions[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(1): 182-196. doi: 10.11862/CJIC.20230375 shu

Route map for 100% completion of solid-state reactions

Lixu LEI ^,

School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China

Corresponding author: Lixu LEI, Lixu.lei@seu.edu.cn
Received Date: 11 October 2023
Revised Date: 18 December 2023

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Although thermodynamics tells us that solid-state reactions without solution will not stop until 100% completion, they may stop far before the exhaust of reactants because of the difficulty of mass transfer among the solid particles. To solve this problem, the author has publicized a novel technique called the less solvent solid-state reaction (LSR), which makes small parts of the solid reactants dissolve and react in a small amount of solvent, thus making the reaction proceed faster and more complete in a stirred reactor. Consequently, LSR could make some of the industrial processes greener. By using numerical calculating and charting of its Gibbs energies with respect to its extent of reaction, this paper proves that (ⅰ) an LSR is a combination of a reaction thermodynamically equivalent to a solution-free solid-state reaction in the middle and semi-solution reactions at both ends. Although the LSR does reach an equilibrium eventually, it goes much further to the 100% completion than the solution reaction; if the solvent is removed gradually at the ending period of the reaction, the LSR can be pushed to 100% completion; (ⅱ) for the consecutive reactions, it is possible to get the sole intermediate product by controlling the molar ratio of the reactants as its stoichiometric ratio; (ⅲ) it is possible to make an LSR with near-zero negative Δ_rG_m^Θ 100% completed by using more solvent or using the solid products as seeds; (ⅳ) it is the dissolution speed of reactants, the speed of chemical reaction, and crystallization speed of products, rather than the solubilities of the substances that control the speed of an LSR. Measures for 100% completion and selection of LSRs of non-spontaneous or coexisting competitive reactions are also discussed.
- less solvent solid-state reaction,
- solid-state reaction,
- solution reaction,
- Gibbs energy,
- greener chemistry,
- 100% conversion
1. [1]
  XIN X Q, ZHENG L M. Solid state synthetic reaction at low heating temperatures[J]. University Chemistry, 1994,9(6):1-7.
2. [2]
  Kaupp G. Organic solid-state reactions with 100% yield[J]. Top. Curr. Chem., 2005,254:95-183.
3. [3]
  Toda F. Solid-state organic chemistry: Efficient reactions, remarkable yields, and stereoselectivity[J]. Acc. Chem. Res., 1995,28(12):480-486. doi: 10.1021/ar00060a003
4. [4]
  YANG C F, LIU W, LIN S Z, XU Z G, CHEN T, WEI T Q, LI B B. Application of the solvent-free method in asymmetric addition reaction of organozinc with aldehyde or ketone[J]. Chinese Journal of Synthetic Chemistry, 2016,24(5):464-468.
5. [5]
  Sarkar A, Santra S, Kundu S K, Hajra A, Zyryanov G V, Chupakhin O N, Charushin V N, Majee A. A decade update on solvent and catalyst-free neat organic reactions: A step forward towards sustainability[J]. Green Chem., 2016,18(16):4475-4525. doi: 10.1039/C6GC01279E
6. [6]
  LEI L X, ZHOU Y M. Solvent-free or less-solvent solid state reactions[J]. Prog. Chem., 2020,32(8):1158-1171.
7. [7]
  JIANG H L, LIU C, LEI L X. Ammonium carnallite prepared from a less-solvent solid state reaction[J]. University Chemistry, 2021,36(12)2102008.
8. [8]
  Wang H L, Liu C, Jiang H L, Guo Z L, Zheng Y P, Qi Q, Lei L X. A laboratory experiment on preparation of 3PbO·PbSO₄·H₂O using less solvent solid state reaction for undergraduate students[J]. Educ. Chem. Eng., 2023,43:92-99. doi: 10.1016/j.ece.2023.02.003
9. [9]
  Guo Z L, Ma L, Wang H L, Lai C G, Ji S, Sun J, Zhang D H, Nie L, Lei L X. Less solvent solid state reaction of sodium sulfite and sulfur. Inorg[J]. Chem. Commun., 2023,151110619.
10. [10]
  Mason P E, Schewe H C, Buttersack T, Kostal V, Vitek M, McMullen R S, Ali H, Trinter F, Lee C, Neumark D M, Thürmer S, Seidel R, Winter B, Bradforth S E, Jungwirth P. Spectroscopic evidence for a gold-coloured metallic water solution[J]. Nature, 2021,595(7869):673-676. doi: 10.1038/s41586-021-03646-5
11. [11]
  Feng D F, Kevan L. Theoretical-models for solvated electrons[J]. Chem. Rev., 1980,80(1):1-20. doi: 10.1021/cr60323a001
12. [12]
  HU C J, MA J. An overview of solvated electrons: recent advances[J]. Journal of Radiation Research and Radiation Processing, 2021,39(1):1-14.
13. [13]
  Kamyshny A. Solubility of cyclooctasulfur in pure water and sea water at different temperatures[J]. Geochim. Cosmochim. Acta, 2009,73(20):6022-6028. doi: 10.1016/j.gca.2009.07.003
14. [14]
  Pavlov D. Lead-acid batteries-science & technology. 2nd ed. Amsterdam: Elsevier, 2017.
15. [15]
  Steele I M, Pluth J J, Richardson Jr J W. Crystal structure of tribasic lead sulfate (3PbO·PbSO₄·H₂O) by X-rays and neutrons: An intermediate phase in the production of lead acid batteries[J]. J. Solid State Chem., 1997,132(1):173-181. doi: 10.1006/jssc.1997.7440
16. [16]
  Moseley P T, Rand D A J. Neutron diffraction enables the formula of 'tribasic lead sulfate' to be corrected[J]. J. Energy Storage, 2023,65107423. doi: 10.1016/j.est.2023.107423
17. [17]
  WANG H L. Researches on a few less solvent solid state reactions. Nanjing: Southeast University, 2023.
18. [18]
  Fogel N, Lin C C, Ford C, Grindstaff W. Behavior of ammonium tetrachlorocobaltate(Ⅱ) on hydration[J]. Inorg. Chem., 2002,3(5):720-726.
19. [19]
  Li C X, Lei L X, Xin X Q. Synthesis of M(biN)_nCl₂ by solid-solid reactions[J]. Chin. Sci. Bull., 1994,39:349-350.
20. [20]
  Lei L X, Wang Z X, Xin X Q. The solid state reaction of CuCl₂·2H₂O and 8-hydroxylquinoline[J]. Thermochim. Acta, 1997,297(1/2):193-197.
21. [21]
  Lei L X, Xin X Q. Solid state synthesis of a new compound Cu(HQ)Cl₂ and its formation reaction[J]. Thermochim. Acta, 1996,273:61-67. doi: 10.1016/0040-6031(95)02683-5
22. [22]
  Lei L X, Xin X Q. Stepwise reaction of CuCl₂·2H₂O with 2,2'-bipyridyl in the solid state[J]. J. Solid State Chem., 1995,119(2):299-303. doi: 10.1016/0022-4596(95)80044-P
23. [23]
  Lei L X, Jing S, Walton R I, Xin X Q, O'Hare D. Investigation of the solid state reaction of FeSO₄·7H₂O with 1,10-phenanthroline[J]. J. Chem. Soc. Dalton Trans., 2002(18):3477-3481. doi: 10.1039/b205625a
24. [24]
  WANG H L, GUO Z L, LIU B Z, WU Z Z, LEI L X. Less solvent solid-state consecutive coordination reaction of copper chloride[J]. Chinese J. Inorg. Chem., 2023,39(8):1536-1544.
25. [25]
  Speight J G. Lange's Handbook of Chemistry. 16th ed. New York: MCGRAW-HILL, 2005.
26. [26]
  Verduzco-Oliva R, Gutierrez-Uribe J A. Beyond enzyme production: Solid state fermentation (SSF) as an Alternative approach to produce antioxidant polysaccharides[J]. Sustainability, 2020,12(2)495. doi: 10.3390/su12020495
27. [27]
  WANG N N, WANG G W. Investigation into condensed-matter organic synthesis under mechanical milling conditions[J]. Prog. Chem., 2020,32(8):1076-1085.
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