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Progress in Chemistry 2020, Vol. 32 Issue (8): 1158-1171 DOI: 10.7536/PC200433 Previous Articles   Next Articles

• Review •

Solvent-Free or Less-Solvent Solid State Reactions

Lixu Lei1,*(), Yiming Zhou2   

  1. 1. School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China
    2. School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China
  • Received: Revised: Online: Published:
  • Contact: Lixu Lei
  • About author:
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According to thermodynamics, solid state reactions will generally proceed to their 100% completion once they start; however, they may stop at the equilibrium state in case that there is a solid solution with continuously changing concentration. Solid state reactions also have the following characteristics:(1) they could produce stereoselective products;(2) the particle size of the products could be very small(nano-sized);(3) there is the lowest temperature for the reaction to be initiated. Here, it is particularly pointed out that a little solvent can be employed to accelerate solid state reactions with consequent safety and effectivity, but not the equilibrium; also, the solvent can make the solid mixture more fluidized, thus the mass transportation can be speeded up by a proper blender. In addition, solid state reactions can be used to assemble materials step by step, since any complex reactions can be decomposed to a series of reactions of two reactants. Consequently, studies on solid state reactions can lead to greener chemical processes. All those are demonstrated in this paper with solid state coordination reactions, which are the reactions of solid inorganic metal compounds and solid organic or inorganic ligands. The solid state coordination reactions are well known that they take place at near room temperature up to 300 ℃ without the help of solvents, just like the solid state organic reactions.

Contents

1 Introduction: how to develop a greener chemical process

1.1 Definition of greener chemical process

1.2 Greener chemical processes based on solid-state reactions

1.3 Brief history of solid-state coordination reactions

2 Physical chemistry of solid-state reactions

2.1 Thermodynamics of solid-state reactions

2.2 Thermodynamics of less solvent reactions

2.3 Kinetics of solid-state reactions

3 Syntheses based on solid-state coordination reactions

3.1 Syntheses based on non-solvation

3.2 Syntheses of nanoparticles based on diffusion difficulty in solids

4 Less solvent reactions and their applications in industrialization of solid-state reactions at near room temperatures

4.1 Examples of a few less solvent reactions

4.2 Problems in industrialization of solid-state reactions at near room temperatures

5 Conclusion and outlook

Key words: condensed state chemistry, solid state coordination reaction, less solvent reaction, green chemistry
Fig.1 The relationship of Gibbs free energy of the system to the amount of solvent used. The blue curve at the bottom is for the solution reaction, in which there is an equilibrium point; the red straight line at the top is for solvent-free solid state reaction, where there will be no equilibrium; and the green spoon-like curve in the middle correspond to the less solvent reaction, which may follow the dashed line if the solvent is removed at the end of the reaction
Fig.2 The diffusion coefficients of silver for bulky dif-fusion Db, grain boundary diffusion Dg and surficial dif-fusion Ds[16]
Fig.3 Data from the reaction of CuCl2·2H2O and 2,2'-bipyridyl (adapted from ref[43]). A: XRD pattern of (a) the reaction mixture of 1∶2 molar ratio when it aggregated, in which diffraction peaks of Cu(bipy)Cl2 can be found; (b) the final product; B: DSC curve of the 1∶1 reaction; C: DSC curve of the 1∶2 reaction; and D: DSC curves of the 1∶1 reaction (a) and Cu(bipy)Cl2 and bipy in 1:1 molar ratio
Fig.4 Data of the solid state reaction of FeSO4·7H2O and o-phenanthroline[45]. A: XRD patterns of (a) phen;(b)FeSO4·7H2O;(c)Fe(H2O)3(phen)SO4;(d)Fe(H2O)3(phen)SO4·5H2O;B:XRD patterns of the initial reaction mixture of Fe(H2O)3(phen)SO4·5H2O and phen in 1∶2 molar ratio (a) and the final (b);C:The EDXRD of the solid state reaction of FeSO4·7H2O and phen in 1∶1 molar ratio as a function of time;D:The intensity of main XRD peak as the function of time at different temperatures
Fig.5 The changes of particles of reactants and products during a solid state reaction
Fig.6 The framework of 2 ~ 7 nuclear clusters formed from the reaction of (NH4)2MoS4 and CuX(X = Cl, Br, I, CN, SCN)[49, 52]
Fig.7 The octahedral Mg(H2O)62+, Cl-(green ball) and NH4+ (blue ball) in crystals of (a)[Mg(H2O)6]Cl2 and (b) NH4[Mg(H2O)6]Cl3
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