2 A B A B A A B Ea 1 51 Ea 1 A B A B B A B B A Ea 2 A B Ea 1 ( )k 1 Ea 1 Ea 2 Arrhenius 53 Ea R T k 1 = χe 1 Ea RT k 2 = χe 2 Ea RT 53 A B A B

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1 5. A B B A B A B B A A B A B 2 A [A] B [B] 51 v = k[a][b] 51 A B A B A B A B A A [A] 52 v= k[a] 52 A B 55

2 2 A B A B A A B Ea 1 51 Ea 1 A B A B B A B B A Ea 2 A B Ea 1 ( )k 1 Ea 1 Ea 2 Arrhenius 53 Ea R T k 1 = χe 1 Ea RT k 2 = χe 2 Ea RT 53 A B A B A A B 56

3 A B G 43 S 54 K G = Ea 2 Ea 1 = TS Ea Ea RT G RT T S RT k2 K = = χe = χe = χe = χe k S RT R 55 57

4 1 27 A B 53 G0 1kcal/mol 3:1 3kcal/mol T van der Waals 58

5 e 0.15 N Ne N S Ar N S Kr Xe

6 l Br N 3 N P 4 2 S 2 S 4 2 Na K Mg a x x Ba x10 3 2x10 2 Al x Fe x10 6 7x Fe o x10 4 4x10 3 4x Ni x10 3 9x u x10 5 3x Zn x10 4 5x

7 52 K Na Mg a Ba Fe Al

8 55 S T Brønsted A A B B 54 1s 1s 2 A A B B 2 Lewis 2 62

9 A A A B A B v=-k a [A]k b [ ][A - ] K A = k a = [ ][A - ] k b [A] [A] [ ]=K A [A - ] pk a =-log(k A ) K A pka 54 pka pka pka B B

10 54 pka25 pka l l 7.00 S 4 S N 3 N S 4 S P 4 P S S 7.04 P 4 P N N B 3 B S S P 4 2 P B 3 B B 3 2 B N 3 N pka 55 pka 64

11 55 pka25 pka 4 6 N 4 5 N NN 3 3 N 3 ( ) 2 ()N N ()N N 4 N 3 2 NN N 0.63 ( ) 2 ( )N N 4 3 ( )N N 4 N 3 ( ) 2 ( )N 3 ( ) 2 ( )N N 3 3 N ( ) 4 ()N pka pka N 4.63 N( ) 4 ( )N N 5 5 N N N 4 N N N N ( 3 ) 3 N ( 3 ) 3 N N 4 N 3 N( ) 4 ( )N 3 3 N 3 ( 3 ) 2 N 5 3 N 4 N 9.83 N( ) 4 ( )N N ( 3 ) 2 N N N v=-k b [ ][B]k a [B ] K B = k a = [ ][B] k b [B ] [ [B ]=K ] B [B] 65

12 Brønsted A A B B (A) (B) B A [B ][A - ] K = A [B][A] KB pka R R N X N X pka R=: X=l: R= : X= 3 : pka pka pk a : pk a :

13 N 4 pka 515 pka A A K A B B K B 55 [ ][N 3 ] KN 4 10 = = = [ - ][N 4 ] K [ ][S - 4 ] K S 4 10 = = = [ - ][ S 4 ] K [ ][ S 4 ] K 3 [ 3 ][S - = = = ] K S

14 ( ) n ( ) n ( ) n n=

15

16

17 m n n m n m Na m n n=15or17,m=31or33or35 Brønsted 2 pka pka pka pka<1 pka pka pka pka 8 pka 4.9 pka pka p 518 pka 56 Na 3 71

18 1 p = pka 2 ( log 14) 3.75 Na Na Na ( ) 2 Na ( ) 3 Na ( ) 4 Na ( ) 5 Na ( ) 6 Na ( ) 7 Na ( ) 8 Na Na Na Na S 3 Na Na Na Na Na SNa ( ) 3 SNa SNa

19 R 1 R S 5 S R S S R 2 3 R 4 2 S R R R P R N R R N R R N 3 N R R R R R R R N 73

20 3 59 R 1218 pka Ka S S Al 2 3 S 4 Na S Na 74

21 n 5914 Ag 2 R Na R 13 Na R R 15 75

22 1950 PET (B) (A) 76

23 van t off A B 519 V b T R ΠV = n b RT 519 c b ρ b M b 520 Π = c b RT ρbrt = M b

36 th IChO : - 3 ( ) , G O O D L U C K final 1

36 th IChO : - 3 ( ) , G O O D L U C K final 1 36 th ICh - - 5 - - : - 3 ( ) - 169 - -, - - - - - - - G D L U C K final 1 1 1.01 2 e 4.00 3 Li 6.94 4 Be 9.01 5 B 10.81 6 C 12.01 7 N 14.01 8 16.00 9 F 19.00 10 Ne 20.18 11 Na 22.99 12 Mg 24.31 Periodic

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30 3 ............................................2 2...........................................2....................................2.2...................................2.3..............................

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