Lecture 1 - Kinetic Theory of Gases.pdf

Lecture 1 - Kinetic Theory of Gases.pdf - Thermodynamics vs...

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Thermodynamics vs Kinetics Chemical Reaction or Biological Process: (Thermo, 107A) (Kinetics, 107B) Thermodynamics predicts how far a rxn proceeds (K eq ). K eq depends on stability of product vs reactant ( G°). Kinetics measures how fast the rxn goes (k f and k rev ). Rate (k f ) depends on barrier height (E a ). C(s) diamond C(s) coal B A Time Conc Rxn coordinate Free Energy A B E a A B k f k rev K eq ~ 10 4 1/k f ~ 10 5 yrs A B k f k rev Glycolysis (glucose pyruvate + NADH) Protein phosphorylation (R + ATP R-P + ADP) Dephosphorylation (R-P + H 2 O R + P i ) ATP hydrolysis (ATP + H 2 O ADP + P i ) ܭ ௘௤ ൌ ሾܤሿ ሾܣሿ ൌ ݇ ݇ ݇ ൌ ݎܽݐ݁ܿ݋݊ݏݐܽ݊ݐ ܭ ௘௤ ൌ ሾܤሿ ሾܣሿ ൌ ݁ ି∆ீ° ோ் ݇ ൌ ݁ ିா ோ்
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Converting Diamonds into Graphite Dia Graphite k f k rev Diamond (C dia ) Graphite (C graph ) 109 120 Bend Bond Angle (109   120 )
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Kinetically Controlled Reactions in Biology Glycolysis (glucose pyruvate + NADH) ATP hydrolysis (ATP + H 2 O ADP + P i ) Protein phosphorylation (R-OH + ATP R-P + ADP) Protein dephosphorylation (R-P + H 2 O R-OH + P i ) Fatty acid oxidation (palmitate + O 2 CO 2 + H 2 O) Photosynthesis (CO 2 + H 2 O + light Glucose + O 2 ) ATPase kinase PPTase oxidase chloroplast
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Kinetic Theory of Gases (Ch 2.6-2.9) Why study gases? Gas properties (Press, Vol, Temp) relate to speed and collisions of moving molecules (hence, kinetics). Gas properties easy to measure (PV = nRT & ܧ ൌ ଷோ் ). Gas reaction kinetics modeled by molecular collisions: A B rate (# of collisions) & (collision speed) Gas properties generalize to kinetics of biological reactions in dilute solution (i.e. ideal soln: <10 -3 M). Ch 2 Homework Problems : 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 76, 85, 98, 100 random motion Thermal energy
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Ideal Gas Properties and States Pressure (P) = Force/area (collisions/area, Pa or atm) Volume (V) = length* width* height (m 3 or ) Temp (T) thermal energy or heat (Kelvin or K ) n = number of gas molecules (moles) = N/N A R = ideal gas constant = 8.31451 J K -1 mol -1 = 0.0820578 L atm K -1 mol -1 PV = nRT (Ideal gas law) Pressure P = nRT V P = Nk B T V Gas: n=1mol P=1 atm T=298 K V=24.4 ~600 Ǻ 4 Ǻ # of gas molecules (N = nN A ) in 1-liter at 298K: molecules mole moles nN N A 22 23 10 46 . 2 1 10 022 . 6 ) 04089 . 0 ( Liq: n=1mol V=0.02 liter molecules V N 22 10 46 . 2 moles K mol K atm L L atm RT PV n 04089 . 0 ) 298 )( 0820578 . 0 ( ) 1 )( 1 ( 1 1 3 3 4 r V liter moles V n 04089 . 0
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