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Geoffrey A. Ozin
Materials Chemistry and Nanochemistry Research Group, Chemistry
Department, 80 St. George Street, University of Toronto, Toronto,
Ontario, Canada M5S 3H6
CnK
K(g)
e- transfer K+(ads)
K(ads)
e-
K+
e- repulsion between sheets K+ migration -
insertion
a = m(t)/m() = 1 - exp[k(t-t)]n
a = m(t)/m()
Depletion
Incubation t Growth
t
CLASSIFYING SOLID STATE REACTIONS
Gas
Solid
Solid + Gas Solid Product
Cu + AgCl CuCl + Ag
Et2O
R Cl
R-Cl Mg
Et2O OEt2
RCl R Cl
Mg Mg Mg(0) Mg Mg(II) Mg Mg Mg Mg Mg Mg Mg Mg Mg Mg Mg Mg Mg
Mg2+
Single crystals of
MgO, Al2O3
t=0 MgO Al2O3
x/4
MgAl2O4 new
3x/4 product layer
thickness x
FACTORS INFLUENCING REACTIONS OF SOLIDS
Structural considerations
Reaction mechanism
O
y
x
hcp O2-
a-Al2O3
CORUNDUM
CRYSTAL
STRUCTURE
Oh BLOCK
REPRESENTATION
SPINEL CRYSTAL STRUCTURE BLOCK REPRESENTATION
ccp O2-, Mg2+ 1/8 Td, Al3+ 1/2 Oh
ARCHETYPE DIRECT SOLID STATE REACTION
QUESTIONS TO ASK
Interfacial linear growth rates 3 : 1 ???
x2 = kt
ARCHETYPE DIRECT SOLID STATE REACTION
O
y
x
RUTILE CRYSTAL STRUCTURE
x
PEROVSKITE CRYSTAL STRUCTURE
A
PEROVSKITE CAMELEON: DEFECTS AND NON-
STOICHIOMETRY CONTROL STRUCTURE-
PROPERTY-FUNCTION-UTILITY RELATIONS
SrxLa1-xMnO3 x control e-/oxide ion conductor - solid oxide fuel cell cathode
NiF2
KF
KF
NiF2
KF
KF
NiF2
SHAPE, SIZE AND DEFECTS ARE EVERYTHING!