SI

CBTI( Thermodynaics25 926251024( Thermodynaics1-1 SISystme International dUnitsm 1/299,792,458 kgs1332 9,1926,31,770AK0 K 273.16 KMol120.012 kgcd 540 1/683 40001197011900111231556295.97471-2SI

SI 1(cal)2(L)3(min)4 (kg) (N)1 SI 1Pa2W3JNHz31kg m s-12kg m-1 s-13kg m-1 s-2kg m2 s-2kg m2 s-3Pa : N m-2N : kg m s-2W : J s-1 10 mL SI 4110-2 m3210-4 m3310-5 m310-6 m310-9 m31 L = 10-3 m31 mL = 10-3 LCBTI( Thermodynamics

2-1(

R. Boyle J.A.C. Charles Benjamin Franklin 178392-2van der Waals

ab

2-2van der Waals

Z

Z = 1 Z < 1Z > 1 Z

BT kB

51V /T = const.2V T = const.3p V = const.p /T = const.p T = const

12341 mol Z = (p V) / (R T) , 1 516 Z = 1 671238123 I( Thermodynaics3-13-23-33-43-53-63-73-1

w qopen systemclosed systeminsulated system isolated system3-2

3-2-1

3-2-2

3-2

extensive property

intensive property 1.0 kg 300 K 1.0 m3 101 kPa 1.2 g/cm3 1.0 kg 300 K 1.0 m3 101 kPa 1.2 g/cm3 2.0 kg 300 K 2.0 m3 101 kPa 1.2 g/cm3123459241234510251234511263-3Mayer 1 cal = 4.184 J

wq Joule 3-4U Nothing comes of nothing.

3-4U

q = +10 kJ, w = +30 kJq = -20 kJ, w = -20 kJ3-4-1 DU

3-4-1DU

3-5 H

DU q U U + PV U & H

3-5 H DH

p

rev DH DH vaporization DvapH transitionDtrsH fusionDfusH solutionDsolH sublimationDsubH reactionDrH combusionDcH formationDfH

3-6C heat capacity C DT q C

C : J K-1

Cm: J K-1mol-1 Cp

Cv Cp CV

3-6C

13-7 DH > 0 DH < 0 DH1.00 bar(105 Pa) 298.15 K DfH1 bar, 2501 mol 12345123712345 DU q w 13

381234514DH < 0 391251bar 201bar 30 K1bar 401bar 50 K1bar 154012345-504-283172.5283504DrH J mol-1

CO -110.5 kJ mol-1CO2 -393.5 kJ mol-11612345174212345184312345CV Cp 19

44 I 4-14-2- S ( ( - S

1 1/51 2 523 53 N N 5 - SDS4-1-1

4-1-2

4-1-3

(J K-1)

q T DS

- S

qw

- S4-1-4

qhw

100 - S4-1-4

qhw - S T = 0 K T = 0 K T = 0 K

DS q T p w 20

54 1 mol T1 T2 Cp 21

55298 K DfusH 22

5612345A 23

57123452458 I 4-14-2 DS

-2

G21

-2 4-2-1

Enthalpy HGibbs enerugy GT S

22

DG < A B DG = DG > B A -2 4-2-1

22-2

4-2-2 A

D A< A BDA = DA > B A 22-2 4-2-3

DGTDGTDGTDGT

DG < 0-2 4-2-4

G G

S > 023-2 4-2-5 ?

S S S V V 0

12345GH T S 25

6812345pGV T 26

6912345277012345() 298.15 K 0 J mol-1 28II298.15 K 0 Jmol-1 7112345G H S 29

7212345H S 30

7312345H S V 31

7412345327512345Vant Hoff 3376U DU = q + wHH = U + p VAA = U T SGG = H T SS

q, w > 0q, w < 024?