side for thermodynamics

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313 231 Physical Chemistry I
???????????? (Thermodynamics)
??. ??. ?????? ??????????? ???? 4511-1
2
?????????????
Physical Chemistry
Basic Physical Chemistry
- Atkins - Alberty - Laidler Meiser
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Thermodynamics
Chemical Thermodynamics - Walls
Physical Chemistry
4
???????????????? 15 ???????
???????????????????????????? (The Basic Concepts
of Thermodynamics)
?????????????????? (System and Surroundings)
????????????? (Properties of System)
5
???????????????? (Chemical Thermodynamics)
?????????????? (Work and Heat)
???????????????????????????? The First Law of
Thermodynamics
???????? - ?????????????? ???????????
6
???????????????? (Chemical Thermodynamics)
???????????? (Standard State)
?????????? (Hesss Law)
7
???????????????? (Chemical Thermodynamics)
????????????????????????????????????? (Enthalpy
Change and Bond Energy)
?????????????????? Enthalpy of Formation
8
???????????????? (Chemical Thermodynamics)
?????????????????????????????? Enthalpy of Phase
Transition
??????????????????? Enthalpy of Solution
9
???????????????? (Chemical Thermodynamics)
?????????????????????????? The Second Law of
Thermodynamics
The Carnot Cycle, ???????? (entropy)
????????????? ????????????????
10
???????????????? (Chemical Thermodynamics)
?????????????????????????? The Third Law of
Thermodynamics
-??????????????? Phase Equilibria
-????????????????????????????
11
???????????????? (Chemical Thermodynamics)
???????????????????????????????
?????????
Fugacity and Activity
12
???????????????? (Chemical Thermodynamics)
?????????????????????????????
?????????????????????????
???????????????????????????? ????????????
?????????????????????
13
??????? Thermodynamics
1. ????????????????????? ??????????????????????
? ????????????????
2. ???????????????????????????????
14
???????????? ??????????????????????? ?????????????
??? ???????? ?????????????? ???????
??????????????????????????? ??????????????????????
? ????????? ???????????? ?????????????????? ????
?????????????????????????? ???????? ??????????????
???????????????????
15
Classical Thermodynamics
Statistical Thermodynamics
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Classical Thermodynamics
?????????????????????????????????????????? ???????
??????? (equilibrium system)
- ?????????? (macroscopic properties) ????
??????? ??????? ???????? ???????
??????????????????????????????????? ?????
???????????
17
System Surroundings
?????? ?????? ????????????
System
system
Surroundings
18
???????? (open system) ??????????????????????
??????
??????? (closed system)
????????????? (isolated system)
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?????????????????????? (HCl, aq) 1 M
?????????????? 1 mol ?????????? 1000 cm3
???????? 1000 cm3 (??? 1000 cm3 ) 55.5 mol
???? ??? 1 mol
??????????? ??? 55 mol, ?????,
????????-??????? ???
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Hydrocarbon O2 (g)
CO2 (g) H2O (g)
21
??????????? ?????????? 298 K ??????????????????
??????? 1 ????
?????????? ? ?????? ??????
????????
22
?????????????????????? ???????????
?????????????? ??? ??????? ???????
????????
??????? ???????????????????
23
???????????????????????????????????
- ????????????? (DT 0)
????????? ??????????????? (Isothermal process)
24
???????????????????????????????????
- ???????????? (DV 0)
????????? (Isochoric process)
25
???????????????????????????????????
- ???????????? (DP 0)
????????? (Isobaric process)
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???????????????????????????????????
- ?????????????????????? ????????????????????????
?
??????????? (Adiabatic process)
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????????????????????? (State and State function)
State Function
Path Function
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??????????????????? (equilibrium
State) ?????????????????????? (Macroscopic
properties) ???? ??????? ???????? ???????
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?????????? (equation of State)
PVnRT
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R Gas constant
R 8.314 J K-1 mol-1 0.0821 lit-atm K-1
mol-1 1.97 cal K-1 mol-1
k Boltzmanns constant R/NA NA Avogadro
constant 6.022 x 1023 mol-1
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Van der Waals equation
32
????????????? ???? ??????????? (State function,
State variable)
??? ?????????? ? ??????????????
??????????????
1. ???????????????????????????????????
???????????????????????? (initaial Stute)
??????????????? (final State) ????????
33
????????????? ???? ??????????? (State function,
State variable)
2.
dX Xf - Xi X2 - X1
3. ?????????????????????????? ?
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????????????????????????
???????????? ???????? ???????? ????????????
??????? ???????? ??????? ????????
35
Extensive Variable
????????????????? ??? ?????????????????????????
????? (???)??????? ???? ???, ??????? , ???????
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Intensive Variable
??????????????? ??? ???????????????? ?????????????
??????????? ???? ??????? ???????????,
??????????
37
?????????????????????????? 1500 cm3
Extensive Variable
1500/1500 1 g cm-3 1500/83.33 18 g mol -1
??? 1500 cm3 ???? 1500 g. 83.33 mol
Intensive Variable
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??????????????
Work W
Physics
??? ??? x ???????????????????????????
?????????
39
h2
W f l
f
W mgh mgh2- mgh1
h1
m
??? ?????????????????????????????
40
a
l1
l2
W (ma) l ma (l2-l1)
l2-l1 (v1v2) t
2
a v2-v1
t
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??? ?????????????????????????
W (ma) l ma (l2-l1)
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????????????????
??? ????????????????????????????
43
????????????????????????
??? ???????????????????????????? ????????????????
????????????? (External pressure)
44
?????
????????????????????????????? (??????????,?????)
????????????
(positive value)
???????????????????????????????
45
l2
fext
l1
A
w - Pext(V2-V1)
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w -Pext DV
PV-work
???????????????????????? ?????????????????????????
?
??????????? J ???? N m ???? kg m2
s-2 ???? dm3 - atm
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??????? Path Function??
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V1, P1
V1, P1
P1
P2
V2, P2
V2, P2
V1
V2
V1
V2
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V1, P1
W - Pext DV - (P1 (V2 -V1) 0)
P1
P2
V2, P2
V1
V2
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V1, P1
W - Pext DV - (0 P2 (V2 -V1))
P1
P2
V2, P2
V1
V2
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Equilibrium Path ??? Reversible Process
A
P
B
V
Dwrev - P dV
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Isothermal reversible expansion of ideal gas
compression
?????????????
(DT 0)

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w - nRT ln (V2/V1) nRT ln (V1/V2)
??? PV nRT ????? T ????? P1V1 P2V2 V1/V2
P2/P1
w nRT ln (P2/P1)
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???????? (Heat)
???????????????? (thermal equilibrium)
???????? ??? ??????????????????????????
?????????????????????????? ??????????????????
???
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T1 gt T2
1
2
?????? T1 gt Tf gt T2
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????? 1 DT Tf - T1 negative value
???????????????????
(exothermic change) q dT
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????? 2 DT Tf - T2 positive value
??????????????????
(endothermic change) q dT
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The First Law of Thermodynamics
??. 1843-1848 Count Rumford, Bayer, Joule
??????????????????????????????? ?????????????????
?????????????????????????????????
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???????? 1 cal ?????????????? 4.184 J
0.42486 kg m
??. 1847 Helmholtz Law of conservation of
energy
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??. 1850 Clausius ?????????????????????????
???????
The total energy of a system and its
surroundings must remain constant , although it
may be changed from one form to another
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?????????
?????????????????????????? ??????????????????????
???????? ????????????????????????? ???????????????
??????????
dU Dq DW
first law
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???????????? (U) (internal or intrinsic energy)
??? ??????????????????? ?????????????????
??????????, ???????, ?????????????????
?????????????????????????? ?????? ???????
??????????????????????????????????????????? ??????
????????????????????? ? ?????????
63
?????? Monoatomic Ideal Gas
Thermal motion U 3 RT 3 PV
2
2
(????? n 1)
U ?????????????????
DU dU U2 - U1
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????????????????????????????????????????
1. Adiabatic process
???????????
q O (isolated system)
0
dU q w
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2. Isothermal Process
DT O
q -W
66
3. Isochoric Process
DV O
qv
dU q w
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Bomb Calorimeter
qp nCvDT
qp msDT
system
H2O
s ???????????????????? 1 cal g-1 K-1

4.184 J g-1 K-1
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4. Isobaric Process
DP O
qv DU
Isochoric Process
qP DH
??????????????????????? ???????????????????????
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?????
H Enthalpy
H U PV
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H ?????????????????
71
??? H U PV
DH DU D (PV)
DU PDV VDP
Dq DW PDV VDP
Dq - PDV PDV VDP
Dq VDP qP
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??????????????????? DH ??? DU
????????????????? DH DU PDV
??????????????????? ???????
PDV 0 ????? DH DU
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?????????????????????????PV nRT ????? DH
DU D (nRT) ???????????????????
DH DU nRDT ????????????????
DH DU RTDn
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??????? w,q, DU ??????????????????????????? ?????
?????????????? ???????? 1 ??? ??????? ???????????
???????? 100 OC ??????????????? ?????
?????????????????????????? ideal gas
????????
???????????????????????????? 100 oC 0.9583
g.cm-3 ???????????????????????????
40.63 kJ mol-1 (Latent heat)
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v2 1. ?? w wrev
- PextdV - Pext (V2-V1)
v1
V1 ?????????? 1 mol ??? 100 OC 18 g
18 g /0.9583 x 10-6 g.m-3 1.88x10-5 m3
76
V2 ?????????????? 1 mol ??? 100 oC
nRT / P (1 mol) (0.082 dm3-atm K-1
mol-1) (373.15 K) 30.6 dm3 3.06 x
10-2 m3
1 atm
1 m3 103 dm3 106 cm3
77
W - (1atm)(3.06 x 10-2- 1.88 x10-5)m3 -
(101325 Nm-2) (3.06 x 10-2) m3 - 3.1 kJ
1 atm 101325 Pa 101325 Nm-2