PHYSICAL CHEMISTRY

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????(?) PHYSICAL CHEMISTRY (19)
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?4 ???25oC,101.325kPa??????25oC ???H,ClO4
-,H2OCl2(g)Pt ?????? ??KClO4(s)?????????0.148
mol.kg-1, KCl(s)??????????4.80 mol.kg-1
?? ?????????????????0.70? 0.59???KClO4(s)
KCl(s) 2O2(g)???? O2(g)????e14.13,H2O(l)???????G
ibbs ???-236.6 kJ.mol-1,??PtCl2(g)Cl-?? ??????1.
359V?
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???? ?(?)????? Fundamentals of
interface(surface) chemistry
??????(?)???
G
??????????? ????
L
???
A? ???????, V ????? m ?????
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?????????????,????? ?????????????????
???????(??)??????? ????????????
??-?? ??-??
??(surface)
??-?? ??-?? ??-??
??(interface)
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??????????????
????(?????????)
????
????(??????????????)
????(????????????)
????(LB?,?????)
????????????
1805 T . Young ???????? 1806 P.S.
Laplase ??????????? 1878 Gibbs
?????? 1916 Langmuir ?????????
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????????????????? ???,??????????????? ????
??????,???????? ??????????????????? ?,????????????
????? ??????????????????? ?????????????,????? ????
??????????????? ????,?????????????? ???????
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11.1 ???Gibbs??????? Gibbs function of specific
surface and surface tension
1.????????????
????????? ????????? ??.
G L
?????????? ????????
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2.(?)??Gibbs?? Gibbs function of specific
surface
?????????,????????(?)? ?????,???(?)???
?????????????????? ???,?????(?)?????
??Gibbs?????--(?)?(?)?Gibbs??
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dG -SdTVdpSµBdnB-dw
dw -?dA
??????????
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?????
????
????
???Helmholtz??
???Gibbs??
?????????????????? ??????????????
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3. ?(?)??? surface (interface) tension
?(?)????????????????? ???????????????
(?)??Gibbs???????????????
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(No Transcript)
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4. ??????????
(1) ???????(???????????, ??????)
(2) ????????
?/(N m-1) ?
----??? 0.0502 ?
0.0350 ?
0.415
???????????????????? ??????????
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(3) ?????
??????? T?,??
R-S ??
Tc ???? Vm ??????? k????,??????????
k2.210-7 J K-1
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Guggenheim ??
?0 ,n ????,?????,n11/9, ???
, n1
?? Cd, Fe, Cu ??????????, T????
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??????????????????, ?????????,
???1 g???????1 nm????, ????3000m2, ????220 J.
??????????????
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11.2 ?????? Curved surface phenomena
p0
1. ??????????
p0
p0
G L
ps
ps
Pi p0 ps
Pi p0 - ps
Pi p0
Pi ???????
Ps ????(additional pressure)
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p0 ps
????????
p0
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Yong - Laplase equation
?????????
r1 , r2 ??????????????? ?
??????(?????)
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??
1. ????(convex) (rgt0) ps gt0 , pi gtpo ????
(concave) (r lt0) ps lt 0 , pi lt po ??
r 8 ps 0 , pi po
Ps ?????????
2. ???,r??,? ps ??
3. ?????????????????? ????,???????????,?
??????????????
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2. ???????? Vapor pressure on curved surface
p0
?????T, p0 ??????
L
p0
????,??T, p0?
L
pv ????,??????
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????? ????
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Kelvins equation
20oC?,????????????? r/m 110-6
110-7 110-8 110-9 p?/p? 1.001
1.011 1.110 2.927
????,r ???, p?lt p?
??????,????????????? ???????????
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3. ????(Metastable state)??????
p
?????????? ?????
????
T
T
100oC?,???pgltp0ps,??????? T??100oC,?????????,pg
p0ps ,????
t
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11.3 ???????? Interface of liquid and
solid
??
???
?????
?????
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L
S
lt 0 ??
???
lt 0 ??
????
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???
Young equation
L
?
S
????
?s-g lt?s-l , cos?lt 0 , ?gt 90o, ???? ?
(?s-g-?s-l)lt?l-g, ,00lt?lt90o ???? (?s-g-?s-l)?l
-g, ,? 00 ???? (?s-g-?s-l)gt?l-g, ,
??
?s-ggt?s-l
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????(Capillarity)
????
????
(1)??????????????
(2)????????????
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po
r
r
?
po
h
r ??????? r ????(?)??
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?? 11.1, 11.2, 11.3 ??6.8, 6.9, 6.10 ??
2, 4 , 5