??????,?????????????,??,???????????????,???????????????????????????Q??,??????Q???

1
2.3 ????
2.3.1 ?????
1) ?????
????????????????????,????????????

• ?????????????????
• ????
• ????
• ????

????
??
??
2
??

• ???????????????
• ?????????????????
• ???????????????????
• ??????,?????????????,??,???????????????,??????????
  ?????????????????Q??,??????Q???

3
2) ?????
?????????

• ???U
• ??T
• ??V
• ??P
• ????N
• ??m

????????

• ??T?P???????,?????,??????????????
• U?V?N?m???????,?????,?????????
• ?????????,????????????????????

4
3) ????????
(1) ????
???????????????,??????????????????????????????????
(??)?????????????,????????????????,?????,?????,???
?????????????
5
(2) ????????
????????,????????????????????????????,??????????
(reversible process)????,?????????,???????????????
?????,??????????? ?????????,????????????????????
?,???????????(irreversible process)????,??????????
,?????????????,?????????????????????,?????????????
?,??????????????,??????????
6
(3) ????????
?????????? ???????????????????????,?????????????
???????????????????????????????
??????????
dU?Q?W (2-1)
???????????????
?????????????0 K??????(The Difference in Entropy
Between States Connected by a Reversible Process
Goes to Zero in Limit T ? 0 K)
7
4) ????????????????
(1) ????(Entropy or entropy change)

• ????????dS
• ????????,??????
• ??????dS ???0
• ???????dS ????
• ?????????????

(2-2)
(2)????,?????????????????T1?????T2,????????,??????

(?????????????)
????????,?????dS ? 0????????????,?dS?????????,????
??
8
(2) ???(Boltzman)???
(2-3)
(3) Helmholtz???(Helmholtz function?Helmholtz
energy)
F ? U - TS (2-4)
?????????/??????
dF ? 0 (2-5)
????????????,??????Helmholtz?????????
9
(4) Gibbs???(Gibbs function?Gibbs energy)
G ? H - TS (2-6)
????
dG dH TdS (2-7)
?????????/??????
dG ? 0 (2-8)
????????????,??????Gibbs?????????
(5) ??H
H ? U pV (2-9)
10
(6) ????????

• ????????????????????????

• ???? ( Maxwell )??

• ???T?S?P?V???

• ???????????? Gibbs-Helmholtz??

11
5) ?????????????
??????????(????????)???,??????????,????,?????????
????????
C Q/?T (2-10)
???????????????????????,??????
dU dQ - PdV
??????
????????????,?????????,????H???U????,??
12
????????????????,??????????
Cp ? CV??????
??
??????
???????
??????G????G?0,????Hf ?????Sf ?????Tm?????
Tm DHf /DSf (2-10)
13
6) ???????????
(1) ????
G?T?P?????,?????T1?????G???????????????????
G?????,?
????????(???????????)
14
(2) ????
G?????????T?p?????,??????T2???????????,???G???????
???
15
2.3.2 ???????
1) ???????
(1) ????? (Differential Thermal Analysis, DTA)
???????????,????????????T?????
?DTA???,?T ???????QS???,??QS??? ?T R ? QS
(????R??????)
(2) ??????? (Differential Scanning Calorimetry,
DSC)
??????????????????????????(????)??????????? DSC???
????????????????????,?????DTA??????????????DTA????
??????????????????????,?????????DTA??,?????????DTA
?
16
??????????(heat flow DSC)
?????????,????????????????????? ???DSC???????????,
?????????????????,????????,?????????,???????
(dQ/dt) ????
17
???????????(heat flux DSC)
?????????????????????????????
Calvet???DSC??????????????????????????????????????
????,????????,???????????,????????????????????????
??
18
Mettler DSC822 FRS5 ???????

• ???????, ???????????!
• ??56????????????
• ?????(??????????)
• ?????? (DSC822e
• 16 00??)
• ???? 1.6 s (20 mg Al ??, He ?)
• ?????????
• ???? 0.04uw

19
????????????(power compensation DSC)
?????(???)??????????????????????,?????????,?????0.
01 K? ?????DSC?????????,??????????????????
????????????(Temperature Modulated DSC, TMDSC)
???DSC???????????,????????????????????????,???????
??????????,?????????,???????????????????????????DS
C?????,?????????????
20
(3) ?????????
????????????????????????????????????,?????????????
???,???DTA??????
DTA?????
Ts-?????,Tr-??????
???DTTs-Tr ??????????????,???????DTA???????
DTF(T?t)
21
??????????????
???DTA??
????DTA???DT ????,?????? DT ????,???????
22
DTA??????????????????????,?????????????Ti
??(?)??Q?
?
????????????????(???),?
(2-11)
KS?KR ???????????????? aS?aR ???????????????(????
???) s ?????????????? o????
23
??????
(2-12)
CS -??????????? DH -??????????? a-???????,?????
CR -????????????? ????????????,?KKSKR,aaSaR,
????R1/(K2sa),????bdTR/dt,TSDTTR,???????
(2-13)
24
?????(3-3)?????
????????DT ????????, I????????t
??DTII?????????????(????DT a)???DT
????????,?III???????????????t ?RCSdDT/dt??

ta
td
III
?Ta
II
?
a
d
?T
I
c
?(2-13)??t a ?td ??????,???????????DH
?DTA????abcda??????A???R??????
b
??????DTA????
(2-14)
25
????????????
(????,?????,2006?,p.91)
26
(4) ???DSC
DTA?????A?????DH ??????????
(2-15)
??,K???????6??????DTA????????,??????? ??,?????????
??DTA??????????????,?????????,????????
DTA??????????
?????????????????????????????DSC???,???DTA????????
???????????K,?????????
27
(5) ??????DSC
?????m?DSC???????,??????Qr??,???????????????KQ
??????????????????????,?????????????725?C
28
(No Transcript)
29
(6) ??????DSC
?????????????,????????,???????190?C?1500?C,??????
?,???????30 K/min?
30
(7) ?????DSC
??????????,???????,?????????,??????????0.3320
K/min,??????????????60 K/min???
31
(8) ?????TMDSC
DSC?????????????(???????)????????????????????????

• ????????,?????????
• ???????????,????????
• ???????????,????????
• ????????????????,????????????,??????????????
• ???????????????
• ??????????????????????(?????????)?

??DSC????????DSC??????,??????DSC?????????????,????
????????????????????
32
TMDSC??
????????????????????????,????????????????????????
????????????????????(??)?????????
33
???????????????????????3???

• ??????
• ????
• ????????

??????????????? ??????????????? ?????????????????
???????DSC???????
34
(No Transcript)
35
??DSC?MDSC?????????????
???? DSC T(t) T0 b t ??T(t)
-???? T0 -???? b -??????,?C/min t
-??,min? MTDSC T(t) T0 b t AT sin(w
t) ??AT -??????,??C w -2?/P,????,s-1 P
-??,s?
(2-16)
(2-17)
36
????? DSC dQ/dt-???? Cp-??T-????? Cpb-?
???(heat capacity component) f (t,
T)-?????heat flow from kinetic (absolute
temperature and time dependent)
processes MTDSC ??(bATwcos(wt))-???????dT
/dt f (t, T)-??????????? Ak-??????????????
??????(deconvolution)???????DSC????,????????
????????(reversing heat flow)???????????(???)(nonr
eversing heat flow)???
(2-18)
(2-19)
37
?MTDSC????????,?????????????(in phase)?????(out
of phase)
In phase??????????,???????????,?????????????????
Out of phase???????,??????????(????),????t(????
?)???T(????)?????????????,???????????????
38
???????
(2-20)
??DSC
(2-21)
39
CP KCP (Qamp/Tamp) (Modulation Period/2p)
MTDSC
(2-22)
where Cp heat capacity KCp heat capacity
calibration constant Qamp heat flow
amplitude Tamp temperature amplitude
40
mW)
Flow (
at
e
H
41
)
C)
g

/
/
J/g
(W
(
w
y
o
t
l
i
F
c
a
t
p
a
Hea
C
t
v
a
e
Re
H
42
(No Transcript)
43
(No Transcript)
44
2.3.3 ???????????????

• ????????,?????????
• ??????????,?????
• ?????????????
• ???????????(noise),??? (repeatability)????(re
  producibility),??
• (linearity),????,???(sensitivity),?
• ??(resolution)
• DSC?????????????????,??
• ??,????,??
• ???????????
• ??????????
• ??????????

45
1) ????
?????????????????????
????

• 23?????
• ????
• ???????,???????????Te
• ????????
• ????????
• ???????????????????????????????

Tf
Te
Ti
dQ/dt ? ??
Tp
T
?????????
46
2) ????
???????????????????????????????
??????
?????CP?????
???????????
?????
??????????DSC??????
???????????
47
3)??????

• ?DSC????????(?????99.999??)
• ?????????
• ????????????????(????)????????????,??????????????
  ???????????,??????????????
• ?????????????????????
• ????????
• ??????

48
??????
49
??a-Al2O3(?????)???? (????101.9613 g mol-1)
50
4) DSC??????????
???
????dQ/dt,???mJ ? s-1 (mW) ?
?????(dQ/dt)/m,???mJ ? s-1 ? mg-1 (mW ?
mg-1) (specific heat flow) ??J ? s-1 ?
g-1 (W ? g-1) ?????????????????????????
??????,???????????????
????????????????? mJ ? mg-1 ? ?C-1 (mW ? mg-1
? ?C-1 )?J ? g-1 ? ?C-1
51
2.4 ????

1. TG-DTA-DIL(DSC)

52
2) TG-EGA-DTA(DSC) 3) DSC-X?? 4)
TMA-DMA-DSC 4) ??DSC
CoSO4?7H2O???????DTA??? A-1 atm B-15 atm C-21
atm D-28 atm E-35 atm F-69 atm