Termodinmica Qumica
MEQ/MEB
2010/2011
Edmundo Gomes de Azevedo
egazevedo@ist.utl.pt
http://web.ist.utl.pt/ist10738/
Miguel Rodrigues (prticas MEQ)
miguelrodrigues@ist.utl.pt
Ana Paula Serro (prticas MEB)
anapaula.serro@ist.utl.pt
2
BIBLIOGRAFIA
Adoptada:
- Edmundo Gomes de Azevedo, Termodinmica Aplicada, 2. Ed., Escolar
Editora (2000).
Aconselhada:
- R. J. Silbey, R. A. Alberty, M.G. Bawendi, Physical Chemistry, 4
. Ed., John
Wiley (2004).
- J. M. Smith, H. C. Van Ness, M. M. Abbott, Introduction to Chem. Eng.
Thermodynamics, 7. ed., McGraw-Hill (2005).
- K. Denbigh, The Principles of Chemical Equilibrium, Cambridge Univ.
Press (1989).
AVALIAO:
Exame final.
HORRIO DE ATENDIMENTO A ALUNOS:
4s. Feiras, 14h - 17h, 11
1
lim
p
T= pV
nR
0
( )
t(C) = T(K) 273.15
-273.15
O
C = 0 K
12
A B
B A
= =
n RT n RT
p p
V V
Misturas de Gases Ideais
= =
= + + =
= + + = = =
+ +
B C A
B C A
B C A
( )
i
i
RT
p n n n
V
RT RT RT
n n n
V V V
nRT
p p p p p
V
=
A A
A
A
= = y
p n RT /V n
n
p
nRT /V
A
A
= y p p
Lei de Dalton
y
y
y
13
=
=
n RT
n RT
nRT RT
p p p n n
V V V V
p p
2
H
2
2
2
He
= ( + )
H He H He
+
H He
= =
Partial Pressure of a Gas:
The pressure that the gas would exert if it were the only gas present in
the container.
15
Gases Reais
16
pV
z
nRT
= Gs Ideal z = 1
B, B = 2. coeficente de virial
C, C = 3. coeficente de virial
17
= = + +... 1
m
m
pV
pV
B
z
nRT RT V
=
B
(
c
m
3
/
m
o
l
)
T (K)
18
Equao de van der Waals
2
-
-
m
m
RT a
p =
V
V b
| |
|
|
\ .
=
2
2
+ ) ( -
n a
p
V
V nb RT
19
20
Equao de van der Waals: clculo de volumes molares
| |
|
|
\ .
=
2
2
+ ) ( -
n a
p
V
V nb RT
2
m m
-
-
RT a
p =
V b V
Exemplo: H
2
O, 200C, 15 bar
a = 5.536 atm L
2
mol
-2
b = 0.03049 L mol
-1
| |
|
\ .
- +
m m m
b
RT
p
a ab
V V V
p p
3 2
+ - = 0
V
m
(1) = 0.044 L
mol
-1
V
m
(2) = 2.505 L
mol
-1
V
m
(3) sem realidade fsica
21
22
c
c
m
2
2
m
0
0
=
=
| | c
=
|
c \ .
| |
c
=
|
c \ .
T T
T T
p
V
p
V
2
m
m
c c c
2
= -
-
8
= = = 3
27
27
RT a
P
V b
V
a a
p T V b
Rb
b
23
= = =
p
T V
p T V
p
T V
r r r
c
c c
=
T
p -
V
V
2
r
r
r
r
8
3
3 -1
Princpio dos Estados Correspondentes
Benzeno: 445 K, 36 atm
Azoto: 100 K, 25 atm
Mesmo p
r
, T
r Mesmo z
Igual desvio ao
comportamento de
gs ideal
24
Princpio dos Estados Correspondentes
z = z (p
r
,T
r
)
25
sat
=0.7
log( ) 1.0 e=
T
p
r
r
Metano: e = 0.011
Azoto: e = 0.039
n-Octano: e = 0.398
z = z
(0)
(p
r
,T
r
) + e z
(1)
(p
r
,T
r
)
Factor acntrico
de Pitzer