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Solucin:
a) V2=10 L.
Expansin isotrmica reversible T= ctte=T2=T1
U=Cv(T2-T1)=0
H=Cp(T2-T1)=0
V2
W=PdV= RTV1
n=
10CO2
44CO2/mol
W=413.18
U=q-Wq=W
= ln
V2
V1
= (1.987
= .
*0.227=93.79cal.
10
)(300 K)ln
=413.18
2
1
2
2
1
1
=( ) =
2
= ( )( )
1 1
=( )
2
3
=1.67
1 1
5 1.671
2 = 1 ( )
= 300 ( )
= . .
2
10
q=0 U=-W = Cv(T2-T1)
3 1.987
U= (
2
H=Cp(T2-T1)= (
2
)(T2-300)= -2atm(10-5)L*(
1.987
0.082
U=nCv(T2-T1)=(0.227mol)( 1.987
)(218.73-300)K= -54.94
)(218.73-300)K= -46.1
ZnO(s)+C(grafito)=Zn(g)+CO(g)
Solucin:
HO298=?
ZnO(s)+C(grafito)=Zn(g)+CO(g)
CpZn(S)=5.35+2.4*10-3T
CpCO(G)=6.8+0.98*10-3T-0.11*105T-2
-CpZnO(S)= -(11.71+1.22*10-3T-2.18*105T-2)
-CpC(grafito)= -(4.03+1.14*10-3T-2.04*105T-2)
ZnO(s)+C(g)=Zn(g)+CO(g)
Cp=CpZn+ CpCO - CpZnO - CpC
CpZn(L)=10
CpCO(G)=6.8+0.98*10-3T-0.11*105T-2
-CpZnO(S)= -(11.71+1.22*10-3T-2.18*105T-2)
- CpC(g)= -(4.03+1.14*10-3T-2.04*105T-2)
Cp=1.06-1.38*10-3T +4.11*105T-2
ZnO(s)+C(g)=Zn(g)+CO(g)
CpZn(G)=7.75
CpCO(G)=6.8+0.98*10-3T-0.11*105T-2
-CpZnO(S)= -(11.71+1.22*10-3T-2.18*105T-2)
-CpC(grafito)=-(4.03+1.14*10-3T-2.04*105T-2)
Cp=1.19-1.38*10-3T +4.11*105T-2
693
1180
1193
H1193=56780
3. La entalpia de combustin del ciclopentano a 25 0C es de -786054 Kcal/mol.
Calcular:
a) La entalpia interna de combustin.
b) La entalpia de formacin del ciclopentano.
Solucin:
15
a) C5H10(L)+ O2(g)=5CO2(g)+5H2O(L)
2
H=U+RTn
n=5-7.5= -2.5
U=H- RTn= -786540-(-2.5)(1.987)(298)
U=-785050cal/mol =-785.05 Kcal/mol
H=-786.54Kcal/mol
b)
15
1) C5H10+ O2=5CO2+5H2O
2
2) C+O2 =CO2
-786.54 Kcal/mol
-97.052 Kcal/mol
-68.17 Kcal/mol
15
- 1) 5CO2+5H2O = C5H10+ O2
2
-786.54 Kcal/mol
5(-97.052 Kcal/mol)
5( -68.17 Kcal/mol)
H=-25.31 Kcal/mol
5C + 5H2 = C5H10
V1=V2
T1=300K
T2=350K
P1=90 atm
P2=110 atm
n=3mol
Solucion:
2
)(v-nb)= nRT
2
)(1 )
1
12
=
2
2
(2 + 2 )(2 )
2
(1 +
(P1+
)=
(P2+
1 2
2 2
2
2
1 2
2 2
P2 P1
= 2
2
1
(1 )
2
2
V1 nb =
)=
)=
1
2
P2- P1
300
)110 90
350
32
300
(1 )
350
0.752
2
1+ 2
1
2 2
P2- P1
1 2
P2+
= 1.875
2
1+ 2
1
b= -
0.75
3
0.082300
1.87532
90+
0.752
= .
V3 56.63l
V1 28.3l
T1 16C 289 K
Cv 2.5R Cv 3.5R
Determinar:
a) El calor suministrado
b) El calor producido
c) La eficiencia del ciclo
d) Demostrar que S del ciclo es
cero
3 1
TV
V1 V3
56.63
T3 1 3 289
578.31K
T1 T3
V1
28.3
23
V
56.63
P3V2 P2V3 P3 P2 3 1atm
V
28
.
3
1.4
1 2
TP
P1 P3
2.641
T2 1 3 289
763.248K
T1 T2
P1
1
2.641atm
n1
P1V1
1atm 28.3l
1.194mol
RT1 0.082 atm l 289 K
k mol
S2 3 Cv ln
T3
V
R ln 3
T2
V2
1.987cal
686.48cal
0.082atm l
S31 Cv ln
T1
V
R ln 1
T3
V3
d)
Neto
qEntrada
S Cv ln
2331
q12
100
1096.9 686.48
100 14.6%
2812.86
T2
T
V
T
V
Cv ln 3 R ln 1 Cv ln 1 R ln 2
T1
T2
V2
T3
V1
T
T
T
Cv ln 2 ln 3 ln 1 Cvln T2 ln T1 ln T3 ln T2 ln T1 ln T3
T2
T3
T1
S 0
2.En la reaccin:
kcal
kcal
; H 40.11
mol
mol
G R RT ln k p log k p
G
32.8
4.575(298)
log k p 32.8
T1 298K
T2 398K
log KP2 ?
log
kp 6.33 1032
KP2
H 1
1
KP1
4.575 T 2 T 1
44110
1
1
3. Considrese la reaccin
mol
44.9 kcal
mol
Ag 2O( g ) 2 Ag ( s ) 1 O2 g
2
G 7740 4.14T log T 27.84T
Kp PO 22
1
G RT ln K RT ln PO 22 0
7740
27.84 4.14 log T
Por tanteos:
T 450 K 450
7740
459 K
27.84 4.14 log 450
T 460 K 460
7740
460.27 K T 460 K
27.84 4.14 log 460
b) log K
log K
G
7740
4.14T log T 27.84T
4.575T
4.575T
4.575T
4.575T
1691.41
0.904 log T 6.083
T
(log K )
H
1691.41 0.904
2
T
4.575T
T2
2.303T
1691(4.575T 2 ) 0.904(4.575T 2 )
T2
2.303T
H 7740 1.79T
S
H G
T
T
T
T
T
T
T
7740
7740
1.79
4.14 log T 27.84
T
T
4.
SnO2 C Sn CO2
i)
ii)
iii)
SnO2 2H 2 Sn 2H 2O
a) Ti 610C
Tii 280C
Tiii 620C
b) PO 2i 10
22
1023 atm
PO 2ii 1045
PO 2iii 1022 atm
c)
PCO
1
1 10 0.74
PCO2 10
d)
Sn O2 SnO2
G1 82kcal
2CO O2 2CO2
G2 90kcal
G3 8kcal
log
PCO
P
G
8000
0.74 CO 100.74
PCO 2
4.575 2 T
4.575 2 1173
PCO2
e)
PH 2
10 1 1
PH 2O
f)
Sn O2 SnO2
G1 82kcal
2H 2 O2 2H 2O
G2 90kcal
SnO2 2H 2 Sn 2H 2O G3 8kcal
log
PH 2
PH 2O
PH
G
8000
0.74 2 100.74
4.575 2 T
4.575 2 1173
PH 2O
cc
y 9.673 g
mol
dP
Hf
dT T (Vliq Vsol )
Para calcular el punto de fusin a 100atm:
dT T (Vliq Vsol )
dP
Hf
Vliq
M Bi
Bi .liq
Vsol
209 g
10 g
M Bi
Bi .sol
mol 20.9 cc
mol
cc
209 g
mol 21.606 cc
mol
g
9.673
cc
cc
cc
dT 543K 20.9 mol 21.606 mol
3.52 103 K
atm
cal
cc
.
atm
dP
2633
41.293
mol
cal
cc
T
3.52 103 K
mol
P
T 3.52 103 K
mol
atm
99atm 0.3485K
SOLUCIONARIO 2 EXAMEN
FISICA QUIMICA
P1 100 Atom
WP
100
T1 600 K
V1 0.492l
I
2
T2 600 K
V2 3.011l
P2 019.34atom
IV
T4 300 L
V4
II
4
P3 1atom
4.01l
P4 6.14atom
III
T3 300 K
V3 24.6l
V3
P3
1
V3 29.6l
V1
0.492 l.
P1
100atm
1
t 1
300 1.331
V2 V3 ( 3 ) 1 24.6 l.
3.011l.
t2
600
Pz P3 (
V3
24.6 1.33
) 1atm(
) 16.34 atm
V2
3.011
Ve V1 (
T1 11
600 1.331 1
) 0.492 l.(
)
4.01l.
T4
300
Pe P1 (
V1
0.492 1.33
) 100atm (
) 6.1 e atm
V2
4.01
Ve
3.011
1.987 x 600 lu
2159.7 cal
V1
0.49e
AS I Co lu
T2
v
3.011
Rlee 2 1.987lee
3.6UR
T1
0.992
v1
AS II colu
t3
V
300
24.6
Rlee 3 6lee
1.987lee
4.17U .R.
600
3.011
t2
V2
AS III Rlee
v4
4.01
1.987 x300lee
1081.29cal
29.6
v3
v4
4.01
1.987lee
3.6U .R.
24.6
v3
Wr
1078.41
x100
x100 50%
2159.7
qi
CH
3
CHOH ( g ) CH 3 co g H 2( g )
2
K 0.36
ACp 4.0
A757.4 K
0
a) AH T AH 298
0
AH 298
14700cal
298
AH T 13508 4T
d log K
AH T
12508
4.0
2952.57
0.8743
2
2
2
dT
4.575T
4.757T
4.575T
T
T
2952.57
i log K 457.9
e
log K 2 log k1
b) KA500 K ?
log K
0.8743
dT
T
2952.57 2952.57
log K 2 0 log K 0
2952.57
2.01579 log T 6.45511 5.3560
T
2952.57
2.01549 log T 0.656
T
AG
a500 K ?
2952.57
2.01579 log 500 0.656
500
log K 0.1833
K SOGR 01.5
9.29cal
1mol
P1 1mol
a ) AS AS1 AS 2 0
T1 )373K
AS1 0 AS 2
T1
CO
Q1
T
dT
dT
CO
T
1
T
T
T
T
T
T
lee
lee
lee
lee
0
T1
T2
T1
T2
T
lee 2 0 T 2 T1 T2 373x 273
T1 T2
P 0.5atom
t 319.1K
Q1 Q2 W
Q2
T 319.1K
1mol
1
T
p 5
319.1
b) ASi Cplee
elee
1.987 lee
1.987lee 3
373
1
T1
p1 2
T2 273K
P2 1atom
Q2 Cp T T2
5
1.987 319.1 373 229.cal / mol
2
cal
xcal 77.4cal
mol
4.
a ) i )800k
ii )850k
iii )860 k
iv) 780k
b) 4k O2 2k2 O
A6 65kcal
65000
11.16
4.575(1273)
Po2 1011.16
1010
Graficamente
1012
c ) 4k
O2 2k2 O
65
2CO
O2 2Co2
53
Pco
101.54
Pco2
Pco
Pco
18000
log
1.5e
Pco2
Pco2 2 x 4.575 x1273
d ) 4k
2H 2
O2 2k2 O
O2 2 H 2 O
2K2O
65
83
2 H 2 4k 2 H 2 O 20kcal
AG 2 x 4.575 xT log
PH 2
PH 2
20000
log
1.71e
PH 2 O
PH 2 O 2 x 4.575 x1273
PH 2
101.71
PH 2 O
5.
T1 47 C 226 K
log
T2 10 C 263K
K2
ArT 1 1
( ) log K 2 log K1
K1
4.575 T2 T1
log K 2
1149
7.481
T2
log K1
1149
7.481
T1
1 1
AH 1 1
log K 2 log K1 1149
T
T
4.575
2
1
T2 T1
AH 1149 x 4.575 54 BO
AH 108.5
cal
g.
cal
1ml
x
108.5cal / g .
mol 50.5 g .
FISICO QUIMICA
ingeniera petrolera
EXAMEN OPTATIVO
El calor suministrado.
El calor producido.
La eficiencia del ciclo.
Demostrar que S del ciclo es cero
2.- En la reaccin:
(CH3)2CHOH(G) = (CH3)2CO(G) + H2(g)
Kp a 457.4 K ES O.36, Cp = HO 298 = 14700 Cal
a) Derivar la expresin para el log. Kp como una funcin de la temperatura .
b) Calcular Kp a 500 K
3.- Deduzca el H0298 para la reaccin:
2 CH4(g) = CH3CH3(g) + H2(g)
a) Conbinando las ecuaciones de los calores de combustion de los tres
reactivos (Tabla 11.1)
b) Determinar el H500 K de la reaccin, utilizando calores molares de la tabla
11.5
23
= 289 (
56.63
28.3
) = 578.51
ADIABATICO
56.63
28.3
) = 2.641 atm.
12
P1
T1
P3
T2
T2 = T 1
3
1
= 298(
2.641
1
) = 763.248
) (763.248 289)k
U = q 1- 2 = 2812.86 cal.
n1 =
11
1
1 .28.3
0.082
289
= 1.194 mol
S1-2 = Cvln
) (578.31 763)
SOLOCION: 2
Kp1 =; T1 = 457.4K; Cp = 4,0; H0 298 = 14700 cal.
2
2
() =
0.36
757.4
13508
4
+
)
2
13508
4,575
2952
LogK (0,4437) =
2952
LogK =
13508
4,575(457,4)
4
4,575
2952
ln(457.4)
+ 2.01logT
+ 0,654
b) LogK =
4
4,575
K = 1.52
SOLUCION: 3
2 CH4(g) = CH3CH3(g) + H2(g)
I.
Hi = -212.80Kcal
II.
C2H6 +
III.
H2 +
1
2
2 = 2CO2 + 3H2O
HII = -372.82Kcal
HIII = -68,317Kcal
O2 = H2O
2CH4 = C2H6 + H2
SOLUCION: 4
a) T1 = 95 0F = 350 C = 303K R1
T2 = 1220F = 502 = 323K R2 = 3R1
2
() =
1
ln( ) =
1
2
H = 14477.86
b) S 2 S = RlnK2 +
S = Rln +
2
1
+ (
2
1
2
RlnK1
15708.35 cal
323
S = 0
303
a)
K1 2
7
K 2 K1
K2 7
2
log
K2
AM 1
1
log
K1
AH 1
1
K1
4.575 343 308
b)T1 :
AS1
T1 :
4.575log k1
T1
T1
AS2
AH 2 4.575T2 log k2 AH 2
4.575log k2
T2
T2
4.575log
AH 2
AH1
4.575log K1
T2
T1
1
K2
1
AH AH1 AH 2 de
K1
T2 T1
7
1
1
4.575log 7487
2.489 2.485
2
393 308
A52 As1 4 x103 cal / xmol
3.2l
P1
15
v1
1/2
P1 r2 P1
P2 r1 p2
1/2
P
V
2 v2 v1 1
V1
p2
1 3
15
3.2l
5
V2 7.5 l 7.45l
V
T1 v1 T2 v2 T2 T1 1
V2
b) q 0
# w
x 1
x 1
AU Cv T2 T1 6.593
x 1
1.31
3.2
293R
7.45
227.38R 45.6 C
Cal
227.38 293 K 2 mol 865.26 Cal
K mol
w 865.26 cal
AH Cp T2 T1 8.58
cal
227.38 293 k 2mol 1126.04 Cal
k mol
3.
a ) (i ) 2k2 O C 4 K CO2
TMIN 800 C
i
a 2 k20
4
TMIN 780 C
iv
a k Po2
1
Po2
AG
65000
c) 4k O2 2k2 O
AG1 65
2CO O2 2CO2
2 1
AG2 82
Pco2
k 2
2
a k2 o P co Pco
AG 17 k cal / ml
2
Pco
Pco2
Pco
AG
17000
Pco
1.45
101.45
Pco2 2 4.575T 2 4.575 1273
Pco2
log
d ) 4k O2 2k2 O
2 H 2 O2 2 H 2 O
AG1 65
AG3 83
ak4 P 2 H O
2
2
k2 O
2
H2
PH O
2
PH
2
PH
PH O
2
log
PH
PH O
2
PH 2
G
18000
1.54
101.54
2 4.575T 2 9.575 1273
PH 2 O
AH10 370 K ?
(i )
0
0
0
3
AH1370
(Cu Cl ) AH1370
i AH1370
Cu 1 2 1H1370
Cl2
0
a) CALCULO DE AH1370
Cu Cl
AH1
AH 2
AH 3
0
1) AH10 AH 298
703
298
Cpdt 32200
703
208
5.87 19.2 10 T dt
3
0
3) OH 3 CpdT 15.8 1370 703 10538.6 Cal / mol
AH10 0 25930.8 Cal / mol
2) OH 30 2450 Cal / mol
0
b)Calculo de AH1370
Cu
AH1
0
1) AH10 AH 298
k
1356
298
AH 2
CpdJ 0
0 5.411356 298
AH 3
1356
298
5.41 1.50 10 T dt
3
1.50 103
13562 2982 7036.3
AH1370 Cu AH1 AH 2 AH 3
0
c)CALCULO DE AH1370
k CL2
1370
298
1370
298
8.82 0.06 10
Cpdt
T 0.68 105 T 2 dt
0.06 103
1
1
8.82 1370 298
13702 2982 0.68 105
2
1370 298
0
AH1370
Cl2 9330 Cal / mol
0
0
0
AH1370
i AH1370 CuCL AH1370 Cu
12942.2 10241.3
1
9330
2
0
0
0
AH1370
i AH1370 CuCl AH1370 Cu
12942.2 10241.3
1
0
AH1370
Cl2
2
10
0
AH1370
Cl2
2
1
9330 27848.5 Cal / mol
2
0
AH1370(
i ) 27.85 Kcal / mol
5. DATOS:
28.3l
n
P1 v1
1x 280
RT1
0.0828289
n 1.194mol
T1 289 K
P1 1atom
V1 283l
Vc V1
V3
P3 1atom
V3 56.83l
Cp 3.5 R
1.4
Co 2.5 R
T3 T1 3
V1 T3
v1
56.63
T3 289 K
28.3
T3 578.31K
ETAPA 2 PROD. ADIABIATICO
V
56.63
P2 V2 P3 V3 P2 P3 3 1atom
28.3
V2
1.4
20641atomCp2
1.917cal
686.484cal W3 1
0.082atom
Warto
0 1096.9 686.484
x100 14.6%
qSUMINISTRADO
2812.87
d ) AS1 Cplee
T2
P
elee 2
T1
P1
AS 2 Cplee
T3
P
elee 3
T2
P2
AS3 Cplee
T1
P
Rlee 1
T3
P3
P1 P3
T T T
P
P
AS Cplee 2 3 1 Rlee 2 Rlee 2 0 AS 0
P1
P1
T1 T2 T3
298
= 10540
24 () 2 6 () + 2()
2 (4 ) = 2(5.65 + 11.44 103 0.46 105 2
(2 6 ) = (2.706 + 29.16 103 0.9059 105 2
(2()) = (6.52 + 0.78 103 + 0.12 105 2
= 2.074 7.06 103 + 1.7059 105 2
500
(500 ) = (298
) + 298 (2.074 7.06 103 + 1.7059 105 2 ) Dt
7.06
103 ( 5002 2982 ) 1.7059
2
1
1
105 (
)
500 298
7.06
103 ( 5002 2982 ) 1.7059
2
1
1
105 (
)
500 298
= 15622.2 cal
2a)
7
b) 2CO2 + 3H2 O = C2 O6 + O2
2
2( 212.8)
372.82
c)
H2 O = H2 +
1
O
2 2
2CH4 = C2 O6 + H2
68.317
OH = 15.537 cal
2) (3)
A) 3 mol de un gas local diatomico se comprimen adiabticamente en
un solo estadocon una presin ctte de oposicin igual a 8 atm.
Sucesivamente el gas esta a 30 y 1 atm de presin; la presin final es de
5
5
2
SOLUCION
1 = 30 = 303; 1 = 1 ; 2 = 8 = 52
PROCESO ADIABATICO: q = 0; U =
5
Cv (T2 303) = PCP (V2 V1 ) = PCP R T
= R(T2 T1 ) =
T
( 2 1) 2
P2 P1
=
5
T2 303
7
R(T2 303) = 8 (
) T2 = 3131.5
2
8
1
2
T2 = 909 K
U =
5
1.987(909 303) = 9030.9 cal
2
= 4595 cal
7
1.987(909 303) = 6363
2
2
2 7 909
8
= ln ln = ln
1.987 ln = 0.3840
1
1 2 303
1
=
B. 1 = 1 1 = 303 2 = 8 =
2
=
= 2 = 1.4
5
2
1
2
8 1.41
2 = 1 ( ) = 303 ( ) 1.4 = 548.85
1
1
5
1.987(548.85 303) = 3663.78
2
7
= 1.987(548.85 303) = 5129.29
2
=
=0
= 3667.78
3) (4) EN UN PROCESO
5
7
1 = 28.3 ; 1 = 2 = 1 ; 1 = 10 ; 3 = 56.63 ; = ; =
2
2
DETERMINAR:
A.
B.
C.
D.
EL
SUMINISTRADO
EL
PRODUCIDO
LA EFICIENCIA DEL CICLO
DEMOSTRAR QUE EL DEL CICLO ES CERO
= ln
2
3
3
1
1
+ ln + 2 ln + ln + 2 ln
1
2
2
3
3
= ln
2 3 1
= ln 1
1 2 3
= 0
( ln ) =
= =
2
2
1
1
ln =
( )
1
2 1
31
1
1
1
1
1
ln
=
( )=
(
)( )
1
2 1
1.987 323 303
= 14477.86
B..
1 = 1 1 1 = ln 1
1 =
1
+ ln 1
1
1 = 2 2 2 = ln 1
2 =
2
+ ln 2
2
= =
1 = 2 =
2 1 = ln 2 +
2
1
ln 1
2
1
= ln
2
1
1
1
1
+ ( ) = 1.987 ln 3 + 14477.86 (
)
1
2 1
323 308
= 2 1 = 1.75 107
=
0
1.
a) Determinar si la reaccin de reduccin de FeO a Fe, segn:
() + () = () + 2()
Es espontanea o posible a 1200 C, sabiendo:
() + 12 2() = () ; = -59830 + 11.94 T
() + 12 2() = 2() ; = -65280 + 17.89 T
a 1200 C.
2
c) Utilizando los diagramas de Ellinghan determine el de la reduccin
de FeO a Fe a 1200 C y compare con el resultado de (a).
d) Graficamente utilizando el diagrama de Ellingham determine la relacin
SOLUCION:
a) () + 12 2() = () ; = -59830 + 11.94 T
T = 1200 C = 1473 K
a) () + 12 2() = () ; = -59830 + 11.94 T
b) () + 12 2() = 2() ; = -65280 + 17.89 T
_________________________________________________________
( b - a ) FeO + CO = Fe + 2
= -5450 + 5.95
T
1473 = -5450 + 5.95 (1473) = -3314.35 cal
b)
Log
4.575
3314.35
= 0.4918
4.575 (1473)
a) 2Fe + 2 = 2 FeO
- 82
b) 2CO + 2 = 222
-72
________________________
1
1
10
= 3.1
___________
= 4000 cal
d)
1200
DEL DIAGRAMA
c)
DEL GRAFICO
2 = 60 C = 333K
a) Log
2
1
2 = 4 1
=
4.575
4.575 4
(
1
2
1
1
1
2
1
1
) = Log
4.575 4
(
1
333
1
)
313
4 1
1
= + 14360 cal
b) = R1 Ln 1 = 4.575 1 Log 1
Log 1
= 10 - 1
4.575 Log 1
= Log 4
H1 - 1 1 = -4.575 1
1 =
1
1
POR SIMILITUD: 2 =
2
2
+ 4.575 Log 2
1 = 2 = = cte
= 2 - 1 =
= (
1
2
) = 4.575 Log
2
1
= + 14360(
1
333
313
) + 4.575 Log
4 = -9 x 10
SOLUCION:
() = ()
= 500 cal/mol
T = 13 C = 280 K
() = 5.75 g/cc
( ) =
( ) =
() = 7.28 g/cc
()
()
( () () )
118.7 /
7.28 /
118.7 /
= 20.64 cc/mol
5.75 /
= 16.3 cc/mol
)(41.293
)
(500
= -0.060119
= 100atm
= -0.060119 K/atm
= ( - 0.060119
2 =
=
=
(0.082
0.082 473
1
1 = 100 1 = 1
)(373)
= ( 2 1 ) = (1.987
1
P = cte = 1 atm
= ( 2 1 ) = (1.987
1 =
= 30.586 l/mol
= 38.785 l/mol
1.987
0.082
198.7
cal/mol
= q w
= ln
- R ln
(1.987) ln
473
373
= 1.179 cal/mol
b) 2 = 12 ; ISOTERMICO Y REVERSIBLE
= ( 2 1 ) = 0
q = w = P(2 1 )
= ( 2 1 ) = 0
1 = 2 = =
1 =
2 =
0.082 373
1
0.082 373
1
2
= 30.586 l/mol
= 61.172 l/mol
1.987
0.082
370.57 /
2
1
= ( )
2
2
3
= 0.9935 cal/mol k
373
c) 2 = 12
1 1 = 2 2
= 37.057 cal/mol =
ADIABATICA Y REVERSIBLE
( )
2
1
2 = 1 ( )
= 1.67
1
2 = 30.586 ( 1 )
1
1.67
1
2
= ( 2)
1
2
2
1
1
2
2
( 2) = ( 2)
2 = 373 (
30.586 1.671
46.32
= (2 1 ) =
= (2 1 ) =
2
2
= ( 2)
2 = 1 ( 1 )
= 282.45 K
( 1.987
( 1.987
= 0 (ADIABATICO)
= - W
W = 269.88
= 0
2 = 98.9
d) = 12 2 = 12
0.0822
= 0.1672
1
ADIABATICO q = 0
2 =
=
3
2
(1.987
(2 1 )
= - (2 1 )
1
1.987
0.082
4.957 2 = 1482.29
= (2 1 )
2 = 298.42
W = 222.26 cal/mol
= (2 1 ) =
= Ln
2
1
0.665 + 0.933
+ R Ln
2
1
5
2
3
2
( 1.987) Ln
298.42
373
+ 1.987 Ln
48.94
30.586
= -
a) d(lnk)= 2dT
a)
ln =
1
41
) ln
1.987 333
313
)=1.386
=2s1= 2+Rlnk2
2
2
1
2 = 2 22
2 = 22
T2:
-RT1lnk1=1-T1s1
s1= 1+Rlnk1
1
1
-RT2lnk2=2-T2s2
s2= 2+Rlnk2
2
= 1 = 2
+Rlnk1
41
+ ( ) = 1.987
+ 14435 (
1
333
1
313
= . . = . -2cal/Kmol
2:
a) Deduzca la variacin de entalpia para la reaccin a 25C de :
2 CH4(g) =CH3CH3(g) + H2(g)
Combinando las ecuaciones de reaccin de formacin y las ecuaciones de calor
de combustin de los tres reactivos
b) Deduzca la variacin de entropa para la reaccin a 25C
c) Calcule la variacin de energa libre para la reaccin a 25C
d) Cual es el valor de la constante de equilibrio para esta reaccin
Solucin:
a) 2CH4(g) = CH3CH3(g) + H2(g)
1. C + 2H2 =CH4
= 17.89 /
2. 2C+3H2 =C2H6
= 20.24 /
2C+3H2 =C2H6
-2(1) 2CH4 =2C +4H2
2CH4
= 20.24 /
= 2(17.89 )
C2H6 + H2
= 15.54 /
7
H 372.82 Kcal
1) C 2 H 6 O2 2CO2 3H 2 O
mol
2
=
1
2) H 2 O2 H 2 O
2
3) CH 4 2O2 CO2 2H 2 O
H 68.317 Kcal
H 212.8 Kcal
mol
mol
H 2(212.8) Kcal
1
H 2 O H 2 O2
2
7
-(1) 2CO2 3H 2 O C 2 H 6 H 2
2
2CH 4 C2 H 6 H 2
H 68.317 Kcal
-(2)
H 372.82 Kcal
H 15.537 Kcal
mol
mol
mol
mol
b)
Kmol
c)
mol
G
16416.12
a) P11 =P22
P1
P2
= ( )
= ( )
1.43
2.86
T1
T2
=( )
= ( )
1.43 1.41
= ( ) =298 K( )
=225.8 K
2.86
) q=0
=Cv(T2 1)n=4.913(225.8298)0.1755=62.4 cal
=Cp(T2 1)n=6.9(225.8298)0.1755= 87.4 cal
W==62.4
4:a) Determinar si la reaccin de reduccin de FeO a Fe, segn:
FeO(s) + CO(g) = Fe(g) + CO2(g)
Es espontanea o possible a 1200C, sabiendo:
Fe(s) + O2 = FeO(s) ;G= -59830+11.94 T
CO(g)+ O2 =CO2(g)G= -65280+17.89 T
b) Determine la reaccion PCO /PCO2 a 1200C
c) Utilizando los diagramas de Ellingham determine el G de la reduccin de
FeO a Fe a 1200C y compare con el resultado de (a)
d) Grficamente utilizando el diagrama de Ellingham determine la relacin PCO
/PCO2para la reduccin de FeO a Fe.
4.
a)
1
FeO Fe O2
2
1
CO O2 CO2
2
FeO CO Fe CO2
G 59830 11.94T
G 59830 11.94T
G 5450 5.95T
G RT ln K
b)
P
P
O2
CO
CO
CO
log PCO2
CO
c)
3314.38
0.49
4.575(1473)
CO
P
P
CO 2
CO
G
4.575(1473)
3.09
P
P
CO 2
CO
3.09
FISICO QUIMICA
Ingeniera
Petrolera
EXAMEN FINAL
G = - 1200 + 41.0 T
G = - 119250 + 67.25 T
4 FeO + O= 6 FeO
G = - 135100 + 41.5 T
2 CO + O = 2 CO
G = - 193725 + 6.04 T
2 Fe + 3/2 O = Fe O
G = - 260775 + 74.75 T
3 Fe + 2 O = Fe O
Sb
Pb
T (C)
630.5
327.4
H, (KJ/mol)
23.1
5.1
El calor suministrado
El calor producido
La eficiencia del ciclo
La entropa del proceso
1. a)
-2(i)
G=-2(1
G= (6
119250+67.25T)
2 CO+1 O= 2 CO
3
3
3
(iii)
G= (3
135100+41.5T)
2 Fe CO + O= FeO +2 CO
2
G=-
40908.3-56.97 T
Log K=
Log K=
(log )
40908.3
4.575
8941.7
56.97
4.575
+ 12.45
8941.7
=-
4.575
H=-40908.3
4.575
b) (i) 2 Fe + 32 O= FeO
G=-
193725+6.04 T
2
- (i)
3
193725+6.04 T)
2 FeO
3
4 Fe + O
3
G=- (3
(iii)
G=-
CO+ O= 2 CO
135100 + 41.5 T
2
3
FeO
G=-
+ 2 CO = Fe + 2 CO
5950+37.47 T
T=
5950
37.47
= 158.8 K
(i) 3 Fe + 2 O
G=-260775 + 74.75
= FeO
T
- 12(i) 12 FeO = 32 Fe + O
G=- (260775 +
2
74.75)
(iii)
2 CO +
G= -135100 + 41.5
= 2 CO
1
2
FeO + 2 CO =
4712.5
T=
4.125
3
2
G= - 4712.5 + 4.125 T
Fe + CO
= 1142.4 K
2. datos:
1
101..325
a) PV=nRT
( 0,082
)(673 )
98.69
= 0.56
18
= 0,03106
V= 0.03106
b) De la tabla A1:
Pr=
Tr=
10
22.06
673
647.1
Tc= 697.1 K
= 0.45
= 1.04
Del diagrama de Z
z= 0.83
V= Z V ideal = 0.83(0.03106
)= 0.036
c)
(P+
)(V-b)= RT
atm Vc=0.056
b=
0.056
= 0.0187
(98.69 +
2.04
)(V-0.018)=55.18
POR TANTEOS
Para v= 0.54
(98.69 +
V=0.54
7.04
)(0.54-0.018)= 55.18
(0.54)
18
= 217.7
101.325
= 0.03
0.026436
3.
Hf (Pb)=5.1
=1.2
Hf (Sb)=20.1
= 4.8
Log X Pb = -
Hf (Pb)
Log X Sb = -
Hf (Sb)
T(C)
4.575
4.575
+
+
Hf (Pb)
4.575 Tf (Pb)
Hf (Sb)
4.575 Tf (Sb)
Log X Pb
Tf (Pb)=327.4 C= 600.4 K
Tf (Sb)= 630.5C=903.5 K
==-
262.29
+ 0.4368
1049.18
X Pb
500
+ 1.1612
Log X Sb
X Sb
-0.196
0.637
300
-0.02094
0.953
-0.6698
0.214
100
-0.26639
0.541
-1.6516
0.022
600C=
()+()
0.2
0.20
0.780
%liq= *100 =
%liq= 25.64
%Sb=74.36
*100
c
0.78
0.2
0.84
0.20
0.840
% E=
*100 =
*100 = 23.8%
84% Pb
16% Sb
%Sb=76.2%
4.
n = 5 mol
Cv= 3/2 R
CP= 5/2 R
q= 0
U= -w
Ev(Tz-T1) = -Pop (V2-V1)= - POP R (T2/PL T1/R)
3/Z R (Tz-T1) = -PopR (T2/PZ-T1/P1)
3/Z Tz 3/2 (298)= -TZ+ 298/10
5/Z Tz = 29.8 + 447
Tz= 190.7K
V= Vc (T2-T1)=3/2 (1,987 cal/kvol)(190,7-298)K-319,8 cal/vol * 5 vol = -1599 cal
w= 1599 cal
5
H=Cp(T2-T1) = (1.987
)(190.7-298)K=-533
1.-
A)
KJ
m
KJ
m
AHf (Pb)
RT
= 1.2
= 4.8
Kcal
Kcal
mol
AHf (Pb)
RTf (Pb)
Log X Pb = -
mol
262.29
T
1200
4.575 T
1200
4.575 (600.4)
0.4368
Log X (Sb) = -
AHf (Sb)
RT
Log X Sb = -
AHf (Sb)
RT(Sb)
1049.18
T
= -
4800
4.575 T
4800
4.575 (403.5)
1.1612
T C
500
Log X (Pb)
X (Pb)
Log X (Sb)
-0.196
X (Sb)
0.637
300
-0.02094
-0.953
-0.6698
0.214
100
-0.26639
-0.541
-1.6516
0.022
B)
T1 : Fase Liquida : Sb (L) + Pb (L)
0.3
0.79
0.3
0.86
T2:
T3:
ab
% LIQ =
bc
% Sb =
%E=
a`b`
``
b`c`
% Sb =
``
x 100 =
x 100 =
x 100 =
x100 =
0.30
0.790
0.790.3
0.790
0.30
0.860
x 100 = 34.88 %
0.860.3
0.560
x 100 =65.12 %
= 1100 C
Tii = 1330 C
C)
Tiii = 1230 C
B)
2 Zn +O2 = 2 Zn O
Log K = -
AG
4.575
=-
Po2 a 500 C = ?
(132000)
44.575 (773)
= 37.32 = Log (
)
Po2 = 10 a la 37.32
C)
K=
1
2
d) 2 Zn + O2 = 2 Zn O
b) 2 CO + O2 = 2 CO2
(-) 2 Zn O + 2 CO = 2 Zn + 2 CO2
K=
Log
PCO2
AG = - 4.575 T Log (
PCO2
AG
24.575
30000
24.575 (773)
PCO
Grficamente
AG () = 30 Kcal
PCO2
) = 2 x 4.575 T Log
= 4.24
PCO
2
PCO2
= 10 a la 4.24
= 10 a la 4
(Ver diagrama)
D)
) 2Zn + O2 = 2ZnO
AG = -132 Kcal
) 2H2 + 2 H2O
AG = -97 Kcal
K=
Log
PH2O
2
PH2O
2
AG = -4575 T Log (
AG
24.575
PH2O
2
35000
24.575 (773)
AG = 35 Kcal
PH2O
2
) = 2 x 4.575 x T Log
= 4.94
= 10 10 a la 5
PH2
2
PH2O
2
= 10 a la 4.94
Graficamente
3)
(ver diagrama)
5 kg 2 = 3000g 2 x
1
18 2
= 166.7mol 2 = 0.867
1
2 kg 6 6 = 2000g 6 6x
6 6 = 0.133
78 6 6
0.1
62.7
6 6 = 195.0 mmHg
0.3
92.1
P = +( )
0.5
121.5
0.7
150.9
0.9
180.3
P = 48 + (195 48)
P = 48 + 147
1 kg 2 =
5 kg 6 6 =
1000
= 55.56 464.3
18
5000
78
= 64.1
= 119.66
2 = 0.464
6 6 = 0.536
=
=
( )
(95)(60)
95(19548)
= 25.6mol
2 = 48.0 mmHg
9360
195147
4)
(i) 2C + O2 = 2CO 1000K =-95.3 Keal
Log K =
(95300)
4.575(1000)
2 CO
O2
(a)
(94000)
4.575(1000)
CO2
O2
(b)
0.1
51.91
0.3
62.02
0.5
77.03
0.7
101.62
0.9
149.28
932
6000
3
2
7400 2 = 399600
932
1000
= 78.87 + 298
= 74,87 + 0,265 ln
= 79,94
5.-
932
298
2500
932
1000
+ 932 "
1000
2 + 932 0,215
5,36 0,215 ln
1000
932
A,-) = = 1 = 2
= (2 1) = 0
= (2 1) = 0
2
= 9 = = = 1
= 1,987298 ln
40
20
= ln
2
1
= 410,43 5 = 2052,15 =
2052,15
298
= 6,98
) = = 1 2
= 0
= 0
= (2 1) = 1 (40 20) ln
= 2423,17 = =
=
2423,17
298
= 8,13
1,987
0,082
= 484,63 5
P=1600 kpa
1
101,325
= 15,79
l
))(498k)
kmol
(0,082(atm
V=
15,79
= 2,58
t=225c = 498k
1
18
1000
1
13
1000
= 0,14362
1000
1
= 0,056
101,325
= 217,7
= 3 2 = 3(217.7) (0.056
=
( +
0,056
= 0,0187
) = 2.048
(15,79 +
2,048
2
) ( 0,0187) = 40,836
2
2
= 2,5
= 2,55
= 2,55
(15,79 +
2,048
2,52
(15,79 +
1
18
2,048
2,552
= 0,1417 = 0,1417
1,6
= =
= 0,072
= =0,9350,14362
22,06
C) {
= 0,935
3
498
=0,1343
= =
= 0,769
647,3
D) de tablas a-6
3
= 1,6
= 0,13293
{
= 225
2.- se tiene una mezcla binaria compuesta por 200kg de benceno y 100kg de
tolueno a 27c, las preciones de vapor de los componentes puros a esta
temperatura son: 103,01 mmhg para el benceno y 32,06 mmhg para el tolueno
determinar:
A) a que precion se formaran las primeras seales de vapor.
B) cual es la composicion de la primera muestra de vapor formada.
C) si se produce aun mas la presion de la primera muestra de vapor. a que
presion desaparese la ltima seal de lquido?
D) cual es la composicion de la ultima seal de liquido.
Sol:
2006 6
1000
1007 8
1000
78
92
= 256066 6 6 = 0,702
= 108778 7 8 = 0,298
= 32,06
= 103,01
Curva burbuja
curva rocio
= + ( ) 6 6
= 32,06 + 70,95 6 6
( )6 6
32,06103,01
103,01(70,95)6 6
3302,5
103,0170,956 6
6 6
6 6
39,155
0,1
34,435
0,1
53,345
0,3
40,41
0,3
67,535
0,5
48,9
0,5
81,725
0,7
61,908
0,7
95,915
0,9
84,394
0,9
120
= 103,1
100
82mmHg
80
62mmHg
60
CURVA BURBUJA
CURVA ROCIO
40
20
0
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
se dejan
2 = 73,5 = 5
= 8,58
= = 6,593
= 1,3
A)
1 1
2 2
15
( ) =
2
2
1
2 = 1 ( ) = 1 =
2
1
1
)(293)
(5)(0,082
15
= 8
2 = 8( )1,30 = 18,62
5
2
1
18,62
= ( 1 )1 2 = 1 ( 1 )1 = 293(
)1,31 = 227,6
B) = 0 ( )
= 0 ( )
= = (2 1 ) = (5) (6,593
W=2162,5 cal
= (2 1 ) = (5) (8,58
2 ()
68,31
()
6 6
94,05
()
780,98
2 2 ()
310,6
(
29,756
()
= 6 6 ()
50,0
A) 62 () + 32 () = 6 6
6()
+ 62
()
= 62
32
+ 2
()
= 32
6 () + 32
()
= 6 6
()
3
2
()
15
2
2 ()
= 780,98 /
= 6(94,05)/
()
= 3(68,31)/
()
B) 32 2
62
()
()
32 2
()
15
2
()
= 62
+ 32 () = 6 6
= 6 6
= 11,75/
()
()
()
+ 32 ()
+
15
2
()
= 3(310,06)/
= 780/
= 151,8 /
()
= 0 3 = 3
= = 151800 + 1,987 298 3 = 150023,6 /
6 + 32 = 6 6
= 29,756
2 + 2 = 2 2
= 50,0
6 + 32 = 6 6
= 29,756
32 2 = 6 + 32
= 150,0
32 2 = 6 6
= =
= 120,244 /
151800(120244)
298
= 105,9 /
4,575
(120244)
4,175(298)
= 88,19 = 1088,19
Ingenieria Petrolera
n=
P= 111 BAR
860
44/
PV= nrt = T
= 109.55 atn
= 19.5454 mol
=
109.55 2
19.5454 0.082
= 136.7 K
(P +
2
2
) (v - nb) = nrt
a = 3Pc ()2
a=
b=
27 2 2
64
Vc =
(304 )(0.082 /)
873.03
T=
b=
(+
) ()
2
= 359
3
8
2
2
= 0.043
T = 327.32 K
Pv = ZnRt
Vr =
(Volumen Molar)
Pr =
3(304 )(0.082
8 73.03
= 0.128
0.8
Pr =
=
= 0.1023
19.5454
109.55
73.03
= 1.5
= 0.8
= 0.85
Vr =
0.1023
0.128
Pr = 1.5
109.55 2
=
= 160.83
= 8.68 = = =
6.593
1 = 15
2 = 73.5
= 5
1 1 = 2 2
1
2
1
2
1
=( ) ( )=
= 2 = 1 ( )
2
1
2
1
2
8.58
6.593
= 1.3
5 0.082 1 2931
15
1 =
1
1
= 8
15 1
2 = 8 ( ) 1.3 = 8(3)0.769 = 18.62
5
2
2
1
2 1
= ( ) = ( 2 ) = ( )( )
1
1
2
1 2
1
1 1
2
1 1
8 1.31
( )
=
2 = 1 ( )
= 29312 (
)
2
1
2
18.62
= 293 0.42960.3
2 = 227.4
q=0
= = (2 1 ) = 5 6.593
= 2162.5
= (2 1 ) = 5 8.58
(227.4 293)
12
= 2814.2
=
=0
() =
2
1
( )
21
1
1
(
)=
(
) = = 6886.45
1
1.987 1300 283
1 : 61 = 1 1 1
1 1 = 1 1 1
61 = 1 1
1 =
2 : 62 = 2 2 2
62 = 2 2
2 1 =
2
2
+ 2
1
1
2 2 = 2 2 2
2 =
1
1
+ 1
2
2
+ 2
2 =
= (
1
1
2
1
1
) +
= 6886.45 (
) + 1.987
2 1
1
300 283
1 =
2 1 = 1.37728 + 1.37728 = 0
2 +
3
= 2 3
2 2
298
= 7400
298
= 74.87
Sabiendo:
Temperatura de fusin del = 659
Calor de fusin del Al en su punto de fusin = 2500 /
(2 3 ) = 25.14
(2 ) = 7.57
= 199800
(() ) = 6.76
(() ) = 7.00
Solucin:
298
= 7400
= 659 = 932
= 1000 = 1273
232
1273
= 298
+
298
1273
1 + +
932
11
3
1 = 2 3 2 (1) 2
2
3
= 25.14 2(6.76) (7.57) = 0.265
2
3
11 = 2 3 2 () + 2
2
3
= 25.14 2(7.00) (757) = 0.215
2
1273
= 199800 + 0.265(932 298) + 282800 0.215(1273 932)
1273
= 194705.315
1273
298
932 1
1273 11
932
298
1273
=
22500
0.215(1273 932)
932
79.99
o
A6 = AH1273
1273AS1273 = 194705.315 1273(79.99)
o
A61673
= 92878.095 cal
o
A61273
= 9.575 TlogK
logK =
92878.095
= 15.8
4.575x1273
K = 8.7X1015
= 195.0
= 48.0 . .
2001000
= 100
1000
= + ( )9
(0 0 )4
XB
Pr
YB
Pruebas
0.1
62.7
0.1
51.91
0.3
92.1
0.3
62.027
0.5
121.5
0.5
77.037
0.7
150.9
0.7
101.62
0.9
180.3
0.9
149.28
180
160
140
= 120 ()
120
= 94.8 ()
100
= 76 ()
80
= 62 ()
60
= 0.64()
= 0.1 ()
40
0.1
= 200
0.3
10008 1
1
78
= 2564
0.5
0.7
0.9
0.10
= 50
1000 1
1
18
=2777.8 mol
=
= 0.48
+
= 0.52