PROBLEMA 6

Deter min amos a y b

bar.mL 2
(83.145 ) .(407.85 K ) 2.5
a  0.42748 mol.K
DATOS DATOS SEGÚN EL HANDBOOK (36.3047bar ).(360.93K ) 0.5
bar.ml 2
P  15.72bar Pc  36.3047bar a  14393449.868100392
mol 2
T  360.93K Tc  407.85K bar.mL
J (83.145 )(407.85 K )
HV  13653 CÁLCULO DE LA ENTALPÍA PARA b  0.08664 mol.K
mol LA ECUACION DE REDLICH 36.3047bar
KWONG ml
USANDO LA ECUACIÓN DE b  80.9267678835
mol
REDLICH KWONG
Deter min amos Z
RT a bar.ml 2
P  2 (14393449.868100392 )(15.72bar )
v  b v  bv A 
* mol 2
 0.25124603
CÁLCULO DEL FACTOR DE bar.mL
Donde : (83.145 * 360.93K ) 2
COMPRESIBILIDAD
mol.K
R 2 .Tc 2.5
a  0.42748 Z 3  Z 2  ( A*  B*  B*2 ) Z  A* .B*  0 ml
Pc.T 0.5 (80.9267678835 )(15.72bar )
aP bP B 
* mol  0.04239216707
R.Tc A*  B*  bar.mL
b  0.08664 ( RT ) 2 RT 83.145 * 360.93K
Pc mol.K
PVreal Vreal
Z 
RT V*
Re emplazamos bar.ml
2 Z *83.145 *360.93K
Z 3  Z 2  ( A*  B*  B*2 ) Z  A* .B*  0 bar.ml mol.K ml
14393449.868100392  80.9267678835
3 mol 2 * Ln( 15.72bar mol )
Z 3  Z 2  (0.25124603  0.04239216707  0.04239216707 2 ) Z h  h*   *
2 ml bar.ml
0.25124603* 0.04239216707  0 80.9267678835 Z *83.145 *360.93 K
mol mol.K
 Z 3  Z 2  0.2070567671* Z  0.01065086368  0 15.72bar
 Z1  0.73947146 bar.mL
( Z  1)83.145 *360.93K
 Z 2  0.18092 mol.K
Re cordar que 1J  10bar.ml
 Z 3  0.0796

Se sabe que :
(h  h* )1  2269,082896 J / mol  Hv  2269,0829 J / mol
PVreal Vreal
Z  (h  h* ) 2  8074,822367 J / mol  Hv  8074,822367 J / mol
RT V*
bar.ml (h  h* )3  14150,66331J / mol  Hv  14150,66331J / mol
Z *83.145 * 360.93K
ZRT mol .K
 Vreal  
P 15.72bar
Por último reemplazamos en la ecuación de entalpías
 𝐵𝑎𝑙𝑎𝑛𝑐𝑒 𝑑𝑒 𝑒𝑛𝑡𝑟𝑜𝑝í 𝑎
𝑃 𝑟𝑜𝑐𝑒𝑠𝑜𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒𝑎𝑑𝑖𝑎𝑏 á 𝑡𝑖𝑐𝑜:
𝑃 1=1000𝑘𝑃𝑎 𝑪𝑶𝑴𝑷𝑹𝑬𝑺𝑶𝑹 𝑃 2=100 00 𝑘𝑃𝑎
𝑆 𝑒 𝑐𝑢𝑚𝑝𝑙𝑒: 0
𝑬𝑵𝑻𝑹𝑨𝑫𝑨 : 𝛿𝑄
˙ 𝑠 − 𝑠𝑒 ∙ 𝑚
𝑠𝑠∙ 𝑚 ˙ 𝑒=
𝑇
𝑃 1=700𝑘𝑃𝑎 𝑠1
𝐶𝑜𝑛𝑠𝑒𝑟𝑣𝑎𝑐𝑖ó 𝑛𝑑𝑒 𝑙𝑎𝑚𝑎𝑠𝑎:
𝑺𝑨𝑳𝑰𝑫𝑨: 𝑚
˙ 𝑒𝑛𝑡𝑟𝑎 =𝑚
˙ 𝑠 𝑎 𝑙𝑒

𝑃 2=100 𝑘𝑃𝑎 𝑠2 =𝑠 1 𝑃 𝑟𝑜𝑐𝑒𝑠𝑜𝑖𝑠𝑒𝑛𝑡𝑟 ó 𝑝𝑖𝑐𝑜 𝑠2 =𝑠 1 𝑚

˙ 𝑒 =𝑚
˙ 𝑠

𝑄𝑢𝑒𝑑𝑎𝑛𝑑𝑜 𝑎𝑠í :
𝑃 𝑜𝑟 𝑡𝑒𝑜𝑟 í 𝑎: 𝑭𝑬𝑬𝑺
❑ ❑ 𝑠 𝑠= 𝑠 𝑒
𝛿𝑄
∑ 𝑠𝑠 ∙ 𝑚˙ 𝑠 − ∑ 𝑠𝑒 ∙ 𝑚˙ 𝑒 ≥ 𝑇 𝑃𝑟𝑜𝑐𝑒𝑠𝑜𝑖𝑠𝑒𝑛𝑡𝑟 ó 𝑝𝑖𝑐𝑜
𝑠 𝑒
𝑷𝑹𝑶𝑪𝑬𝑺𝑶 𝑭𝑬𝑬𝑺:
𝑖 𝑃 𝑜𝑟 𝑡𝑒𝑜𝑟 í 𝑎:

( h𝑒 +
1 2
2 ) (1
˙ 𝑒 − h 𝑠 + 𝑣2𝑠 +𝑔 ∙ 𝑧 𝑠 ∙ 𝑚
𝑣 𝑒 +𝑔 ∙ 𝑧 𝑒 ∙ 𝑚
2
˙ 𝑊
˙ 𝑠 + 𝑄+ )
˙ =0

˙
𝑃 𝑒𝑟𝑜 𝑎𝑙𝑡𝑟𝑎𝑡𝑎𝑟𝑠𝑒 𝑑𝑒 𝑢𝑛𝑎 𝑡𝑢𝑟𝑏𝑖𝑛𝑎𝑎𝑑𝑖𝑎𝑏 á 𝑡𝑖𝑐𝑎 , 𝑠𝑒 𝑐𝑢𝑚𝑝𝑙𝑒: 𝑄=0

(
→ h𝑒 +
1 2
2 ) (1
˙ 𝑒 − h 𝑠 + 𝑣 2𝑠 +𝑔 ∙ 𝑧 𝑠 ∙ 𝑚
𝑣 𝑒 +𝑔 ∙ 𝑧 𝑒 ∙ 𝑚
2
˙ 𝑒 +𝑄 )
˙ +𝑊
˙ =0

𝑄𝑢𝑒𝑑𝑎𝑛𝑑𝑜 𝑎𝑠í :
˙ =𝑚
𝑊 ˙ ∙ ( h 𝑠 − h𝑒 ) ⋯ (𝛼) ˙ =∆ h
𝑊
𝑖 𝑖 𝑃 𝑜𝑟 𝑡𝑒𝑜𝑟 í 𝑎 :

[
𝑑h =𝐶 𝑝 ∙ 𝑑𝑇 + 𝑣 − 𝑇 ∙ ( )]
𝜕𝑣
𝜕𝑇 𝑃
𝑑𝑃 𝑑𝑠=𝐶 𝑝 ∙
𝑑𝑇
𝑇
−
𝜕𝑣
𝜕𝑇 ( ) 𝑑𝑃𝑃

𝑟𝑜
1 : 𝐺𝑎𝑠 𝑖𝑑𝑒𝑎𝑙
𝑇2 𝑇2

∆ h=∫ 𝐶𝑝 ∙𝑑𝑇
𝑘𝐽
→ ∆ h1 − 2=∫ 𝐶 𝑝 ∙ 𝑑𝑇 =∫ ( 20 , 8+52 ∙10 𝑇 )
−3
𝑃 𝑜𝑟 𝑡𝑒𝑜𝑟 í 𝑎: ∙ 𝑑𝑇
𝑇 1 𝑇 1
𝑘𝑚𝑜𝑙 ∙ 𝐾
𝑇2
∆ h1 −2= [ 20 , 8 ∙𝑇 +2 6 ∙ 10 ]
−3 2
∙𝑇
300 𝐾
 ∙ ( 𝑇 2 − ( 300 𝐾 ) ) ⋯(𝛽)
−3 2 2
∆ h1 −2= 20 , 8 ∙ ( 𝑇 2 − 300 𝐾 ) + 26 ∙10

𝑑𝑇
𝑃 𝑜𝑟 𝑡𝑒𝑜𝑟 í 𝑎: ∆ 𝑠=∫ 𝐶 𝑝 ∙ − 𝑅∙𝑙𝑛𝑃
𝑇

( ) ( )
𝑇2 𝑇2
𝑑𝑇 𝑃2 𝑘𝐽 𝑑𝑇 𝑃2
→ ∆ 𝑠1 −2 =∫ 𝐶 𝑝 ∙ − 𝑅 ∙ 𝑙𝑛 =∫ ( 20 , 8+52 ∙ 10 𝑇 )
−3
∙ − 𝑅 ∙𝑙𝑛
𝑇1
𝑇 𝑃1 𝑇 1
𝑘𝑚𝑜𝑙 ∙ 𝐾 𝑇 𝑃1

(
∆ 𝑠 1− 2=20 ,8 ∙ 𝑙𝑛
𝑇2
300 𝐾 ) −3
+52∙ 10 ∙ ( 𝑇 2 −300 𝐾 ) − 𝑅 ∙ 𝑙𝑛 (
100 00 𝑘𝑃𝑎
100 0 𝑘𝑃𝑎 ) 𝑅=8,314
𝐽
𝑚𝑜𝑙 ∙ 𝐾
0
𝑂 𝑝𝑒𝑟𝑎𝑛𝑑𝑜 𝑐𝑢𝑖𝑑𝑎𝑑𝑜𝑠𝑎𝑚𝑒𝑛𝑡𝑒:
→ 20 , 8 ∙ 𝑙𝑛( 𝑇2
300 𝐾 )
+52 ∙10 −3 ∙ ( 𝑇 2 − 300 𝐾 ) = 𝑅 ∙ 𝑙𝑛 ( 10 ) 𝑇 2=480,079 𝐾

𝐴 h𝑜𝑟𝑎𝑟𝑒𝑒𝑚𝑝𝑙𝑎𝑧𝑎𝑚𝑜𝑠 𝑒𝑠𝑎𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑎𝑒𝑛 𝛽 𝑑𝑎𝑛𝑑𝑜 𝑙𝑜 𝑠𝑖𝑔𝑢𝑖𝑒𝑛𝑡𝑒:

∆ h1 −2= 20 , 8 ∙ ( 480,079 𝐾 − 300 𝐾 ) + 26 ∙10 −3 ∙ ( ( 480,079 𝐾 )2 − ( 300 𝐾 )2 )
𝑘𝐽
∆ h1 −2=7398,0152
𝑘𝑚𝑜𝑙
𝐴 h𝑜𝑟𝑎𝑟𝑒𝑒𝑚𝑝𝑙𝑎𝑧𝑎𝑚𝑜𝑠 𝑒𝑠𝑎𝑑𝑖𝑓𝑒𝑛𝑐𝑖𝑎 𝑑𝑒 𝑒𝑛𝑡𝑎𝑙𝑝 í 𝑎𝑒𝑛 𝛼 𝑑𝑎𝑛𝑑𝑜 𝑙𝑜 𝑠𝑖𝑔𝑢𝑖𝑒𝑛𝑡𝑒:
˙ 𝑖𝑑𝑒𝑎𝑙 =7398,0152 𝑘𝐽
˙ =∆ h 𝑄𝑢𝑒𝑑𝑎𝑛𝑑𝑜 𝑎𝑠í : 𝑊
𝑊
𝑘𝑚𝑜𝑙
 𝑑𝑜
2 : 𝐺𝑎𝑠𝑟𝑒𝑎𝑙

𝑃 𝑜𝑟 𝑡𝑒𝑜𝑟 í 𝑎:
[
𝑑h =𝐶 𝑝 ∙ 𝑑𝑇 + 𝑣 − 𝑇 ∙
𝜕𝑣
𝜕𝑇 ( ) ] 𝑑𝑃 ( )
𝑃
𝜕𝑣
𝜕𝑇 𝑃
=
𝑅
𝑃
𝑑𝑠=𝐶 𝑝 ∙
𝑑𝑇
𝑇
− ( ) 𝑑𝑃
𝜕𝑣
𝜕𝑇 𝑃

𝑟𝑎
1 𝑒𝑡𝑎𝑝𝑎 : 𝐼 𝑠𝑜𝑡 é 𝑟𝑚𝑖𝑐𝑜 𝑎 𝑇 1

( ) ( ) ( )
∗
𝜕𝑣 𝑅 𝑎 𝑃 𝑎
− 2 ∙ ( 𝑃 − 𝑃 1)
∗
𝑑𝑠=− 𝑑𝑃 → ∆ 𝑠1 − 𝑎=− + 2 𝑑𝑃=− 𝑅 ∙𝑙𝑛
𝜕𝑇 𝑃 𝑃 𝑇 𝑃1 𝑇1
𝑑𝑎 ∗
2 𝑒𝑡𝑎𝑝𝑎 : 𝐼 𝑠𝑜𝑏 á 𝑟𝑖𝑐𝑜 𝑎 𝑃
𝑇2 𝑇2

∆ 𝑠 𝑎− 𝑏=∫ 𝐶 𝑝 ∙
𝑇 1
𝑑𝑇
𝑇 𝑇
=∫ 20 ,8 +52∙ 10 𝑇 ∙
(
1
−3
) 𝑑𝑇
𝑇
→ ∆ 𝑠𝑎 −𝑏 =20 , 8 ∙ 𝑙𝑛
𝑇2
300 𝐾
−3
( )
+52∙ 10 ∙ ( 𝑇 2 − 300 𝐾 )
𝑟𝑎
3 𝑒𝑡𝑎𝑝𝑎 : 𝐼 𝑠𝑜𝑡 é 𝑟𝑚𝑖𝑐𝑜 𝑎 𝑇 2

∆ 𝑠 𝑏 −2=−
( 𝑅 𝑎
)
+ 2 → ∆ 𝑠 𝑏 −2 =− 𝑅 ∙ 𝑙𝑛
𝑃 𝑇
𝑃2
𝑃 ∗ ( )
𝑎
− 2 ∙ ( 𝑃2− 𝑃 )
𝑇2
∗

𝐴 h𝑜𝑟𝑎:
∆ 𝑠 1− 2=∆ 𝑠 1− 𝑎+ ∆ 𝑠𝑎 − 𝑏 +∆ 𝑠𝑏 − 2

( ) ( ) ( )
∗
𝑃 𝑎 𝑇2 𝑃2 𝑎
∆ 𝑠 1− 2=− 𝑅∙ 𝑙𝑛 − 2 ∙ ( 𝑃 ∗ − 𝑃 1 ) + 20 , 8 ∙ 𝑙𝑛 +52 ∙ 10−3 ∙ ( 𝑇 2 − 300 𝐾 ) − 𝑅 ∙𝑙𝑛 − ∙ ( 𝑃 2 − 𝑃 ∗
)
𝑃1 𝑇1 300 𝐾 𝑃∗ 𝑇 22
 ∆ 𝑠 1− 2= 𝑅 ∙ 𝑙𝑛
( ) (
𝑃2
𝑃1
− 𝑎∙
𝑃2 𝑃1
2
−
𝑇2 𝑇12
+20 ,8 ∙
)
𝑙𝑛
𝑇2
300 𝐾
+52∙ (
10
−3
)
∙ ( 𝑇 2 −300 𝐾 ) =0

𝑅 ∙ 𝑙𝑛
( ) 𝑃2
𝑃1 (
+ 20 , 8 ∙ 𝑙𝑛
𝑇2
300 𝐾 ) −3
+52 ∙10 ∙ ( 𝑇 2 −300 𝐾 ) =𝑎 ∙
𝑃2 𝑃1
−
(
𝑇 22 𝑇 21 )
𝑂 𝑝𝑒𝑟𝑎𝑛𝑑𝑜:
∴ 𝑇 2 =698,373 𝐾

𝐿𝑢𝑒𝑔𝑜 𝑟𝑒𝑝𝑒𝑡𝑖𝑚𝑜𝑠𝑒𝑙𝑚𝑖𝑠𝑚𝑜𝑝𝑟𝑜𝑐𝑒𝑑𝑖𝑚𝑖𝑒𝑛𝑡𝑜 𝑝𝑎𝑟𝑎 h𝑎𝑙𝑙𝑎𝑟 ∆ h :

𝑟𝑎
1 𝑒𝑡𝑎𝑝𝑎 : 𝐼 𝑠𝑜𝑡 é 𝑟𝑚𝑖𝑐𝑜 𝑎 𝑇 1

𝑑 h= 𝑣 −𝑇 ∙
[ ( )]
𝜕𝑣
𝜕𝑇 𝑃
𝑑𝑃 → ∆ h1 −𝑎 = 𝑏−
( 2∙ 𝑎
𝑇1 )∙( 𝑃 − 𝑃1)
∗

𝑑𝑎 ∗
2 𝑒𝑡𝑎𝑝𝑎 : 𝐼 𝑠𝑜𝑏 á 𝑟𝑖𝑐𝑜 𝑎 𝑃
𝑇2 𝑇2

∆ h1 −2=∫ 𝐶 𝑝 ∙ 𝑑𝑇 =∫ ( 20 , 8+52∙ 10 𝑇 ) ∙ 𝑑𝑇 → ∆ h1 −2=20 , 8 ∙ ( 𝑇 2 −300 𝐾 ) +2 6 ∙10 ∙ ( 𝑇 2 − ( 300 𝐾 ) )

−3 −3 2 2

𝑇1 𝑇1
𝑟𝑎
3 𝑒𝑡𝑎𝑝𝑎 : 𝐼 𝑠𝑜𝑡 é 𝑟𝑚𝑖𝑐𝑜 𝑎 𝑇 2

(
∆ h𝑏 − 2 = 𝑏 −
2∙ 𝑎
𝑇2 )∙( 𝑃1− 𝑃 )
∗
𝐹 𝑖𝑛𝑎𝑙𝑚𝑒𝑛𝑡𝑒 :
∆ h1 −2=∆ h1 − 𝑎+ ∆ h𝑎 − 𝑏 +∆ h 𝑏 −2

(
∆ h1 −2= 𝑏 −
2∙𝑎
𝑇1 )
∙ ( 𝑃 − 𝑃 1 ) + 20 , 8 ∙ ( 𝑇 2 −300 𝐾 ) + 26 ∙10 ∙ ( 𝑇 2 − ( 300 𝐾 ) ) + 𝑏 −
∗ −3 2 2
(
2∙ 𝑎
𝑇2 )
∙( 𝑃1− 𝑃 )
∗

∆ h1 −2= 𝑏∙ ( 𝑃 2 − 𝑃 1 ) −2 ∙ 𝑎 ∙
( 𝑃2 𝑃1
−
𝑇2 𝑇1 )
+ 20 , 8 ∙ ( 𝑇 2 −300 𝐾 ) + 26 ∙10 ∙ ( 𝑇 2 − ( 300 𝐾 ) )
−3 2 2

∆ h1−2=0,0152
𝑚3
𝑘𝑚𝑜𝑙
∙ ( 10000𝑘𝑃𝑎−1000𝑘𝑃𝑎 ) −2∙ 0,355 ∙ (
𝑚3 ∙ 𝐾 10000𝑘𝑃𝑎 1000𝑘𝑃𝑎
𝑘𝑚𝑜𝑙 698,373 𝐾
−
300 𝐾 )( )
𝑘𝐽
∆ h1 −2=18756
𝑘𝑚𝑜𝑙

𝐴 h𝑜𝑟𝑎𝑟𝑒𝑒𝑚𝑝𝑙𝑎𝑧𝑎𝑚𝑜𝑠 𝑒𝑠𝑎𝑑𝑖𝑓𝑒𝑛𝑐𝑖𝑎 𝑑𝑒 𝑒𝑛𝑡𝑎𝑙𝑝 í 𝑎𝑒𝑛 𝛼 𝑑𝑎𝑛𝑑𝑜 𝑙𝑜 𝑠𝑖𝑔𝑢𝑖𝑒𝑛𝑡𝑒:

˙ 𝑟𝑒𝑎𝑙 =18756
˙ =∆ h 𝑄𝑢𝑒𝑑𝑎𝑛𝑑𝑜 𝑎𝑠í : 𝑊 𝑘𝐽
𝑊
𝑘𝑚𝑜𝑙