Kw 1-12 1-13 Kw van t Hoff 0 0 0 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
[H + ] [OH - ]=(x + 10-8 ) x = 10-14 x x = 9.51310-8 [H + ] = (x + 10-8 ) = 10.513 10-8 ph=-log (10.513 10-8 ) = 6.976 6.98 1-2 [H + ] [OH - ]=(x + 0.001) x = 10-14 x x = 9.9510-12 [H + ] = (x + 10-3 ) = 1.00000001 x 10-3 ph=-log (1.00000001 x 10-3 ) = 2.999999996 CH3COOH CH3COO - + H + [CH3COO - ] [H + ] [CH3COOH][OH-] Ka = Kb = [CH3COOH] [CH3COO - ] Ka Kb = [H + ][OH-]= Kw =0 ph 9.7 1. H + Lowry & Brnsted H + 2. X Y X Y CH3COOH CH3COO - CH3COO - CH3COOH CH3COOH CH3COO - 3. ph 2
-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
Ka Ka = [H + ][A - ]/[HA] 11. Henderson-Hasselbalch ph=pka + log []/[] 12. pka=4.7 25Ka [CH3COOH][CH3COO - ] ph Ka = 10-4.7 = 2.0 x 10-5 Henderson-Hasselbalch 4.7 3.7 13. 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
17. 18. GGly 19. ph ph 20. 21. Asp25 25 25 22. SI M/s M(=mol/L)mMµMnM [CH3COO - ] [H + ] cc c 2 Ka = = = [CH3COOH] c(1-) 1-1 1-1Ka = c 2 α = K a c [H + ]= c= ck a log -log[h + ] = - 1 2 (log c + log Ka) ph= 2 1 (pka log c) pka = 4.75 ph= 2 1 (4.75 + 1)=2.88 5
(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
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
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 -1 342 s -1 µ -23 i = Ki i = [I] Km (1+ i / Ki) = 8
v = K Vs (1 + i m K i ) + s (1+ i / Ki) i = Ki (1+ i / Ki)=2 1/2 µ 9
µ E S P E + S ES E + P v Vs v = K s m + 1/2 10
Km = [E][S]/[ES] SI Ms -1 1/2 mm Ms -1 Ms -1 s -1 ph 11
* 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
3-2c = 3.0 10 8 m/s = (530 10-9 m) =5.66 10 14 s -1 30 1cm 1.88 10 4 cm -1 c = =/ 3-3 E = hc/ E = hc/e = (6.63 10-34 Js)(3.00 10 8 m/s)(530 10-9 m) = 3.75 10-19 J(3.75 10-19 J) (6.02 10 23 /mol) = 2.26 10 5 J/mol 12.6m 2 5mm 1.9610-5 m 2 1.5610-6 4.410 12 n=1 n=2 exp{-1.64 10-18 J/(1.38 10-23 J K -1 300K)} 0n=2 3.03 10-19 J = (6.63 10-34 Js)(3.00 10 8 m/s)= 656nm = 0.531000M -1 =16.1M1M=12000mg/mL 16.1M 0.194mg/mL 0.0194% 13
= (25500 + 51490 + 1125) M -1 cm -1 = 18575 M -1 cm -1 1M = 25000g/L = 25000mg/mL 18575 1mg/mL 25000mg/mL : 18575 = 1mg/mL : x 0.743 [] 1. vv 2. 400-800nm 3. 4. E h E=h 5. s -1 Hz 6. 7. 8. E exp(-e/rt) 14
9. I0 I T= I / I0 A = logt 10. Lambert-Beer 11. 1cm 12. 13. ph ph 15