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Lecture_18_Kinetics - Kinetics Lect#18 100 min 1 System AX...

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Seoul National University Solid State Ionics Research Lab. Kinetics 1 2 z z A , X , e 1. System: AX 2. Mobile species: - Mobile components: A, X (chemical components) - The electrical phenomena of ionic solids cannot be appropriately described with the neutral components A and X. - Mobile charged components: Subjected to the charge neutrality condition 0 i i z c (1) (2) (3) Lect. #18 (11/29/07; 100 min)
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Seoul National University Solid State Ionics Research Lab. Kinetics 3. How are they mobile? -Via defects (via vacancy or interstitial) in its own sublattice (misplaced ions, energetically unfavorable) i i i i d d d c D c D 1 1 2 2 z z z z i A i X A , V Mobile defec , X , ts V , e , : h 2 A (charged comp.) i A  defects A V  2 X (charged comp.) i O  defects O V  1 e (charged comp.) e defects h A (neutral comp.) 1 z A 1 1 z e X (neutral comp.) 2 z X 1 2 z e
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Seoul National University Solid State Ionics Research Lab. Kinetics 4. Flux equation of mobile charged components i i i i i i J c v c B X i i i i X z F     electric driving force chemical driving force i i i i i i i i J c B = c B ( z F )  
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Seoul National University Solid State Ionics Research Lab. Kinetics 5. Transport properties and inter-relationships 5.1 Einstein equation: 5.2 Electrical conductivity: i i D B RT i i When c =0 or =0 (uniform composition) i i i i J c B z F   2 1 6 i i i where D = , self-diffusion coefficient
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Seoul National University Solid State Ionics Research Lab. Kinetics Electrochemical mobility i i i i i drift velocity unit f v v B X z F( ) orce applied  i i i i drift velocity unit force applied electrochemical v z F mo B bility u  i i i i i v B X B z F( )  1 2 1 i m s m [u ] V m V s i i i i i i J c B z F c u    
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Seoul National University Solid State Ionics Research Lab. Kinetics Partial current by the charged particles i 2 i i i i i i i i z FJ c B (z F) :Ohm's law     2 2 i i i i i i i i i i c B (z F) c (z F)u D c ( Nernst-Einstei z n equati F) RT n : o
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Seoul National University Solid State Ionics Research Lab. Kinetics 6. Transference numbers Charge carriers: 1 2 z z A , X , e Total current: Transference number: 3 3 1 1 i i i i i i ( )  3 1 i i i i t 1 2 3 ion el ionic conductivity electronic conductivity : : 1 ion el t t ion el el ion ion el ionic conductor or electrolytes electronic condu ctor or semiconductor mixed ionic electronic t t t t t conducto t r  
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Seoul National University Solid State Ionics Research Lab.
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