1.

1.

2.

19


1.

2.

20

1.
2.
3.


1.

2.
a.

b.

c.

1.2

1 2 3
1 1

 1.

1.
1.1
2.
1.2
3.
1.3


a.

1.3

b.


1.

2.

m T P

V c

3.
(1)

V m C

(2)

c P

(3)
a.

=m/V

c = C / m

b.

1atm 100C

100C 100C

c.

1/2

T P
n

n
T P


T P n1 n2 ns


1.

2.

3.

A B

 A B
ACB ADB

4.

AB

ACB AC

CB
AC

AC

AB

5.

AB

T P
T = TB TA = 100 K P = PB PA= 4P

T P d T d
P

1.

T1T2

2.

d m

P +
a /Vm2

3.

1.3

 1840 (Joule)
(Meyer)

1 cal = 4.184 (J)

1 (J) = 0.239 (cal)

1.

2.

3.

V P
A B

(I) (II)

A
B (I)
(II)


(I)

(II)
(I) A

(II) B A

B
A B A

A B

A
B
A B

UA UB A
B A
B

U = UB UA


a.
U UA UB
A
UA Ui

Ui = UA + UA i UA i

b. U

c.
UA= 0

d. U
U

V P U
V P

U=UVP

U
dU
U ( P, V )

dU = (U/P)V dP + (U/V)P dV

U = U(T,V )
dU = (U/T)V dT + (U/V)T dV

U = U( P,T )
dU = (U/T)P dT + (U/P)T dP

P T V

1.

2.

A B

3.

Q Q Q

Q
W

U = Q W

U = Q W

Q W U

Q W
U 0
Q W
U 0

dU = Q W
U
dU
Q
U
W
Q W

U Q W
a
b
c

 U
a
+
b
+
c
0
d

0
0

 2 a
U Q W
b
U
Q W

U Q W
a 0
0
0
b 0
0
0

 We
1.

We P dV

We = P dV
P
P

2. We

P P
A dl

We = Fd l = P Ad l = P dV
dV

V1 V2

P = 0

V2

We P dV 0
V1

P =

V2

We P dV P (V2 V1 ) P V
V1

3) P

d P

P = P d P

V2

V2

V2

V1

V1

V1

We P dV (P - dP) dV P
dV

dPdV

P
P

P = n RT/V

( T )

nRT
We P dV P
dV

dV
V1
V1
V1
V
V2 1
V2
nRT

dV nRT ln
V1 V
V1
V2

P1
nRT ln
P2

V2

V2

nRT
We P dV P
dV

dV
V1
V1
V1
V
V2 1
V2
nRT

dV nRT ln
V1 V
V1
V2

V2

V2

P1
nRT ln
P2

1 2

P
dP


P
P
P
dP ( P
dV P

dP )

P
V2


dV dV
We

dP

0 dV 0
V1V2 :
V2
V2
We PdV nRT ln (1)
V1
V1


dP
V1

 dP0
V2V1
V1

V2

V2

V1

W PdV PdV We (2)

We

V2

V1

V2
PdV nRT ln (1)
V1

V1

V2

V2

V1

W PdV PdV We (2)

dP 0 We
dP 0
W

V1V2V1

W = 0

U =

0
Q = U + W = 0

V1 P1 W =

0 Q = 0

1.

 P (V2V1)
V2 V1
+
P1 A
(
+ + )

2.

3.


1.

2.

298K 2mol H2 V1=15

dm3

1) P =
1atm 50 dm3
2) 50 dm3

(1)

T = T = T

T = T = T

T =T =T

 (1) P 1atm
50dm3

W1 =V1V2 P dV = P (V2V1)
=101325(5015)103 = 3546.4 J

(2) 50 dm3

W2 = nRT ln (V2 / V1)

= 28.314298ln (50/15)
= 5973.0 J
> W1 = 3546.4 J

(1) (2)

1atm 100C

P =1atm

373K 1atm
(dP)

We = P dV = PdV = P V
P

P 1atm V

V = Vv V l
Vv Vl


Vv = n RT / P

We = P n RT/ P = n RT
n mol
*

*
We = P
V


P = 0.5 atm ( 373K
P1= 1atm )

( 373K ) T =
373K P2= P = 0.5 atm

Vv = nRT/P Vl

We= P dV= P V = P Vv = P2 Vv =

nRT

We P ( 0 )

We = nRT
P 0

P = 0 We = 0

 373K P1=1atm

W , min = P2P1P dV + P1( Vl Vv )

= nRT ln (P2/P1) P1Vv
= nRT ln (0.5 atm/1atm) nRT
= 1.693 nRT

1.693nRT nRT

0.693 nRT

Wf = 0

dU = Q We = Q P dV

1.

dV0

Q v = dU
V

Qv =U1U2 dU = U2 U1 = U
Wf = 0

a. U
Qv

b.

dV0

dV 0 V1V2 dV = V= 0

V1 = V2

We =V1V2P dV = P V1V2 dV = 0
We 0

Qv = U

We =V1V2 P dV 0

Qv U

Qv= U

Qv = U
Wf = 0

2.

P dP0
P P = P

dU = Q P dV

Qp= U +V1V2 P dV = U +V1V2 P dV

= U + PV1V2 dV = U + PV

Qp = U + PV

= (U2 U1) + P ( V2 V1)

= (U2 + P V2) (U1+ P V1)

P V U

U+PV

U + PV

H U+ PV

H=(U+ PV) = U+ (PV)

H = U+ PV

Qp = U + PV = H

Q P = H
Wf = 0 )


P1 = P2 = P =
dP 0

Q ( ) = U + We = U + P V
= U + P2V2 P1V1
= U + (PV)
= H


, H

QP

Q P = H
Wf = 0 ( )

QP H

QP


U H
U H

U H

QV = U
Wf = 0

QP = H
Wf = 0

 U
H

1. U V

Joule 1843

dT = 0

Q = 0

 We = 0

dU = Q We = 0

U = Q We = 0

U = U (T, V) U

dU = (U/T)V dT + (U/V)T dV

Joule

dU = 0 dT = 0 dV 0

(U/V)T = 0

(U/V)T = 0

U = U (T)

Joule

 (U/V)T 0

(U/V)T 0

(U/P)T = (U/V)T(V/P)T

(U/V)T 0 (V/P)T 0

(U/P)T 0

(U/V )T = 0
(U/P )T = 0

2.

H U + PV

H U + ( PV )

U = 0

PV = nRT =

(PV) = 0

H = 0

H = H (T)

U = Q W = 0

Q=W

Q = W = nRT ln (V2/V1)
= nRT ln (P1/P2)

1. C H U
T1 T2
Q (T1,
T2) Q / T

(T1, T2)

T
Q T
T

C (T) = Q / dT

T=T

CV CP

CV = Qv / dT

CP = QP / dT

Wf = 0

Qv = dU + We = dU

Cv = dU /dT ( V )

Cv = (U/T )v

Wf = 0

Cv = (U/T )v

(dU)v = Cv dT

U = U ( T ) P V

(dU) = Cv dT

(dU) = Cv dT

(dU) = (dU)v,
= (dU)v,

+ (dU)T,

+ 0 = (dU)v = Cv dT

 2
QP = H

QP = dH
CP = QP /dT = dH /dT

CP = (H/T)P

(dH)P = CP dT

(dH) = (H/T)P dT + (H/P)T dP

= (H/T)PdT + 0

(dH) = CP dT

2. Cv CP
1 mol

Qm = dUm + P dVm

Q U V m mol

dUm = Cv, m dT

Qm = dUm + P dVm

dUm = Cv, m dT

PVm = RT Vm = RT/ P

P=P

(dVm)P = d (RT/P) = (R/P) dT

= (R/P ) dT

Q P, m= Cv, m dT + R dT

Q P, m = Cv, m dT + R dT

Q P, m /dT = Cv, m + R

CP, m = Cv, m + R

CP, m Cv, m = R

C P C v = nR

3.


:
CP, m = a + b T + c T2 +

CP, m = a + b T + c / T2 +
CP, m

a b c c

 1atm 1mol CO2 25C

200C

C P, m CO2 =
26.00 + 43.5103 T 148.3107 T2

Q P, m = H m = T1T2 CP, m dT
= 298473 (26.00 + 43.5103T
148.3107T2) dT

4.
1 1mol
CP, m
mol
2

C P, m T

c c

1.

2.

dU = Q W

Q=0
dU = W

(W0)

(dU < 0)

dU = CvdT = n Cv, m dT

W = P dV = PdV

dU = W

n Cv, m dT = P dV = (nRT/V ) dV

Cv, m (dT/T) = R (dV/V)

Wf = 0

dUm / dT =

Cv, m = ( Um/T ) v

Cv, m

Cv, m = (3/2) R ( )

Cv, m = (5/2) R ( )

Cv, m (dT/T) = R(dV/V)

T1T2 Cv, m d lnT = Cv, m T1T2 d lnT

= R V1V2 d lnV

Cv, m ln (T2/T1) = R ln (V2/V1)

Cv, m ln (T2/T1) = R ln (V2/V1)

T2 / T1 = P2V2 / P1V1

CP, m Cv, m = R

Cv, m [ln (P2/P1) + ln (V2/V1)]

= R ln (V2/V1)

Cv, m [ln (P2/P1) + ln (V2/V1)] = R ln (V2/V1)

Cv, m ln (P2/P1)
= R ln (V2/V1) Cv, m ln (V2/V1)
= ( R + Cv, m ) ln (V2/V1)
= CP, m ln (V2/V1)
= CP, m ln (V1/V2)

Cv, m ln (P2/P1) = CP, m ln (V1/V2)

P2 / P1= (V1/ V2)Cp, m /Cv, m = (V1/ V2)
= CP, m /Cv, m = 1 + R /Cv, m 1

P 1 V 1 = P 2 V 2

P V = 1

P V =

P = nRT/V 1

T V 1 =

1
2

V = nRT/P 1

T / P 1 = 3

(1), (2), (3)

Wf = 0 T, V, P

P V =

T V 1 =

T / P 1 =

P V = n

RT

 V, P

P V

(dP/dV)T= d(nRT/V) /dV = nRT/V2

= PV/V2 = P/V
P/V

P V = K
(dP/dV) = d (K V )/dV = K / V 1+
= PV / V 1+ = (P/V)

(dP/dV) = ( P/ V )

= CP, m / Cv, m 1

(P/V) ( V, P )
(P/V)

 V, P

a

b

P1 a
(dP/dV )
(dP / dV ) T

P1
P1

= ( P1/V1)

= P1/ V1

1 V1 < V1

 P1

 V1
b

(dP/dV)

(dP/dV ) T

V1
V1

= ( P1/V1)

= P1/ V1

1 P1 P1

 V1


( b)

dU = W ( )
U = We ( , Wf = 0 )

3.

We= P (V2V1)
, , Wf
=0

U = We = P (V2V1)
( dU ) = Cv dT
U = T1T2 Cv dT , Wf =

U = Cv (T2 T1) = We
Wf = 0

H = U + (PV) = U + nRT
= Cv (T2T1) + nR(T2T1)
= CP (T2T1)

H = CP (T2 T1)
Wf = 0

= CP, m / CV, m = [(3/2) +1]/(3/2) = 5/3

T / P 1 =
T2 = (P2/P1)( 1)/ T1 = (1/5)0.4 273
= 143.5 K

P 1V1 = P2V 2

V2= (P1/P2)1/ V1= (5/1)3/5 10 = 26.3 dm3

:
n = P1V1/ RT1
= 5 101325 10 10 3/(8.314 273) = 2.23

U = n CV, m (T2T1)
= 2.23(3/2) R (143.5 273)
3600 (J)
We = U = 3600 (J)

 1atm

n Cv, m (T2T1) = P (V2V1)

= P ( nRT2/ P2 nRT1/ P1)
( P2 = P = 1atm)

T2= ( P2R / P1+Cv, m) T1/ CP, m = 185.6 K

U = n Cv, m (T2T1) = 2430 J

4. ( )

( )

( P = P2)
( b)

( P-V ) (
)

 -
1.

P1V1

We = P2V2 P1V1
Q = 0

U = U2 U1 = We = P1V1 P2V2

U1 + P1V1 = U2+ P2V2

H2 = H1 H = 0

2. -

J-T = ( T/ P)H

J-T

H2 , He

J-T = 0

H = H ( T, P )
dH = (H/T)P dT + (H/P)T dP

dH = 0

(T/P)H(H/T)P(P/H)T = 1
( P459 )

 J-T = ( T/P )H = (H/P)T /(H/T)P

= [ (U+PV) / P]T / CP
J-T = (1/CP) (U/P)T (1/CP) [(PV)/P]T

(U/P)T = 0
[ (PV)/P]T = [(nRT)/P]T = 0

J-T = 0

( )

 J-T = (1/CP) (U/P)T (1/CP) [(PV)/P]T

(U/P)T < 0

J-T : (1/CP) (U/P)T > 0

J-T [(PV)/P]T

CH4 [ (PV)/P]T < 0

J-T

J-T

[(PV)/P]T > 0

J-T

J-T

H2 [(PV)/P]T > 0
J-T < 0

J-T 0

J-T = 0

H U P52-54

( P + a/Vm2 ) ( Vb) = RT P53

1.4

1.

2.

3.

4.

Q
Q

5.

mol

1.

We = 0
Qv = rU dV = 0 Wf = 0
Qv

Qv

Qv = rU = ( U ) ( U )

2.

We 0

Q P = rH d P = 0 Wf = 0

Q P = rH = ( H ) ( H )

rH rU
rU
r H QP

3. Q P Q v

H U + PV

( rH )p = ( rU )p + ( PV )p
= ( rU )p + P V
( rU )v + P V

Q p Q v + P V

rH = rU + P V

( rU )p ( rU )v

( rU )p = ( rU )v

( rU)p

( rU)v rU
( rU)p ( rU)v

 r H = r U + P V
1 V 0 Qp
Qv

Qp rU
P V

 r H = r U + P V
2 V 0

Q p Q v
3 V = 0 rH = rU
4 V
PV Qp Qv
rH rU

 r H = r U + P V

5
T
P V
mol

V = n ( RT/ P )

n mol

 rH = rU + PV
= rU + n RT
Q p = Q v + n RT

Qv
( rU)
Qp ( rH )

Q p = Q v + n RT

rU n RT ( rU)P
PV

( rU)p ( rU)v = Qv
P V n RT

Q p = Q v + n RT

rH


1.

i R i j P j

= nPj / j

nPj mol

= 1 mol

H2 + I2 2HI

= 1 mol 1 mol H2 1
mol I2 2 mol
HI

= 2 mol 4 mol HI

2.

H U

= 1 mol

rHm

r reaction
fH
cH

m mol

1)
rHm
298.15 K
P rHm
( 298.15K ) P

rHm rHm ( P, T )

2)

a. ( g )
P
b. ( l )
c. ( s )
C C

d.

e. (aq.)
NaOH (aq.) NaCl (aq.)

(aq.)

HCl (aq.) + NaOH (aq.) NaCl (aq.) + H2O (l )

rHm (298.15K) = 57.3 kJ/mol

CO2
C + O2 g CO2 g
rHm (298.15K) = 393.1 kJ/mol

H2 g + I2 g 2HI g
rHm ( 573K ) = 12.8 kJ/mol

3. rHm
rHm

H2 I2

H2

g + I2 g 2HI g

rHm = 2HHI (g) ( HH2 (g) + HI2 (g) )


rHm

rHm ( ) = rHm ( )

= 1 mol

rHm


H2(g) + O2(g) H2O (l)
rHm (298K) = 285.5 kJ/mol
2 H2 (g) + O2 (g) H2O (l)
rHm (298K) = 571.0 kJ/mol

rHm

rHm

1840

1.

2.

1)
Wf = 0 We = P dV

Q = dU + P dV

2) P = P =
dV 0

Qp = rU + PV = rU + (PV)
= ( U +PV ) = rH
rH

Qv = rU
rU

Wf = 0

rH rU

3.

= 0) ( )

(Wf

4.


C (s) + O2 (g) CO (g)

298.15K P
rHm(298.15K)

CO
CO2

C (s) + O2 (g) CO (g)

C : O2 2 : 1
CO2

C CO2

O2

(1) C s + O2 g CO2 g
r1Hm (298.15K) = 392.9 kJ/mol

CO CO CO2

(2)

CO g + O2 g CO2 g
r2Hm (298.15K) = 282.6 kJ/mol

P Wf = 0

C (s) CO2

CO
CO2

r1Hm = rHm + r2Hm

rHm = r1Hm r2Hm
= 392.9 +282.6 = 110.3 kJ/mol

(1) C s + O2 g
CO2 g

(2) CO g + O2 g

CO2 g

C s + O2 g CO g

rHm = r1Hm r2Hm

= 110.3 kJ/mol

 2. rHm (298.15K)
1 CH3COOH (l) + 2O2 (g) 2CO2 (g) + 2H2O (l)
1H = 208 kcal/mol
2 C (s) + O2 (g) CO2 (g)

2H = 94.0 kcal/mol

3 H2 (g) + O2 (g) 2H2O ( l ) 3H = 68.3 kcal/mol

4 2 C (s) + 2 H2 (g) + O2 (g) CH3COOH ( l )

CH3COOH ( l ) 4H = ?

(4) = (2) 2 + (3) 2 (1)

4H = (94.0)2+(68.3)2(208) = 116.6 kcal/mol

P 1 mol

 298K P

H2(g) + Cl2(g) HCl(g)

rHm (298.15K) = 92.0 kJ/mol

1mol HCl (g)

HCl (g) 298.15K P

f Hm ( 298.15K HCl(g) )

HCl (g) 298K P

HCl (g)


1 ) rH

rH = (H)P (H)R

rH

U H U + PV

2 )

rH

A B rH
A HA= 0

rH = HB HA
HB = rH + HA = rH

rH

1mol rH

a.

C ( )

C ( ) C ( )
C ( )

fHm (C, ) = 1.90 kJ/mol

b.

298K P
1 mol

 1 Cl2 g + 2Na s 2NaCl s

r1Hm = 2 fHm NaCl
2 Cl2 g + Mg s MgCl2 s
r2Hm = fHm MgCl2

1 2
3 ) 2Na (s)+ MgCl2 (s) Mg (s)+ 2NaCl (s)

r3Hm = r1Hm r2Hm

= 2 fHm (NaCl) fHm (MgCl2)

rH

rH = ( f H )P ( f H )R

rH = ( H )P ( H )R

( f H)R + rH = ( f H)P

rH = ( f H)P ( f H)R

 rH = ( f H)P ( f
H)R
: fH 0

CH3OH

C + O2 + 2H2 CH3OH

( ) fHm (

1 mol

( )

(P)
298K

CO2 (g)

H2O (l)

S N
SO2 (g) N2 (g)


CH
3OH (l) + 3/2 O2 (g) CO2 (g) + 2H2O (l)
rHm (298.15K) = 725.9 kJ/mol

1mol CH3OH (l)

CO2 H2O
c Hm (298.15K, CH3OH )
= 725.9 kJ/mol

cH )R = rH ( cH )P
rH ( cH )R ( cH )P

rH ( cH )R ( cH )P

rH


1)

2)


C2H5OH (l) 298K cHm = 1368 kJ/mol

C2H5OH (l) + 3O2 (g) 2CO2 (g) + 3H2O (l)

rHm = 1368 kJ/mol

rHm = 2 fHm(CO2) + 3 fHm(H2O)

fHm(C2H5OH 3 fHm(O2)

 fHm(H2O) = 285.84 kJ/mol

fHm(CO2) = 393.51 kJ/mol

fHm(C2H5OH)
= 2 fHm(CO2)+ 3 fHm(H2O) rHm
= 2393.51 3285.84 +1368
= 276.54 kJ/mol

H2O (l)
H2 (g) + O2 (g) H2O (l)
r Hm = 285.84 kJ/mol
r Hm = fHm (H2O) = cHm(H2)

r Hm ( fH )P ( fH )R
( cH )R ( cH )P

 : P6568

rHm (298K) = ( ) R ( ) P
P6970
H+ (, aq. )

P7274

1.5

rH

T P

RP

r H HP H R

( T+dT )

P
r

( rH /T)P = (HP /T)P (HR /T)P

= CP ( P ) CP ( R )
= rC P
rCp

rC P = ( C P ) P ( C P ) R

( rH /T)P = r CP

1 rCP
0 ( rH/T)P 0
( )

2 rCP 0

3 rCP= 0

( rH / T )P = rCP


r H 2

d( H) H
r

T2

r H1

r H 1 r C P dT
T1

rH1 rH2 T1 T2

1
rCP

 rH 2 r H 1 = r C P ( T 2 T 1 )

rCP CP T1, T2

2
C P = a + b T + c T2
rC P = a + b T + c T2
a = ( a)P ( a)R b c

rH2 rH1 = a (T2 T1) + (b/2) (T22 T12)

+ (c/3) (T23 T13)

CP, m= a + bT + cT2
1 mol
rCP


( rH/T)p = rCP
rH = rH0 + rCPdT

rH0 rCP = a + bT

+ cT2

rH = rH0 + aT + (b/2)T2 + (c/3)T3

H0 a b c

 rH = rH0 + aT + (b/2)T2 + (c/3)T3

rH 0
298K

rH0
T = 0 K

H2O l H2O g
373K 298K

CP

H2O

20C 150 C H2O

20C
150C 100C

H2 (g) + O2
20C rH1
QR

(g)

H2O

(l)

QP

H2 (g) + O2 (g)
(150C rH2

H2O (g)

rH2 = rH1 + Q P QR

QP = 293373 CP, m ( )dT + vHm(373K ) + 373423CP, m dT

=
QR = 293373 (CP, m (H2)+ CP, m(O2)) dT =

1.6

rHm = rHm(298K) + Hm(1) + Hm(2) = 0

Hm(1) = T1298 C P (R) dT
Hm(2) = 298T2 C P (P) dT
T2

1.7
( P7985 )

dU = Q

= ni d i

Q = i d ni

Cv = (3/2) R

Cv = (5/2) R
Cv = (7/2) R ( )