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1 Kw Kw van t Hoff H S d ln K H ln K = + = RT R d(1/ T ) R ln KW 1/T H 0 /R H 0 = 51.0 kj mol -1 HCl H + + Cl - H2O H + + OH - [] [H + ] [OH - ]=10-14 M 2 25 OH - x OH - [OH - ]=x [H + ] [OH - ] x 100%10-8 M 1

2 [H + ] [OH - ]=(x ) x = x x = [H + ] = (x ) = ph=-log ( ) = [H + ] [OH - ]=(x ) x = x x = [H + ] = (x ) = x 10-3 ph=-log ( x 10-3 ) = CH3COOH CH3COO - + H + [CH3COO - ] [H + ] [CH3COOH][OH-] Ka = Kb = [CH3COOH] [CH3COO - ] Ka Kb = [H + ][OH-]= Kw =0 ph H + Lowry & Brnsted H + 2. X Y X Y CH3COOH CH3COO - CH3COO - CH3COOH CH3COOH CH3COO - 3. ph 2

3 -log[h + ] H + ah+ -log[ah+] 4. [H + ]=0.001MpH=3[OH ]=10 11MpOH=11 7. HA H HA H + + A - 8. Ka pka Ka = [H + ][A - ]/[HA] pka=-log Ka 9. pka pka pka pka=-log Ka Ka Ka Ka 10. pka Ka pka=-log Ka pka Ka 3

4 Ka Ka = [H + ][A - ]/[HA] 11. Henderson-Hasselbalch ph=pka + log []/[] 12. pka=4.7 25Ka [CH3COOH][CH3COO - ] ph Ka = = 2.0 x 10-5 Henderson-Hasselbalch ph 14. ph Henderson-Hasselbalch pka 15. COO - +H3N-C-H C R R 16. COOH +H3N-C-H H COO - +H3N-C-H H COO - H2N-C-H H 4

5 GGly 19. ph ph Asp SI M/s M(=mol/L)mMµMnM [CH3COO - ] [H + ] cc c 2 Ka = = = [CH3COOH] c(1-) Ka = c 2 α = K a c [H + ]= c= ck a log -log[h + ] = (log c + log Ka) ph= 2 1 (pka log c) pka = 4.75 ph= 2 1 ( )=2.88 5

6 (1) 0.1M AH 0.1M A AH 0.8A 0.6 AH A 0.9 AH A log([a]/[ah]) ph (2) (3) ph7 2-1 kf = (kbt /h )exp(-gf 0 /RT )kb = (kbt /h )exp(-gb 0 /RT ) K kfkb kf (kbt /h )exp(-gf 0 /RT ) K = = kb (kbt /h )exp(-gb 0 /RT ) = exp{-(gf 0 -Gb 0 )/RT } = exp{(-g 0 )/RT } G 0 = RT ln K 6

7 G 0 = kf (kbt /h )exp{(-gf 0 + G)/RT } = exp{-(gf 0 -Gb 0 )/RT } kb (kbt /h )exp((-gb 0 + G) /RT } = exp(-g 0 /RT ) = K µ µ 7

8 µ µ µ s/v s x -3.77mM20.5M min -1 = 3.77mM=20.5M min -1 kcat = V / [E]0 = (20.5 x 10-6 M min -1 ) / (1.0 x 10-9 M) = 2.05 x 10 4 min s -1 µ -23 i = Ki i = [I] Km (1+ i / Ki) = 8

9 v = K Vs (1 + i m K i ) + s (1+ i / Ki) i = Ki (1+ i / Ki)=2 1/2 µ 9

10 µ E S P E + S ES E + P v Vs v = K s m + 1/2 10

11 Km = [E][S]/[ES] SI Ms -1 1/2 mm Ms -1 Ms -1 s -1 ph 11

12 * ph Lineweaver-Burk s v 1/v vs. 1/ss/v vs. sv vs. v/s vs. versus = Lineweaver-Burk 1/v vs. 1/s ph H H 12

13 3-2c = m/s = ( m) = s cm cm -1 c = =/ 3-3 E = hc/ E = hc/e = ( Js)( m/s)( m) = J( J) ( /mol) = J/mol 12.6m 2 5mm m n=1 n=2 exp{ J/( J K K)} 0n= J = ( Js)( m/s)= 656nm = M -1 =16.1M1M=12000mg/mL 16.1M 0.194mg/mL % 13

14 = ( ) M -1 cm -1 = M -1 cm -1 1M = 25000g/L = 25000mg/mL mg/mL 25000mg/mL : = 1mg/mL : x [] 1. vv nm E h E=h 5. s -1 Hz E exp(-e/rt) 14

15 9. I0 I T= I / I0 A = logt 10. Lambert-Beer 11. 1cm ph ph 15

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