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Statistical Thermodynamics and Chemical Kinetics

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Statistical Thermodynamics and Chemical Kinetics Lecture 3 State Key Laboratory for Physical Chemistry of Solid Surfaces ... – PowerPoint PPT presentation

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Title: Statistical Thermodynamics and Chemical Kinetics


1
Statistical Thermodynamics and Chemical Kinetics
Lecture 3
State Key Laboratory for Physical Chemistry of
Solid Surfaces
???????????????????
2
Chapter 4 ????
(??????????)
  • 4.1 ????
  • 4.1.1 ????????
  • ????T?V?N????????,?????????

(4.1)
???0? ?1? ?2????????,????????
(4.2)
q0??????????????????
?VNkT/p, ???

?????
(4.3)
3
?????????????????????
?VNkT/p, ???

??qint,0 ?????????
(4.3)
(4.4)
  • ?????????????
  • ????????,1mol?????????????
  • (?????)

4
  • ?????????????????
  • ????????????

(4.5)
?????????j/mol???,
(4.6)
j/mol???
??
(4.7)
?????0?????,????o?????????
5
4.1.2 ?????
?????,???????????
(4.8)
  • ????????????,?????????????????????????????????????
    ????,???

(4.9)
(4.10)
  • ??,????????,???????

6
4.1.3 ??????? ??
  1. ? ??????A?B???,??????NA?NB, ????????????

(4.11)
Ei(A,B) ?????i???
Ei(A,B) ????A???B??????????????
(4.12)
????????
(4.13)
7
  • (2)? ??????????????

(4.14)
??,?????????????
(4.15)
8
4.1.4 ???
  • ????????????,?????????,???????,????????????Smix

(4.16)
????????,??????????????????????,??????????????????
?????????,??A?B??????????
(4.17)
(4.18)
9
  • ?????, ???????VVAVB, ??

(4.19)
(???)
(???)
(4.20)
??????????
(4.21)
10
????,??N NANB,??
(4.22)
???????????,??
(4.23)
  • ????????????????? ?????????,???????????????????
    ?
  • ???,????????????????????????,????????????????,????
    ????????,?????????????,?????????

????A?B??????????,????????,???????!
11
4.1.5 ?????
  • ?????????????????A?B?????,????????????????????????
    ,???????????????????????????????????
  • ????????,?????????,??????????????????????????????,
    ??????????????????????????,????????,???????????
  • ?????????????,??????

(4.24)
12
(4.25)
  • ?????,????
  • ??A?B?????????,?
  • ???????????????

(4.26)
  • ??????A?B??????,????????????0?????????????????????
    ?Gibbs???,??Gibbs?????????????????????????????????
    ?????

13
(4.27)
  • ????????,?
  • ?A?B??????,??
  • ??
  • ????????????????
  • ???????!

(4.28)
14
4.2 ????
  • 4.2.1 ???Einstein Model. (???????)
  • ???????????????????,???????????????????,??????????
    ????????????????????
  • Einstein Model?????N?????????????,???????????????
    ????,?????????????????????,??????????

(4.29)
???????????
???????
15
  • ????????Einstein??????????
  • U
  • ?????Eh?/k, ????Einstein????????
  • i)????????,?
  • ii)????0K?,?
  • ????????????

????????????
(4.30)
(4.31)
(4.32)
16
  • S
  • ?T?0K?,S? 0????????????????,??????????????1.
  • ?????????,??

(4.33)
(4.34)
(4.35)
17
F ??
?? ?????????
???????
?????
18
4.2.2 ????
  • ??Einsten??,??????????

???????
(4.36)
(4.37)
?
(4.38)
??????
19
??????????
3
2
1
  • ??????,????????3R, ?Dulong-Petit???????
  • ?T? 0K?,?????0, ??????????
  • ????,???????,???????????????????,??Einsten
    model??????

20
4.2.3 ?????????(????)
  • ???A(s)????A(g)???? A(s) ? A(g)
  • ????????'(s) ?'(g)
  • ?A(g)?????,?
  • ?A(s)?Einstein??,?

(4.39)
(4.40)
(4.41)
21
  • ?????

(4.42)
??0 ?0(g) - ?0(s)???A???A??????????
???????,??
????0K??????
?????????,???
(4.43)
??? ???,????????? lnp -?H/RT B ????,??
22
4.3 ?????
  • ????????????,??????????????????????????????,??????
    ??????????????????????
  • 1) ????????????,?????????
  • 2) ???????????????,??????(?????)?
  • 4.3.1 ????????????
  • ?A?B??????????,????????????????(????)
    ???,???????????????????????

23
  • Ei(A,B) Ei(A) Ei(B)
  • ???????,?
  • ????
  • ???A??B??????A?B??????????

(4.44)
(4.45)
(4.46)
24
  • ??
  • ???????
  • ??????????????
  • U ?????,??????????,
  • (2) S

??????
(4.47)
(4.48)
(4.49)
(4.50)
25
  • (3)F ????????
  • ?????????
  • (4) ?'
  • ???-kT lnq????????????????

(4.51)
(4.52)
(4.53)
(4.54)
26
4.3.2 ??????
  • ????????????????????
  • ??????,??????????????????????????????,???????????
    ???---
  • ????? ??????????
  • ????? ??????????????????

27
4.3.3 ???????????
  • ???????,????????????
  • ?????????

(4.55)
28
(4.56)
  • ???????????????
  • (1) ???

(4.57)
(4.58)
29
  • (2) U
  • (3) S ????????????
  • ??????????????

(4.59)
(4.60)
30
  • ???

(4.61)
31
4.4 ????
  • ?????????????????????????????????????????,?
    ?????
  • 4.4.1 Langmuir???? (?????????)
  • Langmuir??????????????????????????,??????????????
    ?,??,??????????????

32
  • ????????????????NS??????,???????,?NA????????
    ?????,????????????
  • ??????????????
  • ????????????????????1,?qA(S)?????A????????,???????
  • ?????A????

(4.62)
33
(4.63)
  • ?0(S)?????A????,?NA/NS???????
  • ?????????????A(g),???????,?????
  • ???????????

(4.64)
34
  • ???
  • ??0 ?0(g) - ?0(S)???A????A????????
  • ?????Langmuir?????,??
  • ??
  • ???????????????

(4.65)
35
4.4.2 ???
  • ????????,????
  • ?????????????,??????????????, ???????????????

(4.66)
36
  • ??????
  • ??????
  • ?????????
  • ??
  • ????????????,?????????????
  • ??(???)?????,??T?0K ????,??????????????

(4.67)
37
  • p213 ??3,4,5.

38
4.4.3 ???? ---B.E.T??
  • ???????,??????????????
  • ??????????????????????????????????????????????????
    ?????????,???????????,?????????????????????
  • Hill?1960??????????? ?????????????????????????,???
    ??????????????

???????
39
??????,?????????????,??????????????
  • ?NS ?NA?????????????????
  • am?????????m???????????
  • ????????????????m?????????????????????,?????q(m)??
    ?????

??q(0)1???????????,q1?????????????,q2????????????
?
40
  • ????????????????????am?
  • ???? m 0, 1, 2, , l
  • ???? a a0, a1, a2,, al
  • ?????????????

?NA?????,??????????????
(4.68)
??X??????????
?X???????amX?NS???????????????
(4.69)
41
  • ?E(m)K??????i?,?K???????m?????????,??

?K????(???m)?????????????????????!
???????(T?NS?NA??)????????
(4.70)
42
  • ?????????????????????,????????????????????
    ?? ??

(4.71)
?A(S) ???????? (???????????????!)
l ????????????????
lNs ??????????????
X? ???NA???????,???
????????????????!
43
  • ???????,?(4.71)????

(4.72)
??,????????????????????
(4.73)
44
  • 1) ????????,m?????1,??

(4.74)
2) ?????,???????(l??)????,??
?
45
  • ??????

?xlt1, ?
(4.75)
?? ??????B.E.T???
(4.76)
????????
?????p??????p0????????V ????????Vm
46
4.5 ??????
qo0??????1mol??????????
  • 4.5.1 Kp??????
  • ?????? aA bB ? cC dD
  • ??????,??????,??
  • ??

(4.77)
(4.6)
(4.78)
(4.79)
47
???????????????
  • ??

(4.80)
??,?????????????,??????????????????!!!
48
  • ??????????????????(KC?KN)???

(4.81)
(4.82)
????????????
49
4.5.2 ???????
  • ??????????????,???????????????????????????
    ??

??????? A ? B (???????) ???????,??
???????????N?????
???????????
(4.83)
50
  • ???

(4.84)
(4.85)
????? ?A ? B? ?A ?B ,???
(4.86)
?????A?B?????????
(4.87)
(4.88)
51
  • ???????????????????

?????????
??KN??,???????????????????
52
4.5.3 ???????
  • ??????????????,???????????????????????????
  • H2 D2 ? 2HD
  • H2 2DI ? 2HI D2
  • (3) O216 2H2O18 ? O218 2H2O16
  • ????????????????????????,????????????????
  • ????(1), ?????????

??????????(????)
(4.89)
??0 ?0(HD) - ?0(H2) - ?0(D2)
53
  • ???????????????????,???????????????,????q00
    ??????????????????????,?
  • ???,??????????????????????0?????????????????????D,
    ?
  • ??????????????????
  • ??,?????????,????????????,??????????,?????????????
    ??????,????????????????????????

(4.90)
(4.91)
(4.92)
54
  • ???????? (???)

(???????0)
  • ???????????(????????)

?????????
????
(???????0)
  • ???????????(?????)

55
  • ??,?????????????????,??
  • ?????????????????????,? Tltlt ?vh?/k, qv,0?1?
    ???????
  • ?
  • ????0657 kjmol-1(???)??????m?I???

(4.93)
(4.94)
(4.95)
56
H2 D2 ? 2HD???Kp??? vs.??
??/K Kp??? Kp???
83 2.24 2.20
195 2.95 2.88
298 3.28 3.27
670 3.78 3.78
  • ??????Re?????????KP?????
  • ??????,???????????????0h?/2, ?0h?/2,????????????
    ?????????????????(????????????),?????????
  • ?????????????????,???????!

57
??
  • ?? 6,8 (pp.212-213)

58
  • N?????????????????H?,??????????,
    ??????????,??????????????
  • ?? ni???i??????,
  • 1)?????(?????N?H)????????????
  • 2)??T?0??????????????
  • ??????M?????
  • ?? , ????? ?
  • ??T?0?,???????? ??????
  • ?????????? ?H?????

59
  • ? ????????,??????,??? /-?H
  • ??????????
  • ???????, ??????????
  • ?????????
  • ?T?0?,U ? -N?H, S?0,??????????,?????????,???, ????

60
  • ???????????????? ????????????????????(m)
    ??,???????Nm , ??
  • ????
  • ???????
  • ??????????m?????????,???????, ??
  • ??????????
  • ????(?????)?????????

61
  • 3)???????????????Nm????????m????,
  • ????????
  • ??????????

62
  • 4)T?0K?,
  • ????????H??,??
  • 5)???????????H????,??1
  • ????????(M Nm?)?????????
  • ??????????()???(-)??????????????H?-?H??????,
    ??

63
  • Further question ?????????????,?????H?????,?????
    N????,???????????????
  • ? ?????M?? ,?Nm???,???H?,????????
  • ???????
  • ????????????????????

64
  • ?N????,?Sterling???
  • ??????????????
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