First Law in
Thermodynamics

1-3

W = K .
.W = - U

.

)(1-3

GV

)d W = F ds = F ds cos , = (F , ds

.


)(2-3

d W = F ds = F ds cos

.
.
PVT.

1 -

2-3

1-2-3

Work in a volume change

) V (1-3
.Pe .
dA .dFe = Pe dA :
ds
)(3-3

dA ds

d W = Pe

:1-3

Pe

dV :
d W = Pe dV

)(4-3

dV dW
. dV

. 1 N.m-2 m-3

2 -

dW

1 N.m

) 1 Joule( .
4-3.

Pe )(
4-3 :
d W = P dV

)(5-3

2-2-3

.Vb
PVT Va
) (2-3 a b PVT .PV
:
Vb

P dV

)(6-3

= W

Va

a .b
a (Va< Vb) b .
b a .

3 -

:2-3

dW=PdV

) ( P V T
P V .W

3-2-3

PdV

: dV = 0 : . :P=constant 3-3 a .(Va < Vb) b

:3-3
Vb

)(7-3

Va ) = P V

P dV = P dV = P ( V

Va

Vb

4 -

Va

= W

) V=(Vb-Va .P
: P V .
:
)(8-3

T
dV
V

Vb

Va

nR T
dV = n R
V

Vb

Vb

= P dV

Va

= W

Va

- T=constant :-4-3 :)(9-3

V > 0 Vb > Va
dV
= n R T ln b
V
Va < 0 Vb <Va

Vb

W = nR T

Va

:4-3
:3-1
) (T v1 .v2
a b
2 kilomole 30 m3 60 m3 .T=100 0C

:


5 -

( :
RT
a
2
v b v

)(10-3

=P

P v 6-3
:
)(11-3

dv
2

v2

v2

v1

v1

R T a dv = R T d v a

v b v2
v b

v2

v2

= w = P dv

v1

v1

:
1
v b
1
w = R T ln 2
+ a
v1 b
v2 v1

)(12-3

( a b :
a(H2O) =580 J kilomole-2 m3 b(H2O) =0.0319 m3 kilomole-2

R 8.314110 J3 kilomole-1K-1 :
30 0.0319
1 1
w = 8.3143 103 373.15 ln
+ 580
15 0.0319
30 15
= 2153780 J kilomole -1

( a b :
:

WVan der Waals=2 w=4307599 J

( 9-3:
60
= 4300952 J
30

WIdeal gas = 2 8.3143 103 373 .15 ln

WVan der Waals WIdeal gas 6674 J

.

6 -

3-3

:
dW = Y dX

)(13-3

Y X . 1-3

.
:

PVT

dW = P dV

dW = - F dL

dW = E dp

:1-3
)(14-3

Y dX = Y1 dX1 + Y2 dX2 + Y3 dX3 +

= dW

4-3

PVT a b .5-3
I II

II )

7 -

( .

:5-3

. dW

.
. dW
a b b a
) .(cyclic process I II
) (Net work ) ( .
b a a b
. :
)(15-3

W = dW = P dV

.
.

8 -

5-3

1-5-3

Configuration workDissipative work

(dW = Y dX = Y1 dX1 + Y2 dX2 + Y3 dX3 + ) 14-3

X3 X2 X1 .
i R . :
W = i 2 R dt .

. .
.

2-5-3

Free expansion of a gas

.
6-3 .
. " " )
"" "" ( .

4-3 .

9 -

:6-3

3-5-3

.

.
.
.

6-3

1-6-3

First Law of
Thermodynamics

10 -

 a :b .

.
.
.
.
7-3 .

:7-3 a

a b .b c a
.-
a c -
. .b
) ( c b
.b c a
.b d a a
b -
.d d

11 -

 - . ) (


.bd a
.
)( e
b e a a e
) .
.b e b
(.
b e a e a
.b e

d (Wde) e e .(Web) b

2-6-3

a b
:
"
" . .
.

12 -

7-3

1-7-3

Internal Energy

:
b

)(16-3

dW

adiabatic

= Wadiabatic

dWadiabatic .



dWadiabatic dWadiabatic .

a b
U
a .b : .
2-7-3

dU

U )

dU

( dU . dU - dWadiabatic :
dU = - dWadiabatic

)(17-3

dU )( )(
. :
Ub

)(18-3

= Wadiabatic

dW

adiabatic

13 -

Ua =

dU = U

Ua

8-3

1-8-3

Heat Flow

.

. " " .

2-8-3

.
W
Wadiabatic Q W
.Wadiabatic
Q = W - Wadiabatic

)(19-3

Q U . Q U
.

3-8-3

14 -

W Wadiabatic Q
) (W > Wadiabatic ) .(W < Wadiabatic Q>0
Q<0 .

.

. ) (Q<0
) .(Q>0 " " ""
.

) ( reversible

4-8-3

W W = Wadiabatic .Q=0

:
.
.

5-8-3

15 -

a
b U :
Wadiabatic = Ua - Ub

)(20-3

) (3-18 :
)(1-21-3

)Q = W - Wadiabatic = W - (Ua - Ub

:
Ub - Ua = Q - W

)(2-21-3

.
:
dU = d Q dW

)(22-3

) (2-21-3 ) (22-3 )(

. 22-3 .
(dW = P dV) PVT
:
dU = d Q P dV

)(23-3

Y :X
)(24-3

Y dX
16 -

dU = d Q

dQ

9-3

dQ

dW = dU + dQ dQ ) (dU

)(dW

dW dQ
dQ
.
"" point function
. a b:
b

Q = d Q

)(25-3

a .b )) Q0=Q(a " " (a

" " .b

:
)(26-3

dQ 0

17 -

= Q

10-3

1-10-3

" "

The Mechanical Equivalent of Heat

a b
) (U = Ub - Ua :
Wd )  = ( G 4 ).(Wconfiguration= 0
" "
.
Wd:
)(27-3

|Ub - Ua = |Wd

.
.
:
)(28-3

Ub - Ua = 0

Wd
. " : "
"" .

.

18 -

3-10-3

U = 0" "

.
R i W
. W = i 2 R dt : .

. U = Q - W .Q = Wd
" : "
.

4-10-3

calorie
. ""
) 0C 1 C 50 C (51 C
14.5 C 15
) (1 15 degree calorie
14.5 C .15.5 C
)
14.5 C (15.5 C 4.1858 J :
1 15-degree calorie = 4.1858 J

19 -

4.1858
):(IT = International Table
1 IT calorie= 4.1860 J

860
15.

5-10-3

.
) (caloric

11-3

1-11-3

Heat Capacity

.
:

)(29-3

Q
T

)(30-3

Q
d Q
=
T 0 T
dT

= C
C = lim

20 -

C .J K-1
Q dQ
dT

.
dQ
dQ "" T .

dQ ) ( ) (
) ( C
- + . CP
.Cv

2-11-3

CP Cv

)(
heat capacity at constant pressure CP
.
heat capacity at constant volume .CV
CV
CP . CP
.

21 -

3-11-3

dQ
. .
R )( R ) i .(3-10-3
dWd i )
(

4-11-3

= G 4

. G :G

specific heat capacity

cP = CP /m : cv = CV /m :
) J K-1 kg-1 J K-1 mole-1 m n (
cP cv
.
8-3
P = 1 atm .

22 -

:8-3 cP cv
- :8-3

P = 1atm

Dulong and Petit value

- ) 250 C( cP cv

P = 1atm

.

cP cv ) 3R (25 KJ kilomole-1 K-1

R .
cv 3R .
" " ) (Dulong and Petit value
)( .

. 9-3 cP cv
T = 0 C 0 atm .7000 atm :

23 -

:9-3 cP cv

T = 0 C

cP cv . - cP 28 KJ kilomole-1 K-1

cv

.3R
2-3 cP/R cv/R
) ( )
(.
cP/R

cv/R

cP c v
R

He

2.50

1.506

0.991

Ne

2.50

1.502

0.975

2.51

1.507

1.005

H2

3.47

2.47

1.00

O2

3.53

2.52

1.01

N2

3.5

2.50

1.00

CO2

4.47

3.47

1.00

NH3

4.41

3.32

1.10

:2-3 cP cv


24 -

:
cv/R 3/2=1.50
cv/R 5/2=2.50

cP/R 5/2=2.50

cP/R 7/2=3.50

- cv = R cP .

12-3

Heat Reservoir

:
T2

)(31-3

T2

dQ = C d T = n c d T
T1

=Q

T1

C :

)(32-3

)Q = C (T2 - T1) = n c (T2 - T1

.

.
.

25 -

13-3

Enthalpy

Heat of Transformation - Enthalpy

. . :
- - - m
.
:
)(33-3

heat absorbed
= l
m

l ) .J/kg m n (
)

(.

:

)(34-3

)w = P (vf - vi

:
)(35-3

)uf ui = l - P (vf - vi

)(36-3

)l (uf - ui) + P (vf - vi) = (uf + P vf) - (ui + P vi

u + P v v P u
"" h = u + P v :

26 -

Enthalpy

) J/kg (J/Kilomole:
)(37-3

l h = hf - hi

.

. llv lsl lsv
. ) (fusion
) (vaporization ) (sublimation ) .
' '' ''' (.
:2-3 100 C
) P = 1 atm v'' = 10-3 m-3 (v''' =1.8 m-3
llv = h - h :

22.6105 J/kg

:
w = P (v - v) = 1.013 105 (18 - 0.001) 1.7 x 105 J kg-1

:
u = u - u = llv - w = 20.9 105 J kg-1 2.1 MJ kg-1

92% 58%
.

10-3 . llv

27 -

Enthalpy

. h
.h = 0
.

:10-3
h .
.
:
h1 = l13 = lsv

)(38-3

:
)(39-3

h2 = - l23 = - llv

h3 = - l12 = - lsl

h = h1 + h2 + h3 = 0 :
)(40-3

l13 - l23 - l12 = 0

)(41-3

l13 = l23 - l12

28 -

14-3

) ( .

EK
.W :
EK = - W

)(42-3

Q
W :
U + EK = Q - W

)(43-3

Wc
.Ep :
Ep = + Wc

)(44-3

*W W- Wc 3-35
:
)(45-3

*U + EK = Q - W = Q - (W* + Wc) = Q - WWc

)(46-3

*U + EK + Ep= Q - W

29 -

)(47-3

E = U + EK + Ep

:
)(48-3

E = U + EK + Ep

a Ea b
Eb :
)(49-3

*E = Eb - Ea = Q - W

dQ *dW dE:
)(50-3

*dE = dQ dW

.*W

.

.

Q = 0 W* = 0 E = 0 46-3

30 -

.
.

31 -