The structure of aqueous solutions of some dihydrogen orthophosphates by laser Raman spectroscopy

Cerreta, Michael K.; Berglund, Kris A.

doi:10.1016/0022-0248(87)90048-0

Cited by 103 publications

(72 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…In other words, dimer clusters may be the growth units in crystal growth, and they can polymerize further within the solid-liquid surface and form polymer clusters. This conclusion is in agreement with the suggestion by Cerreta and Berglund [5].…”

Section: Resultssupporting

confidence: 94%

“…Furthermore, Raman measurement does not damage the interface structure and can be used for in situ inspection of the kinetic processes within the interface boundary layer. Privious Raman spectroscopic studies on interface features of KDP crystals dealt with the assignment of the internal frequency of anions and estimated the anionic association [3][4][5]. Nevertheless, as far as we are aware, the kinetics of cluster formation obtained from spectroscopic studies have not been reported.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Cluster Formation in Solid-Liquid Interface Boundary Layers of KDP Studied by Raman Spectroscopy

Xia

Sun

et al. 2001

phys. stat. sol. (a)

View full text Add to dashboard Cite

The cluster formations in solid-liquid interface boundary layers of KDP crystals have been studied by Raman spectroscopy and ab initio cluster calculations with the density-functional theory. The calculations are made on H 2 PO 4 , H 4 P 2 O 8 , and H 4 P 4 O 16 clusters, which model the cluster structure in different growth layers. Excellent agreement has been achieved between vibrational frequencies predicted by theory and those observed in experiments. The present results also show that the desolvation process of polymer clusters takes place within the characteristic boundary layers. The growth unit of crystal growth is identified as H 4 P 2 O 8 dimer cluster.

show abstract

Section: Resultssupporting

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Cluster Formation in Solid-Liquid Interface Boundary Layers of KDP Studied by Raman Spectroscopy

Xia

Sun

et al. 2001

phys. stat. sol. (a)

View full text Add to dashboard Cite

show abstract

“…5c). This will be most efficient in the conformation that allows double, bidentate hydrogen bond formation between two complexes, as suggested for protonated phosphate groups in solution 35 . This explains the reaction-limited nature of the aggregation process.…”

Section: Resultsmentioning

confidence: 99%

Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate

et al. 2013

View full text Add to dashboard Cite

Despite its importance in many industrial, geological and biological processes, the mechanism of crystallization from supersaturated solutions remains a matter of debate. Recent discoveries show that in many solution systems nanometre-sized structural units are already present before nucleation. Still little is known about the structure and role of these so-called pre-nucleation clusters. Here we present a combination of in situ investigations, which show that for the crystallization of calcium phosphate these nanometre-sized units are in fact calcium triphosphate complexes. Under conditions in which apatite forms from an amorphous calcium phosphate precursor, these complexes aggregate and take up an extra calcium ion to form amorphous calcium phosphate, which is a fractal of Ca 2 (HPO 4 ) 3 2 À clusters. The calcium triphosphate complex also forms the basis of the crystal structure of octacalcium phosphate and apatite. Finally, we demonstrate how the existence of these complexes lowers the energy barrier to nucleation and unites classical and non-classical nucleation theories.

show abstract

“…1 Other studies have suggested the presence of hydrogen-bonded polymerlike species in several dihydrogen orthophosphates, and their implication in crystallization and fast directional growth has been discussed. 2 Prenucleation clusters during crystallization of glycine have also been detected with a combination of NMR, and x-ray and neutron scattering methods. 3 Recently, analytical ultracentrifugation and ion-selective electrode data have provided evidence of large ion clusters in unsaturated solutions of calcium carbonate.…”

Section: Introductionmentioning

confidence: 99%

Microscopic mechanism of nanocrystal formation from solution by cluster aggregation and coalescence

Hassan

2011

The Journal of Chemical Physics

View full text Add to dashboard Cite

Solute-cluster aggregation and particle fusion have recently been suggested as alternative routes to the classical mechanism of nucleation from solution. The role of both processes in the crystallization of an aqueous electrolyte under controlled salt addition is here elucidated by molecular dynamics simulation. The time scale of the simulation allows direct observation of the entire crystallization pathway, from early events in the prenucleation stage to the formation of a nanocrystal in equilibrium with concentrated solution. The precursor originates in a small amorphous aggregate stabilized by hydration forces. The core of the nucleus becomes crystalline over time and grows by coalescence of the amorphous phase deposited at the surface. Imperfections of ion packing during coalescence promote growth of two conjoint crystallites. A parameter of order and calculated cohesive energies reflect the increasing crystalline order and stress relief at the grain boundary. Cluster aggregation plays a major role both in the formation of the nucleus and in the early stages of postnucleation growth. The mechanism identified shares common features with nucleation of solids from the melt and of liquid droplets from the vapor.

show abstract

The structure of aqueous solutions of some dihydrogen orthophosphates by laser Raman spectroscopy

Cited by 103 publications

References 45 publications

Cluster Formation in Solid-Liquid Interface Boundary Layers of KDP Studied by Raman Spectroscopy

Cluster Formation in Solid-Liquid Interface Boundary Layers of KDP Studied by Raman Spectroscopy

Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate

Microscopic mechanism of nanocrystal formation from solution by cluster aggregation and coalescence

Contact Info

Product

Resources

About